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991.
Vaidyanathan Vinoth Kumar Vinohar Stephen Rapheal 《Applied biochemistry and biotechnology》2011,163(3):423-432
Aryl alcohol oxidase (AAO) is an extracellular flavoenzyme involved in lignin degradation by white rot fungi. Screening of
lignolytic and AAO activity from twenty different fungal species were carried out. Among them, seven species showed lignolytic
activity and three of them (Pleurotus ostreatus, Pleurotus eous, and Pleurotus platypus) were found to be AAO positive. Maximal AAO activity was observed in batch cultures of P. ostreatus and was found to be induced by aromatic amino acids and aryl alcohols up to a level of 289 U/l. Purification of AAO was carried
out by three-phase partitioning (TPP). The 67 kDa enzyme was purified up to 10.19-fold by TPP with an overall recovery of
10.95%. Optimum pH and temperature for P. ostreatus AAO activity was found to be around 6 and 40 °C, respectively. From the LB plot, K
m value of AAO for oxidizing veratryl alcohol was determined to be 0.6 mM. Results of the study indicate that P. ostreatus is the best producers of AAO, and they could be employed as promising fungal species for biotechnological applications. 相似文献
992.
993.
Cho DS Gibson SC Bhandari D McNally ME Hoffman RM Cook KD Song L 《Rapid communications in mass spectrometry : RCM》2011,25(23):3575-3580
Batch slurry reactions are widely used in the industrial manufacturing of chemicals, pharmaceuticals, petrochemicals and polymers. However, onsite monitoring of batch slurry reactions is still not feasible in production plants due to the challenge in analyzing heterogeneous samples without complicated sample preparation procedures. In this study, direct analysis in real time mass spectrometry (DART-MS) has been evaluated for the onsite monitoring of a model batch slurry reaction. The results suggested that automation of the sampling process of DART-MS is important to achieve quantitative results. With a sampling technique of manual sample deposition on melting point capillaries followed by automatic sample introduction across the helium beam, relative standard deviation (RSD) of the protonated molecule signals from the reaction product of the model batch slurry reaction ranged from 6 to 30%. This RSD range is improved greatly over a sampling technique of manual sample deposition followed by manual sample introduction where the RSDs are up to 110%. Furthermore, with the semi-automated sampling approach, semi-quantitative analysis of slurry samples has been achieved. Better quantification is expected with a fully automated sampling approach. 相似文献
994.
995.
Osburn S O'Hair RA Black SM Ryzhov V 《Rapid communications in mass spectrometry : RCM》2011,25(21):3216-3222
The gas-phase mechanism of S-nitrosylation of thiols was studied in a quadrupole ion trap mass spectrometer. This was done via ion-molecule reactions of protonated cysteine and many of its derivatives and other thiol ions with neutral tert-butyl nitrite or nitrous acid. Our results showed that the presence of the carboxylic acid functional group, -COOH, in the vicinity of the thiol group is essential for the gas-phase nitrosylation of thiols. When the carboxyl proton is replaced by a methyl group (cysteine methyl ester) no nitrosylation was observed. Other thiols lacking a carboxylic acid functional group displayed no S-nitrosylation, strongly suggesting that the carboxyl hydrogen plays a key role in the nitrosylation process. These results are in excellent agreement with a solution-phase mechanism proposed by Stamler et al. (J. S. Stamler, E. J. Toone, S. A. Lipton, N. J. Sucher. Neuron 1997, 18, 691-696) who suggested a catalytic role for the carboxylic acid group adjacent to cysteine residues and with later additions by Ascenzi et al. (P. Ascenzi, M. Colasanti, T. Persichini, M. Muolo, F. Polticelli, G. Venturini, D. Bordo, M. Bolognesi. Biol. Chem. 2000, 381, 623-627) who postulated that the presence of the carboxyl in the cysteine microenvironment in proteins is crucial for S-nitrosylation. A concerted mechanism for the gas-phase S-nitrosylation was proposed based on our results and was further studied using theoretical calculations. Our calculations showed that this proposed pathway is exothermic by 44.0 kJ mol(-1). This is one of the few recent examples when a gas-phase mechanism matches one in solution. 相似文献
996.
Stephen E Huang D Shaw JL Blake AJ Collison D Davies ES Edge R Howard JA McInnes EJ Wilson C Wolowska J McMaster J Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(37):10246-10258
The NiII complexes [Ni([9]aneNS2‐CH3)2]2+ ([9]aneNS2‐CH3=N‐methyl‐1‐aza‐4,7‐dithiacyclononane), [Ni(bis[9]aneNS2‐C2H4)]2+ (bis[9]aneNS2‐C2H4=1,2‐bis‐(1‐aza‐4,7‐dithiacyclononylethane) and [Ni([9]aneS3)2]2+ ([9]aneS3=1,4,7‐trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal NiIII products, which have been characterized by X‐ray crystallography, UV/Vis and multi‐frequency EPR spectroscopy. The single‐crystal X‐ray structure of [NiIII([9]aneNS2‐CH3)2](ClO4)6?(H5O2)3 reveals an octahedral co‐ordination at the Ni centre, while the crystal structure of [NiIII(bis[9]aneNS2‐C2H4)](ClO4)6?(H3O)3? 3H2O exhibits a more distorted co‐ordination. In the homoleptic analogue, [NiIII([9]aneS3)2](ClO4)3, structurally characterized at 30 K, the Ni? S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn–Teller distorted octahedral stereochemistry. [Ni([9]aneNS2‐CH3)2](PF6)2 shows a one‐electron oxidation process in MeCN (0.2 M NBu4PF6, 293 K) at E1/2=+1.10 V versus Fc+/Fc assigned to a formal NiIII/NiII couple. [Ni(bis[9]aneNS2‐C2H4)](PF6)2 exhibits a one‐electron oxidation process at E1/2=+0.98 V and a reduction process at E1/2=?1.25 V assigned to NiII/NiIII and NiII/NiI couples, respectively. The multi‐frequency X‐, L‐, S‐, K‐band EPR spectra of the 3+ cations and their 86.2 % 61Ni‐enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6 %, 42.8 % and 37.2 % Ni character in [Ni([9]aneNS2‐CH3)2]3+, [Ni(bis[9]aneNS2‐C2H4)]3+ and [Ni([9]aneS3)2]3+, respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S‐thioether centres. EPR spectra for [61Ni([9]aneS3)2]3+ are consistent with a dynamic Jahn–Teller distortion in this compound. 相似文献
997.
Pestovsky O Veysey SW Bakac A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4518-4522
The kinetics of the reaction of benzyl radicals with [L(1)(H(2)O)RhH{D}](2+) (L(1)=1,4,8,11-tetraazacyclotetradecane) were studied directly by laser-flash photolysis. The rate constants for the two isotopologues, k=(9.3±0.6) × 10(7) M(-1) s(-1) (H) and (6.2±0.3) × 10(7) M(-1) s(-1) (D), lead to a kinetic isotope effect k(H)/k(D)=1.5±0.1. The same value was obtained from the relative yields of PhCH(3) and PhCH(2)D in a reaction of benzyl radicals with a mixture of rhodium hydride and deuteride. Similarly, the reaction of methyl radicals with {[L(1)(H(2)O)RhH](2+) + [L(1)(H(2)O)RhD](2+)} produced a mixture of CH(4) and CH(3)D that yielded k(H)/k(D)=1.42±0.07. The observed small normal isotope effects in both reactions are consistent with reduced sensitivity to isotopic substitution in very fast hydrogen-atom abstraction reactions. These data disprove a literature report claiming much slower kinetics and an inverse kinetic isotope effect for the reaction of methyl radicals with hydrides of L(1)Rh. 相似文献
998.
Gardner BM Patel D Cornish AD McMaster J Lewis W Blake AJ Liddle ST 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(40):11266-11273
Four new uranium-ruthenium complexes, [(Tren(TMS))URu(η(5)-C(5)H(5))(CO)(2)] (9), [(Tren(DMSB))URu(η(5)-C(5)H(5))(CO)(2)] (10), [(Ts(Tolyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (11), and [(Ts(Xylyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (12) [Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3); Tren(DMSB)=N(CH(2)CH(2)NSiMe(2)tBu)(3)]; Ts(Tolyl)=HC(SiMe(2)NC(6)H(4)-4-Me)(3); Ts(Xylyl)=HC(SiMe(2)NC(6)H(3)-3,5-Me(2))(3)], were prepared by a salt-elimination strategy. Structural, spectroscopic, and computational analyses of 9-12 shows: i) the formation of unsupported uranium-ruthenium bonds with no isocarbonyl linkages in the solid state; ii) ruthenium-carbonyl backbonding in the [Ru(η(5)-C(5)H(5))(CO)(2)](-) ions that is tempered by polarization of charge within the ruthenium fragments towards uranium; iii) closed-shell uranium-ruthenium interactions that can be classified as predominantly ionic with little covalent character. Comparison of the calculated U-Ru bond interaction energies (BIEs) of 9-12 with the BIE of [(η(5)-C(5)H(5))(3)URu(η(5)-C(5)H(5))(CO)(2)], for which an experimentally determined U-Ru bond disruption enthalpy (BDE) has been reported, suggests BDEs of approximately 150 kJ mol(-1) for 9-12. 相似文献
999.
Park TH Hickman AJ Koh K Martin S Wong-Foy AG Sanford MS Matzger AJ 《Journal of the American Chemical Society》2011,133(50):20138-20141
High reversibility during crystallization leads to relatively defect-free crystals through repair of nonperiodic inclusions, including those derived from impurities. Microporous coordination polymers (MCPs) can achieve a high level of crystallinity through a related mechanism whereby coordination defects are repaired, leading to single crystals. In this work, we discovered and exploited the fact that this process is far from perfect for MCPs and that a minority ligand that is coordinatively identical to but distinct in shape from the majority linker can be inserted into the framework, resulting in defects. The reaction of Zn(II) with 1,4-benzenedicarboxylic acid (H(2)BDC) in the presence of small amounts of 1,3,5-tris(4-carboxyphenyl)benzene (H(3)BTB) leads to a new crystalline material, MOF-5(O(h)), that is nearly identical to MOF-5 but has an octahedral morphology and a number of defect sites that are uniquely functionalized with dangling carboxylates. The reaction with Pd(OAc)(2) impregnates the metal ions, creating a heterogeneous catalyst with ultrahigh surface area. The Pd(II)-catalyzed phenylation of naphthalene within Pd-impregnated MOF-5(O(h)) demonstrates the potential utility of an MCP framework for modulating the reactivity and selectivity of such transformations. Furthermore, this novel synthetic approach can be applied to different MCPs and will provide scaffolds functionalized with catalytically active metal species. 相似文献
1000.
Liu W Chan AS Liu H Cochrane SA Vederas JC 《Journal of the American Chemical Society》2011,133(36):14216-14219
Lantibiotics are antimicrobial peptides produced by bacteria. Some are employed for food preservation, whereas others have therapeutic potential due to their activity against organisms resistant to current antibiotics. They are ribosomally synthesized and posttranslationally modified by dehydration of serine and threonine residues followed by attack of thiols of cysteines to form monosulfide lanthionine and methyllanthionine rings, respectively. Chemical synthesis of peptide analogues is a powerful method to verify stereochemistry and access structure-activity relationships. However, solid supported synthesis of lantibiotics has been difficult due to problems in generating lanthionines and methyllanthionines with orthogonal protection and good stereochemical control. We report the solid-phase syntheses of both peptides of a two-component lantibiotic, lacticin 3147. Both successive and interlocking ring systems were synthesized on-resin, thereby providing a general methodology for this family of natural products. 相似文献