全文获取类型
收费全文 | 33457篇 |
免费 | 5507篇 |
国内免费 | 3928篇 |
专业分类
化学 | 23324篇 |
晶体学 | 386篇 |
力学 | 2212篇 |
综合类 | 352篇 |
数学 | 4234篇 |
物理学 | 12384篇 |
出版年
2024年 | 35篇 |
2023年 | 661篇 |
2022年 | 814篇 |
2021年 | 1066篇 |
2020年 | 1338篇 |
2019年 | 1242篇 |
2018年 | 1116篇 |
2017年 | 1066篇 |
2016年 | 1610篇 |
2015年 | 1528篇 |
2014年 | 1869篇 |
2013年 | 2473篇 |
2012年 | 2929篇 |
2011年 | 3072篇 |
2010年 | 2158篇 |
2009年 | 2045篇 |
2008年 | 2252篇 |
2007年 | 2031篇 |
2006年 | 1867篇 |
2005年 | 1515篇 |
2004年 | 1217篇 |
2003年 | 954篇 |
2002年 | 902篇 |
2001年 | 735篇 |
2000年 | 672篇 |
1999年 | 760篇 |
1998年 | 628篇 |
1997年 | 600篇 |
1996年 | 543篇 |
1995年 | 506篇 |
1994年 | 427篇 |
1993年 | 389篇 |
1992年 | 321篇 |
1991年 | 283篇 |
1990年 | 266篇 |
1989年 | 203篇 |
1988年 | 160篇 |
1987年 | 136篇 |
1986年 | 106篇 |
1985年 | 108篇 |
1984年 | 69篇 |
1983年 | 63篇 |
1982年 | 59篇 |
1981年 | 27篇 |
1980年 | 20篇 |
1978年 | 6篇 |
1976年 | 4篇 |
1969年 | 3篇 |
1957年 | 8篇 |
1928年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
N(1)取代5-氟尿嘧啶乙酸、5-氟尿嘧啶丙酸与Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)的配合物的合成及表征 总被引:1,自引:0,他引:1
合成了N(1)取代5-氟尿嘧啶乙酸、5-氟尿嘧啶丙酸与铜(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)和锰(Ⅱ)的十种金属配合物。通过元素分析、差热-热重分析确定了它们的化学组成,并对这些化合物进行了红外光谱、氢核磁共振谱,电子光谱的表征。讨论了各配合物中金属离子与配体的配位状态。在Cu(Ⅱ)配合物中,Cu(Ⅱ)是与配体的N3原子和C4上的羰基氧原子配位,其他金属配合物中,金属离子是与配体的C2的羰基氧原子和羧基配位。 相似文献
992.
Novel polynuclear Cu(II) complexes containing derivatives of 1,2,4-trizaole and pivalate ligands, [Cu(3)(mu(3)-OH)(mu-adetrz)(2)(piv)(5)(H(2)O)].6.5H(2)O (1) (adetrz = 4-amino-3,5-diethyl-1,2,4-triazole, piv = pivalate), [Cu(4)(mu(3)-OH)(2)(mu-atrz)(2)(mu-piv)(4)(piv)(2)].2MeOH.H(2)O (2) (atrz = 4-amino-1,2,4-triazole), [Cu(4)(mu(3)-OH)(2)(mu-tbtrz)(2)(mu-piv)(2)(piv)(4)].4H(2)O (3) (tbtrz = 4-tert-butyl-1,2,4-trizaole), and [Cu(4)(mu(3)-O)(2)(mu-admtrz)(4)(admtrz)(2)(mu-piv)(2)(piv)(2)].2[Cu(2)(mu-H(2)O)(mu-admtrz)(piv)(4)].13H(2)O [4 = 4a.2(4b).13H(2)O; admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole], have been prepared and structurally characterized. 1 is an asymmetrical triangular complex containing a [Cu(3)(mu(3)-OH)] core with two Cu---Cu edges spanned by bridging adetrz ligands. 2, 3, and 4a are novel tetranuclear compounds containing a [Cu(4)(mu(3)-O)(2)] or [Cu(4)(mu(3)-OH)(2)] core with Cu---Cu edges spanned by bridging 1,2,4-triazole or pivalate ligands. 4b is a dinuclear compound with one admtrz and one water bridge, and it is the first dinuclear Cu(II) triazole complex with one bridging water molecule. 1 is one of few reported triangular Cu(II) complexes with derivatives of 1,2,4-triazole, while 2, 3, and 4a are the first group of the nonlinear tetranuclear Cu(II) compounds with derivatives of 1,2,4-triazole. Variable-temperature magnetic susceptibility studies on the powder samples of 1-3 reveal the overall antiferromagnetic coupling between Cu(II) ions with J values of -55.6 to -12.8 cm(-1) (1), -216.4 to 0 cm(-1) (2), and -259.8 to 4.8 cm(-1) (3). 相似文献
993.
Xian‐Zhong Sun Zhen‐Li Huang He‐Zhou Wang Bao‐Hui Ye Xiao‐Ming Chen 《无机化学与普通化学杂志》2005,631(5):919-923
Two new coordination polymers [Cd(tdc)(bpy)(H2O)]n ( 1 ) and [Cd(tdc)(phen)]n ( 2 ) (H2tdc = thiophene‐2,5‐dicarboxylic acid, bpy = 2,2′‐bipyridine and phen = 1,10‐phenanthroline) have been synthesized under hydrothermal condition. Their crystal structures have been established by X‐ray single‐crystal diffraction. Complex 1 crystallizes in the orthorhombic space group Fdd2 with a = 14.757(7), b = 45.38(2), c = 10.518(5) Å, V = 7044(6) Å3, Z = 16; 2 in the monoclinic space group P21/c with a = 7.262(1), b = 21.970(2), c = 10.051(1) Å, β = 105.01(1)°, V = 1548.8(2) Å3, Z = 4. Both of them are double‐stranded chains and further assembled into three‐dimensional networks by π‐π stacking interactions. 1 and 2 are stable in air, and show blue photoluminescence at 415 nm and 410 nm, respectively. 相似文献
994.
Synthesis, Characterization and Two-Photon Absorption Properties of a Novel Pyridinium Salt 总被引:2,自引:0,他引:2
A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino)styryll-N-metlayl pyridinium iodide (BMSPI) was synthesized and characterized by TG, ^1H NMR spectroscopy and elemental analysis, and the reaction process was studied by using ES-MS. When BMSPI was pumped by a pulsed 1064 nm, 50 ps laser beam, it manifests highly efficient TPA (Two-Photon Absorption) and up-conversion superradiance. The up-conversion efficiency was 6.0% at the pump energy of 4-6 mJ and the lifetime of two-photon fluorescence was measured as 59 ps. 相似文献
995.
Hui‐Bo Zhou Wen Dong Mao Liang Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Peng Cheng 《无机化学与普通化学杂志》2004,630(4):498-500
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2]— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2]— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer. 相似文献
996.
Chaoran Xu Jianglin Qiao Shunxi Dong Yuqiao Zhou Xiaohua Liu Xiaoming Feng 《Chemical science》2021,12(15):5458
Heterocycles have been widely used in organic synthesis, agrochemical, pharmaceutical and materials science industries. Catalytic three-component ylide formation/cycloaddition enables the assembly of complex heterocycles from simple starting materials in a highly efficient manner. However, asymmetric versions remain a yet-unsolved task. Here, we present a new bimetallic catalytic system for tackling this challenge. A combined system of Rh(ii) salt and chiral N,N′-dioxide–Sm(iii) complex was established for promoting the unprecedented tandem carbonyl ylide formation/asymmetric [4 + 3]-cycloaddition of aldehydes and α-diazoacetates with β,γ-unsaturated α-ketoesters smoothly, affording various chiral 4,5-dihydro-1,3-dioxepines in up to 97% yield, with 99% ee. The utility of the current method was demonstrated by conversion of products to optically active multi-substituted tetrahydrofuran derivatives. A possible reaction mechanism was provided to elucidate the origin of chiral induction based on experimental studies and X-ray structures of catalysts and products.Catalytic asymmetric tandem carbonyl ylide formation/[4 + 3]-cycloaddition of β,γ-unsaturated α-ketoesters, aldehydes and α-diazoacetates was achieved by using a bimetallic rhodium(ii)/chiral N,N′-dioxide–Sm(iii) complex catalyst. 相似文献
997.
998.
Chi Chen Chang‐Wei Su Chun‐Wei Yeh Hui‐Ling Hu Jhy‐Der Chen Ju‐Chun Wang 《中国化学会会志》2006,53(2):299-303
The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl2‐4H2O afforded the complex MnCl2(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation. 相似文献
999.
1—取代苯基—1,4—二氢—6—甲基—4—哒嗪酮—3—酰胺的合成 总被引:2,自引:1,他引:2
用杂交方法培育新作物品种是农业增产的重要措施。与常规杂交育种方法相比,采用化学杀雄法(Chemical induction lf male sterility)育种具有程序简单,节省劳力,时间缩短等优点,可以诱导产生非遗传性的雄性不育母本,与另一品种的文本杂交而得优化组合的良种,国外在小麦上已试验成功但在水稻上尚在探索,美国Rohm and Haas公司曾报道一些哒嗪酮类 相似文献
1000.
Yaowu Zhou Huiting Yang Chenxi Wang Yuan Xue Xuebin Wang Chunyan Bao Linyong Zhu 《Chemical science》2021,12(10):3627
Nature or synthetic systems that can self-assemble into biomimetic membranes and form compartments in aqueous solution have received extensive attention. However, these systems often have the problems of requiring complex processes or lacking of control in simulating lipid synthesis and membrane formation of cells. This paper demonstrates a conceptually new strategy that uses a photoligation chemistry to convert nonmembrane molecules to yield liposomes. Lysosphingomyelin (Lyso) and 2-nitrobenzyl alcohol derivatives (NBs) are used as precursors and the amphiphilic character of Lyso promotes the formation of mixed aggregates with NBs, bringing the lipid precursors into close proximity. Light irradiation triggers the conversion of NBs into reactive aldehyde intermediates, and the preassembly facilitates the efficient and specific ligation between aldehyde and Lyso amine over other biomolecules, thereby accelerating the synthesis of phospholipids and forming membrane compartments similar to natural lipids. The light-controllable transformation represents the use of an external energy stimulus to form a biomimetic phospholipid membrane, which has a wide range of applications in medicinal chemistry, synthetic biological and abiogenesis.A photoligation chemistry was used to drive the formation of biomimetic membranes in situ. The preassembly of precursors promotes the synthesis of lipid, which is an important feature as a candidate for simulating natural membrane functions. 相似文献