Optically pumped nuclear magnetic resonance of semiconductors

Optically pumped NMR (OPNMR) of direct gap and indirect gap semiconductors has been an area of active research interest, motivated by both basic science and technological perspectives. Proposals to enhance and to spatially localize nuclear polarization have stimulated interest in this area. Recent progress in OPNMR has focused on exploring the experimental parameter space in order to elucidate details of the underlying photophysics of optical pumping phenomena. The focus of this review is on recent studies of bulk samples of GaAs and InP, namely, the photon energy dependence, the magnetic field dependence, and the phase dependence of OPNMR resonances. Models for the development of nuclear polarization are discussed.     

Order of Reactivity of OH/NH Groups of Glucosamine Hydrochloride and N-Acetyl Glucosamine Toward Benzylation Using NaH/BnBr in DMF

The order of reactivity of OH and NH groups of glucosamine hydrochloride (GlcNH₂^.HCl) and N-acetyl glucosamine (GlcNAc) toward benzylation with NaH/BnBr in DMF was investigated. For GlcNH₂^.HCl, benzyl groups were introduced in the order of N-Bn > N-Bn₂ > 1-O-Bn > 6-O-Bn > 4-O-Bn > 3-O-Bn; for GlcNAc, benzyl groups were introduced in the order of 1-O-Bn > 6-O-Bn > 4-O-Bn > 3-O-Bn > N-Bn. A range of partially benzylated 2-N,N′-dibenzyl glucopyranosides and GlcNAc derivatives were obtained in a single step.     

Structural basis for thrombin activation of a protease-activated receptor: inhibition of intramolecular liganding

Protease-activated G protein-coupled receptors (PAR1-4) are tethered-ligand receptors that are activated by proteolytic cleavage of the extracellular domain (exodomain) of the receptor. PAR1, the prototypic member of the PAR family, is the high-affinity thrombin receptor of platelets and vascular endothelium and plays a critical role in blood coagulation, thrombosis, and inflammation. Here, we describe the solution structure of the thrombin-cleaved exodomain of PAR1. The side chains of a hydrophobic hirudin-like (Hir) sequence and adjacent anionic motif project into solution. Docking of the exodomain Hir sequence to exosite I of thrombin reveals that the tethered ligand in the cleaved exodomain bends away from thrombin, leaving its active site available to another large macromolecular substrate. The N-terminal ligand is longer than anticipated and forms an intramolecular complex with a region located in the C terminus of the exodomain. Mutational analysis confirmed that this C-terminal region is a ligand binding site for both intra- and intermolecular ligands. A lipidated-ligand binding site peptide was found to be an effective inhibitor of thrombin-induced platelet aggregation.     

Synthetic and mechanistic studies of the retro-Claisen rearrangement. 4. An application to the total synthesis of (+)-Laurenyne

[formula: see text] A novel asymmetric total synthesis of marine natural product (+)-Laurenyne has been achieved. The key elements of the strategy are the sequential metal ion-templated SN2' cyclization affording a highly functionalized chiral vinyl cyclobutane and a retro-Claisen rearrangement for the construction of an eight-membered ring ether.     

Overview: The Potential of silanes for chromate replacement in metal finishing industries

Trialkoxysilanes (or silanes) have emerged as a very promising alternative for chromates in metal finishing industries. Compared to the conventional chromating processes, the major merits of silane-based surface treatments include: eco-compliance, easy-control processing, comparable corrosion protection of metals as well as paint adhesion to a variety of topcoats. In this overview paper, we report the recent status of silane studies including results of corrosion performance tests, the mechanism of corrosion protection of metals by silanes and the themal stabilities of silane films. We also address the new fields that we are beginning to explore such as nano-structured silane films, “self-healing” silane films, and “super-primers”.     

Studies on transannulation reactions across a nine-membered ring: the synthesis of natural product-like structures

A series of diverse natural product-like structures have been synthesised by the use of a number of novel transannulation reactions across a cyclononene ring. Transannular cyclisations through oxygen functionality have generated a number of bicyclo[5.3.1]systems containing bridged cyclic ethers and bicyclo[5.2.2]lactones, as well as a tetrahydrofuran-containing bridged analogue of hexacyclinic acid. An unprecedented Br?nsted acid mediated transannular cyclisation between proximal carbons generated bicyclo[4.3.0]nonanes which form the core of the pinguisane and austrodorane families of sesquiterpenoids. In all cases the key factor that determined the mode of reactivity was the conformation of the nine-membered ring and the distance between the reacting centres.     

Synthesis of glycopolymers via click reactions

This mini-review describes recent work in the field of glycopolymer synthesis, with a focus on methods that have employed “click chemistry” and controlled polymerization methodology. A variety of carbohydrates with clickable groups such as azide, alkyne, and thiol moieties provide new routes to glycopolymers. Several studies use copper catalyzed azide-alkyne cycloaddition (CuAAC) reactions to synthesize glycomonomers or to incorporate carbohydrates into a clickable polymeric backbone. Alternatively, there are many thiol based click reactions which provide metal-free synthesis, which are discussed in details.     

Kinetic Analysis of the Reactions between GG-Containing Oligonucleotides and Platinum Complexes. 1. Reactions of Single-Stranded Oligonucleotides with cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) and [Pt(NH(3))(3)(H(2)O)](2+)

Using concentration measurements based on high performance liquid chromatography, we have investigated the kinetics of reaction between single-stranded oligonucleotides containing a d(GpG) sequence, i.e., d(GG), d(TGG), d(TTGG), and d(CTGGCTCA), and the platinum complexes cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) (1) and [Pt(NH(3))(3)(H(2)O)](2+) (2). The rate constants for the substitution of one aqua ligand of platinum in 1 or 2 by each guanine of the oligonucleotides were individually measured, as well as, for 1, those for the subsequent conversion of the monoadducts to the diadduct. For the platination of d(GG) and d(TGG), the rate constants are similar for the 5'- and 3'-guanines. The longer oligonucleotides d(TTGG) and d(CTGGCTCA) are platinated slightly faster on the 5'-G than on the 3'-G. 2 shows a similar slight preference for the 5'-guanine, but it reacts by a factor of 4-10 more slowly than 1. For both complexes, the platination rate constants increase with increasing oligonucleotide length. Platination of the 5'-G by 1 is 1 order of magnitude faster on d(CTGGCTCA) than on d(GG). Concerning the chelation step giving the GG diadduct of 1, the longer the oligonucleotide, the larger is the ratio between the rates of the cyclization of the 3'- and 5'-monoadducts k(3)(')(c) and k(5)(')(c): k(3)(')(c)/k(5)(')(c) equals 1.4 for d(GG) and 3.3 for d(CTGGCTCA).