全文获取类型
收费全文 | 12398篇 |
免费 | 2086篇 |
国内免费 | 2440篇 |
专业分类
化学 | 10238篇 |
晶体学 | 254篇 |
力学 | 637篇 |
综合类 | 144篇 |
数学 | 1162篇 |
物理学 | 4489篇 |
出版年
2024年 | 56篇 |
2023年 | 286篇 |
2022年 | 541篇 |
2021年 | 574篇 |
2020年 | 594篇 |
2019年 | 659篇 |
2018年 | 538篇 |
2017年 | 538篇 |
2016年 | 632篇 |
2015年 | 664篇 |
2014年 | 796篇 |
2013年 | 987篇 |
2012年 | 1069篇 |
2011年 | 1064篇 |
2010年 | 874篇 |
2009年 | 791篇 |
2008年 | 817篇 |
2007年 | 675篇 |
2006年 | 686篇 |
2005年 | 643篇 |
2004年 | 541篇 |
2003年 | 458篇 |
2002年 | 489篇 |
2001年 | 455篇 |
2000年 | 305篇 |
1999年 | 241篇 |
1998年 | 156篇 |
1997年 | 97篇 |
1996年 | 123篇 |
1995年 | 85篇 |
1994年 | 95篇 |
1993年 | 86篇 |
1992年 | 59篇 |
1991年 | 70篇 |
1990年 | 41篇 |
1989年 | 31篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1986年 | 21篇 |
1985年 | 16篇 |
1984年 | 7篇 |
1983年 | 10篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1971年 | 1篇 |
1959年 | 3篇 |
1957年 | 1篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
161.
YingXinLIU ZuoJunWEI JiXiangCHEN JiYanZHANG XinXueLI XiongHuiWEI 《中国化学快报》2005,16(4):531-533
A novel lanthana-promoted nickel catalyst supported on silica for the liquid phase hydrogenation of m-dinitrobenzene to m-phenylenediamine was prepared by an incipient wetness sequential impregnation method. It was found that Ni-La/SiO2 catalyst exhibited high activity and stability for m-dinitrobenzene hydrogenation. Over this catalyst, the conversion of m-dinitrobenzene and the yield of m-phenylenediamine were up to 97.1% and 93.5%, respectively,at 373 K and 2.6 MPa hydrogen pressure after reaction for 1 h. 相似文献
162.
Petrassi HM Johnson SM Purkey HE Chiang KP Walkup T Jiang X Powers ET Kelly JW 《Journal of the American Chemical Society》2005,127(18):6662-6671
Transthyretin (TTR) amyloidogenesis requires rate-limiting tetramer dissociation and partial monomer denaturation to produce a misassembly competent species. This process has been followed by turbidity to identify transthyretin amyloidogenesis inhibitors including dibenzofuran-4,6-dicarboxylic acid (1). An X-ray cocrystal structure of TTR.1(2) reveals that it only utilizes the outer portion of the two thyroxine binding pockets to bind to and inhibit TTR amyloidogenesis. Herein, structure-based design was employed to append aryl substituents at C1 of the dibenzofuran ring to complement the unused inner portion of the thyroxine binding pockets. Twenty-eight amyloidogenesis inhibitors of increased potency and dramatically increased plasma TTR binding selectivity resulted. These function by imposing kinetic stabilization on the native tetrameric structure of TTR, creating a barrier that is insurmountable under physiological conditions. Since kinetic stabilization of the TTR native state by interallelic trans suppression is known to ameliorate disease, there is reason to be optimistic that the dibenzofuran-based inhibitors will do the same. Preventing the onset of amyloidogenesis is the most conservative strategy to intervene clinically, as it remains unclear which of the TTR misassembly intermediates results in toxicity. The exceptional binding selectivity enables these inhibitors to occupy the thyroxine binding site(s) in a complex biological fluid such as blood plasma, required for inhibition of amyloidogenesis in humans. It is now established that the dibenzofuran-based amyloidogenesis inhibitors have high selectivity, affinity, and efficacy and are thus excellent candidates for further pharmacologic evaluation. 相似文献
163.
Wang BB Zhang X Jia XR Li ZC Ji Y Yang L Wei Y 《Journal of the American Chemical Society》2004,126(46):15180-15194
PAMAM dendrimers of the zeroth to fifth generation (G0-5) have been peripherally modified with phenyl, naphthyl, pyrenyl, and dansyl chromophores. Their fluorescence behaviors are strongly affected by the dendritic architectures at different generations. These dendrimers modified with hydrophobic chromphores can self-organize into vesicular aggregates at the low generations G0-3 in water. The size and aggregation number of these vesicles decrease with increasing generation from G0 to G3. Critical aggregation concentration determined by fluorescence spectroscopy reveals that these aggregates can be favorably formed in the order of G3 > G2 > G1. In contrast to the vesicles made from traditional amphiphilic compounds, these dendrimer-based vesicles are very adhesive due to the H-bonding interaction and entanglement of dendritic branches located in the outer layer. A large number of multivesicle assemblies, i.e., "twins" and "quins" consisting of two and five vesicles, were clearly identifiable with transmission electron (TEM) and atomic force microscopy. For the dendrimers with peripheral pyrenyl chromophores, triangle-like vesicles were observed in water. The hydrophobic interphase thickness of the vesicular bilayer is ca. 2.0-3.2 nm determined by fluorescence resonance energy transfer methods, which agrees well with the thickness directly observed with TEM. 相似文献
164.
[structure: see text] The viability of the Diels-Alder (DA) cycloaddition of conjugated dienes onto the sidewalls of single-wall carbon nanotubes is assessed by means of a two-layered ONIOM(B3LYP/6-31G:AM1) approach. Whereas the DA reaction of 1,3-butadiene on the sidewall of an armchair (5,5) nanotube is found to be unfavorable, the cycloaddition of quinodimethane is predicted to be viable due to the aromaticity stabilization at the corresponding transition states and products. 相似文献
165.
Xi Chen Changqing YiMeijin Li Xin LuZhen Li Peiwei LiXiaoru Wang 《Analytica chimica acta》2002,466(1):79-86
Electrogenerated chemiluminescences (ECLs) based on tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)32+) and lupin alkaloids, for instance, sophoridine (SRI), matrine (MT), sophoranol (SR) and sophocarpine (SC) in an aqueous alkaline buffer solution (pH 9.0) are studied. The light emission is mainly caused by an electro-oxidation reaction between tertiary amino group on the alkaloid compounds and Ru(bpy)32+ in a thin layer flow cell equipped with a glassy carbon disc electrode (22.1 mm2) at the potential of +1.50 V (versus Ag/AgCl). The luminescence wavelength of 610 nm confirmed that ECL is caused by Ru(bpy)32+∗ to its ground state. ECL intensities of these lupin alkaloids are affected by the substituent character, three-dimensional conformation of hydrogen on β-carbon atom. Ionization potentials taken from calculation data further confirm the experimental results. In addition, the factors affecting the determination and HPLC separation of the four alkaloids are also investigated. 相似文献
166.
Effects of simultaneously doped and deposited Ag on the photocatalytic activity and surface states of TiO2 总被引:8,自引:0,他引:8
Ag-TiO2 catalysts with different Ag contents were prepared via a sol-gel method in the absence of light. Based on the characterizations of XRD, photoluminescence (PL), surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and XPS as well as the evaluation of the photocatalytic activity for degrading rhodamine B(RhB) solutions, it was found that the Ag dopant promoted the phase transformation as well as had an inhibition effect on the growth of anatase crystallite. The PL and SPS intensities were decreased with increasing Ag content, indicating that the Ag dopant could effectively inhibit the recombination of the photoinduced electrons and holes. However, the active sites capturing the photoinduced electrons reduced, while the Ag content exceeded 5 mol %. At rather low Ag dopant concentrations, the migration and diffusion of Ag+ ions were predominant, while at rather high Ag dopant concentrations, the migration, diffusion, and reduction of Ag ions simultaneously occurred. The Ag-TiO2 photocatalysts with appropriate content of Ag (Ag species concentration is from about 3 to 5 mol %) possessed abundant electron traps so as to be favorable for the separation of the photoinduced electron-hole pairs, which could greatly enhance the activity of the photocatalysts. From the results of FISPS measurements, it could be found that the impurity bands and abundant surface states were introduced into the interfacial layer of TiO2 because of Ag simultaneously doping and depositing, which could improve the absorption capability for visible light of the photocatalysts. 相似文献
167.
The hydrogen donation kinetics of four 3-aryl-benzofuranones with different chemical structures toward tert-butoxyl radicals were studied using laser flash photolysis (LFP) technique. The rate constants of hydrogen reactions, which can be used to evaluate the hydrogen donating abilities of 3-aryl-benzofuranones toward radicals, were obtained. The results showed that the position of substituted methyl group has a very important effect on the hydrogen donating ability of benzofuranone toward tert-butoxyl radicals, i.e. if the methyl group is on 2′-position, the hydrogen donation of 3-aryl-benzofuranone toward tert-butoxyl radicals will be prevented and the hydrogen donating ability will be weakened. 相似文献
168.
A new phenyltin tungstosilicate derivative, [(PhSnOH(2))(2)(gamma-SiW(10)O(36))(2)](10)(-) (1), has been prepared by reaction of phenyltin trichloride with K(8)[gamma-SiW(10)O(36)].xH(2)O. The new heteropolyanion was characterized by elemental analysis, infrared spectroscopy, multinuclear NMR, and X-ray crystallography. The crystals of Cs(9)H[(PhSnOH(2))(2)(gamma-SiW(10)O(36))(2)].16H(2)O (Cs salt of 1) are triclinic, space group P&onemacr;, with lattice constants a = 12.401(3) ?, b = 13.832(3) ?, c = 16.313(3) ?, alpha = 96.17(2) degrees, beta = 109.73(2) degrees, gamma = 97.13(2) degrees, V = 2579.9(10) ?, and Z = 1. Anion 1 has a structure of virtual C(2)(h)() symmetry with two phenyltin groups sandwiched between two gamma-SiW(10) groups. Such a structure is different from all previously reported polytungstates derived from [gamma-SiW(10)O(36)](8)(-) lacunary anions. 相似文献
169.
170.
Hydrogenation of methyl p-hydroxyphenylacetate has been used for the synthesis of p-hydroxyphenyl ethanol. The reaction was catalyzed by CuiZrj-x%(mass fraction) carbon nanotubes(CNTs) catalysts. Incorporation of a minor amount of CNTs into CuiZrj oxide can visibly increase the catalytic activity for the synthesis of p-hydroxyphenyl ethanol. The yield of p-hydroxyphenyl ethanol reaches 94.2% over a co-precipitated catalyst of Cu3Zr1 oxide with 11.0%CNTs. Its catalytic activity shows no obvious decrease after three cycles. This is much better than the CNT-free co-precipitated catalyst with a good yield of 81.1%, Cu3Zr1-0%CNTs. 相似文献