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21.
[reaction: see text] A lipase-catalyzed double monoaminolysis of dimethyl malonate by (+/-)-trans-cyclopentane-1,2-diamine allows the sequential resolution of the latter compound, affording an enantiopure bis(amidoester), which is subsequently transformed into an optically active polyamine. As an alternative, both enantiomers of the diamine can be obtained from enantiopure (+)- or (-)-2-aminocyclopentanol, prepared by enzymatic resolution. 相似文献
22.
The redox catalysis of oxygen reduction was performed on a platinum rotating disk electrode. The Fe(III)/Fe(II)/H2SO4 system at different pH's was used as a MEDIATOR. The catalytic effect of mediator was directly related to the solvation sphere of Fe(III) and Fe(II). Only the redox couple FeHSO
4
2+
/FeHSO
4
+
(pH<0) showed a catalytic effect on oxygen reduction. 相似文献
23.
Strong pulse sequences can be used to control the position and width of the molecular wave packet. In this paper we propose a new scheme to maximally compress the wave packet in a quasistatic way by freezing it at a peculiar adiabatic potential shaped by two laser pulses. The dynamic principles of the scheme and the characteristic effect of the different control parameters are presented and analyzed. We use two different molecular models, electronic potentials modeled by harmonic oscillators, with the same force constants, and the Na(2) dimer, to show the typical yield that can be obtained in compressing the initial (minimum width) molecular wave function. 相似文献
24.
Ignacio Delso 《Tetrahedron letters》2007,48(23):4101-4104
1H-15N HMBC has been evaluated as an efficient and high-speed method to determine 15N chemical shifts for nitrones, which can be used to identify aromatic nitrones and to extract structural information by comparison with reference data. Substituent effects have been measured on C and N aryl groups separately, showing up the influence of electronic effects on C-aryl groups rather than N-aryl groups on the 15N chemical shifts. Steric effects are remarkable in the case of C-aryl-N-alkyl nitrones. Depending on N or C substitution, chemical shift changes in such an additive way that it is possible to predict chemical shifts for unknown nitrones. 相似文献
25.
Palacios F Aparicio D Ochoa De Retana AM de los Santos JM Gil JI Alonso JM 《The Journal of organic chemistry》2002,67(21):7283-7288
A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. The key step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of beta-ketoxime tosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids 4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13. 相似文献
26.
[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11. 相似文献
27.
A quantitative determination method of formic acid in apple juices is proposed by means of the proton nuclear magnetic resonance (1H NMR) technique. Formic acid gives a singlet signal at the 8.2-8.4 ppm interval of the spectrum, and its area is used to determine the concentration of the acid. 1,3,5-Benzenetricarboxylic acid is added to the juice as an internal standard. Since the chemical shift of both species varies with the pH, ascorbic acid is also added to adjust it at 2.74 and to avoid the overlapping of the signals. Recoveries between 95 and 109% are obtained when the standard addition method is applied to the juices of five different cider apple varieties. The coefficient of variation obtained is 3.9% for intra-day repeatability (n = 5), and 4.6% for inter-day repeatability (n = 10). The limit of detection is 1.49 mg/l, calculated from “3Sy/x + intercept”. The described method is direct and no previous derivatization is needed. 相似文献
28.
The reactions F + H2 → HF + H, HF → H + F, F → F+ + e? and F + e? → F? were used as simple test cases to assess the additivity of basis set effects on reaction energetics computed at the MP4 level. The 6-31G and 6-311G basis sets were augmented with 1, 2, and 3 sets of polarization functions, higher angular momentum polarization functions, and diffuse functions (27 basis sets from 6-31Gd, p) to 6-31 ++ G(3df, 3pd) and likewise for the 6-311G series). For both series substantial nonadditivity was found between diffuse functions on the heavy atom and multiple polarization functions (e.g., 6-31 + G(3d, 3p) vs. 6-31 + G(d, p) and 6-31G(3d, 3p)). For the 6-311G series there is an extra nonadditivity between d functions on hydrogen and multiple polarization functions. Provided that these interactions are taken into account, the remaining basis set effects are additive to within ±0.5 kcal/mol for the reactions considered. Large basis set MP4 calculations can also be estimated to within ±0.5 kcal/mol using MP2 calculations, est. EMP4(6-31 ++ G(3df, 3pd)) ≈ EMP4(6-31G(d, p)) + EMP2(6-31 ++ G(3df, 3pd)) – EMP2(6-31G(d, p)) or EMP4(6-31 + G(d, p) + EMP2(6-31 ++ G(3df, 3pd)) – EMP2(6-31 + G(d, p)) and likewise for the 6-311G series. 相似文献
29.
Ethanol production from steam-explosion pretreated wheat straw 总被引:1,自引:0,他引:1
Ignacio Ballesteros Ma José Negro José Miguel Oliva Araceli Cabañas Paloma Manzanares Mercedes Ballesteros 《Applied biochemistry and biotechnology》2006,130(1-3):496-508
Bioconversion of cereal straw to bioethanol is becoming an attractive alternative to conventional fuel ethanol production
from grains. In this work, the best operational conditions for steam-explosion pretreatment of wheat straw for ethanol production
by a simultaneous saccharification and fermentation process were studied, using diluted acid [H2SO4 0.9% (w/w)] and water as preimpregnation agents. Acid-or water-impregnated biomass was steam-exploded at different temperatures
(160–200°C) and residence times (5, 10, and 20 min). Composition of solid and filtrate obtained after pretreatment, enzymatic
digestibility and ethanol production of pretreated wheat straw at different experimental conditions was analyzed. The best
pretreatment conditions to obtain high conversion yield to ethanol (approx 80% of theoretical) of cellulose-rich residue after
steam-explosion were 190°C and 10 min or 200°C and 5 min, in acid-impregnated straw. However, 180°C for 10 min in acid-impregnated
biomass provided the highest ethanol yield referred to raw material (140 L/t wheat straw), and sugars recovery yield in the
filtrate (300 g/kg wheat straw). 相似文献
30.
Regioselectivity in acylation of oligosaccharides catalyzed by the metalloprotease thermolysin 总被引:2,自引:0,他引:2
Investigation of the acylation scope of carbohydrates by metalloprotease thermolysin immobilized on Celite as biocatalyst has been carried out. The reactions were performed in DMSO, a good solvent for carbohydrates, where the enzyme has previously shown its activity in transesterifications of sucrose, maltose and maltose-containing oligosaccharides. Surprisingly, no reaction was observed for glucose or the glucose-containing disaccharides, trehalose and lactose. In contrast, laurate monoesters of several sucrose-containing tri- and tetrasaccharides were synthetized through a one step transesterification using vinyl laurate as the acylating agent. Enzyme regioselectivity was accurately determined by HPLC/MS and the structure of the main regioisomers was established by a combination of NMR experiments. The preferred position of acylation in all cases was the 2-OH of the α-d-glucopyranose moiety linked 1→2 to the β-d-fructofuranose unit. These results correlate with the regioselectivity observed in the case of the disaccharide sucrose. A general carbohydrate binding motif for catalysis by thermolysin is proposed. 相似文献