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1.
The preparation of [PtCl4] [ICl4] is described. Its structure was determined by both X-ray analysis and Raman spectroscopy. This compound is orthorhombic, space group Imma with a = 12.315(1), b = 16.302(2), c = 12.215(1) Å V = 2452(1) Å3 and Z = 8. The structure was refined by least squares to R = 3.2% using 753 observed refiections. The PtCl4+ cation is tetrahedral with Td symmetry, whereas the two crystallographically independent ICl4 anions are square planar - one with an almost ideal D4h symmetry and the other slightly distorted to a C2v symmetry. The I-Cl distances are in the range of 2.461(4)-2.508(3) Å.  相似文献   

2.
The trinitrophenyl group was specifically introduced into the ?-amino group of glucagon by reaction of Nα-citraconyl glucagon with trinitrobenzenesulfonic acid. The Nα-citraconyl blocking group was subsequently removed by acid treatment yielding N?-trinitrophenyl glucagon which was purified by anion-exchange chromatography. The derivative showed less secondary structure as measured by circular dichroism than the native hormone at pH 8.0 and at pH 2.0 in the presence of sodium dodecyl sulfate. The analog possessed 4–5% the potency of glucagon in stimulating adenylate cyclase with 90% maximal stimulation and possessed 30% the potency of glucagon in competing for glucagon-specific receptor sites in hepatic plasma membranes. Although the structure of N?-trinitrophenyl glucagon is very similar to N?-4-azido-2-nitrophenyl glucagon, the photoaffinity antagonist synthesized by M. D. Bregman and D. Levy [(1977) Biochem. Biophys. Res. Commun., 78, 584–590.], the biological activities of the two are different. Possible explanations for these differences are discussed.  相似文献   

3.
Viruses of the Birnaviridae family are characterized by their bisegmented double-stranded RNA genome that resides within a single-shelled non-enveloped icosahedral particle. They infect birds, aquatic organisms, and insects. Tellina virus 1 (TV-1) is an Aquabirnavirus isolated from the mollusk Tellina tenuis. It encodes a polyprotein (NH2-pVP2-X-VP4-VP3-COOH) that is cleaved by the self-encoded protease VP4 to yield capsid precursor protein pVP2, peptide X, and ribonucleoprotein VP3. Here we report the crystal structure of an intramolecular (cis) acyl-enzyme complex of TV-1 VP4 at 2.1-Å resolution. The structure reveals how the enzyme can recognize its own carboxyl terminus during the VP4/VP3 cleavage event. The methyl side chains of Ala830(P1) and Ala828(P3) at the VP4/VP3 junction point into complementary shallow and hydrophobic S1 and S3 binding pockets adjacent to the VP4 catalytic residues: nucleophile Ser738 and general base Lys777. The electron density clearly shows that the carbonyl carbon of Ala830 is covalently attached via an ester bond to the Oγ of Ser738. A highly ordered water molecule in the active site is coordinated in the proper position to act as the deacylating water. A comparative analysis of this intramolecular (cis) acyl-enzyme structure with the previously solved intermolecular (trans) acyl-enzyme structure of infectious pancreatic necrosis virus VP4 explains the narrower specificity observed in the cleavage sites of TV-1 VP4.  相似文献   

4.
The structure of the O-antigen polysaccharides (PS) from the enteroaggregative Escherichia coli strain 94/D4 and the international type strain E. coli O82 have been determined. Component analysis and 1H, 13C, and 31P NMR spectroscopy experiments were employed to elucidate the structure. Inter-residue correlations were determined by 1H, 13C-heteronuclear multiple-bond correlation, and 1H, 1H-NOESY experiments. d-GroA as a substituent is linked via its O-2 in a phosphodiester-linkage to O-6 of the α-d-Glcp residue. The PS is composed of tetrasaccharide repeating units with the following structure:→4)-α-d-Glcp6-(P-2-d-GroA)-(1→4)-β-d-Galp-(1→4)-β-d-Glcp-(1→3)-β-d-GlcpNAc-(1→Cross-peaks of low intensity from an α-d-Glcp residue were present in the NMR spectra and spectral analysis indicates that they originate from the terminal residue of the polysaccharide. Consequently, the biological repeating unit has a 3-substituted N-acetyl-d-glucosamine residue at its reducing end. Enzyme immunoassay using specific anti-E. coli O82 rabbit sera showed identical reactivity to the LPS of the two strains, in agreement with the structural analysis of their O-antigen polysaccharides.  相似文献   

5.
The eukaryotic translation initiation factor eIF4E recognizes the mRNA cap, a key step in translation initiation. Here we have characterized eIF4E from the human parasite Schistosoma mansoni. Schistosome mRNAs have either the typical monomethylguanosine (m7G) or a trimethylguanosine (m2,2,7G) cap derived from spliced leader trans-splicing. Quantitative fluorescence titration analyses demonstrated that schistosome eIF4E has similar binding specificity for both caps. We present the first crystal structure of an eIF4E with similar binding specificity for m7G and m2,2,7G caps. The eIF4E·m7GpppG structure demonstrates that the schistosome protein binds monomethyl cap in a manner similar to that of single specificity eIF4Es and exhibits a structure similar to other known eIF4Es. The structure suggests an alternate orientation of a conserved, key Glu-90 in the cap-binding pocket that may contribute to dual binding specificity and a position for mRNA bound to eIF4E consistent with biochemical data. Comparison of NMR chemical shift perturbations in schistosome eIF4E on binding m7GpppG and m2,2,7GpppG identified key differences between the two complexes. Isothermal titration calorimetry demonstrated significant thermodynamics differences for the binding process with the two caps (m7G versus m2,2,7G). Overall the NMR and isothermal titration calorimetry data suggest the importance of intrinsic conformational flexibility in the schistosome eIF4E that enables binding to m2,2,7G cap.  相似文献   

6.
To investigate the mutation mechanism of purine transitions in DNA damaged with methoxyamine, a DNA dodecamer with the sequence d(CGCAAATTmo4CGCG), where mo4C is 2′-deoxy-N4-methoxycytidine, has been synthesized and the crystal structure determined by X-ray analysis. The duplex structure is similar to that of the original undamaged B-form dodecamer, indicating that the methoxylation does not affect the overall DNA conformation. Electron density maps clearly show that the two mo4C residues form Watson–Crick-type base pairs with the adenine residues of the opposite strand and that the methoxy groups of mo4C adopt the anti conformation to N3 around the C4–N4 bond. For the pair formation through hydrogen bonds the mo4C residues are in the imino tautomeric state. Together with previous work, the present work establishes that the methoxylated cytosine residue can present two alternate faces for Watson–Crick base-pairing, thanks to the aminoimino tautomerism allowed by methoxylation. Based on this property, two gene transition routes are proposed.  相似文献   

7.
C10H26N10ONiZn, tris(1,2-diaminoethane) zinc(II) tetrakis(cyano)niccolate(II) monohydrate (I), orthorhombic, Pbca, a = 1.1680(4), b = 1.5844(3), c = 1.9981(6) nm, Z = 8 d(meas) = 1.54, d(calc) = 1.53 g cm?3. C10H24N10NiZn, tris(1,2-diaminoethane) zinc(II) terakis(cyano)niccolate(II), (II), monoclinic, P21/n, a = 0.7957(2), b = 1.5170(5), c = 1.4932(4) nm, β = 96.41(2)°, Z = 4, d(meas) = 1.49, d(calc) = 1.51 g cm?3. Both the structures (I) and (II) have been solved by the heavy atom method and refined by full-matrix least-squares to R(I) = 0.086 for 1890 independent reflections and R(II) = 0.058 for 1689 independent reflections, respectively. In the case of (II) the superlattice structure problem was solved. The crystal structure of (I) consists of [Zn(en)3]2+ cations, [Ni(CN)4]2? anions and water molecules. Two of the cyano groups in trans positions are bonded to water molecules by hydrogen bonds, the distances CN?O being 0.289 and 0.291 nm, respectively. The crystal structure of (II) is constituted by [Zn(en)3]2+ cations and [Ni(CN)4]2? anions.  相似文献   

8.
The new adduct 3-(2-carboxyethyl)cytosine (3-CEC) was isolated following in vitro reaction of the carcinogen β-propiolactone (BPL) with calf thymus DNA. The structure of 3-CEC was confirmed by synthesis from BPL and dCyd. Reaction of BPL with cCyd (pH 7.0–7.5, 37°C) gave 3-(2-carboxyethyl)deoxycytidine (3-CEdCyd) (9% yield) and 3,N4-bis(2-carboxyethyl)deoxycytidine (3,N4-BCEdCyd) (0.6% yield). 3-CEdCyd and 3,N4-BCEdCyd were hydrolyzed (1.5 N HC1, 100°C, 2 h) to 3-CEC and 3,N4-bis(2-carboxyethyl)cytosine (3,N4-BCEC), respectively. The structure of 3-CEC was assigned on the basis of UV and NMR spectra and the electron impact (EI) mass spectra of 3-CEC and a tri-trimethylsilyl (TMS) derivative of 3 CEC as well as deuterated (d27) tri-TMS derivative of 3-CEC. The structure of 3,N4-BCEC was assigned on the basis of UV spectra and the EI mass spectra of a tri-TMS derivative. EI and isobutane chemical ionization mass spectra of 3-methylcytosine (3-MeCyt) and a di-TMS derivative of 3-MeCyt were obtained and were helpful in deducing the structures of 3-CEC and 3,N4-BCEC. This is the first report of the alkylation by BPL of an exocyclic atom on a base in DNA. Compound 3,N4-BCEC was not detected in BPL-reacted calf thymus DNA. The relative amounts of 1-(2-carboxyethyl)adenine (1-CEA), 7-(2-carboxyethyl)guanine (7-CEG), 3-(2-carboxyethyl)thymine (3-CET) and 3-CEC isolated from BPL-reacted DNA following perchloric acid hydrolysis were 0.23, 1.00, 0.39 and 0.41 respectively, when the alkylation reaction was conducted in phosphate buffer at 0–5°C and pH 7.5 and 0.10, 1.00, 0.29 and 0.28 respectively when the reaction was conducted in H2O at 37°C and pH 7.0–7.5.  相似文献   

9.
《Inorganica chimica acta》1988,147(2):189-197
Complexes of the M(en)3Ag2(CN)4 (M = Ni, Zn, Cd) and M(en)2Ag2(CN)4 (M = Ni, Cu, Zn, Cd) type were prepared and identified by elemental analysis, infrared spectroscopy, measurement of magnetic susceptibility, and X-ray powder diffractometry. The crystal structures of Ni(en)3Ag2(CN)4 (I) and Zn(en)2Ag2(CN)4 (II) were determined by the method of monocrystal structure analysis. Complex I crystallizes in the space group C2/c, a = 1.2639(5), b = 1.3739(4), c = 1.2494(4) nm, β = 113.25(4)°, Dm = 1.86(1), Dc = 1.86 gcm−3 Z = 4, R = 0.0429. The crystal structure of I consists of complex cations [Ni(en)3]2+ and complex anions [Ag(CN)2]. Complex II crystallizes in the space group I2/m, a = 0.9150(3), b = 1.3308(4), c = 0.6442(2) nm, β = 95.80(3)°, Dm = 2.14(1), Dc = 2.15 gcm−3, Z = 2, R = 0.0334. Its crystal structure consists of infinite, positively charged chains of the [-NCAgCNZn- (en)2]nn+ type and isolated [Ag(CN)2] anions. The atoms of Ag are positioned parallely to the z axis and the AgAg distance is equal to 0.3221(2) nm.  相似文献   

10.
The O-polysaccharide of Mesorhizobium loti HAMBI 1148 was obtained by mild acid degradation of the lipopolysaccharide and studied by sugar and methylation analyses, Smith degradation, and 1H and 13C NMR spectroscopies, including 2D 1H/1H COSY, TOCSY, ROESY, and H-detected 1H/13C HSQC experiments. The O-polysaccharide was found to have a branched hexasaccharide-repeating unit of the following structure:where 2-acetamido-2-deoxy-4-O-methyl-d-glucose (d-GlcNAc4Me) and methyl group on 2-substituted d-rhamnose (Me) shown in italics are present in ∼80% and ∼40% repeating units, respectively. Similar studies of the O-polysaccharide from Mesorhizobium amorphae ATCC 19655 by sugar analysis and NMR spectroscopy revealed essentially the same structure but a higher content of 3-O-methyl-d-rhamnose (∼70%).  相似文献   

11.
The crystal structure of the Tl+ form of the G-quadruplex formed from the Oxytricha nova telomere sequence, d(G4T4G4), has been solved to 1.55 Å. This G-quadruplex contains five Tl+ ions, three of which are interspersed between adjacent G-quartet planes and one in each of the two thymine loops. The structure displays a high degree of similarity to the K+ crystal structure [Haider et al. (2002), J. Mol. Biol., 320, 189–200], including the number and location of the monovalent cation binding sites. The highly isomorphic nature of the two structures, which contain such a large number of monovalent binding sites (relative to nucleic acid content), verifies the ability of Tl+ to mimic K+ in nucleic acids. Information from this report confirms and extends the assignment of 205Tl resonances from a previous report [Gill et al. (2005), J. Am. Chem. Soc., 127, 16 723–16 732] where 205Tl NMR was used to study monovalent cation binding to this G-quadruplex. The assignment of these resonances provides evidence for the occurrence of conformational dynamics in the thymine loop region that is in slow exchange on the 205Tl timescale.  相似文献   

12.
A new eudesmane-type sesquiterpenoid together with two known flavonoids were isolated from the chloroform extract of the aerial part of Sclerorhachis platyrachis. The structure of the new compound was deduced from its comprehensive spectroscopic analysis including IR, EI-MS, 1H NMR, 13C NMR, DEPT, COSY, HMBC and HMQC and was shown to be 4R*-hydroxy-6S*-tigloyloxyeudesma-7S*-11 (13)-en-12-oic acid (1). Finally, the structure of the new compound was unambiguously confirmed by single-crystal X-ray analysis. The structure of known compounds 2 and 3 were identified by comparison of their spectral data with those reported in the literature.  相似文献   

13.
The reaction of [(η4-1,5-C8H12)2Ir2(μ-Cl)2] with 2-di-t-butylphosphino-2′-methylbiphenyl (t-Bu2PbiphMe) in the presence of AgBF4 afforded the dichlorido-bridged Ir–Ag complex [(η4-1,5-C8H12)Ir(μ-Cl)2Ag(t-Bu2PbiphMe)] (1) which was fully characterized by a single crystal X-ray diffraction study. Sequential treatment of the diiridium precursor first with the silver salt and then with the phosphine yielded cyclometalated [(η4-1,5-C8H12)Ir(t-Bu2PbiphMe–H+)] (2). Detailed DFT calculations gave evidence that the phosphine ligand of 2 forms a strained four-membered iridaheterocycle through orthometalation rather than a sterically congested six-membered chelate structure through C–H activation on the remote phenyl ring. The phosphonium salt [t-Bu2P(H)biphMe]BF4 was isolated as a by-product of the preparations of 1 and 2; its crystal structure was determined.  相似文献   

14.
An epimeric mixture of two novel cyclopentenoid cyanogenic glycosides, passibiflorin [1-(6-O-β-D-rhamnopyranosyl-β-D-glucopyranosyloxy)-4-hydroxycyclopent-2-en-1-nitrile] and its C-1 epimer, epipassibiflorin, has been isolated from Passiflora biflora and P. talamancensis. The structures were determined by means of 1H NMR and 13C NMR. Another novel cyclopentenoid cyanogenic glycoside, passitrifasciatin [1-(4-O-β-D-rhamnopyranosyl-β-D-glucopyranosyloxy)-4-hydroxycyclopent-2-en-1-nitrile] is described from Passiflora trifasciata. The structure was determined by means of 1H NMR. The identification of the sugar moieties was made by HPLC and TLC. The isolation of a β-1 → 4 and a β-1 → 6-rhamnoglucoside of cyclopentenoid cyanogens from three species of subgenus Plectostemma of Passiflora suggests that diglycosides of this type are taxonomically diagnostic for the section.  相似文献   

15.
《Inorganica chimica acta》1986,117(2):183-185
The new ternary uranium-palladium-sulfide UxPd3S4 (0.9<x<1) crystallizes in the cubic system a =6.639(2) Å, space group Pm3n, with a platinum bronze type structure. Refinement of the structure of a single crystal grown by the chemical vapour transport method revealed an incomplete uranium site filling in the crystal lattice, corresponding to the formula: Uo.92Pd3S4. The crystal radius of the uranium is found to be intermediate between U3+ and U4+. so that the uranium is expected to be in an intermediate valence state.  相似文献   

16.
《Phytochemistry》1987,26(6):1747-1750
The aerial parts of Stevia ovata afforded three sesquiterpene lactones, of which one was new. Its structure was established by spectroscopic methods and chemical reactions. One of the compounds, 4α,5β-epoxy-8-epi-inunolide was chemically correlated with 11,13-dehydroeriolin. The structure of the latter was confirmed by single crystal X-ray diffraction. The conformation of 11,13-dehydroeriolin in the solid is chair-chair [15D5,1D14].  相似文献   

17.
《Inorganica chimica acta》1986,112(2):107-112
The synthesis and crystal and molecular structure of the first zinc(II) mixed ligand chelate containing a dithiolene ligand (maleonitriledithiolate) and N,N- diethyldithiocarbamate are reported. The compound Ph4As[Zn(mnt)(Et2dtc)] crystallizes monoclinic, space group P21/c with four molecules in the unit cell; a=17.834(3), b=12.056(2), c=16.171(4) Å, β=93.73(2)°.The coordination geometry of the ZnS4 unit is nearly tetrahedral, with a dihedral angle of 87.6° between the chelate rings. The structure is compared with those of both the patent compounds (Ph4- As)2[Zn(mnt)2] and Zn2(Et2dtc)4. Ph4As[Zn(mnt)(Et2dtc)] could be used as the host lattice in single- crystal ESR investigations of the planar Cu mixed ligand complex. The rhombic spin-Hamiltonian parameters g and ACu are indicative of a low symmetry of the incorporated [Cu(mnt)(Et2dtc)] complex anions. In order to substantiate the experimental findings about the actual structure of the copper molecules, the principal values of g and ACu were recalculated by means of Extended Hückel MO calculations. However, the calculations performed for the dihedral angles between the ligand planes varying between 0° and 90° suggest that the rotation of the ligands is not larger than 10°  相似文献   

18.
The synthesis and characterization of (TptBu,Me)Yb(BH4)(THF)n (n = 0, 3; n = 1, 4) complexes are reported. The compounds represent rare examples of lanthanide (II) tetrahydroborate complexes. The X-ray crystal structure of complex 4 has been determined and it shows a monomeric, formally seven coordinate ytterbium center, bearing one κ3 bonded TptBu,Me ligand, a tetrahydroborate ligand and a coordinated THF molecule. The tetrahydroborate ligand binds in a κ3 fashion, via three bridging hydrogen atoms. IR spectroscopy data are consistent with the solid-state structure and the corresponding BD4 analog of 4 shows the expected IR isotope shifts. The 1H NMR spectra of 3 and 4 shows one set of resonances each for the BH4 and the pyrazolylborate ligands indicating dynamic solution behavior. For complex 3, although X-ray quality crystals could not be obtained, the IR and NMR data are consistent with its formulation as the solvent-free analog of complex 4 with κ3-bonded BH4 ligand.  相似文献   

19.
(+)-N6-Hydroxyagelasine D, the enantiomer of the proposed structure of (?)-ageloxime D, as well as N6-hydroxyagelasine analogs were synthesized by selective N-7 alkylation of N6-[tert-butyl(dimethyl)silyloxy]-9-methyl-9H-purin-6-amine in order to install the terpenoid side chain, followed by fluoride mediated removal of the TBDMS-protecting group. N6-Hydroxyagelasine D and the analog carrying a geranylgeranyl side chain displayed profound antimicrobial activities against several pathogenic bacteria and protozoa and inhibited bacterial biofilm formation. However these compounds were also toxic towards mammalian fibroblast cells (MRC-5). The spectral data of N6-hydroxyagelasine D did not match those reported for ageloxime D before. Hence, a revised structure of ageloxime D was proposed. Basic hydrolysis of agelasine D gave (+)-N-[4-amino-6-(methylamino)pyrimidin-5-yl]-N-copalylformamide, a compound with spectral data in full agreement with those reported for (?)-ageloxime D.  相似文献   

20.
Myriophyllum elatinoides was reported to effectively treat wastewater by removing nitrogen (N) and phosphorus (P). However, little is known about the abundance and community structure of ammonia-oxidizing microorganisms associated with M. elatinoides purification systems. The objective of this research was to characterize the abundance and community structure of ammonia-oxidizing microorganisms in swine wastewater and determine the main nitrogen removal pathways. In this study, five different waters were treated by M. elatinoides in microcosms for one month. The five waters included tap water (Control), swine wastewater (SW), 50% diluted swine wastewater (50% SW), and two synthetic wastewaters: 200 mg NH4 +-N L−1 (200 NH4 +-N) and 400 mg NH4 +-N L−1 (400 NH4 +-N). The most dramatic changes were in NH4 +-N and total N (TN) concentrations, with average removal rates of 84% and 90%, respectively, in the treatments containing swine wastewater. On days 7, 14, and 28, the dissolved oxygen (DO) increased by 81.8%, 210.4% and 136.5%, respectively, compared with on day 0, in the swine wastewater. The results also showed that the bacterial amoA (AOB) copy numbers in the sediments of the treatments were significantly higher than those of archaeal amoA (AOA) copy numbers (p = 0.015). In addition, the high DO concentrations in swine wastewater responded well to the high abundance of AOB. The AOA and AOB community distributions were positively related with NO3 -N and were negatively related with DO in swine wastewater treatments. In summary, our experimental results suggested that the M. elatinoides purification system could improve the activity of ammonia-oxidizing microorganisms and consequently might contribute to the significant N removal from the swine wastewater.  相似文献   

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