Carbon-13 Nuclear Magnetic Resonance Spectroscopy Study of the Glucose Stress of Human Lenses

The sorbitol theory in diabetic cataractogenesis was based on sorbitol accumulation under glucose stress. Sorbitol accumulation was examined by ¹³C nuclear magnetic resonance spectroscopy (NMR) for the first time in matched human lenses incubated in 5.5 mM and 35.5 mM C-1 ¹³C-enriched glucose up to 28 hours. The results showed that sorbitol and lactate in human tens can be detected at 35.5 mM, but not in 5.5 mM glucose solution. The glycolysis metabolic pathway of human lenses may be quite different from that of animals. The accumulation of metabolites can be traced and quantified by the intensities of ¹³C NMR peaks. Therefore, ¹³C NMR spectroscopy can be used as a valuable tool to investigate human lens carbohydrate metabolism non-interventionally.     

The polymerization of ethylene with a soluble titanium-aluminium complex

The reaction between biscyclopentadienyl titanium dichloride and aluminium alkyls and alkyl chlorides has been examined by ESR spectroscopy, and by the abilities of the various resulting complexes to initiate the polymerization of ethylene at 1 atm and ambient temperature. In general, it is concluded that the active initiating species is a Ti(IV) complex, and not the paramagnetic Ti(III) complexes. Accordingly, the development of an ESR spectrum is accompanied by a fall off in initiating efficiency, decrease in polymerization rate and increased molecular weight of the polymers produced. The reduction of Ti(IV) to Ti(III) during the polymerization accounts for the fall in rate with conversion; addition of an oxidizing agent (1:2-dichloroethane) to the polymerization converts Ti(III) to Ti(IV), as observed by the disappearance of the ESR signal, and increases the efficiency of the polymerization. Block copolymers of ethylene with propylene and butadiene have been prepared with this initiator; the efficiency in producing blocks has been used to study the decomposition of the active sites by a first order reduction process.     

Lack of glycosidase inhibition by,and isolation from xanthocercis zambesiaca (leguminosae) of, 4-O-(β-D-glucopyranosyl)-fagomine [1,2,5-trideoxy-4-O-(β-D-glucopyranosyl)-1,5-imino-D- arabino-hexitol], a novel glucoside of a polyhydroxylated piperidine alkaloid

A COSY spectrum has been used to determine the position of inter-residue linkage in 4-O-(β-D-glucopyranosyl) fagomine (1) an example of a new class of glycosides of polyhydroxylated piperidine alkaloids isolated from seed of the legume Xanthocercis zambesiaca. (Bak.) Dunn. Unlike a number of polyhydroxylated piperidines, neither the glucoside (1) nor free fagomine [1,2,5-trideoxy-1,5-imino-D- arabinohexitol] (3) showed any inhibitory activity towards glycosidase enzymes from a variety of sources.     

Micelle-to-vesicle transition of an iron-chelating microbial surfactant, marinobactin E

Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) techniques have been applied to study the self-assembly processes of a microbially produced siderophore, marinobactin E (ME). ME is one of a series of marinobactins A-E that facilitate Fe(III) acquisition by the source bacterium through coordination of Fe(III) by the marinobactin headgroup. ME is a six-amino-acid peptide amphiphile appended by palmitic acid (C16), and differs only in the nature of the fatty acid moiety from the other marinobactins. Apo-ME (uncoordinated ME) assembles to form micelles with an average diameter of 4.0 nm. Upon coordination of one equivalent of Fe(III), the mean micellar diameter of Fe(III)-ME shrinks to approximately 2.8 nm. However, in the presence of excess Fe(III), Fe(III)-ME undergoes a micelle-to-vesicle transition (MVT). At a small excess of Fe(III) over Fe(III)-ME (i.e., <1.2 Fe(III)/ME), a fraction of the Fe(III)-ME micelles rearrange into approximately 200 nm diameter unilamellar vesicles. At even greater Fe(III)/ME ratios (e.g., 2-3) multilamellar aggregates begin to emerge, consistent with either multilamellar vesicles or lamellar stacks. The MVT exhibited by ME may represent a unique mechanism by which marine bacteria may detect and sequester iron required for growth.     

Stereoselective synthesis of the α-glucosidase inhibitor nectrisine

The α-glucosidase inhibitor nectrisine was synthesised in 12 steps (31% overall yield) starting from d-serine. The three contiguous stereocentres of this iminosugar were introduced via a highly diastereoselective boron mediated glycolate aldol reaction.     

On the preparation of ortho-trifluoromethyl phenyl triflate

In contrast to an earlier report advocating a copper-mediated trifluoromethylation of ortho-iodophenyl triflate, ortho-trifluoromethyl phenyl triflate may be prepared simply by reacting the corresponding phenol with triflic anhydride in the presence of a nucleophilic catalyst and stoichiometric base.     

Palladium-catalyzed synthesis of tetrahydrofurans from gamma-hydroxy terminal alkenes: scope, limitations, and stereoselectivity

A new, stereoselective synthesis of substituted tetrahydrofurans via Pd-catalyzed reactions of aryl and vinyl bromides with gamma-hydroxy terminal alkenes is described. This transformation affords trans-2,5- and trans-2,3-disubstituted tetrahydrofurans with up to >20:1 dr. This methodology also provides access to bicyclic and spirocyclic tetrahydrofuran derivatives in good yield with 10-20:1 dr. The scope and limitations of these transformations are discussed in detail, as are the effect of substrate sterics and electronics on yield and stereoselectivity. A proposed mechanism of these transformations is presented along with a model that rationalizes the stereochemical outcome of the reactions.     

A coordinatively saturated sulfate encapsulated in a metal-organic framework functionalized with urea hydrogen-bonding groups

A functional coordination polymer decorated with urea hydrogen-bonding donor groups has been designed for optimal binding of sulfate; self-assembly of a tripodal tris-urea linker with Ag2SO4 resulted in the formation of a 1D metal-organic framework that encapsulates SO4(2-) anions via twelve complementary hydrogen bonds, which represents the highest coordination number observed for sulfate in a natural or synthetic host.     

Synthesis of 2-azaspiro[4.4]nonan-1-ones via phosphine-catalysed [3+2]-cycloadditions

The phosphine-catalyzed [3+2]-cycloaddition of the 2-methylene γ-lactams 4 and 5 and the acrylate 6 with the ylides derived from the ethyl ester, the amide or the chiral camphor sultam derivative of 2-butynoic acid (7a-c) give directly, or indirectly after reductive cyclization, spiro-heterocyclic products. The acid 32 underwent Curtius rearrangement and then acid hydrolysis to give two novel spiro-cyclic ketones, 41 and 42.     

Theoretical investigations of uranyl-ligand bonding: four- and five-coordinate uranyl cyanide, isocyanide, carbonyl, and hydroxide complexes

The coordination and bonding of equatorial hydroxide, carbonyl, cyanide (CN-), and isocyanide (NC-) ligands with uranyl dication, [UO2]2+, has been studied using density functional theory with relativistic effective core potentials. Good agreement is seen between experimental and calculated geometries of [UO2(OH)4]2-. Newly predicted ground-state structures of [UO2(OH)5]3-, [UO2(CO)4]2+, [UO2(CO)5]2+, [UO2(CN)4]2-, [UO2(CN)5]3-, [UO2(NC)4]2-, and [UO2(NC)5]3- are reported. Four-coordinate uranyl isocyanide complexes are the predicted gas-phase species while five-coordinate uranyl cyanide complexes are energetically favorable in aqueous solution. Small energy differences between cyanide and isocyanide complexes indicate the energetic feasibility of mixed cyanide and isocyanide complexes. A D2d uranyl tetrahydroxide is the dominant gas-phase and aqueous species, but formation of uranyl carbonyl complexes is seen to be exothermic in the gas-phase and endothermic in aqueous solution.