全文获取类型
收费全文 | 1127篇 |
免费 | 26篇 |
国内免费 | 2篇 |
专业分类
化学 | 820篇 |
晶体学 | 22篇 |
力学 | 13篇 |
数学 | 142篇 |
物理学 | 158篇 |
出版年
2023年 | 13篇 |
2022年 | 25篇 |
2021年 | 21篇 |
2020年 | 24篇 |
2019年 | 20篇 |
2018年 | 16篇 |
2017年 | 20篇 |
2016年 | 33篇 |
2015年 | 28篇 |
2014年 | 26篇 |
2013年 | 54篇 |
2012年 | 53篇 |
2011年 | 91篇 |
2010年 | 29篇 |
2009年 | 42篇 |
2008年 | 76篇 |
2007年 | 56篇 |
2006年 | 37篇 |
2005年 | 42篇 |
2004年 | 28篇 |
2003年 | 29篇 |
2002年 | 26篇 |
2001年 | 23篇 |
2000年 | 16篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1994年 | 7篇 |
1993年 | 12篇 |
1992年 | 9篇 |
1991年 | 12篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1978年 | 16篇 |
1977年 | 14篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 7篇 |
1973年 | 9篇 |
1968年 | 5篇 |
排序方式: 共有1155条查询结果,搜索用时 10 毫秒
41.
Sabina Strano-Rossi Erika Castrignanò Luca Anzillotti Sara Odoardi Fabio De-Giorgio Ana Bermejo Vincenzo L. Pascali 《Analytica chimica acta》2013
A method for the screening of various anabolic steroids and their esters in human hair, based on liquid-chromatography–high resolution mass spectrometry using an Exactive benchtop Orbitrap mass spectrometer, has been set up and validated. This method involved methanolic incubation of 30 mg of hair and analysis of the relevant extract in HPLC using a C18 column. The mass detector, with nominal resolving power of 100,000, operated in full scan mode in APCI under positive ionization mode. Analytes were identified by exact mass, correspondence of isotopic cluster and retention times. 相似文献
42.
43.
Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers. 相似文献
44.
Juliana Sih Shyam S. Bansal Stefano Filipini Silvia Ferrati Kunal Raghuwansi Erika Zabre Eugenia Nicolov Daniel Fine Mauro Ferrari Ganesh Palapattu Alessandro Grattoni 《Analytical and bioanalytical chemistry》2013,405(5):1547-1557
Novel drug delivery systems capable of continuous sustained release of therapeutics have been studied extensively for use in the prevention and management of chronic diseases. The use of these systems holds promise as a means to achieve higher patient compliance while improving therapeutic index and reducing systemic toxicity. In this work, an implantable nanochannel drug delivery system (nDS) is characterized and evaluated for the long-term sustained release of atorvastatin (ATS) and trans-resveratrol (t-RES), compounds with a proven role in managing atherogenic dyslipidemia and promoting cardioprotection. The primary mediators of drug release in the nDS are nanofluidic membranes with hundreds of thousands of nanochannels (up to 100,000/mm2) that attain zero-order release kinetics by exploiting nanoconfinement and molecule-to-surface interactions that dominate diffusive transport at the nanoscale. These membranes were characterized using gas flow analysis, acetone diffusion, and scanning and transmission electron microscopy (SEM, TEM). The surface properties of the dielectric materials lining the nanochannels, SiO2 and low-stress silicon nitride, were further investigated using surface charge analysis. Continuous, sustained in vitro release for both ATS and t-RES was established for durations exceeding 1 month. Finally, the influence of the membranes on cell viability was assessed using human microvascular endothelial cells. Morphology changes and adhesion to the surface were analyzed using SEM, while an MTT proliferation assay was used to determine the cell viability. The nanochannel delivery approach, here demonstrated in vitro, not only possesses all requirements for large-scale high-yield industrial fabrication, but also presents the key components for a rapid clinical translation as an implantable delivery system for the sustained administration of cardioprotectants. 相似文献
45.
Szekeres E Acosta E Sabatini DA Harwell JH 《Journal of colloid and interface science》2005,287(1):273-287
Solubilization of dodecanol-limonene binary oil mixtures has been studied in saturated Winsor type I and III sodium dihexyl sulfosuccinate microemulsions. The systems showed different oil solubilization behavior below and above dodecanol volume fraction 0.2. Below 0.2 dodecanol volume fraction regular Winsor type microemulsions formed. The oil solubilization was characterized in this concentration range by the optimum salinity and the maximum characteristic length. Dodecanol showed Langmuirian-type surface excess adsorption at the vicinity of the surfactant layer. Variation of the optimum salinity and middle phase characteristic length with increasing dodecanol concentration could be linked to changes in the dodecanol surface excess. These relationships were used to develop new mathematical models for the optimum salinity and characteristic length as a function of oil phase composition. Both models yield excellent agreement with the data. Above dodecanol volume fraction 0.2 regular Winsor type III microemulsions are not formed. Therefore our new models are not applicable in this concentration range. 相似文献
46.
Prins-type macrocyclizations have recently emerged as a successful strategy in the synthesis of polyketide-derived natural products. This reaction provides a concise and selective means to form tetrahydropyran-containing macrocyclic rings of varying size. A high degree of functionality within the macrocycle is tolerated and the yields for these transformations are typically good to excellent. Since the initial report of a Prins macrocyclization reaction in 1979, examples of this approach did not re-emerge until 2008. However, the use of this method in natural product synthesis has rapidly gained momentum in the synthetic community, with multiple examples of this macrocyclization tactic reported in the recent literature. 相似文献
47.
Patrizia Di Gennaro Silvana Bernasconi Fulvia Orsini Erika Corretto Guido Sello 《Tetrahedron: Asymmetry》2010,21(15):1885-1889
The use of two oxidoreductases (an aldoketo reductase from Escherichia coli JM109 and an alcohol dehydrogenase from Lactobacillus brevis) has demonstrated that it is possible to prepare enatiomerically pure diols in a one-pot operation. The reactions were applied to the synthesis of (1R)-1-[3-(hydroxymethyl)phenyl]ethanol and (1S)-1-phenylethane-1,2-diol, using a two-step procedure. The yield is nearly quantitative and the enantiomeric purity is greater than 95%. A third step has been introduced by adding a cell biocatalyst showing dihydrodiol dehydrogenase activity from Pseudomonas fluorescens N3. This allows for the preparation of 3-[(1R)-1-hydroxyethyl]benzoic acid and (2S)-hydroxy(phenyl)ethanoic acid. 相似文献
48.
Leydi Erika Sarmiento Mildred Rodríguez Lorenzo Echevarria Vito Lubes 《Journal of solution chemistry》2010,39(10):1484-1491
The complex species formed between vanadium(III) and 1,10-phenanthroline (phen), 2,2′-bipyridine (bipy), and 8-hydroxyquinoline
(8hq) were studied in aqueous solution by means of electromotive forces measurements, emf(H), at 25 °C with 3.0 mol⋅dm−3 KCl as the ionic medium. The potentiometric data were analyzed using the least-squares computational program LETAGROP, taking
into account the hydrolytic vanadium(III) species formed in solution. Analysis of the vanadium(III)–phen system data shows
the formation of [VHL]4+, [V(OH)L]2+, [V2OL2]4+ and [V2OL4]4+ complexes. In the vanadium(III)–bipy system the [VHL]4+, [V(OH)L]2+, [V2OL2]4+ and [V2OL4]4+ complexes were observed, and in the vanadium(III)–8hq system the complexes [V(OH)L]+, [V(OH)2L], [VL2]+ and [VL3] were detected. 相似文献
49.
Aye Aye Mar Ali Koohang Nathan D. Majewski Erika L. Szotek David A. Eiznhamer Michael T. Flavin Ze Qi Xu 《中国化学快报》2009,20(10):1141-1144
28-Carboxymethoxy lupane tritepenoids 3 and 4 were synthesized by alkylation of betulin with the THP protected 2-hydroxyethyl iodide followed by oxidation and reduction.Direct reaction of betulin (5) or betulone (10) with ethyl bromoacetate led to 28-O-acylation, instead of 28-O-alkylation.The targeted compounds 3 and 4 were not cytotoxic at the highest concentrationtested (75 mmol/L), suggesting that elongation of the chain length at the 28-position in both betulinic acid (1) and betulonic acid (2)was detrimental to the cytotoxicity.The acylation products 28-O-bromoacetates (8a, 8b and 11) and 28-O-methoxyacetate 13exhibited cytotoxicity against several cancer cell lines tested. 相似文献
50.
Annika Gackstatter Prof. Dr. Holger Braunschweig Dr. Thomas Kupfer Christian Voigt Dr. Nicole Arnold 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16415-16419
Reaction of a N‐heterocyclic silylene (NHSi) with PhBX2 (X=Cl, Br) readily afforded six‐membered silaborinines through an insertion/ring expansion sequence. Increasing the sterics of the borane from phenyl to duryl enabled the selective generation and isolation of the highly colored silylborane intermediates. Theoretical studies on the mechanism and energetics of the silaborinine formation were fully consistent with the experimental observations. 相似文献