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61.
Rolf Jansen Heinrich Steinmetz Wolf-Dieter Schubert Simone C. Albrecht 《Tetrahedron letters》2008,49(40):5796-5799
Rhizopodin was isolated as cytostatic and weakly antifungal macrolide (1) and later characterized as potent actin-depolymerizing agent. It is produced by the myxobacterium Myxococcus stipitatus, which enables a fermentative supply of the drug for biological studies. We here report a revised structure that characterizes rhizopodin (2) as the first known dimeric bis-lactone exhibiting side chains that terminate in N-methyl-vinylformamide groups, which are otherwise found in smaller marine toxins also targeting the actin cytoskeleton. Compound 2 might function as bivalent inhibitor forming ternary complexes with actin which would explain its high efficacy. 相似文献
62.
Christian Pietsch Martin W. M. Fijten Hanneke M. L. Lambermont‐Thijs Richard Hoogenboom Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2009,47(11):2811-2820
Homo‐ and copolymers of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo(ethyleneglycol) methyl ether methacrylate (OEGMA1100) were synthesized with various chain lengths via reversible addition fragmentation chain transfer (RAFT) polymerization in ethanol using [M]/[RAFT] ratios of 100 and 200. Kinetic investigations on the homo‐ and copolymerization of these monomers were performed using a parallel synthesizer resulting in well‐defined polymers with polydispersity indices mostly below 1.3. The polymerization kinetics are presented and discussed in detail surprisingly revealing that the DEGMA homopolymerization is slower than the OEGMA1100 homopolymerization. Transfer coefficients c were estimated to be ~0.5 for the RAFT polymerization of both DEGMA and OEGMA1100 resulting in hybrid behavior at the beginning of the polymerizations. Subsequent copolymerization also revealed fast incorporation of the OEGMA1100 and relatively slow incorporation of DEGMA resulting in well‐defined copolymers with a molecular weight up to 100 kDa and polydispersities around 1.20. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2811–2820, 2009 相似文献
63.
Aresta M Dibenedetto A Fracchiolla E Giannoccaro P Pastore C Pápai I Schubert G 《The Journal of organic chemistry》2005,70(16):6177-6186
Dicyclohexylcarbodiimide (CyN=C=NCy, DCC) promotes the facile formation of organic carbonates from aliphatic alcohols and carbon dioxide at temperatures as low as 310 K and moderate pressure of CO2 (from 0.1 MPa) with an acceptable rate. The conversion yield of DCC is quantitative, and the reaction has a very high selectivity toward carbonates at 330 K; increasing the temperature increases the conversion rate, but lowers the selectivity. A detailed study has allowed us to isolate or identify the intermediates formed in the reaction of an alcohol with DCC in the presence or absence of carbon dioxide. The first step is the addition of alcohol to the cumulene (a known reaction) with formation of an O-alkyl isourea [RHNC(OR')=NR] that may interact with a second alcohol molecule via H-bond (a reaction never described thus far). Such an adduct can be detected by NMR. In alcohol, in absence of CO2, it converts into a carbamate and a secondary amine, while in the presence of CO2, the dialkyl carbonate, (RO)2CO, is formed together with urea [CyHN-CO-NHCy]. The reaction has been tested with various aliphatic alcohols such as methanol, ethanol, and allyl alcohol. It results in being a convenient route to the synthesis of diallyl carbonate, in particular. O-Methyl-N,N'-dicyclohexyl isourea also reacts with phenol in the presence of CO2 to directly afford for the very first time a mixed aliphatic-aromatic carbonate, (MeO)(PhO)CO. A DFT study has allowed us to estimate the energy of each intermediate and the relevant kinetic barriers in the described reactions, providing reasonable mechanistic details. Calculated data match very well the experimental results. The driving force of the reaction is the conversion of carbodiimide into the relevant urea, which is some 35 kcal/mol downhill with respect to the parent compound. The best operative conditions have been defined for achieving a quantitative yield of carbonate from carbodiimide. The role of temperature, pressure, and catalysts (Lewis acids and bases) has been established. As the urea can be reconverted into DCC, the reaction described in this article may further be developed for application to the synthesis of organic carbonates under selective and mild conditions. 相似文献
64.
Inhaltsübersicht. Die Titelverbindungen R2N–CS–S–N[Si(CH3)3]2 mit Ii = CH3 bzw. CH(CH3)2 kristallisieren orthorhombisch bzw. monoklin: Gitterkonstanten für R = CH3 (bei ?165°C) a = 8,397(4) Å, b = 11,917(4) Å, c = 31,966 (11) Å, Pbca (Nr. 61), Z = 8. R = CH(CH3)2 (bei ?80°C) a =13,183(3) Å, b = 10,873(11) Å, c = 14,865(2) Å, β = 105,86(2)° P21/n (Nr. 14), Z = 4. Die Kristallstrukturen wurden unter Verwendung von 4227 bzw. 3 433 symmetrieunabhängigen Reflexen (gemessen bei ?165 bzw. ?80 °C) bestimmt und bis auf Zuverlässigkeitsfaktoren von R = 0,081 bzw. 0,082 verfeinert (Rw = 0,084 bzw. 0,114). Bei beiden Verbindungen ist der C2N–CS–S–N-Teil des Moleküls nahezu planar. Zwischen dem Thiocarbonyl-S-Atom und dem N-Atom der silylierten Aminogruppe bestehen Wechselwirkungen. On Chalcogenolates. 194. S-Bis (trimethylsilyl) amino Esters of Dithiocarbamic Acids. 3. Crystal and Molecular Structure of the Methyl and i-Propyl Derivative The title compounds R2N–CS–S–N[Si(CH3)3]2 with R = CH3 and CH(CH3)2, respectively, crystallize orthorhombic and monoclinic, resp.; cell dimensions and space group see “Inhaltsübersicht”. The structures of both compounds have been determined from single crystal X-ray data measured at ?165°C and ?80°C, resp., and refined to R's of 0.081 and 0.082, resp., (Rw = 0.084 and 0.114, resp.) using 4227 and 3433, resp., independent reflections. In both compounds the C2N–CS–S–N core of the molecule is nearly plane. Between the thiocarbonyl sulfur atom and the nitrogen atom of the amino group interactions exist. In Fortführung unserer Untersuchungen [1, 2] über N, N-Dialkyldithiocarbamidsäure-S-bis(trimethylsilyl)aminoester R2N–CS–S–N[Si(CH3)3]2 haben wir die Kristall- und Molekülstrukturen der Verbindungen mit R = CH3 und CH(CH3)2 bestimmt. Dabei sollte untersucht werden, welchen Einfluß sterisch anspruchsvollere Alkylgruppen (R = CH3 → CH(CH3)2) auf die Molekülgeo-metrie haben. Eine strukturchemische Charakterisierung dieser Verbindungs-klasse ist bis jetzt noch nicht erfolgt; vgl. die Literaturzusammenstellung bei [3]. 相似文献
65.
Vlasov Yu. G. Murzina Yu. G. Legin A. V. Ermolenko Yu. E. Schubert J. Schüoning M. J. Lut H. 《Russian Journal of Applied Chemistry》2002,75(3):351-356
Methods of silicon planar technology and pulsed laser deposition were applied to fabricate fully solid-state chemical sensors for determining ions of copper, lead, cadmium, thallium, and also sulfide and chloride ions on the basis of thin chalcogenide films as ion-sensitive membranes. 相似文献
66.
Sanne Wijnans Berend‐Jan de Gans Frank Wiesbrock Richard Hoogenboom Ulrich S. Schubert 《Macromolecular rapid communications》2004,25(23):1958-1962
Summary: The feasibility of automated, high‐throughput contact‐angle measurements is demonstrated using a modified commercial contact‐angle measuring apparatus. Droplets are automatically dispensed, analyzed and aspirated. The system automatically measures more than 100 contact angles per hour using two test liquids, and calculates surface energies using the equation of state method. A library of poly(2‐oxazoline) homo‐ and block copolymers was investigated. Polymers with a 2‐nonyl‐2‐oxazoline block were found to have considerably lower surface energies.
67.
Daan Wouters Dr. Stephanie Hoeppener Dr. Ulrich S. Schubert Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(10):1732-1739
Surfaces with purposes : The electroinitiated patterning of self‐assembled monolayers enables the fabrication of a variety of complex nanostructures (see picture). The possibilities offered by the introduction of chemical selectivity through the local generation of chemically active groups and subsequent derivatization are reviewed, with a focus on progress in this area of research over the last four years.
68.
Jörg Votteler Elena Iavnilovitch Orit Fingrut Vivian Shemesh Daniel Taglicht Omri Erez Stefan Sörgel Torsten Walther Norbert Bannert Ulrich Schubert Yuval Reiss 《BMC biochemistry》2009,10(1):1-14
Background
The ALG2-interacting protein X (ALIX)/AIP1 is an adaptor protein with multiple functions in intracellular protein trafficking that plays a central role in the biogenesis of enveloped viruses. The ubiquitin E3-ligase POSH (plenty of SH3) augments HIV-1 egress by facilitating the transport of Gag to the cell membrane. Recently, it was reported, that POSH interacts with ALIX and thereby enhances ALIX mediated phenotypes in Drosophila.Results
In this study we identified ALIX as a POSH ubiquitination substrate in human cells: POSH induces the ubiquitination of ALIX that is modified on several lysine residues in vivo and in vitro. This ubiquitination does not destabilize ALIX, suggesting a regulatory function. As it is well established that ALIX rescues virus release of L-domain mutant HIV-1, HIV-1ΔPTAP, we demonstrated that wild type POSH, but not an ubiquitination inactive RING finger mutant (POSHV14A), substantially enhances ALIX-mediated release of infectious virions derived from HIV-1ΔPTAP L-domain mutant (YPXnL-dependent HIV-1). In further agreement with the idea of a cooperative function of POSH and ALIX, mutating the YPXnL-ALIX binding site in Gag completely abrogated augmentation of virus release by overexpression of POSH. However, the effect of the POSH-mediated ubiquitination appears to be auxiliary, but not necessary, as silencing of POSH by RNAi does not disturb ALIX-augmentation of virus release.Conclusion
Thus, the cumulative results identified ALIX as an ubiquitination substrate of POSH and indicate that POSH and ALIX cooperate to facilitate efficient virus release. However, while ALIX is obligatory for the release of YPXnL-dependent HIV-1, POSH, albeit rate-limiting, may be functionally interchangeable. 相似文献69.
N. P. Evlampieva J. Vitz U. S. Schubert E. I. Ryumtsev 《Russian Journal of Applied Chemistry》2009,82(4):666-672
New systems suitable for determination of molecular characteristics of cellulose, mixtures of ionic liquids based on 1-n-alkyl-3-methylimidazolium with pyridine, were found. In ionic liquid-pyridine mixtures, cellulose is dispersed on the molecular level. The cellulose-ionic liquid-pyridine systems with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium diethyl phosphate are stable in time. The dynamic viscosity and refractive index of the mixtures can be controlled by varying the ionic liquid to pyridine ratio. The viscometric and dynamooptical properties of cellulose in these mixtures were compared with those in Cadoxen. 相似文献
70.
Andreas Winter Dr. Christian Friebe Manuela Chiper Dr. Ulrich S. Schubert Prof. Dr. Martin Presselt Benjamin Dietzek Dr. Michael Schmitt Dr. Jürgen Popp Prof. Dr. 《Chemphyschem》2009,10(5):787-798
Leading light : A series of zinc(II) bis‐terpyridine complexes (see picture) is investigated by means of DFT calculations combined with Bader's quantum theory of atoms in molecules. Raman spectroscopy experiments and studies of the electro‐optical properties of the complexes in solution and the solid state are also performed to examine their potential as new emissive materials in light‐emitting devices.