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121.
Qiutian Liu Chunxi Zhang Changneng Chen Hongping Zhu Yuheng Deng Jinhua Cai 《中国科学B辑(英文版)》1997,40(6):616-623
In a reaction system consisting of FeCl2, tetrathiometallate and cycloalkylthiolate, two Fe4S4 cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH2NMe3)2 [ Fe4S4 (SC5H9)4] (I), monoclinic space groupP21/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et4N)2[F4S4(SC6HlI)4] (II), tetragod space group
,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, Dobs = 1. 28 g/cm3, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.
Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China. 相似文献
122.
A racemic solution of (I) crystallizes as a conglomerate from which a crystal we selected was found to be (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), CoClO7N6C8H28. It crystallizes in the enantiomorphic space groupP2l2l2l, with lattice constantsa=18.501(15) å,b=14.433(2) å, andc=6.441(3) å;V=1720.07 å3 andd(calc. M.W.=414.73,Z=4)=1.601 g cm?3. A total of 2305 data were collected over the range of 4?≤2θ ≤55?; of these, 1724 (independent and withI > 3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.920 cm?1), and the relative transmission coefficients ranged from 0.8258 to 0.9565. Refinement was carried out for both lattice enantiomorphs, and at this stage theR(F) andR w (F) residuals were, respectively, 0.0381 and 0.0479 for (+ + +) and 0.0448 and 0.0532 for (? ? ?). Thus, the former was selected as correct for our specimen, and the final cycle of refinement with the (+ + +) model converged toR(F) andR w (F) of 0.0315 and 0.0365. A racemic solution of (II) crystallizes as a conglomerate from which a crystal we selected was found to be (?)589-trans-[Co(3,2,3-tet)Cl2]NO3 (II), CoCl2O3N5C8H22. It crystallizes in the enantiomorphic space groujp,P2l with lattice constantsa=6.395(2) å,b=8.886(2) å,c=13.185(2) å, andΒ=99.24(2)?;V=739.59 å3 andd(calc. M.W.=366.14,Z=2)=1.646 g cm ?3. A total of 2912 data were collected over the range of 4?<2θ<64?; of these, 2147 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ =15.424 cm?1), and the relative transmission coefficients ranged from 0.9632 to 0.9985. Refinement was carried out for both lattice enantiomorphs, and the finalR(F) andR w (F) residuals were, respectively, 0.0326 and 0.0328 for (+ + +) and 0.0347 and 0.0348 for (? ? ?). Thus, the (+ + +) was selected as correct for our specimen. A racemic solution of (III) crystallizes as a conglomerate from which a crystal we selected was found to be (+)589-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III), CoO7N7C8H22. It crystallizes in the enantiomorphic space group,P2l with lattice constantsa=6.295(1) å, b=15.108(3) å,c=8.029(1) å, andΒ=100.28(2)?;V=751.35 å3 andd(calc. M.W.=387.24,Z=2)=1.712 g cm?3. A total of 2393 data were collected over the range of 4?≤2θ≤60?; of these, 1869 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.859 cm?1), and the relative transmission coefficients ranged from 0.8814 to 0.9976. Refinement was carried out for both lattice enantiomorphs and the finalR(F) andR w (F) residuals were, respectively, 0.0463 and 0.0482 for (+ + +) and 0.0441 and 0.0442 for (? ? ?). Thus, the latter was selected as correct for our specimen, and the final cycle of refinement with the (? ? ?) model converged toR(F) andR w (F) of 0.0436 and 0.0421. For all three compounds, the six-membered rings are chairs; the secondary nitrogens are chiral centers, and the five-membered rings are ordered and conformationally dissymmetric, as expected. Coincidentally, in (I), (II), and (III) the central rings are right-handed helices withδ(+50.0?),δ(+53.3?), andδ(+48.3?), respectively. Thus, the secondary nitrogens of all three cations are (R), rendering the cations chiral. The incidence of conglomerate crystallization intrans coordination compounds is rare, and those known are asymmetrically substituted (see Ref. 4 for the four known cases). Thus, the incidence of such crystallization mode in a new series of [trans- Co(amine ligands)X2]+ cations bearing symmetrical pairs oftrans ligands was an unexpected and welcomed event. In all three cases, the counteranions are bonded to the hydrogens of the terminal -NH2 moieties, thus forming an overall entity which resembles a macrocycle. In fact, parallels between the crystallization behavior of our compounds and that of macrocycles bearing related fragments is discussed. Finally, in the three compounds, homochiral cations are linked into infinite strings by hydrogen bonds between the axial ligands and amino hydrogens on adjacent cations of the string. In turn, strings are stitched together by the counteranions which form bonds with amino hydrogens on cations of adjacent strings. 相似文献
123.
Tonggang Jiu Yongjun Li Haiyang Gan Yuliang Li Huibiao Liu Shu Wang Weidong Zhou Chunru Wang Xiaofang Li Xiaofeng Liu Daoben Zhu 《Tetrahedron》2007,63(1):232-240
The oligo(p-phenylene vinylene)-porphyrin-oligo(p-phenylene vinylene) (P-OPVn, n=2, 4, where n is the number of phenyl rings) and the complex with Zn2+ based on P-OPVn were synthesized for investigating their photophysical properties via UV-vis, voltammetry, steady-state and time-resolved fluorescence spectra. In these molecules two OPV moieties as energy donors were linked to porphyrin center by virtue of Wittig reaction. The detailed studies of photophysical properties indicate that OPV group can act as an antenna unit for effective intramolecular energy transfer. 相似文献
124.
The column-switching technique has been widely used to determine trace level ions in the presence of high concentration matrix.
A novel simplified column-switching method is proposed where bromate (as a model compound) was determined using this technique.
The switching time window was confirmed by the retention time of determined ions. This technique can completely carry out
the same function as the other column-switching technique do, but only one extra ten-way injection valve coupled to ion chromatograph
was used. By using column-switching technique, it is possible to determine 0.2 μg L−1 bromate in the presence of 100 mg L−1 chloride by direct injection of 2000 μL without any pretreatment and the relative standard deviation (RSD) of the peak height
for the eleven successive injections of 0.2 μg L−1 bromate solution is 23.1%. The detection limit for bromate is 0.09 μg L−1, which showed the method was very sensitive. The technique has been applied to the determination of bromate in drinking water,
and the spike recovery is in the range of 96–104%. 相似文献
125.
126.
Yajing Yin Ping Wu Yafen Lü Pan Du Yanmao Shi Chenxin Cai 《Journal of Solid State Electrochemistry》2007,11(3):390-397
A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques.
The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and
infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results
demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H2O2. This modified electrode might be used in development of new biosensors and the biofuel cells. 相似文献
127.
Tao He Ying‐Fang Zou Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3367-3378
Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under 60Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under 60Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]0/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002 相似文献
128.
Xiao Wen Hu Zhi Min Zheng Cai Hong Xu 《中国化学快报》2007,18(11):1351-1352
Three new 1,3-bis(phenylethynyl)disilazanes were synthesized from the reaction of 1,3-dichlorodisilazanes with (phenylethy- nyl)lithium,and characterized by infrared (IR) spectra,nuclear magnetic resonance (NMR) and mass spectrometry (MS). 相似文献
129.
Although the theories and potential applications of intermolecular multiple-quantum coherences (iMQCs) have been under active investigations for over a decade, discussion of iMQC NMR signal formation was mainly confined in the time domain. In this paper, a full line-shape theory was developed to describe iMQC signals in the frequency domain. Relevant features of the line shape, such as peak height, linewidth, and phase, were investigated in detail. Predictions based on the theory agree well with experimental and simulated results. Since radiation-damping effects always couple with iMQCs in highly polarized liquid-state NMR systems, and strongly radiation-damped signals have many spectral characteristics similar to those of iMQCs, a detailed comparison was also made between them from different spectral aspects. With detailed comparison of peak height, linewidth, and phase, this work demonstrates that the iMQC and radiation-damping phenomena result from two completely different physical mechanisms despite that both present similar signal features and coexist in highly polarized liquid-state NMR systems. 相似文献
130.
The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. 相似文献