全文获取类型
收费全文 | 5777篇 |
免费 | 246篇 |
国内免费 | 45篇 |
专业分类
化学 | 4099篇 |
晶体学 | 35篇 |
力学 | 139篇 |
数学 | 1071篇 |
物理学 | 724篇 |
出版年
2023年 | 42篇 |
2022年 | 86篇 |
2021年 | 169篇 |
2020年 | 105篇 |
2019年 | 132篇 |
2018年 | 106篇 |
2017年 | 83篇 |
2016年 | 196篇 |
2015年 | 177篇 |
2014年 | 207篇 |
2013年 | 354篇 |
2012年 | 402篇 |
2011年 | 448篇 |
2010年 | 290篇 |
2009年 | 289篇 |
2008年 | 363篇 |
2007年 | 376篇 |
2006年 | 354篇 |
2005年 | 337篇 |
2004年 | 251篇 |
2003年 | 182篇 |
2002年 | 189篇 |
2001年 | 79篇 |
2000年 | 63篇 |
1999年 | 57篇 |
1998年 | 43篇 |
1997年 | 46篇 |
1996年 | 75篇 |
1995年 | 40篇 |
1994年 | 38篇 |
1993年 | 37篇 |
1992年 | 45篇 |
1991年 | 33篇 |
1990年 | 20篇 |
1989年 | 28篇 |
1988年 | 22篇 |
1987年 | 21篇 |
1986年 | 25篇 |
1985年 | 44篇 |
1984年 | 30篇 |
1983年 | 22篇 |
1982年 | 29篇 |
1981年 | 18篇 |
1980年 | 20篇 |
1979年 | 15篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1971年 | 6篇 |
排序方式: 共有6068条查询结果,搜索用时 984 毫秒
921.
A study was undertaken to ascertain the analytical capabilities of combined ICP-OES with ultrasonic nebulization to perform on-line preconcentration and speciation of inorganic V species in urine samples using a micro-column packed with l-methionine immobilized on controlled pore glass (CPG) as solid phase extractant. At pH 5.0, l-methionine is selective only towards V(V) while, total vanadium was quantitatively adsorbed by the solid phase at pH 9.0 [as V(V)] due to V(IV) oxidation in alkali media. Vanadium species retained by l-methionine were quantitatively eluted from the column with 10% HCl. Effects of acidity, sample flow rate, concentration of eluent and interfering ions on the recovery of the analytes have been systematically investigated. The detection limit (3sigma) of V is 0.008ngmL(-1) for USN-ICP-OES with an enhancement factor of 900 (10 for USN and 90 for l-methionine), and the relative standard deviation (R.S.D.) is better than 2%. The proposed method has been applied to the determination of inorganic V(V) and V(IV) in urine. 相似文献
922.
A novel method for cobalt preconcentration by cloud point extraction with on-line phase separation in a PTFE knotted reactor and further determination by electrothermal atomic absorption spectrometry (ETAAS) is proposed. The cloud point system was formed in the presence of non-ionic micelles of polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) and it was retained on the inner walls of a knotted reactor (KR). The surfactant rich-phase was removed from the knotted reactor with 75 microL of methanol acidified with 0.8 mol L(-1) nitric acid, directly into the dosing hole of the L'Vov graphite tube. An enrichment factor of 15 was obtained with a preconcentration time of 60 s, with respect to the direct determination of cobalt by ETAAS in aqueous solutions. The value of the detection limit for the preconcentration of 5 mL of sample solution was 10 ng L(-1). The precision, expressed as the relative standard deviation (R.S.D.), for 10 replicate determinations at 0.5 microg L(-1) Co level was 4.5%. Verification of the accuracy was carried out by analysis of a standard reference material (NIST SRM 1640e "Trace elements in natural water"). The method was successfully applied to the determination of cobalt in drinking water samples. 相似文献
923.
Protein extraction from Phoenix dactylifera L. leaves, a recalcitrant material, for two-dimensional electrophoresis 总被引:1,自引:0,他引:1
This work was aimed at optimizing a protein extraction procedure for date palm (Phoenix dactylifera L.) leaves, a highly recalcitrant plant tissue for 2-DE. Five protein extraction protocols based on different protein precipitation agents (TCA/acetone vs. phenol (Ph) methods) and protein resolubilization methods (physical treatments, e.g., sonication, shaking and/or heating) were tested. Ph/SDS extraction with methanol/ammonium acetate precipitation, followed by DOC preincubation and TCA/acetone precipitation and, finally, solubilization by shaking in rehydration solution was found to be the best protein extraction method. We conclude that DOC with TCA/acetone precipitation step eliminates interfering compounds, thus allowing efficient resolubilization of date palm leaf proteins. This method could be appropriate for proteomic studies such as date palm colonization by entomopathogenic fungi. 相似文献
924.
A general view of the different strategies used in the last years to enhance the detection sensitivity in chiral analysis by CE is provided in this article. With this purpose and in order to update the previous review by García-Ruiz et al., the articles appeared on this subject from January 2005 to March 2007 are considered. Three were the main strategies employed to increase the detection sensitivity in chiral analysis by CE: (i) the use of off-line sample treatment techniques, (ii) the employment of in-capillary preconcentration techniques based on electrophoretic principles, and (iii) the use of alternative detection systems to the widely employed on-column UV-Vis absorption detection. Combinations of two or three of the above-mentioned strategies gave rise to adequate concentration detection limits up to 10(-10) M enabling enantiomer analysis in a variety of real samples including complex biological matrices. 相似文献
925.
Pérez Pavón JL Martín SH García Pinto C Moreno Cordero B 《Journal of chromatography. A》2008,1194(1):103-110
A new method based on the use of a headspace autosampler in combination with a GC equipped with a programmable temperature vaporizer (PTV) and an MS detector has been developed for the screening and quantitative determination of trihalomethanes (THMs) in different aqueous matrices. The use of headspace generation to introduce the sample has the advantage that no prior sample treatment is required, thus minimizing the creation of analytical artifacts and the errors associated with this step of the analytical process. The PTV inlet used was packed with Tenax-TA. The injection mode was solvent vent, in which the analytes are retained in the hydrophobic insert packing by cold trapping, while the water vapour is eliminated through the split line. This allows rapid injection of the sample in splitless mode, very low detection limits being achieved without the critical problem of initial sample bandwidth. The capillary column used allowed rapid separations with half-height widths ranging from 1.68 s (chloroform) to 0.66 s (bromoform). The GC run time was 7.3 min. The use of mass spectrometry allows the identification and quantification of the analytes at the low ppt level. The S/N ratio was at least 10-fold higher when the SIM mode was used in data acquisition as compared to the scan mode. The proposed method is extremely sensitive, with detection limits ranging from 0.4 to 2.6 ppt. 相似文献
926.
Treatment of amines under a carbon dioxide atmosphere with tetramethylphenylguanidine (PhTMG) and diphenylphosphoryl azide (DPPA) in acetonitrile below 0 degrees C provides carbamoyl azides in high to excellent yields. In addition, epimerization is not observed when optically pure alpha-amino esters are used as substrates. 相似文献
927.
The electrophilic/nucleophilic character of a series of captodative (CD) ethylenes involved in polar cycloaddition reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The transition state structures for the electrophilic/nucleophilic interactions of two CD ethylenes toward a nucleophilically activated ethylene, 2-methylene-1,3-dioxolane, and an electrophilically activated ethylene, 1,1-dicyanoethyelene, have been studied, and their electronic structures have been characterized using both NBO and ELF methods. Analysis of the reactivity indexes of the CD ethylenes explains the reactivity of these species. While the electrophilicity of the molecules accounts for the reactivity toward nucleophiles, it is shown that a simple index chosen for the nucleophilicity, Nu, based on the HOMO energy is useful explaining the reactivity of these CD ethylenes toward electrophiles. 相似文献
928.
Gaujac A Emídio ES Navickiene S Ferreira SL Dórea HS 《Journal of chromatography. A》2008,1203(1):99-104
A method based on solid-phase microextraction (SPME) and gas chromatography with flame ionization detection (GC-FID) has been optimized for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in water released from a waste treatment plant. The extraction step was optimized using fractional factorial and central composite designs including the following experimental factors: saline concentration; extraction time; desorption time; agitation velocity; headspace volume. A multiple function was used to describe the experimental conditions for simultaneous extraction of the compounds. The procedure, based on direct SPME at 50 degrees C, using a polydimethylsiloxane fiber, showed good linearity (r>0.997 over a concentration range 2-200 microg L(-1)) and repeatability (relative standard deviation (RSD)<4.23%) for all compounds, with limits of detection ranging from 0.05 to 0.28 microg L(-1), and limits of quantification ranging from 0.14 to 0.84 microg L(-1). Concentrations of the target compounds in these samples were between 145.8 and 1891 microg L(-1). 相似文献
929.
R. Salazar P.A. Navarrete-Encina C. Camargo J.A. Squella Luis J. Núez-Vergara 《Journal of Electroanalytical Chemistry》2008,622(1):29-36
This work reports the electrochemical oxidation of two new synthetic C4-vanillin and -isovanillin-1,4-dihydropyridines in aprotic medium. Its reactivity with alkylperoxyl radicals ABAP-derived at pH 7.4 is also studied. Voltammetry, coulometry, controlled-potential electrolysis, UV–visible spectroscopy and GC–MS techniques were employed to collect data that permitted us to study its oxidation. Effect of TBA-OH addition on the oxidation was electrochemically and spectroscopically followed. In aprotic medium, the oxidation mechanism involves the formation of the pyridine derivative, which was generated by controlled-potential electrolysis (CPE) at 1270 mV and identified by GC–MS technique as the final product of the electrolysis. Spectroelectrochemical experiments also support the formation of the pyridine derivative from the oxidation of both 1,4-dihydropyridines. Direct reactivity of synthesized compounds towards alkylperoxyl radicals ABAP-derived was determined. Results reveal that the inclusion of vanillin radical or its positional isomer, isovanillin in the 4-position of the dihydropyridine ring produced a significant positive effect on the reactivity towards alkylperoxyl radicals, even compared with commercial dihydropyridine drugs with a well-known antioxidant ability. Scavenging mechanism involves the electron-transfer and the formation of a pyridine derivative, which was identified by GC–MS. 相似文献
930.
Coral J Karp SG Porto de Souza Vandenberghe L Parada JL Pandey A Soccol CR 《Applied biochemistry and biotechnology》2008,151(2-3):333-341
Propionic acid (PA) is widely used as additive in animal feed and also in the manufacturing of cellulose-based plastics, herbicides, and perfumes. Salts of propionic acid are used as preservative in food. PA is mainly produced by chemical synthesis. Nowadays, PA production by fermentation of low-cost industrial wastes or renewable sources has been an interesting alternative. In the present investigation, PA production by Propionibacterium acidipropionici ATCC 4965 was studied using a basal medium with sugarcane molasses (BMSM), glycerol or lactate (BML) in small batch fermentation at 30 and 36 degrees C. Bacterial growth was carried out under low dissolved oxygen concentration and without pH control. Results indicated that P. acidipropionici produced more biomass in BMSM than in other media at 30 degrees C (7.55 g l(-1)) as well as at 36 degrees C (3.71 g l(-1)). PA and biomass production were higher at 30 degrees C than at 36 degrees C in all cases studied. The best productivity was obtained by using BML (0.113 g l(-1) h(-1)), although the yielding of this metabolite was higher when using glycerol as carbon source (0.724 g g(-1)) because there was no detection of acetic acid. By the way, when using the other two carbon sources, acetic acid emerged as an undesirable by-product for further PA purification. 相似文献