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991.
Jun Li 《Journal of Cluster Science》2002,13(1):137-163
The electronic structures and bonding of isopoly oxometalates M6O19
2– (M=Cr, Mo, W) have been investigated by using ab initio and relativistic density functional methods. We have discussed the role of the central oxygen atom and the (d-p) conjugation interactions between the metal and bridging oxygen atoms. It is found that there exist 12 three-centered two-electron (d-p-d) bonds for the three M4(-O)4 planar rings in M6O19
2– ions and these hexametalates are considered to have quasi-aromaticity. The (d-p) conjugation effects play essential role in stabilizing these cluster compounds, and the reduced (d-p) conjugation effects account for the instability of the isopoly oxochromate ion, Cr6O19
2–. The vibrational spectra and electronic spectra of M6O19
2– ions are evaluated and assigned theoretically and the calculated spectra are in fairly good agreement with the measured experimental results. 相似文献
992.
-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity. 相似文献
993.
Rondeau D Martineau C Blanchard P Roncali J 《Journal of mass spectrometry : JMS》2002,37(10):1081-1085
Oligothienylenevinylenes/C(60) dyads n-C and triads n-C(2) are studied by electrospray mass spectrometry. A clear correlation is observed between the nature of the charged species detected by mass spectrometry, i.e. protonated molecule [M + H], (+) cation radical M(+.) and dication M(++), and the oxidation potentials of the molecules. Moreover, under defined solubility conditions, mass spectrometry provides conclusive evidences for the reversible dimerization of cation-radicals of n-C(2) compounds. 相似文献
994.
995.
几种改进的CoMFA方法比较研究血小板活化因子拮抗剂 总被引:6,自引:1,他引:6
由于传统的比较分子场分析(CoMFA)方法本身存在一些缺陷,使得分子的叠合 规则以及叠合分子的空间取向和空间位置等因素对q~2的影响很大,因此相继提出 了几种改进的CoMFA方法。为了优化CoMFA结果,应用传统的CoMFA方法和交叉验证 的R~2引导的区域选择法(q~2-GRS)、全取向搜索法(AOS)、全空间搜索法(APS) 以及比较分子相似性指数(CoMSIA)等四种改进的CoMFA方法,对18个pinusolide类 衍生物这类新发现的血小板活化因子(PAF)拮抗剂进行了比较研究。结果表明四 种改进的CoMFA方法得到的q~2值均比传统CoMFA的高。q~2-GRS方法得到的q~2值有 所提高,但综合结果并不理想,AOS与APS得到的q~2较为理想,而在CoMSIA中, q~2几乎不受空间取向或空间位置的影响。同时我们引人基于样本的偏最小二乘法 (SAMPLS)取代原AOS/APS程序中的传统PLS进行统计分析,明显提高了其运行速 度。最后,根据q~2最高的CoMFA模型和CoMSIA模型设计了几个预测活性更高的 pinusolide类似物。 相似文献
996.
Tautomerism of Nunsubstituted benzohydroxamic acids and their anions in the gas phase was investigated by the semiempirical AM1 method. The possibility of estimating pK
a in aqueous solutions using calculated characteristics of molecules is demonstrated. 相似文献
997.
Gololobov Yu. G. Petrovskii P. V. Ivanova E. M. Linchenko O. A. Schmutzler R. Ernst L. Jones P. G. Karaçar A. Freytag M. Okucu S. 《Russian Chemical Bulletin》2003,52(2):427-436
The reactions of meta—para-substituted aryl isocyanates with phosphorus-containing 1,3-zwitterions, which proceed with the CN migration of the CO2Et group to form the corresponding carbamates, were extended to ortho-substituted aryl isocyanates. The influence of the steric and electronic effects of the ortho substituents in the aromatic rings of aryl isocyanates on the ease of this rearrangement is qualitatively considered. 相似文献
998.
Vinogradov M. G. Gorshkova L. S. Chel'tsova G. V. Kurilov D. V. Ferapontov V. A. Shishk O. V. Heise G. L. 《Russian Chemical Bulletin》2003,52(8):1841-1846
An improved procedure was developed for asymmetric reduction of acetophenone and propiophenone by the chiral reagent NaAl(IPTOLate)H2. This procedure is based on isolation of the chiral alcohol that formed as a crystalline host—guest complex with the IPTOL ligand. The enantiomeric enrichment of the product was as high as 97% ee. The ability of IPTOL and its analogs to form host—guest complexes with a number of ether-type solvents, 1-phenylethanol, and 1-phenylpropan-1-ol as well as thermal stabilities of IPTOL-containing complexes with these alcohols were studied. 相似文献
999.
Marc B. Taraban Daniel J. Deredge Margaret E. Smith Katharine T. Briggs Yu Li Zhong-Xing Jiang Patrick L. Wintrode Yihua Bruce Yu 《Magnetic resonance in chemistry : MRC》2019,57(10):861-872
The conformational transition of a fluorinated amphiphilic dendrimer is monitored by the 1H signal from water, alongside the 19F signal from the dendrimer. High-field NMR data (chemical shift δ, self-diffusion coefficient D, longitudinal relaxation rate R1, and transverse relaxation rate R2) for both dendrimer (19F) and water (1H) match each other in detecting the conformational transition. Among all parameters for both nuclei, the water proton transverse-relaxation rate R2(1H2O) displays the highest relative scale of change upon conformational transition of the dendrimer. Hydrogen/deuterium-exchange mass spectrometry reveals that the compact form of the dendrimer has slower proton exchange with water than the extended form. This result suggests that the sensitivity of R2(1H2O) toward dendrimer conformation originates, at least partially, from the difference in proton exchange efficiency between different dendrimer conformations. Finally, we also demonstrated that this conformational transition could be conveniently monitored using a low-field benchtop NMR spectrometer via R2(1H2O). The 1H2O signal thus offers a simple way to monitor structural changes of macromolecules using benchtop time-domain NMR. 相似文献
1000.
Thermal dimerization of N-methyl-flindersine is reported here. This work commenced with the intent to access new Diels-Alder-type dimeric bis-pyranylquinoline alkaloids melicodenines but uncovered and characterized naturally occurring paraensidimerine F, F′and C′, as well as two new bis-quinolone derivatives. 相似文献