全文获取类型
收费全文 | 94556篇 |
免费 | 2904篇 |
国内免费 | 2420篇 |
专业分类
化学 | 36639篇 |
晶体学 | 1012篇 |
力学 | 7736篇 |
综合类 | 149篇 |
数学 | 33803篇 |
物理学 | 20541篇 |
出版年
2024年 | 41篇 |
2023年 | 332篇 |
2022年 | 384篇 |
2021年 | 533篇 |
2020年 | 673篇 |
2019年 | 617篇 |
2018年 | 10778篇 |
2017年 | 10595篇 |
2016年 | 6827篇 |
2015年 | 1523篇 |
2014年 | 1162篇 |
2013年 | 1528篇 |
2012年 | 5271篇 |
2011年 | 11892篇 |
2010年 | 6645篇 |
2009年 | 6962篇 |
2008年 | 7650篇 |
2007年 | 9717篇 |
2006年 | 1146篇 |
2005年 | 2173篇 |
2004年 | 2196篇 |
2003年 | 2517篇 |
2002年 | 1637篇 |
2001年 | 816篇 |
2000年 | 725篇 |
1999年 | 563篇 |
1998年 | 522篇 |
1997年 | 428篇 |
1996年 | 485篇 |
1995年 | 385篇 |
1994年 | 320篇 |
1993年 | 279篇 |
1992年 | 203篇 |
1991年 | 203篇 |
1990年 | 160篇 |
1989年 | 122篇 |
1988年 | 138篇 |
1987年 | 112篇 |
1986年 | 122篇 |
1985年 | 99篇 |
1984年 | 77篇 |
1983年 | 59篇 |
1982年 | 71篇 |
1981年 | 67篇 |
1980年 | 64篇 |
1979年 | 55篇 |
1978年 | 46篇 |
1914年 | 45篇 |
1913年 | 41篇 |
1909年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Two inorganic-organic hybrid solids, Zn2(phen)(HPO3)2 (1) and Zn(phen)(HPO3) (2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, , , , α=75.609(1)°, β=79.145(2)°, γ=67.157(2)°, , Z=2. Compound 2 is monoclinic, C2/c, , , , β=94.175(4)°, , Z=8. Both structures consist of 1D chains constructed from strictly alternating ZnO4 and HPO3 polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)]2+ for 1 and [Zn(phen)2]2+ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π-π interactions of the phen groups, respectively. 相似文献
992.
Joris Van Loco Maureen Moerenhout Hedwig Beernaert 《Accreditation and quality assurance》2003,8(2):61-67
A GLP study can be performed at more than one site. This is called a multi-site study. Although, the study is performed at
different sites, it is still one study and must completely comply with the GLP principles. The fact that different activities
are conducted at different sites implies that the planning, the organization and the communication are crucial for the success
of the study. This means that all the staff involved should know their responsibilities and should have the knowledge and
skills to realize all the phases of the study according to the GLP principles. To achieve a well managed multi-site study,
several strategies for setting up such a study can be followed. This paper focuses on the responsibilities, communication,
and collaboration of the personnel, which are involved in a multi-site study. Several case studies are highlighted, and we
concluded that the basic communication triangle in a single-site GLP study between test facility management, study director,
and the quality assurance unit should be extended to the communication among test facility and test site management, study
director, principle investigator(s), and the quality assurance units at the test sites.
Introduction
Received: 14 August 2002 Accepted: 26 November 2002 相似文献
993.
Stereocontrolled alkynylzirconation of unactivated alkynes was achieved by the reaction of an alkyne with Cp2ZrEt2 and alkynyl halide in this order. After hydrolysis of the alkynylzirconation product, trisubstituted enyne derivatives were obtained in good yields. Functionalized enynes were also prepared by the reaction of the alkynylzirconation products with a variety of electrophiles. Subsequent addition of the second alkynyl halide to the alkynylzirconation products provided an in situ protocol for bisalkynylation of alkynes into (Z)-enediynes in good yields. 相似文献
994.
芥子气模拟剂2-氯乙基乙基硫醚的光催化降解 总被引:4,自引:0,他引:4
利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚(2-CEES)在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S;少量小分子的羧酸、醚和砜;微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C-S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活. 相似文献
995.
In search for a cheaper anode catalyst for the oxidation of ethanol for development of direct alcohol fuel cells, Pd has been
considered here as an interesting substitute for Pt in Pt Ru binary electrodeposite. The binary catalyst when co-deposited
on nickel support has been found to increase the current density and decrease the anodic overvoltage significantly with respect
to pure Pt, Pd and Ni. Its electrocatalytic capability is also comparable with that of the Pt-Ru binary electrocatalyst on
Ni-support, when studied in 1 M EtOH containing 1 M NaOH solution. The effect of loading of Pd Ru electrocatalyst on Ni support has also been tested. The electrocatalytic activity
of the electrodes for oxidation of ethanol has been explained by studies of cyclic voltammetry, chronopotentiometry, steady-state
polarization, and conjugated scanning electron microscopy–energy dispersion X-ray spectroscopy. It has been found that electrode
containing the higher amount of deposit are less affected by carbonaceous poisons. 相似文献
996.
H. Surya Prakash Rao S. Senthilkumar K. Gopu Shaik Rafi 《Chemistry of Heterocyclic Compounds》2007,43(3):292-297
The microwave-mediated reaction of 4-aryl-4-oxobutanoic acids with benzylamines furnished 1-arylmethyl-3-[(E)-1-arylmethylidene]-5-phenyl-2,3-dihydro-1H-pyrrolones.
This result is in contract to the earlier report on this reaction conducted under neat conditions. Structures for the products
were assigned on the basis of spectral data and confirmed by independent synthesis.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 368–373, March, 2007. 相似文献
997.
Norman H. Tennent Sophia R. Su Craig A. Poffenberger Andrew Wojcicki 《Journal of organometallic chemistry》1975,102(4):C46-C48
The reaction of Na[η5-C5H5Fe(CO)2] with large excess of SO2 in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5). 相似文献
998.
CO2部分氧化乙烷制乙烯Pd—Cu/MoO3—SiO2催化剂的研究 总被引:7,自引:0,他引:7
用化学吸附-红外光谱、化学吸附-程序升温脱附(TPD)和微型反应技术研究了Pd-Cu/MoO3-SiO2(MoSO)催化剂对CO2和乙烷的吸附活化和部分氧化反应性能.结果表明,乙烷以C—H键中的H吸附于MoSO载体表面MoO键的端基氧上;Pd-Cu/MoSO催化剂对CO2有良好的化学吸附活化性能,CO2的吸附除有线式吸附态和剪式吸附态外,还有一种新的卧式吸附态;Pd-Cu/MoSO催化剂的晶格氧参与了化学反应.探讨了在Pd-Cu/MoSO催化剂上CO2的部分氧化乙烷反应机理 相似文献
999.
CuO/CeO2和CuO/Al2O3催化剂的催化性能 总被引:13,自引:0,他引:13
本文以CO氧化为模式反应考察了CeO2和Al2O3负载氧化铜催化剂的氧化活性,运用XRD和TPR技术研究了催化剂的还原性能和物相结构,结果表明:载体性质对负载CuO催化剂的CO氧化活性有很大影响,CuO/CeO2催化剂活性明显高于CuO/Al2O3催化剂.催化剂的还原特性随载体不同而不同.同时发现,热处理对催化剂铜物种的存在形式,晶粒大小、还原特性及其催化活性有明显影响,CuO/Al2O3催化剂活性下降的主要因素是生成了活性较低的CuAl2O4相,而CuO/CeO2催化剂活性下降是由于CuO和CeO2发生烧结,晶粒变大 相似文献
1000.
Changlun Shao Zhiyong Guo Hong Peng Guangtian Peng Zhongjing Huang Zhigang She Yongcheng Lin Shining Zhou 《Chemistry of Natural Compounds》2007,43(4):377-380
A new isoprenyl phenyl ether, 3-hydroxy-4-(3-methylbut-2-enyloxy)benzoic acid methyl ester (1), together with 4-hydroxybenzoic acid (2), 2-hydroxy-6-methylbenzoic acid (3), and 4-hydroxy-3-methoxybenzoic acid (4) were isolated from Mangrove fungus (No. B60) from the South China Sea. The structures of the compounds were established
on the basis of NMR spectroscopic and mass spectrometric data. In the preliminary bioassay, compound 1 exhibited antibacterial and antifungal activities. Compound 1 also inhibited cytotoxicity to the hepG2 cell line with an IC50 value of 10.0 μg/mL.
Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 313–314, July–August, 2007. 相似文献