A modular design of ruthenium(II) catalysts with chiral C2-symmetric phosphinite ligands for effective asymmetric transfer hydrogenation of aromatic ketones

Hydrogen-transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. The new chiral C₂-symmetric ligands N,N′-bis-[(1S)-1-sec-butyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 1 and N,N′-bis-[(1S)-1-phenyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 2 and the corresponding ruthenium complexes 3 and 4 have been prepared and their structures have been elucidated by a combination of multi-nuclear NMR spectroscopy, IR spectroscopy, and elemental analysis. ¹H–³¹P NMR, DEPT, ¹H–¹³C HETCOR, or ¹H–¹H COSY correlation experiments were used to confirm the spectral assignments. The catalytic activity of complexes 3 and 4 in transfer hydrogenation of acetophenone derivatives by iso-PrOH has also been studied. Under optimized conditions, these chiral ruthenium complexes serve as catalyst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in iso-PrOH and act as excellent catalysts, giving the corresponding chiral alcohols in 99% yield and up to 75% ee. This transfer hydrogenation is characterized by low reversibility under these conditions.     

The AR-property for Roberts' example of a compact convex set with no extreme points Part 2: Application to the example

In this second part of our paper, we apply the result of Part 1 to show that the compact convex set with no extreme points, constructed by Roberts (1977), is an AR.

     

Ⅱ -Ⅳ族化合物半导体超微粒子光谱性质的研究Ⅱ : 硒化物、碲化物

本文报道了锌、镉、汞、铅硒化物、碲化物半导体超微粒子的制备以及它们的光谱性质 ,比较了它们的粗、细粒子的吸收光谱和荧光光谱的差异 ,以及与硫化物超微粒子的相似性 ,同时讨论了上述物质的超微粒子在老化过程中的行为及其原因.     

Interference effect of an upstream larger cylinder on the lock-in vibration of a flexibly mounted circular cylinder

Experiments have been carried out to investigate the flow-induced vibration response of a flexibly mounted circular cylinder located in the vicinity of a larger cylinder and subjected to cross-flow. The interfering larger cylinder was placed upstream and had a diameter twice that of the vibrating cylinder. Complex interaction was observed between the flow over the two cylinders. The vibration responses of the flexible cylinder were classified into different regimes according to the relative positions of the two cylinders. In the-side-by-side arrangement and the tandem or near-tandem arrangement, flow-induced vibrations of the flexible cylinder were greatly suppressed. In the staggered arrangement which covered a large portion of the relative cylinder positions being investigated, vibrations of the smaller cylinder were greatly amplified. The vibration response curves were also largely modified with a broadening of the lock-in resonance range. A shift of the peak reduced velocity for maximum vibration response was also found. Flow visualizations and wake velocity measurements suggested that the modifications of the vibration responses were related to the presence or absence of constant or intermittent flow through the gap region between the two cylinders. The proposed mechanisms of flow interactions and the resulting vibration response characteristics could explain previous observations on flow-induced vibrations of two equal-sized circular cylinders reported in the literature.     

Direct measurement of weak depletion force between two surfaces

In a mixture of colloidal particles and polymer molecules,the particles may experience an attractive"depletion force"if the size of the polymer molecule is larger than the interparticle separation.This is because individual polymer molecules experience less conformational entropy if they stay between the particles than they escape the inter-particle space, which results in an osmotic pressure imbalance inside and outside the gap and leads to interparticle attraction.This depletion force has been the subject of several studies since the 1980s,but the direct measurement of this force is still experimentally challenging as it requires the detection of energy variations of the order of k_BT and beyond.We present here our results for applying total internal reflection microscopy(TIRM) to directly measure the interaction between a free-moving particle and a flat surface in solutions consisting of small water-soluble organic molecules or polymeric surfactants.Our results indicate that stable nanobubbles(ca.150 nm) exist free in the above aqueous solutions.More importantly,the existence of such nanobubbles induces an attraction between the spherical particle and flat surface.Using TIRM,we are able to directly measure such weak interaction with a range up to 100 nm.Furthermore,we demonstrate that by employing thermo-sensitive microgel particles as a depleting agent,we are able to quantitatively measure and reversibly control k_BYT-scale depletion attraction as function of solution pH.     

On-chip multi-electrochemical sensor array platform for simultaneous screening of nitric oxide and peroxynitrite

In this work we report on the design, microfabrication and analytical performances of a new electrochemical sensor array (ESA) which allows for the first time the simultaneous amperometric detection of nitric oxide (NO) and peroxynitrite (ONOO(-)), two biologically relevant molecules. The on-chip device includes individually addressable sets of gold ultramicroelectrodes (UMEs) of 50 μm diameter, Ag/AgCl reference electrode and gold counter electrode. The electrodes are separated into two groups; each has one reference electrode, one counter electrode and 110 UMEs specifically tailored to detect a specific analyte. The ESA is incorporated on a custom interface with a cell culture well and spring contact pins that can be easily interconnected to an external multichannel potentiostat. Each UME of the network dedicated to the detection of NO is electrochemically modified by electrodepositing thin layers of poly(eugenol) and poly(phenol). The detection of NO is performed amperometrically at 0.8 V vs. Ag/AgCl in phosphate buffer solution (PBS, pH = 7.4) and other buffers adapted to biological cell culture, using a NO-donor. The network of UMEs dedicated to the detection of ONOO(-) is used without further chemical modification of the surface and the uncoated gold electrodes operate at -0.1 V vs. Ag/AgCl to detect the reduction of ONOOH in PBS. The selectivity issue of both sensors against major biologically relevant interfering analytes is examined. Simultaneous detection of NO and ONOO(-) in PBS is also achieved.     

The relationship between redox enzyme activity and electrochemical potential-cellular and mechanistic implications from protein film electrochemistry

In protein film electrochemistry a redox protein of interest is studied as an electroactive film adsorbed on an electrode surface. For redox enzymes this configuration allows quantification of the relationship between catalytic activity and electrochemical potential. Considered as a function of enzyme environment, i.e., pH, substrate concentration etc., the activity-potential relationship provides a fingerprint of activity unique to a given enzyme. Here we consider the nature of the activity-potential relationship in terms of both its cellular impact and its origin in the structure and catalytic mechanism of the enzyme. We propose that the activity-potential relationship of a redox enzyme is tuned to facilitate cellular function and highlight opportunities to test this hypothesis through computational, structural, biochemical and cellular studies.     

Determination of the debris produced from poly(ethylene terephthalate) during KrF excimer laser ablation

Pulsed UV laser beams, which are widely used in the processing of polymers, have many advantages because their photon energy is higher than the binding energy of polymers. Fabricating polymers with a UV laser process is faster, cleaner, and more convenient than with other processes. Nevertheless, some problems occur in the precision microprocessing of polymers. For example, the formation and deposition of surface debris, which is produced from the breakdown of either polymer chains or radical bonds.To determine the formation and origin of surface debris, a KrF excimer laser beam (248 nm) was used in the processing of poly(ethylene terephthalate) (PET). The investigation of the debris formation was facilitated by UV-vis spectroscopy, ATR FT-IR spectroscopy, and NMR spectroscopy. The UV-vis absorption peak indicates that the primary chromophore in the PET is benzoate. Furthermore, because benzoate causes the primary absorption, the absorbed energy is transferred by heat generation to an unsaturated ester. The ATR FT-IR spectrometer measurements show that the phenyl systems in the benzoate are demolished by ablation. This phenomenon indicates that the photochemical reaction causes the benzoate bonds to break down, and this breakdown in turn causes the carbonization to leave debris on the PET.