全文获取类型
收费全文 | 424篇 |
免费 | 19篇 |
专业分类
化学 | 269篇 |
晶体学 | 9篇 |
力学 | 7篇 |
数学 | 60篇 |
物理学 | 98篇 |
出版年
2024年 | 1篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 10篇 |
2017年 | 7篇 |
2016年 | 19篇 |
2015年 | 22篇 |
2014年 | 18篇 |
2013年 | 27篇 |
2012年 | 25篇 |
2011年 | 31篇 |
2010年 | 20篇 |
2009年 | 10篇 |
2008年 | 32篇 |
2007年 | 27篇 |
2006年 | 20篇 |
2005年 | 23篇 |
2004年 | 22篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 1篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1938年 | 1篇 |
1928年 | 2篇 |
排序方式: 共有443条查询结果,搜索用时 250 毫秒
391.
A geometric proof is given of Lee Hwa Chung's theorem for regular Hamiltonian systems, which identifies all the possible differential forms left invariant by the dynamics. Applications of this theorem in the area of canonical transformations are also remarked in a purely geometrical context. 相似文献
392.
The kinetic method is based on the catalytic effect of copper(II) on the atmospheric oxidation of 1,3-cyclopentanedione bis(4-methylthiosemicarbazone) monohydrochloride. The reaction is followed spectrophotometrically at 390 nm. The kinetic parameters of the reaction are reported and a rate equation is suggested. The calibration graphs are linear in the range 0.05–0.5 μg Cu ml?1. Interference by other ions is studied. 相似文献
393.
Braga SS Ribeiro-Claro P Pillinger M Gonçalves IS Pereira F Fernandes AC Romão CC Correia PB Teixeira-Dias JJ 《Organic & biomolecular chemistry》2003,1(5):873-878
Crystalline 1:1 inclusion complexes with beta-cyclodextrin (beta-CD) and the sodium salt of nimesulide (4-nitro-2-phenoxymethanesulfonanilide), and the sodium salt of the derivative 2-phenoxymethanesulfonanilide, have been prepared by co-precipitation from aqueous solution. The presence of true inclusion complexes was supported by elemental analysis, thermogravimetry and powder X-ray diffraction. FTIR and 13C CP MAS NMR spectroscopy confirmed that no chemical modification of the guests occurred upon formation of inclusion complexes. The reaction of the precursors 2-phenoxynitrobenzene and 2-phenoxyaniline with beta-CD was also studied and crystalline inclusion complexes with a 2:1 (host-to-guest) stoichiometry were isolated. The interaction of the different guest species with beta-CD host molecules was studied theoretically by carrying out ab initio calculations. Favourable inclusion geometries were obtained for the four guests mentioned above. On the other hand, it was found that the inclusion of the neutral guests nimesulide and 2-phenoxymethanesulfonanilide was considerably less favourable. This is in agreement with the experimentally observed difficulty in isolating true inclusion complexes containing these guests and beta-CD. The calculated lower stability is attributed to the different steric hindrance arising from the different conformational preferences of neutral and anionic forms. 相似文献
394.
Romão LP Castro GR Rosa AH Rocha JC Padilha PM Silva HC 《Analytical and bioanalytical chemistry》2003,375(8):1097-1100
In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode. 相似文献
395.
A new physically adsorbed capillary coating for capillary electrophoresis-mass spectrometry (CE-MS) of basic proteins is presented, which is easily obtained by flushing the capillary with a polymer aqueous solution for two min. This coating significantly reduces the electrostatic adsorption of a group of basic proteins (i.e., cytochrome c, lysozyme, and ribonuclease A) onto the capillary wall allowing their analysis by CE-MS. The coating protocol is compatible with electrospray inonization (ESI)-MS via the reproducible separation of the standard basic proteins (%RSD values (n = 5) < 1% for analysis time reproducibility and < 5% for peak heights, measured from the total ion electropherograms (TIEs) within the same day). The LODs determined using cytochrome c with total ion current and extracted ion current defection were 24.5 and 2.9 fmol, respectively. Using this new coating lysozymes from chicken and turkey egg white could be easily distinguished by CE-MS, demonstrating the usefulness of this method to differentiate animal species. Even after sterilization at 120 degrees C for 30 min, lysozyme could be detected, as well as in wines at concentrations much lower than the limit marked by the EC Commission Regulation. Adulteration of minced meat with 5% of egg-white could also be analysed by our CE-MS protocol. 相似文献
396.
A simple, sensitive procedure for extractive spectrophotometric determination of nickel has been developed. At pH 8.5, nickel reacts with purpurin (1,2,4-trihydroxyanthraquinone) to form a 1:1 red complex, extractable in methyl isobutyl ketone, with an absorption maximum at 525 nm. The characteristics of the complex, including optimum conditions of formation and extraction, and the adherence to Beer's law, are described. Nickel in cobalt and in iron and aluminum alloys has been determined by this method. 相似文献
397.
Multivariate curve resolution-alternating least squares (MCR-ALS) is shown to be a powerful tool to resolve coelution problems in liquid chromatograpy-mass spectrometry (LC-MS) in scan mode. This investigation was performed using two types of LC columns, one traditional LC column of 25 cm length with a slow gradient and a shorter LC column of 7.5 cm with a rapid gradient which allowed much faster analysis and save of reagents and solvents. Mixtures of multiple biocide compounds were simultaneously analyzed in standard mixtures and in environmental samples (sediment and wastewater samples) with little sample pretreatment. Using the more traditional LC 25 cm column, all biocide compounds were properly resolved by MCR-ALS and quantitatively analyzed with estimated errors always below 20%. When fast chromatography (LC column of 7.5 cm) was used, MCR-ALS resolution of the more strongly coeluted compounds was also achieved but limitations were found in their simultaneous quantitative determination, specially for environmental samples. 相似文献
398.
Contreras C Román R Pérez C Alarcón F Zavala M Pérez S 《Chemical & pharmaceutical bulletin》2005,53(11):1408-1410
A new ulopyranose isolated from aqueous extract of roots and rhizomas of Psacalium peltatum has been determined to have hypoglycemic activity at doses of 100 mg/kg, comparable to that of tolbutamide and insulin in alloxan diabetic mice. The skeletal structure of the new compound was established by spectral analysis. 相似文献
399.
An unusual 3D coordination polymer based on bridging interactions of the nucleobase adenine 总被引:1,自引:0,他引:1
García-Terán JP Castillo O Luque A García-Couceiro U Román P Lezama L 《Inorganic chemistry》2004,43(15):4549-4551
The first 3D coordination polymer containing a nucleobase as a bridging ligand, [[Cu2(mu-ade)4(H2O)2][Cu(ox)(H2O)]2 x approximately 14H2O]n (1), has been synthesized by reaction of adenine (Hade) with a basic solution of K2[Cu(ox)2] x 2H2O (ox = oxalato dianion). Compound 1 crystallizes in the trigonal space group R3 with a = b = 31.350(1) angstroms, c = 14.285(1) angstroms, V = 12158.7(10) angstroms3, and Z = 9. X-ray analysis shows a covalent 3D network in which the copper(II) centers are bridged by tridentate mu-N3,N7,N9 adeninate ligands. The compound has relatively large, nanometer-sized tubes associated with the self-assembly process directed solely by metal-ligand interactions. The covalent 3D framework remains intact upon removal of the guest water molecules trapped in the nanotubes. Magnetic measurements indicate an overall antiferromagnetic behavior of the compound. 相似文献
400.
Rodríguez G Gallardo A Fernández M Rebuelta M Buján J Bellón JM Honduvilla NG Escudero C San Román J 《Macromolecular bioscience》2004,4(6):579-586
Hydrophilic polymeric drugs bearing "Triflusal" (4-trifluoromethylsalicylic acid), a drug widely used as antithrombogenic agent (Disgren), have been prepared by free radical copolymerization of methacryloyloxyethyl [2-(acetyloxy)-4-(trifluoromethyl)] benzoate (HTRF) and N,N'-dimethylacrylamide (DMA). The reactivity ratios of both monomers have been determined by 1H NMR spectra by applying non-linear least square treatments to the copolymerization equation (terminal model), and the kinetic parameters obtained indicated that the microstructure of copolymer chains is homogeneous, with a random distribution of the active HTRF units along the copolymer chains. That means that for the copolymer system THDMA22 used in this work, HTRF units are mainly isolated in relatively long DMA sequences. Therefore, in this structure the intramolecular interactions between adjacent HTRF units are negligible. Release of Triflusal from THDMA22 has been studied in vitro using buffered solutions at pH = 2, 7.4 and 10 and 37 degrees C. The system showed an interesting pseudo-zero order release profile at pH = 7.4 during several months. It has been also evaluated the pharmacological activity and the behavior of the system in contact with biological media. In this sense, we have carried out some in vitro studies about the antiaggregant properties and biocompatibility of THDMA22. Results demonstrate that this copolymer inhibits platelet aggregation in its macromolecular form and presents a good biocompatibility with Human Osteoblastic Cells (HOS). 相似文献