全文获取类型
收费全文 | 11938篇 |
免费 | 722篇 |
国内免费 | 700篇 |
专业分类
化学 | 2256篇 |
晶体学 | 24篇 |
力学 | 672篇 |
综合类 | 102篇 |
数学 | 3222篇 |
物理学 | 1566篇 |
综合类 | 5518篇 |
出版年
2024年 | 26篇 |
2023年 | 83篇 |
2022年 | 113篇 |
2021年 | 133篇 |
2020年 | 187篇 |
2019年 | 178篇 |
2018年 | 198篇 |
2017年 | 234篇 |
2016年 | 243篇 |
2015年 | 267篇 |
2014年 | 441篇 |
2013年 | 551篇 |
2012年 | 515篇 |
2011年 | 598篇 |
2010年 | 567篇 |
2009年 | 673篇 |
2008年 | 753篇 |
2007年 | 850篇 |
2006年 | 729篇 |
2005年 | 690篇 |
2004年 | 560篇 |
2003年 | 565篇 |
2002年 | 626篇 |
2001年 | 458篇 |
2000年 | 364篇 |
1999年 | 333篇 |
1998年 | 321篇 |
1997年 | 258篇 |
1996年 | 264篇 |
1995年 | 234篇 |
1994年 | 213篇 |
1993年 | 183篇 |
1992年 | 146篇 |
1991年 | 126篇 |
1990年 | 99篇 |
1989年 | 106篇 |
1988年 | 76篇 |
1987年 | 73篇 |
1986年 | 56篇 |
1985年 | 46篇 |
1984年 | 31篇 |
1983年 | 18篇 |
1982年 | 35篇 |
1981年 | 41篇 |
1980年 | 23篇 |
1979年 | 25篇 |
1978年 | 19篇 |
1977年 | 5篇 |
1976年 | 9篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 218 毫秒
221.
Gololobov Yu. G. Galkina M. A. Dovgan O. V. Krasnova I. Yu. Petrovskii P. V. Antipin M. Yu. Voronzov I. I. Lyssenko K. A. Schmutzler R. 《Russian Chemical Bulletin》2001,50(2):279-286
The reactions of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with mercuric chloride and aryl isothiocyanates containing Cl atoms in the ortho positions of the benzene ring follow an unusual pathway because this zwitterion represents latent triisopropylphosphine due to the reversibility of the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate. The molecular structures of the adducts of triisopropylphosphine with 2,6-dichloro- and 2,4,6-trichlorophenyl isothiocyanates were confirmed by X-ray diffraction study. Protonation of the adduct of triisopropylphosphine with 2,6-dichlorophenyl isothiocyanate occurred at the nitrogen atom, whereas methylation with methyl trifluoromethanesulfonate afforded an S-methylation product. The results of X-ray diffraction study of the resulting compounds are presented. 相似文献
222.
223.
Singlet oxygen was generated by reaction of sodium hypochlorite and hydrogen peroxide in a micro-channel. The two reagent solutions were delivered into the micro-channel by a syringe pump, providing a laminar flow liquid-liquid interface. The chemiluminescence from the singlet oxygen was emitted in the collapse of the interface due to molecular diffusion under laminar flow conditions. The chemiluminescence intensity was observed continuously and stably for each combination of reagents fed into the micro-channel; while, in the normal batch-type reactor the chemiluminescence peaks from singlet oxygen were observed within ca. 5 s. The features of the chemiluminescence emitted under laminar flow conditions were examined by changing the concentrations of sodium hypochlorite and hydrogen peroxide; the concentrations of 2.5 mM sodium hypochlorite and 7.5 mM hydrogen peroxide provided highest chemiluminescence intensities without bubble formation. Also, the effects of beverages, such as green tea, coffee, white wine, red wine, and sake (rice wine), on the chemiluminescence intensity as well as the concentrations of sodium hypochlorite and hydrogen peroxide were examined. The chemiluminescence intensities observed with addition of the beverages to the reagents decreased in the following orders; green tea > coffee > red wine > rice wine > white wine (being added to sodium hypochlorite); coffee > white wine > green tea > red wine > rice wine (being added to hydrogen peroxide). It was found that coffee decreased the chemiluminescence intensity (ca. 33% chemiluminescence decrease) without altering the concentrations of sodium hypochlorite or hydrogen peroxide. The cause of the decrease in chemiluminescence with coffee is discussed. 相似文献
224.
在电极袭面反应物浓度均匀的近似假设下,得到了微圆盘电极上暂态可逆反应的一般解.然后利用该一般解得到了微圆盘电极上耦合一级均相反应的可逆电极反应CE、EC、EC′和ECE 的稳态电流计算公式. 相似文献
225.
Albert Lévai Gábor Tóth Áron Szőllősy Tibor Timár 《Monatshefte für Chemie / Chemical Monthly》1990,121(5):403-411
Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.
Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen
Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).相似文献
226.
N. N. Zemlyanskii I. V. Borisova A. K. Shestakova Yu. A. Ustynyuk E. A. Chernyshev 《Russian Chemical Bulletin》1998,47(3):469-474
The first stable dibenzosilafulvene, 9-{[8-(dimethylaminomethyl)-1-naphthyl]phenylsil-1-ylium}fluoren-9-ide (7a), was obtained in one step from 9-fluorenyllithium and chloro[8-(dimethylaminomethyl)-1-naphthyl]phenylsilane as a stable
solvate with THF. The structure of the zwitterionic compound7a was established by1H,13C, and29Si NMR in solution and in the solid state. The reactions of compound7a with crotonaldehyde, ethanol, and triethylethylidenephosphorane are described. The data on the synthesis of alkoxy- and alkylthiochloro-9-fluorenylsilanes
and their phosphonium salts are given.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 486–491, March, 1998. 相似文献
227.
Summary A new gas chromatographic method for the simultaneous determination of the degree of hydrogenation of ketopantolactone and the enantiomeric excess of pantolactone does not require any derivatisation.
Bestimmung von Enantiomerenüberschuß und Hydriergrad bei der enantioselektiven Hydrierung von Ketopantolacton (Kurze Mitt.)
Zusammenfassung Zur Bestimmung des Hydriergrads von Ketopantolacton und des Enantiomerenüberschusses von Pantolacton wird ein neues gaschromatographisches Verfahren eingesetzt, das keine Derivatisierung erfordert.相似文献
228.
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
229.
Glass capillary columns have been prepared without acidic additive in the stationary phase, from which free organic acids elute as sharp and symmetrical peaks. The required surface in the borosilicate glass capillary was generated by a combination of leaching with aqueous HCl and deposition of colloidal silica particles; it can be coated with stationary phases have a broad range of polarity. Aqueous samples containing free organic acids can also be analyzed in such columns in an isothermal mode. 相似文献
230.
Carlo Carlini Marco Di Girolamo Alessandro Macinai Mario Marchionna Marilena Noviello Anna Maria Raspolli Galletti Glauco Sbrana 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):137-146
The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst. 相似文献