全文获取类型
收费全文 | 3358篇 |
免费 | 559篇 |
国内免费 | 351篇 |
专业分类
化学 | 2527篇 |
晶体学 | 41篇 |
力学 | 133篇 |
综合类 | 3篇 |
数学 | 339篇 |
物理学 | 1225篇 |
出版年
2024年 | 6篇 |
2023年 | 67篇 |
2022年 | 110篇 |
2021年 | 145篇 |
2020年 | 141篇 |
2019年 | 127篇 |
2018年 | 114篇 |
2017年 | 105篇 |
2016年 | 159篇 |
2015年 | 175篇 |
2014年 | 190篇 |
2013年 | 273篇 |
2012年 | 346篇 |
2011年 | 334篇 |
2010年 | 195篇 |
2009年 | 234篇 |
2008年 | 191篇 |
2007年 | 203篇 |
2006年 | 184篇 |
2005年 | 126篇 |
2004年 | 122篇 |
2003年 | 84篇 |
2002年 | 75篇 |
2001年 | 47篇 |
2000年 | 57篇 |
1999年 | 67篇 |
1998年 | 46篇 |
1997年 | 37篇 |
1996年 | 58篇 |
1995年 | 24篇 |
1994年 | 28篇 |
1993年 | 29篇 |
1992年 | 25篇 |
1991年 | 18篇 |
1990年 | 21篇 |
1989年 | 22篇 |
1988年 | 13篇 |
1987年 | 19篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有4268条查询结果,搜索用时 15 毫秒
91.
When trypsin reacts with Herring sperm DNA (hsDNA), Salmon sperm DNA (sDNA), and Calf thymus DNA (ctDNA) to form a complex,
the resonance Rayleigh scattering (RRS) was remarkably enhanced and new RRS spectra appear. These new spectra have similar
characteristics of RRS spectra. The maximum RRS peaks are at 307 nm (hsDNA, sDNA) and 290 nm (ctDNA), and other peaks are
at 350 nm. The scattering intensity is proportional to the concentration of DNA or trypsin; so this intereaction can be used
to determine trypsin using DNA or DNA using trypsin. In the determination of DNA using trypsin, the linear ranges for hsDNA,
sDNA, and ctDNA are 0–2.3, 0–2.5, and 0–1.9 μg·mL−1, and the detection limits are 0.4, 0.7, and 1.1 ng·mL−1, respectively. In the determination of trypsin using hsDNA, the linear range is 0–30.0 μg·mL−1, and the detection limit is 39.0 ng·mL−1. In this paper, the intereaction conditions were optimized. The affecting factors, chemical properties of the complex, and
the composition ratio of trypsin with DNA were investigated. Using trypsin as RRS probe, a sensitive method for the determination
of trace amounts of DNA was developed.
Translated from Chemical Journal of Chinese Universities, 2006, 27(3) (in Chinese) 相似文献
92.
Yan-Ping Yuan De-Yuan Kong Abraham Clearfield 《Journal of solid state chemistry》2005,178(6):2030-2035
The first organically templated 3d-4f mixed metal sulfates, [H2en]2{La2M(SO4)6(H2O)2} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediamine cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions). 相似文献
93.
The establishment of bioorthogonal chemistry is one of the most significant advances in chemical biology using exogenous chemistry to perturb and study biological processes. Photo-modulation of biological systems has realized temporal and spatial control on biomacromolecules in living systems. The combination of photo-modulation and bioorthogonal chemistry is therefore emerging as a new direction to develop new chemical biological tools with spatiotemporal resolution. This minireview will focus on recent development of bioorthogonal chemistry subject to spatiotemporal control through photo-irradiation. Different strategies to realize photo-control on bioorthogonal bond-forming reactions and biological applications of photo-controllable bioorthogonal reactions will be summarized to give a perspective on how the innovations on photo-chemistry can contribute to the development of optochemical biology. Future trends to develop more optochemical tools based on novel photochemistry will also be discussed to envision the development of chemistry-oriented optochemical biology.The establishment of photo-controllable bioorthogonal chemistry is one of the most significant advances in chemical biology to perturb and study biological processes. 相似文献
94.
纳秒强激光场中苯电离产生高价离子的研究 总被引:2,自引:0,他引:2
用25 ns脉冲Nd-YAG 532 nm的激光,在1010~1011 W•cm-2的光场强度下,利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时,除观察到C2+、C2H2+、C3H3+、C6H6+离子外,还观察到很强的Cq+(q=1~3)高价离子.这些离子都有很高的平动能, C2+的最可几平动能为12.9 eV, C3+为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验,可以认为这些高价离子来源于含苯团簇的库仑爆炸过程. 相似文献
95.
The syntheses of macrocyclic species composed of carborane derivatives joined via their carbon vertices by electrophilic mercury atoms are described. The reaction of closo-1,2-Li(2)[C(2)B(10)H(10)(-)(x)()R(x)()] with HgI(2) gives Li(2)[(1,2-C(2)B(10)H(10)(-)(x)()R(x)()Hg)(4)I(2)] [R = Et, x = 2 (5.I(2)Li(2)); R = Me, x = 2 (6.I(2)Li(2)); R = Me, x = 4 (7.I(2)Li(2))]. 6.I(2)(K.[18]dibenzocrown-6)(2) crystallizes in the monoclinic space group C2/m [a = 28.99(2) ?, b = 18.19(1) ?, c = 13.61(1) ?, beta = 113.74(2) degrees, V = 6568 ?(3), Z = 4, R = 0.060, R(w) = 0.070]; 7.I(2)(NBu(4))(2) crystallizes in the monoclinic space group P2(1)/c [a = 12.77(1) ?, b = 21.12(2) ?, c = 20.96(2) ?, beta = 97.87(2) degrees, V = 5600 ?(3), Z = 2, R = 0.072, R(w) = 0.082]. The precursor to 7, closo-8,9,10,12-Me(4)-1,2-C(2)B(10)H(8) (4), is made in a single step by reaction of closo-1,2-C(2)B(10)H(12) with MeI in trifluoromethanesulfonic acid. The free hosts 5, 6, and 7 are obtained by reaction of the iodide complexes with stoichiometric quantities of AgOAc. A (199)Hg NMR study indicates that sequential removal of iodide from 5.I(2)Li(2) and 6.I(2)Li(2) with aliquots of AgOAc solution leads to formation of two intermediate host-guest complexes in solution, presumed to be 5(6)ILi and 5(2)(6)(2).ILi. Crystals grown from a solution of 6.I(2)Li(2) to which 1 equiv of AgOAc solution had been added proved to be an unusual stack structure with the formula 6(3).I(4)Li(4) [tetragonal, I4/m, a = 21.589(2) ?, c = 21.666(2) ?, V = 10098 ?(3), Z = 2, R = 0.058, R(w) = 0.084]. Addition of 2 equiv of NBu(4)Br ion to 5 or 6 gives 5.Br(2)(NBu(4))(2) and 6.Br(2)(NBu(4))(2), respectively, while addition of 1 equiv of KBr to 6 forms 6.BrK. 5.Br(2)(NBu(4))(2) crystallizes in the triclinic space group P&onemacr;, [a = 10.433(1) ?, b = 13.013(1) ?, c = 15.867(2) ?, alpha = 91.638(2) degrees, beta = 97.186(3) degrees, gamma = 114.202(2) degrees, V = 1492 ?(3), Z = 1, R = 0.078, R(w) = 0.104]. The hosts 5 and 6 form 1:1 supramolecular adducts with the polyhedral anions B(10)I(10)(2)(-) and B(12)I(12)(2)(-) in solution. 相似文献
96.
S. M. Fields R. C. Kong J. C. Fieldsted M. L. Lee P. A. Peaden 《Journal of separation science》1984,7(6):312-318
Fused silica capillary columns with internal diameters from 100 to 25 μm were coated with SE-54 and evaluated under supercritical fluid chromatographic conditions using carbon dioxide as mobile phase. Experimental results compared well with theoretical predictions. At ten times the optimum mobile phase velocity and for a capacity factor, k of 3, efficiencies of 2300 to 5600 plates m?1 were obtained for column diameters of 100 to 25 μm, respectively. 相似文献
97.
Josephine L. Y. Kong Kenneth G. Spears Paul A. Loach 《Photochemistry and photobiology》1982,35(4):545-553
Abstract— The fluorescence properties of a covalently-linked porphyrin-quinone complex and its zinc derivative were studied in a variety of organic solvents. The kinetics of fluorescence decay for both the quinone and hydroquinone oxidation states were measured in acetonitrile, dichloromethane, dimethyl-formamide, and pentane. The fluorescence yield and kinetics of decay at room temperature were little affected in the porphyrin or zinc porphyrin complexes when the attached quinone was reduced. However, for these complexes the fluorescence yield and lifetimes were both substantially decreased in acetonitrile and dichloromethane when the quinone was in its oxidized state. These latter decay kinetics were not explainable by a process having a single exponential decay. On the other hand, little fluorescence quenching or lifetime shortening was observed in dimethylformamide or pentane, indicating unique solvent dependencies for the quenching process. Evidence was obtained for photoproduced charge separation from EPR measurements on the covalently-linked zinc porphyrin-quinone complex. The EPR data showed equivalent concentrations of a Zn porphyrin cation radical and a benzoquinone anion radical in acetonitrile or dichloromethane at both room temperature and 77 K. The charge separated state rapidly decayed at room temperature (in sub-millisecond times) but was quite stable at 77 K. It is concluded that light-induced charge separation in acetonitrile and dichloromethane at room temperature may occur from the excited singlet state with a high quantum efficiency. A photoproduced charge separated state also occurred when the covalently-linked complexes were incorporated into egg yolk phosphatidylcholine liposomes. The quantum yield for radical formation in this latter system was 0.1 and the lifetimes of the radical species formed were many minutes. 相似文献
98.
Electrochemistry and in situ electrochemical scanning tunneling microscopy (STM) were used to study the blocking and structural properties of Shiff base V-ape-V self-assembled monolayers (SAMs) on the surface of Au(111) in perchloric acid solution. The complex-plane impedance plots for the SAM covered Au(111) electrodes, with the redox couple of Fe(CN)64–/3– present in solution, exhibit arc shapes, revealing that the electrochemical kinetics were controlled by the electron-transfer step. For bare Au(111), the electrode process was mass transport limited. The molecules adsorb on Au(111) with a flat-lying orientation and form a long-range well-defined adlayer. A new structure of
was observed in the double-layer potential region. A structural model is proposed to interpret the molecular registry with Au(111) substrate. 相似文献
99.
Biofingerprinting chromatogram analysis, which is defined as the comparison of fingerprinting chromatograms of the extract of traditional Chinese medicines (TCMs) before and after the interaction with biological systems (DNA, protein, cell, etc.), was proposed for screening and analysis of the multiple bioactive compounds in TCMs. A method of microdialysis sampling combined with high performance liquid chromatography (HPLC) was applied to the study of DNA-binding property for the extracts of TCMs. Seven compounds were found to bind to calf thymus DNA (ct-DNA) from the TCMs of Coptis chinensis Franch (Coptis), but only three ones from Phellodendron amurense Rupr. (Phellodendron) and none from Sophoraflavescens Ait. (Sophora) to bind to ct-DNA, respectively. Three of them were identified as berberine, palmatine and jatrorrhizine and their association constants (K) to ct-DNA were determined by microdialysis/HPLC. Competitive binding behaviors of them to ct-DNA were also investigated. 相似文献
100.