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91.
A crystallographic investigation of a series of host–guest complexes in which small-molecule organic guests occupy the central cavity of an approximately cubic M8L12 coordination cage has revealed some unexpected behaviour. Whilst some guests form 1:1 H⋅G complexes as we have seen before, an extensive family of bicyclic guests—including some substituted coumarins and various saturated analogues—form 1:2 H⋅G2 complexes in the solid state, despite the fact that solution titrations are consistent with 1:1 complex formation, and the combined volume of the pair of guests significantly exceeds the Rebek 55±9 % packing for optimal guest binding, with packing coefficients of up to 87 %. Re-examination of solution titration data for guest binding in two cases showed that, although conventional fluorescence titrations are consistent with 1:1 binding model, alternative forms of analysis—Job plot and an NMR titration—at higher concentrations do provide evidence for 1:2 H⋅G2 complex formation. The observation of guests binding in pairs in some cases opens new possibilities for altered reactivity of bound guests, and also highlights the recently articulated difficulties associated with determining stoichiometry of supramolecular complexes in solution.  相似文献   
92.
By transplanting identity elements into E. coli tRNAfMet, we have engineered an orthogonal initiator tRNA (itRNATy2) that is a substrate for Methanocaldococcus jannaschii TyrRS. We demonstrate that itRNATy2 can initiate translation in vivo with aromatic non‐canonical amino acids (ncAAs) bearing diverse sidechains. Although the initial system suffered from low yields, deleting redundant copies of tRNAfMet from the genome afforded an E. coli strain in which the efficiency of non‐canonical initiation equals elongation. With this improved system we produced a protein containing two distinct ncAAs at the first and second positions, an initial step towards producing completely unnatural polypeptides in vivo. This work provides a valuable tool to synthetic biology and demonstrates remarkable versatility of the E. coli translational machinery for initiation with ncAAs in vivo.  相似文献   
93.
A bifunctional iminophosphorane (BIMP)‐catalysed enantioselective synthesis of α,β‐unsaturated cyclohexenones through a facially selective 1,3‐prototropic shift of β,γ‐unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β‐Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings.  相似文献   
94.
Syntheses of a range of chemically well‐defined oligopyrrole/benzenoid hybrids are described using tandem Suzuki‐Miyaura cross‐coupling/bromo‐desilyation reaction sequences for linking borylated pyrroles, halogenated pyrroles and/or dibromobenzenes to one another. By such means, including iterative variants, a range of all α‐linked, all β‐linked oligopyrroles as well as certain combinations thereof have been assembled, some of them for the first time. The conductivities of iodine‐treated thin films formed from certain such systems have been determined.  相似文献   
95.
Finite difference modeling has been used to predict the results of gas transport experiments for a concentration-dependent diffusion coefficient. Experiments on the transport of CO2 in poly(ethylene terephthalate) and poly(ethylene naphthalate) had previously shown a difference between the effective diffusion coefficients for absorption and desorption runs of a double-sided experiment, but this effect had not been seen for single-sided experiments. The finite difference calculations show that such results are to be expected, and the parameters included in the models that attempt to describe the diffusion process in glassy polymers, such as the dual-mode model, and which lead to concentration-dependent diffusion coefficients, can be found by fitting the experimental data for the double-sided experiment using finite difference modeling. The dependence of the effective diffusion coefficient on pressure for the single-sided experiment can be correctly predicted using results from the double-sided experiment for an identical sample. © 1996 John Wiley & Sons, Inc.  相似文献   
96.
Recent progress in basic science and technological innovation is described for three areas of research in the IRC at Leeds University; melt spun high modulus polyethylene fibres, hydrostatic extrusion and die drawing.  相似文献   
97.
Guanidinium organosulfonates (GSs) are a large and well‐explored archetypal family of hydrogen‐bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4‐benzenedisulfonate ( p ‐G2BDS ). p ‐G2BDS is obtained from its acetone solvate, AcMe@ G2BDS , by single‐crystal‐to‐single‐crystal (SC‐SC) desolvation, and exhibits a Type I low‐temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g?1, 77 K). SC‐SC sorption of N2, CO2, Xe, and AcMe by p ‐G2BDS is explored under various conditions and X‐ray diffraction provides a measurement of the high‐pressure, room temperature Xe and CO2 sorption isotherms. Though p ‐G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np ‐G2BDS , a sample of p ‐G2BDS survived for almost two decades under ambient conditions. np ‐G2BDS reverts to zCO2@ p ‐G2BDS or yXe@ p ‐G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.  相似文献   
98.
In a recent paper [H.-E. Hwang, P. Han, Opt. Commun. 282 (2009) 351] a speckle based metrology system is proposed which it is claimed provides significant advantages over existing systems. In this paper, we show that the discussion presented in [H.-E. Hwang, P. Han, Opt. Commun. 282 (2009) 351] is deficient, and that several of the statements made are incorrect and/or misleading.  相似文献   
99.
100.
Ward S 《OR manager》2002,18(12):1, 12-1, 15
Employees and their work performance determine the success of any business. Permitting verbal abuse and other disruptive behaviors is bad management. Well-written policies, physician champions, strong executives, and the willingness of OR managers to try new approaches to assist the staff to develop new skill sets will help to create healthier workplaces where everyone knows words don't hurt.  相似文献   
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