Stereoselective synthesis and 2D NMR study of S-D-glucopyranoside

2, 3, 4-Tri-O-benzyl-6-O trimethylsilyl-α-D-glucopyranosyl bromide reacted with RSH compounds (R = Et, t-Bu, PhCH₂, p-PhBu^t, Ph, 2-benzoxazole, 2-benzothiazole), with diisopropylethylamine as base, to give S-D-glucosides. The α- and β- anomeric ratio was dependent on the pKa. value of the thiol compound. If pKa value was less than or equal to 7, β-anomer was obtained. If pKa value was equal to or more than 11, α anomer was obtained. If pKa value was between 9 and 10.6, a mixture of α- and β-anomer was obtained. The probable mechanism was discussed. The chemical shifts of proton and carbon in these S-D-glucosides were measured and verified by 2D NMR (cosy and hetcor).     

Totalsynthese und absolute Konfiguration von natürlichem Multifloramin

The diphenol 1 was resolved into its antipodes and their absolute configuration was established. The levorotatory isomer R-(?)- 1 was oxidized to the dienone R-(?)- 6 , which was rearranged to afford natural (?)-multifloramine (R-(?)- 7 ), thus establishing that the latter has the R-configuration. By the same reaction sequences, the enantiomeric diphenol S-(+)- 1 was transformed to provide (+)-multifloramine (S-(+)- 7 ) of the S-configuration.     

Differentiation of essential oils in Atractylodes lancea and Atractylodes koreana by gas chromatography with mass spectrometry

Atractylodes rhizome is a valuable traditional Chinese medicinal herb that comprises complex several species whose essential oils are the primary pharmacologically active component. Essential oils of Atractylodes lancea and Atractylodes koreana were extracted by hydrodistillation, and the yield was determined. The average yield of essential oil obtained from A. lancea (2.91%) was higher than that from A. koreana (2.42%). The volatile components of the essential oils were then identified by a gas chromatography with mass spectrometry method that demonstrated good precision. The method showed clear differences in the numbers and contents of volatile components between the two species. 41 and 45 volatile components were identified in A. lancea and A. koreana, respectively. Atractylon (48.68%) was the primary volatile component in A. lancea, while eudesma‐4(14)‐en‐11‐ol (11.81%) was major in A. koreana. However, the most significant difference between A. lancea and A. koreana was the major component of atractylon and atractydin. Principal component analysis was utilized to reveal the correlation between volatile components and species, and the analysis was used to successfully discriminate between A. lancea and A. koreana samples. These results suggest that different species of Atractylodes rhizome may yield essential oils that differ significantly in content and composition.     

Synthesis of 4-substituted 1,4-benzodiazepine-3,5-diones

Synthetic routes leading to the preparation of 4-substituted 1,4-benzodiazepine-3,5-diones are described. Thus, 2-carbobenzoxyaminobenzoic acid was converted to its p-nitrobenzyl ester (I) and the decarbobenzoxylated product (II) gave, with ethyl α-bromoacetate, N-(2-carboxy p-nitrobenzylate)phenylglycine ethyl ester (III). The latter was hydrogenolyzed to N-(2-car-boxy)phenylglycine ethyl ester (IV), which was coupled with benzylamine to give N-(2-carboxy-benzylamido)phenylglycine ethyl ester (VIa). Saponification of VIa afforded N-(2-carboxy-benzylamido)phenylglycine (VIIa) which was cyclized with DCCI to produce 4-benzyl-2H-1,4-benzodiazepine-3,5(lH,4H)dione (VIIIa). Alternatively, 2-nitro-N-phenylbenzamide (Xb) was reduced to 2-amino-N-phenylbenzamide (XIb) which was converted to N-(2-carboxanih'do)-phenylglycine ethyl ester (VIb). The latter was converted to 4-phenyl-2H-1,4-benzodiazepine-3,5(1H,4H)dione (VIIIb) in an analogous fashion described for VIIIa.     

Model Construction for the A–B–C Ring System of Lysergic Acid via Vilsmeier–Haack‐Type Cyclization of 1H‐Indole‐4‐propanoic Acid Derivatives

Vilsmeier–Haack‐type cyclization of 1H‐indole‐4‐propanoic acid derivatives was examined as model construction for the A–B–C ring system of lysergic acid ( 1 ). Smooth cyclization from the 4 position of 1H‐indole to the 3 position was achieved by Vilsmeier–Haack reaction in the presence of K₂CO₃ in MeCN, and the best substrate was found to be the N,N‐dimethylcarboxamide 9 (Table 1). The modified method can be successfully applied to an α‐amino acid derivative protected with an N‐acetyl function, i.e., to 27 (Table 2); however, loss of optical purity was observed in the cyclization when a chiral substrate (S)‐ 27 was used (Scheme 5). On the other hand, the intramolecular Pummerer reaction of the corresponding sulfoxide 20 afforded an S‐containing tricyclic system 22 , which was formed by a cyclization to the 5 position (Scheme 3).     

GC–MS characterisation and antibacterial activity evaluation of Nigella sativa oil against diverse strains of Salmonella

Salmonella resistance is becoming a worldwide serious health issue in these days; therefore, it is an urgent need to develop some alternative approaches to overcome this problem. Twenty bacterial strains were isolated and purified from different environmental sources and confirmed as Salmonella by morphological and biochemical analyses. Further confirmation was done by 16s rRNA sequencing. Antibiotic susceptibility test was performed by well diffusion assay against different concentrations of Ceftriaxone and Ciprofloxacin. The behaviour of both antibiotics was different against diverse strains of Salmonella. Salmonella strains resistant to both antibiotics were analysed for antibacterial activity of natural extracts of Nigella sativa (black seeds). N. sativa oil was found to be more effective against Salmonella species for which even Ceftriaxone and Ciprofloxacin were ineffective. Gas chromatography and mass spectrometry analysis of N. sativa oil was also accomplished, exhibiting 10 compounds including thymoquinone, p-cymene, cis-carveol, thymol, α-phellandrene, α-pinene, β-pinene, trans-anethole, α-longipinene and longifolene.     

Energy transfer of n-hexane-tributyl phosphate (TBP) binary system: Using TBP as a probe for the detection of excited states of n-hexane

In this paper TBP labeled with ³²P was used as a probe for detecting the excited species of n-hexane. Under γ irradiation of n-hexane-TBP binary system, it was found that TBP was sensitized by excited n-hexane molecules and a G value of 1.05 was found for the excited state of n-hexane. An energy transfer mechanism was proposed and kinetic equation of sensitization was obtained. Theoretical calculation is in agreement with experimental results.     

Study of structural parameters on the adsorption selectivity of a molecularly imprinted polymer

This work was focused on the influence of match degree of structure parameters i.e. molecular size, volume and polarity (denoted as R_d, V_d and P_d) between imprinted cavities in Qu-MIP and Xn on the adsorption selectivity. The results presented that the influence of R_d on the adsorption selectivity was the largest and the most regular, while the influence of P_d was the smallest and the most irregular. Besides, the influence degree of V_d was decreased in general with the increase of R_d. However, as R_d was in the threshold of [0.99, 1.02], V_d would rise to the major influence factor. Furthermore, utilizing data obtained from experiment, the influence authority of R_d, V_d and P_d on the adsorption selectivity was calculated theoretically through multiple linear regression and principal component analysis of IBM SPSS Statistics 20, and results showed the authority order was R_d, V_d and P_d at any circumstance despite the value was different, which was in accordance with the result we directly inducted from the experiment.     

Haloaldehyde polymeres XIII. Polydibromofluoroacetaldehyde

Dibromofluoracetaldehyde (DBFA) was prepared by reducing methyl dibromofluoroacetate with lithium aluminium hydride (LAH) at low temperatures whereby theLAH was added to dibromofluoroacetate. The initially obtainedDBFA hydrate was dehydrated to the free aldehyde. Methyl dibromofluoroacetate was synthesized together with methyl bromodifluoroacetate by air oxidation of 1,1-dibromo-2,2-difluoroethylene. The mixture of oxidation products, consisting of two acid halides, was treated with methanol and gave a mixture of the methyl esters which here separated by distillation. DBFA was polymerized with anionic and cationic initiators to crystalline insoluble poly-DBFA. Poly-DBFA degraded quantitatively at elevated temperatures to monomericDBFA. Copolymerization ofDBFA with chloral gave copolymers with nearly the same comonomer composition as the feed.DBFA was also copolymerized with phenyl isocyanate to a copolymer which contained acetal and urethane linkages.Part XII:R. W. Campbell, andO. Vogl, Makromolekulare Chemie, in press.     

Temperature Effect on Drying and Swelling of Kappa Carrageenan Gels: A Steady State Fluorescence Study

Summary: A novel technique based on in situ steady state fluorescence (SSF) measurements is introduced for studying drying and swelling of κ- carrageenan (kappa carrageenan) gels at various temperatures. κ- carrageenan gels were completely dried and then swelled in water vapor. Pyranine was embedded in κ- carrageenan and used as a fluorescence probe. Scattered light intensities, I_sc and fluorescence intensities, I were monitored during the drying and swelling of κ- carrageenan gels. It was observed that the fluorescence intensity decreased linearly as drying time was increased. A simple model consisting of Case II diffusion was used to quantify the drying processes of the κ- carrageenan gels. This moving boundary model provided packing constant, k₀. During swelling, fluorescence intensity increased exponentially as time is increased. The increase in I, was modeled using Li-Tanaka equation from which swelling time constants, τ_c and cooperative diffusion coefficients, D_c were determined. It was observed that swelling time constants, τ_c decreased and diffusion coefficients, D_c increased as the swelling temperature was increased. Activation energies for drying and swelling were also obtained and found to be 53.9 and 47.2 kJ mol⁻¹, respectively.     

Recovery of thick shear bands in atactic polystyrene

The DSC thermograms of the shear band material cut out by a diamond saw to include some undeformed material revealed two T_g's clearly separated by about 10°C. The first T_g was at the same temperature as the T_g of the undeformed material. The second T_g, which was at a higher temperature than the first T_g, appeared shortly after the shear strain recovery during the heating of the shear band material in the DSC. When the shear strain in the shear band was partially reversed by mechanical means before taking the DSC thermogram, the ΔT between the two T_g's decreased and when the shear strain was mechanically reversed to almost zero, the second T_g disappeared. The stored energy of shear band material was found to be similar to that of the bulk compressed material for large strains. Dimensional recovery during heating of specimens with thick and fine bands was similar, both taking place above T_g.     

Theoretical calculation of the steric effects of ortho substituents by the AM1 method

The AM1 calculation was done for ortho-substituted toluenes (o-X-C₆H₄-CH₃) and ortho-substituted tert-butylbenzenes (o-X-C₆H₄-t-Bu). The difference in the calculated heat of formation between o-X-C₆H₄-CH₃ and o-X-C₆H₄-t-Bu was used as a theoretical steric index for ortho-X. The correlation of this theoretical steric index with the empirical steric parameter sets such as our recently defined E_s(AMD) and the Taft–Kutter–Hansch (TKH) E_s was examined. In spite of the simplicity of the model system, the theoretical index was linear with the E_s(AMD) constant with a correlation coefficient of r = 0.972 for 17 substituents of various structures. Including the phenyl group, the correlation with the TKH E_s constant was r = 0.948. The theoretically calculated index was shown to serve as a measure of the ortho steric effect.     

Anionic oligomerization of methacrylonitrile

The anionic oligomerization of methacrylonitrile by alcoholic solutions of sodium alkoxide in dimethyl sulfoxide, methanol and ethanol was studied. The DP of the oligomers was directly proportional to the monomer concentration and inversely proportional to the alcohol concentration, in accordance with the equation DP = K[MAN]/[ROH], K being equal to K_p/K_tr. The value of K in DMSO (with sodium methoxidemethanol) was 2.9 ± 0.2, in methanol was 1.5 ± 0.1, and in ethanol (with sodium ethoxide as initiator) was 1.9 ± 0.1. The physical properties of the oligomers are given.     

Mechanism of styrene emulsion polymerization during interval II

A systematic study of the kinetics of styrene emulsion polymerization in the postnucleation stage by the way of seed particle growth of monodisperse latices was undertaken, in which the colloidally important parameters were varied: R_p was independent (within limits) of (a) ionic strength, (b) pH, (c) initiator concentration (potassium persulfate), and (d) surfactant (sodium dodecyl sulfate) concentration; R_pp was independent (within limits) of (a) seed particle number concentration N, (b) oil:water phase ratio, and (c) monomer:polymer ratio; R_p was directly proportional to seed-particle surface area. The viscosity average molecular weight of the polymer formed during interval II, M_v(i–j), was approximately constant and increased linearly with N. Log M_v(i–j) was inversely proportional to reaction temperature; M_v(i–j) was inversely proportional to initiator concentration. The overall activation energy of polymerization E′_p was equal to the activation energy of propagation E_p during interval II. The value of k_p at 60°C was 615 dm³ mol^?1 s^?1. Trace of oxygen seems to affect the average number of radicals per particle ī during interval II polymerization.     

Thermal stability of para- and ortho-isomers of tris-decyl-(ethyl-benzyl)-ammonium chloride

Thermal stability of para (p--) and ortho (o-) isomers was investigated by CRTG and reaction kinetic analysis. The temperature started the mass decrease of o-isomer was about 20°C lower than that of p-isomer by CRTG. The activation energies of thermal decomposition of o- and p-isomers were 136.9 and 153.4 kJ mol^–1, respectively. The effect of steric hindrance on heat of formation was calculated by AM1 method using Win MOPAC3.0 for the model compound of p- and o-isomers. The lower stability of o-isomer was the results of the steric hindrance between the ethylene unit of aromatic ring and three alkyl chains.     

Interspecies Interaction of Signal Peptide PapR Secreted by <Emphasis Type="Italic">Bacillus cereus</Emphasis> and Its Effect on Production of Antimicrobial Peptide

This study was carried out to investigate the interspecies interaction of PapR peptide secreted by Bacillus cereus on production of BSAP-254, an antimicrobial peptide produced by Bacillus subtilis SC-8 isolated from the Korean fermented soybean paste and exhibited narrow antagonistic activity against the B. cereus group, but not against other foodborne pathogens. PapR is a signal peptide that activates PlcR, which is a pleiotropic regulator controlling the expression of various virulence factors in B. cereus. When B. subtilis SC-8 was co-cultured with B. cereus, it completely inhibited the growth of B. cereus within 12 h, and the rate of BSAP-254 production was increased 34.2% at 12 h. Furthermore, 5 μM of synthetic PapR peptide added to the culture of B. subtilis SC-8 increased the rate of BSAP-254 production up to 59.7%. The growth of B. subtilis SC-8, however, was not significantly different with or without the addition of PapR. When B. cereus papR mutant was co-cultured with B. subtilis SC-8, the growth of the mutant was not inhibited and the rate of BSAP-254 production was decreased by 45%.     

TLC densitometric quantification of picrosides (picroside-I and picroside-II) in Picrorhiza kurroa and its substitute Picrorhiza scrophulariiflora and their antioxidant studies

Picroside‐I and picroside‐II are known bioactive metabolites in Picrorhiza species. In the present study a simple, precise method has been established for the simultaneous determination of picrosides (picroside‐I and picroside‐II) in two different Picrorhiza species, P. kurroa and P. scrophulariiflora. This method was also validated for accuracy, precision, robustness, limit of detection and quantification, repeatability and recovery, according to International Conference of Harmonization guidelines. Separation and quantification was achieved by HPTLC using as the mobile phase chloroform–methanol (88:12, v/v) on precoated silica gel 60F₂₅₄ aluminum plates. Densitometric determination was carried out at wavelength λ_max 254 nm in UV absorbance mode. Comparative study also revealed that picroside‐I and picroside‐II are higher in P. scrophulariiflora than P. kurroa. Picroside‐I content was found to be 1.258 and 1.611%, and picroside‐II was estimated as 0.481 and 0.613% in P. kurroa and P. scrophulariiflora, respectively. Antioxidant potential of these two Picrorhiza species was also studied using DPPH. At a concentration of 0.1 mg/mL the scavenging activities of P. kurroa and P. scrophulariiflora were found to 37.70 and 34.30%, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of 2-[3-(trifluoromethyl)phenyl]furo[3,2-<Emphasis Type="Italic">c</Emphasis>]pyridine derivatives

2-[3-(Trifluoromethyl)phenyl]-4,5-dihydrofuro[3,2-c]pyridin-4-one (I) was prepared by a three-step synthesis. Its reaction with phosphorus sulfide rendered thione II which was methylated to 2-[3-(Trifluoromethyl)phenyl]-4-methylsulfanylfuro[3,2-c]pyridine (III). 5-Methyl-2-[3-(trifluoromethyl)phenyl]-4,5-dihydrofuro[3,2-c]pyridin-4-one (IV) was obtained by the reaction of I with methyl iodide in PTC conditions. The chlorine atom in derivate V was replaced with heterocyclic secondary amines via nucleophilic substitution and 4-substituted furopyridines VIa and VIb were thus prepared. 2-[3-(Trifluoromethyl)phenyl]furo[3,2-c]pyridine-4-carboxylic acid (VII) was obtained by hydrolysis of the corresponding carbonitrile Va.     

Ascorbate oxidase

Ascorbate oxidase fromCucurbita sp. was isolated by ammonium sulfate precipitation and DEAE-dextran-silochrome column chromatography. The thermal and pH stabilities of the purified enzyme were investigated. TheK _M forl-ascorbic acid (1.5 mM) and chlorohydroquinone (0.37 mM) was determined. Substrate specificity of ascorbate oxidase was investigated and compared with those of laccases fromCoriolus hirsutus andCerrena maxima. Ascorbate oxidase was covalently bound to a polymeric membrane and used in an enzyme electrode for ascorbic acid.