全文获取类型
收费全文 | 533篇 |
免费 | 18篇 |
国内免费 | 108篇 |
专业分类
化学 | 434篇 |
晶体学 | 1篇 |
综合类 | 5篇 |
物理学 | 10篇 |
综合类 | 209篇 |
出版年
2023年 | 6篇 |
2022年 | 26篇 |
2021年 | 15篇 |
2020年 | 8篇 |
2019年 | 10篇 |
2018年 | 13篇 |
2017年 | 5篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 20篇 |
2013年 | 35篇 |
2012年 | 22篇 |
2011年 | 30篇 |
2010年 | 30篇 |
2009年 | 20篇 |
2008年 | 34篇 |
2007年 | 40篇 |
2006年 | 34篇 |
2005年 | 28篇 |
2004年 | 32篇 |
2003年 | 50篇 |
2002年 | 27篇 |
2001年 | 26篇 |
2000年 | 19篇 |
1999年 | 28篇 |
1998年 | 18篇 |
1997年 | 17篇 |
1996年 | 10篇 |
1995年 | 12篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有659条查询结果,搜索用时 0 毫秒
31.
Andr Delavault Katarina Ochs Olga Gorte Christoph Syldatk Erwann Durand Katrin Ochsenreither 《Molecules (Basel, Switzerland)》2021,26(2)
Glycolipids are non-ionic surfactants occurring in numerous products of daily life. Due to their surface-activity, emulsifying properties, and foaming abilities, they can be applied in food, cosmetics, and pharmaceuticals. Enzymatic synthesis of glycolipids based on carbohydrates and free fatty acids or esters is often catalyzed using certain acyltransferases in reaction media of low water activity, e.g., organic solvents or notably Deep Eutectic Systems (DESs). Existing reports describing integrated processes for glycolipid production from renewables use many reaction steps, therefore this study aims at simplifying the procedure. By using microwave dielectric heating, DESs preparation was first accelerated considerably. A comparative study revealed a preparation time on average 16-fold faster than the conventional heating method in an incubator. Furthermore, lipids from robust oleaginous yeast biomass were successfully extracted up to 70% without using the pre-treatment method for cell disruption, limiting logically the energy input necessary for such process. Acidified DESs consisting of either xylitol or sorbitol and choline chloride mediated the one-pot process, allowing subsequent conversion of the lipids into mono-acylated palmitate, oleate, linoleate, and stearate sugar alcohol esters. Thus, we show strong evidence that addition of immobilized Candida antarctica Lipase B (Novozym 435®), in acidified DES mixture, enables a simplified and fast glycolipid synthesis using directly oleaginous yeast biomass. 相似文献
32.
对实验室自制的固定化Candida sp. 99-125脂肪酶在正己烷中催化棕榈酸和鲸蜡醇的酯化反应的动力学机制进行了初步研究,结果表明:反应为动力学控制,不存在扩散限制,底物浓度对反应速率的影响符合Ping-Pong Bi-Bi反应机制。但在不同的底物浓度范围内存在不同程度的底物抑制作用,其中以长链醇的抑制为主。本文根据底物浓度由低到高,划分了三个底物浓度范围,在不同的范围内分别研究了两个底物的抑制作用,并选择不同的动力学模型,求得了动力学常数。 相似文献
33.
Investigation of the Impact of Water on the Enantioselectivity Displayed by CALB in the Kinetic Resolution of δ‐Functionalized Alkan‐2‐ol Derivatives 下载免费PDF全文
Bin Yang Richard Lihammar Prof. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13517-13521
It is shown that the low enantioselectivity of Candida antarctica lipase B (CALB)‐catalyzed transesterification of a δ‐functionalized alkan‐2‐ol to its acetate does not correlate at all with the high enantioselectivity of the CALB‐catalyzed hydrolysis of the corresponding acetate in water. This lack of correlation is unusual and for unfunctionalized alkan‐2‐ol derivatives there is a very good correlation between the enantioselectivity of transesterification of the alcohol and hydrolysis of the corresponding acetate (E>200 in both cases). The results confirm previous predictions from molecular modeling. The water effect was mimicked by CALB variant Ala281Ser, which showed an enhanced enantioselectivity in transesterification of δ‐functionalized alkan‐2‐ols compared to wild‐type CALB. 相似文献
34.
A simple and efficient method was developed for the synthesis of 2.2'-arylmethylene dicyclohexane-1,3- dione derivatives via the Knoevenagel-Michael cascade reactions of aromatic aldehydes and 1,3-cyclic diketones catalyzed by "Amano" lipase DF, which expands the application field of enzyme catalytic promiscuity. This protocol provides several advantages over the traditional chemical synthesis, such as simple work-up procedure, high yields Cup to 94%) and environmental friendliness. 相似文献
35.
Nanopolystyrene was used as a solid support for the covalent immobilization of Candida antarctica lipase B (CalB) using the photoreactive reagent 1-fluoro-2-nitro-4-azido benzene (FNAB) as a coupling reagent. The obtained derivative was then used as a biocatalyst in a microwave assisted esterification experiment. Factors such as contact time, pH, and enzyme concentration were investigated during immobilization. The hydrolytic activity, thermal, and operational stability of immobilized-CalB were determined. The maximum immobilized yield (218 μg/mg support) obtained at pH 6.8 exhibited optimum hydrolytic activity (4.42 × 103 mU p-nitrophenol/min). The thermal stability of CalB improved significantly when it was immobilized at pH 10, however, the immobilized yield was very low (93.6 μg/mg support). The immobilized-CalB prepared at pH 6.8 and pH 10 retained 50% of its initial activity after incubation periods of 14 and 16 h, respectively, at 60 ℃. The operational stability was investigated for the microwave assisted esterification of oleic acid with methanol. Immobilized-CalB retained 50% of its initial activity after 15 batch cycles in the microwave-assisted esterification. The esterification time was notably reduced under microwave irradiation. The combined use of a biocatalyst and microwave heating is thus an alternative total green synthesis process. 相似文献
36.
从国内各地采取土样分离筛选产耐有机溶剂脂肪酶的新菌株,通过形态和生理生化特征以及系统进化树分析,筛选到的新菌株命名为Pseudomonas aeruginosa CS-2.来自Pseudomonas aeruginosa CS-2的粗脂肪酶液在乙腈中酶活提高,在苯、氯仿、正己烷、石油醚和异辛烷中表现出较高的稳定性. 相似文献
37.
Xue Hua Hui-Jie Hong Dai-Yan Zhang Qiao Liu Fong Leong Qi Yang Yuan-Jia Hu Xiao-Jia Chen 《Molecules (Basel, Switzerland)》2022,27(4)
In this study, a high-performance thin layer chromatography (HPTLC) method by two step gradient elution with two mobile phases was developed for the simultaneous analysis of seven constituents in Ophiopogonis Radix. The chromatography was performed on silica gel 60 F254 plate with dichloromethane-methanol-ethyl acetate-water (70:25:12:3, v/v/v/v) and dichloromethane-methanol (300:1, v/v) as the mobile phase for two step gradient elution. Then, the HPTLC profiles were observed after derivatization with 10% sulfuric acid in ethanol solution. The obtained HPTLC images were further analyzed by chemometric approaches and the samples could be clustered based on regions and/or growth years, which were two important factors affecting the constituents in Ophiopogonis Radix. Furthermore, five compounds including ophiopogonin D, ophiopojaponin C, ophiopogonin D’, ophiopogonin C’ and methylophiopogonanone B were screened as potential lipase inhibitors from Ophiopogonis Radix by the HPTLC-bioautographic method. The binding modes and interactions between the five compounds and lipase were further explored by molecular docking analysis. The developed HPTLC method could be used for quality control of Ophiopogonis Radix and screening of the potential lipase inhibitors. 相似文献
38.
Langone Marta A. P. De Abreu Melissa E. Rezende Michelle J. C. Sant’Anna Geraldo L. 《Applied biochemistry and biotechnology》2002,98(1-9):987-996
The synthesis of monocaprin, monolaurin, and monomyristin in a solvent-free system was conducted by mixing a commercial immobilized
lipase with the organic reactants (glycerol and fatty acids) in a 20-mL batch reactor with constant stirring. The effects
of temperature, fatty acid/glycerol molar ratio, and enzyme concentration on the reaction conversion were determined. The
addition of molecular sieves in the assays of monomyristin synthesis was also evaluated. The reactions were carried out for
5 to 6 h and the nonpolar phase was analyzed by gas chromatography. The best results in terms of selectivity and conversion
(defined as the percentage of fatty acid consumed) were achieved when the stoichiometric amount of reagents (molar ratio=1)
and 9% (w/w) commercial enzyme were used and the reaction was performed at 60°C. The addition of molecular sieves did not
improve the synthesis of monomyristin. Conversions as high as 80%, with monoglycerides being the major products, were attained.
After 5 h of reaction, the concentration of monoglyceride was about twice that of diglyceride, and only trace amounts of triglyceride
were found. The results illustrate the technical possibility of producing medium chain monoglycerides in a solvent-free medium
using a simple batch reactor. 相似文献
39.
Jacqueline Destain Patrick Fickers Frédéric Weekers Benoît Moreau Philippe Thonart 《Applied biochemistry and biotechnology》2005,121(1-3):269-277
In this article, we report the development and optimization of an industrial culture medium for the production of extracellular
lipase in the yeast Yarrowia lipolytica. Until now olive oil in combination with glucose was used as the carbon source and inducer for the production of lipase.
Our results demonstrate that methyloleate, a cheap hydrophobic compound, could efficiently substitute olive oil as the inducer
and carbon source for lipase production. A new process of lipase production was developed yielding a twofold increase in the
level of production compared with the levels in previous reports. 相似文献
40.
Enzymes can be used in nonpolar reaction media to modify waterinsoluble substrates. A variety of pretreatments, applied to
the enzyme prior to introduction to the nonpolar media, can improve enzyme activity. However, the various pretreatments have
not been studied using directly comparable conditions, nor have they been applied simultaneously to test for interactive effects.
This work evaluates pretreatment of lipase with various classes of additives. The pretreated lipase is used to catalyze esterification
between citronellol and acetic acid in a medium of n-hexane. The effectiveness of a particular pretreatment is presented in terms of relative performance (RP), which is equal
to the number of times faster the pretreated lipase catalyzes the reaction relative to untreated lipase. The individual and
interactive effects of the pretreatment factors were studied and compared. Buffer salts had a much stronger performance-enhancing
effect than nonbuffer salts; pretreatment with 90% (w/w) sodium phosphate yielded lipase with an RP of approx 64. A strong
interaction was found between the treatments with sodium phosphate and pH adjustment. These treatments may mitigate the inhibitory
effect of acetic acid. Activating effects of phase interfaces and active-site protectants are shown to be complementary to
other treatments, demonstrating that they likely act by distinct mechanisms. 相似文献