Cobalt Boryl Complexes: Enabling and Exploiting Migratory Insertion in Base‐Metal‐Mediated Borylation

Cobalt boryl complexes, which have only been sporadically reported, can be accessed systematically with remarkable (but controllable) variation in the nature of the M? B bond. Complexes incorporating a very strong trans σ‐donor display unparalleled inertness, reflected in retention of the M? B bond even in the presence of extremely strong acid. By contrast, the use of the strong π‐acceptor CO in the trans position, results in significant Co? B elongation and to labilization of the boryl ligand via unprecedented CO migratory insertion. Such chemistry provides a pathway for the generation of coordinative unsaturation, thereby enabling ligand substitution and/or substrate assimilation. Alkene functionalization by boryl transfer, a well‐known reaction for noble metals such as Rh or Pt, can thus be effected by an 18‐electron base‐metal complex.     

Approximation of generalized Stokes problems using dual‐mixed finite elements without enrichment

In this work a finite element method for a dual‐mixed approximation of generalized Stokes problems in two or three space dimensions is studied. A variational formulation of the generalized Stokes problems is accomplished through the introduction of the pseudostress and the trace‐free velocity gradient as unknowns, yielding a twofold saddle point problem. The method avoids the explicit computation of the pressure, which can be recovered through a simple post‐processing technique. Compared with an existing approach for the same problem, the method presented here reduces the global number of degrees of freedom by up to one‐third in two space dimensions. The method presented here also represents a connection between existing dual‐mixed and pseudostress methods for Stokes problems. Existence, uniqueness, and error results for the generalized Stokes problems are given, and numerical experiments that illustrate the theoretical results are presented. Copyright © 2010 John Wiley & Sons, Ltd.     

Saturation Effects and the Colored Pump Noise in a Dye Laser

We investigate the statistical properties of two single-mode dye-laser models-the colored-loss-noise model and the colored-gain-noise model. Analytic expressions of the probability,the mean and the variance of the steady-state laser intensity are obtained through the unified expansion theory [Phys. Rev. A43 (1991) 700]. By comparison we find that when the cavity decay rate for the electric field is large and the pump parameter a₀ is small, the differences of the results of the two laser models are small. Otherwise, the differences are large. And the correlation time of the noise has very obvious influence on the results of the two models.     

Defining protease specificity with proteomics: a protease with a dibasic amino acid recognition motif is regulated by a two-component signal transduction system in Salmonella.

Microbial proteases play diverse and important roles in bacterial virulence but their detection and characterisation is often hampered by their limited abundance or lack of expression in the absence of suitable environmental signals. We describe here a sensitive proteomic approach to detect proteases that are under the control of a virulence regulator and to characterise their recognition motifs. Using MG++-depleted growth media or a mutant strain of Salmonella in which the PhoP-PhoQ virulence regulatory system is constitutively active, truncated forms of DnaK, elongation factor G, elongation factor Tu and ribosomal protein S1 proteins were detected. Two other global regulatory mutants and cells exposed to acid or to oxidative stress failed to produce the truncated proteins, indicating specific control of the protease activity by the PhoP-PhoQ system. Our results suggest that at least two proteases are induced. To define the proteolytic cleavage sites of one of the proteases, peptides from each of the truncated proteins were identified by tryptic mass fingerprinting/nanoelectrospray mass spectrometry and mapped onto the sequence of the intact protein. Alignment of the regions around the cut site indicates that the protease recognises a dibasic amino acid motif characteristic of the omptin protease family. The induction of such proteases in bacteria depleted of Mg++ ions may contribute to the PhoPQ-mediated resistance of Salmonella to cationic antimicrobial peptides. Additionally, our results suggest it would be prudent to keep the concentration of this ion above micromolar levels during bacterial sample preparation for proteomic analyses.     

Nanoscale dendritic organoplatinum antitumor drugs

Organoplatinum compounds exhibit broad antitumor activity. Cisplatin [cis- dichlorodiammine platinum (II)] is the most prominent of this family and is currently the most prescribed cancer drug. It is widely used for the treatment of human testicular, ovarian, bladder, head and neck carcinomas. However, it is an extremely toxic compound and side effects such as nephrotoxicity and myelotoxicity are major drawbacks for its use in clinical applications. A way to combat the side effects associated with the administration of platinum drugs would be to generate a prodrug conjugate that, when present in the extracellular fluid, would slowly release active platinum species at a level below the threshold for side effects. Traditionally, linear hydrophilic polymers have been examined for potential application as carrier platforms for these drugs. The advent of dendrimers, which are highly branched macromolecules with precisely controlled nanoscale size, shape and end-group functionality, has provided an excellent opportunity to design and formulate novel multivalent time-release drug systems. For example, treatment of a generation 4.5 (carboxylate surface) poly(amidoamine) [PAMAM] dendrimer with diaquo(1,2-diaminocyclohexane) platinum(II) generates a nanoparticle with forty platinum moieties attached at the surface. This polymer-drug conjugate displays a very good release profile for the platinum species. Under physiological conditions about 80% of the platinum units are released over the first 24 hours. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermodynamics of concentrated electrolyte mixtures. II. Densities and compressibilities of aqueous NaCl−CaCl2 at 25 °C

Densities and ultrasonic velocities of NaCl–CaCl₂ aqueous mixtures at 25 °C have been measured for the ionic strength range I=0.30–20.0. Where NaCl solubility permitted, both properties were measured over the range of compositions from pure NaCl to pure CaCl₂ at constant I. Apparent molar volumes and apparent molar compressibilities of the mixtures were calculated. The Pitzer form of the specific interaction theory is used to predict the properties of the binary mixtures from the properties of the single salt solutions. It provides a good fit over the full range of ionic strength for apparent molar volumes but a much inferior fit for compressibilities. It is also clear that in the high ionic strength range, explicit mixing parameters must be included for an excellent fit.     

网络上两类物资联合最大流问题的极流特征

当网络上(诸如交通网络、通讯网络)有多种不同物资或信息同时分别从相应的发点输送到相应的收点,要求每条线路上各类物资或信息的输送量总和不超过线路的容量时,寻求所有物资的最大输送量的问题,就是所谓网络多种物资的最大流问题,这个问题在生产实际和理论上都有着重要的意义,1963年T.C.Hu提出了求两类物资联合最大流的标号方法,但是为了保证有限步达到最大流,要求边的容量是偶数。 本文是文献[3]的继续,用图论的语言描述了两类物资最大流问题极流的特征,并对标号方法作了一点修改,使得有限步得到最大流,或者在某一步得到极流后,保证以后的迭代是从极流到极流.这样因极流的个数是有限的,并且最大流总可以在极流上达到,从而保证了有限步内得到所要求的最大流,无须对边的容量作任何限制, 本文所提的算法是使图形特征很强的标号算法和线性规划的极点迭代结合起来,这就使得有可能把这种方法,推广到更大的一类问题中,例如,研究容量的改变对最大流量的影响。