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Tryptophan residues in alpha-galactosidase from Trichoderma reesei.

Tryptophan residues in alpha-galactosidase were modified with bromosuccinimide. The fact that galactose, a specific inhibitor of alpha-galactosidase, does not prevent this modification demonstrates that tryptophan residues are not located in galactose binding sites. Analysis of the inactivation kinetics revealed two groups of Trp residues (8.5 and 7.5 residues) with different accessibility for N-bromosuccinimide. We studied specific quenching of alpha-galactosidase fluorescence resulting from modification of an sulfhydryl group in the active site of the enzyme with Hg2+ and Ag+ ions. The specific quenching is due to conformational changes of the enzyme. Forster's radii were determined for various protein--chromophore complexes. Dynamic quenching of alpha-galactosidase fluorescence was investigated. To describe abnormal dynamic quenching in alpha-galactosidase, a modification of the Stern--Volmer equation is suggested.

Bromosuccinimide↗

Measurement of biological thiols and disulfides by high-performance liquid chromatography and electrochemical detection of silver mercaptide formation.

A rapid and sensitive method is described for the measurement of picomole levels of the biological thiols glutathione, cysteine, penicillamine, cysteamine, and ergothioneine by a combination of high-performance liquid chromatography and electrochemical detection (ECD). The compounds were separated isocratically on a reversed-phase C18 column by ion-pair chromatography with a mobile phase containing 5 mM acetic acid and 2.5 mM sodium 1-octanesulfonate. After chromatographic separation, the eluate was combined with silver nitrate dissolved in ammonium nitrate buffer at pH 10.5. A platinum disc electrode was used at -0.1 V vs Ag/AgCl to detect the amount of silver ions that had been consumed by the reaction with thiols. For measurement of disulfide, S-sulfonation with sodium sulfite or electroreduction were used to cleave the disulfide, and the thiol anions produced were detected by HPLC-ECD as for the reduced forms. The method was used to assay thiols and disulfides in biological materials.

Adult↗

Occupational asthma caused by pyrazolone derivative used in silver halide photographic paper.

Occupational asthma has been documented in workers exposed to a wide variety of chemical compounds. Reactive dyes have been described as causing occupational asthma in textile industry workers. We report a case of occupational asthma resulting from exposure to pyrazolone dye used in silver halide photographic paper. There is a need for both further surveys of workers exposed to other reactive dyes and careful preventive measures in the handling of such compounds.

Anti-Inflammatory Agents, Non-Steroidal↗

Further structural and magnetic studies of tricopper dipyridylamido complexes.

The compound Cu3(dpa)4Cl2, 1 (dpa = the anion of dipyridylamine), which was first synthesized and characterized in 1990, has been structurally characterized in three new crystal forms having Cu...Cu separations of 2.47-2.49 A. Its magnetic properties have been studied fully. Reaction of Cu3(dpa)4Cl2 with 2 equiv of silver tetrafluoroborate yields Cu3(dpa)4(BF4)2 (2), a compound with a similar linear trinuclear structure but coordinated BF4 anions in each axial position and having shorter Cu...Cu distances of 2.40 A but similar magnetic properties. Least squares fitting of the magnetic susceptibility data for 1 and 2 gave isotropic g values of 2.007 and 2.130 and exchange parameters of -373 and -411 cm-1, respectively. This suggests the possible existence of an exchange pathway in which the metal atoms interact directly with each other.

Journal Article↗

A cell for in situ incident-light microscopy for the study of electrochromism of solid state electrochemical reactions.

A cell is described which allows in situ incident-light microscopy to be used for the analysis of solid state electrochemical reactions studied by abrasive stripping voltammetry. The cell provides the possibility to screen solid compounds with respect to their electrochromic properties without requiring the preparation of special electrodes on transparent and conducting materials. Silver octacyanomolybdate(IV) and silver octacyanotungstate(IV) have been used to study the performance of the cell because both compounds exhibit a stable electrochromic and voltammetric behaviour.

Journal Article↗

Templated synthesis of the novel layered silver-antimony sulfides [H3NCH2CH2NH2][Ag2SbS3 and [H3NCH2CH2NH2]2[Ag5Sb3S8].

Two new silver-antimony sulfides, [C(2)H(9)N(2)][Ag(2)SbS(3)] (1) and [C(2)H(9)N(2)](2)[Ag(5)Sb(3)S(8)] (2), have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. Compound 1 crystallizes in the space group Pn (a = 6.1781(1) A, b =11.9491(3) A, c = 6.9239(2) A, beta =111.164(1) degrees ) and 2 in the space group Pm (a = 6.2215(2) A, b = 15.7707(7) A, c = 11.6478(5) A, beta = 92.645(2) degrees ). The structure of 1 consists of chains of fused five-membered Ag(2)SbS(2) rings linked to form layers, between which the template molecules reside. Compound 2 contains honeycomb-like sheets of fused silver-antimony-sulfide six-membered rings linked to form double layers. The idealized structure can be considered to be an ordered defect derivative of that of lithium bismuthide, Li(3)Bi, and represents a new solid-state structure type.

Journal Article↗

Stereoselective synthesis of highly substituted Delta1-pyrrolines: exo-selective 1,3-dipolar cycloaddition reactions with azlactones.

We report herein a silver(I)-catalyzed exo-selective synthesis of highly substituted Delta1-pyrroline scaffolds from amino acid-derived münchnones. Silver acetate successfully catalyzed the cycloaddition reaction of azlactones with alkenes, generating Delta1-pyrrolines in very good yields without isomerization to the Delta2-pyrrolines or decarboxylation.

Alkenes↗

Catena-poly[[(trifluoromethanesulfonato-kappaO)silver(I)]-mu-di-2-pyridylamine-kappa2N2:N2'], a chain polymer with short Ag...C contacts.

The title compound, [Ag(CF3O3S)(C10H9N3)]n, is a chain polymer in which neighbouring monomeric units are related by a glide plane. The silver centre is four-coordinate; the donor atoms are one trifluoromethanesulfonate O atom and one pyridine N atom from each of two symmetry-related dipyridylamines, and an additional and unexpected Ag...C contact [2.6464 (16) A] is observed to a pyridine C atom. The chains are reinforced by one classical N-H...O and two 'weak' C-H...O hydrogen bonds.

Journal Article↗

Structural constraints in the design of silver sulfonate coordination networks: three new polysulfonate open frameworks.

Three new silver sulfonate metal-organic frameworks are presented along with a design strategy for future generations. [[Ag6(mesitylenetrisulfonate)2(H2O)5].2H2O]infinity (1), [Ag4(durenetetrasulfonate)(H2O)2](infinity) (2), and [[Ag4(1,3,5,7-tetrakis(4,4'-sulfophenyl)adamantane)(H2O)2].1.3H2O]infinity (3) represent a series of open-framework silver sulfonate solids where the organic linker plays a key role in determining the overall structure. Compound 1 forms a pillared layered structure, while compounds 2 and 3 form 3-D nets derived from cross-linking of 1-D columns of silver sulfonates. All three solids incorporate water molecules, which can be removed to yield a solid stable to in excess of 300 degrees C. Powder X-ray diffraction studies and vapor sorption experiments show, for 1 and 2, that the solids retain their structure when guests are removed and, for all three, that water vapor is resorbed stoichiometrically by the solids. An idealized silver sulfonate framework is proposed, and upon comparison to the reported structures, guidelines are proposed for structural constraints in the design of future generations of 1-D and possibly 0-D aggregate structures.

Journal Article↗