全文获取类型
收费全文 | 5515篇 |
免费 | 1112篇 |
国内免费 | 1078篇 |
专业分类
化学 | 4925篇 |
晶体学 | 186篇 |
力学 | 73篇 |
综合类 | 62篇 |
数学 | 321篇 |
物理学 | 2138篇 |
出版年
2024年 | 11篇 |
2023年 | 70篇 |
2022年 | 136篇 |
2021年 | 167篇 |
2020年 | 266篇 |
2019年 | 217篇 |
2018年 | 180篇 |
2017年 | 185篇 |
2016年 | 284篇 |
2015年 | 263篇 |
2014年 | 293篇 |
2013年 | 497篇 |
2012年 | 380篇 |
2011年 | 366篇 |
2010年 | 367篇 |
2009年 | 366篇 |
2008年 | 369篇 |
2007年 | 359篇 |
2006年 | 376篇 |
2005年 | 297篇 |
2004年 | 330篇 |
2003年 | 271篇 |
2002年 | 189篇 |
2001年 | 176篇 |
2000年 | 179篇 |
1999年 | 151篇 |
1998年 | 132篇 |
1997年 | 120篇 |
1996年 | 98篇 |
1995年 | 108篇 |
1994年 | 93篇 |
1993年 | 71篇 |
1992年 | 65篇 |
1991年 | 68篇 |
1990年 | 43篇 |
1989年 | 34篇 |
1988年 | 25篇 |
1987年 | 15篇 |
1986年 | 13篇 |
1985年 | 16篇 |
1984年 | 11篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有7705条查询结果,搜索用时 250 毫秒
51.
本文用XPS从Rh_4(CO)_(12)在真空条件下的脱羰过程和在氢氧中的还原过程两方面考察了一些非还原性氧化物担载Rh_4(CO)_(12)催化剂的金属载体相互作用,并把这种相互作用称为金属载体非强相互作用(non-strong metal-support interaction,缩写NSMSI).结果表明,铑与一些载体的非强相互作用的顺序是MgO>ZrO_2>γ-Al_2O_3>SiO_2-Al_2O_3≈SiO_2;Rh与载体的非强相互作用形成Rh—O键,使Rh的还原性减弱;形成M—O键是产生NSMSI效应的重要特征;这种相互作用能增加铑羰基物的稳定性,使其在真空中脱羰速率减慢.铑与非还原性氧化物载体间的非强相互作用可用酸-碱机制解释. 相似文献
52.
负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶,李晔(内蒙古工业大学化学工程系,呼和浩特010062)殷元骐,金道森(中国科学院兰州化学物理研究所,兰州730000)关键词一氧化碳加氢,多相催化,双金属簇催化剂,钾效应。1.引言异核金属羰基簇作... 相似文献
53.
Three novel hetero-polyoxovanadates, [Cd(2,2′-bpy)3]{[Cd(dien)]As8V14O42(H2O)} (1, 2,2′-bpy=2,2′-bipyridine, and dien=diethylenetriamine), [Zn(2,2′-bpy)2]2[As8V14O42(H2O)]·H2O (2) and [Ni(en)2]3[As8V14O42(HPO3)]·4H2O (3, en=ethlenediamine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Crystal data: 1 monoclinic, P2(1)/n, a=15.1728(5), b=19.2863(5), , β=96.005(2)°, Z=4. 2, orthorhombic, P2(1)2(1)2(1), a=12.1270(3), b=15.8678(8), , Z=4. 3, triclinic, , a=12.9340(3), b=13.4130(3), , α=87.170(3)°, β=77.517(3)°, γ=68.480(3)°, Z=2. Compounds 1-3 are all made of the {As8V14O42} shells linked by corresponding transition metal complexes into extended structures. Compound 1 and 2 present 1-D wave-like and tubular structures, respectively, while compound 3 exhibits a novel 2-D structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2. 相似文献
54.
55.
A. W. Flounders D. L. Brandon A. H. Bates 《Applied biochemistry and biotechnology》1995,50(3):265-284
Monoclonal antibodies specific for thiabendazole were immobilized to silicon, silicon dioxide, stoichiometric silicon nitride,
and silicon-rich silicon nitride surfaces. This work provides the foundation for the development of a homogeneous sensor system
for rapid detection and quantification of thiabendazole residues in produce and animal tissue. Immobilization was performed
via aqueous silanization of the substrate followed sequentially by treatment with glutaraldehyde and contact with antibody
solution in the presence of detergent. Surfaces were challenged with thiabendazole-horseradish peroxidase conjugate in an
ELISA format to estimate immobilized antibody load. A stable and reproducible surface loading of 2 x 1011 antibodies/cm2 was obtained only after surfaces received postimmobilization treatments to remove nonspecifically adsorbed antibody. No difference
in surface loading was noted when using 30% hydrogen peroxide rather than nitric acid for silanol activation. Little difference
was noted among the antibody loadings achieved on the various silicon substrates. Bound antigen-enzyme conjugate was eluted
with 0.1N acetic acid and reproducible surface activity was measured for up to four consecutive antigen challenges. Immobilized
antibody surfaces were stabilized with 2% sucrose, dehydrated at 37‡C and stored in vacuum or stored at 4‡C in phosphate buffered
saline containing 0.01% sodium azide without significant loss of activity. 相似文献
56.
57.
58.
吡啶二甲酸镓、铟配合物的合成及生物活性 总被引:1,自引:0,他引:1
吡啶二甲酸能与过渡、非过渡、镧系和锕系金属离子螯合形成稳定的配合物,而且配位方式不拘一格,既可以是双齿,三齿,也可以是桥式配位。吡啶二甲酸的另一重要意义在于它们的生物活性。由于镓具有抗癌,抗肿瘤的活性,吡啶二甲酸镓配合物可能会是一种非常有潜力的新型药物。基于上述事实,本文合成了六种新型的吡啶二甲酸(2,3-,2,5-,2,6-)镓(Ⅲ)、铟(Ⅲ)配合物,并进一步测试了三种镓配合物的生物活性。 相似文献
59.
通过键合不同数量的H2PO4^-离子构造了H4P2O8^2-和H4P4O16^8-两种阴离子集 团。利用密度泛函理论对它们的构型进行优化并计算其振动频率和喇曼散射效率。 测量了固—液界面边界层的喇曼光谱并与理论计算结果进行对比分析,进一步研究 了阴离子集团的结构、聚合及脱水等过程。实验和理论研究均表明阴离子二聚体是 KDP晶体的生长基元,他们在固液界面将进一步形成多聚体分子集团,而离子集团 的脱水过程则发生在距KDP晶体表面约50μm的固—液界面边界层中。随着生长层向 界面的推进,这些分子集团将变得越来越有序。本文的研究结果对确定晶体生长界 面动力学过程、发展和完善晶体生长理论有重要意义。 相似文献
60.
Himadri Paul Sumit Bhaduri Goutam Kumar Lahiri 《Journal of organometallic chemistry》2004,689(2):309-316
Fumed silica, silica gel, silica-alumina and cross-linked (5.5%) polystyrene have been functionalized with quaternary ammonium groups and the Chini cluster [Pt12(CO)24]2− has been anchored onto these functionalized materials by ion pairing. A catalyst has also been prepared by the adsorption of Na2[Pt12(CO)24] on unfunctionalized fumed silica. The catalytic activities of the resultant materials, and that of commercially purchased 5% platinum on alumina have been studied for the hydrogenation of a variety of unsaturated compounds. The substrates studied are: α-acetamidocinnamic acid, cyclohexanone, acetophenone, methyl pyruvate, ethyl acetoacetate, nitrobenzene and benzonitrile. Compared to the polystyrene supported catalyst, the inorganic oxide supported catalysts have higher surface areas and for most of the substrates have notably higher activities. The functionalized fumed silica-based catalyst gives higher conversions than functionalized silica gel and silica-alumina-based catalysts. In the hydrogenation of acetophenone and ethyl acetoacetate, the functionalized fumed silica-based catalyst show superior activity compared to the commercial platinum catalyst, and the catalyst made by conventional adsorption method. In benzonitrile hydrogenation with all the cluster-derived catalysts a hydrazine derivative is selectively formed, but when the commercial platinum catalyst is used benzyl amine is the main product. 相似文献