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121.
While there is a growing interest in harnessing synergistic effects of more than one metal in catalysis, relatively little is known beyond bimetallic systems. This report describes the straightforward access to an air‐stable Pd trimer and presents unambiguous reactivity data of its privileged capability to differentiate C?I over C?Br bonds in C?C bond formations (arylation and alkylation) of polyhalogenated arenes, which typical Pd0 and PdI‐PdI catalysts fail to deliver. Experimental and computational reactivity data, including the first location of a transition state for bond activation by the trimer, are presented, supporting direct trimer reactivity to be feasible.  相似文献   
122.
123.
Physisorption and chemisorption of hydrogen on solid-state materials are two fundamentally different interactions, both of which display advantages and drawbacks for hydrogen storage. It has been hypothesised that their combination by merging two classes of materials showing different sorption behaviour towards hydrogen in the same composite may synergistically combine their desirable properties. As representatives of such composites, palladium nanoparticles, nanoclusters, and single atoms have been encapsulated in a metal-organic framework matrix, embedded, or immobilised in its pores, respectively. In this minireview, we review advances on the understanding and potential applications of the combination of Pd with metal-organic framework matrices through the analysis of the nanocomposite materials’ interaction with hydrogen and sorption properties.  相似文献   
124.
Metabolite-sensing mRNAs, or "riboswitches," specifically interact with small ligands and direct expression of the genes involved in their metabolism. Riboswitches contain sensing "aptamer" modules, capable of ligand-induced structural changes, and downstream regions, harboring expression-controlling elements. We report the crystal structures of the add A-riboswitch and xpt G-riboswitch aptamer modules that distinguish between bound adenine and guanine with exquisite specificity and modulate expression of two different sets of genes. The riboswitches form tuning fork-like architectures, in which the prongs are held in parallel through hairpin loop interactions, and the internal bubble zippers up to form the purine binding pocket. The bound purines are held by hydrogen bonding interactions involving conserved nucleotides along their entire periphery. Recognition specificity is associated with Watson-Crick pairing of the encapsulated adenine and guanine ligands with uridine and cytosine, respectively.  相似文献   
125.
Phosphoproteomics, nowadays, represents a front line in functional proteomics as testified by the number of papers recently appearing in the literature. In an attempt to improve and simplify the methods so far suggested we have set up a simple isotope-coded approach to label and quantitate phospho-Ser/-Thr residues in protein mixtures. First of all, after appropriate oxidation of cysteine/cystine residues followed by tryptic hydrolysis, we have optimised and simplified the beta-elimination reaction to get the corresponding alkene moiety from the phosphate esters. This was achieved by (a) separating the elimination reaction from the addition reaction, (b) the use of Ba(OH)(2) as alkali reagent and (c) its further elimination by the simple addition of solid CO(2) to the peptide mixture. The Michael reaction was then performed, after the removal of BaCO(3) by centrifugation, by adding dithiothreitol (DTT) to the peptide mixture. Finally, the direct purification of the modified phosphopeptides was performed on a thiol-sepharose column. The availability of fully deuterated DTT, introducing a 6 Da difference with respect to the non-deuterated species, allows quantitation of the differential extent of signalling modification when analysed by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) and liquid chromatography/mass spectrometry. The entire procedure has been set up by using bovine alpha-casein, and resulted in the identification of all the phosphorylated tryptic peptides, including the tetraphosphorylated peptides, which escaped all previously reported procedures  相似文献   
126.
The surface-enhanced Raman scattering (SERS) spectra of Eriochrome Black T (EBT) and its Cu(II), Fe(III), Mn(II) and Pb(II) complexes were recorded using a hydroxylamine reduced silver colloid. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculation were performed at B3LYP/6-31G(d) level of theory for the EBT molecule and its Cu(EBT), Fe(EBT) and Mn(EBT) metal complexes. Differentiation between EBT complexes of Cu(II), Fe(III), Mn(II) and Pb(II) is shown by the SERS spectral features of each complex.  相似文献   
127.
A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved.  相似文献   
128.
Further investigation of the reaction of Ar*GaCl2 (Ar* = 2,4,6-t-Bu3C6H2) with Na[Mn(CO)5] resulted in the new compound, [Ga(Ar*){Mn(CO)5}2] 2 . The new indium compounds, [In(Ar*){Co(CO)4}2] 3 and [In(Ar*){Mn(CO)5}2] 4 , have been prepared by the treatment of Ar*InBr2 with Na[Co(CO)4] and Na[Mn(CO)5], respectively. The structure of 3 was established by single-crystal X-ray diffraction: space group P1 (No. 2), Z = 2, a = 8.625(1) Å, b = 10.557(2) Å, c = 17.55(2) Å, α = 88.43(1)°, β = 83.45(1)°, γ = 71.14(1)°. The X-ray crystal structure of [Ga{Mn(CO)5}3] is also reported: space group Pbca (No. 61), Z = 8, a = 12.83(3) Å, b = 11.753(2) Å, c = 29.662(6) Å, α = β = γ = 90°.  相似文献   
129.
Electron Transfer and Ion Pair Formation Single Crystal Structure of Bis(sodium 1,1′-biphenyl-2-thiolate-diglyme): An Intermediate in the Reductive Ring Opening of Dibenzothiophene On Na-metal reduction of dibenzothiophene, the five-membered sulfur ring opens to form a colorless 1,1′-biphenyl-2-thiolate sodium salt, which, according to its single-crystal structure determination, is a dimer containing a four-membered, twice diglyme-solvated ring (diglyme···Na?SR)2. Additional measurements provide the following information: cyclic voltammetry in aprotic MeCN solution shows one quasi-reversible electron transfer at E = ?2.58 V. The dibenzothiophene radical anion can be generated in aprotic THF solution at a K mirror and characterized by an 81-line ESR spectrum and its simulation. This blue species is also the first UV/VIS detectable one before the solution changes via green (due to blue + yellow color mixing) to yellow, yielding across an isosbestic point a second and diamagnetic compound. All of the above results suggest a consecutive two-electron reduction followed by an intersystem protonation, M + (e?) → M.? (blue) + (e?) → (M??, yellow?) + (H) → MH? (colorless), to yield the crystallized and structurally characterized reaction intermediate. The diglyme-solvated sodium-salt dimer provides a basis for a quantum-chemical discussion of some facets of the most likely microscopic reduction pathway.  相似文献   
130.
Oximation of ortho-substituted phenylbenz[a]acridinones using hydroxylamine hydrochloride, sodium hydroxide and ethanol as the solvent gave always the benzoquinacridine N-oxide 2 . Oximation of para-substituted phenylbenz[a]acridinones, however, gave only the corresponding oximes. The structure of all products was corroborated by ir, 1H and 13C-nmr and mass spectral data. Theoretical calculations support the experimental findings.  相似文献   
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