Chemo-enzymatic synthesis of unnatural amino acids

A general chemo-enzymatic process has been developed to prepare enantiomerically pure L- and D-amino acids in high yield by deracemisation of racemic starting materials. The method has been developed from initial academic studies to be a robust, scalable industrial process. Unnatural amino acids, in high optical purity, are a rapidly growing class of intermediates required for pharmaceuticals, agrochemicals and other fine chemical applications. However, no single method has proven sufficiently adaptable to prepare these compounds generally at large scale. Our approach uses an enantioselective oxidase biocatalyst and a non-selective chemical reducing agent to effect the stereoinversion of one enantiomer and can result in an enantiomeric excess of > 99 % from a starting racemate, and product yields over 90 %. The current approach compares very favourably to resolution methods which have a maximum single pass yield of 50 %. Efficient methods have been developed to adapt the biocatalyst used in this process towards new target compounds and to optimise key factors which improve the process efficiency and offer competitive economics at scale.

Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.

Effects of four different single exercise sessions on lipids, lipoproteins, and lipoprotein lipase

The purpose of this study was to determine the threshold of exercise energy expenditure necessary to change blood lipid and lipoprotein concentrations and lipoprotein lipase activity (LPLA) in healthy, trained men. On different days, 11 men (age, 26.7 +/- 6.1 yr; body fat, 11.0 +/- 1.5%) completed four separate, randomly assigned, submaximal treadmill sessions at 70% maximal O-2 consumption. During each session 800, 1,100, 1,300, or 1,500 kcal were expended. Compared with immediately before exercise, high-density lipoprotein cholesterol (HDL-C) concentration was significantly elevated 24 h after exercise (P < 0.05) in the 1,100-, 1,300-, and 1,500-kcal sessions. HDL-C concentration was also elevated (P < 0.05) immediately after and 48 h after exercise in the 1,500-kcal session. Compared with values 24 h before exercise, LPLA. was significantly greater (P < 0.05) 24 h after exercise in the 1,100-, 1,300-, and 1,500-kcal sessions and remained elevated 48 h after exercise in the 1,500-kcal session. These data indicate that, in healthy, trained men, 1,100 kcal of energy expenditure are necessary to elicit increased HDL-C concentrations. These HDL-C changes coincided with increased LPLA.

GATA3 : a promising marker for metastatic breast carcinoma in serous effusion specimens

Background The utility of GATA3 as a marker for metastatic breast carcinoma in serous effusion specimens was investigated. Methods Cell block sections from 74 serous effusion specimens (32 ascitic, 2 pericardial and 40 pleural fluids) were stained with an anti-GATA3 murine monoclonal antibody. The specimens included 62 confirmed metastatic carcinomas from breast (30), female genital tract (13), gastrointestinal tract (7), lung adenocarcinoma (9), pancreas (1), kidney (1) and bladder (1). The breast carcinoma cases included 15 ductal carcinomas, 8 lobular carcinomas and in 7 the histology sub-type was not available. Twelve cases containing florid reactive mesothelial cells were also stained. The breast carcinoma cases were also stained for mammaglobin and GCDFP-15 to compare sensitivity with GATA3. Results Positive nuclear staining for GATA3 was present in 90% (27/30) of metastatic breast carcinoma specimens. All non-breast metastatic carcinomas tested were negative with the exception of the single case of metastatic urothelial carcinoma. No staining was observed in any of the benign reactive cases or in benign mesothelial cells present in the malignant cell block preparations. Two cases showed weak positivity of benign lymphoid cells. Staining results were unambiguous as all positive cases showed intense nuclear staining in >50% of tumor cells. Mammaglobin (57%; 17/30) and GCDFP-15 (33%; 10/30) were less sensitive markers of breast carcinoma. If used in a panel, mammaglobin and GCFP-15 staining would have identified only one additional case to those stained with GATA3. Conclusions GATA3 may be a useful addition to immunostaining panels for serous effusion specimens when metastatic breast carcinoma is a consideration.

Enhanced coloration efficiency for electrochromic devices based on anodized N2O5 / Electrodeposited MoO3 Binary Systems

There is a continuous quest for developing electrochromic (EC)transition metal oxides (TMOs) with increased coloration efficiency. As emerging TMOs, Nb2O5 films, even those of ordered anodized nanochannels, have failed to produce the required EC performance for practical applications. This is attributed to limitations presented by its relatively wide bandgap and low capacity for accommodating ions. To overcome such issues, MoO3 was electrodeposited onto Nb2O5 nanochannelled films as homogeneously conformal and stratified α-MoO3 coatings of different thickness. The EC performance of the resultant MoO3 coated Nb2O5 binary system was evaluated. The system exhibited a coloration efficiency of 149.0 cm2 C−1, exceeding that of any previous reports on MoO3 and Nb2O5 individually or their compounds. The enhancement was ascribed to a combination of the reduced effective bandgap of the binary system, the increased intercalation probability from the layered α-MoO3 coating, and a high surface-tovolume ratio, while the Nb2O5 nanochannelled templates provided stability and low impurity pathways for charge transfer to occur.

Tunable “Nano-Shearing” : A physical mechanism to displace nonspecific cell adhesion during rare cell detection

We report a tunable alternating current electrohydrodynamic (ac-EHD) force which drives lateran fluid motion within a few nanometers of an electrode surface. Because the magnitude of this fluid shear force can be tuned externally (e.g., via the application of an ac electric field), it provides a new capability to physically displace weakly (nonspecifically) bound cellular analytes. To demonstrate the utility of the tunable nanoshearing phenomenon, we present data on purpose-built microfluidic devices that employ ac-EHD force to remove nonspecific adsorption of molecular and cellular species. Here, we show that an ac-EHD device containing asymmetric planar and microtip electrode pairs resulted in a 4-fold reduction in nonspecific adsorption of blood cells and also captured breast cancer cells in blood, with high efficiency (approximately 87%) and specificity. We therefore feel that this new capability of externally tuning and manipulating fluid flow could have wide applications as an innovative approach to enhance the specific capture of rare cells such as cancer cells in blood.

Hydrodynamic theory of liquid slippage on a solid substrate near a moving contact line

In this Letter a hydrodynamic theory of liquid slippage on a solid substrate near a moving contact line is proposed. A family of spatially varying slip lengths in the Navier slip law recovers the results of past formulations for slip in continuum theories and molecular dynamics simulations and is consistent with well-established experimental observations of complete wetting. This formulation gives a general approach for continuum hydrodynamic theories. New fluid flow behaviors are also predicted yet to be seen in experiment. © 2013 American Physical Society.

Electromagnetic propulsion and separation by chirality of nanoparticles in liquids

We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope. © 2012 American Physical Society.

Reduction of amplitude equations by the renormalization group approach

This article elucidates and analyzes the fundamental underlying structure of the renormalization group (RG) approach as it applies to the solution of any differential equation involving multiple scales. The amplitude equation derived through the elimination of secular terms arising from a naive perturbation expansion of the solution to these equations by the RG approach is reduced to an algebraic equation which is expressed in terms of the Thiele semi-invariants or cumulants of the eliminant sequence { Zi } i=1 . Its use is illustrated through the solution of both linear and nonlinear perturbation problems and certain results from the literature are recovered as special cases. The fundamental structure that emerges from the application of the RG approach is not the amplitude equation but the aforementioned algebraic equation. © 2008 The American Physical Society.

Secular series and renormalization group for amplitude equations

We have developed a technique that circumvents the process of elimination of secular terms and reproduces the uniformly valid approximations, amplitude equations, and first integrals. The technique is based on a rearrangement of secular terms and their grouping into the secular series that multiplies the constants of the asymptotic expansion. We illustrate the technique by deriving amplitude equations for standard nonlinear oscillator and boundary-layer problems. © 2008 The American Physical Society.

Nanoherding : plasma-chemical synthesis and electric-charge-driven self organization of SiO2 nanodots

We report on the chemical synthesis of the arrays of silicon oxide nanodots and their self-organization on the surface via physical processes triggered by surface charges. The method based on chemically active oxygen plasma leads to the rearrangement of nanostructures and eventually to the formation of groups of nanodots. This behavior is explained in terms of the effect of electric field on the kinetics of surface processes. The direct measurements of the electric charges on the surface demonstrate that the charge correlates with the density and arrangement of nanodots within the array. Extensive numerical simulations support the proposed mechanism and prove a critical role of the electric charges in the self-organization. This simple and environment-friendly self-guided process could be used in the chemical synthesis of large arrays of nanodots on semiconducting surfaces for a variety of applications in catalysis, energy conversion and storage, photochemistry, environmental and biosensing, and several others.

Size- and orientation-selective Si nanowire growth : thermokinetic effects of naeoscale plasma chemistry

A multiscale, multiphase thermokinetic model is used to show the effective control of the growth orientation of thin Si NWs for nanoelectronic devices enabled by nanoscale plasma chemistry. It is shown that very thin Si NWs with [110] growth direction can nucleate at much lower process temperatures and pressures compared to thermal chemical vapor deposition where [111]-directed Si NWs are predominantly grown. These findings explain a host of experimental results and offer the possibility of energy- and matter-efficient, size- and orientation-controlled growth of [110] Si NWs for next-generation nanodevices.

Silica nanoparticles treated by cold atmospheric-pressure plasmas improve the dielectric performance of organic–inorganic nanocomposites

We report on the application of cold atmospheric-pressure plasmas to modify silica nanoparticles to enhance their compatibility with polymer matrices. Thermally nonequilibrium atmospheric-pressure plasma is generated by a high-voltage radio frequency power source operated in the capacitively coupled mode with helium as the working gas. Compared to the pure polymer and the polymer nanocomposites with untreated SiO2, the plasma-treated SiO2–polymer nanocomposites show higher dielectric breakdown strength and extended endurance under a constant electrical stress. These improvements are attributed to the stronger interactions between the SiO2 nanoparticles and the surrounding polymer matrix after the plasma treatment. Our method is generic and can be used in the production of high-performance organic–inorganic functional nanocomposites.

Copper-capped carbon nanocones on silicon : plasma-enabled growth control

Controlled self-organized growth of vertically aligned carbon nanocone arrays in a radio frequency inductively coupled plasma-based process is studied. The experiments have demonstrated that the gaps between the nanocones, density of the nanocone array, and the shape of the nanocones can be effectively controlled by the process parameters such as gas composition (hydrogen content) and electrical bias applied to the substrate. Optical measurements have demonstrated lower reflectance of the nanocone array as compared with a bare Si wafer, thus evidencing their potential for the use in optical devices. The nanocone formation mechanism is explained in terms of redistribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array and passivation of carbon in narrow gaps where the access of plasma ions is hindered. Extensive numerical simulations were used to support the proposed growth mechanism.

Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.