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991.
Dr. Pilar Ventosa‐Andrés Dr. Agustina La‐Venia Dr. Carlos Alfonso Barea Ripoll Dr. Ludmila Hradilová Dr. Viktor Krchňák 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13112-13119
Herein, we describe the synthesis of molecular scaffolds consisting of medium‐sized fused heterocycles using amino acids, which are some of the most useful building blocks used by nature as well as chemists to create structural diversity. The acyclic precursors were assembled by using traditional Merrifield solid‐phase peptide synthesis, and cyclization was carried out through acid‐mediated tandem endocyclic N‐acyliminium ion formation, followed by nucleophilic addition with internal nucleophiles. The synthesis of molecular scaffolds consisting of seven‐, eight‐, and nine‐membered rings proceeded with full stereocontrol of the newly generated stereogenic center in most cases. 相似文献
992.
Single‐Crystal‐to‐Single‐Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene‐Like Compound 下载免费PDF全文
Dr. Naba K. Nath Lukáš Severa Dr. Roman A. Kunetskiy Prof. Ivana Císařová Prof. Michal Fulem Prof. Květoslav Růžička Dr. Dušan Koval Dr. Václav Kašička Dr. Filip Teplý Prof. Panče Naumov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13508-13512
Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid–solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X‐ray diffraction analysis were used to unravel the mechanistic details of this process. The single‐crystal‐to‐single‐crystal course enabled direct monitoring of the structural changes by in situ variable‐temperature X‐ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene‐like compound. 相似文献
993.
High Performance Liquid Chromatography/Electrochemistry/High Resolution Electrospray Ionization‐Mass Spectrometry (HPLC/EC/HR ESI‐MS) Characterization of Selected Cytokinins Oxidation Products 下载免费PDF全文
Michal Karady Ondřej Novák Aleš Horna Miroslav Strnad Karel Doležal 《Electroanalysis》2015,27(2):406-414
Electrochemistry combined with mass spectrometry represents an emerging analytical technique used to study the oxidation pathway of various drugs and in vivo occurring compounds, continuously showing a capability to generate many known metabolites or new oxidation products. An on‐line HPLC/EC/HR ESI‐MS method had been used to investigate the oxidation of selected cytokinin compounds. This setup allowed rapid identification and general structure elucidation of the obtained products. An electrochemical oxidation of isopentenyladenine resulted in five products, including hydroxylated and dehydrogenated products, which correlates very well with its in vivo metabolism. Electrochemical conversion of trans‐zeatin revealed six products, with two dehydrogenation products corresponding to its in vivo occurring metabolites. cis‐Zeatin oxidation in the electrochemical cell gave rise to eight products, resembling similarity to trans‐zeatin oxidation. All three compounds underwent a complete turnover mainly through two oxidation reactions occurring in the electrochemical cell? dehydrogenation and a less typical aliphatic hydroxylation. The resulting products are in correlation with their known in vivo metabolism. 相似文献
994.
Electrochemical Activity of Wedelolactone and Probing its Interaction with DNA Using Voltammetry at a Carbon Electrode 下载免费PDF全文
Wedelolactone (WLA) is a polyphenolic coumestan derivative found in extracts of plants used in traditional medicine. Due to its cytostatic activity, WLA is one of natural compounds tested as potential anticancer drugs. In this work we for the first time studied electrochemical properties of WLA using cyclic (CV) and square‐wave (SWV) voltammetry at the basal‐plane pyrolytic graphite electrode. A reversible pair of peaks, corresponding to catechol/o‐benzoquinone redox system, was observed using CV around 0.275 V vs. Ag|AgCl|3 M KCl reference electrode. Measurements of SWV signal of WLA in the presence of single‐ or double‐stranded DNA suggested a weak interaction without evident preference for double‐stranded DNA. An indirect assay, employing electroactive DNA intercalator doxorubicin as competitor, confirmed absence of intercalative DNA binding of WLA. 相似文献
995.
Enantiomeric separation of 1,3‐dimethylamylamine by capillary electrophoresis with indirect UV detection using a dual‐selector system 下载免费PDF全文
The CE method employing an indirect UV detection for the enantioseparation of 1,3‐dimethylamylamine (DMAA), widely used in various preworkout and dietary supplements labeled as a constituent of geranium extract has been developed. The dual‐selector system consisting of negatively charged sulfated α‐CD (1.1% w/v) and sulfated β‐CD (0.2% w/v) in 5 mM phosphate/Tris buffer (pH 3.0) containing the addition of 10 mM benzyltriethylammonium chloride (BTEAC) as the chromophoric additive was used for the enantiomeric separation of DMAA stereoisomers with the LODs in the range of 7.82–9.24 μg/mL. The method was partly validated and applied for the determination of the stereoisomeric composition of DMAA in commercial dietary supplements to verify the potential natural origin of DMAA. 相似文献
996.
Novel and Stereospecific Synthesis of (2S)‐3‐(2,4,5‐Trifluorophenyl)propane‐1,2‐diol from D‐Mannitol 下载免费PDF全文
Derya Aktaş Meryem Fıstıkçı Özlem Gündoğdu Hasan Seçen M. Fethi Şahin Ramazan Altundaş Yunus Kara 《Helvetica chimica acta》2015,98(8):1127-1131
A stereospecific synthesis of (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol from D ‐mannitol has been developed. The reaction of 2,3‐O‐isopropylidene‐D ‐glyceraldehyde with 2,4,5‐trifluorophenylmagnesium bromide gave [(4R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl](2,4,5‐trifluorophenyl)methanol in 65% yield as a mixture of diastereoisomers (1 : 1). The Ph3P catalyzed reaction of the latter with C2Cl6 followed by reduction with Pd/C‐catalyzed hydrogenation gave (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol with >99% ee and 65% yield. 相似文献
997.
Structural and Functional Implications of the Interaction between Macrolide Antibiotics and Bile Acids 下载免费PDF全文
Simon Glanzer Sergio A. Pulido Sarah Tutz Dr. Gabriel E. Wagner Dr. Manfred Kriechbaum Nina Gubensäk Jovana Trifunovic Markus Dorn Prof. Dr. Walter M. F. Fabian Prof. Predrag Novak Prof. Dr. Joachim Reidl Prof. Dr. Klaus Zangger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4350-4358
Macrolide antibiotics, such as azithromycin and erythromycin, are in widespread use for the treatment of bacterial infections. Macrolides are taken up and excreted mainly by bile. Additionally, they have been implicated in biliary system diseases and to modify the excretion of other drugs through bile. Despite mounting evidence for the interplay between macrolide antibiotics and bile acids, the molecular details of this interaction remain unknown. Herein, we show by NMR measurements that macrolides directly bind to bile acid micelles. The topology of this interaction has been determined by solvent paramagnetic relaxation enhancements (solvent PREs). The macrolides were found to be bound close to the surface of the micelle. Increasing hydrophobicity of both the macrolide and the bile acid strengthen this interaction. Both bile acid and macrolide molecules show similar solvent PREs across their whole structures, indicating that there are no preferred orientations of them in the bile micelle aggregates. The binding to bile aggregates does not impede macrolide antibiotics from targeting bacteria. In fact, the toxicity of azithromycin towards enterotoxic E. coli (ETEC) is even slightly increased in the presence of bile, as was shown by effective concentration (EC50) values. 相似文献
998.
Cover Picture: Intracellular Modulation of Excited‐State Dynamics in a Chromophore Dyad: Differential Enhancement of Photocytotoxicity Targeting Cancer Cells (Angew. Chem. Int. Ed. 18/2015) 下载免费PDF全文
999.
Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics 下载免费PDF全文
Dr. Jiří Brus Libor Kobera Dr. Wolfgang Schoefberger Dr. Martina Urbanová Petr Klein Dr. Petr Sazama Dr. Edyta Tabor Dr. Stepan Sklenak Dr. Anna V. Fishchuk Dr. Jiří Dědeček 《Angewandte Chemie (International ed. in English)》2015,54(2):541-545
Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H‐forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors—“perturbed” AlFR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad 27Al NMR resonance (δi=59–62 ppm, CQ=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the 27Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad 27Al NMR resonance (δi≈67 ppm, CQ≈20 MHz, and η≈0.1). 相似文献