Regioselectivity of olefin oxidation by iodosobenzene catalyzed by metalloporphyrins : control by the catalyst

The regioselectivity of the oxidation of three monosubstituted olefins, 6-phenoxyhex-1-ene, hex-1-ene and styrene, by iodosobenzene in the presence of various Fe-, Mn- or Cr-tetraaryl-porphyrins, was studied. It was found that, besides epoxides, known products from such systems, allylic alcohols and aldehydes were formed, the latter not being derived from the corresponding epoxides. The relative importance of these reactions greatly depends upon both the metal and porphyrin constituents of the catalyst. More particularly, the competition between epoxidation and allylic hydroxylation can be efficiently controlled by non-bonded interactions between the olefin and porphyrin substituents. No hydroxylation of the aromatic rings and no oxidative dealkylation of the ether function was detected.     

DNA damage by sulfite autoxidation catalyzed by cobalt complexes

DNA damage was investigated in the presence of sulfite, dissolved oxygen and cobalt(II) complexes with glycylglycylhistidine, glycylhistidyllysine, glycylglycyltyrosylarginine and tetraglycine. These studies indicated that only Co(II) complexed with glycylglycylhistidine (GGH) induced DNA strand breaks at low sulfite concentrations (1-80 microM) via strong oxidants formed in the reaction. In the presence of the other complexes, some damage occurred only in the presence of high sulfite concentrations (0.1-2.0 mM) after incubation for 4 h. In the presence of GGH, Co(II) and dissolved O2, DNA damage must involve a reactive high-valent cobalt complex. The damaging effect was increased by adding S(IV), due to the oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by the complex. SO3 -, HO and H radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline N-oxide). The results indicate that Co(II) binds O2 in the presence of GGH, and leads to the formation of a DMPO-HO adduct without first forming free superoxide or hydroxyl radical, supporting the participation of a reactive high-valent cobalt complex.     

Antibiotic recognition by binuclear metallo-beta-lactamases revealed by X-ray crystallography

Metallo-beta-lactamases are zinc-dependent enzymes responsible for resistance to beta-lactam antibiotics in a variety of host bacteria, usually Gram-negative species that act as opportunist pathogens. They hydrolyze all classes of beta-lactam antibiotics, including carbapenems, and escape the action of available beta-lactamase inhibitors. Efforts to develop effective inhibitors have been hampered by the lack of structural information regarding how these enzymes recognize and turn over beta-lactam substrates. We report here the crystal structure of the Stenotrophomonas maltophilia L1 enzyme in complex with the hydrolysis product of the 7alpha-methoxyoxacephem, moxalactam. The on-enzyme complex is a 3'-exo-methylene species generated by elimination of the 1-methyltetrazolyl-5-thiolate anion from the 3'-methyl group. Moxalactam binding to L1 involves direct interaction of the two active site zinc ions with the beta-lactam amide and C4 carboxylate, groups that are common to all beta-lactam substrates. The 7beta-[(4-hydroxyphenyl)malonyl]-amino substituent makes limited hydrophobic and hydrogen bonding contacts with the active site groove. The mode of binding provides strong evidence that a water molecule situated between the two metal ions is the most likely nucleophile in the hydrolytic reaction. These data suggest a reaction mechanism for metallo-beta-lactamases in which both metal ions contribute to catalysis by activating the bridging water/hydroxide nucleophile, polarizing the substrate amide bond for attack and stabilizing anionic nitrogen intermediates. The structure illustrates how a binuclear zinc site confers upon metallo-beta-lactamases the ability both to recognize and efficiently hydrolyze a wide variety of beta-lactam substrates.     

Substitution of 2-phosphaindolizines by bromine and by chlorophosphines

Bromine does not add to phosphorus in a 2-phosphaindolizine 1 but substitutes its 1-position. The 1-bromo derivatives 2 are best prepared with Br₂/NEt₃ or N-bromosuccinimide. Their hydrolysis is remarkable; it involves a debromination of C-1, an oxidation of P and a selective opening of the P/C-3 bond. PCl₃ also causes a substitution of the 1-position. The resulting 1-dichlorophosphino derivatives 5 easily undergo a substituent exchange at the exocyclic phosphorus. More 1-phosphino derivatives are formed in the reaction of 1 with phenyl and diazaphospholyl dichlorophosphine.     

Crystal nucleation given rise by fracturing or by mechanical shock

Summary Sudden crystallization takes place frequently in supercooled liquids or in supersaturated solutions (usually of ionic compounds) when solid substances immersed in the liquids are cut or fractured mechanically. Rupture of chemical bonds in the solid is essential for the nucleation and the effect disappears momentarily. Crystallization is also frequently given rise by mechanical shock in the above mentioned liquids, and may be explained as follows: electrons of the shocked molecules become labile and may behave like free electrons in metals momentarily as demonstrated experimentally. Generated free radicals and free electrons cluster into a metal-like structure and are compressed into the closest-packed structure with higher regularity by forces analogous to metallic bond. The cluster may act as the embryo and the nucleus of the crystal, if its structure resembles to that of the crystal or if it is easily convertable to the latter. Nucleation in supercooled liquids given rise by fracturing of solids is explained in an analogous way. Fractured surface of solids is momentarily covered with free radicals. The labile electrons and positively polarized part of liquid molecules in contact with the surface may form a two-dimensional metallic structure and the resulting compressed layer may act as the nucleus, if its structure is appropriate.

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Zusammenfassung Plötzliche Kristallisation geschieht oft in unterkühlten Flüssigkeiten oder in übersättigten Lösungen (gewöhnlich von Ionenverbindungen), wenn feste Substanzen, die in die Flüssigkeiten eingetaucht sind, mechanisch geschnitten oder gebrochen werden. Die Spaltung der chemischen Bindungen in den festen Substanzen scheint notwendig für die Keimbildung zu sein. Plötzliche Kristallisation wird auch durch mechanische Erschütterung in den Flüssigkeiten hervorgerufen. Diese Phänomene werden durch Einfluß delokalisierter Elektronen auf die Keimbildung erklärt.

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With 3 figures and 3 tables     

The Reduction of Benzofuroxans by Ferrous Salts and by Thiophenol

Treatment of benzofuroxan derivatives with ferrous sulphate in DMSO/water solution affords in high yield o-nitroanilines. o-Nitroaniline was also obtained by reduction of benzofuroxan with thiophenol in presence of catalytic amount of Fe²⁺ or Fe³⁺ salts.     

Separation by Flotation

There has been much recent activity in the theory and application of separation by flotation, both in the United. States and abroad. This review primarily addresses new developments in foam flotation, colloid flotation and precipitate flotation. The work in ore flotation represents a major effort and would itself require a lengthy article. Work from ore flotation which significantly impacts on the areas of interest listed above is included here, however. Foam separation of biological materials and the microflotation of bacteria are not routinely discussed in this review. A few recent review articles on these areas are included at the end of the Review Articles and Books Section to afford the interested reader a start on that literature. The development and use of flotation separation techniques for waste treatment and water reuse over the last few years are included in this article.     

Quantitative Particle Uptake by Cells as Analyzed by Different Methods

There is a large number of two‐dimensional static in vitro studies about the uptake of colloidal nano‐ and microparticles, which has been published in the last decade. In this Minireview, different methods used for such studies are summarized and critically discussed. Supplementary experimental data allow for a direct comparison of the different techniques. Emphasis is given on how quantitative parameters can be extracted from studies in which different experimental techniques have been used, with the goal of allowing better comparison.     

Shape changes induced by N-terminal platination of ubiquitin by cisplatin

The three-dimensional conformation of a protein is an important property and plays a key role in its biological activity. We show here that ion mobility-mass spectrometry (IM-MS) can be used to detect conformational changes in the protein ubiquitin in the gas phase induced by reaction with the anticancer drug cisplatin. The primary adduct was ubiquitin-{Pt(NH₃)₂} under denaturing conditions. Up to three different conformations appear to be generated upon platination depending on the charge state. The collision cross-sections (Ω) for each conformation indicate that the conformations of the platinated protein are contracted in size compared with unmodified ubiquitin with generally smaller Ω values. Ion mobility-tandem MS allowed determination of the platinum binding site without a requirement for prior Chromatographic separation. A rapid 30-min digestion of cisplatin-modified ubiquitin with trypsin allowed the platination site to be identified as the N-terminal methionine following low-energy collision-induced dissociation (CID) studies of the modified peptide. The data were generated using a Traveling-Wave based ion mobility-MS approach. Such cisplatin-induced shape changes may have a significant effect on its function in vivo. This work highlights the usefulness of the ion-mobility mass spectrometry technique for shedding new light on such protein interactions.     

Glycosidase inhibition by macrolide antibiotics elucidated by STD-NMR spectroscopy

A glycosynthase approach was attempted to glycodiversify macrolide antibiotics, using DesR, a family-3 retaining beta-glucosidase involved in the self-resistance mechanism of methymycin production. STD-NMR was used to probe enzyme-substrate interactions. Analysis of competitive STD-NMR experiments between erythromycin A and a chromogenic substrate (pNP-beta-d-glucose) with the hydrolytically inactive nucleophile mutants led us to discover a family of unprecedented glycosidase inhibitors. Analysis of kinetic data with wild-type DesR determined that erythromycin is a competitive inhibitor of the glucosidase (IC50 = 2.8 +/- 0.3 microM and Ki = 2 +/- 0.2 microM) with respect to the hydrolysis of pNP-beta-d-glucose. Comparable inhibitory data was obtained for clarithromycin; however, the inhibitory effect of azithromycin was weak and no significant inhibition was observed with methymycin or d-desosamine. This report documents significant inhibition of glycosidases by macrolide antibiotics and provides insight into the design of novel glycosidase inhibitors based on the macrolactone ring of macrolide antibiotics.     

Flocculation mechanism induced by cationic polymers investigated by light scattering

Three cationic polymers with molecular weights and charge densities of 3.0 x 10(5) g/mol and 10%, 1.1 x 10(5) g/mol and 40%, and 1.2 x 10(5) g/mol and 100% were chosen as flocculants to aggregate silica particles (90 nm), under various conditions, including change in polymer dosage, particle concentration, background electrolyte concentration, and shear rate. The size and structure of flocs produced were determined using the static light scattering technique. On the basis of measurements of polymer adsorption and its effect on the zeta potential and floc properties, it has been found that the polymer charge density plays an important role in determining the flocculation mechanism. Polymers with a 10% charge density facilitate bridging, 40% charged polymers bring about either a combination of charge neutralization and bridging or bridging, depending on the polymer dosage, and polymers with the charge density of 100% induce electrostatic patch flocculation mechanism at the optimum polymer dosage and below but bring about bridging mechanism at the polymer dosage approaching the adsorption plateau value. Bridging aggregation can readily be affected by the particle concentration, and an increase in particle concentration results in the formation of larger but looser aggregates, whereas electrostatic patch aggregation is independent of particle concentration. The addition of a background electrolyte aids in bridging aggregation while it is detrimental to electrostatic patch aggregation. It has also been found that the effect of shear rate on the mass fractal dimension depends on polymer charge density.     

Production of Enzymes by Plant Cells Immobilized by Sol-Gel Silica

Ajuga reptans cells are cultivated and used for production of invertase. These plant cells are immobilized by a sol-gel SiO₂ membrane, which is built up directly on the cell surface by exposure to a gaseous flow of silicon alcoxide precursors. The immobilization modifies the metabolic activity of cells, resulting in a 40-fold increase in invertase production with respect of free cells. Results concerning total release of proteins, cell growth and produced invertase activity are discussed, considering the absence of breeding, induced by SiO₂ immobilization, the prominent factor promoting the observed exceptional increase in invertase productivity.     

Membrane solubilization by detergent: resistance conferred by thickness

The commonly held model for membrane dissolution by detergents/surfactants requires lipid transport from the inner to the outer bilayer leaflet ('flip-flop'). Although applicable to many systems, it fails in cases where cross-bilayer transport of membrane components is suppressed. In this paper we investigate the mechanism for surfactant-induced solubilization of polymeric bilayers. To that end, we examine the dissolution of a series of increasingly thick, polymer-based vesicles (polymersomes) by a nonionic surfactant, Triton X-100, using dynamic light scattering. We find that increasing the bilayer thickness imparts better resistance to dissolution, so that the concentration required for solubilization, after a fixed amount of time, increases nearly linearly with membrane thickness. Combining our experimental data with a theoretical model, we show that the dominant mechanism for the surfactant-induced dissolution of polymeric vesicles, where polymer flip-flop across the membrane is suppressed, is the surfactant transport through the bilayer. This mechanism is different both qualitatively and quantitatively from the mechanisms by which surfactants dissolve pure lipid vesicles.     

Photoprotection by melanin

This paper is an attempt to summarize the current state of information on melanin and epidermal melanin pigmentation (EMP) as photoprotective agents. The chemistry and biochemistry of melanin (the particle) and its interaction, in its various forms, with UV radiation are considered. Methods of attenuation of UV radiation are discussed in terms of structure and chemical constituents. Photoprotection by constitutive and facultative pigmentation is reviewed with minimum erythema dose (MED) as the end point. The issue of acclimatization to UV radiation is discussed in terms of UVB phototherapy for psoriasis. Finally, skin cancer is considered as an end point and the reduction of its incidence with pigment level is discussed. It is concluded that whilst EMP provides protection, its extent depends on the end point chosen for evaluation. MED is a convenient photobiological end point but is rather insensitive, whereas skin cancer is sensitive but impractical for laboratory studies. Our current state of knowledge of melanin lacks information on its absorption and scattering coefficients and its refractive index. Methods for the quantitative measurement of EMP are also urgently required.     

Ring opening of aziridines by aromatic thiols followed by amino-substitution

Ring opening of 2-aziridinecarboxylic acid methyl ester by a number of aromatic thiols under solvent-free and non-catalytic conditions resulted in bis-arylsulfanyl propanoic acid esters.     

Dechlorophyllation by electrocoagulation

Electrocoagulation was used for dechlorophyllation of alcoholic extracts from five plants. The results showed that for every plant extract studied, electrocoagulation was more efficient than the classical solvent extraction method in removing plant pigments, while not affecting the important secondary metabolites in those extracts.     

Nanoporous carbons obtained by carbonization of copolymers impregnated by salts

This paper demonstrates the results of research on influence of types of polymer and kinds of salts used for impregnation of the polymer on porous structure formation in the final carbonaceous product. The studies were performed in two stages. In the first stage, the role of polymer structure were mainly studied. To achieve the aim, three different porous copolymers (polyimide and two types of polyester) were impregnated with the same salts (NiSO₄, and the mixture of AgNO₃ and Gd(NO₃)₃). In the second part of the study, only one polymer (polyimide) was impregnated by three mixtures of salts (chlorides, nitrates and sulphates of K, Cu(II) and Fe(III)). This approach allowed to evaluate the impact of the mixture of salts on porosity of the carbons, which were to be prepared. The obtained results revealed that when the impregnation was applied as a method for activation and moulding of porosity of carbonaceous materials prepared from polymers, several factors should be taken into account. First of all, initial decomposition temperatures of the polymers and the salts should be compared to find out if carbonization and activation processes proceed simultaneously or not. If the copolymer was carbonized and gases were released from decomposing salts, they reacted each other and synergic effect of polymer and salts properties were observed. Such conditions favored the development of microporous structure of the obtained carbon. On the contrary, if the processes were separated in time because of high temperature of melting point of the salts more mesopores were retained.     

Desymmetrization of Dicationic Diboranes by Isomerization Catalyzed by a Nucleophile

Cationic monoboranes exhibit a rich chemistry. By constrast, only a few cationic diboranes are known, that all are symmetrically substituted. In this work, the first unsymmetrically substituted dicationic diboranes, featuring sp²–sp²‐hybridized boron atoms, are reported. The compounds are formed by intramolecular rearrangement from preceding isomeric symmetrically substituted dicationic diboranes, a process that is catalyzed by nucleophiles. From the temperature‐dependence of the isomerization rate, activation parameters for this unprecedented rearrangement are derived. The difference in fluoride ion affinity between the two boron atoms and the bonding situation in these unique unsymmetrical dicationic diboranes are evaluated.     

Microwave-assisted oxidation of alcohols by hydrogen peroxide catalysed by tetrabutylammonium decatungstate

This work deals with catalytic activity of tetrabutylammonium decatungstate(VI) in the oxidation of selected alcohols with hydrogen peroxide as an oxidant using 1,2-dichloroethane/water or acetonitrile/water as a solvent system. Different forms of heating were compared. The highest conversions of substrates were achieved in the two phase system acetonitrile/water using microwave irradiation combined with elevated pressure. Finally, optimum parameters for these reactions in a microwave pressurised reactor were established and discussed.     

Metallation of tetratolylporphyrin by Cu2+ catalysed by LiClO4

The kinetic study of tetratolylporphyrin metallation by copper II ions in the presence of lithium salts was undertaken in an aprotic solvent. A catalytic effect of Li⁺ has been observed leading to a great enhancement (× 500 at 30 °C) in the rate of incorporation of Cu²⁺.