全文获取类型
收费全文 | 11998篇 |
免费 | 2007篇 |
国内免费 | 3431篇 |
专业分类
化学 | 8141篇 |
晶体学 | 448篇 |
力学 | 685篇 |
综合类 | 338篇 |
数学 | 1711篇 |
物理学 | 6113篇 |
出版年
2023年 | 90篇 |
2022年 | 374篇 |
2021年 | 350篇 |
2020年 | 401篇 |
2019年 | 329篇 |
2018年 | 403篇 |
2017年 | 512篇 |
2016年 | 394篇 |
2015年 | 492篇 |
2014年 | 656篇 |
2013年 | 941篇 |
2012年 | 814篇 |
2011年 | 951篇 |
2010年 | 874篇 |
2009年 | 926篇 |
2008年 | 1065篇 |
2007年 | 934篇 |
2006年 | 948篇 |
2005年 | 728篇 |
2004年 | 608篇 |
2003年 | 519篇 |
2002年 | 498篇 |
2001年 | 466篇 |
2000年 | 560篇 |
1999年 | 302篇 |
1998年 | 167篇 |
1997年 | 135篇 |
1996年 | 172篇 |
1995年 | 124篇 |
1994年 | 140篇 |
1993年 | 130篇 |
1992年 | 118篇 |
1991年 | 98篇 |
1990年 | 94篇 |
1989年 | 70篇 |
1988年 | 71篇 |
1987年 | 65篇 |
1986年 | 68篇 |
1985年 | 68篇 |
1984年 | 76篇 |
1983年 | 49篇 |
1982年 | 49篇 |
1981年 | 63篇 |
1980年 | 58篇 |
1979年 | 57篇 |
1978年 | 45篇 |
1977年 | 45篇 |
1976年 | 49篇 |
1974年 | 34篇 |
1973年 | 44篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature. 相似文献
993.
994.
报道了35,40-二羟基-6-甲氧基-藤黄酸甲酯(1)、9,10-二羟基-6-甲氧基-藤黄酸甲酯(2)和2-去异己烯-2-(2-甲酰基)乙基-6-甲氧基-藤黄酸甲酯(3)的化学合成和抗肿瘤活性. 采用二维定量构效关系方法经计算机模拟与统计分析, 获得定量构效关系方程. 结果显示, 藤黄酸氧化衍生物的极性体积比、零阶价分子连接性指数、总电荷绝对值和体积与抗肿瘤活性间表现出了良好的线性关系. 相似文献
995.
The bis-phenyltin-substituted, lone-pair-containing tungstoarsenate [(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)](8)(-) (1) has been synthesized and characterized by multinuclear NMR, IR, and elemental analysis. Single-crystal X-ray analysis was carried out on (NH(4))(7)Na[(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)].17.5H(2)O (NH(4)(-1), which crystallizes in the monoclinic system, space group P2(1)/c, with a = 18.3127(17) A, b = 24.403(2) A, c = 22.965(2) A, beta = 106.223(2) degrees, and Z = 4. Polyanion 1 consists of two B-alpha-(As(III)W(9)O(33)) Keggin moieties linked via a WO(H(2)O) fragment and two SnC(6)H(5) groups leading to a sandwich-type structure with nominal C(2)(v) symmetry. Polyanion 1 is stable in solution as indicated by the expected 6-line pattern (4:4:4:4:2:1) in (183)W NMR and the expected (119)Sn, (13)C, and (1)H NMR spectra. Synthesis of 1 was accomplished by reaction of C(6)H(5)SnCl(3) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous acidic medium (pH 2). In the solid-state structure of NH(4)(-1, neighboring polyanions are weakly bound via W-O-Na bonds leading to chains which interact with each other via the phenyl rings resulting in a 2-D assembly. 相似文献
996.
Dr. Lucy Clark Dr. Farida H. Aidoudi Dr. Cameron Black Dr. Kasun S. A. Arachchige Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Russell E. Morris Prof. Dr. Philip Lightfoot 《Angewandte Chemie (International ed. in English)》2015,54(51):15457-15461
The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic–organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C3H5N2][V9O6F24(H2O)2] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V4+ S=${{ 1/2 }}$ ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V4+, means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all samples suggest an absence of conventional long‐range magnetic order down to 2 K despite considerable antiferromagnetic exchange. 相似文献
997.
Improved Spectral Coverage and Fluorescence Quenching in Donor–acceptor Systems Involving Indolo[3‐2‐b]carbazole and Boron‐dipyrromethene or Diketopyrrolopyrrole 下载免费PDF全文
Adis Khetubol Sven Van Snick Melissa L. Clark Eduard Fron Eduardo Coutiño‐González Arvid Cloet Koen Kennes Yuliar Firdaus Maarten Vlasselaer Volker Leen Wim Dehaen Mark Van der Auweraer 《Photochemistry and photobiology》2015,91(3):637-653
A novel π‐conjugated triad and a polymer incorporating indolo[3,2‐b]‐carbazole (ICZ) and 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge‐transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ–π–DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ–π–DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ–π–BODIPY polymer. 相似文献
998.
有机电致发光器件因在全彩平板显示和固态照明领域中具有广阔的应用前景, 而受到人们的广泛关注。 时至今日, 与现有的红色和绿色有机电致发光材料和器件相比, 具有优越综合性能的蓝色有机电致发光材料和器件却始终匮乏。 相对而言, 蓝光材料具有较宽的能隙, 因而很难获得低电压、高效率和良好稳定性的深蓝光器件。 通常, 白色有机电致发光器件可以通过混合三基色或者两种颜色的方法获得。 但是无论哪种方法, 蓝光材料均是必不可少的。 另外, 还可以通过能量传递将蓝光转化为红光和绿光。 因此, 研发出具有优越综合性能的蓝光材料对有机电致发光器件的推广及应用十分关键。 本文综述了近年来蓝色荧光材料、蓝色磷光材料的研究进展以及蓝光材料在蓝色和白色有机电致发光器件中的应用, 并结合现有工作, 对蓝色有机电致发光材料的研究和应用前景进行展望。 相似文献
999.
硫杂杯[4]芳烃氧化膦衍生物的合成与晶体结构 总被引:2,自引:1,他引:2
合成了部分取代的硫杂杯[4]芳烃氧化膦衍生物, 二(亚甲基二苯基氧化膦)对叔丁基硫杂杯[4]芳烃(化合物1), 培养了化合物的单晶, 用Smart 1000 CCD衍射仪测定了其晶体结构. 结果表明, 1的组成为: C66H70O6P2S4•2CH3OH, 属三斜晶系, P1空间群, 晶胞参数a=1.3453(6) nm, b=1.5289(7) nm, c=1.7893(9) nm; α=75.707(9)°, β=69.131(8)°, γ=79.734(9)°, Z=2; V=3.316(3) nm3, d=1.215 g/cm3, F(000)=1288, μ (Mo Kα)=0.244 mm-1, R1=0.0625, wR2=0.1372. 杯芳烃分子采取了锥式构象. 相似文献
1000.
载铜活性炭吸附一氧化碳的密度泛函理论计算 总被引:3,自引:0,他引:3
应用密度泛函理论和相对论有效核势方法, 用C16H10, C13H9, C12H12原子簇模型模拟活性炭表面, 计算得到了CO在载铜活性炭上的吸附位、吸附构型和吸附能. 研究表明: 载铜活性炭吸附CO的过程, 本质上是Cu(I)通过σ-π配键与CO络合, 形成Cu—C键的过程. 载铜活性炭对CO的络合吸附能在50~60 kJ/mol之间, 远大于活性炭对CO的物理吸附能(9.15 kJ/mol), 因而络合吸附更稳定, 选择性也更高. Cu(I)选择吸附在活性炭表面的顶位和桥位, 一个Cu(I)至多可以吸附一个到两个CO分子, 但吸附一个CO比吸附两个CO稳定. 相似文献