全文获取类型
收费全文 | 21065篇 |
免费 | 840篇 |
国内免费 | 18篇 |
专业分类
化学 | 14992篇 |
晶体学 | 142篇 |
力学 | 441篇 |
综合类 | 5篇 |
数学 | 2761篇 |
物理学 | 3582篇 |
出版年
2023年 | 162篇 |
2022年 | 214篇 |
2021年 | 335篇 |
2020年 | 379篇 |
2019年 | 402篇 |
2018年 | 389篇 |
2017年 | 344篇 |
2016年 | 741篇 |
2015年 | 643篇 |
2014年 | 746篇 |
2013年 | 1327篇 |
2012年 | 1565篇 |
2011年 | 1694篇 |
2010年 | 994篇 |
2009年 | 852篇 |
2008年 | 1489篇 |
2007年 | 1412篇 |
2006年 | 1251篇 |
2005年 | 1142篇 |
2004年 | 954篇 |
2003年 | 776篇 |
2002年 | 672篇 |
2001年 | 313篇 |
2000年 | 294篇 |
1999年 | 177篇 |
1998年 | 149篇 |
1997年 | 145篇 |
1996年 | 179篇 |
1995年 | 125篇 |
1994年 | 128篇 |
1993年 | 148篇 |
1992年 | 134篇 |
1991年 | 89篇 |
1990年 | 82篇 |
1989年 | 65篇 |
1988年 | 72篇 |
1987年 | 62篇 |
1986年 | 84篇 |
1985年 | 113篇 |
1984年 | 96篇 |
1983年 | 69篇 |
1982年 | 84篇 |
1981年 | 94篇 |
1980年 | 90篇 |
1979年 | 77篇 |
1978年 | 75篇 |
1977年 | 54篇 |
1976年 | 61篇 |
1975年 | 40篇 |
1974年 | 42篇 |
排序方式: 共有10000条查询结果,搜索用时 265 毫秒
991.
Rosa Ana Pérez José Luis Tadeo Beatriz Albero Esther Miguel Consuelo Sánchez-Brunete 《Analytical and bioanalytical chemistry》2013,405(1):389-400
Different extraction methods, followed by gas chromatography coupled to triple quadrupole mass spectrometry, were evaluated for simultaneous extraction of seven polychlorinated biphenyls (PCBs) and six polybrominated diphenyl ethers (PBDEs) from common weeds. Pressurized liquid extraction (PLE) with in-cell clean-up, ultrasound-assisted extraction (UAE) with in-column clean-up, and UAE with dispersive solid-phase extraction (dSPE) clean-up were evaluated and compared. In-cell clean-up with 4 g Florisil and 0.5 g graphitized carbon black (GCB) and two extraction cycles of 10 min with n-hexane–ethyl acetate 80:20 (v/v) at 60 °C were used for the PLE procedure. UAE with in-column clean-up was conducted under conditions similar to those reported for the PLE method whereas in UAE with dSPE clean-up purification of the extract was performed after extraction using primary and secondary amine sorbent (PSA) and GCB. Recovery from 82 to 104 % was obtained for all the compounds by PLE whereas, in general, lower extraction efficiency was obtained by UAE with in-column clean-up (especially for BDE-17 and BDE-183, for which recovery was 70 and 41 %, respectively) and by UAE with dSPE clean-up, for which the main drawback is that BDE-183 cannot be extracted. Finally, PLE was used for analysis of PCBs and PBDEs in different plants (Lolium rigidum, Lactuca serriola, Malva sylvestris, and Verbascum thapsus) collected from residential and/or rural areas of Madrid (Spain). Several of the analyzed compounds were detected at low levels in these plants, but only PCB-153 could be quantified. Figure
Analysis of PCBs and PBDEs from plants 相似文献
992.
B. M. da Fonseca I. E. D. Moreno M. Barroso S. Costa J. A. Queiroz E. Gallardo 《Analytical and bioanalytical chemistry》2013,405(12):3953-3963
A method using microextraction by packed sorbent (MEPS) and gas chromatography–tandem mass spectrometry (GC-MS/MS) is described for the determination of seven antipsychotic drugs in human plasma. The studied compounds were chlorpromazine (CPZ), haloperidol (HAL), cyamemazine, quetiapine, clozapine, olanzapine (OLZ), and levomepromazine; promazine, protriptyline, and deuterated CPZ were used as internal standards. The validation parameters included selectivity, linearity and limits of detection and quantitation, intra- and interday precision and trueness, recovery, and stability and were studied according to internationally accepted guidelines. The method was found to be linear between the lower limit of quantitation and 1000 ng/mL, except for OLZ and HAL (200 ng/mL), with determination coefficients higher than 0.99 for all analytes, and extraction efficiencies ranged from 62 to 92 %. Intra- and interday precision ranged from 0.24 to 10.67 %, while trueness was within a ±15 % interval from the nominal concentration for all analytes at all studied levels. MEPS has shown to be a rapid procedure for the determination of the selected antipsychotic drugs in human plasma, allowing reducing the handling time and the costs of analysis. Furthermore, GC-MS/MS has demonstrated to be a powerful tool for the simultaneous quantitation of the studied compounds, enabling obtaining adequate selectivity and sensitivity using a sample volume of as low as 0.25 mL. 相似文献
993.
994.
Anderson A. B. C. Júnior Gustavo S. G. De Carvalho Lippy F. Marques Charlane C. Corrêa Adilson D. Da Silva Flvia C. Machado 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(8):934-936
The title compound, C14H11NO4, exists in the solid phase in the zwitterionic form, 2‐{[(4‐carboxy‐3‐hydroxyphenyl)iminiumyl]methyl}phenolate, with the H atom from the phenol group on the 2‐hydroxybenzylidene ring transferred to the imine N atom, resulting in a strong intramolecular N—H...O hydrogen bond between the iminium H atom and the phenolate O atom, forming a six‐membered hydrogen‐bonded ring. In addition, there is an intramolecular O—H...O hydrogen bond between the carboxylic acid group and the adjacent hydroxy group of the other ring, and an intermolecular C—H...O contact involving the phenol group and the C—H group adjacent to the imine bond, connecting the molecules into a two‐dimensional network in the (10) plane. π–π stacking interactions result in a three‐dimensional network. This study is important because it provides crystallographic evidence, supported by IR data, for the iminium zwitterionic form of Schiff bases.<!?tpb=12pt> 相似文献
995.
Size-Exclusion Chromatography of Asphaltenes: An Experimental Comparison of Commonly Used Approaches
Asphaltenes, the heaviest and most polar fraction of crude oil, are responsible for the clogging of oil pipelines and of underground reservoir rocks. Asphaltenes are defined as a solubility class (toluene- or benzene-soluble, n-alkane insoluble), and a consensus is still lacking on the molar mass (M) averages, distribution, and range of these materials. Size-exclusion chromatography (SEC) is among the most widely employed methods for characterizing the M averages and distributions of both natural and synthetic polymers and, as such, has seen widespread application in the study of asphaltenes. SEC analysis of asphaltenes presents a number of challenges, however, some inherent to all low-M materials and some unique to these particular analytes. Here, we have experimentally compared several of the most commonly used approaches to SEC of asphaltenes, in hope of both demonstrating the influence of experimental conditions upon the results obtained as well as to determine optimal conditions of analysis. In the end, while the former goal was met, the latter one remains an open challenge in the field. 相似文献
996.
Aline Bruna da Silva Juliano Marini Genaro Gelves Uttandaraman Sundararaj Rinaldo Gregório Jr. Rosario E.S. Bretas 《European Polymer Journal》2013
The objective of this work was to prepare novel conductive blends of poly(vinylidene fluoride) (PVDF) with polypyrrole (PPy) and to compare their performance with PVDF/multiwall carbon nanotube (MWCNT) composites and novel PVDF/PPy/MWCNT hybrid systems. All the compositions were prepared by melt mixing using a miniature mixer. The mixtures were characterized by Fourier transformed infrared (FTIR), wide angle X-ray diffraction (WAXD), thermogravimetric analyses (TGA), scanning and transmission electron microscopy (SEM and TEM, respectively) and volume electrical resistivity. For the binary PVDF/PPy and PVDF/MWCNT systems, percolation thresholds of 10 and 0.3 wt%, respectively, were found. In the hybrid systems, however, the percolation threshold for each filler was lower than in the binary systems, but the electrical conductivities were always much higher at all concentrations than the conductivities of the binary systems. Therefore, the addition of both fillers had a synergistic effect on the hybrid system conductivity, which was attributed to its morphology: the PPy increased the homogeneity of the MWCNT distribution and decreased the available free volume for the MWCNT; as a result the MWCNT rolled around the PPy particles bridging them through the PVDF matrix, increasing the quantum tunneling effect and thus, the electrical conductivity of the system. 相似文献
997.
Patrícia Santiago de Oliveira Patricio Iaci Miranda Pereira Natália Cristina Ferreira da Silva Eliane Ayres Fabiano Vargas Pereira Rodrigo Lambert Oréfice 《European Polymer Journal》2013
Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology. 相似文献
998.
Anderson Hollerbach Klier Ricardo José Alvea Maria Auxiliadora Fontes Prado José Dias de Bouza Filho Norma Beatriz D'accorso 《合成通讯》2013,43(23):4361-4374
The synthesis of 5-[6′-deoxy-(1′,2′:3′,4′-di-O-isopropylidene-α-D-galactopyranos-6′-yl)]tetrazole and its reaction with acetic anhydride and 1,2:3,4-di-O-isopropylidene-6-O-(4-toluenesulfonyl)-α-D-galactopyranose are described. 相似文献
999.
Núbia Boechat Jorge Carlos Santos da Costa Jorge de Souza Mendonça Karla Ceodaro Paes Elisa Lopes Fernandes Pedro Santos Mello de Oliveira 《合成通讯》2013,43(24):3187-3190
Some heteroaromatic esters were reduced to the corresponding alcohols by using a sodium borohydride–methanol system. The reduction was completed within 0.15–2.0 h in refluxing THF. The alcohol products were isolated after aqueous workup in moderate to excellent yield (48–97%). 相似文献
1000.
Regioselective synthesis of haloaromatic tertiary alcohols can be achieved by ortho deprotonation/electrophilic reactions of (η6- fluoroarene)Cr(CO)3 complexes with halobenzophenones and metal removal. The coexistence of different halogens in the aromatic rings of these molecules make them unique within the group of tertiary alcohols. 相似文献