Structure of arginine overlayers at the aqueous gold interface: implications for nanoparticle assembly.

Adsorption of small biomolecules onto the surface of nanoparticles offers a novel route to generation of nanoparticle assemblies with predictable architectures. Previously, ligand-exchange experiments on citrate-capped gold nanoparticles with the amino acid arginine were reported to support linear nanoparticle assemblies. Here, we use a combination of atomistic modeling with experimental characterization to explore aspects of the assembly hypothesis for these systems. Using molecular simulation, we probe the structural and energetic characteristics of arginine overlayers on the Au(111) surface under aqueous conditions at both low- and high-coverage regimes. In the low-density regime, the arginines lie flat on the surface. At constant composition, these overlayers are found to be lower in energy than the densely packed films, although the latter case appears kinetically stable when arginine is adsorbed via the zwitterion group, exposing the charged guanidinium group to the solvent. Our findings suggest that zwitterion-zwitterion hydrogen bonding at the gold surface and minimization of the electrostatic repulsion between adjacent guanidinium groups play key roles in determining arginine overlayer stability at the aqueous gold interface. Ligand-exchange experiments of citrate-capped gold nanoparticles with arginine derivatives agmatine and N-methyl-l-arginine reveal that modification at the guanidinium group significantly diminishes the propensity for linear assembly of the nanoparticles.

Molecular mechanism of stabilization of thin films for improved water evaporation protection

All-atom molecular dynamics simulations and experimental characterization have been used to examine the structure and dynamics of novel evaporation-suppressing films where the addition of a water-soluble polymer to an ethylene glycol monooctadecyl ether monolayer leads to improved water evaporation resistance. Simulations and Langmuir trough experiments demonstrate the surface activity of poly(vinyl pyrrolidone) (PVP). Subsequent MD simulations performed on the thin films supported by the PVP sublayer show that, at low surface pressures, the polymer tends to concentrate at the film/water interface. The simulated atomic concentration profiles, hydrogen bonding patterns, and mobility analyses of the water-polymer-monolayer interfaces reveal that the presence of PVP increases the atomic density near the monolayer film, improves the film stability, and reduces the mobility of interfacial waters. These observations explain the molecular basis of the improved efficacy of these monolayer/polymer systems for evaporation protection of water and can be used to guide future development of organic thin films for other applications.

Application of advanced experimental techniques for the microstructural characterization of nanobainitic steels

A 0.79C-1.5Si-1.98Mn-0.98Cr-0.24Mo-1.06Al-1.58Co (wt%) steel was isothermally heat treated at 350°C bainitic transformation temperature for 1 day to form fully bainitic structure with nano-layers of bainitic ferrite and retained austenite, while a 0.26C-1.96Si-2Mn-0.31Mo (wt%) steel was subjected to a successive isothermal heat treatment at 700°C for 300 min followed by 350°C for 120 min to form a hybrid microstructure consisting of ductile ferrite and fine scale bainite. The dislocation density and morphology of bainitic ferrite, and retained austenite characteristics such as size, and volume fraction were studied using Transmission Electron Microscopy. It was found that bainitic ferrite has high dislocation density for both steels. The retained austenite characteristics and bainite morphology were affected by composition of steels. Atom Probe Tomography (APT) has the high spatial resolution required for accurate determination of the carbon content of the bainitic ferrite and retained austenite, the solute distribution between these phases and calculation of the local composition of fine clusters and particles that allows to provide detailed insight into the bainite transformation of the steels. The carbon content of bainitic ferrite in both steels was found to be higher compared to the para-equilibrium level of carbon in ferrite. APT also revealed the presence of fine C-rich clusters and Fe-C carbides in bainitic ferrite of both steels.

Ring strain in boroxine rings: computational and experimental considerations

B3LYP/6-311+G(d) calculations indicate that (HBO)₃ (4) and (HBO)₄ (5) possess (zero-point energy corrected) strain enthalpies of 11.4 and 31.6 kJ mol⁻¹, respectively. The absence of eight-membered (RBO)₄ rings is attributed to a combination of ring strain and the lability of the B---O bond. The synthesis, characterization and molecular structure of (PhBO)₃·pyridine (1) are described and chemical phenomena related to the addition of amines to triorganoboroxine rings are rationalized in terms of relief of ring strain in 4.

Processing and characterization of porous aluminum

Aluminum foams are now being introduced into automotive industry to reduce weight, to absorb energy in crash situations and to carry sound or heat absorbing functions. In the present study, a novel Spark Plasma Sintering (SPS) process for producing porous aluminums with controlled pore size and porosity and superior energy absorption has been developed. Experimental procedures included the mixing of starting powders, compacting, SPS sintering and leaching out of the space-holding particles. Porous aluminums with various porosities and a wide range of pore size distributions can be produced by the SPS process. Optical microscopy, scanning electron microscopy (SEM) and quantitative image analyses were used to characterize the porous aluminums. Compressive tests were carried out on the aluminum foams to evaluate the mechanical properties.

Preparation, characterization and dielectric properties of temperature stable SrTiO3/PEEK composites for microwave substrate applications

Poly(ether ether ketone) (PEEK) is a potential candidate for electronic applications due to its low permittivity, low loss, high melting point, better chemical resistance, excellent insulating properties and easy processibility. Present paper discusses the preparation and characterization of SrTiO3 filled PEEK composite for microwave substrate applications. The dielectric constant, dielectric loss and temperature variation of dielectric constant of the composites have been studied up to 1 MHz using an Impedance Analyzer. Different theoretical approaches have been employed to predict the effective permittivity of composite systems and the results are compared with that of the experimental data. The crystallinity of the bulk composite is studied by X-ray diffraction studies. Scanning electron microscopic technique has been employed to study the dispersion of the particulate filler in PEEK matrix. Vickers hardness of pure and filled PEEK composite has been measured using Microhardness Tester. The effect of particle size on the dielectric as well as mechanical properties of SrTiO3/PEEK composite system is also studied by incorporating micronsize and nanosize fillers. Present study shows that a temperature stable composite can be realized by judiciously selecting appropriate filler concentration in the PEEK matrix.

Synthesis, characterization and analytical modelling of mechanical behavior of a conducting polymer actuator

Electrochemical synthesis of a tri-layer polypyrrole based actuator optimized for performance was reported. The 0.05 M pyrrole and 0.05 M tetrabutylammonium hexaflurophosphate in propylene carbonate (PC) yielded the optimum performance and stability. The force produced ranged from 0.2 to 0.4mN. Cyclic deflection tests on PC based actuators for 3 hours indicated that the displacement decreased by 60%. PC based actuator had a longer operating time, exceeding 3 hours, compared to acetonitrile based actuators. A triple-layer model of the polymer actuator was developed based on the classic bending beam theory by considering strain electrode material. A tri-layer actuator was fabricated [4, 6], by initially sputter coating a PVDF film with approximately 100nm of gold layer, resulting in a conductive film with a surface resistance of 8-10Ω. The PVDF film was about ~145µm thick had an approximate pore size of 45μm. A solution containing 0.05M distilled pyrrole monomer, 0.05M (TBAPF6) and 1% (w/w) distilled water in PC (propylene carbonate) solution was purged with nitrogen for 15 minutes. The continuity between PPy and PVDF. Results predicted by the model were in good agreement with the experimental data.

Synthesis and characterization of soluble conducting polymers

Although conducting polymers have various potential applications, lack of solubility is an impediment in their direct application to material surfaces. Synthesis of alkyl pyrrole monomers and subsequent polymerization into soluble conducting polymers are aimed as alternatives to conventional methods of application of conducting polymers on substrates. Alkyl chains are attached to a pyrrole ring to produce solubility in the resulting conducting polypyrroles, which allow direct application of conductive polymer emulsions to any desired surface. Friedel-Crafts acylation of the tosyl-protected pyrrole provides high yields of the 3-acylated product. The conductivity values of poly-3- and 3, 4-substituted pyrroles are generally less than the unmodified polypyrrole. Increasingly bulkier groups attached to the pyrrole means lower conductivity of the resultant polymer. As the carbon chain length attached to the 3-position of pyrrole increases, the solubility also increases. However, the magnitude of change in conductivity of films and pellets of soluble conducting polypyrroles over the alkyl range is not significant.

Identification and characterization of a new class of cognitive enhancers based on inhibition of insulin-regulated aminopeptidase

Approximately one-quarter of people over the age of 65 are estimated to suffer some form of cognitive impairment, underscoring the need for effective cognitive-enhancing agents. Insulin-regulated aminopeptidase (IRAP) is potentially an innovative target for the development of cognitive enhancers, as its peptide inhibitors exhibit memory-enhancing effects in both normal and memory-impaired rodents. Using a homology model of the catalytic domain of IRAP and virtual screening, we have identified a class of nonpeptide, small-molecule inhibitors of IRAP. Structure-based computational development of an initial "hit" resulted in the identification of two divergent families of compounds. Subsequent medicinal chemistry performed on the highest affinity compound produced inhibitors with nanomolar affinities (Ki 20–700 nM) for IRAP. In vivo efficacy of one of these inhibitors was demonstrated in rats with an acute dose (1 nmol in 1 µl) administered into the lateral ventricles, improving performance in both spatial working and recognition memory paradigms. We have identified a family of specific IRAP inhibitors that is biologically active which will be useful both in understanding the physiological role of IRAP and potentially in the development of clinically useful cognitive enhancers. Notably, this study also provides unequivocal proof of principal that inhibition of IRAP results in memory enhancement.

Microstructural characterization of the austenite behaviour during metadynamic recrystallization

The work discusses the recent findings obtained from the microstructural characterization of an austenitic Ni-30%Fe model alloy during metadynamic recrystallization (MDRX) using both EBSD and TEM techniques. The characterization of the grain structure, texture and dislocation substructure evolution of the fully dynamically recrystallized (DRX) microstructure during post deformation annealing revealed a novel softening mechanism occurring under the current experimental conditions. It is proposed that the initial softening stage involves rapid growth of the dynamically formed nuclei and migration of the mobile boundaries in correspondence with the well-established MDRX mechanism. However, the sub-boundaries within DRX grains progressively disintegrate through dislocation climb and dislocation annihilation, which ultimately leads to the formation of dislocation-free grains. Consequently, the DRX texture largely remains preserved throughout the annealing process.

Microstructural characterization and mechanical properties of Mg-Zr-Ca alloys prepared by hot-extrusion for biomedical applications

This paper investigated the microstructural characterization and mechanical properties of Mg-Zr-Ca alloys prepared by hot-extrusion for potential use in biomedical applications. Mg-Zr-Ca alloys were fabricated by commercial pure Mg (99.9%), Ca (99.9%), and master Mg-33% Zr alloy (mass%). The microstructural characterization of the hot-extruded Mg-Zr-Ca alloys was examined by X-ray diffraction analysis and optical microscopy, and the mechanical properties were determined from tensile tests. The experimental results indicate that the hot-extruded Mg-Zr-Ca alloys with 1 mass% Ca are composed of one single phase and those alloys with 2 mass% Ca consist of both Mg2Ca and α phase. The hot-extruded Mg-Zr-Ca alloys exhibit equiaxed granular microstructures and the hot-extrusion process can effectively increase both the tensile strength and ductility of Mg-Zr-Ca alloys. The hot-extruded Mg-1Zr-1Ca alloy (mass%) exhibits the highest strength and best ductility among all the alloys, and has much higher strength than the human bone, suggesting that it has a great potential to be a good candidate for biomedical application.

Novel characterization of monocyte-derived cell populations in the meninges and choroid plexus and their rates of replenishment in bone marrow chimeric mice

The mouse dura mater, pia mater, and choroid plexus contain resident macrophages and dendritic cells (DCs). These cells participate in immune surveillance, phagocytosis of cellular debris, uptake of antigens from the surrounding cerebrospinal fluid and immune regulation in many pathologic processes. We used Cx3cr1 knock-in, CD11c-eYFP transgenic and bone marrow chimeric mice to characterize the phenotype, density and replenishment rate of monocyte-derived cells in the meninges and choroid plexus and to assess the role of the chemokine receptor CX3CR1 on their number and tissue distribution. Iba-1 major histocompatibility complex (MHC) Class II CD169 CD68 macrophages and CD11c putative DCs were identified in meningeal and choroid plexus whole mounts. Comparison of homozygous and heterozygous Cx3cr1 mice did not reveal CX3CR1-dependancy on density, distribution or phenotype of monocyte-derived cells. In turnover studies, wild type lethally irradiated mice were reconstituted with Cx3cr1/-positive bone marrow and were analyzed at 3 days, 1, 2, 4 and 8 weeks after transplantation. There was a rapid replenishment of CX3CR1-positive cells in the dura mater (at 4 weeks) and the choroid plexus was fully reconstituted by 8 weeks. These data provide the foundation for future studies on the role of resident macrophages and DCs in conditions such as meningitis, autoimmune inflammatory disease and in therapies involving irradiation and hematopoietic or stem cell transplantation.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

Molecular dynamics approach to the structural characterization and transport properties of poly(acrylonitrile)/N,N-dimethylformamide solutions

Poly(acrylonitrile) (PAN) in N,N-dimethylformamide (DMF) is a popular solution for producing large variety of polymer products. To precisely describe the behaviours of PAN and DMF in the synthesis processes, it is significant to call for more details about the structure, some thermodynamic and dynamical properties of PAN-DMF solutions. A PAN-DMF solution was simulated via molecular dynamics with an all-atom OPLS type potential in both the NPT and NVT ensembles. The simulation results were evaluated with quantum mechanical calculations (MP2/6-311 ++G(d,p) and counterpoise procedure) and were compared with available experimental results. The liquid structure was illustrated with pair correlation functions and transport and dynamics properties were calculated with the mean-square displacements MSD and the velocity autocorrelation functions. The strong H-bonds of C≡N « H-C=O, CH » O=C-H and CH2 O=C-H, with distances of 2.55 Å, 2.55 Å and 2.65 Å, respectively, were found. The largest interaction energy of - 7.157 kcal/mol between DMF molecules and PAN molecules was found at 4.9 Å center-of-mass distance. A potential profile of intermolecular interaction of DMF with PAN along the interaction distance was presented, clearly showing an increase of DMF vaporisation heat when it getting close to PAN molecules. This provided very useful information to analyse the vaporisation behaviours of DMF at the microscopic level, which is essential to comprehensively understand molecular rearrangements towards the design of synthetic processes. The impact of the presence of the PAN on the DMF solution properties were also benchmarked with pure DMF solution.

Boron carbide reinforced aluminium matrix composite : physical, mechanical characterization and mathematical modelling

This paper investigates the manufacturing of aluminium-boron carbide composites using the stir casting method. Mechanical and physical properties tests to obtain hardness, ultimate tensile strength (UTS) and density are performed after solidification of specimens. The results show that hardness and tensile strength of aluminium based composite are higher than monolithic metal. Increasing the volume fraction of B4C, enhances the tensile strength and hardness of the composite; however over-loading of B4C caused particle agglomeration, rejection from molten metal and migration to slag. This phenomenon decreases the tensile strength and hardness of the aluminium based composite samples cast at 800 °C. For Al-15 vol% B4C samples, the ultimate tensile strength and Vickers hardness of the samples that were cast at 1000 °C, are the highest among all composites. To predict the mechanical properties of aluminium matrix composites, two key prediction modelling methods including Neural Network learned by Levenberg-Marquardt Algorithm (NN-LMA) and Thin Plate Spline (TPS) models are constructed based on experimental data. Although the results revealed that both mathematical models of mechanical properties of Al-B4C are reliable with a high level of accuracy, the TPS models predict the hardness and tensile strength values with less error compared to NN-LMA models.