全文获取类型
收费全文 | 105752篇 |
免费 | 4430篇 |
国内免费 | 3082篇 |
专业分类
化学 | 43648篇 |
晶体学 | 1046篇 |
力学 | 8461篇 |
综合类 | 279篇 |
数学 | 34937篇 |
物理学 | 24893篇 |
出版年
2024年 | 75篇 |
2023年 | 571篇 |
2022年 | 765篇 |
2021年 | 901篇 |
2020年 | 1116篇 |
2019年 | 1067篇 |
2018年 | 11063篇 |
2017年 | 10825篇 |
2016年 | 7159篇 |
2015年 | 1999篇 |
2014年 | 1764篇 |
2013年 | 2280篇 |
2012年 | 6241篇 |
2011年 | 12934篇 |
2010年 | 7190篇 |
2009年 | 7553篇 |
2008年 | 8240篇 |
2007年 | 10263篇 |
2006年 | 1689篇 |
2005年 | 2493篇 |
2004年 | 2433篇 |
2003年 | 2722篇 |
2002年 | 1733篇 |
2001年 | 802篇 |
2000年 | 845篇 |
1999年 | 802篇 |
1998年 | 769篇 |
1997年 | 722篇 |
1996年 | 857篇 |
1995年 | 619篇 |
1994年 | 542篇 |
1993年 | 481篇 |
1992年 | 423篇 |
1991年 | 384篇 |
1990年 | 305篇 |
1989年 | 261篇 |
1988年 | 216篇 |
1987年 | 193篇 |
1986年 | 184篇 |
1985年 | 164篇 |
1984年 | 131篇 |
1983年 | 97篇 |
1982年 | 82篇 |
1981年 | 74篇 |
1980年 | 64篇 |
1979年 | 60篇 |
1978年 | 53篇 |
1975年 | 44篇 |
1914年 | 45篇 |
1909年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Weiping Huang Suwen Liu Xianghai Tang Menachem Motiei Yuri Koltypin A. Gedanken 《Research on Chemical Intermediates》2004,30(7-8):793-805
Ag-TiO2, Cu-TiO2 and Ni-TiO2 were prepared by sonication. The interactions of Ti-gel with silver, copper and nickel ions under ultrasound irradiation are very different, although these ions can be dispersed very well in titania. The results of EDXA and XRD analysis indicate that Ti-gel does not react with AgCl and crystallizes unaffectedly to form rutile. M(OH)2 (M = Cu and Ni), on the other hand, favors polycondensation with Ti-gel and affects the crystallization of Ti-gel. CuO favors stabilization of the anatase phase. Ni2+ ions tend to incorporate more easily into titania than Cu2+ ions do when the samples are calcined. TEM, and BET were also used to characterize the samples. 相似文献
972.
以2-萘甲酸为原料,经硝化,酯化,重氮化,选择性催化氢化,BOC酸酐保护等六步反应,完成了N-BOC-8氨甲基-2-萘甲酸(1a)的合成,为化合物1的合成提供了新的合成途径。 相似文献
973.
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
974.
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
975.
The effect of CuO on the thermal behaviour of Zr/KClO4 primer mixtures was studied by thermoanalytical techniques, and the Bruceton method and its related calculation. It was found that the CuO catalytically promoted the decomposition of Zr/KClO4 primer mixtures and shifted the exothermic peak of DSC curves to lower temperatures. In addition, the Zr/KClO4 primer mixture containing CuO had a significant effect on the firing characteristics of electro-explosive devices. 相似文献
976.
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
977.
Juan?Feng Qian?Wang Xujia?Zhang Youguo?Huang Xicheng?Ai Xingkang?Zhang Jianping?ZhangEmail author 《中国科学B辑(英文版)》2004,47(1):80-90
The LH2 complex from Rhodopsudomonas (Rps.) palustris is unique in the heterogeneous carotenoid compositions. The dynamics of triplet excited state Carotenoids (3Car* has been investigated by means of sub-microsecond time-resolved absorption spectroscopy both at physiological temperature
(295 K) and at cryogenic temperature (77K). Broad and asymmetric T
n
←T
1 transient absorption was observed at room temperature following the photo-excitation of Car at 532 nm, which suggests the
contribution from various carotenoid compositions having different numbers of conjugated C=C double bonds (Nc=c). The triplet absorption bands of different carotenoids, which superimposed at room temperature, could be clearly distinguished
upon decreasing the temperature down to 77 K. At room temperature the shorter-wavelength side of the main Tn04T1 absorption band decayed rapidly to reach a spectral equilibration with a characteristic time constant of ∽1 μs, the same
spectral dynamics, however, was not observed at 77 K. The aforementioned spectral dynamics can be explained in terms of the
triplet-excitation transfer among heterogeneous carotenoid compositions. Global spectral analysis was applied to the time-resolved
spectra at room temperature, which revealed two spectral components peaked at 545 and 565 nm, and assignable to the Tn04 T1 absorption of Cars with Nc=c=11 and Nc=c=13, respectively. Surprisingly, the decay time constant of a shorter-conjugated
Car, i.e. 0.72 ώs (aerobic) and 1.36 ώs (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic)
and 3.75 ώs (anaerobic), which is contradictory to the general rule of carotenoids and relative polyenes. The results are
explained in terms of triplet-excitation transfer among different types of Cars. It is postulated that two Cars with different
conjugation lengths coexist in an α, β-subunit in the LH2 complex. 相似文献
978.
Zhu Hai-Liang Huang Pei Duan Chun-Ying Zheng Li-Min Liu Yong-Jiang Wu Mei-Fang Tang Wen-Xia 《Transition Metal Chemistry》1999,24(4):380-383
An azide-bridged polymeric cationic chain complex, [LCu2(N3)2]n(ClO4)2n
·n(H2O)**, where L=the dinucleating macrocyclic ligand bis-p-xylylBISDIEN, has been prepared and characterized by x-ray crystallography, u.v.-vis and i.r. spectra, and by magnetic measurements. The structure consists of cationic azide-bridged [LCu2(N3)2]2+ (unit) chains, non-coordinated perchlorate anions and crystallized water molecules. The azide anion is bound to two copper atoms in neighboring units with an end-to-end bridging mode. In each unit, the copper atoms have a different coordination geometry; Cu(1) is a four-coordinated, distorted square-planar geometry, whereas Cu(2) is a five-coordinated, distorted square-pyramid. The electronic spectra of the title complex differ in anhydrous and in aqueous MeCN solutions, indicating that dissociation and solvation occur in aqueous solutions. The characteristic i.r. absorptions of azides and perchlorates are described. Magnetic moments vary from 2.05 (B.M.) at 300K to2.01 (B.M.) at 80K, which suggests that very weak interactions exist between the metals. 相似文献
979.
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
980.