全文获取类型
收费全文 | 28553篇 |
免费 | 669篇 |
国内免费 | 111篇 |
专业分类
化学 | 16261篇 |
晶体学 | 207篇 |
力学 | 839篇 |
综合类 | 9篇 |
数学 | 3886篇 |
物理学 | 8131篇 |
出版年
2023年 | 149篇 |
2022年 | 420篇 |
2021年 | 491篇 |
2020年 | 428篇 |
2019年 | 414篇 |
2018年 | 474篇 |
2017年 | 446篇 |
2016年 | 782篇 |
2015年 | 620篇 |
2014年 | 703篇 |
2013年 | 1175篇 |
2012年 | 1498篇 |
2011年 | 1724篇 |
2010年 | 980篇 |
2009年 | 950篇 |
2008年 | 1465篇 |
2007年 | 1416篇 |
2006年 | 1255篇 |
2005年 | 1666篇 |
2004年 | 1679篇 |
2003年 | 1186篇 |
2002年 | 800篇 |
2001年 | 652篇 |
2000年 | 623篇 |
1999年 | 389篇 |
1998年 | 319篇 |
1997年 | 318篇 |
1996年 | 392篇 |
1995年 | 343篇 |
1994年 | 331篇 |
1993年 | 359篇 |
1992年 | 355篇 |
1991年 | 277篇 |
1990年 | 227篇 |
1989年 | 215篇 |
1988年 | 186篇 |
1987年 | 183篇 |
1986年 | 182篇 |
1985年 | 233篇 |
1984年 | 221篇 |
1983年 | 186篇 |
1982年 | 198篇 |
1981年 | 192篇 |
1980年 | 174篇 |
1979年 | 154篇 |
1978年 | 183篇 |
1977年 | 146篇 |
1976年 | 138篇 |
1974年 | 137篇 |
1973年 | 124篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
971.
972.
A solid-phase microextraction (SPME) sampling method is developed to evaluate indoor exposure to benzene, toluene, ethylbenzene, xylene, and styrene with gas chromatography and flame ionization detection for quantitative analysis. An SPME holder with a 100-pm polydimethylsiloxane (PDMS) and 65-pm PDMS-divinylbenzene fiber coating is tested in different air relative humidity conditions. The method gives good resolution, shows a linear response, is repeatable, and presents high sensitivity. This method is compared with National Institute of Occupational Safety and Health (NIOSH) active sampling. 相似文献
973.
In this study, an analytical procedure for the determination in sediment of the most abundant and/or physiological active estrogens (estradiol, estriol, estrone, ethynyl estradiol, and diethylstilbestrol) and progestogens (progesterone, norethindrone. and levonorgestrel) is described. The procedure includes ultrasonic extraction of the lyophilized sediment, clean-up with octadecylsilica cartridges, and analysis by liquid chromatography-diode array detection-mass spectrometry (LC-DAD-MS). MS detection is performed with an electrospray interface in the positive ion mode for determination of the progestogens and in the negative ion mode for determination of the estrogens. The method was applied to the determination of the target compounds in river sediments from the area of Catalonia. Estrogens and progestogens were found at concentrations usually in the low ng g(-1) range. Estriol and norethindrone were the compounds most frequently found whereas maximum concentrations in all sediment samples were obtained for ethynyl estradiol (22.8 ng g(-1)) and estrone (11.9 ng g(-1)). Detection limits were in the range of 0.04-1.00 ng g(-1). Preliminary conjectures with regards to the environmental behavior and impact of estrogens and progestogens in rivers are made. To the authors' knowledge, this is the first work reporting a detailed method for the analysis of estrogens and progestogens in river sediments and data on the environmental occurrence of both groups of compounds. 相似文献
974.
Theodoridis G Haasnoot W Cazemier G Schilt R Jaziri M Diallo B Papadoyannis IN de Jong GJ 《Journal of chromatography. A》2002,948(1-2):177-185
The application of immunoaffinity chromatography for the purification of Taxus plant and cell extracts prior to the HPLC analysis is described. Polyclonal antibodies raised against 10-deacetylbaccatin III (10-DAB III), paclitaxel's main precursor in plant, were characterised by enzymed-linked immunosorbent assay. Immunoglobulins from selected antisera were immobilised on CNBr-activated Sepharose 4B. The immunoaffinity column was used for the purification of plant and plant cell culture extracts prior to their analysis by HPLC. Immunoaffinity chromatography enabled the selective concentration of taxoids and enhanced sample clean-up. 相似文献
975.
Elenise Bannwart de Moraes Patricia Fazzio Martins César Benedito Batistella Mario Eusebio Torres Alvarez Rubens Maciel Filho Maria Regina Wolf Maciel 《Applied biochemistry and biotechnology》2006,132(1-3):1066-1076
Molecular distillation was studied for the separation of tocopherols from soya sludge, both experimentally and by simulation,
under different operating conditions, with good agreement. Evaporator temperatures varied from 100°C to 160°C and feed flow
rates ranged from 0.1 to 0.8 kg/h. The process pressure was maintained at 10−6 bar, the feed temperature at 50°C, the condenser temperature at 60°C, and the stirring at 350 rpm. For each process condition,
samples of both streams (distillate and residue) were collected and stored at −18°C before tocopherols analyses. Owing to
the differences between molecular weights and vapor pressures of free fatty acids and tocopherols, tocopherols preferentially
remained in the residue at evaporator temperatures of 100°C and 120°C, whereas for higher temperatures (140°C and 160°C) and
lower feed flow rate, tocopherols tended to migrate to the distillate stream. 相似文献
976.
H. T. Matsuda B. F. de Araujo J. A. de Araujo 《Journal of Radioanalytical and Nuclear Chemistry》1995,199(6):453-463
Celeste-1 is a lab-scale hot cell intended for R&D work in reprocessing of low burn-up spent fuel elements. The studies are concerned with head-end, first separation cycle by Purex Process using mini mixer-settlers and development of analytical techniques. The analytical monitoring for process control purposes is based on several off-line techniques, such as X-ray fluorescence spectrometry, potentiometric titration, -and -spectroscopy, spectrophotometry, fluorimetry, density measurement and gas chromatography. The analytical treatment takes place in a shielded working place analytical hot cell, glove boxes and hoods and some final measurements are made in the associated analytical laboratory. A pneumatic system is used for transporting analytical samples. All analytical procedures are ready and in operation. 相似文献
977.
Gerard de Leeuw John S. Field Raymond J. Haines Beth McCulloch Elsie Meintjies Christiaan Monberg Gillian M. Olivier Praveen Ramdial Clifford N. Sampson Beate Sigwarth Nick D. Steen Kandasamy G. Moodley 《Journal of organometallic chemistry》1984,275(1):99-111
Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described. 相似文献
978.
Romeiro NC Albuquerque MG de Alencastro RB Ravi M Hopfinger AJ 《Journal of computer-aided molecular design》2005,19(6):385-400
The p38-mitogen-activated protein kinase (p38-MAPK) plays a key role in lipopolysaccharide-induced tumor necrosis factor-alpha (TNF-alpha) and interleukin-1 (IL-1) release during the inflammatory process, emerging as an attractive target for new anti-inflammatory agents. Four-dimensional quantitative structure-activity relationship (4D-QSAR) analysis [Hopfinger et al., J. Am. Chem. Soc., 119 (1997) 10509] was applied to a series of 33 (a training set of 28 and a test set of 5) pyridinyl-imidazole and pyrimidinyl-imidazole inhibitors of p38-MAPK, with IC50 ranging from 0.11 to 2100 nM [Liverton et al., J. Med. Chem., 42 (1999) 2180]. Five thousand conformations of each analogue were sampled from a molecular dynamics simulation (MDS) during 50 ps at a constant temperature of 303 K. Each conformation was placed in a 2 angstroms grid cell lattice for each of three trial alignments. 4D-QSAR models were constructed by genetic algorithm (GA) optimization and partial least squares (PLS) fitting, and evaluated by leave-one-out cross-validation technique. In the best models, with three to six terms, the adjusted cross-validated squared correlation coefficients, Q2adj, ranged from 0.67 to 0.85. Model D (Q2adj = 0.84) was identified as the most robust model from alignment 1, and it is representative of the other best models. This model encompasses new molecular regions as containing pharmacophore sites, such as the amino-benzyl moiety of pyrimidine analogs and the N1-substituent in the imidazole ring. These regions of the ligands should be further explored to identify better anti-inflammatory inhibitors of p38-MAPK. 相似文献
979.
Preparation and sedimentation behavior in magnetic fields of magnetite-covered clay particles 总被引:4,自引:0,他引:4
Galindo-González C de Vicente J Ramos-Tejada MM López-López MT González-Caballero F Durán JD 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4410-4419
This work is devoted to the preparation of magnetite-covered clay particles in aqueous medium. For this purpose, magnetite nanoparticles were synthesized by a coprecipitation method. These magnetic particles are adhered to sodium montmorillonite (NaMt) particles in aqueous suspensions of both materials, by appropriate control of the electrolyte concentrations. The best condition to produce such heteroaggregation corresponds to acid pH and approximately 1 mol/L ionic strength, when the electrokinetic potentials (zeta-potential) of both NaMt and Fe3O4 particles have high enough and opposite sign, as demonstrated from electrophoresis measurements. When a layer of magnetite re-covers the clay particles, the application of an external magnetic field induces a magnetic moment in clay-magnetite particles parallel to the external magnetic flux density. The sedimentation behavior of such magnetic particles is studied in the absence or presence of an external magnetic field in a vertical direction. The whole sedimentation behavior is also strongly affected by the formation of big flocculi in the suspensions under the action of internal colloidal interactions. van der Waals and dipole-dipole magnetic attractions between magnetite-covered clay particles dominate the flocculation processes. The different relative orientation of the clay-magnetite particles (edge-to-edge, face-to-edge, and face-to-face) are discussed in order to predict the most favored flocculi configuration. 相似文献
980.
With measurement uncertainty estimation accounting for all relevant uncertainty contributions, the results of measurements using the same procedure on different objects or samples may no longer be considered as being independent, and correlations have to be taken into account. For this purpose, a simple approximation for the estimation of covariances is derived and applied to the estimation of uncertainty for some basic combinations of two measurement results. This covariance estimate is also applied to the estimation of uncertainty for the mean value of the results of replicate measurements on the same object or sample.
相似文献
W. HaesselbarthEmail: Phone: +49-30-81041101Fax: +49-30-81045577 |