全文获取类型
收费全文 | 1290篇 |
免费 | 213篇 |
国内免费 | 22篇 |
专业分类
化学 | 1333篇 |
力学 | 1篇 |
综合类 | 5篇 |
数学 | 3篇 |
物理学 | 22篇 |
综合类 | 161篇 |
出版年
2024年 | 4篇 |
2023年 | 15篇 |
2022年 | 54篇 |
2021年 | 43篇 |
2020年 | 90篇 |
2019年 | 48篇 |
2018年 | 47篇 |
2017年 | 29篇 |
2016年 | 72篇 |
2015年 | 60篇 |
2014年 | 79篇 |
2013年 | 83篇 |
2012年 | 85篇 |
2011年 | 66篇 |
2010年 | 60篇 |
2009年 | 77篇 |
2008年 | 81篇 |
2007年 | 82篇 |
2006年 | 70篇 |
2005年 | 77篇 |
2004年 | 70篇 |
2003年 | 49篇 |
2002年 | 36篇 |
2001年 | 20篇 |
2000年 | 17篇 |
1999年 | 10篇 |
1998年 | 5篇 |
1997年 | 11篇 |
1996年 | 11篇 |
1995年 | 19篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有1525条查询结果,搜索用时 15 毫秒
51.
52.
Martin Peng Esther Mittmann Lukas Wenger Prof. Dr. Jürgen Hubbuch Dr. Martin K. M. Engqvist Prof. Dr. Christof M. Niemeyer Dr. Kersten S. Rabe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):15998-16001
Continuous flow systems for chemical synthesis are becoming a major focus in organic chemistry and there is a growing interest in the integration of biocatalysts due to their high regio- and stereoselectivity. Methods established for 3D bioprinting enable the fast and simple production of agarose-based modules for biocatalytic reactors if thermally stable enzymes are available. We report here on the characterization of four different cofactor-free phenacrylate decarboxylase enzymes suitable for the production of 4-vinylphenol and test their applicability for the encapsulation and direct 3D printing of disk-shaped agarose-based modules that can be used for compartmentalized flow microreactors. Using the most active and stable phenacrylate decarboxylase from Enterobacter spec. in a setup with four parallel reactors and a subsequent palladium(II) acetate-catalysed Heck reaction, 4-hydroxystilbene was synthesized from p-coumaric acid with a total yield of 14.7 % on a milligram scale. We believe that, due to the convenient direct immobilization of any thermostable enzyme and straightforward tuning of the reaction sequence by stacking of modules with different catalytic activities, this simple process will facilitate the establishment and use of cascade reactions and will therefore be of great advantage for many research approaches. 相似文献
53.
Qianyu Yu Xiaoteng Ma Yingze Liu Prof. Dr. Hanying Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16712-16717
Protein nanogels have found a wide variety of applications, ranging from biocatalysis to drug/protein delivery. However, in practical applications, proteins in nanogels may suffer from enzymic hydrolysis and denaturation. Inspired by the structure and functionalities of the fowl eggshells, biomimetic mineralization of protein nanogels was studied in this research. Protein nanogels with embedded porcine pancreas lipase (PPL) in the cross-linked nanostructures were synthesized through the thiol–disulfide reaction between thiol-functionalized PPL and poly(N-isopropylacrylamide) with pendant pyridyl disulfide groups. The nanogels were further reacted with reduced bovine serum albumin (BSA) and BSA molecules were coated on the nanogels. Mineralization of BSA leads to the synthesis of biomineralized shells on the nanogels. With the growth of CaCO3 on the shells, the nanogels aggregate into suprastructures. Thermogravimetric analysis, XRD, dynamic light scattering, and TEM were employed to study the mechanism of the biomineralization process and analyze the structures of the mineralized nanogels. The biomineralized shells can effectively protect the PPL molecules from hydrolysis by trypsin; meanwhile, the nanosized channels on the mineralized shells allow the transport of small-molecule substrates across the shells. Bioactivity measurements indicate that PPL in the nanogels maintains more than 80 % bioactivity after biomineralization. 相似文献
54.
Summary: Three different cellulosic substrata, like microcrystalline cellulose, cotton cellulose and spruce dissolving pulp, were chosen for biodegradation. The kinetics of the enzymatic hydrolysis of these celluloses by Trichoderma reesei, has been investigated. The experiments proved the fact that both the morphological structure and the crystalline one are crucial to the process and the ratio of the reactions. In addition, in order to obtain the most accessible cellulose substratum it was studied the biodegradation of cellulose allomorphs of spruce dissolving pulp. The insoluble cellulose fraction remaining after enzymatic hydrolysis was examined by X-ray diffraction method and it was established the degree of crystallinity and the average crystallite size. The enzymatic degradation is also proved by the decrease in the degree of polymerization of hydrolyzed samples. 相似文献
55.
Jochen Lutz The Vinh Ho Richard H. Fish Andreas Schmid 《Journal of organometallic chemistry》2004,689(25):4783-4790
The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural 1,4-dihydronicotinamde adenine dinucleotide (NADH) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzyl-1,4-dihydronicotinamide, 1b. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfer, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH2 possibly reacting with the precatalyst, [Cp*Rh(bpy)(H2O)](Cl)2, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH2 groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H2O)](Cl)2, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product. 相似文献
56.
L. I. Valuev G. A. Sytov I. L. Valuev M. V. Ul’yanova L. V. Vanchugova N. A. Plate 《Russian Chemical Bulletin》2004,53(11):2611-2616
Polymeric systems for targeting polypeptide medicinal drugs onto the wall of the small intestine after oral administration were synthesized. These systems are composed of particles of ovomucoid-modified polyacrylamide hydrogel with insulin physically immobilized in its bulk. In vitro experiments have demonstrated the enhanced stability of the immobilized polypeptide against proteolysis and the affinity of polymeric particles to lectin-containing surfaces. The efficiency of the systems obtained was demonstrated in experiments with animals and diabetes patients. The effrct of these systems upon oral administration was qualitatevely similar to that of subcutaneously administered native insulin.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2504–2509, November, 2004. 相似文献
57.
58.
Carbon nanotubes (CNTs) revealing metallic or semiconductive properties depending on the folding modes of the nanotube walls represent a novel class of nanowires. Different methods to separate semiconductive CNTs from conductive CNTs have been developed, and synthetic strategies to chemically modify the side walls or tube ends by molecular or biomolecular components have been reported. Tailoring hybrid systems consisting of CNTs and biomolecules (proteins and DNA) has rapidly expanded and attracted substantial research effort. The integration of biomaterials with CNTs enables the use of the hybrid systems as active field-effect transistors or biosensor devices (enzyme electrodes, immunosensors, or DNA sensors). Also, the integration of CNTs with biomolecules has allowed the generation of complex nanostructures and nanocircuitry of controlled properties and functions. The rapid progress in this interdisciplinary field of CNT-based nanobioelectronics and nanobiotechnology is reviewed by summarizing the present scientific accomplishments, and addressing the future goals and perspectives of the area. 相似文献
59.
Dr. Nadja A. Simeth Thomas Kinateder Dr. Chitra Rajendran Julian Nazet Prof. Dr. Rainer Merkl Prof. Dr. Reinhard Sterner Prof. Dr. Burkhard König Dr. Andrea C. Kneuttinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2439-2451
Light regulation of drug molecules has gained growing interest in biochemical and pharmacological research in recent years. In addition, a serious need for novel molecular targets of antibiotics has emerged presently. Herein, the development of a photocontrollable, azobenzene-based antibiotic precursor towards tryptophan synthase (TS), an essential metabolic multienzyme complex in bacteria, is presented. The compound exhibited moderately strong inhibition of TS in its E configuration and five times lower inhibition strength in its Z configuration. A combination of biochemical, crystallographic, and computational analyses was used to characterize the inhibition mode of this compound. Remarkably, binding of the inhibitor to a hitherto-unconsidered cavity results in an unproductive conformation of TS leading to noncompetitive inhibition of tryptophan production. In conclusion, we created a promising lead compound for combatting bacterial diseases, which targets an essential metabolic enzyme, and whose inhibition strength can be controlled with light. 相似文献
60.
Haiyang Cui Prof. Dr. Karl-Erich Jaeger Dr. Mehdi D. Davari Prof. Dr. Ulrich Schwaneberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2789-2797
The CompassR (computer-assisted recombination) rule enables, among beneficial substitutions, the identification of those that can be recombined in directed evolution. Herein, a recombination strategy is systematically investigated to minimize experimental efforts and maximize possible improvements. In total, 15 beneficial substitutions from Bacillus subtilis lipase A (BSLA), which improves resistance to the organic cosolvent 1,4-dioxane (DOX), were studied to compare two recombination strategies, the two-gene recombination process (2GenReP) and the in silico guided recombination process (InSiReP), employing CompassR. Remarkably, both strategies yielded a highly DOX-resistant variant, M4 (I12R/Y49R/E65H/N98R/K122E/L124K), with up to 14.6-fold improvement after screening of about 270 clones. M4 has a remarkably enhanced resistance in 60 % (v/v) acetone (6.0-fold), 30 % (v/v) ethanol (2.1-fold), and 60 % (v/v) methanol (2.4-fold) compared with wild-type BSLA. Molecular dynamics simulations revealed that attracting water molecules by charged surface substitutions is the main driver for increasing the DOX resistance of BSLA M4. Both strategies and obtained molecular knowledge can likely be used to improve the properties of other enzymes with a similar α/β-hydrolase fold. 相似文献