全文获取类型
收费全文 | 7469篇 |
免费 | 356篇 |
国内免费 | 58篇 |
专业分类
化学 | 5708篇 |
晶体学 | 58篇 |
力学 | 147篇 |
综合类 | 1篇 |
数学 | 707篇 |
物理学 | 1262篇 |
出版年
2023年 | 57篇 |
2022年 | 125篇 |
2021年 | 163篇 |
2020年 | 185篇 |
2019年 | 180篇 |
2018年 | 130篇 |
2017年 | 127篇 |
2016年 | 263篇 |
2015年 | 227篇 |
2014年 | 270篇 |
2013年 | 449篇 |
2012年 | 535篇 |
2011年 | 607篇 |
2010年 | 341篇 |
2009年 | 312篇 |
2008年 | 475篇 |
2007年 | 452篇 |
2006年 | 427篇 |
2005年 | 423篇 |
2004年 | 339篇 |
2003年 | 281篇 |
2002年 | 241篇 |
2001年 | 133篇 |
2000年 | 117篇 |
1999年 | 62篇 |
1998年 | 51篇 |
1997年 | 63篇 |
1996年 | 73篇 |
1995年 | 54篇 |
1994年 | 48篇 |
1993年 | 63篇 |
1992年 | 51篇 |
1991年 | 43篇 |
1990年 | 45篇 |
1989年 | 54篇 |
1988年 | 34篇 |
1987年 | 30篇 |
1986年 | 32篇 |
1985年 | 41篇 |
1984年 | 26篇 |
1983年 | 16篇 |
1982年 | 21篇 |
1981年 | 30篇 |
1980年 | 20篇 |
1979年 | 21篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 13篇 |
1974年 | 19篇 |
1973年 | 11篇 |
排序方式: 共有7883条查询结果,搜索用时 0 毫秒
991.
Sample preparation methods used for genetically modified organisms (GMOs) analysis are often time consuming, require extensive manual manipulation, and result in limited amounts of purified protein, which may complicate the detection of low‐abundance GM protein. A robust sample pretreatment method prior to mass spectrometry (MS) detection of the transgenic protein (5‐enolpyruvylshikimate‐3‐phosphate synthase [CP4 EPSPS]) present in Roundup Ready soya is investigated. Liquid chromatography‐multiple reaction monitoring tandem MS (nano LC‐MS/MS‐MRM) was used for the detection and quantification of CP4 EPSPS. Gold nanoparticles (AuNPs) and concanavalin A (Con A)‐immobilized Sepharose 4B were used as selective probes for the separation of the major storage proteins in soybeans. AuNPs that enable the capture of cysteine‐containing proteins were used to reduce the complexity of the crude extract of GM soya. Con A‐sepharose was used for the affinity capture of β‐conglycinin and other glycoproteins of soya prior to enzymatic digestion. The methods enabled the detection of unique peptides of CP4 EPSPS at a level as low as 0.5% of GM soya in MRM mode. Stable‐isotope dimethyl labeling was further applied to the quantification of GM soya. Both probes exhibited high selectivity and efficiency for the affinity capture of storage proteins, leading to the quantitative detection at 0.5% GM soya, which is a level below the current European Union's threshold for food labeling. The square correlation coefficients were greater than 0.99. The approach for sample preparation is very simple without the need for time‐consuming protein prefractionation or separation procedures and thus presents a significant improvement over existing methods for the analysis of the GM soya protein. 相似文献
992.
Mohanad A. Hussein Uyen P. N. Tran Vien T. Huynh Junming Ho Mohan Bhadbhade Herbert Mayr Thanh V. Nguyen 《Angewandte Chemie (International ed. in English)》2020,59(4):1455-1459
Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β‐bromo‐α‐cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron‐deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine‐ or phosphine‐catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo‐cycloheptatrienylated adducts are reported. 相似文献
993.
Qi Teng Wenxiu Mao Dong Chen Zhen Wang Chen‐Ho Tung Zhenghu Xu 《Angewandte Chemie (International ed. in English)》2020,59(6):2220-2224
A rhodium(I)‐BINAP‐catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo‐, regio‐, diastereo‐, and enantioselectivity. Notable features of these reactions include 100 % atom economy, very broad scope, and mild reaction conditions. 相似文献
994.
Isabel V. L. Wilkinson Kelly J. Perkins Hannah Dugdale Lee Moir Aini Vuorinen Maria Chatzopoulou Sarah E. Squire Sebastian Monecke Alexander Lomow Marcus Geese Philip D. Charles Peter Burch Jonathan M. Tinsley Graham M. Wynne Stephen G. Davies Francis X. Wilson Fraydoon Rastinejad Shabaz Mohammed Kay E. Davies Angela J. Russell 《Angewandte Chemie (International ed. in English)》2020,59(6):2420-2428
Duchenne muscular dystrophy (DMD) is a fatal muscle‐wasting disease arising from mutations in the dystrophin gene. Upregulation of utrophin to compensate for the missing dystrophin offers a potential therapy independent of patient genotype. The first‐in‐class utrophin modulator ezutromid/SMT C1100 was developed from a phenotypic screen through to a Phase 2 clinical trial. Promising efficacy and evidence of target engagement was observed in DMD patients after 24 weeks of treatment, however trial endpoints were not met after 48 weeks. The objective of this study was to understand the mechanism of action of ezutromid which could explain the lack of sustained efficacy and help development of new generations of utrophin modulators. Using chemical proteomics and phenotypic profiling we show that the aryl hydrocarbon receptor (AhR) is a target of ezutromid. Several lines of evidence demonstrate that ezutromid binds AhR with an apparent KD of 50 nm and behaves as an AhR antagonist. Furthermore, other reported AhR antagonists also upregulate utrophin, showing that this pathway, which is currently being explored in other clinical applications including oncology and rheumatoid arthritis, could also be exploited in future DMD therapies. 相似文献
995.
Lee HS Kim do H Cho JH Hwang M Jang Y Cho K 《Journal of the American Chemical Society》2008,130(32):10556-10564
To investigate the effects of the phase state (ordered or disordered) of self-assembled monolayers (SAMs) on the growth mode of pentacene films and the performance of organic thin-film transistors (OTFTs), we deposited pentacene molecules on SAMs of octadecyltrichlorosilane (ODTS) with different alkyl-chain orientations at various substrate temperatures (30, 60, and 90 degrees C). We found that the SAM phase state played an important role in both cases. Pentacene films grown on relatively highly ordered SAMs were found to have a higher crystallinity and a better interconnectivity between the pentacene domains, which directly serves to enhance the field-effect mobility, than those grown on disordered SAMs. Furthermore, the differences in crystallinity and field-effect mobility between pentacene films grown on ordered and disordered substrates increased with increasing substrate temperature. These results can be possibly explained by (1) a quasi-epitaxy growth of the pentacene film on the ordered ODTS monolayer and (2) the temperature-dependent alkyl chain mobility of the ODTS monolayers. 相似文献
996.
A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments. 相似文献
997.
MacLean PD Chapman EE Dobrowolski SL Thompson A Barclay LR 《The Journal of organic chemistry》2008,73(17):6623-6635
The absolute rate constants, k(inh), and stoichiometric factors, n, of pyrroles, 2-methyl-3-ethylcarboxy-4,5-di-p-methoxyphenylpyrrole, 6, 2,3,4,5-tetraphenylpyrrole, 7, and 2,3,4,5-tetra-p-methoxyphenylpyrrole, 8, compared to the phenolic antioxidant, di-tert-butylhydroxyanisole, DBHA, during inhibited oxidation of cumene initiated by AIBN at 30 degrees C gave the relative antioxidant activities (k(inh)) DBHA > 8 > 7 > 6 and n = 2, whereas in styrene, 8 > DBHA. These results are explained by hydrogen atom transfer, HAT, from the N-H of pyrroles to ROO(*) radicals. The k(inh) values in styrene of dimethyl esters of the bile pigments of bilirubin ester (BRDE), of biliverdin ester (BVDE), and of a model compound (dipyrrinone, 1) gave k(inh) in the order pentamethylhydroxychroman (PMHC) > BRDE > 1 > BVDE. These antioxidant activities for BVDE and the model compound, 1, and PMHC dropped dramatically in the presence of methanol due to hydrogen bonding at the pyrrolic N-H group. In contrast the k(inh) of BRDE increased in methanol. We now show that pyrrolic compounds may react by HAT, proton-coupled electron transfer, PCET, or single electron transfer, SET, depending on their structure, the nature of the solvent, and the attacking radical. Compounds BVDE and 1 react by the HAT or PCET pathway (HAT/PCET) in styrene/chlorobenzene with ROO(*) and with the DPPH(*) radical in chlorobenzene according to N-H/N-D kH/kD of 1.6, whereas the DKIE with BRDE was only 1.2 with ROO(*). The antioxidant properties of polypyrroles of the BVDE class and model compounds (e.g., 1) are controlled by intramolecular H bonding which stabilizes an intermediate pyrrolic radical in HAT/PCET. According to kinetic polar solvent effects on the monopyrrole, 8, and BRDE, which gave increased rates in methanol, some pyrrolic structures are also susceptible to SET reactions. This conclusion is supported by some calculated ionization potentials. The antioxidant mechanism for BRDE with peroxyl radicals is described by the PCET reaction. Experiments using the 2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical (DBMP(*)) showed this to be a better radical to monitor HAT activities in stopped-flow kinetics compared to the use of the more popular DPPH(*) radical. 相似文献
998.
This study examines the supercritical carbon dioxide (SC-CO(2)) extraction of oryzanols contained rice bran oil from powdered rice bran. The extraction efficiencies and concentration factors of oryzanols, free fatty acids and triglycerides in the SC-CO(2) extracts were determined. With top-flow type SC-CO(2) extraction the total oil yield was 18.1% and the extraction efficiencies of oryzanols and triglycerides were 88.5 and 91.3% respectively, when 2750 g CO(2 )was consumed during the extraction of 35 g rice bran powder. The concentration factors of oryzanols and triglycerides in SC-CO(2)-extracted oil were higher than in the Soxhlet n-hexane extracted oil. SC-CO(2) extractions indicated that pressure can be used more effectively than temperature to enhance the extraction efficiency and concentration factor of oryzanols. A two-factor central composite scheme of response surface methodology was employed to determine the optimal pressure (300 bar) and temperature (313 K) for increasing the concentration of oryzanols in the SC-CO(2) extracted oil. 相似文献
999.
Srivastava S Ball V Podsiadlo P Lee J Ho P Kotov NA 《Journal of the American Chemical Society》2008,130(12):3748-3749
The exponentially growing layer-by-layer (LBL) films made from poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used to load and unload the CdTe nanoparticles (NPs). The reversible loading of NPs were investigated through UV-vis studies and further confirmed by confocal microscopy. In addition the LBL films were also compared for the release kinetics for pH 9 and 7 and films capped with (PDDA-PSS)10 layers. The amount of released particles at pH 9 was found to be at least 2 orders of magnitude higher than those at pH 7 and with (PDDA-PSS)10 capped layers after 25 h. This variation in film response for CdTe-particle release presents a route for studies in which highly swollen exponentially growing LBL films can be loaded with functionalized NPs for biological applications and explored as carriers to hold the NPs inside the films for self-assembly. 相似文献
1000.
Benzyltriphenylphosphonium trans-tetrachloro(methanol)oxomolybdate(V) has been obtained from methanol suspension of benzyltriphenylphosphonium molybdate(VI) saturated with hydrogen chloride. The crystal structure comprises discrete trans-tetrachloro(methanol)oxomolybdate(V) anions and benzyltriphenylphosphonium cations. The anion has distorted octahedral geometry of central atom with visible trans influence imposed by short Mo-O bond (1.659(2) Å). The methanol O atom is bonded to the Mo atom, the bond being mostly electrostatic in character. A comparison with previously reported structures indicates that the methanol methyl moiety can switch between different positions with respect to the chloride ligands. 相似文献