Purification,Characterization and Mechanistic Study of β-Glucosidase from Flavobacterium meningosepticum (ATCC 13253)

A β-glucosidase (EC 3.2.1.21) from Flavobacterium meningosepticum has been purified and characterized. Purity was enhanced at least 530-fold from crude cell extract with 16.6% yield. The estimated molecular mass of the purified enzyme is 150 kDa by gel filtration and 78 kDa by SDS-PAGE. This dimeric enzyme has a pI = 9.0 and an optimal activity at pH 5.0 and temperature of 50 °C. Divalent metal ions (Hg²⁺, Cu²⁺, Ca²⁺, Mg²⁺) and EDTA have negligible effect on the enzyme activity. The enzyme exhibited a high specificity on the glycon portion of aryl-β-D -glycosides. NMR spectroscopy revealed the enzyme catalyzed hydrolysis of p-nitrophenyl-β-D -glucopyranoside with the retention of anomeric configuration, indicating that a double displacement mechanism was involved. A preliminary study of the Bronsted relationship showed a concave-downward plot, which is consistent with the two-step mechanism.     

A new Sequiterpenoid from Eupatorium adenophorum Spreng

A new sequiterpenoid compound 8aα-hydroxy-1-isopropyl-4,7-dimethyl-1,2,3,4,6,8a-hexahydro-naphthalene-2,6-dione(1),together with seven known compounds anti-HH-dimer-coumarin(2),(-)-5-exo-hydroxy-bomeol(3),O-hydroxyl cinnamic acid(4),9β-hydroxy-ageraphorone(5),10Hα-9-oxo-ageraphorone(6),10Hβ-9-oxo-ageraphorone(7)and 9-oxo-10,11-dehydroageraphorone 8,was isolated from the leaves of Eupatorium adenopho-rum Spreng.The structures were elucidated by IR,~1H and ~(13)C NMR,EIMS,HMBC and single-crystal X-ray spec-tral data.     

Some Novel Dinuclear phenylboronates of biologically potent β‐enaminoesters: Synthesis,Spectroscopic characterization,antimicrobial activity and their antiandrogenic effect

Organoboron derivatives of biologically potent β‐enamino esters of the type [Where R = CH₃(1a), C₂H₅ (1b), C₃H₇(1c) and C (CH₃)₃ (1d)] have been prepared by the reactions of β‐enamino esters and Phenyl boronic acid [PhB (OH)₂] in 1:2 molar ratio in refluxing tetrahydrofuran (THF). All these derivatives have been characterized by physico‐chemical properties, elemental analyses and molecular weight measurements. The structures of these compounds have been proposed on the basis of IR, ¹H, ¹³C, ¹¹B NMR spectral data and GC‐mass spectrometry. Phenyl boronic acid, β‐enamino esters and their respective phenylboronates derivatives have been screened for the antibmicrobial activities against pathogenic bacteria (B. subtilis and E. coli) and fungi (A. niger and P. peniculosum) to access their growth inhibiting potential. In addition to this, antiandrogenic effect of Ligand, L^aH₂ and its boron derivative (1a) has also been tested in male albino rats.     

Reaction of Grignard Reagents with Diethyl Perfluoroacyl (1-Cyanoethyl)phosphonates. Synthesis of Perfluoroalkylated α,β-Unsaturated Nitriles with Predominant Z-Selectivity

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Ground- and excited-state properties of inorganic solids from full-potential density-functional calculations

The development in theoretical condensed-matter science based on density-functional theory (DFT) has reached a level where it is possible, from “parameter-free” quantum mechanical calculations to obtain total energies, forces, vibrational frequencies, magnetic moments, mechanical and optical properties and so forth. The calculation of such properties are important in the analyses of experimental data and they can be predicted with a precision that is sufficient for comparison with experiments. It is almost impossible to do justice to all developments achieved by DFT because of its rapid growth. Hence, it has here been focused on a few advances, primarily from our laboratory. Unusual bonding behaviors in complex materials are conveniently explored using the combination of charge density, charge transfer, and electron-localization function along with crystal-orbital Hamilton-population analyses. It is indicated that the elastic properties of materials can reliably be predicted from DFT calculations if one takes into account the structural relaxations along with gradient corrections in the calculations. Experimental techniques have their limitations in studies of the structural stability and pressure-induced structural transitions in hydride materials whereas the present theoretical approach can be applied to reliably predict properties under extreme pressures. From the spin-polarized, relativistic full-potential calculations one can study novel materials such as ruthenates, quasi-one-dimensional oxides, and spin-, charge-, and orbital-ordering in magnetic perovskite-like oxides. The importance of orbital-polarization correction to the DFT to predict the magnetic anisotropy in transition-metal compounds and magnetic moments in lanthanides and actinides are emphasized. Apart from the full-potential treatment, proper magnetic ordering as well as structural distortions have to be taken into account to predict correctly the insulating behavior of transition-metal oxides. The computational variants LDA and GGA fail to predict insulating behavior of Mott insulators whereas electronic structures can be described correctly when correlation effects are taken into account through LDA+U or similar approaches to explain their electronic structures correctly. Excited-state properties such as linear optical properties, magneto-optical properties, XANES, XPS, UPS, BIS, and Raman spectra can be obtained from accurate DFT calculations.     

Enantioselective syntheses of no-carrier-added (n.c.a.) (s)-4-chloro-2-[f] fluorophenylalanine and (s)-(α-methyl) -4-chloro-2-[f]fluorophenylalanine

(S)-4-Chloro-2-fluorophenylalanine and (S)-(α-methy)-4-chloro-2-fluorophenylalanine were synthesized and labeled with no carrier added (n.c.a.) fluorine-18 through a radiochemical synthesis relying on the highly enantioselective reaction between 4-chloro-2-[¹⁸F]fluorobenzyl iodide and the lithium enolate of (2S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3-methyl-1,3-imidazolidine-4-one for (S)-4-chloro-2-[¹⁸F]fluorophenylalanine and (2S,5S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3,5-dimethyl-1,3-imidazolidine-4-one for (S)-(α-methyl) -4-chloro-2-[¹⁸F] fluorophenylalanine. Quantities of about 20–25 mCi were obtained at the end of sy nthesi s, ready for injection after hydrolysis and high performance liquid chromatography (HPLC) purification, with a radiochemical yield of 17%–20% corrected to the end of bombardment after a total synthesis time of 90–105 min from [¹⁸F] fluoride. The enantiomeric excesses were shown to be 97% or more for both molecules without chiral separation and the radiochemical and chemical purities were 98% or better.     

A Mild Isomerization Reaction for β,γ‐Unsaturated Ketone to α,β‐Unsaturated Ketone

A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions.     

Asymmetric Reduction Using Lithium Aluminum Hydride Modified with Chiral Ligands Prepared from (1R)-(-)-β-Pinene

The reduction of prochiral ketones using chiral reducing reagents, prepared from lithium aluminum hydride and (-)-(1R, 2S, 3S, 5R)-10-anilinopinanediol (5) and (-)-(1R, 2S, 3S, 5R)-10-N-methylanilinopinanediol (6), affords chiral secondary alcohols in useful chemical yields (70 ～ 93%) but in low optical purity (8 ～ 33% ee). Modifiers 5 and 6 are synthesized from (lR)-(-)-β-pinene in three steps.     

Synthesis of Some Novel 3,6‐Bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole Derivatives

The cyclization of 1‐amino‐2‐mercapto‐5‐[1‐(4‐ethoxyphenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐1,3,4‐triazole which was synthesized from p‐ethoxyaniline with various triazole acid in absolute phosphorus oxychloride yields 3,6‐bis(1,2,3‐triazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazole derivatives 9a?j , and their structures are established by MS, IR, CHN and ¹H NMR spectral data.