全文获取类型
收费全文 | 9763篇 |
免费 | 640篇 |
国内免费 | 569篇 |
专业分类
化学 | 8925篇 |
晶体学 | 10篇 |
力学 | 111篇 |
综合类 | 92篇 |
数学 | 168篇 |
物理学 | 1666篇 |
出版年
2024年 | 11篇 |
2023年 | 126篇 |
2022年 | 449篇 |
2021年 | 324篇 |
2020年 | 283篇 |
2019年 | 302篇 |
2018年 | 294篇 |
2017年 | 436篇 |
2016年 | 510篇 |
2015年 | 451篇 |
2014年 | 465篇 |
2013年 | 646篇 |
2012年 | 722篇 |
2011年 | 654篇 |
2010年 | 534篇 |
2009年 | 609篇 |
2008年 | 476篇 |
2007年 | 615篇 |
2006年 | 467篇 |
2005年 | 424篇 |
2004年 | 371篇 |
2003年 | 245篇 |
2002年 | 192篇 |
2001年 | 182篇 |
2000年 | 124篇 |
1999年 | 129篇 |
1998年 | 112篇 |
1997年 | 106篇 |
1996年 | 115篇 |
1995年 | 94篇 |
1994年 | 75篇 |
1993年 | 68篇 |
1992年 | 69篇 |
1991年 | 53篇 |
1990年 | 65篇 |
1989年 | 40篇 |
1988年 | 27篇 |
1987年 | 36篇 |
1986年 | 17篇 |
1985年 | 10篇 |
1984年 | 14篇 |
1983年 | 5篇 |
1982年 | 9篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
Analytical procedures for quantification of peptides in pharmaceutical research by liquid chromatography–mass spectrometry 总被引:6,自引:0,他引:6
John H Walden M Schäfer S Genz S Forssmann WG 《Analytical and bioanalytical chemistry》2004,378(4):883-897
Peptide quantification by liquid chromatography–mass spectrometry (LC–MS) combines the high resolving power of reversed-phase (RP) chromatography with the excellent selectivity and sensitivity of mass spectrometric detection. On the basis of comprehensive practical experience in the analysis of small molecules, pharmaceutical research is developing technologies for analysis of a growing number of peptidic drug candidates. This article is a detailed review of procedures based on LC–MS techniques for quantitative determination of peptides. With the focus on pharmaceutical applications several technologies for sample preparation, various aspects of peptide chromatography, important characteristics of ESI–MS, selectivity of MS-detection modes, the large variability of internal standards, and modern instrumentation are discussed. The demand for reliable, robust, sensitive, and accurate methods is discussed using numerous examples from the literature, complemented by experiments and results from our laboratory. 相似文献
62.
Jenn-Lin Lin 《中国化学会会志》1984,31(4):395-399
The reaction of 3-(4-phenyl-2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PPDT) and tetraphenylborate (TPB) with cobalt (II) has been studied to determine the optimum conditions for the extraction and quantitative spectrophotometry determination of this metal. The ternary complex is extracted into molten naphthalene at pH 3.6–7.4. The solid naphthalene containing the cobalt associated complex is separated by filtration and dissolved in acetonitrile. Beer's law is obeyed in the concentration range 8–140 μg cobalt in 10 ml of acetonitrile solution. The molar absorptivity and sensitivity are 4.2×103 l·mol?1·cm?1 and 0.01408 μg/cm2, respectively. The other factors such as pH, amounts of reagents and naphthalene, shaking and standing times, and the effect of diverse ions are studied. The method has been applied to the determination of cobalt in iron steel alloys. 相似文献
63.
Comparison of adsorbents for on-line solid-phase extraction of polycyclic aromatic hydrocarbons before liquid chromatography with UV detection 总被引:1,自引:0,他引:1
Summary On-line solid-phase extraction (SPE) coupled with reversed-phase liquid chromatography and UV detection at 254 nm has been
used for the determination of trace-level polycyclic aromatic hydrocarbons (PAH) in soil extracts. Five commercially available
adsorbents (C8, C18, PLRP-S, PRP-1, and Bond-Elut Env) were evaluated. Results showed that recovery of the PAH decreased with increasing molecular
weight, because of their poorer solubility. Recovery of high-molecular-weight PAH was significantly improved by addition of
10% (v/v) acetonitrile to the sample before loading of the SPE adsorbent. PAH recovery ranged from 64.0 to 108% when a 50
mL sample spiked with 1 μg L−1 was applied to these adsorbents. Determination of PAH was possible with detection limits below 0.05 μg L−1, which corresponds to 0.2 μg kg−1 soil. The method was successfully used to determine PAH in soil extracts. 相似文献
64.
Ga^3+的新萃取体系的界面特性和胶团化作用研究 总被引:1,自引:0,他引:1
研究了Ga~(3+)协萃体系(Ga~(3+)-D_2EHPA-H_2MPA-正十二烷-H_2SO_4)的界面吸附和胶团形成热力学,发现该萃取体系中[H_2MPA]影响D_2EHPA和H_2MPA的界面吸附性质。在中、高[H_2MPA]范围内D_2EHPA与H_2MPA的界面吸附行为相反,D_2EHPA的存在也影响H_2MPA的界面吸附行为。研究了界面张力与各因素关系的数学模型,并获得某些胶团形成和界面吸附特性的物化参数。 相似文献
65.
Liquid-liquid equilibrium data for mixtures of (ethylene carbonate + benzene + cyclohexane) at temperatures 303.15 and 313.15 K and (ethylene carbonate + BTX + cyclohexane) at temperature 313.15 K are reported, where the BTX is benzene, toluene and m-xylene. The compositions of liquid phases at equilibrium were determined by gas liquid chromatography. The selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene, toluene and m-xylene from (ethylene carbonate + BTX + cyclohexane) are calculated and presented. The obtained results are compared with the selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene from (ethylene carbonate + benzene + cyclohexane). The liquid-liquid equilibrium data were correlated with the UNIQUAC and NRTL activity coefficient models. The phase diagrams for the studied mixtures are presented and the correlated tie line results have been compared with the experimental data. The comparisons indicate the applicability of the UNIQUAC and NRTL activity coefficients model for liquid-liquid equilibrium calculations of the studied mixtures. The tie line data of the studied mixtures also were correlated using the Hand method. 相似文献
66.
建立了酱油中1,3-二氯-2-丙醇、2,3-二氯-1-丙醇、3-氯-1,2-丙二醇和2-氯-1,3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取,提取液浓缩后经N-丙基乙二胺净化,气相色谱-高分辨质谱测定,内标法定量。结果表明,该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%;相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏,可作为酱油中4种氯丙醇的有效检测方法。 相似文献
67.
A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of iron (as its
bathophenanthroline complex) and copper (as its neocuproine complex) using octadecyl silica cartridges and dual wavelength
spectrophotometry is presented. The dual wavelength method (533 nm for the iron-bathophenanthroline and 454 nm for the copper-neocuproine
as the analytical wavelength) is used to eliminate spectral interferences. Extraction efficiency and the influence of flow
rates of sample solution and eluent, pH, amount of neocuproine, bathophenanthroline and hydroxylamine hydrochloride, type
and least amount of eluent for elution of iron and copper complexes from cartridge, break-through volume and limit of detection
are evaluated. The effects of various cationic and anionic interferences on percent recovery of iron and copper are also studied.
Extraction efficiencies >95% are obtained by elution of cartridges with minimal amount of organic solvent. Iron and copper
were determined in the range of 3–100 ng mL−1. The limits of detection are 0.98 and 1.13 ng mL−1 for iron and copper, respectively. The proposed method is applied successfully to the determination of both analytes in river,
tap and well water samples.
Author for correspondence. E-mail: yyamini@modares.ac.ir
Received September 18, 2002; accepted December 12, 2002
Published online May 5, 2003 相似文献
68.
Supercritical fluid extraction of flumetralin in tobacco 总被引:2,自引:0,他引:2
Summary This work evaluates the level of Flumetralin residues in real tobacco samples. Conventional extraction methods were compared with SFE methods in both static and dynamic modes using CO2 and CO2 with modifier. Additionally, in the dynamic SFE mode, different collection approaches, such as collection at room temperature without solvent, collection at room temperature in the presence of solvent (hexane) and collection in an ice bath, without solvent, were studied. SFE showed itself to be a promising extraction technique for pesticide residues in tobacco samples. 相似文献
69.
S. N. Dmitrieva N. I. Sidorenko A. I. Vedernikov L. G. Kuz’mina J. A. K. Howard T. M. Buslaeva S. P. Gromov 《Russian Chemical Bulletin》2007,56(5):993-1002
The condensation reaction of 1,2-bis(2-haloethoxy)-4-nitrobenzenes with acyclic α,ω-(oxa)alkanedithiols in the presence of
alkali metal carbonates produced a series of nitrobenzodithiacrown ethers with macrocycles of different size. The structures
of three ethers were established by X-ray diffraction. A new method was developed for the synthesis of nitrobenzomonothia-15-crown-5
ether. Nitro derivatives of benzodithiacrown ethers were tested as reagents for extraction of palladium(II), platinum(IV), and rhodium(III) from hydrochloric acid solutions. Extraction of PdII salts was found to be highly selective compared to that of PtIV and RhIII salts. Benzodithia-15-crown-5 ether is the most efficient extractant for palladium(II). Reduction of nitrobenzothiacrown ethers with hydrazine hydrate in the presence of a platinum catalyst afforded their amino
derivatives.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 958–966, May, 2007. 相似文献
70.