Fast, copper-free click chemistry: a convenient solid-phase approach to oligonucleotide conjugation

Solid-phase oligonucleotide conjugation by nitrile oxide-alkyne click cycloaddition chemistry has been successfully demonstrated; the reaction, compatible with all nucleobases, requires no metal catalyst and proceeds under physiological conditions.

Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports

A new method for catalyst deposition on the inner walls of capillary microreactors is proposed which allows exact control of the coating thickness, pore size of the support, metal particle size, and metal loading. The wall-coated microreactors have been tested in a selective hydrogenation reaction. Activity and selectivity reach values close to those obtained with a homogeneous Pd catalyst. The catalyst activity was stable for a period of 1000 h time-on-stream.

Phase-Transfer Catalysis in Segmented Flow in a Microchannel: Fluidic Control of Selectivity and Productivity

Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

Control of the thickness of mesoporous titania films for application in multiphase catalytic microreactors

A new method of sol-gel polymer template synthesis of mesoporous catalytic thin films has been proposed which allows controlling the chemical nature of the film, the porosity, thickness and loading with an active species. The mesoporous films with a long-order structure can be obtained in a narrow range of surfactant-to-metal precursor molar ratios from 0.006 to 0.009. The catalytic film thickness was varied from 300 to 1000 nm while providing a uniform catalyst distribution with a desired catalyst loading (1 wt. % Au nanoparticles) throughout the film. The films were characterized by TEM, SEM, ethanol adsorption and contact angle measurements. The calcination of the as-synthesized films at 573 K reduced Ti4+ sites to Ti3+. A 300 nm thick Au-containing film showed an initial TOF of 1.4 s(-1) and a selectivity towards unsaturated alcohols as high as 90% in the hydrogenation of citral. Thicker films demonstrated a high selectivity towards the saturated aldehyde (above 55%) and a lower intrinsic catalytic activity (initial TOF of 0.7-0.9 s(-1)) in the absence of internal diffusion limitations.

Green synthesis of biodiesel using ionic liquids

This paper is a hybrid starting with an overview and history of biodiesel synthesis and finishing with a description with some of our latest unpublished data. Initially, we examine "green" ways of obtaining biodiesel using ionic liquids, which can have an acidic or basic functionality, and can function both as a solvent and catalyst for the (trans)esterification reaction to obtain biodiesel. Both animal and vegetable resources can be utilized as a resource for (trans)esterification reactions depending on the geographical area. Biodiesel is of great interest because it enables motor vehicle transport using a renewable resource, while reducing the amount of carbon dioxide from fossil fuels being released into the environment.

The tip-sample water bridge and light emission from scanning tunnelling microscopy

The light emission spectrum from a scanning tunnelling microscope (LESTM) is investigated as a function of relative humidity and shown to provide a novel and sensitive means for probing the growth and properties of a water meniscus on the nanometre scale. An empirical model of the light emission process is formulated and applied successfully to replicate the decay in light intensity and spectral changes observed with increasing relative humidity. The modelling indicates a progressive water filling of the tip-sample junction with increasing humidity or, more pertinently, of the volume of the localized surface plasmons responsible for light emission; it also accounts for the effect of asymmetry in structuring of the water molecules with respect to the polarity of the applied bias. This is juxtaposed with the case of a non-polar liquid in the tip-sample nanocavity where no polarity dependence of the light emission is observed. In contrast to the discrete detection of the presence/absence of a water bridge in other scanning probe experiments through measurement of the feedback parameter for instrument control, LESTM offers a means of continuously monitoring the development of the water bridge with sub-nanometre sensitivity. The results are relevant to applications such as dip-pen nanolithography and electrochemical scanning probe microscopy.

Women in Ulster, 1600-1800

Some have entertained the belief that early modern Gaelic society conferred substantial rights on women. This could hardly be farther from the truth. In aristocratic Gaelic circles women were used ruthlessly as pawns in political alliances and other manoeuvres. The status of women at the lower levels of society also seems to have been low relative to men. While patriarchal relationships persisted after the Plantation of Ulster, they took new forms. Some women actually benefited in terms of property rights relative to men. Economic change in the eighteenth century, in particular the development of proto-industry, opened up opportunities for poorer women but it is notable that women did not feature at all in the public political sphere before 1800

The Reception of Byzantium in European Culture since 1500

Studies on the reception of the classical tradition are an indispensable part of classical studies. Understanding the importance of ancient civilization means also studying how it was used subsequently. This kind of approach is still relatively rare in the field of Byzantine Studies. This volume, which is the result of the range of interests in (mostly) non-English-speaking research communities, takes an important step to filling this gap by investigating the place and dimensions of ‘Byzantium after Byzantium’.
This collection of essays uses the idea of ‘reception-theory’ and expands it to show how European societies after Byzantium have responded to both the reality, and the idea of Byzantine Civilisation. The authors discuss various forms of Byzantine influence in the post-Byzantine world from architecture to literature to music to the place of Byzantium in modern political debates (e.g. in Russia). The intentional focus of the present volume is on those aspects of Byzantine reception less well-known to English-reading audiences, which accounts for the inclusion of Bulgarian, Czech, Polish and Russian perspectives. As a result this book shows that although so-called 'Byzantinism' is a pan-European phenomenon, it is made manifest in local/national versions.
The volume brings together specialists from various countries, mainly Byzantinists, whose works focus not only on Byzantine Studies (that is history, literature and culture of the Byzantine Empire), but also on the influence of Byzantine culture on the world after the Fall of Constantinople.

Micro-Raman and Spreading Resistance Analysis on Beveled Implanted Germanium for Layer Transfer Applications

Raman and spreading resistance profiling have been used to analyze defects in germanium caused by hydrogen and helium implants, of typical fluences used in layer transfer applications. Beveling has been used to facilitate probing beyond the laser penetration depth. Results of Raman mapping along the projection area reveal that after post-implant annealing at 400°C, some crystal damage remains, while at 600°C, the crystal damage has been repaired. Helium implants create acceptor states beyond the projected range, and for both hydrogen and helium, 1×1016 acceptors/cm2 remain after 600°C. These are thought to be vacancy-related point defect clusters.

On Entropy-Based Molecular Descriptors: Statistical Analysis of Real and Synthetic Chemical Structures

This paper presents an analysis of entropy-based molecular descriptors. Specifically, we use real chemical structures, as well as synthetic isomeric structures, and investigate properties of and among descriptors with respect to the used data set by a statistical analysis. Our numerical results provide evidence that synthetic chemical structures are notably different to real chemical structures and, hence, should not be used to investigate molecular descriptors. Instead, an analysis based on real chemical structures is favorable. Further, we find strong hints that molecular descriptors can be partitioned into distinct classes capturing complementary information.

Activation of Alkanes by Gold-Modified Lanthanum Oxide

Functionalization of alkanes is much sought after for the production of fine and bulk chemicals. In particular, the oxidative activation of alkanes and their conversion to ethene and propene has been studied extensively, owing to the use of these alkenes in polymerization reactions. The greater reactivity of the products in comparison with the reactants has proven a major issue in this reaction as this can result in overoxidation, producing CO and CO2 and, therefore, reducing the alkene yield. Herein, the first application of supported gold catalysts for the direct activation of C2+ aliphatic alkanes with oxygen to form alkenes is demonstrated. This catalyst is particularly notable as it is highly active, selective to propene and ethene, and stable on stream over a 48 h period. Maintaining cationic gold is thought to be critical for the stability and this catalyst design provides the possibility of applying gold-based catalysts over a much wider temperature range than has been reported.

TAP studies of CO oxidation over CuMnOX and Au/CuMnOX catalysts

The mechanism of CO oxidation reactions over undoped and gold-doped CuMnOX (Hopcalite) catalysts has been examined using a temporal analysis of products (TAP) reactor Gold doping has been found to increase the activity of the mixed oxide catalyst significantly however using consecutive pulsing TAP experiments the presence of gold was not found to affect the contribution of the Langmuir-Hinshelwood mechanism Conversely gold doping was found to promote the Mars van Krevelen mechanism Using CO and O-2 multi-pulse TAP experiments the gold was found to modify the catalyst surface such that it stores much more oxygen that is active for the CO oxidation The CO multi-pulse experiments indicated that two distinct types of active oxygen species were found to be involved in the CO oxidation One type was observed in a similar amount on both doped and undoped catalysts and was associated with mixed oxide while the second type was only found on the gold-doped catalyst and was therefore clearly associated with the presence of gold on the catalyst surface The latter was found to be much less active than the oxygen inherent to the oxide but was at a concentration of approximately 10 times larger leading to the enhanced activity observed on gold doping (C) 2010 Elsevier Inc All rights reserved

Remediation of phenol-contaminated water by adsorption using poly(methyl methacrylate) (PMMA)

Recently polymeric adsorbents have been emerging as highly effective alternatives to activated carbons for pollutant removal from industrial effluents. Poly(methyl methacrylate) (PMMA), polymerized using the atom transfer radical polymerization (ATRP) technique has been investigated for its feasibility to remove phenol from aqueous solution. Adsorption equilibrium and kinetic investigations were undertaken to evaluate the effect of contact time, initial concentration (10-90 mg/L), and temperature (25-55 degrees C). Phenol uptake was found to increase with increase in initial concentration and agitation time. The adsorption kinetics were found to follow the pseudo-second-order kinetic model. The intra-particle diffusion analysis indicated that film diffusion may be the rate controlling step in the removal process. Experimental equilibrium data were fitted to five different isotherm models namely Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Redlich-Peterson by non-linear least square regression and their goodness-of-fit evaluated in terms of mean relative error (MRE) and standard error of estimate (SEE). The adsorption equilibrium data were best represented by Freundlich and Redlich-Peterson isotherms. Thermodynamic parameters such as Delta G degrees and Delta H degrees indicated that the sorption process is exothermic and spontaneous in nature and that higher ambient temperature results in more favourable adsorption. (C) 2011 Elsevier B.V. All rights reserved.

Electrical, Thermal and Optical Diagnostics of an Atmospheric Plasma Jet System

Plasma diagnostics of atmospheric plasmas is a key tool in helping to understand processing performance issues. This paper presents an electrical, optical and thermographic imaging study of the PlasmaStream atmospheric plasma jet system. The system was found to exhibit three operating modes; one constricted/localized plasma and two extended volume plasmas. At low power and helium flows the plasma is localized at the electrodes and has the electrical properties of a corona/filamentary discharge with electrical chaotic temporal structure. With increasing discharge power and helium flow the plasma expands into the volume of the tube, becoming regular and homogeneous in appearance. Emission spectra show evidence of atomic oxygen, nitric oxide and the hydroxyl radical production. Plasma activated gas temperature deduced from the rotational temperature of nitrogen molecules was found to be of order of 400 K: whereas thermographic imaging of the quartz tube yielded surface temperatures between 319 and 347 K.