全文获取类型
收费全文 | 3060篇 |
免费 | 144篇 |
国内免费 | 2篇 |
专业分类
化学 | 2281篇 |
晶体学 | 27篇 |
力学 | 84篇 |
数学 | 372篇 |
物理学 | 442篇 |
出版年
2023年 | 27篇 |
2022年 | 20篇 |
2021年 | 32篇 |
2020年 | 51篇 |
2019年 | 48篇 |
2018年 | 58篇 |
2017年 | 48篇 |
2016年 | 116篇 |
2015年 | 77篇 |
2014年 | 84篇 |
2013年 | 199篇 |
2012年 | 269篇 |
2011年 | 274篇 |
2010年 | 147篇 |
2009年 | 126篇 |
2008年 | 215篇 |
2007年 | 217篇 |
2006年 | 172篇 |
2005年 | 169篇 |
2004年 | 155篇 |
2003年 | 113篇 |
2002年 | 101篇 |
2001年 | 76篇 |
2000年 | 83篇 |
1999年 | 49篇 |
1998年 | 38篇 |
1997年 | 22篇 |
1996年 | 29篇 |
1995年 | 16篇 |
1994年 | 23篇 |
1993年 | 18篇 |
1992年 | 20篇 |
1991年 | 15篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1969年 | 1篇 |
排序方式: 共有3206条查询结果,搜索用时 31 毫秒
61.
E. I. Basaldella J. C. Tara G. Aguilar Armenta M. E. Patiño-Iglesias E. Rodríguez Castellón 《Journal of Sol-Gel Science and Technology》2006,37(2):141-146
Samples of mesoporous silica, SBA-15, were prepared under hydrothermal conditions and Cu cations were incorporated into the
framework by two different impregnation techniques. The corresponding adsorption/desorption isotherms of propylene, propane,
and N2 were measured to evaluate the material's effectiveness in the separation of propane/propylene mixtures.
Adsorption uptake of propylene increased and that of propane decreased in Cu containing samples as compared to the uptakes
observed in undoped SBA-15 samples. It was demonstrated that the presence of Cu atoms in the adsorbent lattice led to a greater
selectivity towards propylene. Furthermore, the highest level of Cu(I) were obtained in samples prepared by equilibrium impregnation,
which in turn improved the olefin/paraffin uptake ratio. Under some working conditions, the amount of propylene adsorbed in
selected samples is totally reversible while propane uptake was negligible. 相似文献
62.
A fast and simple procedure is presented for the simultaneous leaching of butyl (mono, di and tributyl) and phenyl organotin species from sediment samples. Leached compounds are further ethylated with sodium tetraethylborate in aqueous medium, and analyzed by gas chromatography. After testing the stability of triphenyltin under different extraction conditions, ultrasound-assisted leaching at room temperature in the presence of acetic acid was been proposed as an extraction procedure compatible with the simultaneous determination of phenyl- and butyltin compounds in sediments. Recoveries between 70 and 90% were obtained for phenyl species in spiked samples prepared in the laboratory. Results for butyltin species were validated by use of the reference material PACS-2. Quantification limits, using GC-MIP-AES as measurement technique, were approximately 5-10 ng g(-1). Precision in the consecutive analysis of three sediment samples varied between 3 and 10%. 相似文献
63.
Georgieva I Trendafilova N Rodríguez-Santiago L Sodupe M 《The journal of physical chemistry. A》2005,109(25):5668-5676
The coordination of Cu2+ by glyoxilic acid oxime (gao)--the oxime analogue of glycine amino acid--and its deprotonated (gao- and gao2-) species has been studied with different density functional methods. Single-point calculations have also been carried out at the single- and double- (triple) excitation coupled-cluster (CCSD(T)) level of theory. The isomers studied involve coordination of Cu2+ to electron-rich sites (O,N) of neutral, anionic, and dianionic gao species in different conformations. In contrast to Cu2+-glycine, for which the ground-state structure is bidentate with the CO2(-) terminus of zwitterionic glycine, for Cu2+-gao the most stable isomer shows monodentate binding of Cu2+ with the carbonylic oxygen of the neutral form. The most stable complexes of Cu2+ interacting with deprotonated gao species (gao- and gao2-) also take place through the carboxylic oxygens but in a bidentate manner. The results with different functionals show that, for these open shell (Cu2+-L) systems, the relative stability of complexes with different coordination environments (and so, different spin distribution) can be quite sensitive to the amount of "Hartree-Fock" exchange included in the functional. Among all the functionals tested in this work, the BHandHLYP is the one that better compares to CCSD(T) results. 相似文献
64.
[reaction: see text] The photoinduced metalation of nonactivated C-Cl bonds of O-acetyl chlorohydrins is promoted by samarium diiodide. As a result of this, beta-elimination of O-acetyl chlorohydrins is achieved, affording the corresponding (Z)-alkenes with total or high stereoselectivity. 相似文献
65.
Wege HA Aguilar JA Rodríguez-Valverde MA Toledano M Osorio R Cabrerizo-Vílchez MA 《Journal of colloid and interface science》2003,263(1):162-169
A new methodology capable of providing reliable and reproducible contact angle (theta) data has been employed to study the effect of clinical treatments grinding, acid etching, and deproteinization on medial dentin tissue. It is based on the application of the ADSA-CD algorithm to the determination of low-rate dynamic contact angles, obtained from slowly growing drops, and on contact angle measurement, as well as spreading behavior analysis, during the relaxation of the system (water on treated dentin) after initial drop growth. The theta data obtained were substantially more reproducible than those obtained with classical methods. A net effect of the treatment on theta was found, increasing dentin wettability: theta (polished) >theta (etched) >theta (deproteinized). The spreading rates correlate with the angles and are adequate for the dentin surface characterization. ANOVA and SNK tests show that for advancing contact angles the means corresponding to all treatments are significantly different. In the relaxing phase, mean angle and spreading rates on polished dentin differ significantly from those on etched and deproteinized dentin, but the latter do not differ significantly from each other. 相似文献
66.
Barluenga J Diéguez A Rodríguez F Flórez J Fañanás FJ 《Journal of the American Chemical Society》2002,124(31):9056-9057
Eight-membered carbocycles with up to five new stereogenic centers are enantioselectively obtained following a one-pot procedure that involves the coupling of three components: an alkenyl Fischer carbene complex, a ketone enolate, and allyl lithium. 相似文献
67.
Batistoni DA Garavaglia RN Rodríguez RE 《Fresenius' Journal of Analytical Chemistry》2000,366(3):221-227
The simultaneous injection of volatile hydride species and hydrogen gas, originating in reagent decomposition, was monitored during the operation of a continuous hydride generation manifold employed for the determination of trace arsenic by HG-ICP-AES. Line and background intensities as well as the FWHM of the hydrogen Hgamma and Hdelta lines were measured, and electron number densities (ne) estimated from Stark broadening of the line profiles. Results were compared with those obtained by conventional pneumatic injection of aqueous solutions. Overlapping with atomic nitrogen lines at 410 nm and 411 nm tends to distort the Hdelta line profile for the hydrogen-seeded plasma, rendering unreliable results. The N I lines seem to be quenched by the presence of water aerosol. More consistent results were obtained with the Hgamma line. When no solutions are pumped through the hydride generation manifold ("dry" plasma), the measured ne value was (1.57 +/- 0.22) x 10(15)cm(-3). Conversely, when the reducing reagent flow was replaced by pure water (corresponding to the injection of water vapor in equilibrium that is swept by the argon carrier gas passing through the phase separator), the electron concentration is 25% higher. In that case the ne value agrees between the experimental error with that obtained for a plasma in which a water aerosol is introduced at a flow rate of 1 mL/min. An enhancement of 52% relative is observed in ne when the system is operated under optimized conditions for arsine generation, employing sodium tetrahydroborate in acidic medium as reducing agent (i.e. hydrogen seeded plasma). It was also observed that the continuum emission near 410 nm for the hydrogen containing plasma correlates with the measured electron number density, suggesting that the background enhancement under hydride generation conditions may respond to the ion-electron recombination mechanism. 相似文献
68.
J. P. Pérez-Trujillo S. Frías M. J. Sáchez J. E. Conde M. A. Rodríguez-Delgado 《Chromatographia》2002,56(3-4):191-197
Summary A study of different extraction techniques for the determination of a selected group of organochlorine compounds in surface
waters is presented. Comparison of liquid-liquid extraction (LLE) with solid-phase extraction (SPE) and solid-phase microextraction
(SPME) with fibers of different polarity shows that SPME with a recently commercialised fiber of polydimethylsiloxane divinylbenzene
allows these compounds to be determined in surface waters with good extraction efficiencies. Extraction time, effect of temperature,
ionic strength and pH were optimised, allowing quantification in agricultural effluents in the range 1.0–60 ng·L−1. 相似文献
69.
Summary The optimization of the heating conditions, absorbance profiles, the influence of different matrix composition and the effect of delivering different volumes of urine samples were examined in order to evaluate the use of simple aqueous standards for the determination of cadmium in urine samples, using atomic absorption spectrometry with electrothermal atomization and the L'vov platform. Three reference materials were analysed for cadmium by the proposed method. The results indicate that a direct and accurate determination of urine cadmium is possible by using simple aqueous calibration standards, independently of the composition of the urine matrix. 相似文献
70.
García G Rodríguez JL Lacconi GI Pastor E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8773-8780
In the present paper, a systematic electrochemical investigation on thiourea (TU) electrooxidation was developed on polycrystalline and (111) single-crystal gold electrodes in 0.1 M perchloric acid. The combination of cyclic voltammetry with in situ Fourier transform infrared spectroscopy (FTIRS) and differential electrochemical mass spectrometry techniques have allowed the nature of the species formed during the electroadsorption and electrooxidation of TU to be established. FTIRS experiments were performed in D2O to clean up the region of the H2O bending around 1600 cm(-1). It was concluded that TU adsorbs tilted on the surface in the 0.05-0.40 VRHE potential range. A dual-path reaction mechanism was evidenced in the oxidation process. The first pathway takes place from adsorbed TU at E > 0.40 VRHE and implies the formation of [Au(I)-(TU)2]+, which is oxidized to NH2CN and S0 at E > 0.80 VRHE. In a following oxidation step at E > 1.20 V, N2, CO2, and HSO4-/SO4(2-) were produced. The second parallel reaction occurs from TU in solution at E > 0.50 VRHE to form (TU)2(2+). All these species were characterized from the spectroscopic experiments. Similar results were obtained for both surfaces. 相似文献