全文获取类型
收费全文 | 15958篇 |
免费 | 486篇 |
国内免费 | 53篇 |
专业分类
化学 | 12833篇 |
晶体学 | 80篇 |
力学 | 254篇 |
数学 | 1937篇 |
物理学 | 1393篇 |
出版年
2023年 | 132篇 |
2022年 | 528篇 |
2021年 | 602篇 |
2020年 | 354篇 |
2019年 | 405篇 |
2018年 | 309篇 |
2017年 | 237篇 |
2016年 | 529篇 |
2015年 | 533篇 |
2014年 | 520篇 |
2013年 | 1000篇 |
2012年 | 1053篇 |
2011年 | 1200篇 |
2010年 | 718篇 |
2009年 | 713篇 |
2008年 | 1019篇 |
2007年 | 933篇 |
2006年 | 822篇 |
2005年 | 771篇 |
2004年 | 645篇 |
2003年 | 532篇 |
2002年 | 517篇 |
2001年 | 188篇 |
2000年 | 155篇 |
1999年 | 122篇 |
1998年 | 127篇 |
1997年 | 118篇 |
1996年 | 147篇 |
1995年 | 88篇 |
1994年 | 91篇 |
1993年 | 85篇 |
1992年 | 66篇 |
1991年 | 83篇 |
1990年 | 61篇 |
1989年 | 81篇 |
1988年 | 67篇 |
1987年 | 56篇 |
1986年 | 53篇 |
1985年 | 67篇 |
1984年 | 85篇 |
1983年 | 45篇 |
1982年 | 72篇 |
1981年 | 60篇 |
1980年 | 57篇 |
1979年 | 47篇 |
1978年 | 54篇 |
1977年 | 38篇 |
1976年 | 33篇 |
1975年 | 24篇 |
1963年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
91.
Vacca A Nativi C Cacciarini M Pergoli R Roelens S 《Journal of the American Chemical Society》2004,126(50):16456-16465
A new tripodal receptor for the recognition of monosaccharides is described. The prototypical host 1 features a 1,3,5-substituted 2,4,6-triethylbenzene scaffold bearing three convergent H-bonding units. The binding ability of the t-octyl derivative 1a toward a set of octylglycosides of biologically relevant monosaccharides, including Glc, Gal, Man, and GlcNAc, was investigated by 1H NMR in CDCl3. A protocol for the correct evaluation of binding affinities was established, which can be generally applied for the recognition of monosaccharides by 1H NMR spectroscopy. A three-constant equilibrium model, including 1:1 and 2:1 host-guest association and dimerization of the receptor, was ascertained for the interaction of 1a with all the investigated glycosides. An affinity index, which we defined median binding concentration BC50 in analogy to the IC50 parameter, intended to address the general issue of comparing dimensionally heterogeneous binding data, and a limiting BC0(50)quantity describing intrinsic binding affinities were developed for evaluating the results. BC0(50) values for 1a range from 1 to 6 mM, indicating an intrinsic binding affinity in the millimolar range and a selectivity factor of 5 toward the investigated glycosides. The treatment has been extended to include any generic host-guest system involved in single or multiple binding equilibria. 相似文献
92.
A new chemical method is reported for the determination of total fluoride in complex liquids and suspensions, such as fruit juices, urine, serum and blood. It is based on the formation of the A1F radical in a graphite furnace afterin situ oxygen-assisted ashing of the untreated sample. The absorbance of this radical is measured at 227.45 nm. The method is relatively easy to use and provides a low detection limit (14 ng/ml) and reasonable reproducibility (5–10%). 相似文献
93.
Jean-Charles Lancelot Bertrand Letois Sylvain Rault Max Robba Maria Rogosca 《Journal of heterocyclic chemistry》1994,31(2):501-504
Cyclization of 3-(1-pyrrolyl)thiophene-2-carboxamide derivatives of methyl 3-(1-pyrrolyl)-2-thiophenecarboxylate afforded imminium salts and resulted in the formation of thieno[2,3-b]pyrrolizine derivatives. 相似文献
94.
Mirella Ferrugia Maria Luisa Bajardi Leopoldo Ceraulo Salvatore Plescia 《Journal of heterocyclic chemistry》1992,29(2):565-568
The fragmentation reactions induced by electron impact of eighteen title compounds has been investigated with the aid of low beam energy spectra (14 eV, nom. value), metastable ion detection, high resolution measurements and labelling experiments. The loss of the 4-carbonyl oxygen together with the 3-substituent, which constitutes a characteristic fragmentation route of 3-aryl and 3-heteroaromatic substituted-4(3H)-quinazolinones, is again observed, but the presence of a carboxyethyl group at the 4′-position of the pyrazole ring is responsible of an anomalous loss of 47 daltons from the molecular ion. Lastly, a comparison with the previously described behaviour of 3-(5′-isoxazolyl) derivatives was carried out. 相似文献
95.
Gaetano Alberghina Maria Emanuela Amato Francesco Agatino Bottino Antonino Corsaro Salvatore Fisichella 《Journal of heterocyclic chemistry》1986,23(6):1747-1752
The 1H-nmr data of some (Z)-α-(p-substituted-phenyl)-β-(2-furyl), -(2-pyrrolyl), and -(N-methyl-2-pyrrolyl)-acrylonitriles have been investigated to indicate the preferred conformation and to establish the conformational preferences of the β-heterocyclic ring. The ultraviolet spectra have been discussed in order to obtain information about the chromophores responsible for the absorption. The infrared spectra have been analyzed for the identification of the main absorption frequencies of cyano and ethylenic groups and to assign the characteristic absorption bands to specific normal vibrations of the heteroaromatic nuclei. 相似文献
96.
María Luisa Moyá Setefilla Escalera Cristina Martín Amalia Rodríguez María Mu?oz María del Mar Graciani 《Reaction Kinetics and Catalysis Letters》2006,89(1):177-182
Summary The reaction methyl 4-nitrobenzenesulfonate + Br- was studied in water-formamide tetradecyltrimethylammonium bromide micellar solutions. A pseudophase kinetic model was used
to quantitatively rationalize the kinetic micellar effects observed 相似文献
97.
Claudio Baggiani Gianfranco Giraudi Cristina Giovannoli Cinzia Tozzi Laura Anfossi 《Analytica chimica acta》2004,504(1):43-52
The current opinion about molecular imprinted polymers (MIPs) is that their molecular recognition properties are due to the presence of nanocavities formed during a polymerization process developed in the presence of a template molecule. According to this principle, the shape of these nanocavities is complementary to that of the template and non-covalent interactions are established between the binding site and a single template molecule. Nevertheless, there are some experimental indications that the real molecular recognition mechanism involves clusters of template molecules being packed into the binding site. Recently, it has been proposed that template molecules covalently linked to the binding site can act as nucleation points, enhancing the formation of these molecular clusters.We have tested this hypothesis by studying the adsorption isotherms of polymers prepared by imprinting them with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Three different polymers were considered: P0, prepared without the template, P1, whose template was represented by 2,4,5-T molecules, and P2, whose template was 1/3 constituted by the polymerisable 2-(2,4,5-trichlorophenoxyacetoxy)-ethylmethacrylate (2,4,5-TEMA) and 2/3 by 2,4,5-T. The polymers were prepared by thermoinduced polymerization of template mixtures, 4-vinylpyridine and ethylene dimethacrylate. The crushed polymers were packed into HPLC columns and frontal chromatographic runs were performed by eluting the columns with a mobile phase containing variable amounts of 2,4,5-T.The experimental adsorption isotherms were fitted by using several isotherm models, and the Freundlich-Langmuir model was found to give the best fitting in terms of F-test. All the models considered showed a significant difference between the affinity constant values measured for the polymer P1 and P2, with a higher value for the polymer P2 (for Freundlich-Langmuir model: polymer P1, k=(2.00±0.43)×104 M−1; polymer P2, k=(1.93±0.0535)×105 M−1; ratio P2/P1, 9.65±2.09). Such experimental results support the hypothesis that a polymer prepared with a limited amount of template covalently attached to the binding site shows an increased affinity for the template itself. 相似文献
98.
E. Anklam Maria Rosa Bassani Thomas Eiberger Stefan Kriebel Markus Lipp Reinhard Matissek 《Analytical and bioanalytical chemistry》1997,357(7):981-984
Pyrolysis Mass Spectrometry (Py-MS) was used for the discrimination of cocoa butters from other vegetable fats. Mass spectra
ranging from 50 amu to 250 amu were analyzed by principal component analysis (PCA) and with neural nets. The application of
neural nets leads to a good discrimination between the two classes. Detailed analysis of the nets revealed that only the first
60 masses were used within the net. The use of PCA requires a careful selection of the number of masses included in the calculation.
Canonical variance analysis was applied to determine the significant masses. Optimal performance of PCA was observed only
using the first 22 significant masses. Most of these masses were different from the ones used by the neural net. It seems
that the mass spectra obtained by Py-MS contain sufficient information for the discrimination of pure cocoa butter from other
vegetable fats, but none of the methods seems to be able to extract all information available. Neural net provides a very
robust method for this task and no prior data selection was necessary.
Received: 13 May 1996 / Revised: 7 August 1996 / Accepted: 7 August 1996 相似文献
99.
Conditions have been found which make possible the determination of thallium and/or lead in cadmium and its salts without preliminary separation. The electrochemical activity of the cadmium, which usually interferes in the determination of thallium, is inhibited by the addition of 0.01% of polyethylene glycol of M.W. 4000. Thallium is determined by electrolysis at ?0.74 V vs. SCE, in 0.1M EDTA solution: 10?1M thallium can be determined in the presence of 0.1M cadmium, while copper and lead at 10?2M and 10?5M respectively do not interfere. Lead is determined in 0.1M acetic acid containing 0.1% cetyltrimethylammonium bromide (CTAB). The addition of CTAB shifts the cadmium peak, as well as the optimum deposition potential for cadmium, to more negative values, making it possible to determine lead in the presence of cadmium as long as the deposition potential lies in the range between ?0.50 and ?0.56 V vs. SCE. Lead can be determined in the presence of ten times as much thallium. 相似文献
100.
An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10?5 M. 相似文献