全文获取类型
收费全文 | 918篇 |
免费 | 45篇 |
国内免费 | 1篇 |
专业分类
化学 | 598篇 |
晶体学 | 9篇 |
力学 | 48篇 |
数学 | 187篇 |
物理学 | 122篇 |
出版年
2024年 | 3篇 |
2023年 | 10篇 |
2022年 | 45篇 |
2021年 | 45篇 |
2020年 | 29篇 |
2019年 | 36篇 |
2018年 | 41篇 |
2017年 | 23篇 |
2016年 | 47篇 |
2015年 | 35篇 |
2014年 | 39篇 |
2013年 | 64篇 |
2012年 | 60篇 |
2011年 | 60篇 |
2010年 | 41篇 |
2009年 | 35篇 |
2008年 | 54篇 |
2007年 | 34篇 |
2006年 | 40篇 |
2005年 | 23篇 |
2004年 | 23篇 |
2003年 | 29篇 |
2002年 | 28篇 |
2001年 | 14篇 |
2000年 | 17篇 |
1999年 | 9篇 |
1998年 | 11篇 |
1997年 | 5篇 |
1995年 | 6篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1976年 | 10篇 |
1975年 | 3篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1965年 | 1篇 |
1961年 | 1篇 |
1960年 | 1篇 |
1929年 | 1篇 |
排序方式: 共有964条查询结果,搜索用时 15 毫秒
1.
2.
Rudovsky J Hermann P Botta M Aime S Lukes I 《Chemical communications (Cambridge, England)》2005,(18):2390-2392
A marked increase of relaxivity has been observed upon rigidifying the internal frame of Gd-containing PAMAM dendrimers: the effect has been attained by either protonation of the dendrimer or by forming supramolecular adducts with cationic polyaminoacids. 相似文献
3.
New five-coordinate Pt(IV) complexes [{(o-R2-p-R'-C6H2)NC(R' ')}2CH]PtMe3 (R, R', R' ' = alkyl or H) are reported. The complex with R = Me, R' = tBu, R' ' = Me generates unsaturated Pt(II) species capable of alkane C-H bond activation and stoichiometric dehydrogenation. 相似文献
4.
Yan-Cong Chen Yan Meng Yan-Jie Dong Xiao-Wei Song Guo-Zhang Huang Chuan-Lei Zhang Zhao-Ping Ni Jakub Navaík Ondej Malina Radek Zboil Ming-Liang Tong 《Chemical science》2020,11(12):3281
Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)2{Au(CN)2}2] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)2{Au(CN)2}2], revealing the hidden multistability of spin states. 相似文献
5.
Jakub Wojciechowski Henryk Krawczyk Marcin
liwiski Karolina Kafarska Wojciech M. Wolf 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(5):o280-o282
The title compound, C14H20O2, adopts a conformation in which the δ‐valerolactone and cyclohexane rings are almost coplanar with one another. The γ‐methyl substituent occupies an axial position with respect to the cyclohexane ring. The δ‐valerolactone moiety adopts an envelope arrangement, while the cyclohexane ring exists in a chair conformation. 相似文献
6.
Shearer J Jackson HL Schweitzer D Rittenberg DK Leavy TM Kaminsky W Scarrow RC Kovacs JA 《Journal of the American Chemical Society》2002,124(38):11417-11428
Nitrile hydratase (NHase) is an iron-containing metalloenzyme that converts nitriles to amides. The mechanism by which this biochemical reaction occurs is unknown. One mechanism that has been proposed involves nucleophilic attack of an Fe-bound nitrile by water (or hydroxide). Reported herein is a five-coordinate model compound ([Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+)) containing Fe(III) in an environment resembling that of NHase, which reversibly binds a variety of nitriles, alcohols, amines, and thiocyanate. XAS shows that five-coordinate [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) reacts with both methanol and acetonitrile to afford a six-coordinate solvent-bound complex. Competitive binding studies demonstrate that MeCN preferentially binds over ROH, suggesting that nitriles would be capable of displacing the H(2)O coordinated to the iron site of NHase. Thermodynamic parameters were determined for acetonitrile (DeltaH = -6.2(+/-0.2) kcal/mol, DeltaS = -29.4(+/-0.8) eu), benzonitrile (-4.2(+/-0.6) kcal/mol, DeltaS = -18(+/-3) eu), and pyridine (DeltaH = -8(+/-1) kcal/mol, DeltaS = -41(+/-6) eu) binding to [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) using variable-temperature electronic absorption spectroscopy. Ligand exchange kinetics were examined for acetonitrile, iso-propylnitrile, benzonitrile, and 4-tert-butylpyridine using (13)C NMR line-broadening analysis, at a variety of temperatures. Activation parameters for ligand exchange were determined to be DeltaH(+ +) = 7.1(+/-0.8) kcal/mol, DeltaS(+ +) = -10(+/-1) eu (acetonitrile), DeltaH(+ +) = 5.4(+/-0.6) kcal/mol, DeltaS(+ +) = -17(+/-2) eu (iso-propionitrile), DeltaH(+ +) = 4.9(+/-0.8) kcal/mol, DeltaS(+ +) = -20(+/-3) eu (benzonitrile), and DeltaH(+ +) = 4.7(+/-1.4) kcal/mol DeltaS(+ +) = -18(+/-2) eu (4-tert-butylpyridine). The thermodynamic parameters for pyridine binding to a related complex, [Fe(III)(S(2)(Me2)N(3)(Pr,Pr))](+) (DeltaH = -5.9(+/-0.8) kcal/mol, DeltaS = -24(+/-3) eu), are also reported, as well as kinetic parameters for 4-tert-butylpyridine exchange (DeltaH(+ +) = 3.1(+/-0.8) kcal/mol, DeltaS(+ +) = -25(+/-3) eu). These data show for the first time that, when it is contained in a ligand environment similar to that of NHase, Fe(III) is capable of forming a stable complex with nitriles. Also, the rates of ligand exchange demonstrate that low-spin Fe(III) in this ligand environment is more labile than expected. Furthermore, comparison of [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) and [Fe(III)(S(2)(Me2)N(3)(Pr,Pr))](+) demonstrates how minor distortions induced by ligand constraints can dramatically alter the reactivity of a metal complex. 相似文献
7.
A variety of branched polyethylenes (PE), ranging from semicrystalline linear low density polyethylene to completely amorphous
low density polyethylene and rubbery PE, can be produced from ethylene alone by tandem catalysis using as oligomerization
catalysts the (imino)pyridyl Co(II) complexes NBTCoCl2 (1) ({6-(benzo[b]thiophen-2-yl)-2-(imine)pyridyl)}CoCl2), NETCoCl2 (2) ({6-(4-ethylthiophen-2-yl)-2-(imine)pyridyl)}CoCl2), or NPhCoCl2 (3) ({6-(phenyl)-2-(imine)pyridyl)}CoCl2) and as a copolymerization catalyst [η5-C5Me4)SiMe2(t-BuN)]TiCl2 (4). The catalytic activity of the systems 1/4/MAO, 2/4/MAO, and 3/4/MAO has been evaluated under comparable experimental conditions (T = 30°C, [ethylene] = 0.35 mol/l), varying the molar fraction of the cobalt precursors. A positive comonomer effect was observed
for all the systems investigated. The maximum productivity (4570 kg PE (mol Ti)−1 h−1) was obtained for the benzothiophenyl-substituted cobalt complex. An effective control of the branching in the polymer backbone
was achieved by varying either the oligomerization catalyst or its molar fraction. Completely amorphous materials with T
g as low as-60°C could be obtained.
The text was submitted by the authors in English. 相似文献
8.
Jakub Kołacz Henry G. Gotjen Robel Y. Bekele Jason D. Myers Jesse A. Frantz Michael Ziemkiewicz 《Liquid crystals》2020,47(4):531-539
ABSTRACTIn a planar dielectric waveguide, weak confinement of a propagating mode in a high index core leads to a measurable evanescent interaction with the cladding. In this work, we study the effect of a reorientable anisotropic cladding on the behaviour of Transverse Electric (TE) and Transverse Magnetic (TM) mode polarisations using a liquid crystal (LC)-clad waveguide architecture. The polarised evanescent field of a guided mode interacts with a voltage-tunable birefringent LC cladding to deflect an out-coupled beam. Experimental measurements are coupled with a theoretical framework and show good consistency with simulation results. We isolate the effect of mode confinement by changing the thickness of the high index core. Interactions between the LC index ellipsoid and the mode polarisation are probed by changing the initial alignment of the LC. Finally, we examine the difference in deflection between TE and TM modes, which incorporates both a change in mode confinement and a difference in LC index components. 相似文献
9.
Sidra Khan Shikha Chauhan Achu Chandran Michał Czerwiński Jakub Herman Ashok M. Biradar 《Liquid crystals》2020,47(2):263-272
ABSTRACT Here, we present the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal (FLC) mixture, namely W302. The FLC mixture, comprising of pyrimidine compounds, was characterised through dielectric spectroscopy, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and other electro-optical methods. The material parameters such as spontaneous polarisation, rotational viscosity, response time and tilt angle of W302 were found to be 14 nC/cm2, 240 mPa.s, 150 µs and 28?, respectively. The phase transition temperatures of W302 were observed through DSC and further confirmed by the dependence of dielectric loss factor in homogeneously aligned FLC sample with temperature. We also demonstrate the observance of a low-frequency dielectric relaxation mode due to the unwinding of the helix, called as partially unwound helical mode (p-UHM) along with Goldstone mode. The behaviour of p-UHM has been systematically studied with temperature and applied bias field. Further, dispersion of nCuO into host W302 has shown a significant increase in dielectric permittivity. Also, the p-UHM relaxation peak in the dielectric regime has disappeared with the incorporation of nCuO. These studies would be useful to fabricate better electro-optical devices for display, switching and beam steering applications. The formulation and characterization of a ferroelectric liquid crystal (FLC) mixture W302 composed of pyrimidine compounds is presented. Then, we observed the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared and characterized FLC mixture. 相似文献
10.
Jakub Stýskala Jan Slouka Iveta Wiedermannov Petr Bedn 《Journal of heterocyclic chemistry》2003,40(5):805-811
A series of 6‐azacytosines 4a‐4k and 5a‐5c were prepared by nucleophilic cleavage of furan ring of [1]benzofuro[2,3‐e][1,2,4]triazine derivative 1 . Some of them were used for the preparation of derivatives of [1,2,4]triazolo[4,3‐d][1,2,4]triazine ( 6a‐6d ) and tetrazolo[1,5‐d][1,2,4]triazine (7). The reaction of 1 with hydrogen sulfide afforded the corresponding 6‐(2‐hydroxyphenyl)‐2‐phenyl‐5‐thioxo‐4,5‐dihydro‐1,2,4‐tri‐azin‐3(2H)‐one ( 8 ), while with hydrogen selenide 6‐(2‐hydroxyphenyl)‐2‐phenyl‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐one ( 9 ) was formed. The prepared compounds were tested for biological activity. 相似文献