全文获取类型
收费全文 | 14816篇 |
免费 | 5005篇 |
国内免费 | 933篇 |
专业分类
化学 | 3191篇 |
晶体学 | 178篇 |
力学 | 539篇 |
综合类 | 78篇 |
数学 | 145篇 |
物理学 | 16623篇 |
出版年
2024年 | 27篇 |
2023年 | 81篇 |
2022年 | 230篇 |
2021年 | 316篇 |
2020年 | 297篇 |
2019年 | 248篇 |
2018年 | 317篇 |
2017年 | 460篇 |
2016年 | 583篇 |
2015年 | 573篇 |
2014年 | 1032篇 |
2013年 | 988篇 |
2012年 | 1074篇 |
2011年 | 1349篇 |
2010年 | 949篇 |
2009年 | 1011篇 |
2008年 | 1089篇 |
2007年 | 1234篇 |
2006年 | 1071篇 |
2005年 | 913篇 |
2004年 | 883篇 |
2003年 | 748篇 |
2002年 | 728篇 |
2001年 | 584篇 |
2000年 | 631篇 |
1999年 | 576篇 |
1998年 | 449篇 |
1997年 | 410篇 |
1996年 | 372篇 |
1995年 | 271篇 |
1994年 | 230篇 |
1993年 | 187篇 |
1992年 | 188篇 |
1991年 | 153篇 |
1990年 | 113篇 |
1989年 | 96篇 |
1988年 | 62篇 |
1987年 | 69篇 |
1986年 | 32篇 |
1985年 | 22篇 |
1984年 | 26篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 18篇 |
1980年 | 11篇 |
1979年 | 4篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 11篇 |
1972年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
131.
示差脉冲伏安法测定黄酒中的酪氨酸 总被引:3,自引:0,他引:3
本文研究了硼砂介质中镍与酪氨酸络合物的示差脉冲吸附伏安特性,实验了仪器参数对示差脉冲阴极吸附伏安法的影响,在最佳条件下络合物峰电流与酪氨酸浓度在2.0×10^-7~4.0×10^-5mol.L^-1范围内有线性关系,并以此法测定了黄酒中酪氨酸的含量。 相似文献
132.
《Electroanalysis》2006,18(22):2225-2231
The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10?8 to 5×10?6 M with a detection limit of 1×10?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity. 相似文献
133.
Attempts to miniaturize electrophoresis (EP) to save time or enhance productivity and efficiency remains a challenge for science
and industry. Other advantages of miniaturization include: increased sensitivity, saving of reagents, greater yield of data,
and enabling studies where only small samples are available. Since electrophoresis that takes hours may be reduced to a matter
of minutes, the limitations of miniaturization in clinical, industrial, and research applications are evaluated. Clinical
electrophoresis (EP) on cellulose acetate media can be performed in 3.5 min instead of 20–45 min and on SDS polyacrylamide
gels in 15–30 min compared with conventional 3–8 h. 相似文献
134.
~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China
@窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@王文锋$Shanghai… 相似文献
135.
Durry G Amarouche N Zéninari V Parvitte B Lebarbu T Ovarlez J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(14):805-3379
Since 1997, two near-infrared laser diode sensors have been developed with the support of the CNES, the French space agency, to provide in situ data of H(2)O, CH(4) and CO(2) in the middle atmosphere. The realized instruments were flown from stratospheric balloons within the framework of European campaigns for the study of stratospheric ozone and water vapor and were involved in the validation of the ODIN and ENVISAT satellites. In this paper, we describe the developed laser probing technique, we report atmospheric measurements and finally we discuss future perspectives, particularly the in situ laser sensing of the lower atmosphere of Mars and the implication of the laser hygrometers in balloon campaigns at mid-latitudes and tropical regions to investigate the sources and sinks of stratospheric H(2)O. 相似文献
136.
137.
Chaikovskaya O. N. Levin P. P. Sul"timova N. B. Sokolova I. V. Kuz"min A. V. 《Russian Chemical Bulletin》2004,53(2):313-317
The spectra and kinetics of short-lived intermediates formed from aqueous (0.1 N NaOH) solutions of the natural mixture of humic and fulvic acids (HFA) were studied by laser flash photolysis using excitation wavelengths of 337, 390, 470, and 520 nm. Laser photolysis of HFA with light of 520 and 470 nm results in the formation of triplet excited states (THFA) characterized by the broad absorption spectrum with a maximum near 630 nm and lifetimes of 0.15 ms in deoxygenated solutions. The formation of two types of THFA with lifetimes of 0.1 and 2 ms and absorption spectra with maxima at 570 nm is observed under photolysis with light of 337 and 390 nm. The estimation of quantum yields of THFA gives 1 and 0.3% under photolysis with excitation wavelengths of 337 and 520 nm, respectively. The rate constants of THFA quenching by molecular oxygen are equal to (7—8)·108 L mol–1 s–1. 相似文献
138.
Voltammetric behaviour and determination of moxifloxacin in pharmaceutical products and human plasma
Erk N 《Analytical and bioanalytical chemistry》2004,378(5):1351-1356
The oxidative behaviour of moxifloxacin was studied at a glassy carbon electrode in different buffer systems using cyclic, differential pulse, and Osteryoung square-wave voltammetry. The oxidation process was shown to be irreversible over the entire pH range studied (2.0–10.0) and was diffusion-controlled. The methods were performed in Britton–Robinson buffer and the corresponding calibration graphs were constructed and statistical data were evaluated. When the proposed methods were applied at pH 6.0 linearity was achieved from 4.4×10–7 to 1.0×10–5 mol L–1. Applicability to tablets and human plasma analysis was illustrated. Furthermore, a high-performance liquid chromatographic method with diode-array detection was developed. A calibration graph was established from 4.0×10–6 to 5.0×10–5 mol L–1 moxifloxacin. The described methods were successfully employed with high precision and accuracy for estimation of the total drug content of human plasma and for pharmaceutical dosage forms of moxifloxacin. 相似文献
139.
Toluidine blue(TB) is a good sensitizer for the polymerization of acrylnmide(AM) induced by He-Ne laser. With TB as a sensitizer and various alcoholamine as donors, the photoredox of TB and the polymerization kinetics of AM induced by He-Ne laser were investigated. It was found that either for the photoredox of TB or for the polymerization of AM, the activity of alcoholamine increases in the order of EOA相似文献
140.
《Electroanalysis》2004,16(5):355-359
Water present in undiluted acetic acid can be monitored in situ with Pt and Au microelectrodes using differential pulse and square‐wave voltammetries. Both reduction and oxidation peaks can be obtained. The best quantitative analytical results were obtained for the anodic peak, the Pt microelectrode, and differential pulse voltammetry. The anodic water peak is located at +1.55 V vs. the quasi reference Pt electrode. The voltammetric peak obtained at Pt electrode is apparently not a diffusional one, however, the calibration plot obtained by employing this peak is linear over a wide concentration range, up to 4 mol dm?3. The detection limit has been estimated as 2.3 mM or 0.0043 v/v%. The developed method may be particularly useful, since the Karl Fischer method can not be used to determine water in glacial acetic acid due to the estrification reaction of acetic acid with methanol. A voltammetric wave of undiluted acetic acid could not be obtained in the positive and negative ranges of potential. 相似文献