全文获取类型
收费全文 | 41285篇 |
免费 | 1741篇 |
国内免费 | 1452篇 |
专业分类
化学 | 29545篇 |
晶体学 | 326篇 |
力学 | 799篇 |
综合类 | 10篇 |
数学 | 5746篇 |
物理学 | 8052篇 |
出版年
2023年 | 298篇 |
2022年 | 527篇 |
2021年 | 707篇 |
2020年 | 677篇 |
2019年 | 688篇 |
2018年 | 792篇 |
2017年 | 773篇 |
2016年 | 1502篇 |
2015年 | 1214篇 |
2014年 | 1282篇 |
2013年 | 2781篇 |
2012年 | 3035篇 |
2011年 | 3263篇 |
2010年 | 1885篇 |
2009年 | 1924篇 |
2008年 | 2536篇 |
2007年 | 2475篇 |
2006年 | 2178篇 |
2005年 | 2066篇 |
2004年 | 2113篇 |
2003年 | 1548篇 |
2002年 | 1425篇 |
2001年 | 911篇 |
2000年 | 776篇 |
1999年 | 589篇 |
1998年 | 482篇 |
1997年 | 385篇 |
1996年 | 463篇 |
1995年 | 344篇 |
1994年 | 306篇 |
1993年 | 360篇 |
1992年 | 308篇 |
1991年 | 220篇 |
1990年 | 212篇 |
1989年 | 173篇 |
1988年 | 172篇 |
1987年 | 158篇 |
1986年 | 161篇 |
1985年 | 261篇 |
1984年 | 230篇 |
1983年 | 172篇 |
1982年 | 148篇 |
1981年 | 153篇 |
1980年 | 119篇 |
1979年 | 130篇 |
1978年 | 105篇 |
1977年 | 103篇 |
1976年 | 96篇 |
1975年 | 93篇 |
1973年 | 99篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
Ruiz-Medina A Ortega-Barrales P Fernández-de Córdova ML Molina-Díaz A 《Journal of AOAC International》2002,85(2):369-374
A simple, rapid, inexpensive, and automated flow-through solid-phase spectroscopic sensing device is proposed for the sequential determination of 2 vitamins: thiamine and ascorbic acid. The vitamins are concentrated on ion-exchange gels, thiamine on Sephadex SP C-25, and ascorbic acid on Sephadex QAE A-25; both solid supports are packed in 2 different flow cells. The absorbance is monitored directly on the solid phase with a double-beam spectrophotometer at 250 nm, without derivatization or additional elution. With the use of 2 carrier/self-eluting solutions (0.1 5M sodium acetate/acetic acid and 0.18M citric acid/K2HPO4) and a sample volume of 1000 microL, the sensor responds linearly in the range of 0.5-15 and 3-50 microg/mL with detection limits of 0.14 and 0.36 microg/mL for thiamine and ascorbic acid, respectively. When the method was applied to synthetic samples and pharmaceutical preparations, precise and accurate values were obtained. 相似文献
952.
A rapid extraction separation of trace amounts of yttrium from strontium with a nitrobenzene solution of sodium dicarbollylcobaltate (NaDCC) and 18-crown-6 in the presence of tetrasodium salt of ethylenediamine-N,N,N",N"- tetraacetic acid (Na4L) in the aqueous phase was developed. The separation factor a(Sr/Y) was substantially higher than 106. This water-nitrobenzene extraction system can be applied for efficient separation of carrier-free 90Y from 90Sr/90Y generator. 相似文献
953.
Fátima Nunes Serralha José Madeira Lopes Francisco Lemos Duarte Prazeres Maria Aires-Barros Joo Rocha Joaquim Cabral Fernando Ramôa Ribeiro 《Reaction Kinetics and Catalysis Letters》2000,69(2):217-222
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
954.
Raúl Comelli Zunilda Finelli Sergio Canavese Nora Fígoli 《Reaction Kinetics and Catalysis Letters》1995,55(1):171-181
The effect of Mg addition to Pd impregnated silica-alumina catalysts and the behavior of these catalysts in synthesis gas to hydrocarbons transformation have been studied. Measurements of H2 chemisorption and temperature programmed NH3 desorption allow us to consider that Mg addition to Pd containing catalysts increases the Pd dispersity, the support acidity not being modified. The presence of Mg enhances hydrocarbon production. Meanwhile, the hydrocarbon distribution is not modified. A large amount of light alkanes in the reaction products is obtained. 相似文献
955.
956.
IntroductionThegenediagnosistechnology ,alsocallednucleicacidprobetechnology ,hasbecomeanattractivemethodinthefieldsofbiochemistryandclinicalmedicine .Itisprovedtobeconvenientandsafeusingnon radioactivereagentswithelectrochemicalandopticaldetector.Espe c… 相似文献
957.
A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS 总被引:2,自引:0,他引:2
Day JA Montes-Bayón M Vonderheide AP Caruso JA 《Analytical and bioanalytical chemistry》2002,373(7):664-668
Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate. 相似文献
958.
In the present study was combined the use of high resolution TGA with the isoconversion method, giving us a suitable methodology for determining the stages that occur during a reaction, and providing further insights about the kinetics of the processes involved. As a model reaction was used the thermal dehydration of KNbWO6·H2O. The results shown that the dehydration process is controlled by internal water diffusion (intra-crystallite); with activation energy values between 43 and 36 kJ/mol. This value is consistent with a diffusion mechanism dominated by van der Waals attractions. The estimated kinetic parameters are supported with a structural analysis, that suggest lower dimensionality character for water diffusion due to the specific orientations of 〈1 1 0〉 open channels in the pyrochlore framework. This would explain why the two-dimensional (D2) mechanism appears to be the most probable. 相似文献
959.
Martínez-Junza V Rizzi A Jolliffe KA Head NJ Paddon-Row MN Braslavsky SE 《Physical chemistry chemical physics : PCCP》2005,7(24):4114-4125
Photophysical studies with semi-rigid, 1, and flexible, 2, donor-bridge-acceptor (D-b-A2+) molecules with D a porphyrin and A2+ a methyl viologen moiety, were performed in neat polar solvents as well as included in surfactant (DTAB) aqueous and in reverse AOT/n-alkane micelles. The micelles acted as nanoreactors for the photoinduced electron transfer reaction upon laser excitation. In spite of the longer lifetime of the charge separated (CS) state in the semi-rigid tetrad 1(ca. 200 ns vs. ca. 100 ns for the flexible dyad 2), the CS formation quantum yield, for example in acetonitrile, was lower for the former (phi(CS) = 0.13) than for the latter (0.58). Comparison of the time-resolved fluorescence data in neat solvent and in the micelles yielded the phi(CS) values in the dilute micellar solutions. Application of laser-induced optoacoustic spectroscopy at various temperatures to 1 dissolved in a polar organic solvent (benzonitrile, BZN) included in aqueous DTAB nanoreactors afforded structural volume changes for the production in hundreds of ps of the CS state upon excitation of a polar molecule. The contraction during CS formation upon excitation of the collapsed conformer in BZN is attributed to the entering of solvent into the open molecular cavity. The opening upon formation of the CS state due to photoinduced electron transfer in the 1 collapsed conformation arises from the repulsion of the two positively charged ends in this state, as previously calculated. Inclusion of 1 in reverse AOT micelles in various n-alkanes also led to a contraction upon excitation, but the data had much more error due to the limited range of variability of the ratio of thermoelastic parameters. The data obtained with the more flexible "supermolecule" 2 showed the predicted large conformation flexibility of these molecules. 相似文献
960.
A. Bumbálová A. Pikulíková M. Komová A. Muchová 《Journal of Radioanalytical and Nuclear Chemistry》1992,164(6):357-364
Determination of Cr, Fe, Cu, Zn and Pb in drinking water preconcentrated on a chelating ion exchanger of Czechoslovak production is described. The analytical system consisted of a radionuclide source238Pu, a Si/Li semiconductor detector and a multichannel analyzer. Results are compared with trehshold limit values recommended for drinking water. 相似文献