全文获取类型
收费全文 | 42859篇 |
免费 | 11759篇 |
国内免费 | 1425篇 |
专业分类
化学 | 42829篇 |
晶体学 | 345篇 |
力学 | 526篇 |
数学 | 2541篇 |
物理学 | 2739篇 |
无线电 | 7063篇 |
出版年
2023年 | 35篇 |
2022年 | 95篇 |
2021年 | 284篇 |
2020年 | 1835篇 |
2019年 | 3236篇 |
2018年 | 1505篇 |
2017年 | 1068篇 |
2016年 | 4038篇 |
2015年 | 4129篇 |
2014年 | 4099篇 |
2013年 | 4682篇 |
2012年 | 3504篇 |
2011年 | 2762篇 |
2010年 | 3265篇 |
2009年 | 3258篇 |
2008年 | 2819篇 |
2007年 | 2168篇 |
2006年 | 1780篇 |
2005年 | 1955篇 |
2004年 | 1703篇 |
2003年 | 1506篇 |
2002年 | 2179篇 |
2001年 | 1458篇 |
2000年 | 1381篇 |
1999年 | 423篇 |
1998年 | 89篇 |
1997年 | 80篇 |
1996年 | 70篇 |
1995年 | 61篇 |
1994年 | 45篇 |
1993年 | 39篇 |
1992年 | 43篇 |
1991年 | 42篇 |
1990年 | 30篇 |
1989年 | 32篇 |
1988年 | 27篇 |
1987年 | 32篇 |
1986年 | 38篇 |
1985年 | 37篇 |
1984年 | 33篇 |
1983年 | 25篇 |
1982年 | 33篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1973年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Sayaka Taji Takeshi Yamada Yasuko In Shun‐ichi Wada Yoshihide Usami Kazuo Sakuma Reiko Tanaka 《Helvetica chimica acta》2007,90(11):2047-2057
Three new lanostane‐type triterpenoids, inonotsulides A, B, and C ( 1 – 3 , resp.) were isolated from the sclerotia of Inonotus obliquus (Pers .: Fr.) (Japanese name: Kabanoanatake; Russian name: Chaga). Their structures were determined to be (20R,24S)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 1 ), (20R,24R)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 2 ), and (20R,24S)‐3β,25‐dihydroxylanosta‐7,9(11)‐dien‐20,24‐olide ( 3 ) on the basis of chemical transformation, NMR spectroscopy including 1D and 2D (1H,1H‐COSY, NOESY, HMQC, HMBC), EI‐MS, and single‐crystal X‐ray analysis. 相似文献
942.
A novel type of phosphated puerarin derivatives were synthesized through a simplified Atheron‐Todd reaction for the first time. The structure of these compounds were elucidated by IR, ESI‐MS and NMR. Moreover, the reason the dialkylphophite reagent had different chemselectivities toward different hydroxys on the puerarin was discussed. 相似文献
943.
Mohammed A. Suliman Mohammed A. Gondal Mohamed A. Dastageer Gaik‐Khuan Chuah Chanbasha Basheer 《Photochemistry and photobiology》2019,95(6):1485-1494
An efficient method of photocatalytic degradation of methylparaben in water using Ag nanoparticles (NPs) loaded AgBr‐mesoporous‐WO3 composite photocatalyst (Ag/AgBr@m‐WO3), under visible light is presented. In this process, quantification of methylparaben in water was carried out by high‐performance liquid chromatography (HPLC) and the HPLC results showed a significant reduction of methylparaben in water due to the enhanced of photocatalytic degradation efficiency of Ag/AgBr@m‐WO3. For the material synthesis, highly ordered mesoporous‐WO3 (m‐WO3) was initially synthesized by sol–gel method and AgBr nanoparticles (NPs) were subsequently introduced in the pores of m‐WO3, and finally, the Ag nanoparticles were introduced by light irradiation. The enhanced photocatalytic degradation of methylparaben in water is attributed to the formation of surface plasmonic resonance (SPR) due to the introduction of Ag NPs on the surface of the catalyst. Also, the formation of heterojunction between AgBr and mesoporous‐WO3 in Ag/AgBr@m‐WO3 significantly inhibited the recombination of light‐induced electron‐hole pairs in the semiconductor composite. The morphological and optical characterizations of the synthesized photocatalysts (Ag/AgBr@m‐WO3) were carried out using SEM, TEM, XDR, N2 adsorption–desorption, UV‐VIS diffuse reflectance spectroscopy (DRS). Also, the photocatalytic studies using radical scavengers were carried out and the results indicated that is the main reactive species. 相似文献
944.
A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions. 相似文献
945.
A general and practical procedure for the syntheses of 3,4-di-hydropyrimidine-2(1H)-thiones by a one-pot condensation of aldehyde,β-ketoester or β-diketone and thiourea using La(OTf)3 as the catalyst is described.Mild reaction conditions,excellent yields as well as the environmentally friendly character of La(OTf)3 make it an important alternative to the classic acid-catalyzed Biginelli‘s reaction. 相似文献
946.
Tao He Ying‐Fang Zou Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3367-3378
Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under 60Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under 60Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]0/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002 相似文献
947.
De‐Chun Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(6):o351-o352
In the title compound, N‐(2‐methoxyphenyl)‐4‐nitrobenzylideneamine, C14H12N2O3, the two phenyl rings make a dihedral angle of 48.0 (2)° and the nitro group is at an angle of 6.5 (1)° with respect to its attached phenyl ring. In the crystal structure, molecules are related as centrosymmetric pairs through π–π interactions and are further connected through strong C—H?O hydrogen bonds [C?O 3.4259 (17) Å and C—H?O 167°], forming molecular stacks along [100]. These stacks associate further through longer C—H?O interactions, forming two‐dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described. 相似文献
948.
Three new eremophilane‐type sesquiterpenes, (6β,8α)‐6‐(acetyloxy)‐8‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 1 ), (6α,8α)‐6‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 2 ), and (6α,8α)‐6‐(acetyloxy)eremophil‐7(11)‐en‐12,8‐olide ( 3 ) ((8α)‐eremophil‐7(11)‐en‐12,8‐olide = (4aR,5S,8aR,9aS)‐4a,5,6,7,8,8a,9,9a‐octahydro‐3,4a,5‐trimethylnaphtho[2,3‐b]furan‐2(4H)‐one), besides the recently elucidated eremoligularin ( 4 ) and bieremoligularolide ( 5 ), as well as a new highly oxygenated monoterpene, rel‐(1R,2R,3R,4S,5S)‐p‐menthane‐1,2,3,5‐tetrol ( 12 ), together with six known constituents, i.e., the sesquiterpenes 6 and 7 , the norsesquiterpenes 8 – 10 , and the monoterpene 13 , were isolated from the roots of Ligularia muliensis. In addition, an attempt to dimerize 1 to a bieremophilenolide (Scheme) resulted in the generation of the new derivative (6β,8β)‐6‐(acetyloxy)‐8‐chloroeremophil‐7(11)‐en‐12,8‐olide ( 11 ). The new structures were established by means of detailed spectroscopic analysis (IR, FAB‐, EI‐, or HR‐ESI‐MS as well as 1D‐ and 2D‐NMR experiments). Compounds 4 and 5 were evaluated for their antitumor effects in vitro (Table 3). 相似文献
949.
Hua Xiao Bei Feng‐Li Wang Xin Yang Xu‐Jie Lu Lu‐De 《International journal of quantum chemistry》2006,106(5):1145-1152
A theoretical study of the polymerization reaction mechanism of maleic anhydride (MA) initiated by hydrate is presented. The reaction pathway has been studied with the density functional theory (DFT) method at the B3LYP/6‐311G** level. The geometrical parameters of transition states (TS) are optimized; intrinsic reaction coordinate (IRC) calculations have also been performed to obtain further credible features. Frequency analyses of all the stationary points are calculated at the same basis sets. The total energies of all geometries are corrected at second‐order Møller–Plesset (MP2)/6‐311G**. Calculation results reveal that the reaction mechanism is attributable to anion polymerization. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
950.
Yi‐Xun Zhang Shauntina H. Jackson Mohamed S. Rajab Frank R. Fronczek Steven F. Watkins 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):o219-o221
3β‐Hydroxy‐7‐drimen‐12,11‐olide hemihydrate, C15H22O3·0.5H2O, (I), has two sesquiterpene molecules and one water molecule in the asymmetric unit. The OH groups of both molecules and both H atoms of the water molecule are involved in near‐linear intermolecular hydrogen bonds, having O⋯O distances in the range 2.632 (3)–2.791 (2) Å. 3β‐Acetoxy‐7‐drimen‐12,11‐olide, C17H24O4, (II), has its ring system in very nearly the same conformation as the two molecules of (I). 相似文献