Publications

The origin of life must have involved an unlikely transition from chaotic chemistry to self-reproducing supramolecular structures. Previous quantitative analyses of self-reproducing mutually catalytic networks made of simple molecules have led to increasing popularity of this pre-RNA scenario for lifes origin. Here, we investigate in detail the reproduction characteristic of the graded autocatalysis replication domain (GARD) computer-simulated physicochemically rigorous lipid-based model. This model displays compatibility with heterogeneous environments, addresses the networks spatial demarcation, and portrays trans-generational compositional information transfer. However, we find that compositionally reproducing states are extremely rare, suggesting that random roaming would be a vastly inefficient path toward reproduction. Rewardingly, the present study shows that all self-reproducing states are also dynamic attractors of the catalytic network. This suggests a greatly enhanced propensity for the spontaneous emergence of reproduction and primal evolution, augmenting the likelihood of protolife appearance.[Display omitted] Lifes origin may have involved self-reproducing supramolecular autocatalytic entitiesSimulated physicochemical model for lipid assemblies shows frequent self-reproductionReproduction is observed only within very rare compositional statesSelf-reproducers prove to be dynamic attractors, improving the chance for lifes origin Simulations of the dynamic behavior of spontaneously formed lipid assemblies can offer insight into the origins of life, but few assembly compositions self-reproduce, presumably necessary for life to begin. Kahana et al. show that some self-reproducing compositions are dynamic attractors, making self-reproduction, and hence lifes emergence, much more plausible.

Suppression of carbon emissions through photovoltaic (PV) energy and carbon sequestration through afforestation provides complementary climate change mitigation (CCM) strategies. However, a quantification of the "break-even time"(BET) required to offset the warming impacts of the reduced surface reflectivity of incoming solar radiation (albedo effect) is needed, though seldom accounted for in CCM strategies. Here, we quantify the CCM potential of PV fields and afforestation, considering atmospheric carbon reductions, solar panel life cycle analysis (LCA), surface energy balance, and land area required across different climatic zones, with a focus on drylands, which offer the main remaining land area reserves for forestation aiming climate change mitigation (Rohatyn S, Yakir D, Rotenberg E, Carmel Y. Limited climate change mitigation potential through forestation of the vast dryland regions. 2022. Science 377:1436-1439). Results indicate a BET of PV fields of -2.5 years but >50× longer for dryland afforestation, even though the latter is more efficient at surface heat dissipation and local surface cooling. Furthermore, PV is -100× more efficient in atmospheric carbon mitigation. While the relative efficiency of afforestation compared with PV fields significantly increases in more mesic climates, PV field BET is still -20× faster than in afforestation, and land area required greatly exceeds availability for tree planting in a sufficient scale. Although this analysis focusing purely on the climatic radiative forcing perspective quantified an unambiguous advantage for the PV strategy over afforestation, both approaches must be combined and complementary, depending on climate zone, since forests provide crucial ecosystem, climate regulation, and even social services.

The future of halide perovskites (HaPs) is beclouded by limited understanding of their long-term stability. While HaPs can be altered by radiation that induces multiple processes, they can also return to their original state by \u201cself-healing.\u201d Here two-photon (2P) absorption is used to effect light-induced modifications within MAPbI₃ single crystals. Then the changes in the photodamaged region are followed by measuring the photoluminescence, from 2P absorption with 2.5 orders of magnitude lower intensity than that used for photodamaging the MAPbI₃. After photodamage, two brightening and one darkening process are found, all of which recover but on different timescales. The first two are attributed to trap-filling (the fastest) and to proton-amine-related chemistry (the slowest), while photodamage is attributed to the lead-iodide sublattice. Surprisingly, while after 2P-irradiation of crystals that are stored in dry, inert ambient, photobrightening (or \u201clight-soaking\u201d) occurs, mostly photodarkening is seen after photodamage in humid ambient, showing an important connection between the self-healing of a HaP and the presence of H₂O, for long-term steady-state illumination, practically no difference remains between samples kept in dry or humid environments. This result suggests that photobrightening requires a chemical-reservoir that is sensitive to the presence of H₂O, or possibly other proton-related, particularly amine, chemistry.

We present the laboratory results of immersion freezing efficiencies of cellulose particles at supercooled temperature ((T) conditions. Three types of chemically homogeneous cellulose samples are used as surrogates that represent supermicron and submicron ice-nucleating plant structural polymers. These samples include microcrystalline cellulose (MCC), fibrous cellulose (FC) and nanocrystalline cellulose (NCC). Our immersion freezing dataset includes data from various ice nucleation measurement techniques available at 17 different institutions, including nine dry dispersion and 11 aqueous suspension techniques. With a total of 20 methods, we performed systematic accuracy and precision analysis of measurements from all 20 measurement techniques by evaluating T -binned (1 °C) data over a wide T range (36 °C< T < 4 °C). Specifically, we intercompared the geometric surface area-based ice nucleation active surface site (INAS) density data derived from our measurements as a function of T , ns;geo.(T). Additionally, we also compared the ns;geo.(T) values and the freezing spectral slope parameter (Δlog.ns;geo=Δ(T) from our measurements to previous literature results. Results show all three cellulose materials are reasonably ice active. The freezing efficiencies of NCC samples agree reasonably well, whereas the diversity for the other two samples spans ≈10 °C. Despite given uncertainties within each instrument technique, the overall trend of the ns;geo.(T) spectrum traced by the T -binned average of measurements suggests that predominantly supermicron-sized cellulose particles (MCC and FC) generally act as more efficient ice-nucleating particles (INPs) than NCC with about 1 order of magnitude higher ns;geo.(T).

The wavelength-dependence of the complex refractive indices (RI) in the visible spectral range of secondary organic aerosols (SOA) are rarely studied, and the evolution of the RI with atmospheric aging is largely unknown. In this study, we applied a novel white light-broadband cavity enhanced spectroscopy to measure the changes in the RI (400-650 nm) of β-pinene and p-xylene SOA produced and aged in an oxidation flow reactor, simulating daytime aging under NO_x-free conditions. It was found that these SOA are not absorbing in the visible range, and that the real part of the RI, n, shows a slight spectral dependence in the visible range. With increased OH exposure, n first increased and then decreased, possibly due to an increase in aerosol density and chemical mean polarizability for SOA produced at low OH exposures, and a decrease in chemical mean polarizability for SOA produced at high OH exposures, respectively. A simple radiative forcing calculation suggests that atmospheric aging can introduce more than 40% uncertainty due to the changes in the RI for aged SOA.

Sea spray aerosols (SSA), have a profound effect on the climate; however, the contribution of oceanic microbial activity to SSA is not fully established. We assessed aerosolization of the calcite units (coccoliths)that compose the exoskeleton of the cosmopolitan bloom-forming coccolithophore, Emiliania huxleyi. Airborne coccolith emission occurs in steady-state conditions and increases by an order of magnitude during E. huxleyi infection by E. huxleyi virus (EhV). Airborne to seawater coccolith ratio is 1:10⁸, providing estimation of airborne concentrations from seawater concentrations. The coccoliths' unique aerodynamic structure yields a characteristic settling velocity of ∼0.01 cm s⁻¹, ∼25 times slower than average sea salt particles, resulting in coccolith fraction enrichment in the air. The calculated enrichment was established experimentally, indicating that coccoliths may be key contributors to coarse mode SSA surface area, comparable with sea salt aerosols. This study suggests a coupling between key oceanic microbial interactions and fundamental atmospheric processes like SSA formation.

Exposure to ambient fine particulate matter (PM_2.5) is a leading risk factor for the global burden of disease. However, uncertainty remains about PM_2.5 sources. We use a global chemical transport model (GEOS-Chem) simulation for 2014, constrained by satellite-based estimates of PM_2.5 to interpret globally dispersed PM_2.5 mass and composition measurements from the ground-based surface particulate matter network (SPARTAN). Measured site mean PM_2.5 composition varies substantially for secondary inorganic aerosols (2.4-19.7 μg/m³), mineral dust (1.9-14.7 μg/m³), residual/organic matter (2.1-40.2 μg/m³), and black carbon (1.0-7.3 μg/m³). Interpretation of these measurements with the GEOS-Chem model yields insight into sources affecting each site. Globally, combustion sectors such as residential energy use (7.9 μg/m³), industry (6.5 μg/m³), and power generation (5.6 μg/m³) are leading sources of outdoor global population-weighted PM_2.5 concentrations. Global population-weighted organic mass is driven by the residential energy sector (64%) whereas population-weighted secondary inorganic concentrations arise primarily from industry (33%) and power generation (32%). Simulation-measurement biases for ammonium nitrate and dust identify uncertainty in agricultural and crustal sources. Interpretation of initial PM_2.5 mass and composition measurements from SPARTAN with the GEOS-Chem model constrained by satellite-based PM_2.5 provides insight into sources and processes that influence the global spatial variation in PM_2.5 composition.

The WeIzmann Supercooled Droplets Observation on Microarray (WISDOM) is a new setup for studying ice nucleation in an array of monodisperse droplets for atmospheric implications. WISDOM combines microfluidics techniques for droplets production and a cryo-optic stage for observation and characterization of freezing events of individual droplets. This setup is designed to explore heterogeneous ice nucleation in the immersion freezing mode, down to the homogeneous freezing of water (235ĝ\u20acK) in various cooling rates (typically 0.1-10ĝ\u20acKĝ\u20acminĝ'1). It can also be used for studying homogeneous freezing of aqueous solutions in colder temperatures. Frozen fraction, ice nucleation active surface site densities and freezing kinetics can be obtained from WISDOM measurements for hundreds of individual droplets in a single freezing experiment. Calibration experiments using eutectic solutions and previously studied materials are described. WISDOM also allows repeatable cycles of cooling and heating for the same array of droplets. This paper describes the WISDOM setup, its temperature calibration, validation experiments and measurement uncertainties. Finally, application of WISDOM to study the ice nucleating particle (INP) properties of size-selected ambient Saharan dust particles is presented.

The radiative effects of biomass-burning aerosols on regional and global scales can be substantial. Accurate modeling of the radiative effects of smoke aerosols requires wavelength-dependent measurements and parameterizations of their optical properties in the UV and visible spectral ranges along with improved description of their chemical composition. To address this issue, we used a recently developed approach to retrieve the time- and spectral-dependent optical properties of ambient biomass-burning aerosols from 300 to 650 nm wavelengths during a regional nighttime bonfire festival in Israel. During the biomass burning event, the overall absorption at 400 nm increased by about 2 orders of magnitude, changing the single scattering albedo from a background level of 0.95 to 0.7. Based on the new retrieval method, we provide parameterizations of the wavelength-dependent effective complex refractive index from 350 to 650 nm for freshly emitted and slightly aged biomass-burning aerosols. In addition, PM_2.5 filter samples were collected for detailed offline chemical analysis of the water-soluble organics that contribute to light absorption. Nitroaromatics were identified as major organic species responsible for the increased absorption at 400 to 500 nm. Typical chromophores include 4-nitrocatechol, 4-nitrophenol, nitrosyringol, and nitroguaiacol; oxidation-nitration products of methoxyphenols; and known products of lignin pyrolysis. Our findings emphasize the importance of both primary and secondary organic aerosols from biomass burning in absorption of solar radiation and in effective radiative forcing. Plain Language Summary The radiative effects of biomass-burning aerosols on regional and global scales are substantial. Accurate modeling of the radiative effects of smoke aerosols requires wavelength-dependent measurements and parameterizations of their optical properties in the UV and visible spectral ranges along with improved description of their chemical composition. To address this issue we used a recently developed approach to retrieve the time- and spectral-dependent optical properties of the ambient aerosol from 300 to 650 nm wavelengths and a high-resolution mass spectrometry analysis of fine particulate matter. We found a significant increase in aerosol light absorption in the UV-Vis spectral range which is correlated to high levels of nitroaromatic compounds identified in the water-soluble extracts of the filter samples. Additionally, for further applications of our results in radiative transfer models, we provide parameterizations of the wavelength-dependent effective complex refractive index from 350 to 650 nm for freshly emitted and aged biomass-burning aerosols.

The multi-pass photoacoustic spectrometer (PAS) is an important tool for the direct measurement of light absorption by atmospheric aerosol. Accurate PAS measurements heavily rely on accurate calibration of their signal. Ozone is often used for calibrating PAS instruments by relating the photoacoustic signal to the absorption coefficient measured by an independent method such as cavity ring down spectroscopy (CRD-S), cavity-enhanced spectroscopy (CES) or an ozone monitor. We report here a calibration method that uses measured absorption coefficients of aerosolized, light-absorbing organic materials and offer an alternative approach to calibrate photoacoustic aerosol spectrometers at 404 nm. To implement this method, we first determined the complex refractive index of nigrosin, an organic dye, using spectroscopic ellipsometry and then used this well-characterized material as a standard material for PAS calibration.

Atmospheric aerosols play an important part in the Earth's energy budget by scattering and absorbing incoming solar and outgoing terrestrial radiation. To quantify the effective radiative forcing due to aerosol-radiation interactions, researchers must obtain a detailed understanding of the spectrally dependent intensive and extensive optical properties of different aerosol types. Our new approach retrieves the optical coefficients and the single-scattering albedo of the total aerosol population over 300 to 650 nm wavelength, using extinction measurements from a broadband cavity-enhanced spectrometer at 315 to 345 nm and 390 to 420 nm, extinction and absorption measurements at 404 nm from a photoacoustic cell coupled to a cavity ring-down spectrometer, and scattering measurements from a three-wavelength integrating nephelometer. By combining these measurements with aerosol size distribution data, we retrieved the time- and wavelength-dependent effective complex refractive index of the aerosols. Retrieval simulations and laboratory measurements of brown carbon proxies showed low absolute errors and good agreement with expected and reported values. Finally, we implemented this new broadband method to achieve continuous spectral- and time-dependent monitoring of ambient aerosol population, including, for the first time, extinction measurements using cavity-enhanced spectrometry in the 315 to 345 nm UV range, in which significant light absorption may occur.

The Surface PARTiculate mAtter Network (SPARTAN) is a long-term project that includes characterization of chemical and physical attributes of aerosols from filter samples collected worldwide. This paper discusses the ongoing efforts of SPARTAN to define and quantify major ions and trace metals found in fine particulate matter (PM_2.5). Our methods infer the spatial and temporal variability of PM_2.5 in a cost-effective manner. Gravimetrically weighed filters represent multi-day averages of PM_2.5, with a collocated nephelometer sampling air continuously. SPARTAN instruments are paired with AErosol RObotic NETwork (AERONET) sun photometers to better understand the relationship between ground-level PM_2.5 and columnar aerosol optical depth (AOD). We have examined the chemical composition of PM_2.5 at 12 globally dispersed, densely populated urban locations and a site at Mammoth Cave (US) National Park used as a background comparison. So far, each SPARTAN location has been active between the years 2013 and 2016 over periods of 2-26 months, with an average period of 12 months per site. These sites have collectively gathered over 10 years of quality aerosol data. The major PM_2.5 constituents across all sites (relative contribution±SD) are ammoniated sulfate (20%±11%), crustal material (13.4%±9.9%), equivalent black carbon (11.9%±8.4%), ammonium nitrate (4.7%±3.0%), sea salt (2.3%±1.6%), trace element oxides (1.0%±1.1%), water (7.2%±3.3%) at 35% RH, and residual matter (40%±24%). Analysis of filter samples reveals that several PM_2.5 chemical components varied by more than an order of magnitude between sites. Ammoniated sulfate ranges from 1.1μg m^-3 (Buenos Aires, Argentina) to 17μg m^-3 (Kanpur, India in the dry season). Ammonium nitrate ranged from 0.2μg m^-3 (Mammoth Cave, in summer) to 6.8 μg m^-3 (Kanpur, dry season). Equivalent black carbon ranged from 0.7μg m^-3 (Mammoth Cave) to over 8μg m^-3 (Dhaka, Bangladesh and Kanpur, India). Comparison of SPARTAN vs. coincident measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network at Mammoth Cave yielded a high degree of consistency for daily PM_2.5 (r² = 0.76, slope = 1.12), daily sulfate (r² = 0.86, slope = 1.03), and mean fractions of all major PM_2.5 components (within 6%). Major ions generally agree well with previous studies at the same urban locations (e.g. sulfate fractions agree within 4% for 8 out of 11 collocation comparisons). Enhanced anthropogenic dust fractions in large urban areas (e.g. Singapore, Kanpur, Hanoi, and Dhaka) are apparent from high Zn:Al ratios. The expected water contribution to aerosols is calculated via the hygroscopicity parameter κv for each filter. Mean aggregate values ranged from 0.15 (Ilorin) to 0.28 (Rehovot). The all-site parameter mean is 0.20±0.04. Chemical composition and water retention in each filter measurement allows inference of hourly PM_2.5 at 35% relative humidity by merging with nephelometer measurements. These hourly PM_2.5 estimates compare favourably with a beta attenuation monitor (MetOne) at the nearby US embassy in Beijing, with a coefficient of variation r² = 0.67 (n = 3167), compared to r² = 0.62 when κv was not considered. SPARTAN continues to provide an open-access database of PM_2.5 compositional filter information and hourly mass collected from a global federation of instruments.

The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are as yet still poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC, was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity-enhanced spectrometer for aerosol optical extinction measurements in the UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high-resolution time-of-flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (p-xylene-d10), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone/OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with p-xylene-d₁₀ showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after approximately the same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have a significant amount of semivolatile components. The influence of anthropogenic VOCs on the oxygenated organic aerosol as well as the atmospheric implications are discussed.

Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions of the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (α-pinene, limonene, and α-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360-420 nm range for these aerosols using broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH₃-aged α-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (±0.01) after 1.5 h of exposure to 1.9 ppm NH₃, whereas the imaginary component (k) remained below. For the limonene and α-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.000 to an average k = 0.029 (±0.021) for α-humulene SOA, and from to an average k = 0.032 (±0.019) for limonene SOA after 1.5 h of exposure to 1.3 and 1.9 ppm of NH₃, respectively. Collected filter samples of the aged and unreacted α-pinene SOA and limonene SOA were analyzed off-line by nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in situ using a Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS), confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH₃ aging reactions scale linearly with time and concentration, which will not necessarily be the case in the atmosphere, then a 1.5 h reaction with 1 ppm NH₃ in the laboratory is equivalent to 24 h reaction with 63 ppbv NH₃, indicating that the observed aerosol absorption will be limited to atmospheric regions with high NH₃ concentrations. This journal is

Alkyl aminium sulfates have been postulated to constitute important components of nucleation and accumulation mode atmospheric aerosols. In this study we present laboratory data on the thermochemical, cloud condensation nuclei (CCN) activity, and optical properties of selected aminium sulfate compounds of atmospheric relevance (monomethyl aminium sulfate (MMAS), dimethyaminium sulfate (DMAS), trimethylaminium sulfate, monoethylaminium sulfate (MEAS), diethylaminium sulfate (DEAS), and triethylaminium sulfate (TEAS)). We found that the vapor pressure of these aminium salts is 1-3 orders of magnitude lower than that of ammonium sulfate and as such they can contribute to new aerosols and secondary aerosols formation. We infer that these species have very high CCN activity, with hygroscopicity parameter that is similar to that ammonium sulfate. Finally, between 360 and 420 nm, these aminium sulfate salts scatter light less efficiently than ammonium sulfate, and do not absorb light. These derived parameters can contribute to the better understanding and characterization of the role that these compounds play in atmospheric chemical reactions, gas-solid partitioning and their possible contribution to the microphysical and radiative effects of atmospheric aerosols.

We compare the charge transport characteristics of heavy-doped p ⁺⁺- and n ⁺⁺-Si-alkyl chain/Hg junctions. Based on negative differential resistance in an analogous semiconductor-inorganic insulator/metal junction we suggest that for both p ⁺⁺- and n ⁺⁺-type junctions, the energy difference between the Fermi level and lowest unoccupied molecular orbital (LUMO), i.e., electron tunneling, controls charge transport. This conclusion is supported by results from photoelectron spectroscopy (ultraviolet photoemission spectroscopy, inverse photoelectron spectroscopy, and x-ray photoemission spectroscopy) for the molecule-Si band alignment at equilibrium, which clearly indicate that the energy difference between the Fermi level and the LUMO is much smaller than that between the Fermi level and the highest occupied molecular orbital (HOMO). Furthermore, the experimentally determined Fermi level - LUMO energy difference, agrees with the non-resonant tunneling barrier height, deduced from the exponential length attenuation of the current.

Metal-organic molecule-semiconductor junctions are controlled not only by the molecular properties, as in metal-organic molecule-metal junctions, but also by effects of the molecular dipole, the dipolar molecule-semiconductor link, and molecule-semiconductor charge transfer, and by the effects of all these on the semiconductor depletion layer (i.e., on the internal semiconductor barrier to charge transport). Here, we report on and compare the electrical properties (current-voltage, capacitance-voltage, and work function) of large area Hg/organic monolayer-Si junctions with alkyl and alkenyl monolayers on moderately and highly doped n-Si, and combine the experimental data with simulations of charge transport and electronic structure calculations. We show that, for moderately doped Si, the internal semiconductor barrier completely controls transport and the attached molecules influence the transport of such junctions only in that they drive the Si into inversion. The resulting minority carrier-controlled junction is not sensitive to molecular changes in the organic monolayer at reverse and low forward bias and is controlled by series resistance at higher forward bias. However, in the case of highly doped Si, the internal barrier is smaller, and as a result, the charge transport properties of the junction are affected by changing from an alkyl to an alkenyl monolayer. We propose that the double bond near the surface primarily increases the coupling between the organic monolayer and the Si, which increases the current density at a given bias by increasing the contact conductance.

The internal structure of SiON films is extracted electrically, demonstrating an efficient, noncontact, nondestructive means for depth compositional analysis in gate oxides. The electrical data, obtained using x-ray photoelectron spectroscopy (XPS) based controlled surface charging (CSC), are compared with independent time of flight secondary ion mass spectroscopy and angle resolved XPS data. Inhomogeneous composition with significant nitrogen enrichment at the top of the oxide layer is observed. Capabilities of the CSC method in treating heterostructures of poor chemical contrast are discussed.

Hydrogen-terminated and alkyl-chain (C₁₈H₃₇)- terminated Si(100) surfaces with different doping levels have been characterized using Kelvin probe force microscopy. n- and p-doped Si(100) and lateral p ⁺⁺n and n⁺⁺p silicon junctions were hydrogenated in dilute HF solution, followed with a self-assembly deposition of organic molecules by thermally activated free-radical reaction between C=C and Si - H. The surface band bending following the two different chemical treatments was almost identical for both p-type silicon (∼0.7 eV, with a surface charge of 9.4 ± 0.5 × 10¹¹cm²) and n-type silicon (0.6 eV, with a surface charge of 8.7 ± 0.5 × 10¹¹/cm ²). These results indicate that the self-assembly of the C ₁₈.H₃₇ monolayer on a Si (100) surface results in electrical properties similar to those of a hydrogenated Si surface, with the advantage of longer stability in an ambient environment. The hydrogen-terminated and alkyl-chain-terminated surface do differ, however, in the surface dipole, which is lower by ∼0.6 eV for the latter, a value deduced from both the measurements and independent first principles electronic structure calculations. This dipole change is essentially due to the change in bond dipole associated with the replacement of Si - H bonds by Si - C bonds and the dipole associated with the methyl group.

We combine electromechanical measurements with ab initio density-functional calculations to settle the controversy about the origin of torsion-induced conductance oscillations in multiwall carbon nanotubes. Contrary to intuition, the observed oscillation period in multiwall tubes exhibits the same inverse-squared diameter dependence as in single-wall tubes with the same diameter. This finding suggests an intrawall origin of the oscillations and an effective electronic decoupling of the walls, which we confirm in calculations of multiwall nanotubes subject to differential torsion. We exclude the alternative origin of the conductance oscillations due to changes in the interwall registry, which would result in a different diameter dependence of the oscillation period.

Monolayers of alkyl chains, attached-through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO₂, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) π* resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.

Carbon nanotubes^{1, 2} can be distinctly metallic or semiconducting depending on their diameter and chirality³. Here we show that continuously varying the chirality by mechanical torsion⁴ can induce conductance oscillations, which can be attributed to metalsemiconductor periodic transitions. The phenomenon is observed in multiwalled carbon nanotubes, where both the torque⁵ and the current are shown to be carried predominantly by the outermost wall^{6, 7}. The oscillation period with torsion is consistent with the theoretical shifting⁸ of the corners of the first Brillouin zone of graphene across different sub-bands allowed in the nanotube. Beyond a critical torsion, the conductance irreversibly drops due to torsional failure, allowing us to determine the torsional strength of carbon nanotubes. Carbon nanotubes could be ideal torsional springs for nanoscopic pendulums^{4, 9, 10}, because electromechanical detection of motion could replace the microscopic detection techniques used at present. Our experiments indicate that carbon nanotubes could be used as electronic sensors of torsional motion in nanoelectro-mechanical systems¹¹.

We elucidate the electronic structure of both filled and empty states of ordered alkyl chains bound to the Si(111) surface by combining direct and inverse photoemission spectroscopy with first principles calculations based on density functional theory. We identify both filled and empty interface-induced gap states, distinguish between those and states extending throughout the monolayer, and discuss the importance of these findings for interpreting transport experiments through such monolayers.

A new approach for the specific detection and mapping of single molecule recognition is presented, based on the nonlinear elastic behavior of a single polymer chain. The process of molecular recognition between a ligand and a receptor is inherently accompanied by a decrease in the translational and rotational degrees of freedom of the two molecules. We show that a polymeric tether linked to the ligand can effectively transduce the configurational constraint imposed by molecular recognition into a measurable force, which is dominated by the entropic elasticity of the polymer. This force is specifically characterized by a strong nonlinearity when the extension of the polymer approaches its contour length. Thus, a polymer chain tethering the ligand to an oscillating cantilevered tip gives rise to a highly anharmonic motion upon ligand-receptor binding. Higher-harmonics atomic force microscopy allows us to detect this phenomenon in real time as a specific signature for the probing and mapping of single-molecule recognition.

Mind the step! Single-wall carbon nanotubes grow along the atomic steps of vicinal α-Al₂O₃ surfaces to give highly aligned arrays of nanometer-wide wires on a dielectric material. The nanotubes (see blue background image) reproduce the atomic features of the surface including steps, facets, and kinks (see model). The direction and morphology of the atomic steps can be controlled by the crystal miscut.

This article presents a general approach for employing lesion analysis to address the fundamental challenge of localizing functions in a neural system. We describe functional contribution analysis (FCA), which assigns contribution values to the elements of the network such that the ability to predict the network's performance in response to multilesions is maximized. The approach is thoroughly examined on neurocontroller networks of evolved autonomous agents. The FCA portrays a stable set of neuronal contributions and accurate multilesion predictions that are significantly better than those obtained based on the classical single lesion approach. It is also used for a detailed synaptic analysis of the neurocontroller connectivity network, delineating its main functional backbone. The FCA provides a quantitative way of measuring how the network functions are localized and distributed among its elements. Our results question the adequacy of the classical single lesion analysis traditionally used in neuroscience and show that using lesioning experiments to decipher even simple neuronal systems requires a more rigorous multilesion analysis.

This article presents a new approach to the important challenge of localizing function in a neurocontroller. The approach is based on the basic functional contribution analysis (FCA) presented earlier, which assigns contribution values to the elements of the network, such that the ability to predict the network's performance in response to multi-unit lesions is maximized. These contribution values quantify the importance of each element to the tasks the agent performs. Here we present a generalization of the basic FCA to high-dimensional analysis, using high-order compound elements. Such elements are composed of conjunctions of simple elements. Their usage enables the explicit expression of sets of neurons or synapses whose contributions are interdependent, a prerequisite for localizing the function of complex neurocontrollers. High-dimensional FCA is shown to significantly improve on the accuracy of the basic analysis, to provide new insights concerning the main subsets of simple elements in the network that interact in a complex nonlinear manner, and to systematically reveal the types of interactions that characterize the evolved neurocontroller.

G protein-coupled potassium channels (GIRK/Kir3.x) are key determinants that translate inhibitory chemical neurotransmission into changes in cellular excitability. To understand the mechanism of channel activation by G proteins, it is necessary to define the structural rearrangements in the channel that result from interaction with Gβγ subunits. In this study we used a combination of fluorescence spectroscopy and through-the-objective total internal reflection microscopy to monitor the conformational rearrangements associated with the activation of GIRK channels in single intact cells. We detect activation-induced changes in FRET consistent with a rotation and expansion of the termini along the central axis of the channel. We propose that this rotation and expansion of the termini drives the channel to open by bending and possibly rotating the second transmembrane segment.