Constituents of holothuroidea, 16. Determination of Absolute configuration of the branched methyl group in ante-iso type side chain moiety on long chain base of glucocerebroside from the sea cucumber Holothuria leucospilota

The absolute configuration of the branched methyl group in ante-iso type side chain moiety on the long chain base of glucocerebroside, HLC-2-A, which was isolated from the sea cucumber Holothuria leucospilota was determined. Oxidation of the glucocerebroside with ozone afforded C13-fragment including the ante-iso moiety. The optically active C13-fragment was synthesized asymmetrically by using the Wittig reaction from chiral synton for comparison with the natural fragment.     

Constituents of holothuroidea, 14. Isolation and structure of new glucocerebroside molecular species from the sea cucumber Stichopus japonicus

Five glucocerebroside molecular species, SJC-1-SJC-5, have been isolated from the less polar lipid fraction of a chloroform/methanol extract of the sea cucumber Stichopus japonicus. The structures of these glucocerebroside molecular species were determined on the basis of chemical and spectroscopic evidence. SJC-1, SJC-2, and SJC-3 are typical sphingosine- and phytosphingosine-type glucocerebroside molecular species with nonhydroxylated and hydroxylated fatty acyl moieties. SJC-4 and SJC-5 are also sphingosine-type glucocerebroside molecular species with hydroxylated fatty acyl moieties, although they are new glucocerebroside molecular species with unique sphingosine bases.     

Biologically active glycosides from Asteroidea, 41. Isolation and structure determination of glucocerebrosides from the starfish Linckia laevigata

A new glucocerebroside, linckiacerebroside A (1) and a known glucocerebroside S-2a-3 (2), have been isolated from the cerebroside molecular species obtained from the less polar fraction of the CHCl3/MeOH extract of the starfish Linckia laevigata, together with three pseudo homogeneous glucocerebroside, 3, 4, and 5. The structures of these cerebrosides were determined on the basis of chemical and spectroscopic evidence.     

Constituents of holothuroidea, 12. Isolation and structure of glucocerebrosides from the sea cucumber Holothuria pervicax

Ten glucocerebrosides, HPC-3-A-HPC-3-J, have been isolated from their obtained parent glucocerebroside molecular species HPC-3, together with other glucocerebroside molecular species HPC-1 and HPC-2, from the less polar lipid fraction of a chloroform/methanol extract of the sea cucumber Holothuria pervicax. The structures of these glucocerebrosides have been determined on the basis of chemical and spectroscopic evidence. Reversed-phase HPLC, including a recycling system, was effective in isolating these glucocerebrosides, revealing a very close resemblance in structure, though the problem due to regio-isomers remains.     

Constituents of Crinoidea, 4. Isolation and structure of ceramides and glucocerebrosides from the feather star Comanthus japonica

Five ceramides, JC-1-JC-5, and four glucocerebrosides, JCer-1-JCer-4, have been isolated from their parent ceramide and glucocerebroside molecular species JC and JCer obtained from the less polar lipid fraction of the chloroform/methanol extract of the feather star Comanthus japonica. The structures of these sphingolipids have been determined on the basis of chemical and spectroscopic evidence. Reversed-phase HPLC was effective at isolating these sphingolipids, revealing very close resemblance in their structures. JC-1, JC-3, JC-4, JC-5 and JCer-2, JCer-4 are newly found ceramides and glucocerebrosides, respectively.     

Liquid Chromatographic Analysis of Regioisomers and Enantiomers of N-(Chlorobenzyl)-α-Methylphenethylamines: Analogues of Clobenzorex

Abstract

The regioisomeric 2-, 3- and 4-chlorobenzylamphetamines were synthesized from racemic and (+)-amphetamine by reductive alkylation. The 2-, 3- and 4-chloro regioisomers were separated by reversed-phase liquid chromatography following phenylisothiocyanate derivatization. The indiviual enantiomers of each regio-isomer were identified by HPLC following derivatization with GITC. Normal phase liquid chromatographic analysis of the diastereomeric GITC derivatives produced α-values of approximately 1.0 for each racemic pair of regioisomers. These methods were developed in order to specifically identify the drug clobenzorex, d-N-(2-chlorobenzyl)-α-methylphenethylamine and distinguish it from its optical and regioisomers.     

Ultrasound assisted synthesis of starch-capped Cu2O NPs towards the degradation of dye and its anti-lung carcinoma properties

A unique starch encapsulated Cu₂O nanoparticles were synthesized through a simple and ‘green’ route using ultrasonic irradiation. The polar functional groups on the starch (OH) facilitate the NP capping and stabilization. Structural features of the material were assessed over several advanced techniques like fourier transformed infra-red (FT-IR), UV–vis spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), energy dispersive X-ray analysis (EDX) elemental mapping, transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis. It was catalytically explored in reducing an organic dye (Methylene blue - MB) in the presence of NaBH₄ at ambient conditions, being monitored in a UV–vis spectrophotometer. The nanocatalyst was recycled 11 times keeping consistency in its reactivity. Biologically, the nanocomposite exhibited excellent cytotoxicity against lung adenocarcinoma (PC-14, LC-2/ad and HLC-1) cell lines without affecting the normal (HUVEC) cell line. IC₅₀values of the nanocomposite were found at 618, 56 and 379 against HLC-1, LC-2/ad, and PC-14 cell lines respectively and accordingly, PC-14 afforded the best adenocarcinoma activity.     

NMR study on iridium(III) complexes for identifying disulfonate substituted bathophenanthroline regio-isomers

A series of novel biscyclometalated iridium (III) complexes with an ancillary disulfonated bathophenanthroline (DSBP(2-)) ligand, Ir(L)(2)DSBPNa, L = 2-phenylpyridine (ppy), 2,4-difluorophenylpyridine (fppy), and 1-phenylisoquinoline (piq) were found to have two isomeric forms. The chemical structures of the isomers were determined by the one- and two-dimensional (1)H and (13)C NMR studies. The isomeric state was proved to have originated from the disulfonate-related regio-isomer of the DSBP(2-) ligand.     

Facile preparation of Kaolin supported silver nanoparticles mediated by Thymbra spicata extract and investigation of the anti-human lung cancer properties

The present work demonstrates the synthesis of kaolin supported Ag nanoparticles (AgNPs@Kaolin) by using an aqueous extract of Thymbra spicata as a green reductant and capping agent. Physicochemical characteristics of the synthesized nanocomposite were studied by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), elemental mapping, X-ray diffraction (XRD) and inductively coupled plasma (ICP) techniques. The biogenic AgNPs are uniformly globular. Owing to the surface modification by the plant derived phytochemicals, the NPs are found to be distributed evenly on the kaolin surface. The AgNPs@Kaolin nanocomposite has been explored biologically in the anticancer and antioxidant assays. In the cellular and molecular part of the recent study, the treated cells with AgNPs@Kaolin nanocomposite were assessed by MTT assay for 48 h about the cytotoxicity and anti-human lung adenocarcinoma properties on normal (HUVEC) and lung adenocarcinoma cell lines i.e. lung well-differentiated bronchogenic adenocarcinoma (HLC-1), lung moderately differentiated adenocarcinoma (LC-2/ad), and lung poorly differentiated adenocarcinoma (PC-14). The viability of malignant lung cell line reduced dose-dependently in the presence of AgNPs@Kaolin nanocomposite. The IC50 of AgNPs@Kaolin nanocomposite were 509, 315, and 189 µg/mL against HLC-1, LC-2/ad, and PC-14 cell lines, respectively. In the antioxidant test, the IC50 of AgNPs@Kaolin nanocomposite and BHT against DPPH free radicals were 125 and 161 µg/mL, respectively. After the clinical study, AgNPs@Kaolin nanocomposite containing T. spicata leaf aqueous extract may be used to formulate a new chemotherapeutic drug or supplement to treat the several types of human lung adenocarcinoma.     

Citrus sinensis leaf aqueous extract green-synthesized silver nanoparticles: Characterization and cytotoxicity,antioxidant, and anti-human lung carcinoma effects

The present work demonstrates the synthesis of Ag nanoparticles (Ag NPs) by using aqueous extract of Citrus sinensis as green reductant and capping agent without any toxic reagent. Physicochemical characteristics of the said nanoparticles were elucidated by field emission scanning electron microscopy (FESEM), fourier transform infrared spectroscopy (FTIR), and ultraviolet–visible spectroscopy (UV-Vids) techniques. The biogenic Ag NPs are uniformly globular. The Ag NPs has been explored biologically in the anticancer and antioxidant assays. In the cellular and molecular part of the recent study, the treated cells with Ag NPs were assessed by MTT assay for 48 h about the cytotoxicity and anti-human lung carcinoma properties on normal (HUVEC) and lung carcinoma cell lines i.e. NCI-H661, HLC-1, NCI-H1563, LC-2/ad, NCI-H1299, and PC-14. The viability of malignant lung cell line reduced dose-dependently in the presence of Ag NPs. The IC50 of Ag NPs were 82, 139, 170, 66, 62, and 50 µg/mL against NCI-H661, HLC-1, NCI-H1563, LC-2/ad, NCI-H1299, and PC-14 cell lines, respectively. In the antioxidant test, the IC50 of Ag NPs and vitamin E against 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals were 21 and 15 µg/mL, respectively. After clinical study, Ag NPs containing Citrus sinensis leaf aqueous extract may be used to formulate a new chemotherapeutic drug or supplement to treat the several types of human lung adenocarcinoma.     

Total synthesis of a macrocyclic spermidine alkaloid,codonocarpine

Total synthesis of codonocarpine ($\text{5}$) and its regio-isomer ($\text{1}$$\text{5}$) utilizing a new cyclization procedure is described.     

Substitution reactions of phenanthro[9,10-d]triazole with benzyl chlorides

The reaction of the potassium salt of phenanthro[9,10-d]triazole and benzyl chloride gave 2-(benzyl)-2H-phenanthro[9,10-d]triazole ( 2a ) in 15% yield. The other regio-isomer, 1-(benzyl)-1H-phenanthro[9,10-d]-triazole ( 1a ), was obtained as a by-product in 3.9% yield. Similar reactions with benzyl chlorides having a methyl, a chloro or a nitro group on the aromatic ring gave the corresponding two products, 1b-j and 2b-j . In all cases, 2b-j were major products in yields of 14–62%, 1b-j were minor ones in yields of 1.4–7.6%. The structures of the isomers were confirmed by X-ray crystal analyses.     

Impact on lipid membrane organization by free branched-chain fatty acids

Here, we exploit the non-invasive techniques of solid-state NMR (nuclear magnetic resonance) and differential scanning calorimetry (DSC) to study the effect of free iso and ante-iso branched chain fatty acids (BCFAs) on the physicochemical properties of lipid membranes. Free fatty acids are present in biological membranes at low abundance, but can influence the cellular function by modulating the membrane organization. Solid state NMR spectra of dimyristoylphosphatidylcholine (DMPC) lipid membranes containing either free 12-methyltetradecanoic acid (a15:0) or free 13-methyltetradecanoic acid (i15:0), show significant differences in their impact on the lipid bilayer. Chain order profiles obtained by deuterium NMR on fully deuterated DMPC-d(67) bilayers revealed an ordering effect induced by both fatty acids on the hydrophobic membrane core. This behavior was also visible in the corresponding DSC thermograms where the main phase transition of DMPC bilayers-indicative of the hydrophobic membrane region-was shifted to higher temperatures, with the iso isomer triggering more pronounced changes as compared to the ante-iso isomer. This is probably due to a higher packing density in the core of the lipid bilayer, which causes reduced diffusion across membranes. By utilizing the naturally occurring spin reporters nitrogen-14 and phosphorus-31 present in the hydrophilic DMPC headgroup region, even fatty acid induced changes at the membrane interface could be detected, an observation reflecting changes in the lipid headgroup dynamics.     

高效液相色谱法分析大豆中磷脂酰胆碱的分子种

用高效液相色谱法（HPLC）在正相半制备硅胶柱上将大豆磷脂酰胆碱与其它组分分离，从柱后收集磷脂酰胆碱（PC），然后在反相C18柱上分析其分子种组成，蒸发光散射检测器检测。在25min内将大豆磷脂酰胆碱分离成11个分子种组分，使用易挥发溶剂，可获得各种分子种的纯物质，供进一步分析。分子种根据HPLC峰的脂肪酸组成分析而确定。     

Efficient stereocontrolled synthesis of sphingadienine derivatives

Sphinga-4,8-dienines, principal long-chain bases of glycolipids in plants and fungi, were efficiently synthesized from l-serine. Hydrozirconation of pentadec-5-en-1-ynes followed by ZnBr₂-catalyzed addition to Garner's aldehyde afforded protected sphinga-4,8-dienines stereoselectively. The (2S,3R,4E,8E)-9-methyl-sphingadienine derivative was then coupled with 2(R)-acetoxypalmitic acid derivative prepared via asymmetric dihydroxylation to give a protected ceramide, which was converted into the corresponding glucocerebroside in two steps.     

Rubber networks containing unattached macromolecules. I. Linear viscoelastic properties of the system butyl rubber–polyisobutylene

Mixtures of butyl rubber with polyisobutylene (molecular weights 0.055 and 2.3 × 10⁶) up to 50% by weight were crosslinked by sulfur, leaving the polyisobutylene molecules free to reptate in the butyl rubber network. Linear viscoelastic properties were measured in shear creep for periods up to 5 × 10⁵ sec at 25°C and oscillating shear deformations from 0.1 to 3 Hz, at temperatures from 2 to 63°C. Comparison with the properties of a butyl rubber crosslinked without polyisobutylene showed contributions to creep and mechanical loss attributable to the reptating species. Comparison with the properties of polyisobutylene (higher molecular weight) showed that the relaxation times associated with the reptating species in the upper part of the terminal zone are the same for different polyisobutylene contents (25% and 50%) and for 100% polyisobutylene in which no permanent network is present; their contributions to modulus appear to be proportional to the volume fraction of polyisobutylene to a power of about 2/3. The time required in stress relaxation for the portion of the modulus attributable to the reptating species to decay to half its plateau value is, based on the two molecular weights employed, proportional to the polyisobutylene molecular weight to the third power. The magnitude of the associated mechanical loss and its location on the frequency scale can thus be controlled independently.     

Comparative analysis of ceramide structural modification found in fungal cerebrosides by electrospray tandem mass spectrometry with low energy collision-induced dissociation of Li+ adduct ions

Fungal cerebrosides (monohexosylceramides, or CMHs) exhibit a number of ceramide structural modifications not found in mammalian glycosphingolipids, which present additional challenges for their complete characterization. The use of Li+ cationization, in conjunction with electrospray ionization mass spectrometry and low energy collision-induced dissociation tandem mass spectrometry (ESI-MS/CID-MS), was found to be particularly effective for detailed structural analysis of complex fungal CMHs, especially minor components present in mixtures at extremely low abundance. A substantial increase in both sensitivity and fragmentation was observed on collision-induced dissociation of [M + Li]+ versus [M + Na]+ of the same CMH components analyzed under similar conditions. The effects of particular modifications on fragmentation were first systematically evaluated by analysis of a wide variety of standard CMHs expressing progressively more functionalized ceramides. These included bovine brain galactocerebrosides with non-hydroxy and 2-hydroxy fatty N-acylation; a plant glucocerebroside having (E/Z)-delta8 in addition to (E)-delta4 unsaturation of the sphingoid base; and a pair of fungal cerebrosides known to be further modified by a branching 9-methyl group on the sphingoid moiety, and to have a 2-hydroxy fatty N-acyl moiety either fully saturated or (E)-delta3 unsaturated. The method was then applied to characterization of both major and minor components in CMH fractions from a non-pathogenic mycelial fungus, Aspergillus niger; and from pathogenic strains of Candida albicans (yeast form); three Cryptococcus spp. (all yeast forms); and Paracoccidioides brasiliensis (both yeast and mycelium forms). The major components of all species examined differed primarily (and widely) in the level of 2-hydroxy fatty N-acyl delta3 unsaturation, but among the minor components a significant degree of additional structural diversity was observed, based on differences in sphingoid or N-acyl chain length, as well as on the presence or absence of the sphingoid delta8 unsaturation or 9-methyl group. Some variants were isobaric, and were not uniformly present in all species, affirming the need for MS/CID-MS analysis for full characterization of all components in a fungal CMH fraction. The diversity in ceramide distribution observed may reflect significant species-specific differences among fungi with respect to cerebroside biosynthesis and function.     

Structural insights into the mechanism of translational inhibition by the fungicide sordarin

The translational machinery has been found to be the target for a number of antibiotics. One such antibiotic sordarin selectively inhibits fungal translation by impairing the function of elongation factor 2 (eEF2) while being ineffective to higher eukaryotes. Surprisingly, sordarin is not even equally effective in impairing translation for all fungal species. The binding cavity of sordarin on eEF2 has been localized by X-ray crystallographic study and its unique specificity towards sordarin has been attributed to the species specific substitutions within a stretch of amino acids (sordarin specificity region, SSR) at the entrance of the cavity. In this study, we have analyzed the sordarin-binding cavity of eEF2 from different species both in isolated and ribosome-bound forms in order to decipher the mechanism of sordarin binding selectivity. Our results reveal that the molecular architecture as well as the microenvironment of the sordarin-binding cavity changes significantly from one species to another depending on the species specific substitutions within the cavity. Moreover, eEF2 binding to ribosome aggravates the effects of these substitutions. Thus, this study, while shedding light on the molecular mechanism underpinning the selective inhibitory effects of sordarin, will also be a helpful guide for future studies aiming at developing novel antifungal drugs with broader spectrum of activity.     

Isolation and structure of a galactocerebroside molecular species from the starfish Culcita novaeguineae

A galactocerebroside molecular species, CNC-2, has been isolated from the less polar lipid fraction of a chloroform/methanol extract of the starfish Culcita novaeguineae. The structure of this galactocerebroside molecular species was determined on the basis of chemical and spectroscopic evidence. CNC-2 is a phytosphingosine-type galactocerebroside molecular species with nonhydroxylated and hydroxylated fatty acyl moieties. The isolation of a galactocerebroside from echinoderms is rare.     

铜磷铝分子筛的合成及其对苯液相氧化制苯酚的催化性能

 以水热法合成了铜磷铝分子筛(Cu-AlPO4-5),并用XRD,ICP,SEM,FT-IR,NH3-TPD,H2-TPR,ESR和N2吸附-脱附等手段对样品进行了表征. 结果表明,所合成的Cu-AlPO4-5分子筛具有AFI拓扑结构,结晶度高,无结晶态杂质; Cu2+进入到分子筛的骨架结构中,并使其Lewis酸和Brnsted酸中心数量增加,弱酸性中心大大增强,强酸性中心消失; 样品中的Cu存在多种形式,以骨架Cu物种为主,还存在 泄羌芡釩uO和双核Cu物种,部分样品具有缺陷结构. Cu-AlPO4-5分子筛中存在着骨架Cu和缺陷结构两种可能的活性中心,对苯液相氧化具有良好的催化性能,苯酚选择性可达96%,收率可达6.9%.