Reaction of C-silylated alpha-diazophosphines as nucleophiles toward carbonyl compounds: a mechanistic study and application to the synthesis of alkynes and alpha-hydroxyphosphonamides

Diversely substituted alpha-hydroxyphosphonamides and alkynes have been efficiently synthesized through the reaction of C-silylated alpha-diazophosphines with different types of aldehydes (2 equiv) in a neutral medium under very mild conditions. The reaction with some chiral aldehydes is highly diastereoselective leading to phosphonamides as single diastereomers. The novel reaction is influenced by electronic and steric effects being precluded for aromatic aldehydes containing electron-releasing substituents on the phenyl ring and for bulky aliphatic aldehydes. The mechanistic studies of these processes, which are highly exothermic, provide evidence for a nucleophilic attack of the diazophosphine to the aldehyde leading to a betaine that rapidly rearranges to a diazomethylenephosphorane, which has been detected or captured in some instances. The diazomethylenephosphorane reacts with a second molecule of aldehyde according to a Wittig-type condensation, and the rate-determining step of the whole process is believed to be the decomposition of the resultant oxaphosphetane to afford the hydroxyphosphonamide and a diazocumulene. Finally, this intermediate loses molecular nitrogen giving a transient carbene that rapidly evolves toward the alkyne.     

Intervalley gap anomaly of two-dimensional electrons in silicon

We report here a systematic study of the energy gaps at the odd-integer quantum Hall states nu = 3 and 5 under tilted magnetic (B) fields in a high quality Si two-dimensional electron system. Out of the coincidence region, the valley splitting is independent of the in-plane fields. However, the nu = 3 valley gap differs by about a factor of 3 (Deltav approximately 0.4 vs 1.2 K) on different sides of the coincidence. More surprisingly, instead of reducing to zero, the energy gaps at nu = 3 and 5 rise rapidly when approaching the coincidence angles. We believe that such an anomaly is related to strong couplings of the nearly degenerate Landau levels.     

Soft nanotechnology with soft nanoparticles

The last decade of research in the physical sciences has seen a dramatic increase in the study of nanoscale materials. Today, "nanoscience" has emerged as a multidisciplinary effort, wherein obtaining a fundamental understanding of the optical, electrical, magnetic, and mechanical properties of nanostructures promises to deliver the next generation of functional materials for a wide range of applications. While this range of efforts is extremely broad, much of the work has focused on "hard" materials, such as Buckyballs, carbon nanotubes, metals, semiconductors, and organic or inorganic dielectrics. Meanwhile, the soft materials of current interest typically include conducting or emissive polymers for "plastic electronics" applications. Despite the continued interest in these established areas of nanoscience, new classes of soft nanomaterials are being developed from more traditional polymeric constructs. Specifically, nanostructured hydrogels are emerging as a promising group of materials for multiple biotechnology applications as the need for advanced materials in the post-genomic era grows. This review will present some of the recent advances in the marriage between water-swellable networks and nanoscience.     

Efficient mutation detection in MEN1 gene using a combination of single-strand conformation polymorphism (MDGA) and heteroduplex analysis

For facilitated genotypic analysis of multiple endocrine neoplasia type 1 (MEN1), a familial syndrome associated with tumors of the parathyroid and neuroendocrine tissues, we developed two screening methods, heteroduplex mutation assay (HMA) and mutation detection gel analysis (MDGA), both based on electrophoretic discrimination of polymerase chain reaction (PCR) products, to detect the mutations. Forty-three genomic DNA samples were used for the evaluation of these techniques. The whole coding region of MEN1 was PCR-amplified with fluorescent primers and then denatured/renatured before electrophoresis on an automated sequencer. 100% of the mutations were detected, subsequently confirmed and identified by sequencing. "Negative" samples were used to evaluate the specificity and reproducibility of the two techniques. The combination of the two methods allows high throughput cost-effective mutation screening which is less laborious than systematic sequencing of the whole coding region of MEN1. Together, these methods provide an efficient screen for MEN1 mutations.     

MECHANICAL BEHAVIORS OF POLYURETHANE-UREA ELASTOMERIC FIBERS UNDER STATIC STRETCHING DEFORMATION

The mechanical behaviors of polyether (ET) and polyester (ES) soft segment urethane-ureaelastomeric fibers constrained at different levels of elongation have been investigated by means ofdynamic mechanical tests and force-temperature measurements. The dynamjc mechanical re-sponse of the ET urethane-urea showed some difference from that of the ES as a function of exten-sion ratio. For force-temperature measuring the existence of a low temperature transition corre-sponding to the glass transition (T_(g's)) of the ester or ether soft segments, stress-softening tempera-ture (T_s) and initial melting temperature (T_(mh)) of hard segment crystallites was observed. The resultof cyclic testing of a constrained sample as a function of temperature indicated that the irreversibledecrease in stress implied a permanent change in sample microstructure.     

HSulf-2, an extracellular endoglucosamine-6-sulfatase, selectively mobilizes heparin-bound growth factors and chemokines: effects on VEGF, FGF-1, and SDF-1

Background  

Heparin/heparan sulfate (HS) proteoglycans are found in the extracellular matrix (ECM) and on the cell surface. A considerable body of evidence has established that heparin and heparan sulfate proteoglycans (HSPGs) interact with numerous protein ligands including fibroblast growth factors, vascular endothelial growth factor (VEGF), cytokines, and chemokines. These interactions are highly dependent upon the pattern of sulfation modifications within the glycosaminoglycan chains. We previously cloned a cDNA encoding a novel human endosulfatase, HSulf-2, which removes 6-O-sulfate groups on glucosamine from subregions of intact heparin. Here, we have employed both recombinant HSulf-2 and the native enzyme from conditioned medium of the MCF-7-breast carcinoma cell line. To determine whether HSulf-2 modulates the interactions between heparin-binding factors and heparin, we developed an ELISA, in which soluble factors were allowed to bind to immobilized heparin.     

Positivity preserving pointwise implicit schemes with application to turbulent compressible flat plate flow

A family of positivity preserving pointwise implicit schemes applicable to source term dominated problems is constructed, where the minimum order of spatial accuracy is one and the maximum is three. It is designed for achieving steady state numerical solutions and is constructed through the analysis of appropriate model problems, where the convective fluxes for the higher‐order members are prescribed by the Chakravarthy–Osher family of total variation diminishing (TVD) schemes. Multidimensionality is facilitated by operator splitting. Numerical experimentation confirms the stability, convergence, accuracy, positivity, and computational efficiency associated with the proposed schemes. These schemes are ideally suited to solving the low‐Reynolds number turbulent k–ϵ equations for which the positivity of k and ϵ and the presence of stiff source terms are critical issues. Hence, using a finite volume formulation of these schemes, the low‐Reynolds number Chien k–ϵ turbulence model is implemented for a flat plate geometry and a series of turbulent flow (steady state) computations are carried out to demonstrate the positivity, robustness, and reliability of the algorithm. The free‐stream and initial k and ϵ values are specified in a very simple manner. Algorithm convergence acceleration is achieved using Multigrid techniques. The k–ϵ model flow predictions are shown to be in agreement with empirical profiles. Copyright © 2001 John Wiley & Sons, Ltd.     

Electron spin coherence in Si

We discuss pulsed electron spin resonance measurements of electrons in Si and determine the spin coherence from the decay of the spin echo signals. Tightly bound donor electrons in isotopically enriched ²⁸Si are found to have exceptionally long spin coherence. Placing the donors near a surface or interface is found to decrease the spin coherence time, but it is still in the range of milliseconds. Unbound two-dimensional electrons have shorter coherence times of a few microseconds, though still long compared to the Zeeman frequency or the typical time to manipulate a spin with microwave pulses. Longer spin coherence is expected in two-dimensional systems patterned into quantum dots, but relatively small dots will be required. Data from dots with a lithographic size of 400 nm do not yet show longer spin coherence.     

JT-60U装置温度分布剖面不变性的实验研究

在一系列H模放电条件下，建立了一个旨在研究等离子体温度分布剖面不变性的数据库。介绍了数据库建立过程中要解决的关键问题和所用软件，对等离子体温度分布剖面不变性及芯部约束与边缘参数的关系进行了研究。