Events

The development of sustainable methods for the closed-loop production and recycling of plastics is an important challenge of current times. Reactions based on catalytic (de)hydrogenation are atom-economic, and sustainable routes for organic transformations.1 Using the following examples, this lecture will discuss the application of homogeneous (de)hydrogenative catalysis for the synthesis and degradation of polymers to enable a circular economy: (a) synthesis of polyamides/nylons from the ruthenium catalysed dehydrogenative coupling of diamines and diols and its reverse reaction i.e. hydrogenative depolymerisation of nylons,2 (b) synthesis of polyureas from the ruthenium/manganese catalysed dehydrogenative coupling of diamines3,4 and methanol, and its reverse reaction, i.e. hydrogenative depolymerisation of polyureas (Figure 1B)5, (c) Synthesis of polyethyleneimines from manganese catalysed coupling of ethylene glycol and ethylenediamine or the self-coupling of ethanolamine,6 and (d) Synthesis of polyureas and polyurethanes from the dehydrogenative coupling of diformamides and diamines/diols and its reverse reaction i.e. hydrogenative depolymerisation of polyureas and polyurethanes to diformamides and diamines/diols.7 Some applications of some of the polymers made using dehydrogenative processes in the field of batteries will also be discussed.8

Mantle fluids are the primary carriers of key volatile elements that make the Earth’s long-term planetary habitability possible. The interaction of such volatile-rich fluids with the mantle rocks, especially the sub-cratonic lithospheric mantle leads to alteration of the mantle as well as its melting. High-density fluids encased inside diamonds are the best natural representation of mantle fluid compositions, suggesting their compositions are saline, silicic or carbonatitic. However, the origin and role in the mantle as well as their role in altering the mantle are still unclear. In my research, we approach these questions by experimentally simulating the interaction of volatile-rich fluids with mantle rocks at known pressure and temperature relevant to the mantle. Examining different mixtures of volatiles (H2O and CO2) and mantle rocks (peridotite and eclogite), we attempt to understand the origin of each type of fluid found in diamonds as well as study the effect of such interaction on the mantle chemistry and mineralogy. Compiling many experimental studies reveals that fluids ranging from silicic to low-Mg carbonatitic are formed in systems of eclogite+H2O+CO2, the more CO2 in the system, the more carbonatitic the fluid is. Fluids ranging from low-Mg carbonatitic to high-Mg carbonatitic in nature are the results of the formation of fluids in the peridotite-H2O-CO2 system. The more CO2 in the system, the more high-Mg carbonatitic the fluid composition is. These results suggest that the various fluids found in the mantle result from changes in the bulk composition of the mantle rocks. The mantle rocks are significantly affected during percolation of such fluids through them. For example, experimentally interacting silicic fluid with peridotite demonstrated the formation of various metasomatic peridotites as a function of pressure and temperature, composing of amphibole and mica. The mineral assemblages, chemistry, and P-T conditions in the experiments are similar to those found in metasomatic xenoliths from Kimberly, South Africa, and surrounding localities.

In recent decades, various temperature proxies have been developed and further established in the scientific community, at both low and high accuracy, however, not every method can be applied without restriction to all minerals or rocks. Evaporitic rocks, for example, are abundant chemical sediments at the Earth's surface that are deposited from supersaturated brines in marine, terrestrial, and lacustrine environments. Halite is the most abundant rock-forming mineral in this group, which during crystal formation entraps tiny water droplets (fluid inclusions, FIs) that store the chemical composition of the parent brine at a specific pressure-temperature dependent density. Such FIs are therefore excellent records of the original physicochemical conditions of the source brine. Brillouin spectroscopy (BS) is a novel laser-based technique that uses density fluctuations in FIs to directly measure entrapment temperatures and thus the initial brine temperature during crystal growth. In this seminar, the BS method will be introduced and two application cases will be presented using salt layers from the Dead Sea which were deposited during two interglacial periods. In addition to the basic principles, both the recommended sampling strategy and pitfalls along with associated limitations will be presented. The conclusion will be that the salt layers commonly deposited in the Dead Sea basin consist of two types that formed preferentially in summer (coarse-grained crystals) and winter (fine-grained crystals), which is mainly controlled by the degree of salt saturation of the lake water. Furthermore, it will be shown how (1) lake bottom temperatures have fluctuated seasonally (summer/winter), and that (2) paleo temperature trends can be reconstructed for an entire halite layer that was deposited during holomictic periods in the Dead Sea basin. This method is particularly promising for evaporites that formed near the surface if the material has not been affected by external processes such as tectonic burial/uplift, erosion, or mineral replacement.

Scanning transmission electron microscopy (STEM) is one of the most popular materials science methods to characterize the structure and chemistry of nanoscale samples, owing to its high resolution and many flexible operating modes. In a conventional STEM experiment, we focus the electron beam down to a probe from nanometer to sub-angstrom scale, and scan it over the sample surface while recording diffracted signals which are transmitted through the specimen. STEM can also record analytic signals such as x-rays generated by the electron beam to measure composition, or energy loss of the transmitted electrons to probe the electronic structure of samples. Conventional STEM imaging detectors experiments produce only a few intensity values at each probe position, but modern high-speed detectors allow us to measure a full 2D diffraction pattern, over a grid of 2D probe positions, forming a four dimensional (4D)-STEM dataset. These 4D-STEM datasets record information about the local phase, orientation, deformation, and other parameters, for both crystalline and amorphous materials. 4D-STEM datasets can contain millions of images and therefore require highly automated and robust software codes to extract the target properties. In this talk, I will introduce our open source py4DSTEM analysis toolkit, and show how we use these codes to perform data-intensive studies of material properties over functional length scales. I will also demonstrate some applications of modern machine learning tools, to perform measurements on electron diffraction patterns where property signals have been scrambled by multiple scattering of the electron beam.

Finding new materials for the conversion of CO2 into useful products is a complex task. Simulations can provide mechanistic and stability insights trying to accelerate the process. In my talk I will present the different degrees of complexity that we try to address in the simulations and which are the major challenges in the field.

Liquid-Liquid phase separation (LLPS) has been of fundamental importance in the assembly of thermally driven materials and has recently emerged as an organizational principle for living systems. Biological phase separation is driven out of equilibrium through complex enzyme composition, chemical reactions, and mechanical activity, which reveals a gap in our understanding of this fundamental phenomenon. Here we study the impact of mechanical activity on LLPS. We design a DNA-based LLPS system coupled to flows through molecular motors and a cytoskeleton network. Active stress at an interface of a liquid droplet suppressed phase separation and stabilized a single-phase regime well beyond the equilibrium binodal curve. The phase diagram out of equilibrium revealed a 3-dimensional phase space that depends on temperature and local molecular activity. Similar dynamics and structures are observed in simulations, suggesting that suppression of liquid phase separation by active stress is a generic feature of liquid phase separation.

The global oceanic overturning circulation and the transport of heat and dissolved gases are strongly controlled by upper ocean turbulent mixing that is driven by the breaking of internal gravity waves (IWs). Understanding the life cycle of oceanic IWs, from generation to dissipation, is therefore crucial for improving the representation of ocean mixing in climate models, which do not resolve the IW field.  Oceanic IWs are observed to have a continuous energy distribution across spatial and temporal scales – an internal wave continuum – despite being forced primarily at near-inertial and tidal frequencies at large scales. The formation of the IW continuum and the associated energy transfer to dissipative scales have been traditionally attributed to wave-wave interactions and to Doppler shifting of wave frequencies by currents. Here, we provide evidence from realistic numerical simulations that oceanic eddies rapidly diffuse storm-forced wave energy across spatiotemporal scales, thereby playing a dominant role in the formation of the IW continuum and the corresponding spatiotemporal distribution of energy dissipation. We further demonstrate that winds can play an important role in damping oceanic IWs through current feedback.  This results in a substantial reduction in wind power input at near inertial frequencies and a net energy sink for internal tides.

Thermal Pressurization (TP) is expected to be a dominant frictional weakening mechanism during earthquakes. However, due to experimental limitations there is a lack of direct evidence for the activation of TP in controlled laboratory conditions and most of our knowledge is derived from field studies and theoretical predictions. We present experiments performed by a rotary-shear apparatus where TP is activated in localized faults in Frederick diabase under constant normal stress of 50 MPa, confining pressure of 45 MPa and initial pore water pressure of 25 MPa. We show that by changing the permeability of the host rock we can control the shear stress drop during a TP event in the experimental fault. The TP events are short-lived in bare-surface faults as the opening of existing fractures around the fault plane drains the excess pore fluid. Wider, gouge-filled faults show more persistent frictional weakening, but at a slower rate, which is attributed to the compressibility of the gouge. In addition, we test the effects of transient fault dilation on the duration of a TP event through an expansion of the prevailing TP model, using a one-dimensional numerical simulation. We conclude that dynamic changes to the hydraulic diffusivity around the fault plane and persistent fault dilation, due to geometrical irregularities, are the most likely mechanisms to arrest TP during an earthquake.

Machine learning (ML) became a premier tool for modeling chemical processes and materials properties. For instance, ML interatomic potentials have become an efficient alternative to computationally expensive quantum chemistry simulations. In the case of reactive chemistry designing high-quality training data sets is crucial to overall model accuracy. To address this challenge, we develop a general reactive ML interatomic potential through unbiased active learning with an atomic configuration sampler inspired by nanoreactor molecular dynamics. The resulting model is then applied to study five distinct condensed-phase reactive chemistry systems: carbon solid-phase nucleation, graphene ring formation from acetylene, biofuel additives, combustion of methane and the spontaneous formation of glycine from early-earth small molecules. In all cases, the results closely match experiment and/or previous studies using traditional model chemistry methods. Altogether, explosive growth of user-friendly ML frameworks, designed for chemistry, demonstrates that the field is evolving towards physics-based models augmented by data science. I will also overview some applications of Non-adiabatic EXcited-state Molecular Dynamics (NEXMD) framework developed at several institutions. The NEXMD code is able to simulate tens of picoseconds photoinduced dynamics in large molecular systems. As an application, I will exemplify ultrafast coherent excitonic dynamics guided by intermolecular conical intersections. Here X-ray Raman signals are able to sensitively monitor the coherence evolution. The observed coherences have vibronic nature that survives multiple conical intersection passages for several hundred femtoseconds at room temperature. These spectroscopic signals are possible to measure at XFEL facilities and our modeling results allow us to understand and potentially manipulate excited state dynamics and energy transfer pathways toward optoelectronic applications. References: 1. N. Fedik, R. Zubatyuk, N. Lubbers, J. S. Smith, B. Nebgen, R. Messerly, Y. W. Li, M. Kulichenko, A. I. Boldyrev, K. Barros, O. Isayev, and S. Tretiak “Extending machine learning beyond interatomic potentials for predicting molecular properties” Nature Rev. Chem. 6, 653 (2022). 2. G. Zhou, N. Lubbers, K. Barros, S. Tretiak, B. Nebgen, “Deep Learning of Dynamically Responsive Chemical Hamiltonians with Semi-Empirical Quantum Mechanics,” Proc. Nat. Acad. Sci. USA, 119 e2120333119 (2022) 3. S. Zhang, M. Z. Makos, R. B. Jadrich, E. Kraka, B. T. Nebgen, S. Tretiak, O. Isayev, N. Lubbers, R. A. Messerly, and J. S. Smith “Exploring the frontiers of chemistry with a general reactive machine learning potential,” (2023) https://chemrxiv.org/engage/chemrxiv/article-details/6362d132ca86b84c77ce166c 4. A. De Sio, E. Sommer, X. T. Nguyen, L. Gross, D. Popović, B. Nebgen, S. Fernandez-Alberti, S. Pittalis, C. A. Rozzi, E. Molinari, E. Mena-Osteritz, P. Bäuerle, T. Frauenheim, S. Tretiak, C. Lienau, “Intermolecular conical intersections in molecular aggregates” Nature Nanotech. 16, 63 – 68 (2021). 5. V. M. Freixas, D. Keefer, S. Tretiak, S. Fernandez-Alberti, and S. Mukamel, “Ultrafast coherent photoexcited dynamics in a trimeric dendrimer probed by X-ray stimulated-Raman signals,” Chem. Sci., 13, 6373 – 6384 (2022).

Proteins are the fundamental building blocks of life. They form high performance materials and carry out cellular functions. They are able to fulfil these roles by assembling together to form sophisticated structures and architectures, which in many cases extend to mesoscopic liquid or solid phases. This talk focuses on understanding the transitions between these phases, their fundamental material properties and the way that the modulate biological function and malfunction. I will then discuss two areas opened up by the control of protein assembly. I will first focus on the understanding of the mechanism of protein aggregation and the discovery of molecules that can ameliorate malfunctioning protein self-assembly in a range of age-associated disease states. I will then outline some of our efforts to control protein self-assembly to form silk-inspired sustainable materials

In this talk, I will present theoretical and computational chemistry approaches to describe excited-states in quantum matter, and predicting emergent states created by external drives. Understanding the role of such light-matter interactions in the regime of correlated electronic systems is of paramount importance to fields of study across chemical and condensed matter physics, and ultrafast dynamics1. The simultaneous contribution of processes that occur on many time and length-scales have remained elusive for state-of-the-art calculations and model Hamiltonian approaches alike, necessitating the development of new methods in computational chemistry. I will discuss our work at the intersection of ab initio cavity quantum-electrodynamics and electronic structure methods to treat electrons, photons and phonons on the same quantized footing, accessing new observables in strong light-matter coupling. Current approximations in the field almost exclusively focus on electronic excitations, neglecting electron-photon effects, for example, thereby limiting the applicability of conventional methods in the study of polaritonic systems, which requires understanding the coupled dynamics of electronic spins, nuclei, phonons and photons. With our approach we can access correlated electron-photon and photon-phonon dynamics2–7, essential to our latest work on driving quantum materials far out-of-equilibrium to control the coupled electronic and vibrational degrees-of-freedom 8–19. In the second part of my talk, I will demonstrate how the same approach can be generalized in the context of control of molecular quantum matter and quantum transduction. As a first example, I will discuss a cavity-mediated approach to break the inversion symmetry allowing for highly tunable even-order harmonic generation (e.g. second- and fourth-harmonic generation) naturally forbidden in such systems. This relies on a quantized treatment of the coupled light-matter system, similar to the driven case, where the molecular matter is confined within an electromagnetic environment and the incident (pump) field is treated as a quantized field in a coherent state. When the light-molecule system is strongly coupled, it leads to two important features: (i) a controllable strong-coupling-induced symmetry breaking, and (ii) a tunable and highly efficient nonlinear conversion efficiency of the harmonic generation processes 20–22. Both of these have implications for molecular quantum architectures. Being able to control molecules at a quantum level gives us access to degrees of freedom such as the vibrational or rotational degrees to the internal state structure. Finally, I will give an outlook on connecting ideas in cavity control of molecules with quantum information science.

Carbon efflux from soils is the largest terrestrial carbon source to the atmosphere, yet it remains one of the most uncertain fluxes in the Earth’s carbon budget. A dominant component of this flux is heterotrophic respiration, influenced by several environmental factors, most notably soil temperature and moisture. We developed a mechanistic model from micro to global scale to explore how changes in soil water content and temperature affect soil heterotrophic respiration. Simulations, laboratory measurements, and field observations validate the new approach. Estimates from the model show that heterotrophic respiration has been increasing since the 1980s at a rate of about 2% per decade globally. Using future projections of surface temperature and soil moisture, the model predicts a global increase of about 40% in heterotrophic respiration by the end of the century under the worst-case emission scenario, where the Arctic region is expected to experience a more than two-fold increase, driven primarily by declining soil moisture rather than temperature increase.  

Magnetism is one of the largest, most fundamental, and technologically most relevant fields of condensed-matter physics. Traditionally, two elementary magnetic phases have been distinguished - ferromagnetism and antiferromagnetism. The spin polarization in the electronic band structure reflecting the magnetization in ferromagnetic crystals underpins the broad range of time-reversal symmetry-breaking responses in this extensively explored and exploited type of magnets. By comparison, antiferromagnets have vanishing net magnetization. Recently, there have been observations of materials in which strong time-reversal symmetry-breaking responses and spin-polarization phenomena, typical of ferromagnets, are accompanied by antiparallel magnetic crystal order with vanishing net magnetization, typical of antiferromagnets [1]. A classification and description based on spin-symmetry principles offers a resolution of this apparent contradiction by establishing a third distinct elementary magnetic phase, dubbed altermagnetism [2]. We will start the talk with an overview of the still emerging unique phenomenology of this unconventional d-wave (or higher even-parity wave) magnetic phase, and of the wide array of altermagnetic materials. We will then show how altermagnetism can facilitate a development of ultra-fast and low-dissipation spintronic information technologies, and can have impact on a range of other modern areas of condensed matter physics and nanoelectronics. References [1] L. Šmejkal, A. H. MacDonald, J. Sinova, S. Nakatsuji, T. Jungwirth, Nature Reviews Mater. 7, 482 (2022). [2] L. Šmejkal, J. Sinova & T. Jungwirth, Phys. Rev. X (Perspective) 12, 040501 (2022).

Magnetism is one of the largest, most fundamental, and technologically most relevant fields of condensed-matter physics. Traditionally, two elementary magnetic phases have been distinguished - ferromagnetism and antiferromagnetism. The spin polarization in the electronic band structure reflecting the magnetization in ferromagnetic crystals underpins the broad range of time-reversal symmetry-breaking responses in this extensively explored and exploited type of magnets. By comparison, antiferromagnets have vanishing net magnetization. Recently, there have been observations of materials in which strong time-reversal symmetry-breaking responses and spin-polarization phenomena, typical of ferromagnets, are accompanied by antiparallel magnetic crystal order with vanishing net magnetization, typical of antiferromagnets [1]. A classification and description based on spin-symmetry principles offers a resolution of this apparent contradiction by establishing a third distinct elementary magnetic phase, dubbed altermagnetism [2]. We will start the talk with an overview of the still emerging unique phenomenology of this unconventional d-wave (or higher even-parity wave) magnetic phase, and of the wide array of altermagnetic materials. We will then show how altermagnetism can facilitate a development of ultra-fast and low-dissipation spintronic information technologies, and can have impact on a range of other modern areas of condensed matter physics and nanoelectronics. References [1] L. Šmejkal, A. H. MacDonald, J. Sinova, S. Nakatsuji, T. Jungwirth, Nature Reviews Mater. 7, 482 (2022). [2] L. Šmejkal, J. Sinova & T. Jungwirth, Phys. Rev. X (Perspective) 12, 040501 (2022).

Molecular plasmonics has been a hot topic for the past several years. At the heart of the primary interest in plasmonics is the strong electromagnetic field localization at resonant frequencies corresponding to surface plasmon-polariton modes. Thanks to riveting advancements in nanofabrication technologies, we have achieved nearly 1 nm spatial resolution (and in some cases even below that!) and are able to fabricate a wide variety of nanosystems ranging from nanoparticles of various shapes to metasurfaces comprised of periodic arrays of nanoparticles and/or nanoholes of any imaginable geometry. Such systems have recently emerged as new platforms for strong light-matter interactions. Combined with molecular ensembles, these constructs exhibit a remarkable set of optical phenomena ranging from the exciton-plasmon strong coupling to the second harmonic generation altered by molecular resonances. In this talk I will discuss both linear and nonlinear optical properties of plasmonic materials coupled to quantum emitters of various complexity. I will also introduce a newly developed computational approach that can be used to efficiently simulate a large number of complex molecules driven by electromagnetic radiation crafted at plasmonic interfaces.

I will discuss the synthesis and properties of a range of aromatic-, anti-aromatic- and helical aromatic molecules.1 The talk will feature molecules with 'weird' magnetic properties, helical chirality and abnormal reactivity due to close proximity. I will discuss some of the unusual properties (and some of the very trivial and unsurprising properties) of these large well-defined conjugated molecules. I will describe the journey from fundamental studies of the acid-mediated oligomerization of simple 1,4-benzoquinones to the controlled synthesis of heterocyclic [8] circulenes (featuring an antiaromatic planar cyclooctatetraene) and even a larger planar [9] helicene. In the simplest picture two units of benzoquinone gives a dihydroxy-dibenzofuran + water, thus forming a new furan ring. This sets up a 1+1=3 ‘logic’ for elongation of the -system. The synthetic methodology has allowed us to prepare a range of fully conjugated helicenes, including the longest known optically resolved chiral [13] helicenes. The helicenes and circulenes have been explored in a range of properties including as the blue fluorescent component in OLEDs, as G-quadruplex binding ligands and in fundamental studies of antiaromaticity and chirality.

The so-called CISS phenomenon refers to the observation, that when electrons are transported through a chiral molecule, as e.g. a helix, then they will emerge spin polarized even though when entering they are not spin polarized. Often this effect is observed using magnetized leads. Remarkably, it seems that many experiments break the Onsager reciprocity principle. Onsager’s principle is very deep and depends on very few assumptions about the system - mainly about behavior under time reversal. I will present a possible solution to this conundrum

Multiple proteins function as nanomachines, and carry out multiple specific tasks in the cell by alternating chemical steps with conformational transitions. Single-molecule FRET spectroscopy is a powerful tool for studying the internal motions of proteins. In recent years, we have been using this technique to study a range of protein machines, surprisingly finding in each case microsecond-time-scale internal dynamics. What is the role of these fast motions in the much-slower functional cycles of these machines?

Click chemistry has revolutionized many facets of the molecular sciences, with the realization of reactions that are ‘‘modular, wide in scope, give very high yields, generate only inoffensive byproducts that can be removed by nonchromatographic methods and are stereospecific”. Yet surprisingly little attention has been given to the development of intrinsically chiral click reactions (potentially enantiospecific, rather than ‘only’ enantioselective due to chiral auxiliary groups), while the modularity of many click reactions is best compared to one-dimensional LEGO. Of course, much could be done within the constraints – hence forementioned revolution – but it drove attention towards an extension of available click chemistries. Kolb, H. C.; Finn, M.; Sharpless, K. B., Click chemistry: diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 2001, 40, 2004-2021. The talk will focus on the resulting investigations in the field of S(VI) exchange chemistry, with specific emphasis on two fields: a) the development of the intrinsically enantiospecific click reactions and their use to e.g. make synthetic polymers with 100% backbone chirality that combine stability & degradabbility, and b) the development of multimodular click chemistry and single-polymer studies by a combination of AFM, TEM, scanning Auger microscopy

The remarkable properties of excitons in transition-metal-dichalcogenides (TMDs), together with the ability to readily control their charge carriers, have attracted a significant amount of interest in recent years. Despite the atomic dimensions of the hosting 2D semiconductors, TMD excitons exhibit strong interaction with light, both in absorption and photoemission processes, and practically dominate the optical response of these 2D materials. In this talk, I will introduce several approaches for achieving extremely strong light-exciton interactions. First, by optical and electrical manipulation of TMD excitons inside a van der Waals heterostructure cavity [1], second, via the formation of highly-confined, in-plane exciton polaritons [2], and third, through the realization of valley-polarized hyperbolic exciton polaritons [3]. These enhanced light–exciton interactions may provide a platform for studying excitonic phase-transitions, quantum nonlinearities and the enablement of new possibilities for 2D semiconductor-based optoelectronic devices. [1] I. Epstein et al, "Near-unity Light Absorption in a Monolayer WS2 Van der Waals Heterostructure Cavity", Nano letters 20 (5), 3545-3552 (2020). [2] I. Epstein et al, "Highly Confined In-plane Propagating Exciton-Polaritons on Monolayer Semiconductors", 2D Materials 7, 035031 (2020). [3] T. Eini, T. Asherov, Y. Mazor, and I. Epstein, "Valley-polarized Hyperbolic Exciton Polaritons in Multilayer 2D Semiconductors at Visible Frequencies", Phys. Rev. B 106, L201405 (2022).

Medicine is taking its first steps toward patient-specific cancer care. Nanoparticles have many potential benefits for treating cancer, including the ability to transport complex molecular cargoes, including siRNA and protein, as well as targeting specific cell populations. The talk will explain the fundamentals of nanotechnology, from ‘barcoded nanoparticles’ that target sites of cancer where they perform a programmed therapeutic task. Specifically, liposomes diagnose the tumor and metastasis for their sensitivity to different medications, providing patient-specific drug activity information that can be used to improve the medication choice. The talk will also describe how liposomes can be used for degrading the pancreatic stroma to allow subsequent drug penetration into pancreatic adenocarcinoma and how nanoparticle’ biodistribution and anti-cancer efficacy are impacted by the patient’s sex and, more specifically, the menstrual cycle. The evolution of drug delivery systems into synthetic cells, programmed nanoparticles that have an autonomous capacity to synthesize diagnostic and therapeutic proteins inside the body, and their promise for treating cancer and immunotherapy, will be discussed. References: 1) Theranostic barcoded nanoparticles for personalized cancer medicine, Yaari et al. Nature Communications, 2016, 7, 13325 2) Collagenase nanoparticles enhance the penetration of drugs into pancreatic tumors, Zinger et al., ACS Nano, 13 (10), 11008-11021, 2019 3) Targeting neurons in the tumor microenvironment with bupivacaine nanoparticles reduces breast cancer progression and metastases, Science Advances, Kaduri et al., 7 (41), eabj5435, 2021 4) Nanoparticles accumulate in the female reproductive system during ovulation affecting cancer treatment and fertility, Poley et al., ACS nano, 2022

Over years’ transition metal-catalyzed C-H activation has propelled the field of organic synthesis for the construction of structurally complex and diverse molecules in resource-economical fashion. In this context, non-directed C-H activation has gained unprecedented attention for attaining region-specific C-H functionalizations in a step-economic mode. Unlike traditional Fujiwara-Moritani reaction, this approach relies on ligand assistance and thus uses arene as the limiting reagent. However, all existing non-directed C-H functionalizations utilize high thermal energy to induce the functional group which eventually put the regioselectivity at stake. In addition, use of super stoichiometric costly silver salts to regenerate the catalyst produces unwanted metal waste. In aid of developing a more sustainable and environmentally benign approach, we have established a photoredox catalytic system by a merger of palladium/organo-photocatalyst(PC) which forges highly regeiospecific C-H olefination of diverse arenes and heteroarenes. Visible light nullifies the requirement of silver salts and thermal energy in executing “region-resolved” Fujiwara-Moritani reaction.

The major concerns about industrially used catalytic systems today are: i) the high cost of catalysts; ii) the toxicity of heavy transition metals; iii) difficulties in removing trace amounts of toxic-metal residues from the desired product; and, finally, iv) rare transition metal depletion, which does not meet the requirement of sustainable development. Developing environmentally friendly catalysts is an excellent option in this regard. Naturally, the most recent catalyst development trend heralded a new era of metal-free catalysis or catalysts based on earth-abundant, nontoxic, and low-cost metals. This talk will go over our recent advances [1-4] in using small molecules to systematically mimic transition metal-based catalysis. We designed electron transfer catalysis using the smallest polycyclic odd alternant hydrocarbon, phenalenyl (PLY)-based molecules, which was inspired by a completely different field of molecular spin materials [5]. This talk will focus on how to avoid transition metals when performing various cross-coupling catalysis.

The traditional approach to weather forecasting on one- to two-week timescales utilizes weather forecasting models, but on timescales longer than two weeks, the value of deterministic (or ensemble-based probabilistic) forecasts weakens. This is due to the presence of chaotic variability in the atmosphere. Yet certain modes of variability in the climate system have timescales longer than this two-week threshold, and the key to longer-scale prediction is to take advantage of these modes when they open up windows of opportunity. By understanding the impacts of these modes of variability on surface weather, the potential for improved forecasts on a monthly timescale can be demonstrated and eventually realized.  Two such classes of modes of variability are stratospheric variability (both in the tropical and polar stratosphere) and tropical tropospheric variability (e.g. the Madden-Julian Oscillation and El Nino). For example, both polar stratospheric sudden warmings and the Madden-Julian Oscillation have been shown to influence European and Mediterranean weather, but it is unclear (1) what mechanism(s) underlie these connections, (2) how far in advance the impacts can be predicted, (3) what governs the magnitude of the surface impact, and (4) how well models capture these connections. This talk will review progress made towards addressing these issues over the past several years in my group.

Over the last 2½ millenia, the world economy depended on prevailing currencies: the Athenian owl (530- 168 BCE), the Roman denarius (211 BCE-250 AD), the Spanish piece-of-eight (16th to 18th C), and today the US dollar. These reference monies were accepted everywhere and all, at least in the beginning, were made of silver. What is so special about this metal? Silver is useless and rare, but still abundant enough to match the wealth of nations and of their long-distance trade. Silver ores are associated with rare and recent tectonic environments, the Mediterranean world, notably the periphery of the Aegean Sea and Southern Iberia, and the American cordillera, Peru and Mexico. In contrast, they were markedly scarce in South and East Asia. After the virtual destruction of soils by the Anatolian farmers at the end of the Bronze Age, the Near and Middle East societies depended almost exclusively on the agriculture of Egypt and Mesopotamia. The Late Bronze Age collapse (ca. 1200 BCE) corresponded to the migration of Greek people and resulted in the annihilation of all the empires outside of the flood plains. Silver by weight was nevertheless used to save populations from famine and trade wheat, barley and copper. Military innovations, hoplites and their phalanx, were, with silver mines, the main resources of the Greeks. Mercenaries received their wages in silver, notably through the tributes exacted in silver by the Achaemenid (Persion) kings. By minting silver, the returning Greek mercenaries emerged as strong middle classes . They soon claimed their share of the power, toppled the tyrants, and installed democracy in many poleis from Greece and Southern Italy. Modern economics teaches us that egalitarian distribution of wealth is unfortunately unstable and this case is well illustrated by Syracuse. At the beginning of the common era, the Roman Empire found itself the owner of centuries of silver extracted from Greece and from Iberia. This bullion was used to buy luxury products, frankincense from Arabia, spices and cotton from India, ivory and precious wood from Africa. Leakage of silver towards the Indian Ocean was so strong that coins were quickly debased by copper and by 250 AD most of the silver had been lost. The progressive replacement of silver by a bimetallic system, gold for the rich and bronze for the working class, progressively fractured the society and ushered the brutal Middle Age regimes. Silver famine had finally destroyed the democratic ideal of the Greeks. This is food for thought as disappearing mining resources may severely affect our current vision of societies.

Layered materials exhibit unique charge and energy transfer characteristics, making them promising candidates for emerging photophysical and photochemical applications, and particularly in energy conversion and quantum information science. In two-dimensional systems, spatial confinement in a certain dimension causes reduced dielectric screening and enhanced Coulomb interaction compared to bulk materials. Upon light excitation, the relaxation processes of the charge and energy carriers, as well as their rearrangement in the lateral plane, allow for unique and structure-specific interaction dynamics of the electrons and holes in these systems and of their bound states - neutral and charged excitons. In particular, these dimensionality effects induce strong exciton-electron and exciton-hole interactions in doped or gated systems, where optical excitations coexist alongside electronic excitations. These interactions dominate the exciton decay and diffusion and introduce bound three-particle states in such systems. A many-particle theoretical picture of the formation and propagation of these states is crucial for proper tracking and understanding of the interaction pathways, crystal momentum effects, the involved particle-particle coupling and their relation to the underlying structure, dimensionality, and symmetry.

The Mediterranean region stands out among other subtropical regions in its projected drying response to the global rise in atmospheric greenhouse gas concentrations. This drying trend has already emerged out of the normal, random climate variability in the sensitive Eastern Mediterranean (EM) region. To better understand the dynamical mechanisms responsible for this regional sensitivity, we turn to past protracted EM drying states during warm geological epochs. A unique view of the historical and pre-historical hydroclimate of the EM-Levant has been gleaned from the continued study of the sedimentary and geochemical record left by the lakes that filled the tectonic basin of the Dead Sea. We revisit the Late Quaternary sediment record retrieved during the 2010-2011 Dead Sea Deep Drilling Project (DSDDP). The sediments clearly indicate that the Levant was drier during past warm interglacials than during the adjacent glacials but nonetheless experienced large variations in the intensity of the regional aridity. During each interglacial, extended thick deposits of salts accumulated at the Lake bottom, during millennia of significant regional aridity and severely reduced Mediterranean rains. These dry states were interrupted by extended wet intervals, fed by rains that were supplied by a blend of tropical and Mediterranean moisture. To understand the underlying causes of the EM-Levant interglacial hydroclimate variations, we put the Dead Sea record in the context of the Northern Hemisphere orbital insolation variations and their impact on the global climate system. We show that the changes in EM hydroclimate portrayed by the DSDDP record during the interglacials, are entirely consistent with the response of the North Atlantic Ocean and the overlying atmosphere and surrounding land areas to the changes in the latitudinal insolation gradient, as determined by climate models and evident by surface temperature proxies. This perspective provides new information regarding the dynamical processes responsible for the ongoing, greenhouse gas forced, EM drying.

"Molecules in a Quantum-Optical Flask" When confined to small dimensions, the interaction between light and matter can be enhanced up to the point where it overcomes all the incoherent, dissipative processes. In this "strong coupling" regime the photons and the material start to behave as a single entity, having its own quantum states and energy levels. In this talk I will discuss how such cavity-QED effects can be used in order to control material properties and molecular processes. This includes, for example, modifying photochemical reactions [1], enhancing excitonic transport up to ballistic motion close to the light-speed [2-3] and potentially tailoring the mesoscopic properties of organic crystals, by hybridizing intermolecular vibrations with electromagnetic THz fields [4-5]. 1. J. A. Hutchison, T. Schwartz, C. Genet, E. Devaux, and T. W. Ebbesen, "Modifying Chemical Landscapes by Coupling to Vacuum Fields," Angew. Chemie Int. Ed. 51, 1592 (2012). 2. G. G. Rozenman, K. Akulov, A. Golombek, and T. Schwartz, "Long-Range Transport of Organic Exciton-Polaritons Revealed by Ultrafast Microscopy," ACS Photonics 5, 105 (2018). 3. M. Balasubrahmaniyam, A. Simkovich, A. Golombek, G. Ankonina, and T. Schwartz, "Unveiling the mixed nature of polaritonic transport: From enhanced diffusion to ballistic motion approaching the speed of light," arXiv:2205.06683 (2022). 4. R. Damari, O. Weinberg, D. Krotkov, N. Demina, K. Akulov, A. Golombek, T. Schwartz, and S. Fleischer, "Strong coupling of collective intermolecular vibrations in organic materials at terahertz frequencies," Nat. Commun. 10, 3248 (2019). 5. M. Kaeek, R. Damari, M. Roth, S. Fleischer, and T. Schwartz, "Strong Coupling in a Self-Coupled Terahertz Photonic Crystal," ACS Photonics 8, 1881 (2021).

Ice melts at 0 [˚C], however, water can be super-cooled homogeneously down to ~-40 [˚C] without freezing. The ability to control the temperature of freezing of super-cooled water is highly important in many scientific sub-fields. Freezing can be induced at higher temperatures by the application of electric fields (known as electro-freezing). Despite the importance of the process of electro-freezing, its mechanism at the molecular level is still not fully understood. Recently, icing experiments performed by our group have demonstrated that electro-freezing comprises of the interactions of an electric field with specific ions of trigonal planar configuration, creating arm-chair hexagons that mimic the hexagons of the crystal ice. In my research, I investigated the effect of electro-freezing of super-cooled water on silver and copper electrodes. I found that the mechanism of electro-freezing of super-cooled water as induced by the silver electrodes is very complex and irreproducible. In contrast, the high icing temperature (~-4 [˚C]) on the copper (111) face is induced primarily by a mechanism of epitaxy.

Plastic (irreversible) deformation of crystals requires disrupting the crystalline order, which happens through nucleation and motion of topological line defects called dislocations. Interactions between dislocations lead to the formation of complex networks that, in turn, dictate the mechanical response of the crystal. The severe difficulty in atomic systems to simultaneously resolve the emerging macroscopic deformation and the evolution of these networks impedes our understanding of crystal plasticity. To circumvent this difficulty, we explore crystal plasticity by using colloidal crystals; the micrometer size of the particles allows us to visualize the deformation process in real-time and on the single particle level. In this talk, I will focus on two classical problems: instability of epitaxial growth and strain hardening of single crystals. In direct analogy to epitaxially grown atomic thin films, we show that colloidal crystals grown on mismatched templates to a critical thickness relax the imposed strain by nucleation of dislocations. Our experiments reveal how interactions between dislocations lead to an unexpectedly sharp relaxation process. I will then show that colloidal crystals can be strain-hardened by plastic shear; the yield strength increases with the dislocation density in excellent accord with the classical Taylor equation, originally developed for atomic crystals. Our experiments reveal the underlying mechanism for Taylor hardening and the conditions under which this mechanism fails.

Recent severe summertime weather extremes in the Northern hemisphere extratropics such as the extraordinary 2021 North American Heatwave and the record-breaking floods in central Europe were in part driven by persistent circulation patterns in the tropospheric Jetstream. To what degree such circulation patterns will modulate extreme weather risk in a warming world is still uncertain and remains a highly debated topic in climate science. I will present results from recent studies that investigate physics of extraordinary extremes, future changes in weather persistence diagnosed by a feature tracking algorithm and future risks from concurrent extremes and associated impacts on crop production based on latest GGCMI-runs. A special emphasis will be placed on benchmarking the skill of CMIP5 and CMIP6 models to reproduce atmosphere dynamical mechanisms and associated extreme weather against reanalysis data short bio: Kai Kornhuber is an adjunct Associate Research Scientist at the Lamont-Doherty Earth Observatory, Columbia University in New York and a Senior Fellow on Climate Risks at the German Council on Foreign Relations. His research is concerned with physical drivers of extreme weather and climate events and associated societal impacts and risks under current and future climatic conditions. He is Founding Member of the EarthNetwork on Sustainable and Resilient Living in an Era of Increasing Disasters at Columbia’s Climate School, Co-Chair of the Compound Events Working Group at Risk-Kan, Steering Committee member of the HiWeather Project and a Co- Pi of the Project PERSEVERE within the BMBF Consortium.

Interfaces between systems with different properties are a common feature of Nature. However, the physics of interactions across such interfaces is often neglected. In this talk, I will focus on the case of biological tissue-tissue interfaces and show they can exhibit emergent electrical excitability, a phenomenon that has not been explored before. Using cultured cells and optical tools, I have found that interfaces between tissues with dissimilar electrophysiological properties can behave differently compared to the tissues on either side. In particular, the interface between non-excitable tissues can become excitable. Excitability of cells therefore depends on their position, not just the proteins they express. Moreover, my simulations reveal that interface excitability is extremely robust to parametric variation. I will briefly discuss the roots of this difference in the structures of the underlying dynamical systems, and will show examples of other excitable systems that can exhibit interfacial excitation, such as predator-prey dynamics and oscillating chemical reactions.

Cells carefully regulate the movement of solutes across their membrane using an intricate array of interconnected transport pathways. While beneficial for mediating essential cellular activities, the abundance of complex transport pathways severely limits the elucidation of particular translocation mechanisms in live-cell studies. We alleviate this impediment by taking a reductionist approach to incorporate specific transport pathways (e.g., transport proteins) in simplified artificial cell models, using giant unilamellar vesicles (GUVs) as a biologically-relevant chassis. To gain maximal control over the bioengineering process, we developed an integrated microfluidic platform capable of high-throughput production and purification of monodispersed GUV-based cell models. Using single-vesicle fluorescence analysis, we quantified the passive permeation rate of two biologically important electrolytes, protons (H+) and potassium ions (K+), and correlated their flux with electrochemical gradient buildup across the GUV lipid bilayer. Applying similar analysis principles, we also determined the H+/K+ selectively of two archetypal ion channels, gramicidin A and outer membrane porin F (OmpF). Altogether, our results provide an insight into the transport mechanism of ions across lipid bilayers and set a framework for elucidating protein-based transport in artificial cell models.

Self-assembly of inorganic nanoparticles (NPs) into ordered structures has led to a wide range of materials with unique optical, electronic, and catalytic properties. Various interactions have been employed to direct the crystallization of NPs, including van der Waals forces, hydrogen bonding, and magnetic dipolar interactions. Among them, Coulombic interactions have remained largely unexplored, owing to the rapid charge exchange between spherical NPs bearing high densities of opposite charges (superionic NPs). In this talk, I will describe a new method to assemble superionic NPs under conditions that preserve their native surface charge density. Our methodology was used to assemble oppositely charged NPs (“spherical polyelectrolytes”) into highly ordered assemblies exhibiting previously unknown morphologies.

Inorganic semiconductor nanomaterials have been under extensive research for the last few decades for their fascinating optical and electronic properties. Our group demonstrated the guided growth approach for planar semiconductor nanowires (NWs), by taking advantage of the epitaxial relations between the substrate and the inorganic overlayer. Epitaxy enables one to control crystallographic orientation, growth directions, and properties of the nanostructures. Among the inorganic semiconductors, the family of chiral inorganic semiconductor nanomaterials has recently become a focal point of many studies owing to their unique behavior in condensed matter physics and their potential in spintronics and circularly polarized optoelectronics for information technology. Despite the extensive studies on the enantioselective growth of chiral crystals induced by chiral molecules, “chiral epitaxy”, namely the enantioselective growth of chiral crystals by epitaxy on chiral crystal surfaces has not yet been demonstrated. Here, we explore the interaction between intrinsically chiral inorganic semiconductor nanomaterials and various chiral and asymmetric surfaces. In one chapter, we demonstrate the enantioselective guided growth of Te NWs on a chiral plane of ReSe2. In order to determine the handedness of the NWs and the substrate, we made special modifications to a known handedness-determination STEM method, which allowed us to analyze both Te and ReSe2 structures. To the best of our knowledge, this is not just the first guided growth of Te on ReSe2, but it is also the first demonstration of enantioselective crystallization of a chiral crystal induced by its epitaxial relations with a chiral surface of a different crystal. Namely, this is the first demonstration of chiral epitaxy. In the second chapter, we study the guided growth of the chiral wide-bandgap semiconductor α-TeO2 along the asymmetric nanogrooves of annealed M-plane sapphire (α-Al2O3). The NWs show both straight and helical morphologies depending on their crystallographic orientation. This is the first demonstration of the guided growth of TeO2 NWs. In addition, this system demonstrates the formation of helical nanostructures with coherent handedness, controlled by interaction with an asymmetric substrate. All the NWs were characterized with SEM, AFM, TEM, EDS, and Raman spectroscopy. Overall, this work presents a new approach for enantioselective growth of chiral nanocrystals based on epitaxy. This gas-phase process should be suitable for a wide range of inorganic nanomaterials, and compatible with fabrication processes for integration into functional devices.

The need for affordable large scale energy storage has risen dramatically with the increase in usage of renewable energy sources. In recent years, beyond Li batteries such as Na ion batteries (SIB), gained much interest due to limited Lithium resources. However, SIBs are still far from meeting the demands in terms of electrochemical performance, rendering research on SIBs very important. During battery cycling, chemical and electrochemical processes result in the formation of an interphase between the anode and electrolyte called the solid electrolyte interphase (SEI). The effect of the SEI on electrochemical performance cannot be overstated, as its composition and structure dictate interfacial ionic transport in the battery cell. Since the SEI is very thin (10-50 nm) and is composed of disordered, organic, and inorganic phases it is extremely difficult to characterize at the atomic-molecular level. In this seminar I will present methodology developed for probing the native SEI formed in SIBs by using nuclear magnetic resonance (NMR) and signal enhanced NMR by exogenous and endogenous dynamic nuclear polarization (DNP). Employing these techniques enabled us to gain information on the chemical composition of the SEI together with important insights into the SEI’s structural gradient formed with different Na electrolytes. Correlating the compositional and structural information acquired with the SEI’s function can assist in designing SIBs with improved performance and longer lifetime.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3- and sp2- hybridized carbon atoms, respectively. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. In this talk, I will introduce graphullerene, a new two-dimensional superatomic allotrope of carbon combining three- and four-coordinate carbon atoms. The constituent subunits of graphullerene are C60 fullerenes that are covalently interconnected within a molecular layer, forming graphene-like hexagonal sheets. The most remarkable thing about the synthesis of graphullerene is that the solid-state reaction produces large polyhedral crystals (hundreds of micrometers in lateral dimensions), rather than an amorphous or microcrystalline powder as one would typically expect from polymerization chemistry. Similar to graphite, the crystals can be mechanically exfoliated to produce molecularly thin flakes with clean interfaces—a critical requirement for the creation of heterostructures and optoelectronic devices. We find that polymerizing the fullerenes leads to a large change in the electronic structure of C60 and the vibrational scattering mechanisms affecting thermal transport. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices. The discovery of a superatomic cousin of graphene demonstrates that there is an entire family of higher and lower dimensional forms of carbon that may be chemically prepared from molecular precursors.

Creation of reconfigurable and multi-functional materials can be achieved by incorporating architecture into material design. In our research, we design and fabricate three-dimensional (3D) nano-architected materials that can exhibit superior and often tunable thermal, photonic, electrochemical, biochemical, and mechanical properties at extremely low mass densities (lighter than aerogels), which renders them useful and enabling in technological applications. Dominant properties of such meta-materials are driven by their multi-scale nature: from characteristic material microstructure (atoms) to individual constituents (nanometers) to structural components (microns) to overall architectures (millimeters and above). Our research is focused on fabrication and synthesis of nano- and micro-architected materials using 3D lithography, nanofabrication, and additive manufacturing (AM) techniques, as well as on investigating their mechanical, biochemical, electrochemical, electromechanical, and thermal properties as a function of architecture, constituent materials, and microstructural detail. Additive manufacturing (AM) represents a set of processes that fabricate complex 3D structures using a layer-by-layer approach, with some advanced methods attaining nanometer resolution and the creation of unique, multifunctional materials and shapes derived from a photoinitiation-based chemical reaction of custom-synthesized resins and thermal post-processing. A type of AM, vat polymerization, has allowed for using hydrogels as precursors, and exploiting novel material properties, especially those that arise at the nano-scale and do not occur in conventional materials. The focus of this talk is on additive manufacturing via vat polymerization and function-containing chemical synthesis to create 3D nano- and micro-architected metals, ceramics, multifunctional metal oxides (nano-photonics, photocatalytic, piezoelectric, etc.), and metal-containing polymer complexes, etc., as well as demonstrate their potential in some real-use biomedical, protective, and sensing applications. I will describe how the choice of architecture, material, and external stimulus can elicit stimulus-responsive, reconfigurable, and multifunctional response

Most electrical activity in vertebrates and invertebrates occurs at extremely low frequencies (ELF), with characteristic maxima below 50 Hz. The origin of these frequency maxima is unknown and remains a mystery. We propose that over billions of years during the evolutionary history of living organisms on Earth, the natural electromagnetic resonant frequencies in the atmosphere, continuously generated by global lightning activity, provided the background electric fields for the development of cellular electrical activity. In some animals, the electrical spectrum is difficult to differentiate from the natural background atmosphericelectric field produced by lightning. In this talk I will present evidence for the link between the natural ELF fields and those found in many living organisms, including humans.  Furthermore, recent experiments show links between the ELF fields and photosynthesis in plants.

Accumulating work points out relevant genes and signaling pathways hampered in human disorders as potential candidates for therapeutics. Developing nucleic acid-based tools to manipulate gene expression, such as siRNAs, mRNA and genome editing strategies, open up opportunities for personalized medicine. Yet, although major progress was achieved in developing RNA targeted delivery carriers, mainly by utilizing monoclonal antibodies (mAbs) for targeting, their clinical translation has not occurred. In part because of massive development and production requirements and high batch-to-batch variability of current technologies, which relies on chemical conjugation. Here we present a self-assembled modular platform that enables to construct theoretically unlimited repertoire of RNA targeted carriers. The platform self-assembly is based on a membrane-anchored lipoprotein, incorporated into RNA-loaded novel, unique lipid nanoparticles that interact with the antibody Fc domain. We show that a simple switch of 8 different mAbs, redirects specific uptake of siRNAs by diverse leukocyte subsets in vivo. The platform therapeutic potential is demonstrated in an inflammatory bowel disease model, by targeting colon macrophages to reduce inflammatory symptoms, and in Mantle Cell Lymphoma xenograft model, by targeting cancer cells to induce cell death and improve survival. In addition, I will discuss novel approach for delivering modified mRNA to specific cell types in vivo utilizing this platform. I will also share some data on mRNA vaccines for COVID19 and Finally, I will share new data showing very high efficiency genome editing in glioma and metastatic ovarian cancer. This modular delivery platform can serve as a milestone in turning precision medicine feasible.

Atoms in the highly excited Rydberg states possess unique properties, including long lifetimes and huge dipole moments, which facilitate their use in various quantum technology applications. I will discuss recent progress in quantum simulations of many-body physics with strongly-interacting Rydberg atoms and coherent interfaces of Rydberg atoms with superconducting microwave resonators and optical photons, and present some of our results in this research.

In this lecture, the theoretical and technical base for atomic imaging of defects in inorganic 2D materials in the low-voltage transmission electron microscope SALVE will be discussed. Atomic defects can significantly change the properties of the material: Using 2D-TMDs and 2D-TMPTs and corresponding heterostructures, this is shown experimentally and verified by corresponding quantum mechanical calculations. We also use the electron beam for the targeted formation of new phases in the inorganic 2D matrix. Since the interaction cross-sections of electron beam and organic 2D materials differ strongly from the inorganic case, we explore highest-resolution imaging conditions for 2D polymers and various 2D MOFs and show that there is a trend towards lower voltage TEM as well. We may conclude that low-voltage TEM and low-dimensional materials are just made for each other.

Electrostatic interactions between polyelectrolyte (PE) charges and dissociated counterions provide PEs with intriguing properties and significantly determine their conformation and dynamics. This research shows how weak PE chains form a global network when they are oppositely charged and how strong electric fields lead to orientational order. The development of controlled drug release and responsive structures is demonstrated by the use of ordered PE with tunable intermolecular interactions.

Neurodegenerative diseases are often clinically, genetically, and pathologically heterogeneous. The clinical impact of understanding heterogeneity is perhaps best observed in cancer, where subtype-specificity within diagnoses, prognoses, and treatments have had a critical impact on clinical decision making and patient outcomes. A better understanding of how mechanisms are related to or drive heterogeneity within diseases such as Amyotrophic Lateral Sclerosis (ALS), will have a direct impact on patient outcomes, with a conscious effort to move towards precision medicine and targeted therapeutics for patients, which are urgently needed. For this reason, neuroscientists and oncologists have long aspired to achieve an understanding of the mechanisms governing pathophysiology. Our interdisciplinary work integrates technologies across a wide range of fields to surpass the current barriers in understanding disease pathophysiology. This talk will highlight a series of optical and photoacoustic imaging tools as well as multi-omics analysis that have been developed and studied in Dr. Smith’s lab to address the urgent need for non-invasive cancer detection and the characterization of neurological disorders. Through this work, we aim to develop translational technologies and methodologies to better characterize, understand, and detect disease pathogenesis, beyond current capabilities.

One of the most surprising discoveries in exoplanet science has been the existence of compact systems of Earth to super-Earth sized planets. These multi-planet systems have nearly circular, coplanar orbits located at distances of only ∼ 0.01 − 0.1 AU, a region devoid of planets in our Solar System. Although compact systems comprise a large fraction of known exoplanetary systems, their origin remains debated. Common to all prior models of compact system origin is the assumption that infall to the stellar disk ends before planets form. However, there is growing observational, theoretical, and meteoritical evidence of the early growth of mm-sized “pebbles” during the infall phase. We propose that accretion of compact systems occurs during stellar infall. As a cloud core collapses, solids are gradually accumulated in the disk, producing favorable conditions for the formation and survival of close-in planets. A key feature of this model is that the reduced gas-to-solids ratio in the planet accretion region can allow for the formation and survival of compact systems, even with Type-I migration. Accretion within infall-supplied disks has been studied in the context of gas planet satellite origin. Formation models predict that the total mass of the satellite system during this evolution maintains a nearly constant mass ratio ∼10^−4 compared to the host planet’s mass. The maximum mass ratio of compact exoplanetary systems compared to the stellar mass are similar to those of the giant satellite system, suggesting that accretion of compact systems may be similar to regular satellite formation.

High-Performance, Rechargeable Li-ion Batteries (LIBs) are key to the global transition from fossil fuels to renewable energy sources. LIBs utilizing lithium metal as the anode are particularly exciting due to their exceptional energy density and redox potential, yet their advancement is hindered by growth of metallic filaments and unstable surface layers. Efficient cationic transport, which is crucial for battery performance, largely depends on the heterogeneous and disordered interphase formed between the anode and the electrolyte during cycling. Directly observing this interphase as well as the dynamic processes involving it is a great challenge. Here we present an approach to elucidate these dynamic processes and correlate them with the corresponding interfacial chemistry, focusing on the first step of cationic transport: surface adsorption. Employing Dark State Exchange Saturation Transfer (DEST) by 7Li NMR, we were able to detect the exchange of Li-ions between the homogenous electrolyte and the heterogeneous surface layer, highlighting the hidden interface between the liquid and solid environments. This enabled determination of the kinetic and energetic binding properties of different surface chemistries, advancing our understanding of cationic transport mechanisms in Li-ion batteries. 

We introduce a variant of SELEX in-vitro selection to study the evolution of a population of oligonucleotides starting from a seed of random-sequence DNA 50mers (our evolving individuals) and introducing selectivity by an affinity capture gel formed by beads carrying DNA 20mers of fixed sequence that act as targets (our resources). We PCR amplify the captured strands and proceed to the next generation. Because of the simplicity of the process, we could investigate what plays the role of “fitness" in this synthetic evolution process. We find that, across generations, evolution is first driven by the need of binding to the capture gel, while, on a later stages it appear dominated by the emerging of motifs related to inter-individual interactions.

Our organs and tissues are made of different cell types that communicate with each other in order to achieve joint functions. However, little is known about the universal principles of these interactions. For example, how do cell interactions maintain proper cellular composition, spatial organization and collective division of labor in tissues? And what is the role of these interactions in tissue-level diseases where the healthy balance in the tissue is disrupted such as excess scarring following injury known as fibrosis? In this talk, I will discuss my work in developing theoretical frameworks that explore the collective behavior of cells that emerges from cell-cell communication circuits. I will present work on the cell circuit that controls tissue repair following injury and how it may lead to fibrosis. I will discuss a new approach to explore how cell interactions can be used to provide symmetry breaking and optimal division of labor in tissues, and how this approach can help to interpret complex patterns in real data. I will introduce a new concept in complex networks – network hyper-motifs, where we explore how small recurring patterns (network motifs) are integrated within large networks, and how these larger patterns (hyper-motifs) can give rise to emergent dynamic properties. Finally, I will conclude with future directions that are aimed at revealing principles that unify our understanding of different tissues.

How animals navigate and perform directional decision making while migrating and foraging, is an open puzzle. We have recently proposed a spin-based model for this process, where each optional target that is presented to the animal is represented by a group of Ising spins, that have all-to-all connectivity, with ferromagnetic intra-group interactions. The inter-group interactions are in the form of a vector dot product, depending on the instantaneous relative, and deformed, angle between the targets. The deformation of the angle in these interactions enhances the effective angular differences for small angles, as was found by fitting data from several animal species. We expose here the rich variety of trajectories predicted by the mean-field solutions of the model, for systems of three and four targets. We find that depending on the arrangement of the targets the trajectories may have an infinite series of self-similar bifurcations, or have a space-filling property. The bifurcations along the trajectories occur on "bifurcation curves'', that determine the overall nature of the trajectories. The angular deformation that was found to fit experimental data, is shown to greatly simplify the trajectories. This work demonstrates the rich space of trajectories that emerge from the model.

Neuromorphic computing designs have an important role in the modern ‘big data’ era, as they are suitable for processing large amount of information in short time, eliminating the von Neumann (VN) bottleneck. The neuromorphic hardware, taking its inspiration from the human brain, is designed to be used for artificial intelligence tasks via physical neural networks, such as speech or image recognition, bioinformatics, visual art processing and much more. The memristor (memory + resistor), is one of the promising building blocks for this hardware, as it mimics the behavior of a human synapse, and can be used as an analog non-volatile memory. The memristor has been proven as a viable memory element and has been used for constructing resistive random access memory (RRAM) as a replacement for current VN hardware. However, the mechanism of operation and the conducting bridge formation mechanisms in electrochemical metallization memristors still require further investigation. A planar single-nanowire (NW) based memristor is a good solution for elucidating the mechanism of operation, thanks to the high localization of switching events, allowing in-situ investigation as well as post-process analysis. Our group, which has developed the guided-growth approach to grow guided planar NWs on different substrates, has used this method to integrate guided epitaxial NWs into functional devices such as field-effect transistors (FETs), photodetectors and even address decoders. However, the guided-growth approach has not been used for creating memristors up to date. In this work, I successfully synthesized guided NWs of two metal-oxides on flat and faceted sapphire substrates – ZnO and β-Ga2O3 were successfully grown in the VLS mechanism as surface guided NWs. I successfully grew planar guided β-Ga2O3 NWs on six different sapphire substrates, for the first time as far as we know. We characterized the newly grown β-Ga2O3 NWs with SEM, TEM, EDS and Raman spectroscopy. The monoclinic NWs grew along surprising directions on the flat sapphire surfaces and I demonstrated a new mode of growth – epitaxy favored growth on a faceted surface, when graphoepitaxy is also possible. I created electrochemical metallization memristors with the obtained NWs and successfully demonstrated the effect of resistive switching for β-Ga2O3 guided NW based devices. With the abovementioned achievements, we expanded the guided-growth approach on flat and faceted sapphire surfaces, and opened the opportunity for creating surface guided-NW based neuromorphic hardware.

From a perovskite photovoltaic device standpoint, the Al2O3 ALD can be thought of as a thin film encapsulate to protect the underlined material from the extrinsic entities. However, as per the literature is concerned, the role of Al2O3 ALD in the perovskite photovoltaic devices is much beyond a mare passive component. This raises a severe ambiguity over the choice of surface (or interface) on which ALD needs to be done for optimized device performance, in terms of the device efficiency and stability. In my presentation, I would like to elucidate the characteristic differences between the surface limited and substrate enhanced ALD processes which is important to perovskite devices. The objective here is to discuss a unified correlation between the role of the Al2O3 ALD mechanism with the perovskite device performance by excluding popular overestimated assumption about the conformality on non-ideal surface, like perovskite or organic thin films. In addition, I would like to emphasize on the fact that how the ALD process can be used to passivate the buried interfacial defect and enhancing the VOC, PL and ELQE.

Not a day goes by when we don’t hear about the “climate crisis”; some effects are well documented, like the rise in the average global temperature and the shrinking of the polar ice caps. Undoubtedly, carbon dioxide levels in the atmosphere have been increasing, but what does “science” say about the potential consequences? The combination of the atmosphere, oceans, cryosphere and biosphere is the ultimate non-linear coupled complex system. How well do we understand what might happen? In the first part of my talk, I shall review my exploration of the original literature to try and separate out speculation, hypothesis, results of computational models, and most significantly actual observations. In the second part of my talk, I shall discuss what will actually work to reduce carbon dioxide emissions (complete elimination or Net Zero is an impossibility). Although it has become fashionable for governments to impose mandates enshrined in laws, the only laws that matter are the laws of thermodynamics and Ohm’s law.

Aromatic dichalcogenides exhibits a rich reductive and oxidative redox chemistry and the one and two electron reductions and oxidations of such Ar2Ch2 species appears at rather mild potentials. The successive 1e–-reductions often have very similar potentials as the one electron process results in the formation of an odd-electron bond, which stabilizes the radical anion, for example in hypothetical Ph2S2•− by about 30 kcal/mol. Inspired by the natural dithiol/disulfide 2H+/2e− couple, we investigated a 2,2′-bipyridine that is equipped with a disulfide/dithiolate unit in the backbone for storing multiple electrons and protons.[2] The synchronized transfer of electrons and protons is a critical step in many chemical and biological transformations. In particular, hydride and H atom transfer reactions are important in, for example, catalytic hydrogenation or small molecule activation reactions relevant to renewable energy storage. We examined in depth the fundamental 2e–, 2e–/2H+ and 1e–/H+ reactivity of the switch depending on the metalation. It appears that the Re compound overcomes the drawback of many metal-free hydride donors, which show a large gap between the first and second reduction process, and detrimental side reactions of the radical intermediate. Furthermore, we applied such Ar2Se2 in the anodic amination and esterification of nonactivated alkenes. Amination and esterfication reactions are of considerable importance since C–N and C–O bond motifs can be found in numerous organic compounds associated with biological, pharmaceutical, or material scientific applications. We developed versatile protocols for the electrochemical functionalization and a detailed kinetic and thermodynamic analysis gave valuable insights into the mechanism of the reaction as well as the impact of, e.g. solvent, additives, on the organocatalysis.

Somitogenesis, the segmentation of the antero-posterior axis in vertebrates, is thought to result from the interactions between a genetic oscillator and a posterior-moving determination wavefront. I will introduce the current state of knowledge of that important stage in the development of vertebrate embryos. Surprisingly while the oscillator period is very sensitive to temperature changes, the size of the segments is not. I shall describe our results pertaining to the importance of the decrease in time of the Fgf8 gradient on the propagation of the wavefront and the observation that the somitogenetic period, embryo growth rate, PSM shortening rate and Fgf8 decay rate all slow down as 1/(T-Tc) with Tc=14.4°C, suggesting that critical slowing may affect the embryo metabolism resulting in a natural compensation of thermal effects on somite size.

https://weizmann.zoom.us/j/97641167767?pwd=YURCbjI5VjdJZ2hmWXAwMTVCS1p3UT09 Nearly 100 years ago, Jones and Dole experimentally pointed out a puzzle associated with the incremental modification of the bulk viscosity of water induced by small concentrations of salt. The strange behavior relates to cation specificity. This puzzle remains unsolved. This talk will remind you about this problem and suggest a possible approach. I hope that I can engender some ideas from you.

The successes and failures of approximate density functionals are due to their connection with semiclassical expansions. In the semiclassical limit, relative errors in local density approximations vanish. Carefully derived corrections to that limit have been shown to be far more accurate than our usual DFT approximations. I will discuss important new results in our 20-year-long quest to derive density functional approximations as expansions in hbar. These include both a new correction to the expansion of the exchange energy of atoms and an orbital-free calculation with sub-milli-Hartree accuracy. [1] Semiclassical Origins of Density Functionals Elliott, Peter, Lee, Donghyung, Cangi, Attila and Kieron Burke, Phys. Rev. Lett. 100, 256406 (2008). [2] Leading correction to the local density approximation for exchange in large-Z atoms Nathan Argaman, Jeremy Redd, Antonio C. Cancio, and Kieron Burke, Phys. Rev. Lett. 129, 153001 (2022). [3] Orbital-free functional with sub-milliHartree accuracy, Pavel Okun and Kieron Burke, in preparation.

Heterostructures (HS) of two-dimensional materials offer unlimited possibilities to design new materials for applications to optoelectronics and photonics. In such HS the electronic structure of the individual layers is well retained because of the weak interlayer van der Waals coupling. Nevertheless, new physical properties and functionalities arise beyond those of their constituent blocks, depending on the type and the stacking sequence of layers. In this presentation we use high time resolution ultrafast transient absorption (TA) and two-dimensional electronic spectroscopy (2DES) to resolve the interlayer charge scattering processes in HS. We first study a WSe2/MoSe2 HS, which displays type II band alignment with a staggered gap, where the valence band maximum and the conduction band minimum are in the same layer. By two-colour pump-probe spectroscopy, we selectively photogenerate intralayer excitons in MoSe2 and observe hole injection in WSe2 on the sub-picosecond timescale, leading to the formation of interlayer excitons (ILX). The temperature dependence of the build-up and decay of interlayer excitons provide insights into the layer coupling mechanisms [1]. By tuning into the ILX emission band, we observe a signal which grows in on a 400 fs timescale, significantly slower than the interlayer charge transfer process. This suggests that photoexcited carriers are not instantaneously converted into the ILX following interlayer scattering, but that rather an intermediate scattering processes take place We then perform 2DES, a method with both high frequency and temporal resolution, on a large-area WS2/MoS2 HS where we unambiguously time resolve both interlayer hole and electron transfer with 34 ± 14 and 69 ± 9 fs time constants, respectively [2]. We simultaneously resolve additional optoelectronic processes including band gap renormalization and intralayer exciton coupling. Finally, we investigate a graphene/WS2 HS where, for excitation well below the bandgap of WS2, we observe the characteristic signal of the A and B excitons of WS2, indicating ultrafast charge transfer from graphene to the semiconductor [3]. The nonlinear excitation fluence dependence of the TA signal reveals that the underlying mechanism is hot electron/hole transfer, whereby a tail the hot Fermi-Dirac carrier distribution in graphene tunnels through the Schottky barrier. Hot electron transfer is promising for the development of broadband and efficient low-dimensional photodetectors. [1] Z. Wang et al., Nano Lett. 21, 2165–2173 (2021). [2] V. Policht et al., Nano Lett. 21, 4738–4743 (2021). [3] C. Trovatello et al., npj 2D Mater Appl 6, 24 (2022).

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Coexistence of optical and electrical excitations in semiconductors has a long history of research. This scenario typically involves simultaneous presence of Coulomb-bound electron-hole pairs, known as excitons, and free charge carriers. Conceptually similar to related phenomena in the ultra cold atom gases, exciton-carrier mixtures strongly influence the properties of excited semiconductors and their response to external fields. It involves the formation of bound three-particle states known as charged excitons or trions, Fermi polarons, renormalization and screening effects, as well as the Mott-transition in the high-density regime. These phenomena offer fertile ground to merge the realms of optics and transport, motivated by the availability of excitations that are both electrically tunable and couple strongly to light. Van der Waals monolayer semiconductors and layered metal-halide perovskites recently emerged as particularly suitable platforms to study exciton-carrier mixtures due to exceptionally strong Coulomb interactions on the order of many 100’s of meV. In this talk, I will discuss a number of intriguing phenomena associated with coupling of excitons to free charge carriers in these systems. I will present experimental evidence for dressing of excited exciton states by continuously tunable Fermi sea. These quasiparticles are reminiscent of two-electron excitations of the negatively charged hydrogen ion and are subject to autoionization - a unique scattering pathway available for excited states. I will further illustrate the impact of free carriers on the exciton transport revealing non-monotonous density dependence and highly efficient propagation of charged exciton complexes. Finally, I will demonstrate electrically tunable trions in hybrid organic-inorganic semiconductors. These three-particle complexes feature unusually large binding energies combined with substantial mobility at elevated temperatures.

Transition metal catalyzed carbonylation reactions of a wide range of organic compounds provide entry to some molecules of value to the pharmaceutical, commodity, and petrochemical industries. Examples to be presented include the preparation of indolizine derivatives by palladium-catalyzed oxidative alkoxycarbonylation, the synthesis of N-fused heterocycles via dearomatic carbonylation, the highly regioselective and chemoselective carbonylation of bifunctional organic reactants with haloarenes, styrenes, and alkynes. These transformations were successfully applied to the synthesis of natural products including Avenanthramide A

Catalysis is a general process that speeds up the reaction rate without altering the process thermodynamics. It is often essential to study the kinetics of the reaction to infer the mechanism of catalysis, an insight that can help in catalyst design. However, bulk catalysis, and specifically electrocatalysis, cannot capture the inherent heterogeneity of seemingly identical catalysts. This talk aims to provide basic principles behind electrocatalysis and introduce a new way to study electrocatalysts at the single entity level. Together, we will review the latest progress in the field and conclude with future directions that can be applied to the vast majority of catalysts ranging from organic, bio, and inorganic materials.

Functional materials are the main building blocks of advanced technologies based on energy storage and conversion systems essential for our modern life including batteries, solar cells, and heterogeneous catalysis. Improvements in materials performance and development of new materials rely on our ability to obtain structure-function correlation as well as understand degradation processes when the materials are integrated into a device. To this end, advanced analytical tools that can provide information at the atomic level are essential. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy is well suited for this task, especially when equipped with high sensitivity by Magic Angle Spinning - Dynamic Nuclear Polarization (MAS-DNP). However, to date, the majority of materials studied by MAS-DNP were non-reactive and non-conductive materials with DNP from exogenous sources of polarization such as nitroxide radicals. This approach cannot be simply extended to functional materials as the properties that stem from the material’s functionality in the device, including electrical conductivity, chemical reactivity and defects, often pose challenges in the study of the materials by DNP. In this talk I will frame the challenges associated with the application of MAS-DNP to functional materials and describe approaches to address them. Results will be presented from three ubiquitous material systems spanning a range of applications: carbon allotropes, transition metal dichalcogenides (TMDs) and metallic microstructures. We systematically investigated the deleterious effect of materials’ conductivity and formulated means to reduce the effect. We explored the feasibility of utilizing inherent unpaired electrons for endogenous DNP and applied it to probe buried phases in all-solid-state lithium-metal battery and the surface chemistry in carbons. I will show that wealth of information achieved by DNP on various functional materials, can place DNP-NMR as a preferable tool for materials scientists. Our findings are expected to apply to many other systems where functional materials are dominant, making DNP a more general technique.

Colloidal nanocrystals possess high surface area-to-volume ratios; as a result, many nanocrystal properties are heavily influenced by their surfaces. At these surfaces exist a complex interface between the inorganic solid (governed by the crystal structure and particle morphology) and organic ligands. The organic ligands play a key role in controlling nucleation and growth, passivating under-coordinated surface sites, and providing steric stabilization for solvent dispersibility. Depending on the particular application of the nanocrystal, the native organic ligands may then need to be removed or exchanged. We use a complement of NMR spectroscopic techniques to understand the nature of the nanocrystal surface and ligand binding. Then, using principles of inorganic coordination chemistry, we rationally enact ligand exchange reactions on these surfaces to maximize nanocrystal functionality. This talk will briefly discuss the surface chemistry of three different platforms. (1) I will discuss how we experimentally developed an atomistic picture of perovskite nanocrystal surface termination, and then used that information to better understand how common surface treatments can “heal” halide perovskite nanocrystal surfaces. (2) I will discuss how different -donating, L-type ligands were installed on the surface of metal phosphide nanocrystals, and how they affected the hydrogen evolving ability of these electrocatalysts. (3) I will discuss a new strategy for thermally activating metal carbide nanocrystal CO2 reduction catalysts using labile ligands that decompose at significantly lower temperatures than the native ligands. This circumvents issues commonly encountered with high-temperature thermolysis (coking) or acid treatments (etching, poisoning) that are used to activate nanocrystal catalysts.

The development of advanced photovoltaic devices, including those that might overcome the single junction efficiency limit, as well as the development of new materials, all rely on advanced characterization methods. Among all the existing methods optically based ones are very well adapted to quantitatively probe optoelectronic properties at any stage. We here present the use of multidimensional imaging techniques that record spatially, spectrally and time resolved luminescence images. We will discuss the benefits (and challenges) of looking into energy conversion systems from high dimensions perspective and those of dimensional reduction for improved intelligibility through some examples, mostly drawn from halide perovskite materials and device. These examples will help visit questions related to efficient transport and conversion in solar cells, as well as questions related to chemical and operational stability of the devices.

This lecture presents an overview on major research work of the Fellow’s group in the areas of polymer nanoparticles for drug delivery, control of protein adsorption on materials surfaces and protein nanofibers. In addition, the new excellence graduate school (Research Training Group) RTG 2723: Materials‐Microbe‐Microenvironments: Antimicrobial biomaterials with tailored structures and properties (M‐M‐M) funded by the German Science Foundation will be introduced. Polymer nanoparticles (PNP) became recently exceedingly popular through novel vaccination technologies but have also major potential for fighting inflammation and cancer. These drug release properties of the PNP depend on their structure. Yet, the literature reports little about the structure and the properties of most PNPs, except the chemical composition. The PNP’s crystallinity, thermal and mechanical properties are frequently ignored, even though they may play a key role in the drug delivery properties of the PNPs. Protein adsorption on biomaterials is the first process after implantation and determines much of the fate of the biomaterial, such as cell adhesion, blood coagulation or infection at the implant site. Despite decades of research, only rules of thumb exist to predict protein adsorption behavior. We present nanotechnological approaches to control protein adsorption using nanostructured semicrystalline polymers and crystal facets of TiO2. Selfassembled protein nanofibers consisting of one or more proteins, potentially allow to tailor the properties of biomaterials interfaces and to create bone mimetic structures. Finally, the new DFG‐RTG 2723: Materials‐Microbe‐Microenvironments: Antimicrobial biomaterials with tailored structures and properties (M‐M‐M) in Jena will be introduced. The aim of the RTG is to provide excellent training for approximately 40 international doctoral researchers in antimicrobial biomaterials in interdisciplinary tandem projects, connecting materials science and medical science. The RTG pursues a new strategy by developing antibiotic free biomaterials, where the antimicrobial action is based mainly on physical principles. The new RTG offers ample opportunity for fruitful cooperation and exchange with leading research institutions in Israel.

This colloquium will be divided into two applications parts, dealing with synthesis of supported molecular catalysts and solid catalysts for photoprotection. In the first of these areas, we describe a mechanical approach for stabilizing supported weakly interacting active sites (i.e. those that interact non-covalently with the support) against aggregation and coalescence. We use silica as a prototypical example of a support, and an iridium pair-site catalyst incorporating bridging calixarene ligands as an active site. Atomic-resolution imaging of the Ir centers before and after ethylene-hydrogenation catalysis show the metals resisted aggregation and deactivation, remaining atomically dispersed and accessible for catalysis. When active sites are located at unconfined environments, the rate constants for ethylene hydrogenation are markedly lower compared with confining external-surface pockets [1], in line with prior observations of similar effects in olefin epoxidation catalysis [2,3]. Altogether, these examples represent new opportunities for enhancing reactivity on surfaces by synthetically controlling mechanical features of active site catalyst environments. In the second of these areas, reactive oxygen species (ROS) are associated with several human health pathologies and are invoked in the degradation of natural ecosystems as well as building materials that are used in modern infrastructure (e.g., paints and coatings, polymers, etc). Natural antioxidants such as vitamin E function as stoichiometric reductants (i.e. reaction with ROS synthesizes rancid oils). While enzymes such as superoxide dismutase working in tandem with catalase decompose decompose ROS to H2O and O2 through H2O2 as an intermediate, these enzymes are fragile and costly. Other non-stoichiometric commercial antioxidants that degrade ROS include hindered amine light stabilizers (HALS). Here, we demonstrate that cerium carbonate acts as a degradation catalyst for photogenerated ROS, and describe the performance and characterization of this new catalyst using X-ray photoelectron spectroscopy, and in comparison with HALS and stoichiometric reductants. Our results demonstrate catalytic antioxidant activity of cerium carbonate when dispersed in polymethylmethacrylate polymer. FTIR data demonstrate that a dispersion of 2 wt. % cerium carbonate within the polymer essentially stops degradation by photogenerated ROS, which otherwise cause oxidation of the polymer backbone, in the control polymer lacking cerium carbonate. Experiments with methylene blue dye in aqueous solution demonstrate that cerium carbonate decreases the rate of ROS degradation of dye, in the presence of UV irradiation and air by 16 fold. These effects become even more pronounced (over 600 fold decrease in rate of ROS dye degradation) when cerium carbonate is paired with a photoactive metal oxide. The mechanism involved in this latter case crudely mimics the enzyme tandem sequence referred to above. [1] C. Schöttle, E. Guan, A. Okrut, N. A. Grosso-Giordano, A. Palermo, A. Solovyov, B. C. Gates, A. Katz*, Journal of the American Chemical Society, J. Am. Chem. Soc. 2019, 141, 4010-4015. [2] N. A. Grosso-Giordano, C. Schroeder, A. Okrut, A. Solovyov, C. Schottle, W. Chasse, N. Marinkoyic, H. Koller, S. I. Zones, A. Katz, Journal of the American Chemical Society 2018, 140, 4956-4960. [3] N. A. Grosso-Giordano, A. S. Hoffman, A. Boubnov, D. W. Small, S. R. Bare, S. I. Zones, A. Katz, Journal of the American Chemical Society 2019, 141, 7090-7106. [4] M. K. Mishra, J. Callejas, M. Pacholski, J. Ciston, A. Okrut, A. Van Dyk, D. Barton, J. C. Bohling, A. Katz, ACS Applied Nano Materials 2021, 4, 11, 11590-11600.

Most of the Pacific Northwest (PNW, USA) and British Columbia experienced extraordinarily high air temperatures during an extreme heat wave event (“heat dome”) in late June of 2021. In many locations, alltime record high air temperatures (Tair) exceeding 40-45 °C were observed. In this talk I will present evidence of the widespread impacts of this extreme heat event. These impacts include foliar damage observed in many locations of this region, along with some tree mortality. Additionally, I will present data from dendrometers and eddy covariance towers in contrasting forest types highlighting the impacts on tree growth and ecosystem-atmosphere CO2, H2O, and energy fluxes. Better understanding the environmental drivers, biophysical and physiological mechanisms, and ecological consequences of heat damage incurred by forests is of broad relevance and societal importance.

https://weizmann.zoom.us/j/95467631640?pwd=MHZBNThNQlRUeU1CM29kQXZZcGxOdz09 password:864419 Solid oxide fuel cells (SOFCs), especially proton conducting (PC)-based, and electrolyzes (SOEs), operating above 250°C, demonstrate rapid electrode kinetics, but are limited in their long term stability due to thermal stresses related to on/off cycling. Thermal stress could be reduced dramatically, for PC-SOFCs devices operating in the temperature range of 150-250°C, which would still benefit from fast electrode kinetics and would not require Pt-containing catalytic electrodes. However, a proton-conducting ceramic electrolyte, operating below 250°C hasn’t been identified yet. In this work I investigated the synthesis, preparation protocols and properties of La(OH)_3 and La_2 Ce_2 O_7 (LCO50) powder and ceramics to explore their suitability as proton conductors. Preparation of appropriate pellet samples of La(OH)_3 from the synthesized powder requires (i) elimination of the presence of carbonate oxides followed by (ii) hydration of the remaining La2O3 in boiling deionized water. Room temperature compaction of these powders into solid pellet samples requires prolonged dwell uniaxial pressure. Although the primarily protonic conductivity of the compacted sample reached only 3·10-11 S/cm at 90°C and is insufficient for practical applications; the grain boundaries are apparently not blocking, making it attractive to look for dopants that may potentially enhance the low temperature conductivity. Nominally anhydrous LCO50 has an unexpectedly high conductivity 10-11 S/cm at 110 °C, which is probably due to oxygen vacancies. LCO50 undergoes hydration with a large lattice expansion, which combined with low hydration enthalpy (5.2 kJ/mol) restricted compact crack-free sample. Hydration of LCO50 by 7.5% of the maximum possible showed to have non-blocking grain boundaries, and increases the conductivity by an order of magnitude, which has to be attributed to protonic conduction. Findings describe in this work, point that both investigated materials are promising candidates for further studies as proton conductors.

Subsurface systems, such as alluvial aquifers and soils, store and govern the quality of groundwater by sustaining a unique balance of biogeochemical and hydrological processes. The complex characteristics of subsurface systems are demonstrated in both spatial and compositional sediment heterogeneities that ultimately control the rate and extent of elemental cycling. Different redox environments commonly form within the subsurface and may largely influence these cycles. Heavy metals, occurring naturally (geogenic) or as anthropogenic contaminants, are particularly sensitive to varying redox conditions, even if they are not directly redox active. In this seminar, I will show how sediment hotspots and interfaces influence elemental cycling, contaminant attenuation, and groundwater quality. I will present examples of how an alluvial aquifer system exhibiting redox heterogeneities may influence heavy metal mobility by preferential retention in fine-grained sediment lenses embedded within the coarse aquifer. Several mechanisms contribute to the retention in fine-grained sediments, and we also observe a significant impact of nitrate-rich conditions on the extent and phases of metal retention. Further, I will share our findings on the dynamic and unique composition of iron-rich colloids, detected in reducing zones of a floodplain subsurface. Our results demonstrate the presence of partially oxidized iron rich colloids in otherwise reducing conditions, thanks to a protective organic-silicon coating. The lifecycle and composition of these colloids may have direct effects on element cycling as they may serve as vectors for the transport of nutrients and organic matter into groundwater and surface water recipients. Lastly, I will present my future research visions, in a lab devoted to the study of biogeochemical heterogeneity and coupled elemental cycling under dynamic conditions.

Catalysis is a key technology, since it allows for increased levels of selectivity and efficacy of chemical transformations. While significant progress can be made by rational design or engineered step-by-step improvements, many pressing challenges in the field require the discovery of new and formerly unexpected results. Arguably, the question “How to discover?” is at the heart of the scientific process. In this talk, (smart) screening strategies for accelerated discovery and improved reproducibility will be presented, together with new photocatalytic transformations. In addition, two other exciting areas will be addressed: N-heterocyclic carbenes (NHCs) are powerful ligands in catalysis due to their strong electron-donating properties and their ability to form very stable bonds to transition metals. In addition, they can stabilize and modify nanoparticles or flat metals surfaces, outperforming established phosphine or thiol ligands regarding structural flexibility, electron-donating properties and stability. Current research is highly interdisciplinary and focusses on the basic understanding of the binding mode, mobility and the elucidation of the impact on the surface properties. Exciting applications in materials science, heterogeneous catalysts and beyond are within reach. Biological membranes and their constituents are some of the most important and fundamental building blocks of life. However, their exact role in many essential cellular processes as well as in the development of diseases such as cancer or Alzheimer's is still not very well understood. Thus, we design, synthesize and evaluate imidazolium-based lipid analogs that can integrate into biological membranes and can be used as probes for live cell imaging or to manipulate membranes.

Thick halite sequences are common in the Earth’s geologic record; they were accumulated in deep perennial hypersaline water bodies, saturated to halite and subjected to negative water balance. For decades, evaporites research gained insights from exploring modern shallow hypersaline environments, including the relations between the hydroclimatic forcing and the deposited halite layers. However, there is a knowledge gap in understanding limnological controls on accreted halite sequences in deep water bodies. Such water bodies rarely exist today on Earth, but were common through Earth geological history. The Dead Sea is currently the closest and probably the only modern analog for such environments. Recently, based on direct field measurements, laboratory experiments, direct numerical simulations, and sedimentological investigation, we have shown that there are fundamental differences between deposition at deep basins versus shallow basins, specifically in the seasonal to multi-annual scales and variations of halite solubility with depth. We have found that during the dry summer the epilimnion is warmer, saltier and undersaturated to halite, and that double diffusion flux delivers dissolved salt from the epilimnion into the hypolimnion, resulting in the continuously supersaturated hypolimnion and seasonally undersaturated epilimnion. Thus the stratified structure of the lake’s water column results in focusing of halite deposits into the deep parts of the basin and thinned deposits, or entirely dissolved, in the marginal parts. We further explore the role of laterally variable hydroclimatic conditions to the spatiotemporal dynamics of evaporitic deposits in a deep hypersaline waterbody. We focus on the role of diluted buoyant plume, overlaying part of the Dead Sea surface that laterally spreads from freshwater inflow. The lateral surface salinity variations results in lateral variations in evaporation, double diffusion fluxes, and hence evaporitic layer thickness. These can contribute to the study of the depositional environments of halite units throughout the geological record, following the concept of “the present as key to the past”. At the end of the talk, I will share some management ideas regarding the future of the Dead Sea.

Charge transfer and transport processes through molecular interfaces are ubiquitous and of a crucial role in determining functionality of biological systems and in enabling energy conversion applications. We study computationally such processes to understand structure-function relationships at the molecular level. We will discuss studies in the following two primary fields: (1) Photovoltaic and charge transfer properties of organic semiconductors materials. (2) Charge transport through voltage-biased molecular scale bridges. Importantly we establish predictive computational scheme that addresses key challenges. Our studies are employed in conjunction with experimental efforts to design materials and applications that control and tune relevant physical properties

Over the past decade, there has been tremendous progress in the measurement, modeling and understanding of structure-function relationships in single molecule circuits. Experimental techniques for reliable and reproducible single molecule junction measurements have led, in part, to this progress. In particular, the scanning tunneling microscope-based break-junction technique has enabled rapid, sequential measurement of large numbers of nanoscale junctions allowing a statistical analysis to readily distinguish reproducible characteristics. Although the break-junction technique is mostly used to measure electronic properties of single-molecule circuits, in this talk, I will demonstrate its versatile uses to understand both physical and chemical phenomena with single-molecule precision. I will discuss some recent experimental and analysis aimed at understanding quantum interference in single-molecule junctions. I will then show an example where molecular structure can be designed to utilize interference effects to create a highly non-linear device. Finally, I will discuss some new areas of research aiming to demonstrate that electric fields can catalyze chemical reactions.

The mathematical analogy between information and thermodynamical entropy has recently led to promising developments in chemistry and physics, and information theory tools are increasingly important in chemical and biological data analysis. In this talk I will describe a few of our ideas at the intersection of physical chemistry, information theory, and computer science, with the focus on single-molecule data analysis. Single-molecule experimental studies have opened a new window into the elementary biochemical steps, function of molecular machines, and cellular phenomena. The information contained in single-molecule trajectories is however often underutilized in that oversimplified models such as one-dimensional diffusion or one-dimensional random walk are used to interpret experimental data. I will show that much finer details of single-molecule dynamics, such as conformational memory and static disorder, can be deduced from an analysis that is similar to Shannon’s analysis of printed English; in particular, this method relates conformational memory to the information-theoretical compressibility of single-molecule signals.

One of the key advances in nanoscience and nanotechnology has been our increasing ability to reach the limits of atomically precise structures. By having developed the “eyes” to see, to record spectra, and to measure function at the nanoscale, we have been able to fabricate structures with precision as well as to understand the important and intrinsic heterogeneity of function found in these assemblies. The physical, electronic, mechanical, and chemical connections that materials make to one another and to the outside world are critical. Just as the properties and applications of conventional semiconductor devices depend on these contacts, so do nanomaterials, many nanoscale measurements, and devices of the future. We discuss the important roles that these contacts can play in preserving key transport and other properties. Initial nanoscale connections and measurements guide the path to future opportunities and challenges ahead. Band alignment and minimally disruptive connections are both targets and can be characterized in both experiment and theory. I discuss our initial forays into this area in a number of materials systems.

Molecular crystals are supramolecules “par excellence"1 as they are macroscopic objects composed by millions of molecules periodically disposed and held together by non-covalent interactions with specific physico-chemical properties dictated by their architectures. This offers a vibrant solid-state chemistry playground to build organic solids with tailored functionalities, such as novel luminescent materials,2 solid-state molecular machines,3 and multicomponent crystals with complex topologies.4 The inherent dynamic nature of the weak intermolecular forces that are driving organic crystals self-assembly is also conferring adaptive responsiveness, e.g., mechanical reconfiguration and shape-memory effect, to this class of materials making them ideal building blocks for the design and synthesis of multifunctional crystalline systems that can be exploited as actuators, flexible single-crystalline optoelectronic devices, and self-healing materials.5

The studies of magnetic atoms adsorbed on non-magnetic surfaces provide a fundamental insights into the quantum many-body phenomena at the nanoscale. They imprint non-trivial signatures in STM measurements, and can serve as a prototype for potential applications in quantum information technology. Our work aims at the investigation of the electronic structure, spin and orbital magnetic character for the Co adatom on the top of Cu(100) surface. We make use of DFT combined with exact diagonalization of the multi-orbital Anderson impurity model, including the spin-orbit coupling. For the Co atom d-shell occupation nd=8, a singlet many-body ground state and Kondo resonance are found, when the spin-orbit coupling is included in the calculations. The differential conductance is evaluated in a good agreement with the STM measurements. This comparison is the most direct way to demonstrate the validity of our theoretical approximation. Our results illustrate the very essential role which the spin-orbit coupling is playing in a formation of Kondo singlet for the multi-orbital impurity in low dimensions.

Self-assembly and self-organization are two big challenges in the natural sciences. What are the rules governing the emergence of greater structures from unassuming elements? Does statistical-mechanics restrict their complexity? Biochemical processes can shape highly specific structures and function on the macro-scale using only molecular information. Although stereochemistry has been a central focus of molecular sciences since Pasteur, its synthetic province has been restricted to the nanometric scale. In my talk, I will describe how to propagate molecular information to self-assemble free-form architectures on the micron-scale and beyond. These architectures are a thousand times greater than their constituent molecules yet have a preprogrammed geometry and chirality. I will then show how to animate such synthetic microstructures into bacteria-like micro-swimmers. Previous artificial microswimmers relied on an external chemical fuel to drive their propulsion which restricted their operational concentration as they competed locally over fuel. I will demonstrate how to use material science and physical chemistry to self-assemble fuel-free micro-swimmers that are driven solely by light. The fuel independence allows the swimmers to stay active even at high densities, where they form turbulent flow structures (previously seen in living fluids), and cooperate to perform a greater task.

Decadal Climate Predictions Using Sequential Learning Algorithms Ensembles of climate models are commonly used to improve climate predictions and assess the uncertainties associated with them. Weighting the models according to their performances holds the promise of further improving their predictions. Using an ensemble of climate model simulations from the CMIP5 decadal experiments, we quantified the total uncertainty associated with these predictions and the relative importance of model and internal uncertainties. Sequential learning algorithms (SLAs) were used to reduce the forecast errors and reduce the model uncertainties. The reliability of the SLA predictions was also tested, and the advantages and limitations of the different performance measures are discussed. The spatial distribution of the SLAs performance showed that they are skillful and better than the other forecasting methods over large continuous regions. This finding suggests that, despite the fact that each of the ensemble models is not skillful, the models were able to capture some physical processes that resulted in deviations from the climatology and that the SLAs enabled the extraction of this additional information. If time permits I will also present a method for estimating the uncertainties associated with ensemble predictions and demonstrate the resulting improved reliability. References: 1. Improvement of climate predictions and reduction of their uncertainties using learning algorithms, Atmospheric Chemistry and Physics 15, 8631-8641 (2015). 2. Decadal climate predictions using sequential learning algorithms, Journal of Climate 29, 3787-3809 (2016). 3. The contribution of internal and model variabilities to the uncertainty in CMIP5 decadal climate predictions, Climate Dynamics 49, 3221 (2017). 4. Quantifying the uncertainties in an ensemble of decadal climate predictions. Journal of Geophysical Research: Atmospheres 122, 13,191–13,200 (2017). 5. Learning algorithms allow for improved reliability and accuracy of global mean surface temperature projections. Nature Communications 11, 451 (2020).

The maker movement (cheap electronics + sharing), automated microscopy, autonomous platforms and small footprint satellites have been revolutionizing oceanography, opening a variety of new avenues for research and requiring a different education model. In this talk I will summarize a few activities my lab has been involved in that are associated with these disruptive technologies and why I am very optimistic for the future of our field in the coming years.

Zoom Link: https://weizmann.zoom.us/j/93495966390?pwd=T3hDNXY1WFh6bFpIbDh3OEFxZlcwZz09 The fibre-matrix interface plays a vital role in the overall mechanical behaviour of a fibre-reinforced composite, but the classical approach to improving the interface through chemical sizing is limited by material properties. Achieving a simultaneous improvement in strength and toughness in a composite is a particular challenge since these properties are mutually exclusive, and the chemical modification of the interface often results in one property being improved at the expense of the other. In contrast, the geometrical modification of the fibre-matrix interface to allow for mechanisms such as mechanical interlocking of components is a promising approach to resolving this challenge. This study explores a novel type of topographical obstacle – polymer droplets at the fibre-matrix interface. Discrete epoxy droplets are deposited onto glass fibres and embedded in an epoxy matrix to form model composites. The effect of the interfacial epoxy droplets is investigated using single fibre experiments.

It is by now well established that certain stratospheric flow configurations may alter tropospheric dynamical variability. Such flow configurations include the aftermath of sudden stratospheric warming events (SSWs) or strong polar vortex events (SPVs). Although the detailed mechanisms behind this stratosphere-troposphere coupling remain elusive, most aspects of it are well-known. For example, the coupling involves feedbacks between upward propagating planetary waves of tropospheric origin and the mean flow, the tropospheric response involves synoptic-scale eddy feedbacks, SSWs tend to project onto negative anomalies of the Arctic and North-Atlantic Oscillation (AO, NAO), whereas SPVs tend to project onto positive anomalies of the AO and NAO. Here I will highlight some recent results on 1) the potential role of a planetary wave source near the tropopause in troposphere-stratosphere coupling, 2) the stratospheric influence on the evolution of baroclinically unstable waves during their non-linear decay phase, 3) the improved quantification of the stratospheric modulation of AO extremes from extended-range ensemble forecasts.

Zoom Link: https://weizmann.zoom.us/j/99290579488?pwd=cUIyV05SMUQ0VDErNUtma1RTL3BIQT09 In the last decade, halide perovskites (HaPs) have developed as promising new materials for a wide range of optoelectronic applications, notably solar energy conversion. Although their technology has advanced rapidly towards high solar energy conversion efficiency and advantageous optoelectronic properties, many of their properties are still largely unknown from a basic scientific standpoint. Due to the highly dynamical nature of HaPs, one of the main avenues for basic science research is the use of molecular dynamics (MD) simulations, which provide a full atomistic picture of those materials. One of the main limiting factors for such analysis is the time scale of the MD simulation. Because of the complexity of the HaP system, classical force field approaches do not yield satisfactory results and the most widely used force calculation approach is based on first-principles, namely on density functional theory (DFT). In recent years, a new type of force calculation approach has emerged, which is machine learned force fields (MLFF). These methods are based on machine learning (ML) algorithms. Their wide spread use is enabled by the ever-increasing computational power and by the availability of large-scale shared repositories of scientific data. Here, we have applied one MLFF algorithm, known as domain machine learning (GDML). After training a MLFF based on the GDML model, we observed that the MLFF fails in a dynamical setting while still showing low testing error. This has been found to be due to lack of full coverage of the simulation phase space. To address this issue, we have suggested the hybrid temperature ensemble (HTE) approach, where we create rare events that are training samples on the edge of the phase space. We achieve this by combing MD trajectories from a range of temperatures to a single dataset. The MLFF model, trained on the HTE dataset, showed increasing accuracy during the training process, while being dynamically stable for a long duration of MD simulation. The trained MLFF model also exhibited high accuracy for long-term simulations, showing remaining errors of the same magnitude of inherent errors in DFT calculation.

The Great Lakes of the Earth are freshwater seas, and many of the geochemical processes that take place in their bottom sediments parallel those that happen in marine environments. The conditions, however, are different enough to significantly modify the geochemical cycles of key elements. By analyzing those differences, we can not only understand the functioning of the planet's largest freshwater ecosystems, but can also gain insight into the elemental cycling (C, N, P, S...) in the oceans during the past geological epochs.

Methodologies that rely on the addition and removal of molecular hydrogen from organic compounds are one of the most oft-employed transformations in modern organic chemistry, representing a highly relevant tactic in synthesis. Despite their overall simplicity, organic chemists are still pursuing sustainable and scalable processes for such transformations. In this regard, electrochemical techniques have long been heralded for their innate sustainability as efficient methods to perform redox reactions. In our first report, we discovered a new oxidative electrochemical process for the a,b-desaturation of carbonyl functionalities. The described desaturation method introduces a direct pathway to desaturated ketones, esters, lactams and aldehydes simply from the corresponding enol silanes/phosphates, and electricity as the primary reagent. This electrochemically driven desaturation exhibits high functional group tolerance, is easily scalable (1–100 g), and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Our second report demonstrated the reductive electrochemical cobalt-hydride generation for synthetic organic applications inspired by the well-established cobalt-catalyzed hydrogen evolution chemistry. We have developed a silane- and peroxide-free electrochemical cobalthydride generation for formal hydrogen atom transfer reactions reliant on the combination of a simple proton source and electricity as the hydride surrogate. Thus, a versatile range of tunable reactivities involving alkenes and alkynes can be realized with unmatched efficiency and chemoselectivity, such as isomerization, selective E/Z alkyne reduction, hydroarylation, hydropyridination, strained ring expansion, and hydro-Giese.

Zoom Link: https://weizmann.zoom.us/j/95952232097?pwd=OW9SL2JlNkNYQVJ1cW5FT05HcEh2QT09 The optimally-tuned range separated hybrid (OT-RSH) functional is a non-empirical method within density functional theory, which is known to yield accurate fundamental gaps for a variety of systems. Here we extend its applicability to magnetic resonance parameters, enhance its accuracy by designing OT-RSH based double-hybrid functionals, and increase its precision for solid-state calculations by designing and generating RSH pseudopotentials.

By economy of scale, imaging sensors can now be deployed densely and operated in a coordinated manner at large numbers in space, air, underwater and on the ground. Such distributed imaging systems enable multi-view setups across heterogeneous media of importance to geoscience. These create new observation modes. One outcome is 4D volumetric spatiotemporal recovery of scatterers in the atmosphere, specifically cloud content (the core of the CloudCT space mission). This is in addition to computed tomography of underwater sediment suspension and atmospheric turbulence distributions. We describe several such systems - demonstrated in the field, including both distributed imaging and the basis of the algorithms to analyze the data.

Extreme temperatures have warmed substantially over recent decades and are expected to continue warming in response to future climate change. Warming of extreme temperatures is projected to be amplified over land, with severe implications for human health, wildfire risk and food production. Using simulations from coupled climate models, I show that hot days over tropical land warm substantially more than the average day. For example, warming of the hottest 5% of land days is a factor of 1.2 larger than the time-mean warming averaged across models. The climate-change response of extreme temperatures over tropical land is interpreted using a theory based on convective coupling and the weak temperature gradient approximation. According to the theory, warming is amplified for hot land days because those days are dry: this is termed the “drier get hotter” mechanism. Changes in near-surface relative humidity further increase tropical land warming, with decreases in land relative humidity particularly important. The theory advances physical understanding of the tropical climate and highlights climatological land-surface dryness as a key factor determining how extreme temperatures respond to climate change.

Zoom Link: https://weizmann.zoom.us/j/97777492731?pwd=YXZDR0lqYUtMbHVidUlIWkl2TGxjdz09 Protein-metal interactions play an important regulatory role in the modulation of protein folding and in enabling the “correct” biological function. In material science, protein self-assembly and metal-protein interaction have been utilized for the generation of multifunctional supramolecular structures beneficial for bio-oriented applications, including biosensing, drug delivery, antibacterial activity, and many more. Even though, the nature and the mechanisms of metal-protein interaction have been extensively studied and utilized for the functionalization of protein-based materials, mainly with metal-based nanoparticles, our understanding of how metals shape protein folds, the inter-and intramolecular interactions, the associative behavior, and evolve material characteristics of protein constructs, is limited. To address these highly challenging scientific questions, I have explored the self-assembling behavior of silk fibroin protein and its’ interaction with metal nanoparticles for the formation of multifunctional composites. The central goal of my research was to explore the full potential of metal nanoparticles (NP), in particular, copper oxide (CuO) to modify the self-assembly pathway of fiber-forming protein- silk fibroin. CuO NP has been chosen as a candidate for this study, due to its versatile properties and bio-relevant functionalities applicable for sensing, antibacterial function, and capability to regulate cellular activity. Thus, to address this challenge I first focused on the understanding of metal NP-induced structural transformations in natively folded protein and on probing whether these structural changes can be artificially imposed on the assembled, β-sheet rich protein complexes. My experimental results showed that CuO NPs are indeed capable of template the assembly of natively folded silk fibroin, on the one hand, and on the other hand, exhibited variations in NPs-silk fiber interaction when added at the post-synthetic stage. Yet, the fundamental questions of how RSF-CuO NPs self-assembly occurs remain to be addressed. The exploration of biomaterial applications for silks is only a relatively recent advance; therefore, the future for this family of structural proteins appears promising.