全文获取类型
收费全文 | 33885篇 |
免费 | 5489篇 |
国内免费 | 4689篇 |
专业分类
化学 | 25975篇 |
晶体学 | 485篇 |
力学 | 1899篇 |
综合类 | 398篇 |
数学 | 3610篇 |
物理学 | 11696篇 |
出版年
2024年 | 74篇 |
2023年 | 506篇 |
2022年 | 955篇 |
2021年 | 1055篇 |
2020年 | 1168篇 |
2019年 | 1244篇 |
2018年 | 1021篇 |
2017年 | 942篇 |
2016年 | 1576篇 |
2015年 | 1559篇 |
2014年 | 1916篇 |
2013年 | 2493篇 |
2012年 | 2882篇 |
2011年 | 3053篇 |
2010年 | 2237篇 |
2009年 | 2083篇 |
2008年 | 2404篇 |
2007年 | 2048篇 |
2006年 | 1983篇 |
2005年 | 1730篇 |
2004年 | 1464篇 |
2003年 | 1243篇 |
2002年 | 1484篇 |
2001年 | 1069篇 |
2000年 | 928篇 |
1999年 | 738篇 |
1998年 | 568篇 |
1997年 | 480篇 |
1996年 | 447篇 |
1995年 | 415篇 |
1994年 | 347篇 |
1993年 | 315篇 |
1992年 | 278篇 |
1991年 | 225篇 |
1990年 | 199篇 |
1989年 | 143篇 |
1988年 | 133篇 |
1987年 | 99篇 |
1986年 | 105篇 |
1985年 | 105篇 |
1984年 | 61篇 |
1983年 | 59篇 |
1982年 | 40篇 |
1981年 | 45篇 |
1980年 | 23篇 |
1979年 | 27篇 |
1978年 | 11篇 |
1974年 | 12篇 |
1973年 | 10篇 |
1957年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 18 毫秒
991.
JiKuanZHAO XiaoCHEN ChunJieYANG ZhenMingSUI YongCunCHAI GuoDongZHANG JieLIU 《中国化学快报》2005,16(4):557-560
Silver and gold organosols are easily prepared by transferring nanoparticles from aqueous phase into isooctane with high efficiency (>90%). Concentrations of sodium oleate and magnesium chloride have crucial effects on the transfer efficiency. Based on the UV-visible absorption spectra, TEM micrographs of nanoparticles, as well as molecular modeling calculation about the adsorption conformation of sodium oleate molecules, a possible phase transfer mechanism is proposed. 相似文献
992.
ThecombinationofstrippingvoltammetrywithUPDcanleadtotheimprovementofsensitivity ,selectivi tyandreversibilityforelectroanalyticalpurposeandavoidtheuseoftoxicmercuryastheworkelectrode1andthenanalyticalapplicationshavebeendescribed .2 4 Inthiswork ,wedevelo… 相似文献
993.
Three new serratane triterpenoids, (3α,14α,15α,21α)‐3,14,15,21,29‐pentahydroxyserratan‐24‐oic acid ( 1 ), (3α,21β)‐serrat‐14‐ene‐3,21,24,30‐tetraol ( 2 ), and (3α,21α)‐serrat‐14‐ene‐3,21,24,29‐tetraol ( 3 ), were isolated from Phlegmariurus squarrosus, together with eight known compounds. Their chemical structures were elucidated on the basis of in‐depth spectroscopic analyses. 相似文献
994.
Hitchcock PB Hu J Lappert MF Severn JR 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4193-4201
Treatment of [Li(L1)]2 (1) or K(L2) (2) with SnX2 in Et2O yielded the heteroleptic beta-diketiminatotin(II) halides Sn(L1)Cl (3a), Sn(L1)Br (3b) or Sn(L2)Cl (4), even when an excess of the alkali metal beta-diketiminate was used [L1={N(R)C(Ph)}2CH, L2={N(R)C(Ph)CHC(But)N(R)}, R = SiMe3]. From and half an equivalent each of SnCl2.2H2O and SnCl2, or one equivalent of SnCl2.2H2O, the product was Sn(L3)Cl (5) or Sn(L4)Cl (6), in which one or both of the N-R bonds of L1 had been hydrolytically cleaved; the compound Sn(L5)Cl (7) was similarly obtained from and an equivalent portion of SnCl2.2H2O [L3={N(R)C(Ph)CHC(But)N(H)}, L4={N(H)C(Ph)CHC(But)N(H)} and L5={N(H)C(Ph)}2CH]. The halide exchange between 3a and 3b, studied by two-dimensional (119)Sn{1H}-NMR spectroscopy, is attributed to implicate a (mu-Cl)(mu-Br)-dimeric intermediate or transition state. The 13C{1H}-NMR spectra of or showed two distinct resonances for each group, which coalesced on heating, corresponding to DeltaG(338 K)= 69.4 (3a) or 72.8 (3b) kJ mol(-1). The chloride ligand of was readily displaced by treatment with NaNR2, CF3SO3H or CH2(COPh)2, yielding Sn(L1)X [X = NR2 (8), O3SCF3 (9) or {OC(Ph)}2CH (10)]. Oxidative addition of sulfur or selenium to gave the tin(IV) terminal chalcogenides Sn(E)(L1)(NR2)[E = S (11) or Se (12)]. The X-ray structures of the cocrystal of 3a/3b and of the crystalline compounds 5, 6, 8, 11 and are presented, as well as multinuclear NMR spectra of each of the new compounds. 相似文献
995.
The four new lariciresinol‐based lignan glycosides, (?)‐lariciresinol 4′‐(6″‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 1 ), (?)‐lariciresinol 4′‐(4″,6″‐di‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 2 ), 5,5′‐dimethoxylariciresinol 4′‐(4″,6″‐di‐O‐feruloyl)‐β‐D ‐glucopyranoside) ( 3 ), and 4‐O‐[α‐(1,2‐dihydroxyethyl)syringyl]‐5,5′‐dimethoxylariciresinol 4′‐(4″,6″‐di‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 4 ), together with two known ones, lariciresinol 4′‐β‐D ‐glucopyranoside) ( 5 ) and tortoside B ( 6 ), were isolated from the BuOH extract of Rhus javanica var. roxburghiana roots, and their structures were established by means of various spectroscopic techniques. 相似文献
996.
Allylic and benzylic Grignard reagents smoothly open phenylalkynyl-activated cyclic trisubstituted epoxides at the more substituted carbon atom to give secondary alcohols with a chiral quaternary center. These alcohols are good substrates for the construction of enantiomerically pure carbobicyclic scaffolds through intramolecular alkylation. 相似文献
997.
Angelica sinensis (Danggui in Chinese), a well-known traditional Chinese medicine, is also used as a health food product for women's care in Europe and America. Therefore, the demand for Danggui is enormous throughout the world. Due to the shortage of Angelica sinensis, Angelica acutiloba and Angelica gigas are commonly used as the substitutes of Danggui in the market of southeast Asia. However, the three common Angelica roots showed variation in their genetic and chemical composition. Up to date, it is thought that ferulic acid, ligustilide and other phthalides such as butylidenephthalide are the biologically active components of Danggui. In this paper, the contents of 13 compounds including ferulic acid, Z-ligustilide, E-ligustilide, Z-butylidenephthalide, E-butylidenephthalide, 3-butylphthalide, 3-butylidene-4-hydroxyphthalide, senkyunolide A, 6,7-epoxyligustilide, senkyunolide F, senkyunolide H, senkyunolide I, and 6,7-dihydroxyligustilide were determined or estimated by using gas chromatography-mass spectrometry (GC-MS) coupled with pressurized liquid extraction (PLE). The results showed that GC-MS coupled with PLE offered a simple, rapid and high sensitive method to analysis of components in Angelica root. And the contents of investigated compounds in Angelica sinensis, Angelica acutiloba and Angelica gigas, which are used as Danggui in China, Japan and Korea, respectively, were highly variant. It is thought that interaction of multiple chemical compounds contributes to the therapeutic effects of Chinese medicines. However, the overall clinical efficacy of these different Danggui has not been determined. Therefore, comparison of chemical components and pharmacological activities of different Angelica root is helpful to elucidate the mechanism of therapeutic effects of Danggui. 相似文献
998.
To increase the solubility and film forming ability of polybenzimidazole (PBI), poly(N‐methylbenzimidazole) (PNMBI) with different degrees of methylation was synthesized. Chemical structure, degree of substitution, and solubility of PNMBI was studied. PNMBI is easier to be doped with acid than PBI. The basicity of PNMBI was improved with the introduction of methyl groups on the imidazole moiety. Effects of methylation degree, H3PO4 content and temperature on proton conductivity of PNMBI doped H3PO4 was studied. Proton conductivity of H3PO4 doped PNMBI‐1.2 membranes increases with increasing doping level. Temperature dependence of proton conductivity of H3PO4 doped PNMBI‐1.2 membranes follows the Arrhenius law. With an increase in the degree of substitution, proton conductivity of H3PO4 doped PNMBI decreases dramatically. The proton transport mechanism was also discussed. The proton conductivity of PNMBI/H3PO4 is mainly contributed by proton hopping or Grotthuss mechanism. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
999.
Alexander J. Blake Binod B. De Wan‐Sheung Li Neil R. Thomas 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):m570-m574
In the title compounds, [N‐(phenyl{2‐[N‐(S)‐(2‐picolyl)prolylamino]phenyl}methylene)‐(S)‐phenylalaninato]nickel(II), [Ni(C33H30N4O3)], (I), [N‐(phenyl{2‐[N‐(S)‐(3‐picolyl)prolylamino]phenyl}methylene)‐(S)‐phenylalaninato]nickel(II) hemihydrate, [Ni(C33H30N4O3)]·0.5H2O, (II), and [N‐({2‐[N‐(S)‐ethylprolylamino]phenyl}phenylmethylene)‐(S)‐phenylalaninato]nickel(II), [Ni(C29H29N3O3)], (III), the NiII centres have approximate square‐planar coordination geometries from N3O donor sets. The picolyl N atoms in (I) and (II) are too remote from the metal centres to interact significantly, but the metal coordination geometries experience tetrahedral distortion and/or displacement of the metal centre from the N3O plane. These are linked to conformational differences between the ligands of the symmetry‐independent complexes (Z′ = 2), which in turn are related to molecular packing. In (III), where a less sterically demanding ethyl group replaces the picolyl substituents, there are none of the distortions or displacements seen in (I) and (II). 相似文献
1000.
Ming Li Huazheng Yang Guilong Zhao Lirong Wen Wei Cao Shusheng Zhang 《Journal of heterocyclic chemistry》2005,42(2):209-215
A series of new 2‐aryl‐7‐cyano/ethoxycarbonyl‐6‐methylthio‐1H‐imidazo[1,2‐b]pyrazoles ( 5 ) have been synthesized in moderate to good yields, via a two‐step cyclocondensation procedure of 5‐amino‐4‐cyano/ethoxycarbonyl‐3‐methylthio‐1H‐pyrazole ( 1 ) and α‐bromoacetophenones ( 3 ) or α‐tosyloxyacetophenones ( 2 ), which were prepared by the reactions of acetophenones with [hydroxy(tosyloxy)iodo]benzene (HTIB). The intermediates, 5‐amino‐1‐(aroylmethyl)‐4‐ cyano/ethoxycarbonyl‐3‐methylthio‐1H‐pyrazoles ( 4 ), have been isolated, serving as evidence for the regioselectivity. When utilizing α‐tosyloxy‐acetophenones, the reactions were more eco‐friendly, the reaction time was significantly reduced and the synthetic procedure was more convenient and easier to manipulate. Surprisingly, using potassium carbonate to displace sodium carbonate in the synthesis of 4 , in the case of 1 (R? CN), two novel cyclocondensation products have been isolated and fully characterized, followed by the proposal of a plausible mechanism. 相似文献