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V Wray

Publications and source records attributed to V Wray.

At least 73 records · Page 4Linked to original sources

Four new bioactive polybrominated diphenyl ethers of the sponge Dysidea herbacea from West Sumatra, Indonesia.

The marine sponge Dysidea herbacea collected from Indonesia yielded four new polybrominated diphenyl ether congeners 2-5 and the known derivatives 1, 6, and 7. The structures of the new compounds were unambiguously established on the basis of NMR spectroscopic (1H, 13C, COSY, 1H-detected direct and long-range 13C-1H correlations) and mass spectrometric (EIMS) data. All of the compounds were active against the Gram-positive bacteria Bacillus subtilis and the phytopathogenic fungus Cladosporium cucumerinum. The isolated polybrominated compounds were also active in the brine shrimp lethality test. In the latter bioassay, compounds 1 and 6 were the most active with LC50's of 0.96 [SE +/- 0.19] and 0.94 [SE +/- 0.70] microg/mL, respectively.

Animals↗

Assessment by 1H NMR spectroscopy of the structural behaviour of human parathyroid-hormone-related protein(1-34) and its close relationship with the N-terminal fragments of human parathyroid hormone in solution.

Human parathyroid-hormone-related protein (hPTHrP) is a hormone that is over-expressed by a large number of tumors and is produced by a variety of normal cells. Its main biological functions are shown by the N-terminal fragment (1-34) and are similar to those of parathyroid hormone with which it shares a common G-protein-coupled receptor. Hence to gain insight into the structure-function relationship of these hormones we have investigated the solution structure of hPTHrP(1-34) in pure water alone and have monitored the effect of adding TFE. CD spectra in pure water showed that it only possesses a small content of alpha-helical secondary structure, which from the NMR data, consists of a short unstable helix between Gln-16 and Leu-24 with the rest of the peptide in an essentially unstructured state. On adding 50% TFE (v/v) there was a considerable increase in stable secondary structure, without any evidence of stable tertiary structure. The subsequent structure calculations showed the presence of two well defined helices, from Ser-3 to Gly-12 and from Asp-17 to Thr-33, connected by a flexible linker. The similarity in behaviour of hPTHrP(1-34) and the N-terminal fragments of PTH under various solution conditions is shown from the 1H NMR data presented here and an extensive review of the literature data.

Amino Acid Sequence↗

Structure of stewartan, the capsular exopolysaccharide from the corn pathogen Erwinia stewartii.

Stewartan, the acidic exopolysaccharide of Erwinia stewartii, was purified from agar grown cells. To facilitate its structural analysis, chemical and enzymatic depolymerizations were carried out using hydrofluoric acid and E. amylovora phage phi-Ea1h, respectively. Structural characterization of the resulting oligosaccharides was performed by a combination of mass spectrometric and one- and two-dimensional (1D/2D) NMR spectroscopic techniques. A branched repeating unit with seven monosaccharide residues, all in their pyranose forms, was found: [Table: see text]

Bacterial Capsules↗

Structure of amylovoran, the capsular exopolysaccharide from the fire blight pathogen Erwinia amylovora.

The acidic exopolysaccharide (EPS) of Erwinia amylovora, amylovoran, was purified from culture supernatants of bacteria in minimal medium and cleaved chemically either by treatment with trifluoracetic acid or hydrofluoric acid, and enzymatically by digestion with depolymerase from E. amylovora phage phi-Ealh. Structural characterization of the resulting oligosaccharides was performed by a combination of mass spectrometric and NMR [one- and two-dimensional (1D and 2D)] spectroscopic techniques. A branched repeating unit with five monosaccharide residues and various substituents was determined: [sequence: see text] The terminal monosaccharide of the side branch, which bears a 4,6-bound pyruvate residue in the R-configuration, was found to be modified with 2-linked (26%), 3-linked (24%), 2-,3-linked (40%) O-acetyl groups, or these were absent (10%). An additional glucose residue is linked to approximately 10% of the core alpha-galactose of the repeating unit.

Bacterial Capsules↗

NMR spectroscopic evidence that helodermin, unlike other members of the secretin/VIP family of peptides, is substantially structured in water.

The structure in water and additionally in 50% trifluoroethanol (TFE) solution of helodermin, an amidated peptide consisting of 35 amino acids, was elucidated by 2D 1H NMR spectroscopy initially from H alpha chemical shifts and qualitative NOE data. Detailed structures were calculated from the quantitative NOE data which were used as distance restraints in molecular dynamics and energy minimization calculations. Regions of stable secondary structure were defined from the resulting final peptide conformations using a new fitting program that takes into account the summed RMS differences between all structures for short segments of 2-5 residues in length. This procedure allows a reasonably objective method of defining the edges of stable structure. In contrast to other members of the secretin/VIP family of peptides, helodermin shows a defined secondary structure in water alone and possesses an alpha-helix from Glu-9 to Leu-23 that was further stabilized and slightly extended (Phe-6 to Ala-24) on addition of TFE. The N- and C-termini were unstructured in both solutions. Such features, in particular the observation of a linear helix 18 +/- 2 residues in length, are common to other members of the family and become more pronounced in hydrophobic environments. The data provide further circumstantial evidence that an alpha-helix conformation is necessary for receptor binding. The prolonged physiological action of helodermin, compared to its C-terminal deletion analogues and VIP, is at least in part due to the unusual stable secondary structure.

Amino Acid Sequence↗

Metabolism of 5-chlorosubstituted muconolactones.

The stereochemistry of the four stereoforms of 5-chloro-3-methylmuconolactones could be deduced from NMR and stability data, and from the comparison with authentic (4R, 5S)-5-chloromuconolactone. Muconolactone isomerase of Alcaligenes eutrophus JMP 134 was shown to catalyze syn-elimination of hydrogen chloride from (4R, 5R)-5-chloro-3-methylmuconolactone, (4R, 5S)-5-chloro-3 -methylmuconolactone and (4R, 5S)-5-chloromuconolactone to form 3-methyl-trans-dienelactone, 3-methyl-cis-dienelactone and a 3:1 mixture of cis- and trans-dienelactone, respectively. 3-Methyl-trans-dienelactone was a substrate of pJP4-encoded dienelactone hydrolase of A. eutrophus JMP 134, whereas 3-methyl-cis-dienelactone transformation was negligible indicating a restricted substrate specificity of this enzyme. Both substrates were transformed into 3-methylmaleylacetate which in turn was a substrate for maleylacetate reductase. This compound was shown to possess a cyclic structure (4-hydroxy-3-methyl-muconolactone) under acidic conditions.

4-Butyrolactone↗

Triterpenoid saponins from Bellium bellidioides. Structures of the minor deacylsaponins.

A new deacylsaponin of polygalacic acid, desacylbellidioside B4, was obtained from the whole plants of Bellium bellidioides L. The structure has been elucidated by a general strategy involving mass spectrometry (ESI-MS, including tandem MS, and GC-MS) and high-field one- and two-dimensional NMR spectroscopy (1H and 13C NMR, COSY-45, HMQC, HMBC) as 3-O-alpha-L-rhamnopyranosyl-2 beta, 3 beta, 16 alpha, 23-tetrahydroxyolean-12-en-28-oic acid 28-O-alpha-L-rhamnopyranosyl(1-->3)-beta-D-xylopyranosyl(1-->4)-alpha-L- rhamnopyranosyl(1-->2)-[alpha-L-arabinofuranosyl(1-->3)-beta-D-fucopyran oside. Moreover, bellissaponin BS2 and besysaponin C12 have also been isolated, demonstrating the close chemical relationship of B. bellidioides to the Bellis genus.

Carbohydrate Conformation↗

A cyanogenic glycoside from Canthium schimperianum.

A new cyanogenic glycoside esterified with an iridoid glycoside, 2R-[(2-methoxybenzoylgenoposidyl)-5-O-beta-D-apiofuranosyl-( 1-->6)-beta-glucopyranosyloxy]-2-phenyl acetonitrile, was isolated from the seeds of Canthium schimperianum and identified from its spectroscopic data. The new compound showed weak growth retarding activity towards neonate larvae of Spodoptera littoralis (ED50 8580 ppm) compared to the co-occurring hydroxycinnamic acids, 3,4-dicaffeoylquinic acid (ED50 550 ppm) and 3,5-dicaffeoylquinic acid (ED50 520 ppm).

Animals↗

Betacyanins from plants and cell cultures of Phytolacca americana.

Betacyanins from cell cultures of Phytolacca americana were characterized and compared with those of the stems and ripening fruits of the plant. Whereas in fruits prebetanin (betanin 6'-O-sulphate) and its isoform predominate, in the stem and cell cultures feruloylated derivatives occur as the major components. These were rigorously identified by various spectroscopic techniques (DAD-HPLC, NMR, LC-MS and electrospray MS-MS) and carbohydrate analyses as betanidin 5-O-[(5"-O-E-feruloyl)-2'-O-beta-D-apiofuranosyl] -beta-D-glucopyranoside, a new betacyanin of higher plants, and betanidin 5-O-(6'-O-E-feruloyl)-beta-D-glucopyranoside (lampranthin II), together with their isoforms.

Betacyanins↗

Dhurrin-6'-glucoside, a cyanogenic diglucoside from Sorghum bicolor.

A novel cyanogenic diglucoside has been isolated from methanolic extracts of young seedlings of Sorghum bicolor. Its structure was established as dhurrin-6-glucoside from NMR, mass spectrometry and enzymatic hydrolysis data. Compared with dhurrin, which is the major cyanogenic glucoside in sorghum leaves, dhurrin-6-glucoside occurs only in low concentrations. In contrast, however, the diglucoside is present in significant amounts in guttation droplets of young Sorghum seedlings. The presence of the diglucoside and its occurrence in apoplasmic exudates supports the hypothesis that diglucosides represent metabolites of cyanogenic monoglucosides which can be translocated within the plant.

Hydrolysis↗

Triterpenoid saponins from Bellis sylvestris. 2. Structures of partially deacylated saponins.

Four saponins have been isolated from the herbal parts of Bellis sylvestris and the same, together with three further compounds, from the underground parts. The structures were elucidated by electrospray ionization mass spectrometry, including tandem mass spectrometry, and by 1D and 2D homonuclear and heteronuclear NMR spectroscopy. Two of the compounds are new saponins with the structures 3-O-beta-D-glucopyranosyl-2 beta, 3 beta, 23-trihydroxyolean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl (1-->3)-[alpha-L-rhamnopyranosyl (1-->2)]-beta-D- glucopyranoside and 3-O-beta-D-glucopyranosyl-2 beta, 3 beta,16 alpha, 23-tetrahydroxyolean-12-en- 28-oic acid 28-O-alpha-L-rhamnopyranosyl (1-->3)-beta-D-xylopyranosyl(1-->4)-alpha-L- rhamnopyranosyl(1-->2)-[(E)-2-butenoic acid (1-->3)]-beta-D-fucopyranoside. Taxonomically these data provide significant evidence of a link between the Bellis genus and Bellium bellidioides.

Carbohydrate Sequence↗

Triterpenoid saponins from Bellis bernardii.

Nine saponins were isolated from the deacylated saponin mixture obtained from the whole plants of Bellis bernardii. Their structures have been elucidated from NMR and MS data and by chemical derivatization. Three were glycosides of the recently reported bellisonic acid (2 beta, 3 beta,-23-trihydroxy-16-oxoolean-12-en-28-oic acid), with the major compounds being related glycosides of polygalacic acid (2 beta, 3 beta, 16 alpha, 23-tetrahydroxyolean-12-en-28-oic acid). In addition, a saponin of bayogenin (2 beta, 3 beta, 23-trihydroxyolean-12-en-28-oic acid) was obtained and is the first acyl glycoside of this aglycon with a free hydroxyl group at C-3.

Carbohydrate Sequence↗

Four new bioactive manzamine-type alkaloids from the Philippine marine sponge Xestospongia ashmorica.

Analysis of the Philippine marine sponge Xestospongia ashmorica afforded four new manzamine congeners 1-4 and four known compounds 5 and 7-9. Compound 1 is the 6-deoxy derivative of manzamine X, while 2-4 are the N-oxides of manzamine J (5), 3,4-dihydromanzamine A (6), and manzamine A (7), respectively. The structures of the new compounds were unambiguously established on the basis of NMR spectroscopic (1H, 13C, COSY, 1H-detected direct, and long-range 13C-1H correlations) and mass spectrometric (EI, FAB-MS, and electrospray ionization) data. Alkaloid N-oxide structures were confirmed by conversion to the corresponding tertiary bases by reduction with Zn/HCl. This is the first report of the occurrence of bioactive manzamine N-oxides in marine sponges. Compound 7 exhibited insecticidal activity toward neonate larvae of the polyphagous pest insect Spodoptera littoralis (with an ED50 of 35 ppm) when incorporated in artificial diet and offered to larvae in a chronic feeding bioassay. Compound 7 was also active against the Gram-positive bacteria Bacillus subtilis and Staphylococcus aureus. Cytotoxicity was studied in vitro using L1578y mouse lymphoma cells. From the alkaloids studied, the N-oxides 3 and 4 were the most active (ED50 = 1.6 micrograms/mL) followed by compound 7 (ED50 = 1.8 micrograms/mL).

Alkaloids↗

Application of MS-MS for the rapid, comparative analysis of saponin mixtures as exemplified by the deacylated and partially deacylated triterpenoid saponins of Bellis annua.

While most species of the Bellis genus are characterized by saponins in concentrations of ca.4% dry weight, Bellis annua only contains ca.0.3% saponins. Hence positive-ion electrospray ionization mass spectrometry, including MS-MS analysis, has been used extensively for the rapid identification of the saponins of B. annua obtained after mild alkaline hydrolysis. The saponin composition is similar to that of other Bellis species and, in addition, glycosides of the rare bellisonic acid, which has recently been found in B. bernardii, have been identified.

Carbohydrate Conformation↗

Solution structure of the cytoplasmic domain of the human immunodeficiency virus type 1 encoded virus protein U (Vpu).

The HIV-1-specific Vpu protein is an 81 amino acid class I integral membrane phosphoprotein that induces degradation of the virus receptor CD4 in the endoplasmic reticulum and enhances the release of virus particles from infected cells. Vpu is of amphipathic nature and consists of a hydrophobic N-terminal membrane anchor proximal to a polar C-terminal cytoplasmic domain. In our recent work, focussed on the structural analysis of the cytoplasmic tail, we established an alpha-helix-flexible-alpha-helix-turn model. Now we present the experimental solution structure of the Vpu cytoplasmic domain which has been elucidated in aqueous 50% trifluoroethanol solution by 2D 1H NMR spectroscopy, and restrained molecular dynamics and energy minimization calculations. Under these conditions the peptide, Vpu32-81, is predominantly monomeric and adopts a well defined helix-interconnection-helix-turn conformation, in which the four regions are bounded by residues 37-51, 52-56, 57-72 and 73-78. The presence of the cis isomer of Pro-75 manifests itself as a doubling of cross peaks of neighbouring residues in the 2D spectra. A related variant peptide, Vpum32-81, in which the Vpu-phosphoacceptor sites Ser52 and Ser56 were exchanged for Asn, adopts a very similar structure and, taken together, provides evidence that the second helix and the turn form a comparatively rigid region. Both helices are amphipathic in character, but show different charge distributions. In general the cytoplasmic region is N-terminally positively charged, passes through a region of alternating charges in helix 1 and then becomes negatively charged. The flexibility of the interconnection permits orientational freedom of the two helices. The motif found here is the first experimentally refined solution structure of the cytoplasmic domain of Vpu, and it is conceivable that these alpha-helices are important for a previously defined physical interaction with an alpha-helical Vpu-responsive element located within the cytoplasmic tail of CD4.

Amino Acid Sequence↗

Structure of recombinant human parathyroid hormone in solution using multidimensional NMR spectroscopy.

The solution structure of human parathyroid hormone, in the form of recombinant prolyl-hPTH(1-84), has been investigated by multidimensional NMR spectroscopy under conditions (aqueous trifluoroethanol) which favour the structured-state of the protein. Spin systems were identified from 3D 1H DQF (double-quantum filtered)-COSY and TOCSY spectra and sequence-specific assignments were from 2D 1H phase-sensitive NOESY spectra. Signal overlap was resolved in a 3D-NOESY-TOCSY spectrum and assignments were confirmed with 2D NOESY-15N-HMQC (heteronuclear multiple-quantum coherence) spectra taken of a sample universally labeled with 15N. A satisfactory set of final structures was calculated from the quantitative NOE data using restrained molecular dynamics and energy minimization calculations. The N-terminus is dominated by three, well defined helices between Ser-3 to Asn-10, Ser-17 to Lys-27 and Asp-30 to Leu-37, while the most significant structural features in the C-terminus are a short, less-well defined helix between Asn-57 to Ser-62 and a series of loose turns. These two terminal units are joined by an unstructured mid-region. The molecule shows a tendency towards tertiary structure, defined by a number of long-range NOEs. A detailed RMS deviation analysis allowed the final refined structures to be classified into a limited ensemble of stable conformations that reflect the inherent flexibility of the hormone in solution.

Amino Acid Sequence↗

Recognition of pituitary adenylate cyclase-activating polypeptide/vasoactive intestinal polypeptide (PACAP/VIP) hybrids and related peptides by rat brain membranes.

The binding to [125I]PACAP27 and adenylate cyclase activity have been investigated using rat brain membranes with substituted analogues of PACAP and VIP, including their hybrid peptides. Binding of [125I]PACAP27 was rapid, specific and reversible. Scatchard analysis revealed a single class of binding site, with a Kd = 457 +/- 117 pM, and a Bmax = 2.63 +/- 0.24 pmol.mg protein-1. Hybrids of PACAP, in which specific residues were substituted with the corresponding residues of VIP, and vice versa, as well as related analogues, were then tested for binding and adenylate cyclase activity. The results showed that N-terminal residues were important for recognition. In particular, multiple substituted analogues of PACAP by VIP, and vice versa, demonstrated that positions 4, 5 and 9 play a dominant role in the recognition of PACAP Type I receptor in rat brain membranes and account for the differences observed between PACAP and VIP. Substitutions in the C-terminal region at positions 24, 25 and 26 are not crucial for recognition specificity. PACAP-analogues provide evidence that positions 1 and 6 are essential for receptor recognition. The flexibility at position 21 also appears to play a role as substitution with Ala or Phe is tolerated, while Pro shows a significant loss both in binding affinity and adenylate cyclase activity.

Adenylyl Cyclases↗