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81.
The stability and structure of non-covalent complexes of various peptides contatining basic amino acid residues (Arg, Lys) with metalloporphyrins were studied in a quadrupole ion trap mass spectrometer. The complexes of heme and three other metalloporphyrins with a variety of basic peptides and model systems were formed via electrospray ionization (ESI) and their stability was probed by energy-variable collision-induced dissociation (CID). A linear dependence for basic peptides and model compounds/metalloporphyrin complexes was observed in the plots of stability versus degrees of freedom and was used to evaluate relative bond strength. These results were then compared with previous data obtained for complexes of metalloporphyrins with His-containing peptides and peptides containing no basic amino acids. The binding strengths of Lys-containing peptide complexes in the gas phase was found to be almost as strong as that of Arg-containing complexes. Both systems showed stronger binding than His- containing peptides studied previously. To probe the structure of Arg and Lys non-covalent complexes (charge solvation versus salt bridges), two techniques, CID and ionmolecule reactions, were used. CID experiments indicate that the gas-phase complexes are most likely formed by charge solvation of the central metal ion in the metalloporphyrin by basic side chains of Arg or Lys. Results from the ionmolecule reaction studies are consistent with the charge solvation structure as well. 相似文献
82.
An investigation of heparinase immobilization 总被引:1,自引:0,他引:1
Bernstein Howard Yang Victor C. Langer Robert 《Applied biochemistry and biotechnology》1987,16(1):129-143
A systematic investigation of the parameters that affect the efficiency of immobilizing heparinase onto cyanogen bromide activated
crosslinked 8% agarose beads was conducted. Two experimental measures, the “fraction bound” and the “fraction retained,” were
used to monitor the coupling efficiency. The fraction bound is the portion of the total initial enzyme that is bound to the
agarose gel. The fraction retained is the fraction of bound enzyme that is active. The product of the two measures indicates
the coupling efficiency. The activity of the immobilized heparinase was measured under conditions free of both internal and
external mass transfer limitations, and thus, the fraction retained represents the true immobilized enzyme activity.
Increasing the degree of activation of the beads results in an increase in the fraction bound, the fraction retained, and
consequently, the coupling efficiency. As the ratio of enzyme solution to gel volume increases from 1.5 to 2.2, the fraction
bound remains constant but the fraction retained decreases (heparinase concentration; 0.15 mg/mL and degree of activation;
9.5 μmol of cyanate esters/g of gel). At volume ratios greater than 2.2, both the fraction bound and the fraction retained
decline continuously. Changing the heparinase concentration in the coupling solution changes the coupling efficiency in a
manner similar to that of the volume ratio change.
When heparin is added during the coupling process, the fraction bound declines as the heparin concentration increases, whereas
the fraction retained increases up to a heparin concentration of 12 mg/mL and decreases thereafter. When arginine, lysine,
and glycine are used to block the unreacted cyanate ester groups after the coupling process, the immobilized heparinase shows
different pH optima of 6.5, 6.9, and 7.2, respectively. Based upon these findings, a protocol to optimize heparinase immobilization
is developed. 相似文献
83.
Joseph P. Kennedy Tung-Ping Liao Suhas Guhaniyogi Victor S. C. Chang 《Journal of polymer science. Part A, Polymer chemistry》1982,20(11):3219-3227
β-Pinene was polymerized with H2O/BCl3 (protic) and p-dicumyl chloride and sym-tricumyl chloride (nonprotic) inifer systems in CH2Cl2 or CH2Cl2/n-C6H14 solvents from ?10 to ?70°C. The effect of solvent polarity, temperature, and monomer and inifer concentration on conversions and molecular weights was investigated. Low conversions and molecular weights, M?n = 1300–2500, obtained under these conditions suggest rapid termination. 相似文献
84.
Victor E. Meyer 《Journal of polymer science. Part A, Polymer chemistry》1967,5(6):1289-1296
From the conversion–composition data of Gruber and Elias, the reactivity ratios of styrene (M1) and methyl methacrylate (M2) were calculated to be r1 = 0.55 ± 0.02 and r2 = 0.58 ± 0.06 at 90°C. The least-squares method was then used on these and literature values at other temperatures to obtain the Arrhenius expressions: In r1 = 0.04736 – (235.45/T), and ln r2 = 0.1183 – (285.36/T). Using literature values for the homopolymerization steps, A11 = 2.2 × 107l./mole-sec., E11 = 7.8 kcal./mole, and A22 = 0.51 × 107 l./mole-sec.?1, E22 = 6.3 kcal./mole, activation energies and frequency factors were then calculated for the cross-polymerization steps: A12 = 2.1 × 107 l./mole-sec., E12 = 7.3 kcal./mole, and A21 = 0.45 × 107 l./mole-sec., E21 = 5.7 kcal./mole. 相似文献
85.
Natalia V. Loginova Tat’yana V. Koval’chuk Rimma A. Zheldakova Anna A. Chernyavskaya Nikolai P. Osipovich Gennady K. Glushonok Henry I. Polozov Victor L. Sorokin Oleg I. Shadyro 《Central European Journal of Chemistry》2006,4(3):440-457
Cu (II) complexes with the sterically hindered diphenol derivatives 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzenetriol (II) and the sulfur-containing 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements.
Compounds I–III can coordinate in their singly deprotonated forms and act as bidentate ligands. These compounds yield Cu (II) complexes of the stoichiometry Cu(L)2, which have square planar geometry (g| > g⊥ > ge). Unlike them, compound IV behaves as a terdentate ligand, and its complex Cu(LIV)2 has distorted octahedral geometry. According to ESR data, only the Cu(LII)2 complex contains a very small amount of phenoxyl radicals. Antimicrobial activities of these ligands and their respective
Cu (II) complexes have been determined with respect to Gram-positive and Gram-negative bacteria, as well as on yeasts. Their
phytotoxic properties against Chlorella vulgaris 157 were also examined. 相似文献
86.
Christian NP Reilly JP Mokler VR Wincott FE Ellington AD 《Journal of the American Society for Mass Spectrometry》2001,12(6):744-753
To probe the mechanism of gas-phase oligonucleotide ion fragmentation, modified oligonucleotides were studied using matrix-assisted laser desorption/ionization. The oligonucleotides were of the form 5'-TTTTXTTTTT, where X was a modified nucleotide. Modifications included substitution of hydroxy, methoxy, amino, and allyl groups at the 2'-position of the deoxyribose. The modified ribose contained adenine, guanine, cytosine, or uracil bases. For comparison, we studied oligomers where X was an unmodified adenosine, guanosine, cytidine, thymidine, or uridine deoxyribonucleotide. We found a very strong dependence of the matrix-to-analyte ratio on fragmentation for these oligomers. Analysis of these modifications suggests that the initial fragmentation step in MALDI-MS involves a two-step (E1) elimination of the base. 相似文献
87.
The standard (p(o) = 0.1 MPa) molar enthalpy of formation of crystalline 2H-1,3-benzoxazine-2,4(3H)dione was measured, at T= 298.15 K, by static bomb calorimetry and the standard molar enthalpy of sublimation, at T= 298.15 K, was obtained using Calvet microcalorimetry. These values were used to derive the standard molar enthalpy of formation in the gaseous phase, T= 298.15 K, of -(401.0 +/- 3.5) kJ mol(-1). The standard molar enthalpy of sublimation of isatoic anhydride was recalculated, and our recommended experimental value for the standard molar enthalpy of formation in the gaseous phase, T= 298.15 K, is -(406.2 +/- 3.4) kJ mol(-1). Density functional calculations for the two isomers 2H-1,3-benzoxazine-2,4(3H)dione and isatoic anhydride, in which the ring nitrogen and oxygen have been transposed, confirm the experimental evidence of nearly identical thermochemical stability for these isomers. 相似文献
88.
Roberto Dallocchio Barbara Sechi Alessandro Dessì Bezhan Chankvetadze Sergio Cossu Victor Mamane Robin Weiss Patrick Pale Paola Peluso 《Electrophoresis》2021,42(17-18):1853-1863
2’-(4-Pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs (TCIBP = 3,3’,5,5’-tetrachloro-2-iodo-4,4’-bipyridyl) are chiral compounds that showed interesting inhibition activity against transthyretin fibrillation in vitro. We became interested in their enantioseparation since we noticed that the M-stereoisomer is more effective than the P-enantiomer. Based thereon, we recently reported the enantioseparation of 2’-substituted TCIBP derivatives with amylose-based chiral columns. Following this study, herein we describe the comparative enantioseparation of both 2’-(4-pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs on four cellulose phenylcarbamate-based chiral columns aiming to explore the effect of the polymer backbone, as well as the nature and position of substituents on the side groups on the enantioseparability of these compounds. In the frame of this project, the impact of subtle variations of analyte and polysaccharide structures, and mobile phase (MP) polarity on retention and selectivity was evaluated. The effect of temperature on retention and selectivity was also considered, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van ’t Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal were observed. In particular, the EEO was shown to be dependent on polysaccharide backbone, the elution sequence of the two analytes being P-M and M-P on cellulose and amylose tris(3,5-dimethylphenylcarbamate), respectively. In this regard, a theoretical investigation based on molecular dynamics (MD) simulations was performed by using amylose and cellulose tris(3,5-dimethylphenylcarbamate) nonamers as virtual models of the polysaccharide-based selectors. This exploration at the molecular level shed light on the origin of the enantiodiscrimination processes. 相似文献
89.
90.
A rigorous and practical methodology for evaluating thermal-equilibrium density matrices, finite-temperature time-dependent expectation values, and time-correlation functions is described. The method involves an extension of the matching-pursuit/split-operator-Fourier-transform method to the solution of the Bloch equation via imaginary-time propagation of the density matrix and the evaluation of Heisenberg time-evolution operators through real-time propagation in dynamically adaptive coherent-state representations. 相似文献