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61.
The mild (DCM/20 °C), quantitative, regioselective, O-acylative cleavage of tetrahydrofurans using organic acid halides with catalytic Bi(III) halides is reported. X-ray crystallography is used to rationalise the failure of the reaction in the case of certain crowded acid chlorides, and a useful aspect of chemoselectivity is revealed. The synthetic potential of this reaction is illustrated with a highly efficient O-acylative cleavage/intramolecular alkylation approach to tetralins. 相似文献
62.
Melissa L. E. Gutarra Elisa D. C. Cavalcanti Leda R. Castilho Denise M. G. Freire Geraldo L. Sant’Anna Jr. 《Applied biochemistry and biotechnology》2005,121(1-3):105-116
The production of lipase by Penicillium simplicissimum in solid-state fermentation was studied using babassu cake as the basal medium. Tray-type and packed-bed bioreactors were employed. In the former, the influence of temperature; content of the medium, and medium supplementation with olive oil, sugarcane molasses, corn steep liquor, and yeast hydrolysate was studied. For all combinations of supplements, a temperature of 30°C, a moisture content of 70%, and a concentration of carbon source of 6.25% (m/m, dry basis) provided optimum conditions for lipase production. When used as single supplements olive oil and molasses also were able to provide high lipase activities (20 U/g). Using packed-bed bioreactors and molasses-supplemented medium, optimum conditions for enzyme production were air superficial velocities above 55 cm/min and temperatures below 28°C. The lower temperature optimum found for these reactors is probably related to radial heat gradient formation inside the packed bed. Maximum lipase activities obtained in these bioreactors (26.4 U/g) were 30% higher than in tray-type reactors. 相似文献
63.
Jan P. Weyrauch Dr. A. Stephen K. Hashmi Prof. Dr. Andreas Schuster Dipl.‐Chem. Tobias Hengst Dipl.‐Chem. Stefanie Schetter Anna Littmann Dipl.‐Chem. Matthias Rudolph Dr. Melissa Hamzic Dr. Jorge Visus Jan W. Bats Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):956-963
The substrate scope, the mechanistic aspects of the gold‐catalyzed oxazole synthesis, and substrates with different aliphatic, aromatic, and functional groups in the side chain were investigated. Even molecules with several propargyl amide groups could easily be converted, delivering di‐ and trioxazoles with interesting optical properties. Furthermore, the scope of the gold(I)‐catalyzed alkylidene synthesis was investigated. Further functionalizations of these isolable intermediates of the oxazole synthesis were developed and chelate ligands can be obtained. The use of Barluenga’s reagent offers a new and mild access to the synthetically valuable iodoalkylideneoxazoles from propargylic amides, this reagent being superior to other sources of halogens. 相似文献
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65.
Hill MP Carroll EC Vang MC Addington TA Toney MD Larsen DS 《Journal of the American Chemical Society》2010,132(47):16953-16961
The mechanisms of pyridoxal 5'-phosphate (PLP)-dependent enzymes require substrates to form covalent "external aldimine" intermediates, which absorb light strongly between 410 and 430 nm. Aspartate aminotransferase (AAT) is a prototypical PLP-dependent enzyme that catalyzes the reversible interconversion of aspartate and α-ketoglutarate with oxalacetate and glutamate. From kinetic isotope effects studies, it is known that deprotonation of the aspartate external aldimine C(α)-H bond to give a carbanionic quinonoid intermediate is partially rate limiting in the thermal AAT reaction. We show that excitation of the 430-nm external aldimine absorption band increases the steady-state catalytic activity of AAT, which is attributed to the photoenhancement of C(α)-H deprotonation on the basis of studies with Schiff bases in solution. Blue light (250 mW) illumination gives an observed 2.3-fold rate enhancement for WT AAT activity, a 530-fold enhancement for the inactive K258A mutant, and a 58600-fold enhancement for the PLP-Asp Schiff base in water. These different levels of enhancement correlate with the intrinsic reactivities of the C(α)-H bond in the different environments, with the less reactive Schiff bases exhibiting greater enhancement. Time-resolved spectroscopy, ranging from femtoseconds to minutes, was used to investigate the nature of the photoactivation of C(α)-H bond cleavage in PLP-amino acid Schiff bases both in water and bound to AAT. Unlike the thermal pathway, the photoactivation pathway involves a triplet state with a C(α)-H pK(a) that is estimated to be between 11 and 19 units lower than the ground state for the PLP-Val Schiff base in water. 相似文献
66.
Simas ER Gehlen MH Pinto MF Siqueira J Misoguti L 《The journal of physical chemistry. A》2010,114(47):12384-12390
Polyfluorene end-capped with N-(2-benzothiazole)-1,8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity. Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CT) of the end group BNI. The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state, polyfluorene backbone decay, and ICCT deactivation. Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0.8-1.4 ns depending on the solvent, showing that depolarization occurs from two different processes: energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time. Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF-BNI ascribed to the conversion of S(1) to the ICCT excited state. From the ratio of asymptotic and initial amplitudes of the transient absorption measurement, the efficiency of intrachain ICCT formation is estimated in 0.5, which means that, on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state. 相似文献
67.
Melissa D. Zolodz John T. Herberg Halyna E. Narepekha Emily Raleigh Matthew R. Farber Robert L. Dufield Denis M. Boyle 《Journal of chromatography. A》2010,1217(2):225-234
Obtaining sufficient amounts of pure glycoprotein variants to characterize their structures is an important goal in both functional biology and the biotechnology industry. We have developed preparative HIC conditions that resolve glycoform variants on the basis of overall carbohydrate content for a recombinant transferrin-exendin-4 fusion protein. The fusion protein was expressed from the yeast Saccharomyces cerevisiae from high density fermentation and is post-translationally modified with mannose sugars through O-glycosidic linkages. Overall hydrophobic behavior appeared to be dominated by the N-terminal 39 amino acids from the exendin-4 and linker peptide sequences as compared to the less hydrophobic behavior of human transferrin alone. In addition, using LC techniques that measure total glycans released from the pure protein combined with new high resolution technologies using mass spectrometry, we have determined the locations and chain lengths of mannose residues on specific peptides derived from tryptic maps of the transferrin-exendin-4 protein. Though the protein is large (80,488 kDa) and contains 78 possible serine and threonine residues as potential sites for sugar addition, mannosylation was observed on only two tryptic peptides located within the first 55 amino acids of the N-terminus. These glycopeptides were highly heterogeneous and contained between 1 and 10 mannose residues scattered among the various serine and threonine sites which were identified by electron transfer dissociation mass spectrometry. Glycan sequences from 1 to 6 linear mannose residues were detected, but mannose chain lengths of 3 or 4 were more common and formed 80% of the total oligosaccharides. This work introduces new technological capabilities for the purification and characterization of glycosylated variants of therapeutic recombinant proteins. 相似文献
68.
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70.
The ‘characteristic function’ with two empirically determined parameters α and β, is proposed as a general purpose function to describe the variation of
precision (in terms of standard deviation σ), or uncertainty, with analyte concentration c (here denoting any compositional quantity), for specific analytical methods applied to a defined type of test material. In
this study it is applied to examples of analytical data collected under ‘instrumental’ conditions for estimating precision.
The function fitted the data well, with no systematic lack of fit. The study therefore extends the range of applications of
this function. 相似文献