全文获取类型
收费全文 | 1345篇 |
免费 | 30篇 |
国内免费 | 14篇 |
专业分类
化学 | 794篇 |
晶体学 | 6篇 |
力学 | 40篇 |
数学 | 325篇 |
物理学 | 224篇 |
出版年
2023年 | 6篇 |
2022年 | 16篇 |
2021年 | 14篇 |
2020年 | 22篇 |
2019年 | 12篇 |
2018年 | 28篇 |
2017年 | 24篇 |
2016年 | 48篇 |
2015年 | 54篇 |
2014年 | 41篇 |
2013年 | 91篇 |
2012年 | 76篇 |
2011年 | 98篇 |
2010年 | 79篇 |
2009年 | 48篇 |
2008年 | 78篇 |
2007年 | 80篇 |
2006年 | 48篇 |
2005年 | 53篇 |
2004年 | 60篇 |
2003年 | 35篇 |
2002年 | 43篇 |
2001年 | 21篇 |
2000年 | 31篇 |
1999年 | 17篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1974年 | 5篇 |
1966年 | 6篇 |
1965年 | 4篇 |
1962年 | 6篇 |
1959年 | 7篇 |
1958年 | 7篇 |
1957年 | 22篇 |
1956年 | 13篇 |
1955年 | 15篇 |
排序方式: 共有1389条查询结果,搜索用时 15 毫秒
51.
Piotr Cmoch Anna Korda Lucie Rárová Jana Oklešťková Miroslav Strnad Roman Luboradzki Zbigniew Pakulski 《Tetrahedron》2014
A concise synthesis of lupane triterpenes with an elongated carbon chain at the C-28 position, as well as saponins containing d-mannose, l-arabinose, and l-rhamnose moieties at the C-3 position is described. The overall synthesis of the new triterpenes involved seven linear steps starting from natural betulin: selective protection of a hydroxyl group, oxidation, elongation of the carbon chain by Grignard reaction, and deoxygenation. O-Glycosides were obtained by glycosylation of triterpenes with classical Schmidt's donors. Additionally, all new compounds were evaluated in vitro for their cytotoxic activities. Several triterpenes and the corresponding saponins exhibited an interesting cytotoxic activity profile against human cancer cell lines. The therapeutical index of active triterpenes is very high, since almost none of them were cytotoxic for normal BJ fibroblasts. These results open the way to the synthesis of various lupane-type saponin derivatives as potentially bioactive compounds. 相似文献
52.
The paper deals with the classical fiber bundle model with brittle Weibull fibers and equal load sharing. This model is significant for the strength of fibrous materials and composites, and the generally random strength of quasi-brittle structures. The model is also relevant for the analysis of the reliability of various parallel systems (computer components, infrastructure etc.). An improved closed-form Gaussian approximation of the standard deviation of bundle strength is presented and compared with accurate solution calculated by recursive formula proposed by Daniels. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
53.
Petrovic Jelena Savovic Jelena Rankovic Dragan Kuzmanovic Miroslav 《Plasma Chemistry and Plasma Processing》2022,42(3):519-533
Plasma Chemistry and Plasma Processing - This work presents a study of the applicability of laser-induced breakdown spectroscopy based on infrared transversally excited atmospheric CO2 pulsed laser... 相似文献
54.
Karoll Ferrer Katy Díaz Miroslav Kvasnica Andrs F. Olea Mauricio Cuellar Luis Espinoza 《Molecules (Basel, Switzerland)》2021,26(4)
The metabolism of brassinosteroid leads to structural modifications in the ring skeleton or the side alkyl chain. The esterification and glycosylation at C-3 are the most common metabolic pathways, and it has been suggested that conjugate brassinosteroids are less active or inactive. In this way, plants regulate the content of active brassinosteroids. In this work, the synthesis of brassinosteroid 24-norcholane type analogs conjugated at C-3 with benzoate groups, carrying electron donor and electron attractant substituents on the aromatic ring, is described. Additionally, their growth-promoting activities were evaluated using the Rice Lamina Inclination Test (RLIT) and compared with that exhibited by brassinolide (used as positive control) and non-conjugated analogs. The results indicate that at the lowest tested concentrations (10−8–10−7 M), all analogs conjugated at C-3 exhibit similar or higher activities than brassinolide, and the diasteroisomers with S configuration at C-22 are the more active ones. Increasing concentration (10−6 M) reduces the biological activities of analogs as compared to brassinolide. 相似文献
55.
Veronika Petrulova Maria Vilkova Zuzana Kovalikova Matus Sajko Miroslav Repcak 《Molecules (Basel, Switzerland)》2020,25(23)
Phytochemical investigations of Matricaria chamomilla L. (Asteraceae) stated the presence of several compounds with an established therapeutic and antioxidant potential. The chamomile non-enzymatic antioxidant system includes low molecular mass compounds, mainly polyphenols such as cinnamic, hydroxybenzoic and chlorogenic acids, flavonoids and coumarins. The objective of this work was to evaluate the role of the non-enzymatic antioxidant system after stimulation by ethylene in tetraploid chamomile plants. Seven days of ethylene treatment significantly increased the activity of phenylalanine ammonia-lyase, which influenced the biosynthesis of protective polyphenols in the first step of their biosynthetic pathway. Subsequently, considerable enhanced levels of phenolic metabolites with a substantial antioxidant effect (syringic, vanillic and caffeic acid, 1,5-dicaffeoylquinic acid, quercetin, luteolin, daphnin, and herniarin) were determined by HPLC-DAD-MS. The minimal information on the chlorogenic acids function in chamomile led to the isolation and identification of 5-O-feruloylquinic acid. It is accumulated during normal conditions, but after the excessive effect of abiotic stress, its level significantly decreases and levels of other caffeoylquinic acids enhance. Our results suggest that ethephon may act as a stimulant of the production of pharmaceutically important non-enzymatic antioxidants in chamomile leaves and thus, lead to an overall change in phytochemical content and therapeutic effects of chamomile plants, as well. 相似文献
56.
Kamil Motyka Jan Hlavá?Miroslav Soural Pavel HradilPetr Krej?í Lubomír KvapilMiloš Weiss 《Tetrahedron letters》2011,52(6):715-717
2-(4-Amino-substituted-3-nitrophenyl)-3-hydroxyquinolin-4(1H)-ones have been studied to evaluate their fluorescence properties and possible use as molecular fluorescent probes. The amino group was substituted with various alkyl moieties possessing a suitable terminal functional group (such as hydroxy or amino group) that could serve to bind a 3-hydroxyquinolin-4(1H)-one (3HQ) fluorescence label to a biomolecule. Besides simple hydrocarbon chains, ligands containing ethylenoxy units as optimal spacers were also tested. The structure-fluorescence properties and theoretical applicability of the studied molecules are discussed. 相似文献
57.
Miroslav Pohanka 《Chemical Papers》2015,69(1):4-16
Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) are enzymes expressed in the human body under physiological conditions. AChE is an important part of the cholinergic nerves where it hydrolyses neurotransmitter acetylcholine. Both cholinesterases are sensitive to inhibitors acting as neurotoxic compounds. In analytical applications, the enzymes can serve as a biorecognition element in biosensors as well as simple disposable sensors (dipsticks) and be used for assaying the neurotoxic compounds. In the present review, the mechanism of AChE and BChE inhibition by disparate compounds is explained and methods for assaying the enzymes activity are shown. Optical, electrochemical, and piezoelectric biosensors are described. Attention is also given to the application of sol-gel techniques and quantum dots in the biosensors’ construction. Examples of the biosensors are provided and the pros and cons are discussed. 相似文献
58.
Luk Fojt Bohumír Grüner Jan Nekvinda Ece Zeynep Tzn Ludk Havran Miroslav Fojta 《Molecules (Basel, Switzerland)》2022,27(6)
In this study we explore the effect on the electrochemical signals in aqueous buffers of the presence of hydrophilic alkylhydroxy and carboxy groups on the carbon atoms of cobalta bis(dicarbollide) ions. The oxygen-containing exo-skeletal substituents of cobalta bis(dicarbollide) ions belong to the perspective building blocks that are considered for bioconjugation. Carbon substitution provides wider versatility and applicability in terms of the flexibility of possible chemical pathways. However, until recently, the electrochemistry of compounds substituted only on boron atoms could be studied, due to the unavailability of carbon-substituted congeners. In the present study, electrochemistry in aqueous phosphate buffers is considered along with the dependence of electrochemical response on pH and concentration. The compounds used show electrochemical signals around −1.3 and +1.1 V of similar or slightly higher intensities than in the parent cobalta bis(dicarbollide) ion. The signals at positive electrochemical potential correspond to irreversible oxidation of the boron cage (the C2B9 building block) and at negative potential correspond to the reversible redox process of (CoIII/CoII) at the central atom. Although the first signal is typically sharp and its potential can be altered by a number of substituents, the second signal is complex and is composed of three overlapping peaks. This signal shows sigmoidal character at higher concentrations and may be used as a diagnostic tool for aggregation in solution. Surprisingly enough, the observed effects of the site of substitution (boron or carbon) and between individual groups on the electrochemical response were insignificant. Therefore, the substitutions would preserve promising properties of the parent cage for redox labelling, but would not allow for the further tuning of signal position in the electrochemical window. 相似文献
59.
Miroslav M. Ristić Muna M. Aoneas Mirjana M. Vojnović Goran B. Poparić 《Plasma Chemistry and Plasma Processing》2017,37(5):1431-1443
Excitation of electronic states of the N2 molecule by electron impact is recognized as an essential process in nitrogen plasmas that strongly impacts their chemical reactivity and other properties. Many surface and coating technologies are based on radio-frequency plasma discharges in nitrogen. In this paper the electron impact excitation rate coefficients for singlet and triplet electronic states of the N2 molecule have been calculated in non-equilibrium conditions in the presence of a radio-frequency electric field. A Monte Carlo simulation has been performed in order to determine non-equilibrium electron energy distribution functions within one period of the electric field. By using these distribution functions, the excitation rate coefficients have been obtained in the frequency range from 13.56 up to 500 MHz, at reduced electric field values from 200 to 700 Td. 相似文献