全文获取类型
收费全文 | 5940篇 |
免费 | 254篇 |
国内免费 | 32篇 |
专业分类
化学 | 3727篇 |
晶体学 | 25篇 |
力学 | 201篇 |
数学 | 1207篇 |
物理学 | 1066篇 |
出版年
2023年 | 54篇 |
2022年 | 96篇 |
2021年 | 184篇 |
2020年 | 158篇 |
2019年 | 153篇 |
2018年 | 130篇 |
2017年 | 117篇 |
2016年 | 252篇 |
2015年 | 233篇 |
2014年 | 245篇 |
2013年 | 342篇 |
2012年 | 418篇 |
2011年 | 473篇 |
2010年 | 275篇 |
2009年 | 249篇 |
2008年 | 379篇 |
2007年 | 339篇 |
2006年 | 318篇 |
2005年 | 305篇 |
2004年 | 239篇 |
2003年 | 182篇 |
2002年 | 193篇 |
2001年 | 76篇 |
2000年 | 49篇 |
1999年 | 65篇 |
1998年 | 53篇 |
1997年 | 67篇 |
1996年 | 48篇 |
1995年 | 49篇 |
1994年 | 47篇 |
1993年 | 38篇 |
1992年 | 26篇 |
1991年 | 29篇 |
1990年 | 22篇 |
1989年 | 22篇 |
1988年 | 25篇 |
1987年 | 30篇 |
1986年 | 22篇 |
1985年 | 27篇 |
1984年 | 22篇 |
1983年 | 14篇 |
1982年 | 22篇 |
1981年 | 17篇 |
1980年 | 16篇 |
1979年 | 14篇 |
1978年 | 17篇 |
1977年 | 11篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1973年 | 8篇 |
排序方式: 共有6226条查询结果,搜索用时 93 毫秒
81.
Csar Ricardo Teixeira Tarley Srgio Luis Costa Ferreira Marco Aurlio Zezzi Arruda 《Microchemical Journal》2004,77(2):163-175
The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l−1 NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (24) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min−1 preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent), the system achieved a detection limit of 1.14 μg l−1 and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min−1 preconcentration flow rate, 300 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent) from which a detection limit of 14.1 μg l−1 and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used. 相似文献
82.
Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending
on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient,
give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This
review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry
(FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS),
Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and
atom trapping mechanisms are presented.
Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970
Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br
Received December 20, 2001; accepted October 11, 2002 相似文献
83.
84.
Rain water samples collected at three different locations in Italy during 1999 were analysed for heavy metals determination. Results for V, Cr, Mn, Co, Cu, Cd, Sb, Pb, Al and Ni are reported in this paper. For most of the elements higher concentration values have been measured in the samples from Alpe Gera (rural site): only for Cd and V were the concentrations higher at Pisa. The total annual deposition (microg m(-2) y(-1)) shows a similar behaviour, with Alpe Gera being the location with highest total annual input for Cr, Mn, Co, and in particular for Cu, Sb, Pb and Al. The reason of the higher deposition at a rural site in comparison to a urban one (Milan) is not known: further experimental work and investigations are needed. Generally, no evident seasonal trends have been observed for the measured concentrations, while few correlations have been found among elements within the same station. Crustal contribution to total concentration varies from about 20% for V to less than 1% for Cu, Cd, Sb, Pb and Ni. 相似文献
85.
The adsorption of N-acetyl-L-cysteine from ethanol solution on gold has been studied by in situ attenuated total reflection infrared (ATR-IR) spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and a quartz crystal microbalance. After an initial fast adsorption, in situ ATR-IR revealed two considerably slower processes, besides further adsorption. The appearance of carboxylate bands and the partial disappearance of the carboxylic acid bands demonstrated that part of the molecules on the surface underwent deprotonation. In addition, the C=O stretching vibration of the carboxylic acid group shifted to lower and the amide II band to higher wavenumbers, indicating hydrogen-bonding interactions within the adsorbate layer. Based on the initial ATR-IR spectrum, which did not reveal deprotonation, the orientation of the molecule within the adsorbate layer was determined. For this, density functional theory was used to calculate the transition dipole moment vectors of the vibrational modes of N-acetyl-l-cysteine. The projections of the latter onto the z-axis of the fixed surface coordinate system were used to determine relative band intensities for different orientations of the molecule. The analysis revealed that the amide group is tilted with respect to and points away from the surface, whereas the carboxylic acid is in proximity to the surface, which is also supported by a shift of the C-O-H bending mode. This position of the acid group favors its deprotonation assisted by the gold surface and easily enables intermolecular interactions. Periodic acid stimuli revealed reversible protonation/deprotonation of part of the adsorbed molecules. However, only non-hydrogen-bonded carboxylic acid groups showed a response toward the acid stimuli. 相似文献
86.
Alberto Bolognesi Chiara Botta Clara Mercogliano Marco Marinelli W. Porzio Luigi Angiolini Elisabetta Salatelli 《先进技术聚合物》2003,14(8):537-543
The degree of orientation of thin films of eight different polymeric structures, belonging to the class of soluble polyalkylthiophenes (PATs) has been studied. Thin films of the polymers, obtained by spin coating onto glass substrates, were oriented by means of the rubbing technique. The degree of orientation is related to the regioregularity of the system: highly regioregular polymers can be oriented, while regiorandom materials are not oriented. The degree of orientation can be improved by thermal annealing of the oriented films. As a result of annealing, which was performed at different temperatures according to the thermal behavior of the polymers, it was possible to increase the polarization ratio for poly(3-decylthiophene) up to 12–13 as detected from the UV-vis spectra in polarized light. Moreover in the investigated PATs, both the key role of molecular weight and its distribution for achieving a high orientation degree has been assessed. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
87.
Summary A simple and general scheme to exploit any discrete point group symmetry in two-electron integral transformations is introduced. It has been implemented together with integral pre-screening techniques in direct two-electron integral transformations. Its application has also been extended to subsequent MO integral processing steps like MP2 or solution of the coupled-perturbed Hartree-Fock equations (CPHF). Timings for representative applications are presented. 相似文献
88.
A convenient route to new 3-quinolinonyl-pyrazoles and isoxazoles is described through cyclization of 3-[(E)-3-(dimethylamino)-2-propenoyl]-4-hydroxy-1-methyl-2(1H)-quinolinone. The phototoxicity as well as the cytotoxic activities of the title compounds are evaluated against leukemia- and adenocarcinoma-derived cell lines in comparison to the normal human keratinocytes. 相似文献
89.
Substituted polythiophene and triethylenglycolpyrrolidino-C(60) blends are examined by time-resolved electron paramagnetic resonance (TR-EPR) at different temperatures. TR-EPR spectra recorded on the microsecond time scale after a short laser pulse are assigned to polythiophene and fullerene radical ion pairs, generated by electron transfer from the excited state of polythiophene to fullerene. At low temperatures, TR-EPR spectra show polarized lines with an antiphase emission/absorption pattern. The origin of the polarization pattern is described in the frame of spin correlated radical pair theory, in which two unpaired electron spins (on radical cation and anion, respectively) interact through isotropic spin exchange and anisotropic dipolar interactions. The polarization pattern is accounted for assuming a singlet excited state as the precursor of the charge-separated state. Spectral simulations yield dipolar and spin exchange coupling constants between unpaired electrons of the radical ion pair. Their values correspond to a mean distance between opposite charges of 22 A. When the temperature is increased, the spectra gradually loose their antiphase character and eventually consist of a signal totally in emission. This behavior is explained by a polarization mechanism involving a spin-selective charge recombination (ST(-1) mixing). The polarization pattern at different temperatures is examined in detail, and its generating mechanism is discussed. 相似文献
90.
Agnusdei M Bandini M Melloni A Umani-Ronchi A 《The Journal of organic chemistry》2003,68(18):7126-7129
A simple multistep synthetic strategy to 4-substituted 1,2,3,4-tetrahydro-beta-carboline and 1,3,4,9-tetrahydro-pyrano[3,4-b]indole derivatives starting from commercially available indole 2-carboxylic acid (5) is described. The final intramolecular Michael addition promoted by catalytic amount of InBr(3) (5-10 mol %) provided the expected polycyclic compounds in excellent yields (up to 97%) both in anhydrous organic and aqueous media. 相似文献