Covalent and Hydrogen Bonding in Adsorption of Alanine Molecules on Si(111)7×7.

Molecular adsorption bonding configurations and specific interfacial chemistry of alanine on Si(111)7×7 have been determined by combining the results from scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) with ab initio calculations based on the density functional theory (DFT). XPS spectra of the N 1s region show that alanine molecules bind to the 7×7 surface by N-Si covalent bonding, while STM imaging reveals that such N-H dissociative adsorption of alanine occurs on an adjacent Si adatom-restatom pair, with the dehydrogenated alanine moiety and dissociated H atom occupying the Si adatom and restatom sites, respectively. At a sample bias above +2 V, the dehydrogenated alanine appears as a bright round protrusion, slightly off-center from a Si adatom site and leaning toward the opposite Si adatom across the dimer wall. The off-center character can be attributed to an electrostatic attraction between the electron-rich carbonyl O of the dehydrogenated alanine and electron-deficient nearest Si adatom across the dimer wall. Our DFT calculation also shows that the monodentate O-Si bonding configuration resulting from O-H dissociative adsorption is more thermodynamically favorable than the experimentally observed N-Si bonding configuration, suggesting that the interfacial dissociative adsorption reaction is a kinetically controlled rather than a thermodynamically driven process. Alanine molecules in the second adlayer (transitional layer) are found to attach to those in the first adlayer (interfacial layer) by N···HO hydrogen bonding, as supported by the presence of the N 1s feature at 401.0 eV. An alanine molecule H-bonded to a dehydrogenated alanine in the first adlayer has also been observed in STM as a brighter and larger protrusion close to the expected location of the free OH group in the dehydrogenated first-adlayer alanine. No thick zwitterionic alanine film can be obtained at room temperature possibly due to steric constraint caused by the methyl group.

Are we mis-estimating chemotherapy-induced peripheral neuropathy? Analysis of assessment methodologies from a prospective, multinational, longitudinal cohort study of patients receiving neurotoxic chemotherapy.

BACKGROUND: There are inconsistencies in the literature regarding the prevalence and assessment of chemotherapy-induced peripheral neuropathy (CIPN). This study explored CIPN natural history and its characteristics in patients receiving taxane- and platinum-based chemotherapy. PATIENTS AND METHODS: Multi-country multisite prospective longitudinal observational study. Patients were assessed before commencing and three weekly during chemotherapy for up to six cycles, and at 6,9, and 12 months using clinician-based scales (NCI-CTCAE; WHO-CIPN criterion), objective assessments (cotton wool test;10 g monofilament); patient-reported outcome measures (FACT/GOG-Ntx; EORTC-CIPN20), and Nerve Conduction Studies. RESULTS: In total, 343 patients were recruited in the cohort, providing 2399 observations. There was wide variation in CIPN prevalence rates using different assessments (14.2-53.4%). Prevalence of sensory neuropathy (and associated symptom profile) was also different in each type of chemotherapy, with paclitaxel (up to 63%) and oxaliplatin (up to 71.4%) showing the highest CIPN rates in most assessments and a more complex symptom profile. Peak prevalence was around the 6-month assessment (up to 71.4%). Motor neurotoxicity was common, particularly in the docetaxel subgroup (up to 22.1%; detected by NCI-CTCAE). There were relatively moderately-to-low correlations between scales (rs = 0.15,p < 0.05-rs = 0.48 p < 0.001), suggesting that they measure different neurotoxicity aspects from each other. Cumulative chemotherapy dose was not associated with onset and course of CIPN. CONCLUSION: The historical variation reported in CIPN incidence and prevalence is possibly confounded by disagreement between assessment modalities. Clinical practice should consider assessment of motor neuropathy for neurotoxic chemotherapy. Current scales may not be all appropriate to measure CIPN in a valid way, and a combination of scales are needed.

High-Performance Single-Active-Layer Memristor Based on an Ultrananocrystalline Oxygen-Deficient TiOx Film.

The theoretical and practical realization of memristive devices has been hailed as the next step for nonvolatile memories, low-power remote sensing, and adaptive intelligent prototypes for neuromorphic and biological systems. However, the active materials of currently available memristors need to undergo an often destructive high-bias electroforming process in order to activate resistive switching. This limits their device performance in switching speed, endurance/retention, and power consumption upon high-density integration, due to excessive Joule heating. By employing a nanocrystalline oxygen-deficient TiOx switching matrix to localize the electric field at discrete locations, it is possible to resolve the Joule heating problem by reducing the need for electroforming at high bias. With a Pt/TiOx/Pt stacking architecture, our device follows an electric field driven, vacancy-modulated interface-type switching that is sensitive to the junction size. By scaling down the junction size, the SET voltage and output current can be reduced, and a SET voltage as low as +0.59 V can be obtained for a 5 × 5 µm2 junction size. Along with its potentially fast switching (over 105 cycles with a 100 µs voltage pulse) and high retention (over 105 s) performance, memristors based on these disordered oxygen-deficient TiOx films promise viable building blocks for next-generation nonvolatile memories and other logic circuit systems.

Deep-core photoabsorption and photofragmentation of tetrachloromethane near the Cl K-edge.

The fragmentation of the tetrachloromethane molecule following core-shell photoexcitation and photoionization in the neighborhood of the chlorine K-edge has been studied by using time-of-flight mass spectroscopy and monochromatic synchrotron radiation. Branching ratios for ionic dissociation were derived for all the detected ions, which are informative of the decay dynamics and photofragmentation patterns of the core-excited species. In addition, the absorption yield has been measured with a new assignment of the spectral features. The structure that appears above the Cl 1s ionization potential in the photoionization spectrum has been ascribed to the existing connection with electron-CCl4 scattering through experimental data and calculations for low-energy electron-molecule cross sections. In addition, the production of the doubly ionized Cl fragment, Cl2+, as a function of the photon energy has been analysed in the terms of a simple and an appealing physical picture, the half-collision model.

Performance Enhancement by Secondary Doping in PEDOT:PSS/Planar-Si Hybrid Solar Cells.

Solar cells depend on effectively absorbing light and converting it into electrical current. It is therefore essential to increase conductivity and to limit both reflection and parasitic absorbance to achieve higher photoconversion efficiency. Here, we examine the effect of post-treatment on the absorbance and conductivity of hybrid solar cells comprised of p-type poly(3,4-ethylene-dioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) on an n-type silicon substrate. Three sets of cells based on pristine PEDOT:PSS film, cosolvent enhanced PEDOT:PSS film using ethylene glycol as a cosolvent, and post-treated PEDOT:PSS film using a novel 1:1 binary mixture of ethylene glycol and methanol have been studied. Markedly different film conductivities have been found for the pristine (∼0.8 S/cm), cosolvent added (637 S/cm), and post-treated films (1334 S/cm). The photoconversion efficiency obtained over a large set of samples (72 cells) was used to evaluate the cosolvent addition and post-treatment. Post-treatment is found to reproducibly provide films with not only the highest conductivities but also the highest efficiencies along with higher open-circuit voltage and fill factor but lower short-circuit current density when compared to those of the cosolvent added films. The decrease in the latter is attributed to the increase in absorbance in the PEDOT:PSS film. The present work illustrates the delicate challenge in improving the conductivity and carrier collection efficiency of the cells not at the expense of other properties such as absorption.

Surface-Mediated Hydrogen Bonding of Proteinogenic α-Amino Acids on Silicon.

Understanding the adsorption, film growth mechanisms, and hydrogen bonding interactions of biological molecules on semiconductor surfaces has attracted much recent attention because of their applications in biosensors, biocompatible materials, and biomolecule-based electronic devices. One of the most challenging questions when studying the behavior of biomolecules on a metal or semiconductor surface is "What are the driving forces and film growth mechanisms for biomolecular adsorption on these surfaces?" Despite a large volume of work on self-assembly of amino acids on single-crystal metal surfaces, semiconductor surfaces offer more direct surface-mediated interactions and processes with biomolecules. This is due to their directional surface dangling bonds that could significantly perturb hydrogen bonding arrangements. For all the proteinogenic biomolecules studied to date, our group has observed that they generally follow a "universal" three-stage growth process on Si(111)7×7 surface. This is supported by corroborating data obtained from a three-pronged approach of combining chemical-state information provided by X-ray photoelectron spectroscopy (XPS) and the site-specific local density-of-state images obtained by scanning tunneling microscopy (STM) with large-scale quantum mechanical modeling based on the density functional theory with van der Waals corrections (DFT-D2). Indeed, this three-stage growth process on the 7×7 surface has been observed for small benchmark biomolecules, including glycine (the simplest nonchiral amino acid), alanine (the simplest chiral amino acid), cysteine (the smallest amino acid with a thiol group), and glycylglycine (the smallest (di)peptide of glycine). Its universality is further validated here for the other sulfur-containing proteinogenic amino acid, methionine. We use methionine as an example of prototypical proteinogenic amino acids to illustrate this surface-mediated process. This type of growth begins with the formation of a covalent-bond driven interfacial layer (first adlayer), followed by that of a transitional layer driven by interlayer and intralayer hydrogen bonding (second adlayer), and then finally the zwitterionic multilayers (with intralayer hydrogen bonding). The important role of surface-mediated hydrogen bonding as the key for this universal three-stage growth process is demonstrated. This finding provides new insight into biomolecule-semiconductor surface interactions often found in biosensors and biomolecular electronic devices. We also establish the trends in the H-bond length among different types of the hydrogen bonding for dimolecular structures in the gas phase and on the Si(111)7×7 surface, the latter of which could be validated by their STM images. Finally, five simple rules of thumb are developed to summarize the adsorption properties of these proteinogenic biomolecules as mediated by hydrogen bonding, and they are expected to provide a helpful guide to future studies of larger biomolecules and their potential applications.

Direct-write three-dimensional nanofabrication of nanopyramids and nanocones on Si by nanotumefaction using a helium ion microscope.

The recently commercialized helium ion microscope (HIM) has already demonstrated its outstanding imaging capabilities in terms of resolution, surface sensitivity, depth of field and ease of charge compensation. Here, we show its exceptional patterning capabilities by fabricating dense lines and three-dimensional (3D) nanostructures on a Si substrate. Small focusing spot size and confined ion-Si interaction volume of a high-energy helium ion beam account for the high resolution in HIM patterning. We demonstrate that a set of resolvable parallel lines with a half pitch as small as 3.5 nm can be achieved. During helium ion bombardment of the Si surface, implantation outperforms milling due to the small mass of the helium ions, which produces tumefaction instead of depression in the Si surface. The Si surface tumefaction is the result of different kinetic processes including diffusion, coalescence and nanobubble formation of the implanted ions, and is found to be very stable structurally at room temperature. Under appropriate conditions, a linear dependence of the surface swollen height on the ion doses can be observed. This relation has enabled us to fabricate nanopyramids and nanocones, thus demonstrating that HIM patterning provides a new 'bottom-up' approach to fabricate 3D nanostructures. This surface tumefaction method is direct, both positioning and height accurate, and free of resist, etch, mode and precursor, and it promises new applications in nanoimprint mold fabrication and photomask clear defect reparation.

Biofunctionalization of Si(111)7×7 by "renewable" L-cysteine transitional layer.

Surface functionalization of an inorganic surface with bio-organic molecules is often aimed at creating a "permanent" bio-organic surface with receptor functional groups. We show here that L-cysteine can be used to transform a highly reactive Si(111)7×7 surface to not just a permanent bio-organic surface but also a semipermanent (or renewable) and a temporary bio-organic surfaces by manipulating the exposure. In the early growth stage, the strong bonding between the first cysteine adlayer and the Si substrate through Si-N or Si-S linkages in unidentate or bidentate arrangement provides permanent biofunctionalization by this interfacial layer. This interfacial layer can be used to build a transitional layer (second adlayer) mediated by interlayer vertical hydrogen bonding between an amino group and a carboxylic acid group. Further exposure of cysteine eventually leads to a zwitterionic multilayer film involving electrostatic interactions between cation (-NH3(+)) and anion moieties (-COO(-)). The interlayer hydrogen bonding therefore provides temporary trapping of bio-organic molecules as the second transitional layer that is stable up to 175 °C. This transitional layer can be easily removed by annealing above this temperature and then regenerated with the same molecular layer or a different one by "renewing" the interlayer hydrogen bonds. We also illustrate coverage-dependent adsorption structures of cysteine, from bidentate to unidentate attachments and to self-assembled multimers, involving formation of intralayer horizontal N···H-O hydrogen bonds, by combining our X-ray photoemission data with the local density-of-state images obtained by scanning tunnelling microscopy.

Bimetallic FeNi concave nanocubes and nanocages.

Concave nanostructures are rare because of their thermodynamically unfavorable shapes. We prepared bimetallic FeNi concave nanocubes with high Miller index planes through controlled triggering of the different growth kinetics of Fe and Ni. Taking advantage of the higher activity of the high-index planes, we then fabricated monodispersed concave nanocages via a material-independent electroleaching process. With the high-index facets exposed, these concave nanocubes and nanocages are 10- and 100-fold more active, respectively, toward electrodetection of 4-aminophenol than cuboctahedrons, providing a label-free sensing approach for monitoring toxins in water and pharmaceutical wastes.

Interfacial micropore defect formation in PEDOT:PSS-Si hybrid solar cells probed by TOF-SIMS 3D chemical imaging.

Conducting p-type polymer layers on n-type Si have been widely studied for the fabrication of cost-effective hybrid solar cells. In this work, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to provide three-dimensional chemical imaging of the interface between poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS) and SiOx/Si in a hybrid solar cell. To minimize structural damage to the polymer layer, an Ar cluster sputtering source is used for depth profiling. The present result shows the formation of micropore defects in the interface region of the PEDOT:PSS layer on the SiOx/Si substrate. This interfacial micropore defect formation becomes more prominent with increasing thickness of the native oxide layer, which is a key device parameter that greatly affects the hybrid solar cell performance. Three-dimensional chemical imaging coupled with Ar cluster ion sputtering has therefore been demonstrated as an emerging technique for probing the interface of this and other polymer-inorganic systems.

FePt alloy nanoparticles for biosensing: enhancement of vitamin C sensor performance and selectivity by nanoalloying.

Electrocatalytic activity of supported FePt alloy nanoparticles (NPs) with different compositions (Fe25Pt75, Fe30Pt70, Fe35Pt65) for the electro-oxidation of vitamin C is investigated. These spherical FePt NPs with nanocrystallite size of 7-9 nm are found to consist of a nanoalloy core with a more Pt-rich shell. The FePt alloy NPs are superior catalysts than Pt NPs for vitamin C electro-oxidation, with a linear concentration range of 0.01-1 mM, a high sensitivity of 4.347 mA cm(-2) mM(-1), and a low detection limit of 0.1 µM (S/N = 3). By effectively reducing the overpotential for the electro-oxidation, these alloy NPs are significantly more selective to the detection of vitamin C against other common interference species, including dopamine, citric acid, uric acid, glucose, and NaCl. Enhancement in sensor performance can be attributed to the increase in surface area due to reduction of nanocrystallite size and to modification in the Pt electronic structure as a result of nanoalloying. These are supported by the X-ray diffraction data and binding energy shifts as observed by X-ray photoelectron spectroscopy, respectively. Alloying therefore represents a powerful approach to introduce synergetic properties for new biosensor applications.

Self-directed growth of aligned adenine molecular chains on Si(111)7×7: direct imaging of hydrogen-bond mediated dimers and clusters at room temperature by scanning tunneling microscopy.

The early stage of adsorption of adenine on Si(111)7×7 is studied by scanning tunneling microscopy (STM). Bright protrusions are observed in both empty-state and filled-state STM images, indicative of molecular adsorption of adenine through dative bonding. The majority of these bright protrusions appear as dimer pairs formed by hydrogen bonding at the initial adsorption stage. The formation of dative bonds between the substrate and adenine and the feasibility of the H-bond mediated dimers are supported by ab initio DFT/B3LYP/6-31G++(d,p) calculations, and are in excellent accord with our recent X-ray photoemission data. Remarkably, these dimers are found to undergo self-organization into aligned superstructures, evidently with common link arrangements, including straight, offset, and zigzag chains, square quartets, double quartets, and other multiple dimer structures. As the exposure of adenine increases, the populations of dimers as well as the self-organized double dimer and other higher-order structures also increase. The end-to-end dimer links are found to be most prominent in the growth of adenine molecular chains, most notably aligned along the Si dimer-wall or [-1 1 0] direction of the 7×7 unit cell. The self-aligned adenine dimer molecular chains offer a natural template for catch-and-release biosensing, lithography, and molecular electronic applications.

Electro-oxidation of ascorbic acid by cobalt core-shell nanoparticles on a H-terminated Si(100) and by nanostructured cobalt-coated Si nanowire electrodes.

Determination of the concentration of ascorbic acid in a solution has attracted intense recent interest. Here we demonstrate the feasibility of electro-oxidation of ascorbic acid on spherical cobalt core-shell nanoparticles (10-50 nm dia.) prepared by electrochemical deposition on a H-terminated Si(100) substrate. Depth-profiling X-ray photoelectron spectroscopy reveals that these nanoparticles consist of a metallic cobalt core covered by a Co(OH)2 shell without any evidence of CoOx. Glancing-incidence X-ray diffraction studies further show that the metallic Co core consists of a mixture of hexagonal close packed and face centered cubic structures, the relative composition of which can be easily controlled by the deposition potential. We further demonstrate that when these Co nanoparticles are deposited on a high-surface-area electrode as provided by a Si nanowire template, the resulting nanostructured Co-coated Si nanowire electrode offers a promising high-performance sensor platform for ascorbic acid detection.

Growth of randomly oriented single-crystalline tin (IV) oxide nanobelts: control on the predominant crystalline growth axis.

One-dimensional nanobelts of tin (IV) oxide are synthesized by using a newly introduced catalyst-assisted pulsed laser deposition method along two growth directions of [010] and [101]. An ex situ mask-induced growth gradient technique is employed to investigate the growth evolution of the nanobelts on oxidized-Si, H-terminated Si, and Al2O3(0001) substrates by helium ion microscopy, which reveals four stages of growth including catalyst detachment, horizontal nanorod growth, deflection, and the final nanobelt growth. X-ray diffraction and transmission electron microscopy studies show that in spite of the deflections and changes in the growth direction, the nanobelts have, remarkably, maintained their single-crystalline structure throughout the growth by only changing their crystalline growth axis. This has enabled us to influence the preferred growth axis by establishing a crystalline relation between the nanobelts and an appropriate substrate that pins the nanobelts in the initial growth stage. This growth control provides an important means to selectively promote growth of the predominant side planes of the nanobelts, which can then be separated for appropriate applications based on the different growth kinetics of [010] and [101] growth direction.

Formation of Au-Pt alloy nanoparticles on a Si substrate by simple dip-coating at room temperature.

Spherical Au-Pt alloy nanoparticles of 10 nm average size have been prepared on a H-terminated Si(100) substrate by an extremely simple method of dip-coating. X-ray photoelectron spectroscopy and glancing-incidence X-ray diffraction confirm the formation of Au-Pt alloy. The Au(3+) ions are first reduced on the Si substrate upon dipping, and the freshly formed Au nuclei then work as a "catalyst" by promoting the reduction of PtCl(6)(2-) ions on the Au nuclei. The subsequent interdiffusion of Au and Pt atoms leads to the observed alloy formation. The present method provides an environment-friendly, low-cost route to preparing anode electrodes in fuel cells.

Nano-environment effects on the luminescence properties of Eu(3+)-doped nanocrystalline SnO2 thin films.

Nanocrystalline tin (IV) oxide thin films doped with Eu(3+) ions are synthesized using a simple spin-coating method followed by postannealing in an O(2) flow at 700 °C. Transmission electron microscopy and x-ray photoelectron spectroscopy studies illustrate the incorporation of Eu(3+) ions in the films with a high atomic percentage of 2.7%-7.7%, which is found to be linearly dependent on the initial concentration of Eu(3+) in the precursor solution. Glancing incidence x-ray diffraction results show that the crystalline grain sizes decrease with increasing the Eu(3+) concentration and decreasing the postannealing temperature with the emergence of the Eu(2)Sn(2)O(7) phase at high Eu(3+) concentrations (≥5.3 at.%). Luminescence spectra of these doped samples show the characteristic narrow-band magnetic dipole emission at 593 nm and electric dipole emission at 614 nm of the Eu(3+) ions, arising from UV absorption at the SnO(2) band-edge followed by energy transfer to the emission centers. Manipulating the crystallite size, composition, and defect density of the samples greatly affects the absorption edge, energy transfer, and therefore the emission spectra. These modifications in the environment of the Eu(3+) ions allow the emission to be tuned from pure orange characteristic Eu(3+) emission to the broadband emission corresponding to the combination of strong characteristic Eu(3+) emission with the intense defect emissions.

Effect of freezing on photoreactivation of Escherichia coli and Enterococcus faecalis.

The effect of freezing on photoreactivation of two strains of Escherichia coli (ATCC strain 25922 and O157:H7 strain 961019) and two strains of Enterococcus faecalis (strain ATCC 51299, vancomycin-resistant and strain ATCC 29212, vancomycin-sensitive) following ultraviolet irradiation were examined. The level of log photoreactivation of the freezing treated test organisms (frozen at -7, -15, or -30 degrees C then thawed at room temperature prior to ultraviolet irradiation) was compared with that of the samples that had not been frozen. Freezing had obvious impact on the response of the test organisms to visible light following ultraviolet irradiation. Significantly lower levels of photoreactivation were observed in the freezing treated cells. The effect of freezing on the ability of the test microbes to photoreactivate seems to be strain and species dependent. Overall, the experimental results suggest that less photoreactivation could be expected if freezing is used as a treatment method prior to ultraviolet disinfection.