The preferred Cu(+) sites and formation of mono-, di-, and tricarbonyl complexes in the Cu-FER were investigated at the periodic density functional theory level and by means of FTIR spectroscopy. The site-specificity of adsorption enthalpies of CO on Cu-FER and of vibrational frequencies of polycarbonyl complexes were investigated for various Cu(+) sites in Cu-FER. Large changes in the Cu(+) interaction with the zeolite framework were observed upon the formation of carbonyl complexes. The dicarbonyl complexes formed on Cu(+) in the main channel or on the intersection of the main and perpendicular channels are stable and both, adsorption enthalpies and CO stretching frequencies are not site-specific. The fraction of Cu(+) ions in the FER cage, that cannot form dicarbonyl can be determined from IR spectra (about 7% for the Cu-FER with Si/Al = 27.5 investigated here). The tricarbonyl complexes can be formed at the Cu(+) ions located at the 8-member ring window at the intersection of main and perpendicular channel. The stability of tricarbonyl complexes is very low (DeltaH degrees (0 K)>or=-4 kJ mol(-1)). 相似文献
Intein-mediated protein splicing is a self-catalytic process in which the intervening intein sequence is removed from a precursor protein and the flanking extein segments are ligated with a native peptide bond. Splice junction proximal residues and internal residues within the intein direct these reactions. The identity of these residues varies in each intein, as groups of related residues populate conserved motifs. Although the basics of the four-step protein splicing pathway are known, mechanistic details are still unknown. Structural and kinetic analyses are beginning to shed some light. Several structures were reported for precursor proteins with mutations in catalytic residues, which stabilize the precursors for crystallographic study. Progress is being made despite limitations inherent in using mutated precursors. However, no uniform mechanism has emerged. Kinetic parameters were determined using conditional trans-splicing (splicing of split precursor fragments after intein reassembly). Several groups concluded that the rate of the initial acyl rearrangement step is rapid and Asn cyclization (step 3) is slow, suggesting that this latter step is rate limiting. Understanding the protein splicing pathway has allowed scientists to harness inteins for numerous applications. 相似文献
Bridged Ca 2+ ???CO???Ca 2+ complexes are formed on dual‐cation sites, constituted by a pair of nearby Ca2+ cations, when CO is adsorbed on zeolite Ca‐A. Two types of such species can be formed, designated S2–S1 and S1–S1 (see picture). Ca2+???CO monocarbonyl species are also identified, and at a relatively high CO equilibrium pressure, dicarbonyl complexes can also form.
A series of oligo(ethylene glycols) was efficiently tosylated by ultrasound procedure within dichloromethane in the presence of triethylamine. Results show that sonochemical synthesis of oligo(ethylene glycol) ditosylates has a double advantage since it does not use catalysts and it drastically reduces the reaction time. This straightforward method represents an eco-friendly alternative to the traditional tosylation by pyridine synthesis. 相似文献
In this work, we study the low-energy electronic spectrum of a graphene layer structure with a disclination in the presence
of a magnetic field. We make this study using the continuum approach, where we use the geometric theory of topological defects
to introduce a disclination in a graphene layer, and the electrons are described by the massless Dirac equation in this curved
background. The bound states energy spectrum and eigenfunctions are also obtained and an explicit dependence was found on
the parameter that characterizes the topological defect and on the magnetic field. 相似文献
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献