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21.
The utility of organoboranes in the synthesis of a wide variety of functional groups is now well established.1 There have been, however, only a limited number of reports where an organoborane containing a β-functionalized carbon was utilized in organic synthesis. Part of the reason for this is the difficulty in preparing β-functional organoboranes and their tendency to undergo elimination under a variety of reaction conditions.2 Those β-functionalized organoboranes utilized synthetically, which we could find in the literature are the β-ethoxy3, 1, and β-carboethoxyvinyl-boranes4, 2, of Zweifel and coworkers and the trans-β-tert-butyldimethylsilyloxy organoborane, 3, of Corey and Ravindranathan,5 who proposed this system as a potential precursor to prostanoids. 相似文献
22.
Julie P. Vanegas Lucas E. Peisino Dr. Salvador Pocoví‐Martínez Dr. Ramón J. Zaragozá Dr. Elena Zaballos‐García Dr. Julia Pérez‐Prieto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16248-16255
Gold nanoparticles capped with simple adenosine derivatives can form colloidal aggregates in nonpolar solvents. Theoretical calculations indicate the formation of organic channels by the supramolecular assembly of the nanoparticles by means of hydrogen bonds between the adenine moieties. The aggregates were only negligibly sensitive to nPrOH, iPrOH, and tBuOH, whereas some showed a similar response to MeOH and EtOH, and others showed high selectivity toward MeOH. DNA nucleoside derivatives (1‐(2‐deoxy‐β‐D ‐ribofuranosyl)‐5‐methyluracil and 2′,3′‐O‐isopropylideneadenosine) as well as thymine and other aromatic compounds such as pyrene derivatives (pyrene, 1‐chloropyrene, 1‐hydroxypyrene, (1‐pyrenyl)methanol, and 2‐hydroxynapthalene) did not induce disassembly of the nanoparticle aggregates. Data suggest that the nucleoside channels allow access to alcohols according to their size, and an efficient interaction between the alcohol and the adenine units destabilizes the hydrogen bonds, which eventually leads to nanoparticle disassembly. 相似文献
23.
Dr. Adrián Leandro Lewandowski Dr. Sergio Tosoni Leonard Gura Dr. Zechao Yang Dr. Alexander Fuhrich Dr. Mauricio J. Prieto Dr. Thomas Schmidt Dr. Denis Usvyat Prof. Wolf-Dieter Schneider Dr. Markus Heyde Prof. Gianfranco Pacchioni Prof. Hans-Joachim Freund 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1870-1885
The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO4 (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth. 相似文献
24.
Freezing Capture of Polymorphic Aggregates of Bolaamphiphilic L‐Valine‐Based Molecular Hydrogelators 下载免费PDF全文
Dr. Vicent J. Nebot Dr. Santiago Díaz‐Oltra Dr. Johan Smets Susana Fernández Prieto Dr. Juan F. Miravet Dr. Beatriu Escuder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5762-5767
Nanostructured xerogels have been prepared by the freeze‐drying of hydrogels and aggregates formed by bolaamphiphilic L ‐valine derivatives after aging under different environmental conditions. A wide variety of shapes and sizes has been achieved by a simple methodology. These nanostructures have been studied by SEM and WAXD and a dramatic influence of structural flexibility on the kinetics of aggregation has been observed. Such flexibility and a modulation of the hydrophobic effect have shown a profound influence in the packing of these compounds and revealed a high degree of polymorphism. 相似文献
25.
Dr. Bidyut B. Sarma Jonglack Kim Jonas Amsler Dr. Giovanni Agostini Dr. Claudia Weidenthaler Norbert Pfänder Dr. Raul Arenal Dr. Patricia Concepción Dr. Philipp Plessow Prof. Dr. Felix Studt Dr. Gonzalo Prieto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5855-5864
Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
26.
Bidyut B. Sarma Jonglack Kim Jonas Amsler Giovanni Agostini Claudia Weidenthaler Norbert Pfnder Raul Arenal Patricia Concepcin Philipp Plessow Felix Studt Gonzalo Prieto 《Angewandte Chemie (International ed. in English)》2020,59(14):5806-5815
Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
27.
Elena Blanco J. M. Ruso J. Sabín G. Prieto F. Sarmiento 《Journal of Thermal Analysis and Calorimetry》2007,87(1):211-215
The interactions of lysozyme and myoglobin with anionic surfactants
(hydrogenated and fluorinated), at surfactant concentrations below the critical
micelle concentration, in aqueous solution were studied using spectroscopic
techniques. The temperature conformational transition of globular proteins
by anionic surfactants was analysed as a function of denaturant concentration
through absorbance measurements at 280 nm. Changes in absorbance of protein-surfactant
system with temperature were used to determine the unfolding thermodynamics
parameters, melting temperature, T
m,
enthalpy, ΔH
m,
entropy, ΔS
m
and the heat capacity change, ΔC
p,
between the native and denatured states. 相似文献
28.
An equation of state for solids, in reduced variables, is obtained within the context of a system-independent formulation of the thermodynamics of high pressures. This formulation is valid for materials obeying a linear relationship between shock and particle velocities. An adequate set of scaling factors for pressure, compression, specific energy, and temperature, is first introduced. A modified Mie-Grüneisen equation, as well as many other thermodynamic relationships and coefficients, are then expressed in terms of reduced variables. Explicit expressions for the temperature along the Hugoniot, and for the equation of state, are obtained. It is also shown that when given in their reduced form, each of the two thermodynamic coefficients appearing in the equation of state can be considered as having the same constant value for many different materials. The possibility and convenience of using a “standard material” is discussed. Numerical results obtained using this reduced variables formalism are in good agreement with those computed or measured, by different authors, for various materials over a wide range of pressures. This is a good indication of the “universality” of the reduced equations obtained, and of the usefulness of the formalism. 相似文献
29.
The Michael addition of nitroalkanes to alpha,beta-unsaturated enones catalyzed by a novel chiral imidazolidine-2-yltetrazole organocatalyst has been investigated. The new more soluble organocatalyst decreases reaction times and improves enantioselectivities compared to other catalysts. The Michael addition adducts were obtained with up to 92% ee. [reaction: see text] 相似文献
30.
The reactions of the tert-butyldimethylsilylated acyloins of five-, six- and seven-membered rings with the lithium reagents of benzyltrimethylsilane, thiophenoxymethyltrimethylsilane and tri-methylsilyl acetonitrile were studied. These reactions favor formation of the substituted (Z) exo methylidene silyl ethers in moderate yields. 相似文献