全文获取类型
收费全文 | 3889篇 |
免费 | 182篇 |
国内免费 | 12篇 |
学科分类
数理化 | 4083篇 |
出版年
2023年 | 38篇 |
2022年 | 65篇 |
2021年 | 81篇 |
2020年 | 87篇 |
2019年 | 85篇 |
2018年 | 72篇 |
2017年 | 58篇 |
2016年 | 126篇 |
2015年 | 110篇 |
2014年 | 144篇 |
2013年 | 180篇 |
2012年 | 303篇 |
2011年 | 342篇 |
2010年 | 153篇 |
2009年 | 146篇 |
2008年 | 286篇 |
2007年 | 247篇 |
2006年 | 243篇 |
2005年 | 239篇 |
2004年 | 202篇 |
2003年 | 118篇 |
2002年 | 135篇 |
2001年 | 39篇 |
2000年 | 30篇 |
1999年 | 32篇 |
1998年 | 15篇 |
1997年 | 28篇 |
1996年 | 33篇 |
1995年 | 16篇 |
1994年 | 24篇 |
1993年 | 27篇 |
1992年 | 30篇 |
1990年 | 18篇 |
1989年 | 14篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 24篇 |
1984年 | 23篇 |
1983年 | 16篇 |
1982年 | 19篇 |
1981年 | 24篇 |
1980年 | 14篇 |
1979年 | 18篇 |
1978年 | 20篇 |
1977年 | 20篇 |
1976年 | 16篇 |
1975年 | 16篇 |
1974年 | 16篇 |
1973年 | 9篇 |
排序方式: 共有4083条查询结果,搜索用时 15 毫秒
101.
Dr. Jessica Flores Gonzalez Vincent Montigaud Dr. Vincent Dorcet Dr. Kevin Bernot Dr. Boris Le Guennic Dr. Fabrice Pointillart Prof. Olivier Cador 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10160-10168
Single-Molecule Magnet (SMM) property is by essence molecular, while commonly measured in solid crystalline state. Solvent crystallization molecules are usually neglected in the analysis and interpretation of solid-state properties. The solvation/desolvation process in the polyoxometalate(POM)-based Na9[Er(W5O18)2] ⋅ 35 H2O SMM demonstrates that the dehydrated form relaxes more than 1000 times faster than the initial state, while the rehydration process allows the quasi complete recovering of the initial magnetic behaviour. This dehydration process is monitored by thermogravimetric analysis (TGA) and temperature-dependent X-ray powder diffraction, and rationalized by periodic quantum chemical calculations evidencing the tremendous role of the labile water molecules in the stability of the edifice. Ab-initio calculations highlight that sodium ions localization in the structure drive the magnetic responses. Isotopic enrichment with nuclear spin free (166Er, I=0) ErIII ions shows that the relaxation dynamics in the quantum regime depends on the nuclear spin. 相似文献
102.
Erwann Le Coz Joanna Hammoud Dr. Thierry Roisnel Marie Cordier Dr. Vincent Dorcet Dr. Samia Kahlal Prof. Dr. Jean-François Carpentier Prof. Dr. Jean-Yves Saillard Dr. Yann Sarazin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(46):11966-11982
Barium complexes ligated by bulky boryloxides [OBR2]− (where R=CH(SiMe3)2, 2,4,6-iPr3-C6H2 or 2,4,6-(CF3)3-C6H2), siloxide [OSi(SiMe3)3]−, and/or phenoxide [O-2,6-Ph2-C6H3]−, have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2-X1)(X2)]2 depends largely on the given pair of ligands X1 and X2. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3)2}2)]−<[N(SiMe3)2]−<[OSi(SiMe3)3]−<[O(2,6-Ph2-C6H3)]−<[OB(2,4,6-iPr3-C6H2)2]−. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ2-N(SiMe3)2}(OB{CH(SiMe3)2}2)]2 (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ2-X1)(X2)]2 heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands. 相似文献
103.
Dr. Marta Meneghello Dr. Christophe Léger Dr. Vincent Fourmond 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(70):17542-17553
Only two enzymes are capable of directly reducing CO2: CO dehydrogenase, which produces CO at a [NiFe4S4] active site, and formate dehydrogenase, which produces formate at a mononuclear W or Mo active site. Both metalloenzymes are very rapid, energy-efficient and specific in terms of product. They have been connected to electrodes with two different objectives. A series of studies used protein film electrochemistry to learn about different aspects of the mechanism of these enzymes (reactivity with substrates, inhibitors…). Another series focused on taking advantage of the catalytic performance of these enzymes to build biotechnological devices, from CO2-reducing electrodes to full photochemical devices performing artificial photosynthesis. Here, we review all these works. 相似文献
104.
Couture Alex Wittman Richard Morrison Erin C. Bowen James M. Pierson Bruce Greenwood Larry Woods Vincent Dorman Eric 《Journal of Radioanalytical and Nuclear Chemistry》2021,330(3):603-607
Journal of Radioanalytical and Nuclear Chemistry - Calculations were performed to support method development for simultaneous production of Ni and Ir isotopes. The work scope included development... 相似文献
105.
Journal of Computer-Aided Molecular Design - Accurate predictions of acid dissociation constants are essential to rational molecular design in the pharmaceutical industry and elsewhere. There has... 相似文献
106.
The use of recombinant baculoviruses as high level expression systems is becoming more and more popular. This review aims to provide a summary of the impact of this expression system in biochemistry and biotechnology, highlighting important advances that have been made utilizing the system. The potential of newly developed multiple baculovirus expression systems to enable the reconstruction of complex biological molecules and processes is also reviewed. 相似文献
107.
Sessler JL Roznyatovskiy V Pantos GD Borisova NE Reshetova MD Lynch VM Khrustalev VN Ustynyuk YA 《Organic letters》2005,7(23):5277-5280
[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate. 相似文献
108.
Taylor P Lahti PM Carroll JB Rotello VM 《Chemical communications (Cambridge, England)》2005,(7):895-897
Stable radical 2-(6-uradinyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl (1) binds to hydrogen-bonding complement 2,6-di(propylamido)pyridine (DAP) in chloroform with Ka=220 M(-1) at 33 degrees C; ESI-MS shows not only 1:DAP complementary dyad formation, but also 1:(DAP)2 formation at higher concentrations of DAP. 相似文献
109.
Tia Jarvis Carl Jacky Saint-Louis Alexander R. Fisch Korry L. Barnes Dolan Dean Luis A. Flores Thomas F. Hunt Lyndsay Munro Tyler J. Simmons Vincent J. Catalano Lei Zhu Alan K. Schrock Michael T. Huggins 《Tetrahedron》2018,74(14):1698-1704
Pyrrole β-amides are useful building blocks for the preparation of novel molecular architectures that can be used in supramolecular chemistry and sensor development. Under basic conditions, pyrrole β-amides with an α-aldehyde produce different condensation products when reacted with pyrrolinones depending on the amide substitution. Secondary amides form the expected dipyrrinones, but unexpectedly undergo a subsequent trans-amidation with the pyrrolinone nitrogen to produce an unsymmetrical imide (an N-confused fluorescent dipyrrinone). Under the same conditions, tertiary amides produce the expected dipyrrinone carboxylic acids, which have been shown to have strong self-association properties as determined by vapor pressure osmometry measurements, NMR studies, and X-ray crystal structure determination. Furthermore, an N-confused fluorescent dipyrrinone was produced from the same trans-amidation reaction during attempts to decarboxylate a dipyrrinone amide with a 9-carboxylic moiety. 相似文献
110.
Modifying the Steric Properties in the Second Coordination Sphere of Designed Peptides Leads to Enhancement of Nitrite Reductase Activity 下载免费PDF全文
Dr. Karl J. Koebke Dr. Fangting Yu Elvin Salerno Casey Van Stappen Dr. Alison G. Tebo Prof. James E. Penner‐Hahn Prof. Vincent L. Pecoraro 《Angewandte Chemie (International ed. in English)》2018,57(15):3954-3957
Protein design is a useful strategy to interrogate the protein structure‐function relationship. We demonstrate using a highly modular 3‐stranded coiled coil (TRI‐peptide system) that a functional type 2 copper center exhibiting copper nitrite reductase (NiR) activity exhibits the highest homogeneous catalytic efficiency under aqueous conditions for the reduction of nitrite to NO and H2O. Modification of the amino acids in the second coordination sphere of the copper center increases the nitrite reductase activity up to 75‐fold compared to previously reported systems. We find also that steric bulk can be used to enforce a three‐coordinate CuI in a site, which tends toward two‐coordination with decreased steric bulk. This study demonstrates the importance of the second coordination sphere environment both for controlling metal‐center ligation and enhancing the catalytic efficiency of metalloenzymes and their analogues. 相似文献