全文获取类型
收费全文 | 18944篇 |
免费 | 1315篇 |
国内免费 | 1409篇 |
专业分类
化学 | 14727篇 |
晶体学 | 253篇 |
力学 | 658篇 |
综合类 | 64篇 |
数学 | 927篇 |
物理学 | 5039篇 |
出版年
2024年 | 19篇 |
2023年 | 154篇 |
2022年 | 324篇 |
2021年 | 353篇 |
2020年 | 452篇 |
2019年 | 419篇 |
2018年 | 271篇 |
2017年 | 348篇 |
2016年 | 589篇 |
2015年 | 624篇 |
2014年 | 719篇 |
2013年 | 1492篇 |
2012年 | 906篇 |
2011年 | 968篇 |
2010年 | 880篇 |
2009年 | 1069篇 |
2008年 | 1205篇 |
2007年 | 1269篇 |
2006年 | 1114篇 |
2005年 | 1037篇 |
2004年 | 1042篇 |
2003年 | 888篇 |
2002年 | 712篇 |
2001年 | 499篇 |
2000年 | 544篇 |
1999年 | 468篇 |
1998年 | 452篇 |
1997年 | 399篇 |
1996年 | 369篇 |
1995年 | 359篇 |
1994年 | 282篇 |
1993年 | 244篇 |
1992年 | 268篇 |
1991年 | 154篇 |
1990年 | 122篇 |
1989年 | 125篇 |
1988年 | 108篇 |
1987年 | 91篇 |
1986年 | 63篇 |
1985年 | 39篇 |
1984年 | 44篇 |
1983年 | 20篇 |
1982年 | 33篇 |
1981年 | 21篇 |
1980年 | 13篇 |
1979年 | 31篇 |
1978年 | 20篇 |
1977年 | 11篇 |
1976年 | 13篇 |
1972年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
102.
103.
Renzo C. Silva Giovanna F. Carneiro Lúcio L. Barbosa Valdemar Lacerda Jr. Jair C. C. Freitas Eustáquio V. R. de Castro 《Magnetic resonance in chemistry : MRC》2012,50(2):85-88
Low‐field 1H NMR was used in this work for the analysis of mixtures involving crude oils and water. CPMG experiments were performed to determine the transverse relaxation time (T2) distribution curves, which were computed by the inverse Laplace transform of the echo decay data. The instrument's ability of quantifying water and petroleum in biphasic mixtures following different methodologies was tested. For mixtures between deionized water and petroleum, one achieved excellent results, with root mean squared error of cross‐validation (RMSECV) of 0.8% for a regression between the water content (wt %) and the relative area of the water peak in the T2 distribution curve, or a standard deviation of 0.9% for the relationship between the water content and the relative water peak area, corrected by the relative hydrogen index of the crude. In the case of biphasic mixtures of Mn2+‐doped water and crude oils, the best result of RMSECV = 1.6% was achieved by using the raw magnetization decay data for a partial least squares regression. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
104.
Nikolaus M. Loening Barth‐Jan van Rossum Hartmut Oschkinat 《Magnetic resonance in chemistry : MRC》2012,50(4):284-288
In nuclear magnetic resonance spectroscopy, experimental limits due to the radiofrequency transmitter and/or coil means that conventional radiofrequency pulses (“hard pulses”) are sometimes not sufficiently powerful to excite magnetization uniformly over a desired range of frequencies. Effects due to nonuniform excitation are most frequently encountered at high magnetic fields for nuclei with a large range of chemical shifts. Using optimal control theory, we have designed broadband excitation pulses that are suitable for solid‐state samples under magic‐angle‐spinning conditions. These pulses are easy to implement, robust to spinning frequency variations, and radiofrequency inhomogeneities, and only four times as long as a corresponding hard pulse. The utility of these pulses for uniformly exciting 13C nuclei is demonstrated on a 900 MHz (21.1 T) spectrometer. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
105.
Swagata Chakraborty Susmitha A. L. Ramakrishna V. Hosur 《Magnetic resonance in chemistry : MRC》2012,50(9):587-591
Direct detection of 13C nucleus can be used as a valuable alternative where 1H detection poses a challenge due to relaxation effects, chemical exchange and poor chemical shift dispersion. In this context, we have designed a suite of 2D 13Cα‐detected hNCA experiments that provide sequential correlations of 13Cα with 15N on one hand and efficient spectroscopic labeling of certain groups of residues, namely, Gly, Ala, Ser and Thr, on the other. These residues act as checkpoints in the sequential walk, which in turn offer new possibilities of backbone assignment of small proteins from a set of 2D experiments, thereby providing great economy in terms of spectrometer time. The direct identification of peptide segments around Gly, Ala, Ser and Thr residues along a protein chain will be highly valuable for deriving important information on sites of ligand binding, phosphorylation, inhibitor/substrate binding, understanding protein folding pathways, comprehending local conformational dynamics etc. without having to obtain complete sequence‐specific assignments, which can be time consuming and at times formidable, especially in large proteins. We have illustratively demonstrated the multifaceted applications of these variants of 2D experiments on ubiquitin and M‐crystallin. We foresee that these 2D hNCA experiments will provide economic and efficient strategies for studying the structure and function of proteins. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
106.
107.
108.
Kevin J. Pastoor Charles V. Rice 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1374-1382
NMR spectra were collected for poly(N‐isopropylacrylamide) (PNIPAAm) hydrogel using high‐resolution magic angle spinning (HRMAS) after gel pieces were hydrated in the presence of D2O, NaF, NaCl, and NaI aqueous solutions. Changes in the peak height intensity of the spectra provide quantitative insight into the phase transition process. The thermodynamic values of the phase transition were calculated using a van't Hoff analysis of the NMR data. Unlike the trend observed for decreases in the (LCST), changes in the enthalpy and entropy did not clearly display a linear dependence with respect to salt concentration. Rather, it was observed that increases in salt concentration did not affect the enthalpy and entropy to the extent as the initial change observed between no salt and 100 mM solutions. Finally, the effect of salts on the hysteresis of the rehydrating process was observed. Hysteresis occurs due to the need for hydrophobic interactions to break down before water is able to infiltrate the polymer matrix. NaF stabilizes hydrophobic interactions while NaI destabilize hydrophobic interactions, causing them to break down at higher temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
109.
Dipl.‐Chem. Alexander Zhdanko Dr. Markus Ströbele Prof. Dr. Martin E. Maier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14732-14744
Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh3, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf??Me2S<2,6‐lutidine<4‐picoline<CF3CO2?≈DMAP<TMTU<PPh3<OH?≈Cl?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh3 causes abstraction of one gold atom to give mononuclear complexes LLAuPPh3+ and (Ph3P)nAu+, but other N and S ligands give ordinary dicationic species LL(AuNu)22+. In reactions with different bases, LAu+ provided new oxonium ions whose chemistry was also studied: (DTBPAu)3O+, (L2Au)2OH+, (L2Au)3O+, (L3Au)2OH+, and (IMesAu)2OH+. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)2OH+, (L2Au)3O+, and L2AuOH are described. Reactions of dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)2]3O22+, L8(Au)2OH+, and [L8(Au)2]3O22+, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe+ with S2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined. 相似文献
110.