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11.
Cycloadducts of hexafluorothioacetone (HFTA) were prepared in high yield by a CsF catalyzed reaction between readily available 2,2,4,4-tetrakis-(trifluoromethyl)-1,3-dithietane (as a source of HFTA) with conjugated electron-rich hydrocarbon dienes, such as cyclopentadiene, 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene or (1Z,3Z)-cyclohepta-1,3-diene. Cyclohexa-1,4- and (1Z,5Z)-cycloocta-1,5-dienes, also undergo the reaction with in situ generated HFTA, but form the products of insertion of HFTA into the C-H bond of the diene as a result of ene-reaction. The highly selective reaction of HFTA with (1Z,3Z,5Z)-cyclohepta-1,3,5-triene and (1Z,3Z,5Z,7Z)-cycloocta-1,3,5,7-tetraene leads to the formation of cycloadducts derived from exclusive addition of thioacetone to the corresponding bicyclic isomers—bicyclo[4.1.0]hepta-2,4-diene or bicyclo[4.2.0]octa-2,4,7-triene, respectively. The corresponding cycloadducts of HFTA with 2,3-dimethylbutadiene-1,3-cyclohexa-1,3-cyclohexa-1,4-dienes and (1Z,3Z,5Z)-cyclohepta-1,3,5-triene were also prepared by direct reaction of sulfur/hexafluoropropene/KF and the corresponding hydrocarbon substrate at 35-45 °C in DMF. 相似文献
12.
Inhaltsübersicht. Diphenylphosphin und rac-Cyclophosphamid (ClCH2CH2)2NP(O)N(H)(CH2)3O (1) reagieren in Gegenwart von n-Butyllithium zu einem Zwischenprodukt, das mit Wasser das diphenylphosphinsubstituierte Cyclophosphamid, (Ph2PCH2CH2)2NP(O)N(H)(CH2)3O, (2) bildet. Metallierung von 2 mit n-BuLi am N(3)-Atom und Umsetzung mit D2O führt zum N(3)-Deuteroderivat 2a. Mit H2O2 reagiert 2 zur all-Phosphinoxid Verbindung, [Ph2P(O)CH2CH2]2NP(O)N(H)(CH2)3O, (4), die mit 0,5 Mol Wasser auskristallisiert und von der zur Charakterisierung des H-Bückenbindungssystems eine Röntgenstrukturanalyse angefertigt wurde. Die NMR-Spektren (1H, 13C, 31P, 14N) weisen 2–4 als dynamische Moleküle aus. Chemistry of Polyfunctional Molecules. 101. Synthesis of a Diphenylphosphinesubstituted Cyclophosphamide and the X-ray Diffraction of its Oxidation Product Diphenylphosphine and rac-cyclophosphamide, (ClCH2CH2)2NP(O)N(H)(CH2)3O, (1) react in the presence of n-BuLi to an intermediate which hydrolyses to the diphenylphosphine substituted Cyclophosphamide, (Ph2PCH3CH2)2NP(O)N(H)(CH2)3O, (2). Metallation of 2 with n-BuLi at the N(3) atom, followed by treatment with D2O yields the N(3)-deuterated derivative 2a. With H2O2 2 forms the all-phosphine-oxide compound, [Ph2P(O)CH2CH2]2NP(O)N(H)(CH2)3O, ( 4 ), which crystallizes with 0.5 mole of water. In order to characterize the H-bridge bonding system a X-ray structure analysis of 4 was carried out. The NMR-Spectra (1H, 13C, 31P, 14N) indicate 2–4 as dynamic molecules. 相似文献
13.
L. G. Kostova W. Andrejtscheff L. K. Kostov L. Funke E. Will A. I. Vdovin 《Zeitschrift für Physik A Hadrons and Nuclei》1992,342(2):145-148
Using the (,n) reaction, the half-life of the first 11/2– level in97Mo has been determined as T1/2(1437.0 keV)=2.5±0.3 ns by means of the pulsed beam method. The experimentally obtainedB(M2) value between theh
11/2 andg
7/2 configurations in97Mo has been satisfactorily described within the quasiparticle-phonon model usingg
s
eff
=0.6g
s
free
. Similar calculations and comparisons with experminental data have been performed also for95,99Mo as well as for99Ru and101Pd.This work is partly supported by the Bulgarian National Research Foundation 相似文献
14.
Herein, we report the 1,2-dialkylation of simple feedstock acrylates for the synthesis of valuable tertiary carboxylic acids by merging Giese-type radical addition with an Ireland–Claisen rearrangement. Key to success is the utilization of the reductive radical-polar crossover concept under photocatalytic reaction conditions to force the [3,3]-sigmatropic rearrangement after alkyl radical addition to allyl acrylates. Using readily available alkyl boronic acids as radical progenitors, this redox-neutral, transition-metal-free protocol allows the mild formation of two C(sp3)–C(sp3) bonds, thus providing rapid access to complex tertiary carboxylic acids in a single step. Moreover, this strategy enables the efficient synthesis of highly attractive α,α-dialkylated γ-amino butyric acids (GABAs) when α-silyl amines are used as radical precursors – a structural motif that was still inaccessible in related transformations. Depending on the nature of the radical precursors and their inherent oxidation potentials, either a photoredox-induced radical chain or a solely photoredox mechanism is proposed to be operative.A photocatalytic 1,2-dialkylation of α-substituted acrylates is enabled by a reaction cascade combining reductive radical-polar crossover with the established Ireland–Claisen rearrangement for the synthesis of valuable tertiary carboxylic acids. 相似文献
15.
Dr. James Biggs Dr. Karsten Danielmeier Dr. Julia Hitzbleck Dr. Jens Krause Tom Kridl Dr. Stephan Nowak Dr. Enrico Orselli Dr. Xina Quan Dirk Schapeler Will Sutherland Dr. Joachim Wagner 《Angewandte Chemie (International ed. in English)》2013,52(36):9409-9421
We present the development and applications of dielectric elastomers. For the last 10 years the significance of this class of polymers has risen as more applications seem possible and first products have been commercialized. 相似文献
16.
We classify which complete multipartite graphs are intrinsically chiral. 相似文献
17.
David J. Lunn Emre H. Discekici Javier Read de Alaniz Will R. Gutekunst Craig J. Hawker 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):2903-2914
The development of “controlled” and “living” polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chain-end functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2903–2914 相似文献
18.
19.
Dr. Jing Zhang Bingwen Wang Prof. Dr. Eranda Nikolla Prof. Dr. J. Will Medlin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(23):6694-6698
Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. 相似文献
20.
Thorsten Will Michael C. Hutter Johann Jauch Volkhard Helms 《Journal of computational chemistry》2013,34(28):2485-2492
Besides all their conformational degrees of freedom, drug‐like molecules and natural products often also undergo tautomeric interconversions. Compared to the huge efforts made in experimental investigation of tautomerism, open and free algorithmic solutions for prototropic tautomer generation are surprisingly rare. The few freely available software packages limit their output to a subset of the possible configurational space by sometimes unwanted prior assumptions and complete neglection of ring‐chain tautomerism. Here, we describe an adjustable fully automatic tautomer enumeration approach, which is freely available and also incorporates the detection of ring‐chain variants. The algorithm is implemented in the MolTPC framework and accessible on SourceForge. © 2013 Wiley Periodicals, Inc. 相似文献