Enhancing regiocontrol in carboaluminations of terminal alkynes. Application to the one-pot synthesis of coenzyme Q10

Two new "generations" of methodological advances are reported for the Negishi carboalumination of terminal alkynes. Use of simple, inexpensive additives that alter the Al-Zr complex formed between Me(3)Al and Cp(2)ZrCl(2) give rise to an especially effective reagent mix that results in virtually complete control of regiochemistry upon carboalumination of 1-alkynes. One timely application to coenzyme Q10 is highlighted. Regioisomers from subsequent coupling, which would otherwise be very difficult to separate, are avoided.     

Analysis of tear glucose concentration with electrospray ionization mass spectrometry

We have developed a mass spectrometry-based method that allows one to accurately determine the glucose concentration of tear fluid. We used a 1 microL micro-capillary to collect tear fluid from the tear meniscus with minimal irritation of the eye. We analyzed the 1 muL volume of collected tear fluid with liquid-chromatography electrospray ionization mass spectrometry with the use of D-glucose-6,6-d2 as an internal standard. Repeated measurements and a recovery experiment on pooled, onion-induced tears showed that the analysis of the glucose in tears was precise (4% relative standard deviation) and provided 100% recovery. We found the tear glucose concentration of one fasting nondiabetic subject to be 13 to 51 microM while the onion-induced tear glucose concentration of a different nondiabetic subject to be 211 to 256 microM.     

Preparative separation of isomeric and stereoisomeric dicarboxylic acids by pH-zone-refining counter-current chromatography

This work involves the preparative separation of some isomeric dicarboxylic acids using pH-zone-refining counter-current chromatography (CCC), a relatively new preparative technique for the separation of ionizable compounds. The paper concentrates especially on the separation of a synthetic mixture of closely related cis and trans pairs of 1-methyl- and 1,3-dimethyl-1,3-cyclohexanedicarboxylic acids. The elution sequence of the isomers is discussed in terms of their relative acidities (pK(a) values) in solution and gas phase, hydrophobicities, and steric configuration. Two possible explanations are suggested for the mechanism of separation. They both involve the amount of retainer acid used, as it affects the separation and plays a role in the chemohydrodynamic equilibrium of the dicarboxylic acids in the column.     

A Photonic Crystal Protein Hydrogel Sensor for Candida albicans

We report two‐dimensional (2D) photonic crystal (PC) sensing materials that selectively detect Candida albicans (C. albicans). These sensors utilize Concanavalin A (Con A) protein hydrogels with a 2D PC embedded on the Con A protein hydrogel surface, that multivalently and selectively bind to mannan on the C. albicans cell surface to form crosslinks. The resulting crosslinks shrink the Con A protein hydrogel, reduce the 2D PC particle spacing, and blue‐shift the light diffracted from the PC. The diffraction shifts can be visually monitored, measured with a spectrometer, or determined from the Debye diffraction ring diameter. Our unoptimized hydrogel sensor has a detection limit of around 32 CFU/mL for C. albicans. This sensor distinguishes between C. albicans and those microbes devoid of cell‐surface mannan such as the gram‐negative bacterium E. coli. This sensor provides a proof‐of‐concept for utilizing recognition between lectins and microbial cell surface carbohydrates to detect microorganisms in aqueous environments.     

催化光度法测定痕量钒——钒(Ⅴ)-溴甲酚紫-过氧化氢体系

催化光度法测定钒已有报道[1～3],在0.45 mol·L-1磷酸介质及加热条件下,过氧化氢氧化溴甲酚紫褪色反应非常缓慢,而痕量钒对此反应具有较高的催化活性,且在一定浓度范围内,钒量与褪色反应程度呈线性关系,据此可建立测定痕量钒的方法.方法的检出限为1.9×10-6g·L-1,测定范围为0.003～1.8 mg·L-1.方法操作简便,重现性好,用于钢样中痕量钒的测定,结果满意.     

Regular and chaotic motion of coupled rotators

We consider a classical Hamiltonian H = L_z+M_z+L_xM_x, where the components of L and M satisfy Poisson brackets similar to those of angular momenta. There are three constants of motion: H, L² and M². By studying Poincaré surfaces of section, we find that the motion is regular when L² or M² is very small or very large. It is chaotic when both L² and M² have intermediate values. The interest of this model lies in its quantization, which involves finite matrices only.     

Low-energy proton-proton scattering

The discrepancies which have been reported in experimental data for low-energy proton-proton scattering can be partly explained by various relativistic, radiative and finite proton size effects.     

Neumark's theorem and quantum inseparability

The most efficient way of obtaining information about the state of a quantum system is not always a direct measurement. It is sometimes preferable to extend the original Hilbert space of states into a larger space, and then to perform a quantum measurement in the enlarged space. Such an extension is always possible, by virtue of Neumark's theorem. The physical interpretation usually given to that theorem is the introduction of an auxiliary quantum system, prepared in a standard state, and the execution of a quantum measurement on both systems together. However, this widespread interpretation is unacceptable, because the statistical properties of the supposedly standard auxiliary system are inseparably entangled with those of the original, unknown system. A different method of preparing the auxiliary system is proposed, and shown to be physically acceptable.Dedicated to John S. Bell, whose profound insight helped us to overcome deeply ingrained prejudices.