Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms

Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies.     

One-way EZ-isomerization of bis(n-butylammonium) (Z,Z)-muconate under photoirradiation in the crystalline state

One-way EZ-isomerization of bis(n-butylammonium) (Z,Z)-muconate [(Z,Z)-hexa-2,4-diene-1,6-dioate] to the corresponding (E,E)-isomer quantitatively proceeded in the crystalline state under photoirradiation with a high-pressure mercury lamp, being a new type of crystal-to-crystal reaction.     

Hexakis(2-pyridyl)- and hexakis(3-pyridyl)[3]radialene: novel,water-soluble [3]radialenes with potential utility for supramolecular chemistry

The titled [3]radialenes are the first, water-soluble hexaaryl[3]radialenes with considerably high electron affinity, their alkali metal reduction giving rise to anion-radicals and dianions stepwise as fairly stable species in degassed tetrahydrofuran.     

Surface structure and electrochemical characteristics of natural graphite fluorinated by ClF3

Natural graphite samples with average particle sizes of 5, 10 and 15 μm (NG5 μm, NG10 μm and NG15 μm, respectively) were fluorinated by ClF₃ (3 × 10⁴ Pa) at 200 and 300 °C for 2 min. X-ray photoelectron spectra of surface-fluorinated samples showed that surface fluorine concentration increased with increase in the particle size of graphite and reaction temperature. Small amounts of chlorine were also detected in all the fluorinated samples. Raman spectra of original and surface-fluorinated samples indicated that the surface disordering was increased for NG10 μm and NG15 μm. Surface areas were decreased by the fluorination for NG5 μm and NG10 μm but unchanged for NG15 μm. The mesopores with diameter of 1.5-2 nm increased while those of 2-3 nm decreased for all the samples. First coulombic efficiencies for NG10 μm and NG15 μm were highly increased by surface fluorination in 1 mol/dm³ LiClO₄-EC/DEC/PC (EC: ethylene carbonate, DEC: diethyl carbonate, PC: propylene carbonate) solution.     

Chemically modified "polar patch" mutants of subtilisin in peptide synthesis with remarkably broad substrate acceptance: designing combinatorial biocatalysts

A significant enhancement of the applicability of the serine protease subtilisin Bacillus lentus (SBL) in peptide synthesis was achieved by using the strategy of combined site-directed mutagenesis and chemical modification to create chemically modified mutant (CMM) enzymes. The introduction of polar and/or homochiral auxiliary substituents, such as X=oxazolidinones, alkylammonium groups, and carbohydrates at position 166 at the base of the primary specificity S(1) pocket created SBL CMMs S166C-S-X with strikingly broad structural substrate specificities. These CMMs are capable of catalyzing the coupling reactions of not only L-amino acid esters but also D-amino acid esters as acyl donors with glycinamide to give the corresponding dipeptides in good yields. These powerful enzymes are also applicable to the coupling of L-amino acid acyl donors with alpha-branched acyl acceptor, L-alaninamide. Typical increases in isolated yields of dipeptides of 60-80 % over SBL-WT (e.g. 0 % yield of Z-D-Glu-GlyNH(2) using SBL-WT-->74 % using S166C-S-(CH(2))(2) NMe(3) (+)) demonstrate the remarkable synthetic utility of this "polar patch" strategy. Such wide-ranging systems displaying broadened and therefore similarly high, balanced yields of products (e.g. 91 % Z-L-Ala-GlyNH(2) and 86 % yield of Z-D-Ala-GlyNH(2) using S166C-S-(3R,4S)-indenooxazolidinone) may now allow the use of biocatalysts in parallel library synthesis.     

Synthetic oligopeptides as isoelectric point markers for capillary isoelectric focusing with ultraviolet absorption detection

Sixteen peptides (trimers to hexamers) were designed for use as a set of pI markers for capillary isoelectric focusing (CIEF). Each peptide contains one tryptophan residue for detection by UV absorption and other amino acid residues having ionic side chains, which are responsible for focusing to its pI. The pIs of these peptides were determined by slab-gel IEF using commercial carrier ampholytes. The focused peptides in the gel were detected by absorption measurement at 280 nm using a scanning densitometer and the pH gradient was determined by measuring the pH of the gel using an oxidized metal membrane electrode. The pI values of the peptides ranged from 3.38 to 10.17. The obtained values agreed well with the predicted ones, which were calculated based on amino acid compositions, with root mean square differences of 0.15 pH unit. The peptides were detected at 280 nm as very sharp peaks when separated by CIEF. The pI values of some standard proteins were redetermined by CIEF by using this set of peptide pI markers and the values agreed closely with those reported previously. The sharp focusing, stability, high purity and high solubility of these synthetic pI markers should facilitate the profiling of a pH gradient in a capillary and the determination of the pI values of proteins.     

Nitriding of titanium with plasma jet under reduced pressure

The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10^–10–10^–8 g² cm^–4 s^–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed.     

Determination of optimal formulation for extrusion granulation by compression test of wet kneaded mass

The purpose of this study is to propose the application of a compression test to the determination of an optimal formulation for extrusion granulation. The electric current during extrusion was measured and the characteristics of the wet kneaded mass in the compression test were analyzed under various operating conditions, with different types of extruders and several formulations of kneaded mass. It was found that addition of a binder (HPC-L) to pharmaceutical powders lowered the load of a high-compressing type extruder, since the binder reduced the friction among the wet mass during extrusion. Also, the support stress was found to be proportional to the compression pressure without a binder, although an inflection point appeared on the support stress curve when a binder was present. This inflection point suggested large water retention of the wet kneaded mass, at which the medium of pressure was changed from a discontinuous solid powder to a continuous liquid, and large water retention contributed to the low friction of the wet mass. The friction of the wet kneaded mass and the aptitude of the formulation for extrusion were understood by using the compression test. The compression test is a very useful procedure at the first stage of a formulation study.     

The dependence of cyclopolymerizability of acrylic and methacrylic anhydrides on various conditions: New interpretation of temperature dependency of cyclization constant in radical cyclopolymerization of nonconjugated dienes

The cyclization constant K_c in the radical cyclopolymerization of acrylic and methacrylic anhydrides was evaluated in detail under various conditions. No linear relationship between in K_c and 1/T was observed; cyclization was acceleratively enhanced at elevated temperatures. The K_c values also increased with decreased monomer concentration and increased solvent polarity. These increasing dependencies of K_c are ascribed to the increased significance of depropagation, demonstrating a new interpretation of the temperature dependence of the cyclization constant in the radical cyclopolymerization of nonconjugated dienes.