全文获取类型
收费全文 | 765篇 |
免费 | 36篇 |
国内免费 | 4篇 |
专业分类
化学 | 627篇 |
晶体学 | 7篇 |
力学 | 9篇 |
数学 | 96篇 |
物理学 | 66篇 |
出版年
2023年 | 4篇 |
2022年 | 17篇 |
2021年 | 21篇 |
2020年 | 26篇 |
2019年 | 17篇 |
2018年 | 13篇 |
2017年 | 10篇 |
2016年 | 32篇 |
2015年 | 37篇 |
2014年 | 20篇 |
2013年 | 40篇 |
2012年 | 50篇 |
2011年 | 61篇 |
2010年 | 39篇 |
2009年 | 28篇 |
2008年 | 39篇 |
2007年 | 51篇 |
2006年 | 41篇 |
2005年 | 37篇 |
2004年 | 32篇 |
2003年 | 29篇 |
2002年 | 18篇 |
2001年 | 9篇 |
2000年 | 13篇 |
1999年 | 16篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1973年 | 2篇 |
1923年 | 1篇 |
排序方式: 共有805条查询结果,搜索用时 15 毫秒
791.
Muftah M. Basher Yuri E. Corilo Regina Sparrapan Mario Benassi Rodinei Augusti Marcos N. Eberlin José M. Riveros 《Journal of mass spectrometry : JMS》2012,47(11):1526-1535
Gas‐phase reactions of model carbosulfonium ions (CH3‐S+ = CH2; CH3CH2‐S+ = CH2 and Ph‐S+ = CH2) and an O‐analogue carboxonium ion (CH3‐O+ = CH2) with acyclic (isoprene, 1,3‐butadiene, methyl vinyl ketone) and cyclic (1,3‐cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6‐311 G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4 + 2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S‐analogues, CH3‐O+ = CH2 (as well as C2H5‐O+ = CH2 and Ph‐O+ = CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2 = CH‐O+ = CH2 ion forms an abundant [4 + 2+] cycloadduct with isoprene, but similar to the behavior of such α,β‐unsaturated carboxonium ions in solution, seems to occur across the C = C bond. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
792.
Costa EV Dutra LM Nogueira PC Moraes VR Salvador MJ Ribeiro LH Gadelha FR 《Natural product communications》2012,7(2):265-266
The essential oil from the leaves of Annona vepretorun was obtained by hydrodistillation using a Clevenger-type apparatus and analyzed by GC-MS and GC-FID. Eighteen compounds representing 98.1% of the crude essential oil were identified. The major compounds identified were bicyclogermacrene (43.7%), spathulenol (11.4%), alpha-felandrene (10.0%), alpha-pinene (7.1%), (E)-beta-ocimene (6.8%), germacrene D (5.8%), and p-cymene (4.2%). The trypanocidal activity against Trypanosoma cruzi epimastigote forms, as well as, the antimicrobial and antioxidant proprieties was investigated. The essential oil showed a potent trypanocidal activity with IC50 value of 31.9 +/-1.3 microg x mL(-1). For antimicrobial activity, the best result was observed against Candida tropicalis with a MIC value of 100 microg x mL(-1). For antioxidant capacity the essential oil showed weak activity. 相似文献
793.
The validation of a microbiological assay, applying cylinder plate method for determination of the activity of lomefloxacin in coated tablets is described. Using a strain of Bacillus subtilis ATCC 9372 as the test organism, lomefloxacin was measured in concentrations ranging from 2.0 to 8.0 microg/mL. The method validation showed that it is linear (r = 0.9999), precise (relative standard deviation = 1.15%), and accurate (it measured the added quantities). The excipients did not interfere in the determination. It was concluded that the microbiological assay is satisfactory for quantitation of lomeflox tablets. 相似文献
794.
de Sousa GF Deflon VM Gambardella MT Francisco RH Ardisson JD Niquet E 《Inorganic chemistry》2006,45(11):4518-4525
The synthesis and the IR, NMR (1H, 13C, and 119Sn), and M?ssbauer spectroscopies and single-crystal X-ray diffraction studies of seven-coordinated diorganotin(IV) complexes, namely, [Ph2Sn(Hdapsc)]Cl.H2O.DMF [7; H(2)dapsc = 2,6-diacetylpyridine bis(semicarbazone)], [Me(2)Sn(H2,6Achexim)]Br.H2O [8; H(2)2,6Achexim = 2,6-diacetylpyridine bis(3-hexamethyleneiminylthiosemicarbazone)], [Me(2)Sn(dapmts)] [9; H(2)dapmts = 2,6-diacetylpyridine bis(4-methythiosemicarbazone)], and [nBu2Sn(dapmdtc)] [10; H(2)dapmdtc = 2,6-diacetylpyridine bis(S-methydithiocarbazate)], were done. The determination of the structures of [Ph(2)Sn(Hdapsc)]+, [Me2Sn(H2,6Achexim)]+ and [Me2Sn(dapmts)], [nBu2Sn(dapmdtc)] revealed the presence of monocationic and neutral complexes, respectively. The structures consist of monomeric units in which the Sn(IV) ions exhibit distorted pentagonal-bipyramidal geometries, with the X,N,N,N,X-donor (X = O, S) systems of the ligands lying in the equatorial plane and the organic groups in the apical positions. The C-Sn-C angle in the seven-coordinated diorganotin(IV) complexes was estimated using a correlation between M?ssbauer and X-ray data based on the point-charge model and using new values obtained in this work for [alkyl] = -1.00 mm s(-1) and [aryl] = -0.80 mm s(-1) for complexes containing O,N,N,N,O-pentadentate ligands and new values for [alkyl] = -0.87 mm s(-1) and [aryl] = -0.75 mm s(-1) for complexes containing S,N,N,N,S-pentadentate ligands. 相似文献
795.
Haddad R Sparrapan R Eberlin MN 《Rapid communications in mass spectrometry : RCM》2006,20(19):2901-2905
Sonic spray ionization is shown to create a supersonic cloud of charged droplets able to promote efficient desorption and ionization of drugs directly from the surfaces of commercial drug tablets at ambient conditions. Compared with desorption electrospray ionization (DESI), desorption sonic spray ionization (DeSSI) is advantageous since it uses neither heating nor high voltages at the spray capillary. DeSSI therefore provides a more friendly environment in which to perform ambient mass spectrometry (MS). DeSSI-MS is herein evaluated for the analysis of drug tablets, and found to be, in general, as sensitive as DESI-MS. The (high) voltage-free DeSSI method provides, however, cleaner mass spectra with less abundant solvent cluster ions and with enough abundant analyte signal for tandem mass spectrometry (MS/MS). These features may therefore facilitate the DeSSI-MS detection of low molar mass components or impurities, or both. The higher-velocity supersonic DeSSI spray also facilitates matrix penetration thus providing more homogenous sampling and longer lasting ion signals. 相似文献
796.
Czerwonka R Reddy KR Baum E Knölker HJ 《Chemical communications (Cambridge, England)》2006,(7):711-713
The first enantioselective total synthesis of neocarazostatin B, the determination of its absolute configuration and transformation into carquinostatin A are described. 相似文献
797.
Occurrence and chemical speciation analysis of organotin compounds in the environment: A review 总被引:3,自引:0,他引:3
Regina de Carvalho Oliveira 《Talanta》2010,82(1):9-24
Environmental concerns regarding organotin compounds have increased remarkably in the past 20 years, due in large part to the use of these compounds as active components in antifouling paints [mainly tributyltin (TBT)] and pesticide formulations [mainly triphenyltin (TPhT)]. Their direct introduction into the environment, their bio-accumulation and the high toxicity of these compounds towards “non-target” organisms (for example: oysters and mussels) causes environmental and economic damage around the world. As a consequence, the presence and absence of organotin compounds is currently monitored in a range of environmental matrices (e.g., water, sediment and shellfish) to examine the utility of controls meant to regulate the level of contamination as required in some EC Directives and the Water Framework Directive 2000/60/EC. To evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for organotin determination in the environment. Most of these methods include different steps such as extraction, derivatisation and clean up. The aim of the present review is to evaluate the environmental distribution, fate and chemical speciation of organotin compounds in the environment. 相似文献
798.
Betânia H. Lunelli Rafael R. Andrade Daniel I. P. Atala Maria Regina Wolf Maciel Francisco Maugeri Filho Rubens Maciel Filho 《Applied biochemistry and biotechnology》2010,161(1-8):227-237
Lactic acid is an important product arising from the anaerobic fermentation of sugars. It is used in the pharmaceutical, cosmetic, chemical, and food industries as well as for biodegradable polymer and green solvent production. In this work, several bacterial strains were isolated from industrial ethanol fermentation, and the most efficient strain for lactic acid production was selected. The fermentation was conducted in a batch system under anaerobic conditions for 50 h at a temperature of 34 °C, a pH value of 5.0, and an initial sucrose concentration of 12 g/L using diluted sugarcane molasses. Throughout the process, pulses of molasses were added in order to avoid the cell growth inhibition due to high sugar concentration as well as increased lactic acid concentrations. At the end of the fermentation, about 90% of sucrose was consumed to produce lactic acid and cells. A kinetic model has been developed to simulate the batch lactic acid fermentation results. The data obtained from the fermentation were used for determining the kinetic parameters of the model. The developed model for lactic acid production, growth cell, and sugar consumption simulates the experimental data well. 相似文献
799.
The martensitic transformation is described using a phase field model which is in mathematical terms the regularization of a sharp interface approach. In this work, up to two martensitic orientation variants are considered. The evolution of microstructure is assumed to follow a time dependent Ginzburg-Landau equation. The coupled problem of the mechanical balance equation and the evolution equations is solved using finite elements and an implicit time integration scheme. In this work, the global energy evolution during the martensitic transformation and the influence of external loads on the formation of the different martensitic phases are studied in 2d. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
800.
Francisco Carlos Serbena Carlos Eugênio Foerster Alcione Roberto Jurelo Alexandre Mikowski Pedro Rodrigues Júnior Célia Regina Carubelli Carlos Maurício Lepienski 《Brazilian Journal of Physics》2012,42(5-6):330-339
A natural mixture of heavy rare-earth oxides extracted from xenotime mineral have been used to prepare large single crystals of the high-temperature REBa2Cu3O7??? superconductor, grown using the CuO?CBaO self-flux method. Its mechanical properties along the ab-plane were characterized using instrumented indentation. Hardness and elastic moduli were measured by the Oliver and Pharr method, which yielded 7.4?±?0.2?GPa and the range 135?C175?GPa at small depths, respectively. Increased loads promote the nucleation of lateral cracks, which reduce hardness and measured elastic modulus, as indicated by instrumented indentation at higher loads. The indentation fracture toughness, estimated by measuring the radial crack length from cube corner indentations at various loads, was found to be 0.8?±?0.2?MPa m1/2. The observed slip systems of REBa2Cu3O7??? single crystals were [100](001) and [010](001), the same as for YBa2Cu3O7??? single crystals. The initial stages of deformation and fracture in the indentation process were investigated. The hardness and elastic modulus are not strongly modified by the crystallographic orientation in the ab-plane. This was interpreted in terms of resolved shear stresses in the active slip systems. Evidence of cracking along the {100} and {110} planes on the ab-plane was observed. In conclusion, the mechanical properties of REBa2Cu3O7??? single crystals prepared from xenotime are equivalent to those of YBa2Cu3O7??? single crystals from conventional rare-earth oxides. 相似文献