The nanoindentation responses of nickel surfaces with different crystal orientations

Molecular dynamics (MD) simulations are applied to elucidate the anisotropic characteristics in the material responses for crystallographic nickel substrates with (100), (110) and (111) surface orientations during nanoindentation, compensating for the experimental limitation of nanoindentation—particularly for pure nickel substrates of three crystallographic orientations. This study examines several factors under indentation: three-dimensional phases of plastic deformation which correspond to atomic stress distributions, pile-up patterns at maximum indentation depth, and extracted material properties at different crystallographic orientations. The present results reveal that the strain energy of the substrate exerted by the tip is stored by the formation of the homogeneous nucleation, and is dissipated by the dislocation sliding of the {111} plane. The steep variations of the indentation curve from the local peak to the local minimums are affected by the numbers of slip angle of {111} sliding plane. The pile-up patterns of the three nickel substrates prove that the crystalline nickel materials demonstrate the pile-up phenomenon from nanoindentation on the nano-scale. The three crystallographic nickel substrates exhibit differing amounts of pile-up dislocation spreading at different crystallographic orientations. Finally, the effects of surface orientation in material properties of FCC nickel material on the nano-scale are observable through the slip angle numbers of {111} sliding planes which influence hardness values, as well as the cohesive energy of different crystallographic surfaces that indicate Young's modulus.     

3D Cube‐Maze‐Like Li‐Rich Layered Cathodes Assembled from 2D Porous Nanosheets for Enhanced Cycle Stability and Rate Capability of Lithium‐Ion Batteries

Li‐rich oxide is a promising candidate for the cathodes of next‐generation lithium‐ion batteries. However, its utilization is restricted by cycling instability and inferior rate capability. To tackle these issues, three‐dimensional (3D), hierarchical, cube‐maze‐like Li‐rich cathodes assembled from two‐dimensional (2D), thin nanosheets with exposed {010} active planes, are developed by a facile hydrothermal approach. Benefiting from their unique architecture, 3D cube‐maze‐like cathodes demonstrate a superior reversible capacity (285.3 mAh g^?1 at 0.1 C, 133.4 mAh g^?1 at 20.0 C) and a great cycle stability (capacity retention of 87.4% after 400 cycles at 2.0 C, 85.2% after 600 cycles and 75.0% after 1200 cycles at 20.0 C). When this material is matched with a graphite anode, the full cell achieves a remarkable discharge capacity (275.2 mAh g^?1 at 0.1 C) and stable cycling behavior (capacity retention of 88.7% after 100 cycles at 5.0 C, capacity retention of 84.8% after 100 cycles at 20.0 C). The present work proposes an accessible way to construct 3D hierarchical architecture assembled from 2D nanosheets with exposed high‐energy active {010} planes and verifies its validity for advanced Li‐rich cathodes.     

Direct electron transfer and electrocatalysis of hemoglobin adsorbed on mesoporous carbon through layer-by-layer assembly

Using chitosan as an effective linker between CMK-3 and glassy carbon electrode surface, {Hb/CMK-3}n multilayer film-modified electrodes were constructed through layer-by-layer assembly. The morphology of thus-formed {Hb/CMK-3}n film was characterized by scanning electron micrographs, and the interaction of hemoglobin (Hb) with CMK-3 was studied by UV-vis spectroscopy and electrochemical methods. Under optimal conditions, {Hb/CMK-3}6 film showed a couple of stable and well-defined redox peaks at about -377 and -296 mV in pH 7.0 buffers. Furthermore, the {Hb/CMK-3}6 film displayed excellent electrocatalysis to the reduction of both H2O2 and O2. Based on thus-formed film and its direct electron transfer behavior, a novel biosensor was presented for the determination of H2O2 ranging from 1.2 to 57 muM with the detection limit of 0.6microM at S/N=3. CMK-3 provided a desirable matrix for protein immobilization and biosensor preparation.     

Degradation behavior of chitosan chains in the 'green' synthesis of gold nanoparticles

The degradation behavior of chitosan chains in the synthesis of Au nanoparticles by a 'green' method was investigated in this paper for the first time. UV-vis absorption spectra suggested the formation of Au nanoparticles and TEM images showed that their sizes were between 10 and 50nm. During the process of synthesis, the intrinsic viscosity [eta] of chitosan was observed to decrease gradually, implying that the chitosan chains degraded under the reaction conditions. Further studies showed that the degree of degradation of the chitosan chains was changed with different reaction temperatures, reactant ratios, and the molecular weights of chitosan.     

Engineering Catalytic Active Sites on Cobalt Oxide Surface for Enhanced Oxygen Electrocatalysis

Tuning the catalytic active sites plays a crucial role in developing low cost and highly durable oxygen electrode catalysts with precious metal‐competitive activity. In an attempt to engineer the active sites in Co₃O₄ spinel for oxygen electrocatalysis in alkaline electrolyte, herein, controllable synthesis of surface‐tailored Co₃O₄ nanocrystals including nanocube (NC), nanotruncated octahedron (NTO), and nanopolyhedron (NP) anchored on nitrogen‐doped reduced graphene oxide (N‐rGO), through a facile and template‐free hydrothermal strategy, is provided. The as‐synthesized Co₃O₄ NC, NTO, and NP nanostructures are predominantly enclosed by {001}, {001} + {111}, and {112} crystal planes, which expose different surface atomic configurations of Co²⁺ and Co³⁺ active sites. Electrochemical results indicate that the unusual {112} plane enclosed Co₃O₄ NP on rGO with abundant Co³⁺ sites exhibit superior bifunctional activity for oxygen reduction and evolution reactions, as well as enhanced metal–air battery performance in comparison with other counterparts. Experimental and theoretical simulation studies demonstrate that the surface atomic arrangement of Co²⁺/Co³⁺ active sites, especially the existence of octahedrally coordinated Co³⁺ sites, optimizes the adsorption, activation, and desorption features of oxygen species. This work paves the way to obtain highly active, durable, and cost‐effective electrocatalysts for practical clean energy devices through regulating the surface atomic configuration and catalytic active sites.     

Does the antibacterial activity of silver nanoparticles depend on the shape of the nanoparticle? A study of the Gram-negative bacterium Escherichia coli

In this work we investigated the antibacterial properties of differently shaped silver nanoparticles against the gram-negative bacterium Escherichia coli, both in liquid systems and on agar plates. Energy-filtering transmission electron microscopy images revealed considerable changes in the cell membranes upon treatment, resulting in cell death. Truncated triangular silver nanoplates with a {111} lattice plane as the basal plane displayed the strongest biocidal action, compared with spherical and rod-shaped nanoparticles and with Ag(+) (in the form of AgNO(3)). It is proposed that nanoscale size and the presence of a {111} plane combine to promote this biocidal property. To our knowledge, this is the first comparative study on the bactericidal properties of silver nanoparticles of different shapes, and our results demonstrate that silver nanoparticles undergo a shape-dependent interaction with the gram-negative organism E. coli.     

Photoproduction and Detoxification of Hydroxyl radicals in Chloroplasts and Leaves and Relation to Photoinactivation of Photosystems I and II

The light-dependent production of hydroxyl radicals (HO{dot})by thylakoids, chloroplasts and leaves of Spinacia oleraceawas investigated using dimethylsulfoxide as HO{dot} trappingagent. Maximum rates of HO{dot} production by thylakoids asindicated by the formation of methane sulfinic acid were observedunder aerobic conditions in the absence of added electron acceptors.They were higher than 2 µmol (mg Chl h)^–1. Saturationof HO{dot} production occurred at the low photon flux densityof 100 µmol m^–2 s^–1. Trapping of HO{dot} bydimethylsulfoxide suppressed, but did not eliminate light-dependentinactivation of PSI and II suggesting that HO{dot} formationcontributed to the photosensitivity of isolated thylakoids.DCMU inhibited HO{dot} formation. Importantly, methylviologendecreased HO{dot} formation in the absence, but stimulated itin the presence of Fe³⁺. In intact chloroplasts, HO{dot} formation became appreciableonly after KCN had been added to inhibit effective H₂O₂ scavengingby ascorbate peroxidase. It was stimulated by ferrisulfate,but not by ferricyanide which does not penetrate the chloroplastenvelope. Infiltrated spinach leaves behaved similar in principleto intact chloroplasts in regard to HO{dot} formation but HO{dot}production was very slow if detectable at all by the formationof methylsulfinic acid indicating effective radical detoxification. HO{dot} formation is interpreted to be the result of a Fenton-typereaction which produces HO{dot} in chloroplasts from H₂O₂ andreduced ferredoxin, when O₂ is electron acceptor in the Mehlerreaction and radical detoxification reactions are inhibited. (Received November 13, 1996; Accepted April 23, 1996)     

Effects of cooling treatment and glutaraldehyde on the morphology of Au nanostructures synthesized from chitosan

A facile approach for the synthesis of chitosan-based Au nanostructures that have interesting absorptions in the near-infrared (NIR) region is presented. The effects of cooling treatment and the cross-linking agent glutaraldehyde on the formation of Au nanostructures based on chitosan were investigated. It has been demonstrated that the size and shape, and thus the optical properties of Au nanostructures, could be modulated via cooling treatment. The optical absorption extension of these Au nanostructures in the NIR region is promising in biomedical applications. The presence of a cross-linking agent, glutaraldehyde, during synthesis accelerated the reduction of the Au precursor and favored the growth of isotropic Au nanoparticles. A possible mechanism for the change in growth modality of Au nanostructures with and without glutaraldehyde was elucidated.     

Solution behaviour and biological activity of bisamidine complexes of platinum(II)

A series of platinum(II) amidine complexes were previously prepared with the aim of obtaining a new class of platinum-based antitumour drugs. This series includes compounds of the type cis--[PtCl2{Z-HN=C(NHMe)Me}2] and trans-[PtCl2{Z-HN=C(NHMe)Me}2] (1, 2), cis-[PtCl2{E-HN=C(NMe2)Me}2] and trans-[PtCl2{E-HN=C(NMe2)Me}2] (3, 4), cis-[PtCl2{Z-HN=C(NHMe)Ph}2] and trans-[PtCl2{Z-HN=C(NHMe)Ph}2] (5, 6), and cis-[PtCl2{HN=C(NMe2)Ph}2] and trans-[PtCl2{HN=C(NMe2)Ph}2] (7, 8). The reactions with dimethyl sulfoxide were studied for complexes 5-8; the formation of cationic species containing coordinated dimethyl sulfoxide was demonstrated by NMR experiments and electrospray ionization mass spectrometry. In this work, the amidine platinum(II) complexes were tested for their in vitro cytotoxicity on a panel of various human cancer cell lines. The results indicate that the benzamidine complex 8 was the most effective derivative also circumventing acquired cisplatin resistance as demonstrated by chemosensitivity tests performed on cisplatin-sensitive and cisplatin-resistant cell lines. The studies concerning the cellular DNA damage on both parental chemosensitive and resistant sublines suggest for the new trans-amidine complex a different mechanism of action compared with that exhibited by cisplatin.     

Single‐Crystalline Ultrathin Co3O4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

The role of vacancy defects is demonstrated to be positive in various energy‐related processes. However, introducing vacancy defects into single‐crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this study deliberately introduces oxygen defects into single‐crystalline ultrathin Co₃O₄ nanosheets with O‐terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As‐prepared defect‐rich Co₃O₄ nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec^?1 for the oxygen evolution reaction (OER), which is among the best Co‐based OER catalysts to date and even more active than the state‐of‐the‐art IrO₂ catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second‐layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. This mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect‐based electrocatalysts.     

Graphene Multilayer Supported Gold Nanoparticles for Efficient Electrocatalysts Toward Methanol Oxidation

This study reports a simple method of integrating electroactive gold nanoparticles (Au NPs) with graphene oxide (GO) nanosheet support by layer‐by‐layer (LbL) assembly for the creation of 3‐dimensional electrocatalytic thin films that are active toward methanol oxidation. This approach involves the alternating assembly of two oppositely charged suspensions of Au NPs with GO nanosheets based on electrostatic interactions. The GO nanosheets not only serve as structural components of the multilayer thin film, but also potentially improve the utilization and dispersion of Au NPs by taking advantages of the high catalytic surface area and the electronic conduction of graphene nanosheets. Furthermore, it is found that the electrocatalytic activity of the multilayer thin films of Au NPs with graphene nanosheet is highly tunable with respect to the number of bilayers and thermal treatment, benefiting from the advantageous features of LbL assembly. Because of the highly versatile and tunable properties of LbL assembled thin films coupled with electrocatalytic NPs, we anticipate that the general concept presented here will offer new types of electroactive catalysts for direct methanol fuel cells.     

Formation of oriented polypeptides on Au(111) surface depends on the secondary structure controlled by peptide length.

We synthesized three different lengths of poly(L-lysine) containing an -SH group at the terminal (PLL(n)-SH, n (polymerization degree) = 4, 10, 30) and adsorbed them on an Au(111) surface. To analyze the formation process and the structure of self-assembled monolayers (SAMs), we used atomic force microscopy (AFM) and Fourier transform infrared reflection absorption spectra (FT-IR RAS). At the initial stage of SAM growth, formation of nanosize domains was confirmed by AFM imaging. The alpha-helical PLL(30)-SH exhibited a well-defined SAM structure after adsorption reached equilibrium. The alpha-helical PLL(30)-SH was almost perpendicular to the gold surface and exhibited interesting molecular packing due to the secondary structure of PLL(30)-SH and the underlying Au(111) array. The tilt angle of the helix axis from the substrate normal was estimated to be about 50 degrees (AFM) and 44 degrees (FT-IR RAS) respectively. On the other hand, PLL(4)-SH and PLL(10)-SH formed beta-sheet-type SAMs on the Au(111) surface based on the structure determined by FT-IR RAS spectrum.     

Adsorption properties of gold onto a chitosan derivative

In order to find a material which can be used for the recovery of Au(III), a chitosan derivative was synthesized by carboxymethylation and grafting sulfur groups onto cross-linked chitosan backbone. Adsorption studies were carried out at different pH values to optimize the pH condition. Batch method was conducted to study the effects of parameters such as reaction time, initial metal concentration and temperature on Au(III) sorption. The maximum adsorption affinity for Au(III) was found to be 8.32mmol/g at pH 4.0, 25°C. The results of kinetic study showed that the adsorption reaction followed the pseudo second order model. The derivative showed high adsorption ability and reusability toward Au(III). All results suggested that the chitosan derivative had potential to be utilized in the recovery of Au(III) from aqueous medium.     

Potential use of sulfite as a supplemental electron donor for wastewater denitrification

Biological denitrification typically requires the addition of a supplemental electron donor, which can add a significant operating expense to wastewater treatment facilities. Most common electron donors are organic, but reduced inorganic sulfur compounds (RISCs), such as sulfide (HS^?) and elemental sulfur (S⁰), may be more cost-effective. S⁰ is an inexpensive and well characterized electron donor, but it provides slow denitrification rates due to its low solubility. A lesser-known RISC is sulfite (\({\text{SO}}_{3}^{2 - }\)), which can be easily produced from S⁰ by a simple combustion process. Unlike S⁰, \({\text{SO}}_{3}^{2 - }\) is highly soluble, and therefore may provide higher denitrification rates. However, very little is known about microbial denitrification with \({\text{SO}}_{3}^{2 - }\). Also, \({\text{SO}}_{3}^{2 - }\) is a strong reductant that reacts abiotically with oxygen and has toxic effects on microorganisms. This paper reviews \({\text{SO}}_{3}^{2 - }\) in the environment, \({\text{SO}}_{3}^{2 - }\) chemistry, microbiology, toxicity, and its potential use for denitrification. Since \({\text{SO}}_{3}^{2 - }\) is an intermediate in the sulfur oxidation pathway of most sulfur-oxidizing microorganisms, it is an energetic electron donor and it should select for a \({\text{SO}}_{3}^{2 - }\)-oxidizing community. Our review of the literature, as well as our own lab experience, suggests that \({\text{SO}}_{3}^{2 - }\) can effectively serve as an electron donor for denitrification. Further research is needed to determine the kinetics of \({\text{SO}}_{3}^{2 - }\)-based denitrification, its toxic threshold for sulfur-oxidizing microorganisms, and its potential inhibition of sensitive species such as nitrifying microorganisms and potential formation of nitrous oxide. Its effect on sludge settling efficiency also should be explored.     

Adsorption of microorganisms onto an artificial siderophore-modified Au substrate

The hydroxamate-type artificial siderophore, tris[2-{3-(N-acetyl-N-hydroxamino)propylamido}propyl]aminomethane (TAPPA) and its Fe(III) complex, Fe(III)-TAPPA were prepared and characterized by several spectroscopic methods. Fe(III)-TAPPA exhibits biological activity for the hydroxamate-type siderophore auxotrophic microorganism, Microbacterium flavescens, suggesting that Fe(III)-TAPPA can permeate the cell membrane of the microorganism. The adsorption of the Fe(III)-siderophore complex onto a deposited Au substrate was achieved by a stepwise self-assembling method. The modification of Fe(III)-TAPPA on the surface was confirmed from the cyclic voltammogram of the resultant Au electrode, Fe(III)-TAPPA/Au. The adsorption experiments of M. flavescens with Fe(III)-TAPPA/Au were monitored by optical, scanning electron, and atomic force microscopy and quartz crystal microbalance (QCM) measurements. These results clearly indicate that Fe(III)-TAPPA/Au can immobilize M. flavescens. This adsorption characteristic is due to the interaction between Fe(III)-TAPPA on an Au electrode and a receptor/binding protein within the cell membrane.     

External-circulation-loop airlift bioreactors: study of the liquid circulating velocity in highly viscous non-Newtonian liquids

In order to obtain further information on the behavior and optimal design of external-circulation-loop airlift (ECL-AL) bioreactors, the liquid circulating velocity, gas holdup and average bubble diameter in the downcomer were studied using highly viscous pseudoplastic solutions of various types of CMC. A few comparative measurements also were made using a viscous Newtonian aqueous sucrose solution. For the liquid velocity measurements, an ultrasonic flow meter (Doppler frequency shift principle) was applied for the first time to the gas/non-Newtonian liquid dispersion in downward flow and satisfactory results were obtained. For viscous liquids, the circulating liquid velocity in the riser section of an ECL-AL (u(LR)) is shown to be dependent mainly on the downcomer-to-riser cross-sectional area ratio (A(d)/A(r)), the effective viscosity (eta(eff)) and the gas superficial velocity (u(GR)) as described by the following equation \documentclass{article}\pagestyle{empty}\begin{document}$$ u_{LR} = 0.23u_{GR};{0.32} (A_d /A_r);{0.97} \eta _{eff};{ - 0.39} $$\end{document} The circulating liquid velocity exerts opposing effects on the mass transfer and liquid-phase mixing performances of ECL-AL fermentors. Therefore, it is proposed that the optimum operating conditions for a given fermentation may be best achieved by means of independently regulating the circulating liquid velocity.     

Morphological and Crystallographic Transformation from Immature to Mature Coccoliths, <Emphasis Type="Italic">Pleurochrysis carterae</Emphasis>

Morphology and crystallographic orientations of coccoliths, Pleurochrysis carterae, at the various growth stages were investigated using electron back-scattered diffraction analyses and scanning electron microscope (SEM) stereo-photogrammetry to understand the developments of two different coccolith units, namely V and R units. SEM observation indicates that the immature coccolith units at the earliest stage were not perfectly fixed on the organic base plates and several units were often lacked. The all units showed platy morphology and often lay parallel to the organic base plate. Their crystal orientations were close to that of the mature R units. With further growth, the platy morphology changes to a trapezoid to anvil-shape for both units, resulting in the interlocking structure of VR units. Morphological analyses present that the edges of the platy crystals parallel to the organic base plate were estimated as $<48\;\overline 1>$<48\;\overline 1>, and their inner/upper surfaces were estimated as { 10  [`1]  4} \{ 10\;\overline 1 \,4\} . As they interlocked further, R units inclined more outward to develop the inner tube elements with { 10  [`1]  4} \{ 10\;\overline 1 \,4\} and then each unit develops differently distal and proximal shield elements, which are respectively estimated as { 10  [`1]  4} \{ 10\;\overline 1 \,4\} in the distal view and { 2 [`1]   [`1]  0} \{ 2\,\overline 1 \;\overline 1 \,0\} planes in the proximal view. Based on the above results, the formation of different coccolith units and their growth were discussed.     

Kinetics of aflatoxin biosynthesis by Aspergillus parasiticus in the presence of N(alpha)-palmitoyl-L-lysyl-L-lysine-ethyl ester dihydrochloride or dichlorvos

N(alpha)-Palmitoyl-L-lysyl-L-lysine-ethyl ester dihydrochloride (PLL) has antimicrobial properties and may be useful as a food preservative. This study was conducted to see if PLL can inhibit growth and synthesis of aflatoxin by Aspergillus parasiticus. Growth of mold and accumulation of aflatoxins were monitored for up to 15 days. To compare these data with those of a known inhibitor of aflatoxin synthesis, dichlorvos was added to media, and mold growth and aflatoxin accumulation were monitored. The kinetic model of Brown and Vass that correlates growth and formation of secondary metabolites was applied to results of this study, and values for maturation time (t(m)) and aflatoxin accumulation rate constant (alpha) were calculated. Values of t(m) decreased when cultures contained PLL, whereas presence of dichlorvos resulted in a considerable increase. The lag phase of mold growth increased in the presence of PLL. The values of alpha increased with an increasing amount (up to 300 ppm) of PLL in media. Higher concentrations of PLL decreased the value of alpha. All levels of dichlorvos tested decreased the value of alpha. The aflatoxin accumulation rate constant (alpha) as a function of concentration of additive (C) followed the general equation: \documentclass{article}\pagestyle{empty}\begin{document}$$\alpha = \frac{{\alpha _m C\exp (- {C \mathord{\left/ {\vphantom {C {K_i }}} \right. \kern-\nulldelimiterspace} {K_i }})}}{{C + K_a }}$$\end{document} where alpha(m), K(a), and K(i) are constants.