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81.
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
82.
Structure and Photoelectric Characteristics of Functional Polymers and of Compositions Based on Them 总被引:1,自引:0,他引:1
The electronic processes in disordered organic solids were analyzed, classified, and summarized. They include the photogeneration of charge pairs, electron transport, geminal and bimolecular recombination, and the capture of charge carriers in local electronic states. General criteria were formulated for the targeted search for and the creation of new prospective polymers and their compositions with organic pigments and related compounds having specific photoelectric characteristics for electrographic and holographic media, photoelectric converters, and electroluminescent and photorefractive devices. 相似文献
83.
Andri Zaitsevskii Christian Teichteil 《International journal of quantum chemistry》2002,88(4):426-432
A quasirelativistic perturbative method of ab initio calculations on ground and excited molecular electronic states and transition properties within the relativistic effective core potential approximation is presented and discussed. The method is based on the construction of a state‐selective many‐electron effective Hamiltonian in the model space spanned by an appropriate set of Slater determinants by means of the second‐order many‐body multireference perturbation theory. The neglect of effective spin–orbit interactions outside of the model space allows the exploitation of relatively high nonrelativistic symmetry during the evaluation of perturbative corrections and therefore dramatic reduction of the cost of computations without any contraction of the model‐space functions. One‐electron transition properties are evaluated via the perturbative construction of spin‐free transition density matrices. Illustrative calculations on the X0+ ? A1, B0+, and (ii)1 transitions in the ICl molecule are reported. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
84.
85.
Ken-Ichi Ito Masamichi Nishimura Minoru Sashio Masahiro Tsunooka 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2177-2185
It was found that amines were formed efficiently by the photolysis of O-acyloximes followed by hydrolysis in polystyrene films and the relationship between structures of O-acyloximes and yields of amines were investigated. O-phenylacetyl acetophenone oxime (PaApO), O-pivaloyl acetophenone oxime (PApO), and O-benzoyl acetophenone oxime (BApO) as monofunctional O-acyloximes and O,O′-succinyl diacetophenone oxime (SDApO) and O,O′-glutaryl diacetophenone oxime (GDApO) as bifunctional O-acyloximes were examined. The yields of amines for PaApO and SDApO under N2 were ca. 70%, which was the highest among O-acyloximes examined in this experiment. On the other hand, the yields for PApO, BApO, and GDApO were less than 15% and it was verified that the hydrogen abstraction by imino radicals via 6-membered cyclic intermediates resulted in the lowering of yields. Although the effect of oxygen under photolysis on the yields of amine for PaApO was negligible under 50% conversion of PaApO, the yield decreased with further increase in the conversion and was 50% at 90% conversion. © 1994 John Wiley & Sons, Inc. 相似文献
86.
Mechanism of Back Electron Transfer in an Intermolecular Photoinduced Electron Transfer Reaction: Solvent as a Charge Mediator 下载免费PDF全文
Sudhakar Narra Dr. Yoshifumi Nishimura Prof. Dr. Henryk A. Witek Prof. Dr. Shinsuke Shigeto 《Chemphyschem》2014,15(14):2945-2950
Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4‐dicyanobenzene (DCB) in acetonitrile (ACN) by using time‐resolved near‐ and mid‐IR spectroscopy. The Py dimer radical cation (Py2.+) and DCB radical anion (DCB.?) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB.? to the solvent and charge recombination between the resulting ACN dimer anion and Py2.+. The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye‐sensitized solar cells. 相似文献
87.
A two‐step reaction scheme leading to singlet carbene species that can be detected under matrix conditions for the reaction of Zr(3F) with either CH3F or CH3CN 下载免费PDF全文
Ana E. Torres Guadalupe Castro Ricardo Pablo‐Pedro Fernando Colmenares 《Journal of computational chemistry》2014,35(11):883-890
The results obtained from CASSCF‐MRMP2 calculations are used to rationalize the singlet complexes detected under matrix‐isolation conditions for the reactions of laser‐ablated Zr(3F) atoms with the CH3F and CH3CN molecules, without invoking intersystem crossings between electronic states with different multiplicities. The reaction Zr(3F) + CH3F evolves to the radical products ZrF· + ·CH3. This radical asymptote is degenerate to that emerging from the singlet channel of the reactants Zr(1D) + CH3F because they both exhibit the same electronic configuration in the metal fragment. Hence, the caged radicals obtained under cryogenic‐matrix conditions can recombine through triplet and singlet paths. The recombination of the radical species along the low‐multiplicity channel produces the inserted structures H3C? Zr? F and H2C?ZrHF experimentally detected. For the Zr(3F) + CH3CN reaction, a similar two‐step reaction scheme involving the radical fragments ZrNC· + ·CH3 explains the presence of the singlet complexes H3C? Zr? NC and H2C?Zr(H)NC revealed in the IR‐matrix spectra upon UV irradiation. © 2014 Wiley Periodicals, Inc. 相似文献
88.
研究了染料敏化太阳能电池(DSCs)中N3/Al2O3/N749交替组装结构的作用. 该结构使用Al2O3作为介质层吸附第二层染料, 可以有效拓宽DSCs的光响应范围, 提高电池的光电转化效率. UV-Vis 吸收光谱和单色光转换效率(IPCE)谱测试结果表明, 相对于单一染料, 使用交替组装结构的电池光响应范围变宽. 电流-电压(I-V)曲线结果表明, 该结构有效增加了DSCs 电池的光电转化效率, 从单一N3 和N749 染料的4.22%和3.09%增加到了5.75%, 分别增加了36%和86%. 为了研究该结构的作用机理, 本文对其界面修饰作用及界面电子过程进行了讨论. 暗电流测试结果表明交替组装结构可以有效阻止电荷复合过程; 电化学阻抗谱(EIS)结果表明在黑暗条件下, N3/Al2O3/N749结构可以提高界面电阻, 从而抑制电荷复合过程; 本文建立了等效电路模型, 并使用该模型讨论了交替组装结构的界面电子过程; 调制强度光电流谱(IMPS)和调制强度光电压谱(IMVS)的结果表明该结构可以提高电子寿命和改善电子扩散. 相似文献
89.
Nail M. Shavaleev Dr. Svetlana V. Eliseeva Dr. Rosario Scopelliti Dr. Jean‐Claude G. Bünzli Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(41):10790-10802
A series of tridentate benzimidazole‐substituted pyridine‐2‐carboxylic acids have been prepared with a halogen, methyl or alkoxy group in the 6‐position of the benzimidazole ring, which additionally contains a solubilising N‐alkyl chain. The ligands form neutral homoleptic nine‐coordinate lanthanum, europium and terbium complexes as established from X‐ray crystallographic analysis of eight structures. The coordination polyhedron around the lanthanide ion is close to a tricapped trigonal prism with ligands arranged in an up–up–down fashion. The coordinated ligands serve as light‐harvesting chromophores in the complexes with absorption maxima in the range 321–341 nm (ε=(4.9–6.0)×104 M ?1 cm?1) and triplet‐state energies between 21 300 and 18 800 cm?1; the largest redshifts occur for bromine and electron‐donor alkoxy substituents. The ligands efficiently sensitise europium luminescence with overall quantum yields ( ) and observed lifetimes (τobs) reaching 71 % and 3.00 ms, respectively, in the solid state and 52 % and 2.81 ms, respectively, in CH2Cl2 at room temperature. The radiative lifetimes of the Eu(5D0) level amount to τrad=3.6–4.6 ms and the sensitisation efficiency ηsens= (τrad/τobs) is close to unity for most of the complexes in the solid state and equal to approximately 80 % in solution. The photophysical parameters of the complexes correlate with the triplet energy of the ligands, which in turn is determined by the nature of the benzimidazole substituent. Facile modification of the ligands makes them promising for the development of brightly emissive europium‐containing materials. 相似文献
90.
V. Lj. Marković M. M. Pejović Z. Lj. Petrović 《Plasma Chemistry and Plasma Processing》1996,16(2):195-208
The late afterglow in nitrogen with iron electrode is studied by the breakdown time delay method, i.e., by measuring the breakdown time delay td as a function of the afterglow time . It is proposed that the cause of the secondary electrons initiating the breakdown is the energy of the surface recombination of nitrogen atoms on the iron electrode. The gas-phase and macrokinetic diffusive models are used to describe the experimental breakdown time delay data. By fitting the theoretical curve to the experimental data: (1) it has been confirmed that the recombination on the molybdenum glass is of the second order and the value of the surface recombination coefficient is determined at 4 mbar; (2) it has been shown that the surface recombination on the iron electrode is of the second order, and the effective recombination coefficients are determined; (3) the analytical form of the recombination coefficient as a function of the adsorption characteristics of surfaces and the pressure of the parent gas has been derived. In addition, the orders of surface recombination on the molybdenum-, aluminum-, and gold-plated electrode were determined by the same method. 相似文献