全文获取类型
收费全文 | 5026篇 |
免费 | 233篇 |
国内免费 | 22篇 |
专业分类
化学 | 3801篇 |
晶体学 | 40篇 |
力学 | 82篇 |
数学 | 643篇 |
物理学 | 715篇 |
出版年
2024年 | 6篇 |
2023年 | 38篇 |
2022年 | 119篇 |
2021年 | 122篇 |
2020年 | 101篇 |
2019年 | 119篇 |
2018年 | 104篇 |
2017年 | 57篇 |
2016年 | 191篇 |
2015年 | 161篇 |
2014年 | 176篇 |
2013年 | 326篇 |
2012年 | 369篇 |
2011年 | 391篇 |
2010年 | 226篇 |
2009年 | 225篇 |
2008年 | 339篇 |
2007年 | 315篇 |
2006年 | 277篇 |
2005年 | 270篇 |
2004年 | 236篇 |
2003年 | 150篇 |
2002年 | 212篇 |
2001年 | 70篇 |
2000年 | 54篇 |
1999年 | 50篇 |
1998年 | 43篇 |
1997年 | 52篇 |
1996年 | 44篇 |
1995年 | 40篇 |
1994年 | 22篇 |
1993年 | 36篇 |
1992年 | 25篇 |
1991年 | 28篇 |
1990年 | 24篇 |
1989年 | 23篇 |
1988年 | 11篇 |
1987年 | 16篇 |
1986年 | 23篇 |
1985年 | 23篇 |
1984年 | 26篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 13篇 |
1980年 | 17篇 |
1979年 | 9篇 |
1978年 | 21篇 |
1977年 | 10篇 |
1976年 | 6篇 |
1970年 | 7篇 |
排序方式: 共有5281条查询结果,搜索用时 31 毫秒
141.
The use of aerosol produced in a nebulization chamber is proposed as an alternative to gas sample capture in flow systems. This paper describes the coupling of a sampling interface with a flow system, for in situ gas monitoring. Aspects related with the behavior of aerosol formation and gas solubilization in liquid drops are discussed. The method is applied to the determination of residual lime in acidic soils. Aliquots of 5.0 ml of 1.0 mol l−1 HCl were mixed with soil samples (1 g). The CO2 released from these samples was captured by a nebulized aerosol and determined conductivity. The analytical curve from 1.0×10−2 to 5.0×10−2 mol kg−1 CaCO3 was ploted applying the matrix matching approach. This proposition, allowed an increase in the sensibility with detection limit of 6.0×10−3 mol kg−1. The precision was good (R.S.D. <3%) for an analytical frequency of 22 determinations per hour. A fair agreement, at 95% confidence level, was found between the results from the proposed method and certified values of the investigated samples. 相似文献
142.
Jose′ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Fresenius' Journal of Analytical Chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
143.
The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential V(A) on a one-atom density rho(A) or rho(B). To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale. 相似文献
144.
Purification of plasmid DNA vectors by aqueous two-phase extraction and hydrophobic interaction chromatography 总被引:4,自引:0,他引:4
The current study explores the possibility of using a polyethyleneglycol(PEG)-ammonium sulphate aqueous two-phase system (ATPS) as an early step in a process for the purification of a model 6.1 kbp plasmid DNA (pDNA) vector. Neutralised alkaline lysates were fed directly to ATPS. Conditions were selected to direct pDNA towards the salt-rich bottom phase, so that this stream could be subsequently processed by hydrophobic interaction chromatography (HIC). Screening of the best conditions for ATPS extraction was performed using three PEG molecular weights (300, 400 and 600) and varying the tie-line length, phase volume ratio and lysate load. For a 20% (w/w) lysate load, the best results were obtained with PEG 600 using the shortest tie-line (38.16%, w/w). By further manipulating the system composition along this tie-line in order to obtain a top/bottom phase volume ratio of 9.3 (35%, w/w PEG 600, 6%, w/w NH4)2 SO4), it was possible to recover 100% of pDNA in the bottom phase with a three-fold increase in concentration. Further increase in the lysate load up to 40% (w/w) with this system resulted in a eight-fold increase in pDNA concentration, but with a yield loss of 15%. The ATPS extraction was integrated with HIC and the overall process compared with a previously defined process that uses sequential precipitations with iso-propanol and ammonium sulphate prior to HIC. Although the final yield is lower in the ATPS-based process the purity grade of the final pDNA product is higher. This shows that it is possible to substitute the time-consuming two-step precipitation procedure by a simple ATPS extraction. 相似文献
145.
F. B. Belaribi G. Belaribi-Boukais A. Ait-Kaci J. Jose 《Journal of Thermal Analysis and Calorimetry》1995,44(4):911-927
The authors have measured the vapour pressure of four binary systems, morpholine+piperidine, morpholine+1,4-dioxane, morpholine+tetrahydropyrane and 1,4-dioxane+tetrahydropyrane. The measurements were carried out using an isoteniscope built by J. Jose [1]. The vapour pressure, excess Gibbs free energies at 298.15, 303.15, 313.15, 323.15, 333.15 and 343.15 K are reported for these mixtures. The excess Gibbs free energies have been fitted to the Redlich-Kister equation. 相似文献
146.
The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson’s disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)5RuIIIORuIV(NH3)4ORuIII(NH3)5]6+ (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2×10−4 and 1.0×10−2 mol l−1 (r=0.9988) with a detection limit of 8.5×10−5 mol l−1. The variation coefficient for a 1.0×10−3 mol l−1 L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. 相似文献
147.
Flow injection system with gas diffusion for the sequential determination of total nitrogen and phosphorus in vegetables 总被引:1,自引:0,他引:1
Jose´ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Analytical and bioanalytical chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
148.
Rodinei Augusti Marcos N. Eberlin Concetta Kascheres 《Journal of heterocyclic chemistry》1995,32(4):1355-1357
The reactions of carbethoxycarbene (:CH2-CO2Et, 2) with several acyclic enaminones (RCOCH=CR1NHR2, 3) lead to the unexpected formation of 2-Me, 3-CO2Et, 4-H, 5-R1-pyrroles 4 . Structural variations of the enaminones show that the structural fragments C(3)-CO2Et and C(2)-Me are provided by 2 and that the fragment C(5)-R1NHR2 originates from the enaminones 3 , while the RCO group from 3 is eliminated during the course of reaction. Reactions with cyclic and nitrogen-hindered enaminones do not lead to pyrrole formation but occur by simple insertion of 2 to the Cα-H bond. 相似文献
149.
Rosario Pardo Marcos Zayat David Levy 《Journal of Sol-Gel Science and Technology》2006,40(2-3):365-370
A photochromic naphthopyran derivative was embedded in sol-gel prepared thin ormosil films. The resulting samples show high
transparency and exhibit a strong red colouration upon irradiation with UV light. The photostability of the photochromic molecules
is strongly related to the nature of the embedding ormosil matrix. The introduction of organic functional groups into the
inner pore surface of the matrix allows tailoring the chemical environment where the dye molecules will be allocated, in terms
of the effectiveness of the interaction between the photochromic molecules and the Si-OH groups on the surface of the pores,
affecting the stability of the molecules upon prolonged exposition to UV light.
The photostability of the molecules was increased in matrices functionalized with larger organic groups, or with larger amount
of modifying groups. In this way the photodegradation of the photochromic molecules could be reduced by a factor of 5, as
compared with the photodegradation of the molecules in unfunctionalized silica matrix. 相似文献
150.
Determination of pirimicarb and endosulfan in commercial pesticide formulations by Fourier transform infrared spectrometry 总被引:1,自引:0,他引:1
Quintás G Moros J Armenta S Garrigues S de la Guardia M 《Journal of AOAC International》2005,88(2):399-405
A routine method based on Fourier transform infrared spectrometry was developed for the simultaneous determination of pirimicarb and endosulfan in commercially available pesticide formulations. The method is based on peak area absorbance measurements between 1362 and 1352 cm(-1), corrected with a baseline fixed at 1338 cm(-1), for pirimicarb and peak area absorbance measurements between 919 and 909 cm(-1) with a baseline fixed at 931 cm(-1) for endosulfan; chloroform solutions for analysis were obtained by direct dilution of emulsifiable concentrates or by solvent extraction from solid samples. Various extraction conditions and appropriate band selection were investigated, and interference studies were performed. Under the experimental conditions selected, limits of detection of 13 microg/g for pirimicarb and 150 microg/g for endosulfan were obtained that correspond to 0.13 and 1.6% (w/w), respectively, in commercial samples. Results from analyses of commercial samples by the developed method compared well with those obtained by a liquid chromatography reference method. 相似文献