全文获取类型
收费全文 | 8509篇 |
免费 | 267篇 |
国内免费 | 24篇 |
专业分类
化学 | 5658篇 |
晶体学 | 63篇 |
力学 | 263篇 |
综合类 | 1篇 |
数学 | 1166篇 |
物理学 | 1649篇 |
出版年
2023年 | 61篇 |
2022年 | 122篇 |
2021年 | 271篇 |
2020年 | 167篇 |
2019年 | 177篇 |
2018年 | 170篇 |
2017年 | 158篇 |
2016年 | 354篇 |
2015年 | 272篇 |
2014年 | 287篇 |
2013年 | 523篇 |
2012年 | 577篇 |
2011年 | 609篇 |
2010年 | 457篇 |
2009年 | 409篇 |
2008年 | 560篇 |
2007年 | 519篇 |
2006年 | 411篇 |
2005年 | 374篇 |
2004年 | 306篇 |
2003年 | 282篇 |
2002年 | 217篇 |
2001年 | 162篇 |
2000年 | 145篇 |
1999年 | 102篇 |
1998年 | 93篇 |
1997年 | 71篇 |
1996年 | 86篇 |
1995年 | 68篇 |
1994年 | 60篇 |
1993年 | 58篇 |
1992年 | 57篇 |
1991年 | 53篇 |
1990年 | 39篇 |
1989年 | 32篇 |
1988年 | 38篇 |
1987年 | 27篇 |
1986年 | 33篇 |
1985年 | 52篇 |
1984年 | 38篇 |
1983年 | 27篇 |
1982年 | 29篇 |
1981年 | 27篇 |
1980年 | 35篇 |
1979年 | 19篇 |
1978年 | 26篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 14篇 |
1973年 | 17篇 |
排序方式: 共有8800条查询结果,搜索用时 31 毫秒
101.
Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT)
species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase
extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column
derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C18 enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors
up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole
process have been determined. The method has been applied to the determination of organotin species in spiked natural water
samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low
ng L−1 level (1–3 ng Sn L−1 for DPhT, DBT, and PhT and 40 ng Sn L−1 for TBT when 250 mL spiked sea water is processed.) 相似文献
102.
J. V. Kunzler W. Schreiner A. Bristoti D. E. BrandÃo 《Journal of Thermal Analysis and Calorimetry》1977,11(1):81-86
Saturation magnetization measurements as a function of temperature were performed on Cu2Mn(Al1–xSnx) Heusler alloys to study the existence of stable structures. The derivatograph was applied to study the thermal effects.
Work supported in part by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and Banco Nacional de Desenvolvimento Economico, Brasil. 相似文献
Zusammenfassung Sättigungsmagnetisierungsmessungen als Funktion der Temperatur sowie Derivatographie wurden an Heusler-Legierungen der Formel Cu2Mn(Al1–xSnx) zu Untersuchungen der Existenz einer stabilen Struktur vorgenommen.
Résumé Etude de l'existence d'une structure stable dans les alliages de Heusler Cu2Mn(Al1–xSnx), à l'aide d'un Derivatograph et par des mesures de magnétisation à saturation en fonction de la température.
XecnepaCu2Mn(Al1–xSnx), , , . .
Work supported in part by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and Banco Nacional de Desenvolvimento Economico, Brasil. 相似文献
103.
H. Langfelderová L'. Macášková K. Otrubová J. Gažo 《Journal of Thermal Analysis and Calorimetry》1986,31(5):1143-1151
The thermal decompositions of Cu(en)2(NCS)X. where X–=Cl–, Br–, NO
3
–
, BF
4
–
and ClO
4
–
, have been studied in comparison with the courses of Cu(en)2(SCN)2 and Cu(en)2X2 decomposition. It is shown that the presence of the thiocyanate group in the complexes Cu(en)2(NCS)X is the most important factor in the decomposition course, in agreement with the fact that the anions X– are not coordinated. or are only semicoordinated. Significant differences were found in the courses of thermal decomposition of two forms of Cu(en)2(NCS)(BF4) differing in the structure of their coordination polyhedra.
Zusammenfassung Die thermische Zersetzung von Cu(en)2(NCS)X (X=Cl Br, NO3, BF4 und ClO4) wurde untersucht und mit der von Cu(en2(SCN)2 und Cu(en)2X2 verglichem. Der den Verlauf der Zersetzung entscheidend bestimmende Faktor isi die Anw esenheit der Thiocyanat-Gruppe in den Cu(en)2(NCS)X-Komplexen, was in Übereinstimmung damit steht,. daß die Anionen X nicht oder nur teilweise koordiniert sind. Es wurden signifikante Unterschiedeim Verlauf der thermischen Zersetzung von zwei sich in der Struktur ihrer Kordinationspolyeder unter-, heidenden Formen von Cu(en)2(NCS)(BF4) gefunden.
Cu(en)2(NCS)X (X–=Cl–, Br–, NO 4 – , NO 3 – , BF4 ClO4, Cu(en)2(SCN)2 Cu(en)2(X)2. , Cu(en)2(NCS)X X Cu(en) (NCS)BF4 i .相似文献
104.
Guimarães KL Castro RH Gouvêa D 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11645-11650
The standard methods for obtaining adsorption isotherms on colloidal suspensions are usually very time consuming and involve a large number of steps and assumptions that increase the experimental errors. In this work, an alternative method is proposed to evaluate the adsorption behavior of electrosteric-stabilized systems based on electrokinetic sonic amplitude signal measurements. The new method, entitled "zeta-sorption", is noticeably less time-consuming when compared to conventional procedures but showed great precision and reliability confirmed by comparison with data obtained from conventional routes on alumina-polyacrylate and alumina-citric acid aqueous suspensions. The experimental conditions that restrict the applicability of the new method were identified and justified by discussing the possible ion exchanges. 相似文献
105.
The main features of transition structures associated with eight-electron electrocyclic reactions have been studied with Density Functional Theory. It is found that conrotatory electrocyclization reaction of (3Z,5Z)-octa-1,3,5,7-tetraenes takes place via M?bius aromatic transition structures of helical conformation. The reaction is completely periselective. In general, transition structures having outward substituents are preferred with respect to the inward transition structures, irrespective of the pi-donor or pi-acceptor character of the substituent. In contrast with four-electron thermal conrotatory electrocyclic reactions, there is no satisfactory correlation between the difference in energy of activation between inward and outward substituents and the Taft resonance sigma(R) parameter. 相似文献
106.
AurelioG. Cskÿ Rocío Medel M.Carmen Murcia Joaquín Plumet 《Helvetica chimica acta》2005,88(6):1387-1396
A new method for the synthesis of spiro‐β‐lactams tethered to tetrahydrofuran rings is described. The procedure is based on Ru‐catalyzed metathesis sequences with oxanorbornene precursors easily obtained by the Staudinger [2+2] cycloaddition of related imines. 相似文献
107.
Immobilization of protein on ferromagnetic Dacron 总被引:1,自引:0,他引:1
A. M. A. Carneiro LeÃo E. A. Oliveira L. B. Carvalho 《Applied biochemistry and biotechnology》1991,31(1):53-58
Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant. 相似文献
108.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
109.
del Río JC Gutiérrez A Martínez AT 《Rapid communications in mass spectrometry : RCM》2004,18(11):1181-1185
A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin. 相似文献
110.
The first example of an organic reduction with boranes catalyzed by a high valent oxo-complex is reported. The systems catecholborane/MoO2Cl2(H2O)2 (5 mol %) and BH3·THF/MoO2Cl2 (5 mol %) proved to be very efficient for the reduction of sulfoxides to the corresponding sulfides in excellent yields. 相似文献