全文获取类型
收费全文 | 92171篇 |
免费 | 9278篇 |
国内免费 | 12903篇 |
专业分类
化学 | 77274篇 |
晶体学 | 2174篇 |
力学 | 2978篇 |
综合类 | 1043篇 |
数学 | 8855篇 |
物理学 | 22028篇 |
出版年
2024年 | 176篇 |
2023年 | 921篇 |
2022年 | 1980篇 |
2021年 | 3153篇 |
2020年 | 2921篇 |
2019年 | 2691篇 |
2018年 | 2153篇 |
2017年 | 2420篇 |
2016年 | 3237篇 |
2015年 | 3241篇 |
2014年 | 3917篇 |
2013年 | 6675篇 |
2012年 | 5931篇 |
2011年 | 4952篇 |
2010年 | 4370篇 |
2009年 | 5320篇 |
2008年 | 5697篇 |
2007年 | 5976篇 |
2006年 | 5160篇 |
2005年 | 4309篇 |
2004年 | 4201篇 |
2003年 | 3842篇 |
2002年 | 5851篇 |
2001年 | 3004篇 |
2000年 | 2633篇 |
1999年 | 2161篇 |
1998年 | 1955篇 |
1997年 | 1532篇 |
1996年 | 1544篇 |
1995年 | 1360篇 |
1994年 | 1267篇 |
1993年 | 1075篇 |
1992年 | 1097篇 |
1991年 | 716篇 |
1990年 | 606篇 |
1989年 | 493篇 |
1988年 | 483篇 |
1987年 | 362篇 |
1986年 | 359篇 |
1985年 | 492篇 |
1984年 | 364篇 |
1983年 | 235篇 |
1982年 | 382篇 |
1981年 | 562篇 |
1980年 | 517篇 |
1979年 | 541篇 |
1978年 | 432篇 |
1977年 | 336篇 |
1976年 | 283篇 |
1973年 | 169篇 |
排序方式: 共有10000条查询结果,搜索用时 140 毫秒
961.
The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects. 相似文献
962.
ResearchonReactivitiesofMoCluster.ASelectiveSubstitutionReactionoftheBridging(dtp)LigandandStructureofTetranuclearMolybdenumC... 相似文献
963.
B. T. Ibragimov S. A. Talipov T. F. Aripov 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(4):317-324
The structures of gossypol complexes are extremely sensitive to the halogenomethane present as the guest; e.g. changing the number of Cl atoms in chloromethane derivatives changes the structure of the gossypol complex. The crystals of C30H30O8·CH2Cl2 are monoclinic, space groupC2/c,a=21.320(4),b=19.199(6),c=15.765(2)Å, =113.05(2)o,V=5916(2)Å3,Z=8,D
x=1.35 g/cm3,T=295 K. The structure has been solved by direct methods and refined to the finalR value of 0.084 for 1828 reflections. In the structure H-bonded gossypol molecules form columns, generating channels in the structure which are filled by guest molecules. After decomposition (desolvation) monocrystals of the complexes are conserved without destruction, in which there are rather wide and empty channels though slightly smaller than in the complex. An attempt is made to explain some peculiarities of the behavior of the gossypol polymorph formed on the basis of its structure with empty channels.
Supplementary data relevant to this article have been deposited with the British Library Publication No. SUP 82165 (17 pages). 相似文献
964.
Z. S. Klemenkova B. V. Lokshin L. I. Strunkina M. Kh. Minacheva 《Russian Chemical Bulletin》1994,43(9):1516-1521
Raman and IR spectra (4000-50 cm–1) of solid cyclopentadienyl zirconium and hafnium hydrides Cp2MH2, Cp2MD2, Cp2Zr(H)X, and Cp2Zr(D)X (Cp = 5-C5H5; M = Zr, Hf; X = Cl, Br) have been studied. The vibrational modes of MH groups, Cp-rings, and metal-ligand bonds are discussed and the band assignments are proposed. In the solid state, these complexes form polymers with linear hydride bridges of the M-H-M type. The force constants of the M-H and M-Cp bonds increase on going from Zr to Hf.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1604–1609, September, 1994. 相似文献
965.
Alkaline-earth (Ae) metals have attracted a wealth of interdependent research from synthetic chemists. In Ae-catalyzed organometallic reactions, β-diketiminate is a typical ligand used to stabilize Ae catalysts by forming six-membered rings comprising Ae metals. Herein, studies focusing on the configuration of β-diketiminate-coordinated Ae compounds observed that the CC and CN bonds are homogeneous and unchanged. Furthermore, energetic studies observed that the formation of the Ae-incorporated six-membered rings results in enhanced stability of >20 kcal/mol. The nucleus-independent chemical shifts, anisotropy of the induced current density, and molecular orbital analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The improved stability of these compounds can be explained by the delocalization of the π electrons derived from the β-diketiminate moiety. 相似文献
966.
设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析. 相似文献
967.
在自然界中,α-羟基羧酸广泛的存在于动植物体内,在羧酸循环、碳水化合物代谢和氨基酸的合成中起到重要的作用。Tapscott等详细总结了有关羟基羧酸及其金属配合物的合成化学[1]。芴的9位上2个氢原子被羟基和羧基取代可生成9-羟基-芴-9-羧酸(简称芴酸),它是α-羟基乙酸的衍生物,是一种具有生理活性的植物生长整形素,它能够延缓植株生长,影响植株根的向地性和茎的向光性[2]。由于芴酸含有羟基和羧基两种不同的氧配位原子,使其又可以作为一种潜在的构筑配合物的组织基元。目前有关芴酸与金属离子的合成与结构化学研究相对较少,仅见铜、镉的单… 相似文献
968.
A.C. Marques R.M. Almeida A.R. Ramos E. Alves 《Journal of Sol-Gel Science and Technology》2004,32(1-3):287-291
Photosensitive organic-titania hybrid materials have been prepared from metal alkoxides and various organic ester compounds with
double bonds. The refractive index of the film increases with the decrease of the concentration of the organic ester compound, and the highest refractive index of 1.62 is obtained when 2-hydroxymethyl acrylate (HOA) is used as the organic ester and the molar ratio of HOA to Ti is 0.5. The material with the highest refractive index is exposed to femtosecond pulse using the multi-beam laser interference technique. After laser irradiation, the irradiated parts of the material are photopolymerized and periodic structures can be obtained by development of the unirradiated parts. In the case of laser irradiation of 120 J total energy for 5 min, the periodic structure obtained corresponds to 2D photonic crystal structure which is composed of two parts; the material with the highest refractive index and the air. 相似文献
969.
配合物形成的三维超分子体系—[Ni(C_6H_4O_2N)_2(H_2O)_4]的水热法合成、晶体结构及热分析 总被引:7,自引:0,他引:7
采用水热法用Ni(NO3)26H2O和异烟酸制备出了一种新的由配合物形成的三维超分子体系—[Ni(C6H4O2N)2(H2O)4],并通过X射线衍射对其晶体结构进行了测定。 该晶体属三斜晶系,空间群为Pī, 所得晶胞参数为: a = 6.9228(4), b = 9.6664(19),c = 6.322(1) , a = 96.86(3), b = 113.33(3), g = 110.35(3)°, V = 347.6(1) 3, Z = 1, Mr = 374.98, Dc = 1.791 g/cm3, F(000) = 194, m = 1.443 mm-1。用1362个可观察的 (I > 2s(I))衍射点,修正123个结构参数, 最终偏离因子R = 0.0444,wR = 0.1271。在组成该化合物的基本结构单元[Ni(C6H4O2N)2(H2O)4]中,Ni处于1个稍微拉长的八面体的中心; 各个结构单元之间通过氢键OH…O相互连接,形成了无限伸展的具有层状结构的三维超分子体系。 另外,从差热及热重曲线可以看出,该化合物加热到154 ℃时开始分解, 首先失去4个H2O,再失去2个异烟酸根,最后残余物为NiO。 相似文献
970.
ZHANG Jing HUANG Ru-dan ZHU Oin-lei HU Chang-wen 《高等学校化学研究》2007,23(4):483-485
Introduction In recent years,considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields,such as,catalysis,optics,sensors, magnetism,and molecular recognition[1-3].On the ba- 相似文献