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271.
Jonathan W. Dube Cameron M. E. Graham Prof. Charles L. B. Macdonald Dr. Zachary D. Brown Prof. Philip P. Power Prof. Paul J. Ragogna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6739-6744
Two unique systems based on low‐coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element–phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents. 相似文献
272.
Iridium(I)‐Catalyzed Regioselective CH Activation and Hydrogen‐Isotope Exchange of Non‐aromatic Unsaturated Functionality
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Prof. Dr. William J. Kerr Richard J. Mudd Dr. Laura C. Paterson Dr. Jack A. Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14604-14607
Isotopic labelling is a key technology of increasing importance for the investigation of new C?H activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium‐catalyzed C?H activation and hydrogen‐isotope exchange at the β‐position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3)][PF6] (cod=1,5‐cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β‐activation and labelling of a range of α,β‐unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading. 相似文献
273.
Matthew N. O'Brien Dr. Boya Radha Dr. Keith A. Brown Matthew R. Jones Prof. Chad A. Mirkin 《Angewandte Chemie (International ed. in English)》2014,53(36):9532-9538
Many nanoparticle adsorption processes are dictated by the collective interactions of surface‐bound ligands. These adsorption processes define how nanoparticles interact with biological systems and enable the assembly of nanoparticle‐based materials and devices. Herein, we present an approach for quantifying nanoparticle adsorption thermodynamics in a manner that satisfies the assumptions of the Langmuir model. Using this approach, we study the DNA‐mediated adsorption of polyvalent anisotropic nanoparticles on surfaces and explore how deviations from model assumptions influence adsorption thermodynamics. Importantly, when combined with a solution‐based van’t Hoff analysis, we find that polyvalency plays a more important role as the individual interactions become weaker. Furthermore, we find that the free energy of anisotropic nanoparticle adsorption is consistent across multiple shapes and sizes of nanoparticles based on the surface area of the interacting facet. 相似文献
274.
Azmi Mohamed Argo Khoirul Anas Suriani Abu Bakar Azira Abd. Aziz Masanobu Sagisaka Paul Brown Julian Eastoe Azlan Kamari Norhayati Hashim Illyas Md Isa 《Colloid and polymer science》2014,292(11):3013-3023
The performance of single-, double- and triple-chain anionic sulphosuccinate surfactants for dispersing multiwall carbon nanotubes (MWNCTs) in natural rubber latex (NR-latex) was studied using a range of techniques, including field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy. The conductivities of the nanocomposites were also investigated using four-point probe measurements. Here, MWCNTs were efficiently dispersed in NR-latex with the aid of hyperbranched tri-chain sulphosuccinate anionic surfactants, specifically sodium 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulphonate (TC14). This paper highlights that TC14 performs much better than that of the commercially available surfactant sodium dodecyl sulphate (SDS), demonstrating how careful consideration of surfactant architecture leads to improved dispersibility of MWCNTs in NR-latex. The results should be of significant interest for improving nanowiring applications suitable for aerospace-based technology. 相似文献
275.
276.
Dongshun Ni Brittany P. Witherspoon Hong Zhang Chen Zhou K. N. Houk M. Kevin Brown 《Angewandte Chemie (International ed. in English)》2020,59(28):11432-11439
A method for the stereoselective [4+2]‐cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N‐protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C?B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity. 相似文献
277.
Structural Chemistry - Because electrostatic flux does not depend on the location of the charges it links, it is independent of the quantum mechanical charge distribution in a molecule. By... 相似文献
278.
V. Caldas G. R. Brown R. S. Nohr J. G. MacDonald 《Journal of Polymer Science.Polymer Physics》1996,34(12):2085-2098
The double melting endotherm of spunbonded isotactic polypropylene (iPP) fabrics was investigated by monitoring changes in the solid-state NMR spectrum that result from thermal annealing. The DSC melting thermogram was found to change from a double to a single endotherm at anneal temperatures ≥156°C, with a concomitant increase in percent crystallinity. All of the carbon resonances in the CP/MAS NMR spectrum of the purely crystalline phase of iPP were found to be composed of multiple peaks with relative intensities that depend on anneal temperature. By monitoring the changes in the distribution of intensity among the various peaks of a given resonance, a transition temperature of 156°C was identified. Arguments are presented that this redistribution of intensity within a given carbon resonance characterizes the transformation from the α1 to the α2 monoclinic crystal form. The exothermicity associated with this transformation is responsible for the observation of a double melting endotherm by DSC. The splitting patterns observed in the NMR spectrum are discussed in terms of interlayer distances between layers of isochiral helices and the density of exposed methyls at the contact faces of these interlayers. © 1996 John Wiley & Sons, Inc. 相似文献
279.
280.
Herbert C. Brown P. Veeraraghavan Ramachandran J. Chandrasekharan 《Heteroatom Chemistry》1995,6(2):117-131
A series of diisopinocampheylhaloboranes and monoisopinocampheyldihaloboranes were synthesized by the reaction of the corresponding boranes with the respective HX or X2 (X = halogen) or by the hydroboration of α-pinene with the corresponding haloboranes. Stabilities of these haloboranes in various solvents were studied. Most of these haloboranes proved capable of reducing prochiral ketones to the alcohols with significant optical induction. When tested against a representative aromatic and aliphatic prochiral ketone, acetophenone and 3-methyl-2-butanone, respectively, α-phenethyl alcohol in 65–98% ee and 3-methyl-2-butanol in 28–59% ee were obtained. Some of them exhibited anomalous behavior. 相似文献