全文获取类型
收费全文 | 80234篇 |
免费 | 13232篇 |
国内免费 | 5519篇 |
专业分类
化学 | 71118篇 |
晶体学 | 988篇 |
力学 | 2549篇 |
综合类 | 384篇 |
数学 | 7192篇 |
物理学 | 16754篇 |
出版年
2023年 | 445篇 |
2022年 | 672篇 |
2021年 | 1295篇 |
2020年 | 2316篇 |
2019年 | 3600篇 |
2018年 | 1978篇 |
2017年 | 1701篇 |
2016年 | 4731篇 |
2015年 | 4938篇 |
2014年 | 5303篇 |
2013年 | 6878篇 |
2012年 | 6497篇 |
2011年 | 6107篇 |
2010年 | 5475篇 |
2009年 | 5358篇 |
2008年 | 5669篇 |
2007年 | 4761篇 |
2006年 | 4378篇 |
2005年 | 4209篇 |
2004年 | 3588篇 |
2003年 | 3029篇 |
2002年 | 3774篇 |
2001年 | 2654篇 |
2000年 | 2337篇 |
1999年 | 1117篇 |
1998年 | 610篇 |
1997年 | 535篇 |
1996年 | 545篇 |
1995年 | 413篇 |
1994年 | 405篇 |
1993年 | 394篇 |
1992年 | 359篇 |
1991年 | 310篇 |
1990年 | 223篇 |
1989年 | 212篇 |
1988年 | 189篇 |
1987年 | 161篇 |
1986年 | 125篇 |
1985年 | 206篇 |
1984年 | 130篇 |
1983年 | 110篇 |
1982年 | 127篇 |
1981年 | 96篇 |
1980年 | 92篇 |
1978年 | 97篇 |
1977年 | 92篇 |
1976年 | 102篇 |
1975年 | 104篇 |
1974年 | 80篇 |
1973年 | 104篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Peter Lindemann Silvia E. Braslavsky Marie-Michle Cordonnier Lee H. Pratt Kurt Schaffner 《Photochemistry and photobiology》1993,58(3):417-424
Abstract–Thc kinetics of the microsecond phototransformation intermediates of 124 kDa Avena phytochrome (17001,2) were studied in the prcsence of bound monoclonal antibodies at various temperatures. A global analysis was applied to the decays at all wavelengths at each temperature in order to derive the rate constants and the decay-associated spectra of the three decay components. Monoclonal antibodies bound to specific epitopes altered the Arrhenius parameters of both 17001,2 decay components. The strongest influence on these parameters was observed with OAT 8 (epitope between residues 624 and 686), which decreased by more than 50% the activation parameters of both components. This decrease is interpreted to result from an increased flexibility induced by this antibody in the ground state or in the transition state of bonds changing during the decay of both 1700 transients. Thus, the OAT 8 cpitope appears to be functionally important during the decay of the 17001,2 intermediates. For the case of 11001 bound OAT 23 and OAT 25 (epitopes between residues 1 and 66) reduced even further the relatively small flexibility of these bonds in the red light-absorbing form of phytochrome (P1) without antibodies, as reflected by the high preex-ponential factors for its decay. This resulted also in higher activation energies for this decay in the presence of the antibodies. Thus, the amino-terminus should act as a rigid spacer of the chromophore cavity without affecting it during the microsecond transformation, because the Arrhenius parameters for these decays are similar to those for small phytochrome. The possible implications of the influence of the various antibodies on the bleaching remaining after the decay of 17001,2 are discussed. 相似文献
992.
Summary A simple and rapid systematic optimization scheme was described for the micellar electrokinetic chromatographic separation of a group of flavonoids. The scheme employed an interpretative optimization approach to predict the optimum conditions for the separation of a group of flavonoids by micellar electrokinetic chromatography. By performing a set of nine pre-planned experiments conducted over the maximum working range for the system, global optimum separation conditions could be determined. To validate the optimization procedure, additional experiments were performed using the optimum experimental conditions derived from the optimization scheme. The results showed that satisfactory separation of all the peaks could be obtained. In addition, the application of the method in micropreparative micellar electrokinetic chromatography of the flavonoids was demonstrated. 相似文献
993.
Synthesis of six new triorganosiloxybenzaldehydes, two m-methoxy-(triorganosiloxy)benzaldehydes, and seven methoxy(triorganosiloxy)benzenes are reported. From comparison of the stability of these compounds in the atmosphere, it is concluded that formyl group shows unfavorable influence and methoxy group shows favorable influence on the stability of these compounds. The oposite influences of these two groups on phenoxysilane linkage seems to connect with the oposite directiones of inductive effect of formyl group and resonance effect of methoxy group on the benzene ring. 相似文献
994.
NdOx作为助催化剂对PtRu/C电催化氧化甲醇活性的影响 总被引:5,自引:0,他引:5
采用沉积-还原法制备了PtRu-NdOx/C催化剂, 借助TEM、EDS和XRD等测试手段对其进行了微结构和组成的表征. 结果表明, 催化剂中Pt与Ru以合金形式存在, 而Nd的氧化物则以无定形形态存在. 催化剂粒子的平均粒径在2 nm左右, 晶胞参数为0.3896 nm, Nd氧化物的加入对PtRu合金的晶体结构影响不明显. 采用循环伏安法和计时电流法, 比较了PtRu-NdOx/C催化剂和PtRu /C催化剂对甲醇氧化的电催化活性, 结果表明, 加入Nd的氧化物作为助催化剂能明显提高PtRu /C催化剂对甲醇氧化的电催化性能. 相似文献
995.
996.
Lee D Pervushin K Bischof D Braun M Thöny-Meyer L 《Journal of the American Chemical Society》2005,127(11):3716-3717
The heme chaperone CcmE is essential for the delivery of heme to c-type cytochromes. It forms an unusual transient, yet covalent, bond between an essential histidine, H130, and heme. We report on the discovery of the chemical structure of this bond solved by NMR, where the heme vinyl is cross-linked at the beta carbon to the Ndelta1 of H130. As this type of heme linkage has not been described previously in any cytochrome or hemoprotein, it represents a novel type of heme-histidine complex. 相似文献
997.
The hydrothermal reaction of VOSO4, As2O5, piperazine and H2O produces [H2N(CH2)4NH2]4[β‐As8V14O42(SO4)]·2HSO4 ( 1 ), which is the first arsenic‐vanadium cluster containing a spherical β‐As8V14O42 shell. The structure of this compound was characterized by single crystal X‐ray diffraction, elemental analysis, TG, and IR spectrum. Crystal data for 1 : Orthorhombic, Cmcm, a = 15.369(1) Å, b = 16.404(1) Å, c = 25.772(1) Å, V = 6497.4(9) Å3, Z = 4. 相似文献
998.
999.
Poly(decyl methacrylate)-based fluorescent PEBBLE swarm nanosensors for measuring dissolved oxygen in biosamples 总被引:1,自引:0,他引:1
150-250 nm Poly(decyl methacrylate)(PDMA) fluorescent ratiometric nanosensors for dissolved oxygen have been developed. Platinum octaethylporphine ketone (PtOEPK), the oxygen-sensitive dye, and octaethylporphyrin (OEP), the oxygen-insensitive dye, have been incorporated into PDMA nanoparticles to make the sensors ratiometric. Based on the corresponding Stern-Volmer plot, these nanosensors exhibit almost complete linearity over the whole range of dissolved molecular oxygen from 0 to 42.5 ppm (deoxygenated to pure oxygen-bubbled water). The overall quenching response is up to 97.5%, the best so far for all dissolved oxygen optical sensors. These PEBBLE nanosensors also show very good reversibility and stability to leaching and photobleaching, as well as very short response times and no perturbation by proteins. In human plasma they demonstrate a robust oxygen sensing capability, little affected by light scattering and autofluorescence. Potential applications include intracellular oxygen imaging and microresolved pressure profiles in biological and other heterogenous environments. 相似文献
1000.
Xiu‐Li Dong Zheng‐Yu Zhou Lai‐Jin Tian Gang Zhao 《International journal of quantum chemistry》2005,102(4):461-469
The hydrogen bonding complexes HO(H2O)n (n = 1–3) were completely investigated in the present study using DFT and MP2 methods at varied basis set levels from 6‐31++G(d,p) to 6‐311++G(2d,2p). For n = 1 two, for n = 2 two, and for n = 3 five reasonable geometries are considered. The optimized geometric parameters and interaction energies for various complexes at different levels are estimated. The infrared spectrum frequencies and IR intensities of the most stable structures are reported. Finally, thermochemistry studies are also carried out. The results indicate that the formation and the number of hydrogen bonding have played an important role in the structures and relative stabilities of different complexes. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献