全文获取类型
收费全文 | 5967篇 |
免费 | 1113篇 |
国内免费 | 799篇 |
专业分类
化学 | 4384篇 |
晶体学 | 103篇 |
力学 | 383篇 |
综合类 | 44篇 |
数学 | 693篇 |
物理学 | 2272篇 |
出版年
2024年 | 23篇 |
2023年 | 136篇 |
2022年 | 246篇 |
2021年 | 252篇 |
2020年 | 344篇 |
2019年 | 299篇 |
2018年 | 273篇 |
2017年 | 282篇 |
2016年 | 354篇 |
2015年 | 392篇 |
2014年 | 359篇 |
2013年 | 504篇 |
2012年 | 561篇 |
2011年 | 537篇 |
2010年 | 395篇 |
2009年 | 374篇 |
2008年 | 387篇 |
2007年 | 319篇 |
2006年 | 307篇 |
2005年 | 262篇 |
2004年 | 215篇 |
2003年 | 150篇 |
2002年 | 160篇 |
2001年 | 114篇 |
2000年 | 104篇 |
1999年 | 101篇 |
1998年 | 39篇 |
1997年 | 45篇 |
1996年 | 39篇 |
1995年 | 35篇 |
1994年 | 12篇 |
1993年 | 29篇 |
1992年 | 25篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 19篇 |
1986年 | 15篇 |
1985年 | 16篇 |
1984年 | 14篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 5篇 |
1973年 | 5篇 |
排序方式: 共有7879条查询结果,搜索用时 15 毫秒
131.
Single crystals of {[Cu(TO)2(H2O)2](NO3)2}n (TO: 1, 2, 4‐triazol‐5‐one) were grown by slow evaporation from aqueous solution. It crystallizes in the orthorhombic space group Pbca, with a = 7.082(1), b = 10.285(1), c = 17.911(3)Å, V = 1304.6(3)Å3, Z = 4. The CuII distorted octahedra are bridged by bidentate TO ligands into infinite 2‐D interlaced rhombic grid‐like network planes, {[Cu(TO)2(H2O)2]2+}n. Hydrogen bonds, electrostatic interactions, and weak van der Waals' forces assemble these planes and the NO3— anions to a layered structure. The title compound decomposes at 153.4 °C to the final products, Cu(CN)2 and CuO. 相似文献
132.
A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of tyrosine-containing peptides. A tyrosyl residue in the peptide is first formylated in an alkaline medium in the presence of chloroform, and the resulting aldehyde is then converted into a fluorescent derivative by reaction with 1,2-diamino-4,5-dimethoxybenzene. The derivative is separated on a reversed-phase column (LiChrosorb RP-18) by isocratic elution with an aqueous acetonitrile-containing potassium chloride-hydrochloric acid buffer (pH 2.2) and sodium 1-hexanesulphonate. The method is selective and fairly sensitive; the lower limits of detection for the tyrosine-containing peptides tested are in the range 3.4-26.2 pmol in a 100-microliter injection volume. 相似文献
133.
Duanjun Xu Kunio Miki Yasushi Kai Nobutami Kasai Masanori Wada 《Journal of organometallic chemistry》1985,287(2):265-273
The structure of a nickel(II) complex, trans-[Ni(C6Cl5)(PMe2Ph)2{C(OMe)Me}]BF4, containing the simplest alkyl(alkoxy)carbene ligand has been determined by X-ray crystallography (R = 0.091). The geometry around the nickel atom is square-planar. The comparatively short NiC(1) bond length of 1.843(10) Å showed the presence of π-bonding in the nickel-carbene bond. 相似文献
134.
Huang WL Cui SH Liang KM Gu SR Yuan ZF 《Journal of colloid and interface science》2002,246(1):129-134
Silica xerogels were prepared by thermal drying wet gels in an electric oven (70 degrees C) after certain duration of ambient drying, and the relevant effect is investigated on the mesopore structures and surface fractal dimensions of the resultant xerogels. The silica gels were derived from a hydrochloric acid-catalyzed TEOS (tetraethylorthaosilicate) system, and both magnetic stirring and ultrasonic vibration were adopted during sol preparation. The percentage mesoporosity and surface fractal dimensions are evaluated using image analysis methods, based on FE-SEM (field emission gun-scanning electron microscopy) images. The results show that the mesoporosity of the resultant xerogels decreases with the duration of ambient drying for samples prepared using magnetic stirring and low-intensity ultrasonic vibration, while samples subjected to high-intensity ultrasound show a somewhat reverse trend. Samples prepared with magnetic stirring have almost constant surface fractal dimensions (nearly 3), irrespective of the ambient drying before thermal drying. The surface fractal dimensions of samples prepared using ultrasound increase with the duration of ambient drying. 相似文献
135.
The emission spectra of a series of naphthalene end-labeled oligo-oxyethylene(N-Pn-N) and their facilitated transport of cations across liquid membranes have been investigated.Alkali-metal cations enhance or inhibit the intramolecular excimer formation of N-Pn-N remarkably,suggesting that the polyether chain of N-Pn-N in solution complexes with the cations,and the orientation of the terminal chromophores depends on the cation size and the length of the polyether chain. These compounds are able to act as carriers to facilitate transport of alkali-metal cations through organic liquid membranes.The transport efficiencies are comparable with those of cyclic carriers such as crown ethers,and show remarkable selectivity. 相似文献
136.
Meseguer B Alonso-Díaz D Griebenow N Herget T Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(21):3943-3957
Protein kinaseC (PKC) is linked to the signal-induced modulation of a wide variety of cellular processes, such as growth, differentiation, secretion, apoptosis, and tumor development. The design and synthesis of small molecules that regulate these different cellular signaling systems is at the forefront of modern drug design. Herein we report a) an efficient method for the synthesis of indolactamV (6), a PKC activator, and its N13-des(methyl) analogues (19) using a regioselective organometallic transformation, a convenient aminomalonate derivative (10) to introduce the appropriate functionality and an enantiospecific enzymic hydrolysis as key steps; b) the use of this method in the first solid-phase synthesis of a teleocidin library modifying the N-13, C-12 and C-7 alkyl chains, and, therefore, producing a library of potential activators and/or inhibitors of PKC of the general structure (32); c) the activation of PKC by selected members of the library using a MARCKS translocation in vivo assay system; d) the observation that some of these analogues are nearly as effective as the natural PKC activators phorbol dibutyrate and (-)-indolactam V (6), and e) the observation that some of these analogues have different potential to induce down-regulation of members of the PKC gene family after chronic stimulation. 相似文献
137.
Jian Zhang Zhao‐Ji Li Yi‐Hang Wen Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《无机化学与普通化学杂志》2004,630(15):2731-2735
Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C4H4O4)·1/4H2O ( 1 ) and Cu(2, 2′‐bpy)(C4H4O4)0.5(NO3)(H2O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) Å3, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) Å3, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the CuII atom adopts a distorted octahedral in which the CuII atoms are bridged by two H2O molecules into an infinite zigzag chain, [Cu2(H2O)2(C4H4O4)]n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure. 相似文献
138.
A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs. 相似文献
139.
140.