全文获取类型
收费全文 | 68414篇 |
免费 | 4305篇 |
国内免费 | 8538篇 |
专业分类
化学 | 56822篇 |
晶体学 | 529篇 |
力学 | 912篇 |
综合类 | 906篇 |
数学 | 8063篇 |
物理学 | 14025篇 |
出版年
2024年 | 102篇 |
2023年 | 858篇 |
2022年 | 1271篇 |
2021年 | 2298篇 |
2020年 | 1598篇 |
2019年 | 1782篇 |
2018年 | 1402篇 |
2017年 | 1616篇 |
2016年 | 2046篇 |
2015年 | 1987篇 |
2014年 | 2428篇 |
2013年 | 4856篇 |
2012年 | 3578篇 |
2011年 | 3379篇 |
2010年 | 2994篇 |
2009年 | 3877篇 |
2008年 | 4078篇 |
2007年 | 4425篇 |
2006年 | 3772篇 |
2005年 | 3006篇 |
2004年 | 2814篇 |
2003年 | 2586篇 |
2002年 | 4789篇 |
2001年 | 2253篇 |
2000年 | 1804篇 |
1999年 | 1529篇 |
1998年 | 1370篇 |
1997年 | 1133篇 |
1996年 | 1149篇 |
1995年 | 1007篇 |
1994年 | 941篇 |
1993年 | 858篇 |
1992年 | 882篇 |
1991年 | 620篇 |
1990年 | 509篇 |
1989年 | 485篇 |
1988年 | 430篇 |
1987年 | 308篇 |
1986年 | 294篇 |
1985年 | 403篇 |
1984年 | 300篇 |
1983年 | 195篇 |
1982年 | 356篇 |
1981年 | 517篇 |
1980年 | 461篇 |
1979年 | 498篇 |
1978年 | 394篇 |
1977年 | 297篇 |
1976年 | 262篇 |
1973年 | 172篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
载银磷酸活化剑麻基活性炭纤维的抗菌性能研究 总被引:5,自引:0,他引:5
本文利用磷酸化方法,制备各种剑麻基活性炭纤维,并利用活性炭纤维的氧化还原特性及吸附性能,在其上负载金属银,研究并比较了这些载银活性炭纤维对大肠杆菌和金黄色葡萄球菌的杀灭作用,结果表明,磷酸浓度,活化方法,活化时间,纤维的比表面积等因素的均对材料的抗菌性能有一定的影响,磷酸活化的活性炭纤维表现出强的抗菌杀菌能力,高浓度磷酸活化后的纤维抗菌能力有所提高,并且抗菌能力随活化时间的延长而增加,抗菌前后纤维上负载的银未曾大量脱落,经5次抗菌试验后材料仍显示出很强的抗菌能力。 相似文献
992.
K. Grob 《Journal of separation science》1978,1(5):263-267
During one year continuous use of on-column injection, the typical advantages described in our first report have fully been confirmed. In addition the analysis of large sample volumes has proved promising. Only minor modifications have been applied to the on-column injector device. Broad evidence has been gathered showing that full separation efficiency of the capillary columns after on-column injection is attained only when cold trapping or the solvent effect, as band shortening mechanisms, are working- While, under the conditions of on-column injection, cold trapping is less efficient than with other injection techniques, the opposite holds true for the solvent effect. Compared with splitless injection, the danger of excessive solvent condensation on the column is increased. A working rule is presented for establishing the optimal chromatographic conditions for handling large sample volumes while ensuring full separation efficiency yet avoiding harm to the column. 相似文献
993.
W. Kunz J. Barthel L. Klein T. Cartailler P. Turq B. Reindl 《Journal of solution chemistry》1991,20(9):875-891
A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere. 相似文献
994.
土壤胡敏酸的^13C核磁共振研究 总被引:1,自引:0,他引:1
胡敏酸(HA)是土壤有机质的重要组分,其结构性质与土壤形成和肥力特性有密切关系,长期以来一直是土壤化学研究的难点和重点之一。NMR是研究HA结构的有效手段。自Bar-ton和Schnitzer(1963)首次用~1H NMR研究土壤有机质以来,国外已先后应用~1H、~(13)C NMR和CP-MAS-~(13)C NMR等对土壤及其它来源的HA进行了许多研究,并取得引人注目的进展。但在国内,这方面研究还刚刚开始。本文应用~(13)C NMR方法对东北几种主要耕作土壤以及泥炭和猪粪的HA进行了结构表征,为土壤腐殖酸化学的基础研究提供了资料。 相似文献
995.
The interaction of aryldiazonium ions with some Schiff-base complexes of cobalt and ruthenium have been studied. With cobalt, one-electron oxidation of [Co(II)Salen] occurred; with [Co(I)Salen] the corresponding Co(III)-aryl complexes were isolated. In the case of ruthenium oxidation also occurs, [Ru(Salen)(CO)py] gave the corresponding monocation. The results, especially for ruthenium, are in contrast to the stabilisation of both nitrosyl and aryldiazonium adducts in analogous porphyrin complexes. 相似文献
996.
Halina Y. Neujahr 《Applied biochemistry and biotechnology》1982,7(1-2):107-111
The enzyme phenol 2-hydroxylase was immobilized on Sepharose and used in conjunction with an O2 electrode for quantitating phenol. Similarly, catechol 1,2-oxygenase was used for quantitating catechol. A third probe was
prepared by immobilization ofTrichosporon cutaneum cells rather than purified phenol 2-hydroxylase for phenol quantitation. The whole cell system gave results comparable to
the immobilized enzyme system. 相似文献
997.
A comparison of different nebulisers for direct hyphenation of capillary and nano liquid chromatography (Cap-LC, Nano-LC) and quadrupole-based collision cell inductively coupled plasma mass spectrometry (CC-ICP–MS) for phosphorylation profiling of tryptic protein digests is described. Helium was used as cell gas and specially tuned instrumental conditions were used to achieve background minimisation at the mass of phosphorus, because of kinetic energy discrimination of the interfering polyatomic ions. The proposed set-up is based on a modified capillary electrophoresis interface and a home-made 4 mL spray chamber. It enables the use of gradient conditions with a highly concentrated organic mobile phase as often used in protein phosphorylation analysis, without the need to apply membrane desolvation for removal of the organic phase or further background minimisation. No significant signal suppression or other negative effects caused by the organic mobile phase occur, because of the low flow rates used in Cap-LC and the robust plasma conditions of the CC-ICP–MS instrument. A tryptic digest of beta-casein was investigated as model compound to demonstrate the applicability of the proposed set-up for phosphorylation profiling in protein analysis using quadrupole based collision-cell ICP–MS as phosphorus-specific detector. Detection limits for phosphorylated peptides down to the sub picomole level were obtained. As a complementary technique, electrospray ionisation tandem mass spectrometry (ESI–MS–MS) with data base searching was used for further characterisation of the phosphorylated peptides detected. 相似文献
998.
Barbara Dogan Hans-Dieter Beckhaus Hermann Birkhofer Christoph Rüchardt 《欧洲无机化学杂志》1990,123(6):1365-1368
Effects of Substituents on the Strength of C - C Bonds, 81. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol -1, s. d. in parentheses) ΔH°c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔHv = 14.3 (± 0.3) and the heat of sublimation of 2 ΔHsub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (s) of 15.9 and 8.0 kcal mol-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group. 相似文献
999.
A systematic extension of Ruedenberg's expansion formula is applied to evaluate two-electron integrals occurring in calculations on molecular structure. Minimum STO basis sets are used for all SCF-calculations within the framework of the MEDO-method (Multipole Expansion of Diatomic Overlap). The errors due to this approximation scheme are almost negligible compared to those introduced by the truncated basis set: LiH, Li2 and N2 are chosen as examples. 相似文献
1000.
The exchange part of the usual Hartree-Fock potential in the unrestricted Hartree-Fock (UHF) theory is suitablyaveraged to construct an, average one-electron model Hamiltonian which generates a set of spin-restricted one-electron orbitals in
a self-consistent manner. These orbitals are then used to calculate the electronic energy of the open-shell system by using
the proper functional form for the energy which handles the exchange terms correctly. The eigenvalues ofF
av can be used for calculating either the spin-polarised or spin-averaged ionisation potentials of different orbitals at theKoopmans’ theorem level of approximation. Comparison ofE
ac with the UHF-energy shows thatE
UHF<E
ac in each case revealing some kind of an upper bound nature ofE
ac. An approximate variational argument is given. Relationship of our model with the hyper-Hartree-Fock theory of slater is
explored and the general problem of eliminating ‘self-interaction’ terms in average Fock-operator based theories is discussed. 相似文献