全文获取类型
收费全文 | 3211篇 |
免费 | 121篇 |
国内免费 | 766篇 |
专业分类
化学 | 3695篇 |
晶体学 | 13篇 |
力学 | 41篇 |
综合类 | 16篇 |
数学 | 54篇 |
物理学 | 279篇 |
出版年
2024年 | 5篇 |
2023年 | 36篇 |
2022年 | 77篇 |
2021年 | 73篇 |
2020年 | 84篇 |
2019年 | 90篇 |
2018年 | 72篇 |
2017年 | 93篇 |
2016年 | 102篇 |
2015年 | 103篇 |
2014年 | 127篇 |
2013年 | 270篇 |
2012年 | 169篇 |
2011年 | 194篇 |
2010年 | 163篇 |
2009年 | 203篇 |
2008年 | 202篇 |
2007年 | 202篇 |
2006年 | 172篇 |
2005年 | 170篇 |
2004年 | 166篇 |
2003年 | 134篇 |
2002年 | 133篇 |
2001年 | 96篇 |
2000年 | 100篇 |
1999年 | 99篇 |
1998年 | 69篇 |
1997年 | 78篇 |
1996年 | 78篇 |
1995年 | 76篇 |
1994年 | 70篇 |
1993年 | 73篇 |
1992年 | 40篇 |
1991年 | 56篇 |
1990年 | 31篇 |
1989年 | 26篇 |
1988年 | 42篇 |
1987年 | 26篇 |
1986年 | 33篇 |
1985年 | 13篇 |
1984年 | 14篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 1篇 |
1978年 | 10篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有4098条查询结果,搜索用时 0 毫秒
131.
Radiation formation of polymeric nanogels 总被引:4,自引:0,他引:4
An alternative method of synthesis of polymeric nanogels is proposed, based not on polymerization, but on intramolecular crosslinking of polymer chains, initiated by pulse irradiation in dilute aqueous solutions. Kinetic data show that for many water-soluble polymers irradiation under these conditions result in intramolecular crosslinking. Preliminary product studies on poly(vinyl alcohol) indicate that in fact internally crosslinked macromolecules can be obtained by this technique. 相似文献
132.
Markku J. Oila 《Tetrahedron》2005,61(45):10748-10756
A novel supported amino alcohol linker was synthesized and utilized for attachment of picolinic acid derivatives onto different supports. When the resin bound molecule was further activated, the PyOX-moiety could be constructed reliably in enantiopure form. Furthermore, an efficient Pd-catalyzed modification of a picolinic acid derivative is presented. 相似文献
133.
微波诱导低级醇的等离子体化学反应 总被引:1,自引:0,他引:1
微波诱导低级醇的等离子体化学反应王真,洪品杰,张承聪,戴树珊(云南大学化学系,昆明,650091)关键词微波,等离子体化学,低级醇等离子体能产生大量的活性自由基、亚稳态粒子和激发态离子,它所包含的能量传递过程和反应过程不仅与反应碰撞理论有关,而且还涉... 相似文献
134.
Antonio L. Braga Helmoz R. Appelt Claudio C. Silveira Ludger A. Wessjohann Paulo H. Schneider 《Tetrahedron》2002,58(52):10413-10416
The enantioselective alkynylation reaction of aldehydes with alkynes and diethylzinc, catalyzed by chiral disulfide–oxazolidine ligands, provides a simple, practical and inexpensive method to access chiral propargylic alcohols in good yields and satisfactory ee's. 相似文献
135.
Summary The efficiency of packed columns was measured as a function of flow rate, temperature, outlet density, and the density differential across the column, unsing pure carbon dioxide as the mobile phase. Although density differentials are often blamed for a serious loss in efficiency in packed column supercritical fluid chromatography, the results show that efficiency was not a function of the density differential. Peak shapes suggest that apparent loss in efficiency is actually due to inadequate solubility of the solute in carbon dioxide. 相似文献
136.
A. J. Berry D. E. Games I. C. Mylchreest J. R. Perkins S. Pleasance 《Journal of separation science》1988,11(1):61-64
A frit restrictor interface for capillary column supercritical fluid chromatography/mass spectrometry (SFC/MS) has been constructed and used for the analysis of high boiling point alkanes. Packed column SFC/MS is described using both a moving belt liquid chromatographic/mass spectrometric interface and a thermospray source in the filament-on mode. 相似文献
137.
KANG Qiao-xiang YANG Zhi-wang LI Cui-lin MA Heng-chang GUO Zhen WANG You-peng XU Da-hai LEI Zi-qiang 《合成化学》2004,12(Z1)
Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results. 相似文献
138.
Peter Hald Martin Bremholm Jacques Chevallier Bo B. Iversen 《Journal of solid state chemistry》2006,179(8):2674-2680
Highly crystalline anatase TiO2 nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials. 相似文献
139.
L. H. Johnston S. R. Raju G. R. Sudhakaran R. M. Lees 《International Journal of Infrared and Millimeter Waves》1982,3(4):517-527
Laser-Stark spectra have been observed for methyl alcohol using the 311 m line of the HCN laser. Partial assignments are presented for the three most distinctive structures in the spectra. The low field structure is clearly associated with a member of the J=2019qRa-type multiplet, and is tentatively identified as the k=13 A vt=0 transition. The other two structures originate from the 9382 E vt=0 transition, and from a member of the k= 65 A vt=1 Q branch, tentatively assigned as the J=32 member. 相似文献
140.
Luiz A. F. Coelho Jos V. Oliveira Saul G. D'vila Janete H. Y. Vilegas Fernando M. Lanas 《Journal of separation science》1997,20(8):431-436
The effects of temperature and solvent density on the characteristics of the extracts obtained from supercritical fluid extraction (SFE) of the volatile compounds from Brazilian rosemary (Rosamarinus officianalis L., Labiatae) using carbon dioxide (CO2) as solvent were investigated. The experiments were performed in a semi-batch laboratory scale home-made unit at two temperatures, viz. 310.15 and 320.15 K, over the pressure range of 100-160 bar. This study allowed to determine the crossover point and the maximum solubility of the oil. The products were analyzed by HRGC-MS, and compounds grouped in three different classes according to their molecular mass distribution in order to evaluate the influence of the variables studied on the characteristics of the extracts. The model proposed by Sovová was adopted in an attempt to interpret the mass transfer phenomena in the extraction process. 相似文献