全文获取类型
收费全文 | 926篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 643篇 |
晶体学 | 10篇 |
力学 | 27篇 |
数学 | 67篇 |
物理学 | 189篇 |
出版年
2023年 | 5篇 |
2020年 | 14篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2016年 | 9篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 32篇 |
2012年 | 36篇 |
2011年 | 45篇 |
2010年 | 21篇 |
2009年 | 19篇 |
2008年 | 36篇 |
2007年 | 49篇 |
2006年 | 53篇 |
2005年 | 53篇 |
2004年 | 36篇 |
2003年 | 35篇 |
2002年 | 41篇 |
2001年 | 22篇 |
2000年 | 16篇 |
1999年 | 20篇 |
1998年 | 22篇 |
1997年 | 9篇 |
1996年 | 13篇 |
1995年 | 13篇 |
1994年 | 9篇 |
1993年 | 9篇 |
1992年 | 16篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 9篇 |
1983年 | 15篇 |
1982年 | 16篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 14篇 |
1977年 | 15篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 13篇 |
1973年 | 11篇 |
1972年 | 5篇 |
1937年 | 4篇 |
1887年 | 4篇 |
排序方式: 共有936条查询结果,搜索用时 15 毫秒
51.
52.
(NH4)2[Mo6Cl14] · H2O ( 1 ) was prepared from reactions of MoCl2 in ethanol with aqueous NH4Cl solution. It crystallizes in the monoclinic space group I2/a (no. 15), Z = 4 with a = 912.3(1), b = 1491.2(2), c = 1724.8(2) pm, β = 92.25(1)°; R1 = 0.023 (based on F values) and wR2 = 0.059 (based on F2 values), for all measured X‐ray reflections. The structure of the cluster anion can be given as [(Mo6Cl)Cl]2– (i = inner, a = outer ligands). Thermal stability studies show that 1 loses crystal water followed by the loss of NH4Cl above 350 °C to yield MoCl2. The water‐free compound (NH4)2[Mo6Cl14] ( 2 ) was synthesized by solid state reaction of MoCl2 and NH4Cl in a sealed quartz ampoule at 270 °C. No single‐crystals could be obtained. Decompositions of 1 and 2 under nitrogen and argon exhibited the loss of NH4Cl at about 350 °C. Decomposition under NH3 resulted in the formation of MoN and Mo2N at 540 °C and 720 °C, respectively. 相似文献
53.
Bryant WS Jones JW Mason PE Guzei I Rheingold AL Fronczek FR Nagvekar DS Gibson HW 《Organic letters》1999,1(7):1001-1004
[formula: see text] Inspired by folded, nonpseudorotaxane complexes of bis(m-phenylene)-32-crown-10 systems, we synthesized a new bicyclic crown ether containing two 1,3,5-phenylene units linked by three tetra(ethyleneoxy) units. The new cryptand forms a "pseudorotaxane-like" inclusion complex with N,N'-dimethyl-4,4'-bipyridinium bis(hexafluorophosphate) with association constant Ka = 6.1 x 10(4) M-1, 100-fold greater than that of an analogous simple crown ether. 相似文献
54.
Unique "cradled barbell" complex between a secondary diammonium ion and bis(m-phenylene)-32-crown-10
[formula: see text] The complexation between N,N'-dibenzyl(m-xylylene)diammonium bis(hexafluorophosphate) (2) and bis(m-phenylene)-32-crown-10 (5) was shown to occur in solution by nuclear magnetic resonance with 1:1 stoichiometry and a Ka value of 189 +/- 19 M-1. A crystal structure of 2:5 revealed a unique 1:1 "exo" or "cradled barbell" complex, instead of the expected pseudorotaxane. This unexpected result illustrates that caution be used in interpreting the results from these types of complexes in the solution and "gas" phases on the basis of crystal structures. 相似文献
55.
A supramolecular poly[3]pseudorotaxane was prepared by self-assembly of a homoditopic cylindrical bis(crown ether) host and a bisparaquat derivative in solution by host-guest complexation. 相似文献
56.
Huang F Switek KA Zakharov LN Fronczek FR Slebodnick C Lam M Golen JA Bryant WS Mason PE Rheingold AL Ashraf-Khorassani M Gibson HW 《The Journal of organic chemistry》2005,70(8):3231-3241
Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats. 相似文献
57.
Blackmore IJ Gibson VC Hitchcock PB Rees CW Williams DJ White AJ 《Journal of the American Chemical Society》2005,127(16):6012-6020
The 2,6-bis(alpha-iminoalkyl)pyridines 2,6-[ArNC(CR(3))](2)C(5)H(3)N [R = H, D; Ar = 2,6-i-Pr(2)C(6)H(3) (DIPP), 2,6-Me(2)C(6)H(3) (DMP)] react with MeLi in Et(2)O to give a binary mixture of products: the pyridine N-methylated species 2,6-[ArNC(CR(3))](2)C(5)H(3)N(Me)Li(OEt(2)) and the deprotonated/dedeuterated species 2-[ArNC(CR(3))],6-[ArNC(=CR(2))]C(5)H(3)NLi(OEt(2)). For R = D, the product ratio is 2:1 in favor of the N-methylated product, while, for R = H, the deprotonated product is favored by 5:1, increasing to 8:1 in toluene solvent. Warming solutions of the N-methylated species leads to clean conversion to the thermodynamically preferred deprotonated species. Crossover experiments show that MeLi is re-formed and dissociates from the terdentate ligand before deprotonating the ketimine methyl unit. For MgR(2) (R = Et, i-Pr) and ZnR(2) (R = Et) reagents, N-alkylation products are formed exclusively, but derivatives containing bulky aryl substituents are found to undergo further rearrangement to 2-alkylated species, arising by migration of the alkyl group of the N-alkyl moiety to the adjacent ring carbon atom. The reversibility of the N-alkylation process has been probed using deuterio-labeled Mg alkyl reagents and mixed alkyl zinc species. A cationic zinc derivative is shown to undergo "reverse" alkyl migration, from the heterocycle nitrogen atom to the zinc center. EPR spectroscopy reveals a paramagnetic intermediate in which the unpaired electron is delocalized over the heterocycle and di-imine moieties of the ligand, indicating that the N-alkylation reactions proceed via single electron-transfer processes. 相似文献
58.
Gibson SE Kaufmann KA Loch JA Steed JW White AJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2566-2576
Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species. 相似文献
59.
60.
Sebastian G. Spain Matthew I. Gibson Neil R. Cameron 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2059-2072
Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) postpolymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included. The authors offer some suggestions as to future developments and remaining challenges in this topical area of polymer chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem45: 2059–2072, 2007 相似文献