Sensitivity-enhanced IPAP-SOFAST-HMQC for fast-pulsing 2D NMR with reduced radiofrequency load

The SOFAST-HMQC experiment [P. Schanda, B. Brutscher, Very fast two-dimensional NMR spectroscopy for real-time investigation of dynamic events in proteins on the time scale of seconds, J. Am. Chem. Soc. 127 (2005) 8014-8015] allows recording two-dimensional correlation spectra of macromolecules such as proteins in only a few seconds acquisition time. To achieve the highest possible sensitivity, SOFAST-HMQC experiments are preferably performed on high-field NMR spectrometers equipped with cryogenically cooled probes. The duty cycle of over 80% in fast-pulsing SOFAST-HMQC experiments, however, may cause problems when using a cryogenic probe. Here we introduce SE-IPAP-SOFAST-HMQC, a new pulse sequence that provides comparable sensitivity to standard SOFAST-HMQC, while avoiding heteronuclear decoupling during (1)H detection, and thus significantly reducing the radiofrequency load of the probe during the experiment. The experiment is also attractive for fast and sensitive measurement of heteronuclear one-bond spin coupling constants.     

N—甲基异靛蓝在不同溶剂中的^1H—NMR研究

用选择照射方法研究了N-甲基异靛蓝(isoindigatin)在(CD_3)_2CO、CDCl_3、DMSO-d_6溶剂中及重水交换后的~1H NMR谱。得到了化学环境极为类似的两芳环质子在不同溶剂中的NMR谱线归属和偶合常数。     

The role of co-adsorbed O2 on the catalytic reduction of NO with C2H5OH on the surface of Pt(3 3 2)

The influence of pre-dosed O₂ on the catalytic reduction of NO with ¹³C₂H₅OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of ¹³C₂H₅OH with O₂ is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of ¹³C₂H₅OH irrespective of the annealing temperature. For the case of O₂ + ¹³C₂H₅OH + NO co-adlayers, oxidation of ¹³C₂H₅OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N₂ are detected.The influence of O₂ on the production and desorption of N₂ is intimately related to both O₂ and ¹³C₂H₅OH coverage. The presence of pre-dosed O₂ does not greatly promote N₂ desorption. In fact, N₂ desorption is suppressed quantitatively with increasing O₂ coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O₂ does not play a role of activating reactants in the catalytic reduction of NO with ¹³C₂H₅OH on the surface of Pt(3 3 2).     

Minimum energy pulse synthesis via the inverse scattering transform

This paper considers a variety of problems in the design of selective RF-pulses. We apply a formula of Zakharov and Manakov to directly relate the energy of an RF-envelope to the magnetization profile and certain auxiliary parameters used in the inverse scattering transform (IST) approach to RF-pulse synthesis. This allows a determination of the minimum possible energy for a given magnetization profile. We give an algorithm to construct both the minimum energy RF-envelope as well as any other envelope that produces a given magnetization profile. This includes an algorithm for solving the Gel'fand-Levitan-Marchenko equations with bound states. The SLR method is analyzed in terms of traditional scattering data, and shown to be a special (singular) case of the IST approach. RF-envelopes are computed for a variety of examples.     

电子转移速率理论研究：运动谱窄化所导致的非马尔可夫电子转移过程

严格的速率方程理论得到的总是非马尔可夫的，可是大部分实验都可以用马尔可夫的、即传统的速率常数基础上的反应动力学方程来描述．针对这一问题研究了电子转移过程中的马尔可夫/非马尔可夫特性．以最简单的两态电子转移反应为体系，以其在德拜溶剂中的严格动力学解为标定，采用光谱领域著名的Kubo运动谱窄化线型函数及其特性参数来描述电子转移过程中的马尔可夫/非马尔可夫本质．该马尔可夫特性参数是相干转移耦合与溶剂环境涨落相互影响共同作用的结果，以它为基础说明了大部分实验确实可以通过传统的速率方程来描述，而非马尔可夫速率过程最     

原子-腔-光纤复合系统中的纠缠特性

采用Negativity熵来描述两子系统间的纠缠,研究了由两个二能级原子与光纤联接的单模腔构成的系统的纠缠特性.利用数值计算方法讨论了原子与腔场的耦合强度和原子选择性测量对纠缠特性的影响.研究结果表明:对一个原子的选择性测量,可增强原子间与腔场间和腔场与腔场间的纠缠.     

Densification behavior of gas and water atomized 316L stainless steel powder during selective laser melting

The densification during selective laser melting (SLM) process is an important factor determining the final application of SLM-part. In the present work, the densifications under different processing conditions were investigated and the densification mechanisms were elucidated. It was found that the higher laser power, lower scan speed, narrower hatch spacing and thinner layer thickness could enable a much smoother melting surface and consequently a higher densification.The gas atomized powder possessed better densification than water atomized powder, due to the lower oxygen content and higher packing density of gas atomized powder. A large number of regular-shaped pores can be generated at a wider hatch spacing, even if the scanning track is continuous and wetted very well. The densification mechanisms were addressed and the methods for building dense metal parts were also proposed as follows: inhibiting the balling phenomenon, increasing the overlap ratio of scanning tracks and reducing the micro-cracks.     

Fabrication of BDD quantum node switches on embedded GaAs quantum wires grown by selective MBE

In view of applications to hexagonal binary decision diagram (BDD) LSIs, a first attempt is made to form quantum BDD node switches on selectively grown (SG) embedded quantum wires (QWRs) by molecular beam epitaxy (MBE). SG branch switches controlled by a Schottky wrap gate (WPG) were successfully fabricated by MBE growth and subsequent device processing. Gate control characteristics were studied by gate-dependent Shubnikov–de-Haas measurements, and the behavior was found to be similar to that of devices fabricated on wires by etching. The switch exhibited clear conductance quantization at low temperature, and temperature dependence of the voltage slope of conductance jump was clarified. A Y-branch BDD node device using two SG branch switches was successfully fabricated, and realized clear path switching characteristics.     

Off-resonance frequency filtered magnetic resonance imaging

One of the main problems with rapid magnetic resonance imaging (MRI) techniques is the artifacts that result from off-resonance effects. The proposed off-resonance frequency filtered MRI (OFF-MRI) method focuses on the elimination of off-resonance components from the image of the observed object. To maintain imaging speed and simultaneously achieve good frequency selectivity, MRI is divided into two steps: signal acquisition and post-processing.     

Kinetics of Alkaline Hydrolysis of Quaternary Phosphonium Salts. The Influence of Protic and Aprotic Solvents on the Hydrolysis of Alkyl Phenylphosphonium Salts

Abstract

Third order rate constants have been determined for the alkaline hydrolysis of four series of alkylphenylphosphonium salts and alkylphenylbenzylphosphonium salts at various temperatures in 50%–70% ^v/_v aqueous tetrahydrofuran and 70% ^v/_v aqueous methanol. Thermodynamic activation parameters have been calculated for the reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as revealed by trends in entropy of activation, plays a largely counter-balancing role with respect to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation parameters actually reverse.