全文获取类型
收费全文 | 2438篇 |
免费 | 79篇 |
国内免费 | 274篇 |
专业分类
化学 | 2186篇 |
晶体学 | 16篇 |
力学 | 8篇 |
数学 | 6篇 |
物理学 | 575篇 |
出版年
2024年 | 2篇 |
2023年 | 29篇 |
2022年 | 43篇 |
2021年 | 48篇 |
2020年 | 61篇 |
2019年 | 64篇 |
2018年 | 39篇 |
2017年 | 78篇 |
2016年 | 83篇 |
2015年 | 86篇 |
2014年 | 117篇 |
2013年 | 120篇 |
2012年 | 174篇 |
2011年 | 189篇 |
2010年 | 158篇 |
2009年 | 192篇 |
2008年 | 165篇 |
2007年 | 188篇 |
2006年 | 153篇 |
2005年 | 123篇 |
2004年 | 113篇 |
2003年 | 91篇 |
2002年 | 65篇 |
2001年 | 59篇 |
2000年 | 48篇 |
1999年 | 44篇 |
1998年 | 45篇 |
1997年 | 29篇 |
1996年 | 33篇 |
1995年 | 31篇 |
1994年 | 24篇 |
1993年 | 20篇 |
1992年 | 19篇 |
1991年 | 18篇 |
1990年 | 14篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
排序方式: 共有2791条查询结果,搜索用时 570 毫秒
51.
The relativistic ground and low-lying excited state potential energy curves of AgH and AuH in the presence of a cylindrical
harmonic confining potential were calculated using the multi-state multi-reference perturbation theory with the spin-free
no-pair Hamiltonian obtained via the third-order Douglas–Kroll transformation, incorporated with the full two-electron Breit–Pauli
spin–orbit operator. The spectroscopic parameters were obtained for both the scalar- and quasi-relativistic potentials. The
spin–orbit coupling constants were calculated for several strengths of the confining potential, and the effects of the applied
potential on the coupling constants were analyzed using configuration interaction.
This paper is dedicated to Serafín Fraga—colleague, mentor, and friend. 相似文献
52.
Tarek A.?SalamaEmail author Bernd?Lackner Heinz?Falk 《Monatshefte für Chemie / Chemical Monthly》2003,134(8):1113-1119
Summary. An efficient synthesis of tri-O-methylemodin aldehyde was achieved via bromination of tri-O-methylemodin utilizing N-bromosuccinimide yielding the monobromo and dibromo derivatives. Sommelet reaction of the monobromomethyl derivative as well as hydrolysis of the dibromomethyl analog with aqueous silver nitrate afforded the protected aldehyde in good yield. Accordingly, both bromo derivatives can be used even when they are obtained as a mixture of the bromination reaction, which could not be controlled easily to yield the bromo products selectively. From the aldehyde the tri-O-methylemodin nitrile was prepared in a one-pot reaction using hydroxylamine-O-sulfonic acid.Received February 18, 2003; accepted March 3, 2003
Published online June 2, 2003 相似文献
53.
Jiaming L Wenqi L Xuelin L Hailing C Qiaomei L Longdi L Zhimin L Guohui Z Cuilian C 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):3077-3081
Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed. 相似文献
54.
Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids 总被引:1,自引:0,他引:1
Thompson RQ Phinney KW Sander LC Welch MJ 《Analytical and bioanalytical chemistry》2005,381(7):1432-1440
An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C8, C18, C30, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC–ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate–methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl–cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids. 相似文献
55.
《Electroanalysis》2003,15(17):1369-1376
Silver‐gold alloy electrodes have been studied for the purpose of the quantitative determination of heavy metals by subtractive anodic stripping voltammetry, (SASV). The results have been compared with those obtained with the silver and gold electrodes. The 50/50 a/o Ag/Au alloy electrode is the most suitable for quantifying thallium in the presence of lead and cadmium. The separation of its peak from those of lead and cadmium is 200 mV, which is about twice the separation obtained on the pure metal electrodes and is also better than on mercury. The silver electrode is suitable for the simultaneous determination of thallium, lead and cadmium. The peaks of lead and cadmium overlap on the 50/50 alloy. Pure silver or pure gold can be used for simultaneous quantification of these two metals. The use of gold for quantifying lead and cadmium is more limited because the peak potential of cadmium is shifted in the negative direction as its concentration increases and at [Cd2+]>200 nM, the two peaks merge. SASV enables correction for background currents and is of utmost importance for obtaining well‐defined peaks. The peaks of lead, cadmium and thallium appear over a relatively narrow potential range (ca. 200 mV) on all the electrodes presented in this work. For this reason, the quantifying of a peak is based on the derivative at the inflection point of only one of its branches (ascending or descending). All SASV measurements were carried out without removal of oxygen. 相似文献
56.
57.
On the Oxoargentato(I)-aurat(III): Ba4AgAuO6 The hitherto unknown compound Ba4AgAuO6 was prepared by oxidizing Ba/Au/Ag alloy with BaO2/Ba(OH)2 mixture in closed Ag tubes. X-ray single crystal investigation led to orthorhombic symmetry space group D-Cmcm; a = 13.275; b = 5.782; c = 11.396 Å; Z = 4. Ba4AgAuO6 shows distorted pentagonal bipyramidal polyhedra around Ba2+ and square planar AuO4 polygones. Ag+ shows an unusual 2 + 2 coordination by O2?. 相似文献
58.
Hui‐Bo Zhou Wen Dong Mao Liang Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Peng Cheng 《无机化学与普通化学杂志》2004,630(4):498-500
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2]— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2]— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer. 相似文献
59.
Drochioiu G 《Talanta》2002,56(6):1163-1165
A very simple, accurate, fast, selective and sensitive assay of cyanide based on its reaction with 2,2-dihydroxy-l,3-indanedione at basic pH is proposed. As little as 0.01 μg ml−1 of cyanide can be determined. The molar absorptivity may reach 5.1–8.0×104 l mol−1 cm−1 depending on the reaction conditions. Thus, 1 ml of sample solution is mixed with 500 μl of 5 mg ml−1 solution of 2,2-dihydroxy-1,3-indanedione monohydrate in 2% sodium carbonate. The absorbance of the purple color is measured at 510 nm in 1-cm glass cuvettes, 10–15 min after mixing the reagents. The procedure could also be used to identify free CN− in natural waters and hydrocyanic acid in the environment. 相似文献
60.
Silver(I)‐Selective PVC Membrane Potentiometric Sensor Based on a Recently Synthesized Calix[4]arene
《Electroanalysis》2006,18(10):1019-1027
A new PVC membrane potentiometric sensor for Ag(I) ion based on a recently synthesized calix[4]arene compound of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dihydroxy‐calix[4]arene‐thiacrown‐4 is developed. The electrode exhibits a Nernstian response for Ag(I) ions over a wide concentration range (1.0×10?2?1.0×10?6 M) with a slope of 53.8±1.6 mV per decade. It has a relatively fast response time (5–10 s) and can be used for at least 2 months without any considerable divergence in potentials. The proposed electrode shows high selectivity towards Ag+ ions over Pb2+, Cd2+, Co2+, Zn2+, Cu2+, Ni2+, Sr2+, Mg2+, Ca2+, Li+, K+, Na+, NH4+ ions and can be used in a pH range of 2–6. Only interference of Hg2+ is found. It is successfully used as an indicator electrode in potentiometric titration of a mixture of chloride, bromide and iodide ions. 相似文献