全文获取类型
收费全文 | 2725篇 |
免费 | 363篇 |
国内免费 | 497篇 |
专业分类
化学 | 1620篇 |
晶体学 | 36篇 |
力学 | 40篇 |
综合类 | 70篇 |
数学 | 777篇 |
物理学 | 1042篇 |
出版年
2024年 | 6篇 |
2023年 | 96篇 |
2022年 | 109篇 |
2021年 | 123篇 |
2020年 | 130篇 |
2019年 | 95篇 |
2018年 | 141篇 |
2017年 | 136篇 |
2016年 | 173篇 |
2015年 | 177篇 |
2014年 | 190篇 |
2013年 | 215篇 |
2012年 | 240篇 |
2011年 | 258篇 |
2010年 | 169篇 |
2009年 | 209篇 |
2008年 | 151篇 |
2007年 | 159篇 |
2006年 | 133篇 |
2005年 | 72篇 |
2004年 | 71篇 |
2003年 | 67篇 |
2002年 | 59篇 |
2001年 | 44篇 |
2000年 | 27篇 |
1999年 | 60篇 |
1998年 | 35篇 |
1997年 | 15篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 24篇 |
1987年 | 50篇 |
1986年 | 65篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1959年 | 5篇 |
1936年 | 3篇 |
排序方式: 共有3585条查询结果,搜索用时 31 毫秒
51.
A chemiluminescence method for the determination of folic acid by the sodium hypochlorite–folic acid–semicarbazide hydrochloride system with a new flow injection technique has been established. The new method can perform simple, sensitive and rapid determinations of folic acid. The response to the concentration of folic acid, in the range of 1.0×10−75.0×10−5 g/ml, is linear. The relative standard deviation of the method is 2.3% (Cs=4.0×10−6 g/ml, n=11). The detection limit is 2.7×10−8 g/ml. This method is suitable for automatic and continuous analysis, and has been successfully tested for the determination of folic acid in a folic acid tablet. 相似文献
52.
Andreas Rahm Evgeni M. Kaidashev Heidemarie Schmidt Mariana Diaconu Andreas Pöppl Rolf Böttcher Christoph Meinecke Tilman Butz Michael Lorenz Marius Grundmann 《Mikrochimica acta》2006,153(1-2):21-25
A flow injection chemiluminescence method is proposed for the determination of cobalt, based on the strong catalytic effect
of Cobalt(II) (1,10-phenanthroline)3 complex on the lucigenin-periodate reaction in alkaline medium. Under the optimum experimental conditions, the chemiluminescence
signal responded linearly to the concentration of cobalt(II) in the 1.0 × 10−9–3.0 × 10−7 g mL−1 range with a detection limit of 4.4 × 10−10 g mL−1 cobalt(II). The relative standard deviation for the determination of 5.0 × 10−8 g mL−1 of cobalt was 2.3% in eleven replicated measurements. The method was successfully applied to the determination of cobalt(II)
in pharmaceutical preparations. 相似文献
53.
By combining the layer-by-layer (LBL) self-assembly technique with the electrochemical polymerization method, multilayer Ni(II)-polyluminol
films were modified on the surface of a vaseline-impregnated graphite electrode. It was found that, compared with an electrode
modified by direct electrochemical polymerization, this modified electrode offered a suitable ECL reaction micro-environment
created by the special multilayer films, which was beneficial to the ephedrine hydrochloride enhancing effect for luminol
ECL intensity. The ECL enhancing effect of ephedrine hydrochloride on the electro-oxidation luminol was improved on this modified
electrode. Based on this finding, a new sensitive ECL method was developed for ephedrine hydrochloride determination under
the optimal conditions. At the same time, a new idea is proposed for improving the analytical performance of the luminol ECL
system by modifying the ECL reaction micro-environment with the layer-by-layer self- assembly method. Under the optimum experimental
conditions, the ephedrine hydrochloride concentration in the range of 2.0 × 10−8–7.0 × 10−6 mol L−1 was proportional to the enhanced ECL signal, and it offered an 8.0 × 10−9 mol L−1 detection limit for ephedrine hydrochloride. 相似文献
54.
Speciation of chromium by in-capillary reaction and capillary electrophoresis with chemiluminescence detection 总被引:3,自引:0,他引:3
A sensitive method for the simultaneous determination of chromium(III) (Cr3+) and chromium(VI) (CrO4(2-)) using in-capillary reaction, capillary electrophoresis (CE) separation and chemiluminescence (CL) detection was developed. The chemiluminescence reaction was based on luminol oxidation by hydrogen peroxide in basic aqueous solution catalyzed by Cr3+ ion followed by capillary electrophoresis separation. Based on in-capillary reduction, chromium(VI) can be reduced by acidic sodium hydrogensulfite to form chromium(III) while the sample is running through the capillary. Before the electrophoresis procedure, the sample (Cr3+ and CrO4(2-)), buffer and acidic sodium hydrogensulfite solution segments were injected in that order into the capillary, followed by application of an appropriate running voltage between both ends. As both chromium species have opposite charges, Cr3+ ions migrate to the cathode, while CrO4(2-) ions, moving in the opposite direction toward the anode, react with acidic sodium hydrogensulfite which results in the formation of Cr3+ ions. Because of the migration time difference of both Cr3+ ions, Cr(III) and Cr(VI) could be separated. The running buffer was composed of 0.02 mol l(-1) acetate buffer (pH 4.7) with 1 x 10(-3) mol l(-1) EDTA. Parameters affecting CE-CL separation and detection, such as reductant (sodium hydrogensulfite) concentration, mixing mode of the analytes with CL reagent, CL reaction reagent pH and concentration, were optimized. The limits of detection (LODs) of Cr(III) and Cr(VI) were 6 x 10(-13) and 8 x 10(-12) mol l(-1) (S/N=3), respectively. The mass LODs for Cr(III) and Cr(VI) were 1.2 x 10(-20) mol (12 zmol) and 3.8 x 10(-19) mol (380 zmol), respectively. 相似文献
55.
《Tetrahedron: Asymmetry》2006,17(1):79-91
Reductions of (1R,3R,4R)-3-([1,2,4]triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and their lactone analogues, prepared from (1R)-(+)-camphor, were studied. Catalytic hydrogenation selectively led to partial saturation of the [1,2,4]triazolo[4,3-x]azine residue, while in reactions with borane–methylsulfide coordination of borane to the 1-position of [1,2,4]triazolo[4,3-x]azine system took place. On the other hand, activation of the carbonyl group in (1R,3R,4R)-3-([1,2,4]triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones with boron trifluoride etherate followed by reaction with borane–methylsulfide furnished the corresponding isoborneols, stereoselectively. The structures of all representative compounds were confirmed by X-ray diffraction. 相似文献
56.
Ju‐You Lu Hong Wan Jianwei Zhang Zhixuan Wang Yang Li Yongmei Du Chunying Li Prof. Zhao‐Tie Liu Prof. Zhong‐Wen Liu Prof. Jian Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17542-17546
A palladium‐catalyzed direct C‐arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides. 相似文献
57.
Ho3+ doped TTB–BaTa2O6 phosphors were produced by the solid state reaction method. XRD analysis confirmed the formation of BaTa2O6 single phase which was accomplished by heat treatment at 1425 °C for 20 h. The crystal structure of TTB–BaTa2O6 allowed doping concentration of Ho3+ ions up to 10 mol%, maintaining a single phase composition. A second phase of HoTaO4 begins to appear at 15 mol%. The lattice structure and the crystallite sizes changed with the concentration of Ho3+. In SEM analysis, it was also shown that BaTa2O6 grain sizes changed with the concentration of Ho3+. EDS analysis revealed that the Ta/Ba ratio increased on the grains depending on Ho3+ concentration. Charge balance of the structure was formulated through the EDS results. In fluorometer analysis, a strong green emission (λem = 546.9 nm) was observed in the visible spectral region. The emission increased with the doping concentration of up to 2.5 mol%, and above this level decreased due to concentration quenching. 相似文献
58.
In this work, we focus on the time-domain simulation of the propagation of electromagnetic waves in non-homogeneous lossy coaxial cables. The full 3D Maxwell equations, that described the propagation of current and electric potential in such cables, are classically not tackled directly, but instead a 1D scalar model known as the telegraphist's model is used. We aim at justifying, by means of asymptotic analysis, a time-domain “homogenized” telegraphist's model. This model, which includes a nonlocal in time operator, is obtained via asymptotic analysis, for a lossy coaxial cable whose cross section is not homogeneous. 相似文献
59.
Shuangqi Pi Quansong Li Ling Yue Prof. Dr. Ya-Jun Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(18):5712-5720
A first-generation pair of chemiluminescent formaldehyde (FA) probes (CFAP540 and CFAP700) was reported recently. CFAP540 and CFAP700, with high selectivity and sensitivity to FA, are, respectively, suitable in cell and in vivo. Experimentalists have confirmed that both probes utilize a general 2-aza-Cope FA-reactive trigger and a chemiluminogenic phenoxydioxetane scaffold. The mechanism and detailed process of CFAP chemiluminescence (CL) remain largely unknown. In the present paper, (time-dependent) density functional theory calculations are performed on the entire reaction process of CFAP540 with FA to produce CL. The calculations elucidated the CL-producing process: FA initiates the decomposition of CFAP540 by dehydration condensation, and a phenoxy 1,2-dioxetane is formed through a series of reactions of aza-Cope rearrangement, hydrolysis of imine, and β-elimination of alkoxyl group. Afterwards, the produced phenoxy 1,2-dioxetane decomposes to produce the m-oxybenzoate derivative in the first singlet state (S1) via two crossings between potential energy surfaces of the ground state (S0) and S1 state. This m-oxybenzoate derivative was assigned as the light emitter of the CFAP540 CL. The CL-producing process and assignment of the light emitter of CFAP700 CL are similar with the corresponding ones of CFAP540. By analyzing the D-π-A architecture of the light emitters of CFAP540 and CFAP700, a series of CFAPs is theoretically designed and a scheme to modulate their CL from visible to near-infrared region is proposed by adjusting the length and structure of the π-bridge. 相似文献
60.
In this note, it is proved for n ≤ 5 that if Q is a finite quantale with |Q| ≥ n, then there are at least n subquantales of Q. However, the result does not hold when |Q| ≥ 6. Also, an example is given of a sequence of quantales of cardinality p + 2 for p prime, each of which have exactly 5 subquantales. 相似文献