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81.
    
Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C2H4)][BArF4] (n=12, 14, 16; ArF=3,5-(CF3)2C6H3)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH2)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C2H4)][BArF4] and solvent effects.  相似文献   
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The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling.  相似文献   
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The application of powders to fingerprints has long been established as an effective and reliable method for developing latent fingerprints. Fingerprints developed in situ at a crime scene routinely undergo lifting with specialist tapes and are then stored in evidence bags to allow secure transit and also to preserve the chain of evidence. In a previous study we have shown that exogenous material within a fingerprint can be detected using Raman spectroscopy following development with powders and lifting with adhesive tapes. Other reports have detailed the use of Raman spectroscopy to the detection of drugs of abuse in latent fingerprints including cyanoacrylate-fumed fingerprints. This study involves the application of Raman spectroscopy for the analysis of drugs of abuse in latent fingerprints for fingerprints that had been treated with powders and also subsequently lifted with adhesive tapes. Samples of seized ecstasy, cocaine, ketamine and amphetamine were supplied by East Sussex Police and by the TICTAC unit at St. Georges Hospital Tooting. Contaminated fingerprints were deposited on clean glass slides. The application of aluminium or iron based powders to contaminated fingerprints did not interfere with the Raman spectra obtained for the contaminants. Contaminated fingerprints developed with powders and then lifted with lifting tapes were also examined. The combination of these two techniques did not interfere with the successful analysis. The lifting process was repeated using hinge lifters. As the hinge lifters exhibited strong Raman bands the spectroscopic analysis was more complex and an increase in the number of exposures to the detector allowed for improved clarification. Spectral subtraction was performed to remove peaks due to the hinge lifters using OMNIC software. Raman spectra of developed and lifted fingerprints recorded through evidence bags were obtained and it was found that the detection process was not compromised. Although the application of powders did not interfere with the detection process the time taken to locate the contaminant was increased due to the physical presence of more material within the fingerprint.  相似文献   
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Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energy-dependent electrospray ionization mass spectrometry (EDESI-MS).  相似文献   
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Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4′-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)]n (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a “5+1” extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)]n neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses.  相似文献   
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C-Glycosides were successfully prepared via dehydrative alkylation under Mitsunobu conditions, using substituted sulfonyl methanes as nucleophiles. The materials prepared were converted to useful C-glycoside intermediates. An application of this approach toward the synthesis of C-glycolipids is presented.  相似文献   
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