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At least 883 records · Page 49

Effect of bentonite modification on hardness and mechanical properties of natural rubber nanocomposites

The effect of sodium activation, ion-exchange with tertiary amine salt, surface treatment with non-ionic surfactant, and wet grinding of bentonite on hardness and mechanical properties of natural rubber nanocomposites (NRN) was studied using full factorial design of experiment. Results of X-ray diffraction (XRD) show increase in basal spacing d of bentonite due to modification, while attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirm the organic modification of bentonite. Analysis of variance (ANOVA) shows that the main effect of surface treatment increases the hardness and decreases the tensile modulus of the NRN. The surface treatment and wet grinding of bentonite decrease the tensile stresses at 100, 200 and 300% strain of NRN. Sodium activation and ion-exchange negatively affect the compressive properties, while surface treatment significantly improves the compressive properties of NRN.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

30S subunit recognition and G1405 modification by the aminoglycoside-resistance 16S ribosomal RNA methyltransferase RmtC

Acquired ribosomal RNA (rRNA) methylation has emerged as a significant mechanism of aminoglycoside resistance in pathogenic bacterial infections. Modification of a single nucleotide in the ribosome decoding center by the aminoglycoside-resistance 16S rRNA (m 7 G1405) methyltransferases effectively blocks the action of all 4,6-deoxystreptamine ring-containing aminoglycosides, including the latest generation of drugs. To define the molecular basis of 30S subunit recognition and G1405 modification by these enzymes, we used a S-adenosyl-L-methionine analog to trap the complex in a postcatalytic state to enable determination of a global 3.0 Å cryo-electron microscopy structure of the m 7 G1405 methyltransferase RmtC bound to the mature Escherichia coli 30S ribosomal subunit. This structure, together with functional analyses of RmtC variants, identifies the RmtC N-terminal domain as critical for recognition and docking of the enzyme on a conserved 16S rRNA tertiary surface adjacent to G1405 in 16S rRNA helix 44 (h44). To access the G1405 N7 position for modification, a collection of residues across one surface of RmtC, including a loop that undergoes a disorder-to order transition upon 30S subunit binding, induces significant distortion of h44. This distortion flips G1405 into the enzyme active site where it is positioned for modification by two almost universally conserved RmtC residues. Further, these studies expand our understanding of ribosome recognition by rRNA modification enzymes and present a more complete structural basis for future development of strategies to inhibit m 7 G1405 modification to resensitize bacterial pathogens to aminoglycosides.

59 BASIC BIOLOGICAL SCIENCES↗

Photoassisted physical vapor epitaxial growth of semiconductors: a review of light-induced modifications to growth processes

Herein, we review the remarkable range of modifications to materials properties associated with photoexcitation of the growth surface during physical vapor epitaxy of semiconductors. We concentrate on mechanisms producing measureable, utilizable changes in crystalline perfection, phase, composition, doping, and defect distribution. We outline the relevant physics of different mechanisms, concentrating on those yielding effects orthogonal to the primary growth variables of temperature and atomic or molecular fluxes and document the phenomenological effects reported. Based on experimental observations from a range of semiconductor systems and growth conditions, the primary effects include enhanced anion desorption, molecular dissociation, increased doping efficiency, modification to defect populations and improvements to the crystalline quality of epilayers grown at low temperatures. Future research directions and technological applications are also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Density functional study on the mechanism for the highly active palladium monolayer supported on titanium carbide for the oxygen reduction reaction

The adsorption, diffusion, and dissociation of O{sub 2} on the palladium monolayer supported on TiC(001) surface, MLPd/TiC(001), are investigated using ab initio density functional theory calculations. Strong adhesion of palladium monolayer to the TiC(001) support, accompanied by a modification of electronic structure of the supported palladium, is evidenced. Compared with Pt(111) surface, the MLPd/TiC(001) can enhance the adsorption of O{sub 2}, leading to comparable dissociation barrier and a smaller diffusion barrier of O{sub 2}. Whilst the adsorption strength of atomic O (the dissociation product of O{sub 2}) on MLPd/TiC(001) is similar to that on the Pt(111) surface, possessing high mobility, our theoretical results indicate that MLPd/TiC(001) may serve as a good catalyst for the oxygen reduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solution-Deposited and Patternable Conductive Polymer Thin-Film Electrodes for Microbial Bioelectronics

Microbial bioelectronic devices integrate naturally occurring or synthetically engineered electroactive microbes with microelectronics. These devices have a broad range of potential applications, but engineering the biotic–abiotic interface for biocompatibility, adhesion, electron transfer, and maximum surface area remains a challenge. Prior approaches to interface modification lack simple processability, the ability to pattern the materials, and/or a significant enhancement in currents. We report a novel conductive polymer coating that significantly enhances current densities relative to unmodified electrodes in microbial bioelectronics is reported. The coating is based on a blend of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) crosslinked with poly(2-hydroxyethylacrylate) (PHEA) along with a thin polydopamine (PDA) layer for adhesion to an underlying indium tin oxide (ITO) electrode. When used as an interface layer with the current-producing bacterium Shewanella oneidensis MR-1, this material produces a 178-fold increase in the current density compared to unmodified electrodes, a current gain that is higher than previously reported thin-film 2D coatings and 3D conductive polymer coatings. The chemistry, morphology, and electronic properties of the coatings are characterized and the implementation of these coated electrodes for use in microbial fuel cells, multiplexed bioelectronic devices, and organic electrochemical transistor based microbial sensors are demonstrated. It is envisioned that this simple coating will advance the development of microbial bioelectronic devices.

patterned bioelectronics↗

Structure and Properties of VT6 Alloy Obtained by Layered Selective Sintering of a Powder

This paper is focused on a clarification and analysis of the regularities of formation of the structure and properties of samples of the titanium-based alloy VT6, obtained by methods of conventional metallurgy and formed by layered selective electron-beam sintering in vacuum (using the Arcam A2X (3D printer) system (Arcam, Sweden)) of VT6 titanium powder with particle size 40–100 μm. Additional modification of the samples was realized by irradiating the surface with an intense pulsed electron beam (15 keV, 45 J/cm{sup 2}, 200 μs, 10 pulses, 0.3 s{sup –1}, 3.5·10{sup –2} Pa). It is shown that the action of a pulsed electron beam on the surface of samples formed by layered selective electron-beam sintering leads to a significant reduction in the porosity of the surface layer of the material and formation in the surface layer of a polycrystalline structure (grain size 15–60 μm) with a substructure in the form of crystallization cells (cell size 0.5–1.2 μm). Electron-beam processing of samples prepared by methods of conventional metallurgy for the indicated electron-beam parameters leads to the formation in the surface layer of a polycrystalline structure (grain size 50–800 μm) with a laminar intragrain substructure. Mechanical tests, performed by stretching flat samples, showed that the highest combination of mechanical strength and plasticity is possessed by samples obtained by layered selective electron-beam sintering with subsequent irradiation by an intense pulsed electron beam.

36 MATERIALS SCIENCE↗

Layer-by-layer assembled PEI-based vector with the upconversion luminescence marker for gene delivery

The upconversion luminescence (UCL) marker based on upconversion nanoparticles (UCNPs) shows unique advantages over traditional fluorescence markers, such as enhanced tissue penetration, better photostability, and less autofluorescence. Herein, we constructed a new UCL gene-delivery nonviral vector via layer-by-layer self-assembly of poly(ethylene imine) (PEI) with UCNPs. To reduce the cytotoxicity of PEI, citric acid (CA) was introduced for aqueous modification, and PEI assembly was introduced on the UCNP surface. Our data show that the nonviral vector for UCL gene-delivery demonstrates excellent photostability, low toxicity, and good stability under physiological or serum conditions and can strongly bind to DNA. Moreover, this UCL PEI-based vector could serve as a promising fluorescent gene-delivery carrier for theranostic applications.

60 APPLIED LIFE SCIENCES↗

Cross-Sections of Nanocellulose from Wood Analyzed by Quantized Polydispersity of Elementary Microfibrils

Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. Additionally, the cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.

36 MATERIALS SCIENCE↗

Climate Conundrum: A Wet or Dry European and Northern African Climate During the Middle Miocene

Abstract End of 21st‐century hydroclimate projections suggest an expansion of subtropical dry zones, with Mediterranean and Sahel regions becoming much drier. However, paleobotanical assemblage evidence from the middle Miocene (17‐12 Ma), suggests both regions were instead humid environments. Here we show that by modifying regional sea surface temperatures (SST) in an Earth System Model (CESM1.2) simulation of the middle Miocene, the increased ocean evaporation and integrated water vapor flux overrides any drying effects associated with warming‐induced land‐surface evaporation driven by atmospheric CO 2 concentrations. These modifications markedly reduce the bias in the model‐data comparison for this period. A vegetation model (BIOME4) forced with simulated climatologies predicts both regions were dominated by mixed forest, which is largely consistent with the paleobotanical record. This study unveils the potential for wetter subtropical Mediterranean climates associated with warming, presenting an alternative scenario from future drying projections with localized SST warming governing regional climate change.

Acosta, R. P.↗

Engineering on-chip nanoporous gold material libraries via precision photothermal treatment [Precision Photothermal Annealing of Nanoporous Gold Thin Films for the Microfabrication of a Single-ship Material Libraries]

Single-chip material libraries of thin films of nanostructured materials are a promising approach for high throughput studies of structure-property relationship in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material of specific interest in both these fields. One attractive property of np-Au is its self-similar coarsening behavior by thermally induced surface diffusion. However, traditional heat application techniques for the modification of np-Au are bulk processes that cannot be used to generate a library of different pore sizes on a single chip. Laser micromachining offers an attractive solution to this problem by providing a means to apply energy with high spatial and temporal resolution. In our present study we use finite element multiphysics simulations to predict the effects of laser mode (continuous-wave vs. pulsed) and supporting substrate thermal conductivity on the local np-Au film temperatures during photothermal annealing and subsequently investigate the mechanisms by which the np-Au network is coarsening. Our simulations predict that continuous-wave mode laser irradiation on a silicon supporting substrate supports the widest range of morphologies that can be created through the photothermal annealing of thin film np-Au. Using this result we successfully fabricate a single-chip material library consisting of 81 np-Au samples of 9 different morphologies for use in increased throughput material interaction studies.

36 MATERIALS SCIENCE↗

Atmospheric pressure X-ray photoelectron spectroscopy apparatus: Bridging the pressure gap

One of the main goals in catalysis is the characterization of solid/gas interfaces in a reaction environment. The electronic structure and chemical composition of surfaces become heavily influenced by the surrounding environment. However, the lack of surface sensitive techniques that are able to monitor these modifications under high pressure conditions hinders the understanding of such processes. This limitation is known throughout the community as the “pressure gap.” We have developed a novel experimental setup that provides chemical information on a molecular level under atmospheric pressure and in presence of reactive gases and at elevated temperatures. This approach is based on separating the vacuum environment from the high-pressure environment by a silicon nitride grid—that contains an array of micrometer-sized holes—coated with a bilayer of graphene. Using this configuration, we have investigated the local electronic structure of catalysts by means of photoelectron spectroscopy and in presence of gases at 1 atm. The reaction products were monitored online by mass spectrometry and gas chromatography. The successful operation of this setup was demonstrated with three different examples: the oxidation/reduction reaction of iridium (noble metal) and copper (transition metal) nanoparticles and with the hydrogenation of propyne on Pd black catalyst (powder).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excitation of fishbone-like mode in tokamaks due to bounce resonances of trapped thermal ions

When the drift kinetic effect of thermal ions is taken into account, a high-frequency fishbone-like mode (FLM) is found to be driven unstable by trapped thermal ions (TTIs) in tokamak plasmas, according to self-consistent magneto-hydrodynamic (MHD)-kinetic hybrid modeling utilizing the MARS-K code [Liu et al., Phys. Plasmas 15, 112503 (2008)] as well as an analytic theory. It is found that, similar to energetic particles, TTIs can also stabilize the internal kink mode, whereas the FLM is excited when the effective beta of TTIs exceeds a threshold value. The real frequency of the FLM is comparable to the bounce frequency of TTIs. The mode structure of the FLM can be significantly different from the conventional step-like function for the associated plasma radial displacement. This drift kinetic induced modification of the mode structure near the q = 1 surface is captured by non-perturbative MHD-kinetic hybrid computations with MARS-K. Furthermore, the FLM can only be triggered by TTIs at sufficiently high thermal temperatures. Both the FLM and the internal kink can be stabilized by sufficiently fast plasma toroidal rotation and parallel sound wave damping. These two conditions of high thermal temperature and (fast) flow stabilization, though making it challenging to observe the TTI-driven FLM in present day experiments, are favorable for the mode excitation in future reactor scale devices.

36 MATERIALS SCIENCE↗

Effects of Extractive Ammonia Pretreatment on the Ultrastructure and Glycan Composition of Corn Stover

Lignocellulosic biomass is highly recalcitrant and requires a pretreatment step to improve the enzyme accessibility and fermentable sugar yields during enzymatic hydrolysis. Our previous studies demonstrated the rearrangement of the hydrogen bond network within CIII, makes it “amorphous-like” and facilitates easier glucan chain extraction by enzyme. Also, these changes increase the number of solvent-exposed glucan chain hydrogen bonds with water ~50% lowering the surface-bound cellulase by 60–70%. Also, major chemical modifications to lignin occur via ammonolysis of ester-linked ferulate and coumarate linkage. These apparent ultrastructural changes help the enhancement of cellulase activity resulting in higher production of fermentable sugars during enzyme hydrolysis of EA pretreated corn stover relative to Ammonia Fiber Expansion (AFEX) pretreatment. To understand ultra-structural modifications that occur during EA pretreatment, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were used to examine untreated and EA-pretreated corn stover in an effort to visualize changes in the biomass resulting from the pretreatment. In addition, Immunofluorescence Microscopy was applied to both untreated and pretreated plant cell walls using glycan-directed monoclonal antibodies to reveal possible changes in the spatial distributions of wall glycan epitopes resulting from EA pretreatment. This evaluation was complemented with glycome profiling to determine the glycan epitope compositions of EA-pretreated cell walls relative to untreated and AFEX pretreated corn stover, where lignin and carbohydrates are not extracted. Distinct differences could be observed in the case of xyloglucan, unsubstituted and substituted pectin- and pectic-arabinogalactan-epitope levels in the plant cell wall after EA pretreatment compared with untreated and AFEX-pretreated walls. Liquid ammonia induced de-lignification of cell wall has helped to clearly identify the glucans that are intact after pretreatment. These studies support some of our hypothesis that liquid ammonia cleaves lignin–carbohydrate ester linkages, partially solubilizing lignin and its associated carbohydrates. Specifically, the imaging studies clearly show that some of the cell wall components are extracted as a separate liquid stream during the EA process, thereby creating porous, interconnected tunnel-like networks in the plant cell walls thereby providing better access of carbohydrate polymers to enzymes and thereby increasing the sugar yield from the EA-pretreated biomass.

09 BIOMASS FUELS↗

Femtosecond laser-induced formation of submicrometer spikes on a semiconductor substrate

The present invention generally provides semiconductor substrates having submicronsized surface features generated by irradiating the surface with ultra short laser pulses. In one aspect, a method of processing a semiconductor substrate is disclosed that includes placing at least a portion of a surface of the substrate in contact with a fluid, and exposing that surface portion to one or more femtosecond pulses so as to modify the topography of that portion. The modification can include, e.g., generating a plurality of submicron-sized spikes in an upper layer of the surface.

36 MATERIALS SCIENCE↗

Femtosecond laser-induced formation of submicrometer spikes on a semiconductor substrate

The present invention generally provides semiconductor substrates having submicron-sized surface features generated by irradiating the surface with ultra short laser pulses. In one aspect, a method of processing a semiconductor substrate is disclosed that includes placing at least a portion of a surface of the substrate in contact with a fluid, and exposing that surface portion to one or more femtosecond pulses so as to modify the topography of that portion. The modification can include, e.g., generating a plurality of submicron-sized spikes in an upper layer of the surface.

Mazur, Eric↗

Femtosecond laser-induced formation of submicrometer spikes on a semiconductor substrate

The present invention generally provides semiconductor substrates having submicron-sized surface features generated by irradiating the surface with ultra short laser pulses. In one aspect a method of processing a semiconductor substrate is disclosed that includes placing at least a portion of a surface of the substrate in contact with a fluid, and exposing that surface portion to one or more femtosecond pulses so as to modify the topography of that portion. The modification can include, e.g., generating a plurality of submicron-sized spikes in an upper layer of the surface.

36 MATERIALS SCIENCE↗

Laser-induced transient grating setup with continuously tunable period

We present a modification of the laser-induced transient grating setup enabling continuous tuning of the transient grating period. The fine control of the period is accomplished by varying the angle of the diffraction grating used to split excitation and probe beams. The setup has been tested by measuring dispersion of bulk and surface acoustic waves in both transmission and reflection geometries. The presented modification is fully compatible with optical heterodyne detection and can be easily implemented in any transient grating setup.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗