全文获取类型
收费全文 | 99411篇 |
免费 | 3795篇 |
国内免费 | 2808篇 |
专业分类
化学 | 39553篇 |
晶体学 | 1053篇 |
力学 | 7962篇 |
综合类 | 187篇 |
数学 | 34012篇 |
物理学 | 23247篇 |
出版年
2024年 | 68篇 |
2023年 | 423篇 |
2022年 | 740篇 |
2021年 | 810篇 |
2020年 | 850篇 |
2019年 | 834篇 |
2018年 | 10971篇 |
2017年 | 10808篇 |
2016年 | 6972篇 |
2015年 | 1859篇 |
2014年 | 1451篇 |
2013年 | 1900篇 |
2012年 | 5575篇 |
2011年 | 12343篇 |
2010年 | 6838篇 |
2009年 | 7229篇 |
2008年 | 7960篇 |
2007年 | 9993篇 |
2006年 | 1414篇 |
2005年 | 2238篇 |
2004年 | 2274篇 |
2003年 | 2594篇 |
2002年 | 1612篇 |
2001年 | 700篇 |
2000年 | 737篇 |
1999年 | 630篇 |
1998年 | 610篇 |
1997年 | 566篇 |
1996年 | 658篇 |
1995年 | 481篇 |
1994年 | 454篇 |
1993年 | 364篇 |
1992年 | 307篇 |
1991年 | 295篇 |
1990年 | 213篇 |
1989年 | 187篇 |
1988年 | 175篇 |
1987年 | 154篇 |
1986年 | 152篇 |
1985年 | 131篇 |
1984年 | 100篇 |
1983年 | 85篇 |
1982年 | 79篇 |
1981年 | 66篇 |
1980年 | 77篇 |
1979年 | 62篇 |
1978年 | 44篇 |
1914年 | 45篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
901.
双邻苯二酚锑二甲基羟乙铵的晶体结构 总被引:3,自引:1,他引:3
含锑配合物是治疗血吸虫病、肿瘤等的常用药物,我们曾对双邻苯二酚锑二乙基羟乙胺进行了晶体结构测定,本文简要报导双邻苯二酚锑二甲基羟乙胺的结构.锑化合物的制法与其二乙基羟乙铵衍生物类似.产物为淡黄色晶体,它在水溶液中长时间放置会变成紫黑色,因此,制得的晶体须立即用丙酮溶解进行重结晶.晶体的密度为1.667g/cm~3.按C_(16)H_(20)O_5NSb的元素分析结果(%)如下:Sb 28.3(28.5),C 43.9(44.9),N 3.3(3.3),H 4.7(4.7).括号内为理论值. 相似文献
902.
本文报导了与硅原子直接相连的有机基团(R)对杂氮硅三环成环速率的影响。利用气相色谱检测成环反应的产物之一——乙醇的生成速率和数量,并同与硅相连的R基团对成环反应速率的影响作比较。实验结果表明五种杂氮硅三环成环速度顺序为Cl_2CH—>ClCH_2—>ClCH_2CH_2CH_2—>CH_2=CH—>CH_3—,这与理论推断相符。 相似文献
903.
The behavior of three-dimensional bond fluctuation model chains tethered on an adsorbing flat surface was simulated by the Monte Carlo method. The dependence of the number of surface contacts M on the interaction strength e and the chain length N was investigated by a finite-size scaling law M = N[a0 + a1N1/vk + O((N 1/vk)2)] for e near the critical adsorption point ec, i.e., k ≡(e-ec)/ec closes to 0. The critical adsorption point was estimated to be ec = 0.93, and the exponents 61542; = 0.49 and 1/v= 0.57. 相似文献
904.
905.
Juan Hong Liang-Fu Tang Zhi Yang Yu-Ping Zhai Mujia Nan 《Transition Metal Chemistry》2005,30(4):439-444
A series of [M(CO)5I]− and [M2(CO)10I]− anion complexes have been synthesized by the photochemical reaction of PhCH2N(CH3)3I or FcCH2N(CH3)3I (Fc=ferrocenyl) with M(CO)6 (M = Cr, Mo or W), and characterized by elemental analyses, i.r., 1H-n.m.r. and 13C-n.m.r. spectra in the case of the molybdenum and tungsten complexes. These complexes exhibit considerably different electrochemical behavior, when investigated by cyclic voltammetry. The crystal structures of [PhCH2N(CH3)3][Cr(CO)5I] and [FcCH2N(CH3)3][W2(CO)10I] have been determined by X-ray diffraction, indicating that only weak contacts maybe exist between anions and cations by the I...H bond in the former, and there are no direct interactions between anions and cations in the latter. 相似文献
906.
Vukadin M. Leovac Goran A. Bogdanović Valerija I. Češljević Ljiljana S. Jovanović Sladjana B. Novaković Ljiljana S. Vojinović-Ješić 《Structural chemistry》2007,18(1):113-119
The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H2SalGT]Cl (1), and two complexes [Cu(HSalGT)X2]·H2O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural
complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the
basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH3)3 group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions.
The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption
spectra. 相似文献
907.
A binuclear complex [Cu2(DTB)(DMF)4(H2O)]·2DMF (DTB = 1,4-dinitro-2,3,5,6-tetracarboxylatobenzenic anion; DMF = N,N-dimethylformamide) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex Cu ion is located in a distorted square pyramidal environment with two oxygen atoms O(1) and O(3) from two carboxylate groups, another two oxygen atoms O(7) and O(8) from terminal ligands of two DMF molecules, and a fifth coordinated oxygen atom O(9) from the terminal ligand of one H2O molecule, in which the O(8) atom is situated in the apex of the pyramid. DTB as bridging ligand coordinates two Cu ions through its four carboxylate groups. The variable-temperature magnetic susceptibility of the complex was measured in the 5–300 K range. The magnetic coupling parameter is consistent with a ferromagnetic exchange between the two copper(II) centers and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = -2J12, 1 = 2= 1/2), giving the ferromagnetic coupling parameter of 2J = 1.80 cm- 1. This is the first example of a tetracarboxylatobenzenic bridging complex exhibiting ferromagnetic interaction. 相似文献
908.
The MnIV complex of tetra-deprotonated 1,8-bis(2-hydroxybenzamide)-3,6-diazaoctane (MnIVL) engrossed in phenolate-amido-amine coordination is reduced by HSO3− and SO32− in the pH range 3.15–7.3 displaying biphasic kinetics, the MnIIIL− being the reactive intermediate. The MnIIIL− species has been characterized by u.v.–vis. spectra {λ max, (ε, dm3 mol−1 cm−1): 285(15 570), 330 sh (7570), 469(6472), 520 sh (5665), pH=5.42}. SO42− was the major oxidation product of SIV; dithionate is also formed (18 ± 2% of [MnIV]T) which suggests that dimerisation of SO3−• is competitive with its fast oxidation by MnIV/III. The rates and activation parameters for MnIVL + HSO3− (SO32−) → MnIIIL−; MnIIIL− + HSO3− (SO32−) → MnIIL2− are reported at 28.5–45.0 °C (I=0.3 mol dm−3, 10% (v/v) MeOH + H2O). Reduction by SO32− is ca. eight times faster than by HSO3− both for MnIVL and MnIIIL−. There was no evidence of HSO3−/SO32− coordination to the Mn centre indicating an outer sphere (ET) mechanism which is further supported by an isokinetic relationship. The self exchange rate constant (k22) for the redox couple, MnIIIL−/MnIVL (1.5 × 106 dm3 mol−1 s−1 at 25 °C) is reported. 相似文献
909.
滴定量效法是研究反应热化学和热力学的重要手段之一.用这种方法对冠醚与金属离子的配位反应热力学性质进行研究一直受到很大关注【且S习.但是对氨杂冠林,尤其是一系列结构相似的氨杂冠醚体系进行系统的热力学性质研究的报导不多.前文K则曾报导了用自组装的消定量热计对银(I)-a吹体系和铜(11)·N,N’一问位取代革基乙二胺体系的配位反应热化学研究结果·本文报导从(对位取代革基)k杂15冠5卜RPW15CS,R=CIZH;CHa;CHso)与碘化钠和碘化钾在25T、无水乙过溶液中进行配位反应的消定量效研究结果.讨论了配体上取代基的电… 相似文献
910.
本文介绍了一种以氟气和惰性气体为原料合成 Kr F2 和 Xe F2 的热催化合成方法并对合成机理和条件作了简单的讨论 ,利用合成的 Kr F2 作为氟化剂合成了含氟高能氧化剂 NF4BF4,纯度约为 93%,其红外光谱和拉曼光谱基本与文献值吻合。元素分析结果表明产品 NF4BF4中含 B5.8%(mass) ,自由氟原子含量为 9.95%(mass) ,与理论值基本一致 ,此结果也间接证明了 Kr F2 质量的可靠性。粉末状的 Xe F2 经升华 -再结晶纯化后可得纯净晶体产品。 相似文献