全文获取类型
收费全文 | 65148篇 |
免费 | 18284篇 |
国内免费 | 62篇 |
专业分类
化学 | 69012篇 |
晶体学 | 218篇 |
力学 | 2416篇 |
数学 | 6582篇 |
物理学 | 5266篇 |
出版年
2024年 | 384篇 |
2023年 | 4171篇 |
2022年 | 1522篇 |
2021年 | 2617篇 |
2020年 | 4836篇 |
2019年 | 2562篇 |
2018年 | 2711篇 |
2017年 | 1002篇 |
2016年 | 6283篇 |
2015年 | 6054篇 |
2014年 | 5513篇 |
2013年 | 6527篇 |
2012年 | 4567篇 |
2011年 | 2463篇 |
2010年 | 4214篇 |
2009年 | 4052篇 |
2008年 | 2302篇 |
2007年 | 2056篇 |
2006年 | 1274篇 |
2005年 | 1166篇 |
2004年 | 1019篇 |
2003年 | 796篇 |
2002年 | 690篇 |
2001年 | 549篇 |
2000年 | 475篇 |
1999年 | 370篇 |
1997年 | 302篇 |
1996年 | 372篇 |
1995年 | 349篇 |
1994年 | 319篇 |
1993年 | 417篇 |
1992年 | 296篇 |
1988年 | 258篇 |
1985年 | 296篇 |
1984年 | 304篇 |
1982年 | 263篇 |
1981年 | 300篇 |
1980年 | 334篇 |
1979年 | 281篇 |
1978年 | 287篇 |
1977年 | 411篇 |
1976年 | 444篇 |
1975年 | 546篇 |
1974年 | 525篇 |
1973年 | 355篇 |
1972年 | 400篇 |
1971年 | 391篇 |
1970年 | 572篇 |
1969年 | 441篇 |
1968年 | 471篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
991.
Carlos Rodríguez-Abreu Massimo Lazzari Dharmesh Varade Masaya Kaneko Kenji Aramaki Manuel Arturo López Quintela 《Colloid and polymer science》2007,285(6):673-680
The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations
in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates
that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer
in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside
the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally,
viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles
with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent;
namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献
992.
993.
Molekulare Zusammensetzung von flüssigem Schwefel. Teil: 3 Quantitative Analyse im Bereich 115–350°C
Molecular Composition of Liquid Sulfur. Part 3: Quantitative Analysis in the Temperature Region 115–350°C Relative concentrations of S6, S7, S8, Sx (x > 8) and Sμ (insoluble sulfur) in equilibrium melts of elemental sulfur have been determined from i. r. and Raman spectra. At the freezing point (115°C) the melt consists of 0.6% S6, 2.8% S7, 1.5% Sx, and 95.1% S8. – The solubility of S7 in CS2 has been determined at −77 to −26°C; the solubilities of both S7 and S8 in CS2 are considerably enhanced by the presence of Sx. The thermal decomposition of S8 and Sμ formation from S6, S7, and Sx has been investigated. 相似文献
994.
Katarzyna Kaszyńska Ewa Banachowicz Genowefa Ślósarek Adrian Morawiec Iwona Gawrońska Jan Barciszewski 《Journal of solution chemistry》2002,31(12):987-993
We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of 1H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated. 相似文献
995.
J. Zsakó 《Journal of Thermal Analysis and Calorimetry》1996,46(6):1845-1864
Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable. 相似文献
996.
Summary Previous studies have indicated that non-ionic surface active agents, such as n-dodecylhexaoxyethylene glycol monoether, confer considerable protection on silver iodide sols to flocculation by inorganic cations. In the present study the effects of hydrolysis of the flocculating cations, lanthanum, aluminium and thorium have been examined. It was found that with the hydrolysed cations the protective action of the non-ionic surface active agent was considerably diminished. It was deduced that the hydrolysed species are more strongly adsorbed than the nonionic surface active agent and either displace the latter from the surface or form species which are large enough to cause flocculation by interparticle bridging.
With 6 figures and 1 table 相似文献
Zusammenfassung Vorausgehende Untersuchungen haben gezeigt, daß nichtionische oberflächenaktive Substanzen wie n-Dodecylhexaoxyäthylen-glykol-monoäther beträchtliche Schutzwirkung Silberjodidsolen gegenüber Flokkung durch anorganische Kationen verleihen. In der vorliegenden Untersuchung wird die Wirkung der Hydrolyse flockender Kationen, Lanthan, Aluminium und Thorium, geprüft. Es wurde gefunden, daß durch die hydrolisierten Kationen die Schutzwirkung der nichtionischen oberflächenaktiven Substanz beträchtlich vermindert wird. Daraus ist zu schließen, daß die hydrolisierte Ionenart stärker als das nichtoberflächenaktive Agens adsorbiert wird und deshalb das letztere von der Oberfläche entfernt wird oder genügend große interpartikuläre Brücken, bildet, um Flockung zu verursachen.
With 6 figures and 1 table 相似文献
997.
Zusammenfassung Es wurde die Absorption und Dispersion verschiedener Polyäther im Mikrowellengebiet und im fernen IR untersucht. Mit wachsender Sauerstoffzahl in der Kette werden die Torsions- und Biegeschwingungen wachsend IR-aktiv. Ihre Frequenzlagen ändern sich mit dem zunehmend polaren Charakter der Struktur. Die Analogie zwischen der Verschiebung der Schwingungsfrequenzen und dem Verlauf der Schmelztemperaturen wird diskutiert.Mit zunehmend polarem Charakter steigen der Temperaturkoeffizient der Molpolarisation und die Differenz (–n
2) der Dielektrizitätskonstanten im Mikrowellengebiet und im optischen Bereich stark an. Ein Vergleich mit der Höhe der Dispersionsstufen im fernen IR und deren Temperaturabhängigkeit ergab, daß diese zusätzliche Polarisation nicht allein durch die IR-aktiven Banden bedingt ist. Sie muß gekoppelt sein mit dem ebenfalls stark anwachsenden Untergrundverlust im gesamten mm- und sub-mm-Gebiet.
Mit 10 Abbildungen in 14 Einzeldarstellungen und 2 Tabellen 相似文献
Summary Absorption and dispersion of several polyethers were measured in the microwave region and in the far infrared. The torsional vibrations become increasingly iractive with increasing number of oxygens in the chain. Their frequencies shift, too, in a manner analogues to the variation of the melting temperatures.The temperature coefficient of the mol polarization at 32 GHz and the difference (–n 2) between microwave and optical dielectric constant rise rapidly with increasing polar character of the structure. It was tried to correlate (–n 2) with the overall absorption of the skeletal vibrations. Height and temperature dependence of the far ir dispersion show, however, that the larger part of this additional polarization cannot be accounted for by the resonance absorption bands. It must be correlated with the background loss which extends over the whole mm and sub-mm range and also increases rapidly with increasingly polar structure.
Mit 10 Abbildungen in 14 Einzeldarstellungen und 2 Tabellen 相似文献
998.
Dr. Aaron R. Finney Dr. Sébastien Lectez Dr. Colin L. Freeman Prof. John H. Harding Dr. Stephen Stackhouse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8725-8740
A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of LnIII association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl3(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd3+, Gd3+ and Er3+ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of LnIII–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water. 相似文献
999.
Jiang He Florian Rauch Dr. Alexandra Friedrich Dr. Daniel Sieh Dr. Tatjana Ribbeck Dr. Ivo Krummenacher Prof. Dr. Holger Braunschweig Prof. Dr. Maik Finze Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13777-13784
N-heterocyclic olefins (NHOs), relatives of N-heterocyclic carbenes (NHCs), exhibit high nucleophilicity and soft Lewis basic character. To investigate their π-electron donating ability, NHOs were attached to triarylborane π-acceptors (A) giving donor (D)–π–A compounds 1 – 3 . In addition, an enamine π-donor analogue ( 4 ) was synthesized for comparison. UV–visible absorption studies show a larger red shift for the NHO-containing boranes than for the enamine analogue, a relative of cyclic (alkyl)(amino) carbenes (CAACs). Solvent-dependent emission studies indicate that 1 – 4 have moderate intramolecular charge-transfer (ICT) behavior. Electrochemical investigations reveal that the NHO-containing boranes have extremely low reversible oxidation potentials (e.g., for 3 , =−0.40 V vs. ferrocene/ferrocenium, Fc/Fc+, in THF). Time-dependent (TD) DFT calculations show that the HOMOs of 1 – 3 are much more destabilized than that of the enamine-containing 4 , which confirms the stronger donating ability of NHOs. 相似文献
1000.
Terbium-sensitized luminescence determination of levofloxacin in tablets and human urine and serum 总被引:3,自引:0,他引:3
A selective and sensitive luminescence method for the determination of levofloxacin is described. The method is based in the luminescence signal from a terbium(III)-levofloxacin complex, in a micellar solution of sodium dodecyl sulfate (SDS), using a chemical deoxygenation agent (Na2SO3). The method allows the determination of 8-600 ng mL-1 of levofloxacin in 10 mM SDS solution containing 0.04 M acetic acid-sodium acetate buffer (pH 6) and 7.5 mM Na2SO3 with lambda exc = 292 nm and lambda em = 546 nm. The luminescence method was applied to the determination of the levofloxacin in a Spanish commercialized pharmaceutical formulation Tavanic (Hoechst Marion Roussel). Good concordance was found between the nominal and experimental values (500 and 488 mg, respectively), with a relative standard deviation (RSD) of 0.6%. The proposed method was shown to be 100-fold more sensitive than the spectrophotometric method, and nearly 2-fold more sensitive than the fluorescence method. The method was also applied to levofloxacin determination in human serum (by external calibration method) and urine (by standard additions method), spiked at levels found after drug administration at normal clinical doses. Average recoveries found were 90.1 (RSD 1%) and 102 (RSD 1.9%), respectively. 相似文献