全文获取类型
收费全文 | 5184篇 |
免费 | 49篇 |
国内免费 | 50篇 |
专业分类
化学 | 4273篇 |
晶体学 | 1篇 |
力学 | 19篇 |
数学 | 70篇 |
物理学 | 920篇 |
出版年
2024年 | 7篇 |
2023年 | 25篇 |
2022年 | 22篇 |
2021年 | 20篇 |
2020年 | 6篇 |
2019年 | 11篇 |
2018年 | 14篇 |
2017年 | 5篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 24篇 |
2013年 | 6篇 |
2012年 | 436篇 |
2011年 | 649篇 |
2010年 | 127篇 |
2009年 | 35篇 |
2008年 | 516篇 |
2007年 | 530篇 |
2006年 | 550篇 |
2005年 | 509篇 |
2004年 | 391篇 |
2003年 | 283篇 |
2002年 | 255篇 |
2001年 | 173篇 |
2000年 | 173篇 |
1999年 | 77篇 |
1998年 | 47篇 |
1997年 | 23篇 |
1996年 | 64篇 |
1995年 | 38篇 |
1994年 | 50篇 |
1993年 | 61篇 |
1992年 | 60篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1983年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1969年 | 3篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有5283条查询结果,搜索用时 15 毫秒
941.
Tuomikoski S Virkkala N Rovio S Hokkanen A Sirén H Franssila S 《Journal of chromatography. A》2006,1111(2):258-266
Integrated solid-phase extraction-zone electrophoresis (SPE-ZE) device has been designed and fabricated on microchip. The structures were fabricated by using multiple layers of SU-8 polymer with a novel technique that enables easy alignment and high yield of the chips. SU-8 adhesive bonding has two major advantages: it enables bonding of high aspect ratio pillars and it results in fully SU-8 microchannels with uniform electrokinetic flow properties. The SPE-ZE device has a fluidic reservoir with 15:1 high aspect ratio pillars for bead filters that act as a SPE part in the chip structure. The separation unit is a 25 mm long electrophoresis channel starting from the outlet of SPE reservoir. Argon laser-induced fluorescence (LIF) detector was used to monitor simultaneously the SPE reservoir and the detection site at the end of the electrophoresis channel. Flow characteristics and electric field distributions were simulated with Femlab software. Fluorescein was used as the analyte for detecting the operational performance of the chip. Adsorption, bead rinsing, elution and detection were tested to verify functioning of the chip design. 相似文献
942.
Teijón C Olmo R Blanco MD Teijón JM Romero A 《Journal of colloid and interface science》2006,295(2):393-400
Polymeric matrices of poly(2-hydroxyethyl methacrylate) (PHEMA) crosslinked with different percentages of ethylene glycol dimethacrylate (EGDMA) as well as different loads of nickel salt were synthesized. Nickel release from the polymeric systems, and their thermal stability were analyzed. A high percentage of the nickel loaded was released, although strong interactions between the polymeric matrices and the nickel ion must be established since a total nickel release did not take place. The values of the diffusion coefficients showed that nickel release depended on the amount of nickel salt loaded in the polymeric matrix and also on the crosslinking degree of the gels. On the other hand, the presence of nickel salt induced an evident thermal instability in the polymeric matrices, although all the polymeric systems can be considered thermally stable. 相似文献
943.
Ramos-Tejada MM Ontiveros-Ortega A Giménez-Martín E Espinosa-Jiménez M Molina Díaz A 《Journal of colloid and interface science》2006,297(1):317-321
Data are presented on the kinetics, electrokinetics, and surface free energy in the process of adsorption of polyethyleneimine (PEI) as a pretreatment of Leacril, later dyed with the reactive dye Remazol Brilliant Blue R (RBBR). The electrokinetic potential of Leacril is negative, due probably to the presence of sulfonate and sulfate end-group onto Leacril fibers. The zeta potential of Leacril decreases in absolute value as a function of NaCl concentration in solution, probably because of compression of the electrical double layer. The zeta potential of Leacril as a function of the concentration of PEI in solution increases because of the adsorption of PEI ions through chemical reaction between the sulfonate end-groups of Leacril and the amine groups of PEI. The adsorption kinetics shows that an increase in the concentration of PEI, brings about an increase in the amount of RBBR adsorbed onto the fiber. This may be an indication of the chemical reaction between the reactive groups of the polyelectrolyte and dye molecules. The behavior of the surface free energy of the systems involved confirms these conclusions. 相似文献
944.
Pérez Pavón JL del Nogal Sánchez M Fernández Laespada ME García Pinto C Moreno Cordero B 《Analytica chimica acta》2006,576(2):156-162
A high-speed determination of benzene in gasoline samples using a non-separative method based on direct injection into the mass spectrometer is proposed. The results obtained are very similar to those provided with fast GC-MS.The calibration set was made up of gasoline samples in which the benzene was determined chromatographically and samples of gasoline subjected to a process of evaporation - until the complete disappearance of the original benzene - to which known concentrations of this compound had been added. A PLS1 multivariate calibration model was constructed. Cross-validation was used to select the optimum number of PLS components. The prediction capacity of the model was checked with an additional group of gasoline samples that had not been used either in the construction or in the validation of the model.With the direct injection method proposed here it was possible to analyse 24 samples over a period of 1 h. The direct injection method is rapid, simple and - in view of the results - highly suitable for the determination of benzene in gasoline samples. 相似文献
945.
Reino JL Durán-Patrón RM Daoubi M Collado IG Hernández-Galán R 《The Journal of organic chemistry》2006,71(2):562-565
[reaction: see text] The biosynthetic origin of the botcinolide skeleton was investigated by means of feeding 13C- and 2H-labeled precursors to Botrytis cinerea. Three new compounds, two homobotcinolide derivatives, 3-O-acetylhomobotcinolide (5) and 8-methylhomobotcinolide (6), and a new 11-membered lactone (7), were isolated. Their structures were elucidated on the basis of spectroscopic data, including one-bond and long-range 1H-13C correlations. The relative stereochemistries were determined by combined analyses of NOE data and 1H-1H coupling constants. According to the results of feeding experiments with 13C- and 2H-labeled acetate and l-S-methylmethionine, 5 is an acetate-derived polyketide whose methyl groups originate from l-S-methylmethionine. This is a rare example of the incorporation of a methyl from methionine into a supposed C3 starter unit of the polyketide synthesis. 相似文献
946.
Alajarín M Cabrera J Pastor A Sanchez-Andrada P Bautista D 《The Journal of organic chemistry》2006,71(14):5328-5339
The reaction of 2-(phenylamino)- and 2-(dimethylamino)thiazoles with dimethyl acetylenedicarboxylate led unexpectedly to dimethyl 6-(phenylamino)- and 6-(dimethylamino)-3,4-pyridinedicarboxylates. Those compounds reasonably result from a sequence of reactions initiated by a [2 + 2] cycloaddition of the alkyne to the formal C=C of the thiazole ring. These pyridines were obtained in nearly all the cases assayed as the exclusive reaction products under rather mild conditions and in fair to good yields. In contrast, the regioisomeric 2-amino-3,4-pyridinedicarboxylates, which would result from a [4 + 2] cycloaddition followed by sulfur extrusion, were only obtained in one particular case. The two reaction paths leading alternatively to both regioisomers were investigated computationally. The respective [2 + 2] and [4 + 2] cycloadducts were found to be formed stepwise from a common dipolar intermediate. Notably, the step following the [2 + 2] cycloaddition (i.e., the ring opening of the fused cyclobutene intermediate to give an all-cis 1,3-thiazepine) was found to take place in a disrotatory mode. Although geometric constraints and electronic factors may reduce the energy for the disrotation, the implication of the fused five-membered ring in the electronic reorganization leading to the 1,3-thiazepine is determinant. In this sense, this step could be regarded also as a thermally allowed six-electron five-center disrotatory electrocyclic ring opening. The proposed mechanism was experimentally supported by the isolation of several intermediates and other experimental facts. 相似文献
947.
Kirgöz UA Odaci D Timur S Merkoçi A Alegret S Beşün N Telefoncu A 《Analytica chimica acta》2006,570(2):165-169
A gelatin membrane with carboxyl esterase and alcohol oxidase was subsequently integrated onto the surface of a graphite epoxy composite electrode (GECE). The developed biosensors showed linearity in the range of 2.5–400 μM for aspartame and 2.5–25 μM for ethanol with response times of 170 and 70 s for each analyte, respectively. The resulting bienzyme biosensor was used for aspartame detection in diet coke samples and ethanol detection in beer and wine samples. From the obtained results, it can be concluded that the developed biosensor is a selective, practical and economic tool for aspartame and ethanol detection in real samples. 相似文献
948.
Repositories for the disposal of radioactive waste generally rely on a multi-barrier system to isolate the waste from the biosphere. This multi-barrier system typically comprises the natural geological barrier provided by the repository host rock and its surroundings and an engineered barrier system (EBS). Bentonite is being studied as an appropriated porous material for an EBS to prevent or delay the release and transport of radionuclides towards biosphere. The study of pore water chemistry within bentonite barriers will permit to understand the transport phenomena of radionuclides and obtain a database of the bentonite-water interaction processes. In this work, the measurement of some chemical parameters in bentonite pore water using solid-state microsensors is proposed. Those sensors are well suited for this application since in situ measurements are feasible and they are robust enough for the long periods of time that monitoring is needed in an EBS. A probe containing an ISFET (ion sensitive field effect transistor) for measuring pH, and platinum microelectrodes for measuring conductivity and redox potential was developed, together with the required instrumentation, to study the chemical changes in a test cell with compacted bentonite. Response features of the sensors’ probe and instrumentation performance in synthetic samples with compositions similar to those present in bentonite barriers are reported. Measurements of sensors stability in a test cell are also presented. 相似文献
949.
A novel complex-assisted hydrothermal route is presented to fabricate ultralong Ag/C nanocables with length ranging from 100 to 180 microm on a large scale, based on the reaction of sulfamic acid silver and salicylic acid. By chemical etching of these Ag/C nanocables, high-quality carbonaceous nanotubes can be obtained at room temperature. Using the as-prepared Ag/C nanocables as templates, a new strategy for introducing guest materials into hollow nanotubes is addressed. We take Ag(2)Se as an example and validate the feasibility of this strategy. All of the products are characterized in detail by multiform techniques: X-ray diffraction, Fourier transform IR, energy-dispersive X-ray analysis, field emission scanning electron microscopy, transmission electron microscopy (TEM), and high-resolution TEM. The formation mechanisms of these products are tentatively proposed. 相似文献
950.
Canoa P González-Moa MJ Teijeira M Terán C Uriarte E Pannecouque C De Clercq E 《Chemical & pharmaceutical bulletin》2006,54(10):1418-1420
Novel nucleoside analogues of structure 3-5 were synthesized starting from (+/-)-cis-2-amino-3-cyclopentenylmethanol (1). The chlorine derivative 3 inhibited both HIV-1 and HIV-2 replication in MT-4 cells with IC(50) values of 10.67 microM and of 13.79 microM, respectively. 相似文献