Nickel‐Catalyzed Cross‐Coupling of Redox‐Active Esters with Boronic Acids

A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross‐coupling between alkyl‐carboxylic acids and boronic acids is described. This Ni‐catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox‐active ester derivatives, specifically N‐hydroxy‐tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl₂?6 H₂O—$9.5 mol^?1, Et₃N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption.     

Protein-nanoparticle labelling probed by surface enhanced resonance Raman spectroscopy

A benzotriazole dye has been attached to a heme protein via a Michael addition and the unique potential of surface enhanced resonance Raman scattering (SERRS) to provide informative in situ recognition of more than one label on one protein demonstrated.     

Investigation into the factors affecting accuracy of mass measurements on a time-of-flight mass spectrometer using Design of Experiment

The results of an investigation of the parameters which have the most significant effect on the accuracy of mass measurements on a quadrupole orthogonal acceleration time-of-flight mass spectrometer (q-oaToF) are reported. The influence of eight factors is investigated: ion abundances of reference and analyte compounds, mass difference between analyte and reference compounds, quality of calibration, number of reference acquisitions averaged and TDC (time-to-digital converter) settings (resolution, Np multiplier (number of pushes correction factor), minimum number of points, i.e. minimum acquisition width which defines a peak). To extract the maximum information from as few experiments as possible, a Design of Experiment approach was used. The data will be used as a basis for developing guidance on accurate mass measurement on q-oaToF instruments.     

Time correlations and the second entropy

The authors study the transport of mass and heat in simulations of a Lennard-Jones fluid and demonstrate the calculation of transport coefficients, and of both the first and second entropies. These entropies are calculated from time correlation functions, as are the transport coefficients. They discuss the role of the second entropy in providing a physical explanation for the link between dynamic fluctuations and response. They illustrate the physical significance of the various contributions to the second entropy and how they simplify in the case of relaxation by steady-state flow. Certain approximations proposed for the calculation of the first entropy, common in the literature, are shown to break down under certain circumstances, and they give an improved method of calculation. They pay particular attention to the coupling between variables of opposite time parity in the transport matrix, and show that in general this cannot be neglected.     

Quasi-Stationarity of Discrete-Time Markov Chains with Drift to Infinity

We consider a discrete-time Markov chain on the non-negative integers with drift to infinity and study the limiting behavior of the state probabilities conditioned on not having left state 0 for the last time. Using a transformation, we obtain a dual Markov chain with an absorbing state such that absorption occurs with probability 1. We prove that the state probabilities of the original chain conditioned on not having left state 0 for the last time are equal to the state probabilities of its dual conditioned on non-absorption. This allows us to establish the simultaneous existence, and then equivalence, of their limiting conditional distributions. Although a limiting conditional distribution for the dual chain is always a quasi-stationary distribution in the usual sense, a similar statement is not possible for the original chain.     

微波等离子体原子发射光谱法(MP-AES)测定地质样品中的常量和微量元素

建立了微波等离子体原子发射光谱法(MP-AES)测定地质样品中的常量和微量元素的方法,四酸(盐酸+硝酸+高氯酸+氢佛酸)消解样品,得出了使用4200 MP-AES仪分析地化认证参考物质中常规金属元素(Ag,Cu,Ni,Pb和Zn)的结果,测定样品结果的相对标准偏差落在±10%范围内,另外,IEC和FLIC模型可成功校正光谱干扰。MP-AES仪无需使用乙炔等危险气体,极大提高了实验室安全性并显著降低了运行成本。MP-AES仪已成功应用于地化样品的分析中,结果准确可靠。