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Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides 下载免费PDF全文
Bardia Soltanzadeh Dr. Arvind Jaganathan Dr. Richard J. Staples Prof. Dr. Babak Borhan 《Angewandte Chemie (International ed. in English)》2015,54(33):9517-9522
An organocatalytic and highly regio‐, diastereo‐, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio‐ and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. 相似文献
54.
18‐Crown‐6 Catalyzed Microwave‐mediated Synthesis of Symmetric Bis‐Heterocyclic Compounds under Solvent‐free Condition 下载免费PDF全文
Rathnasamy Rishikesan Kamalakannan Prabakaran Rajamani Murugesan Ramaswamy Venkataraman Pakkath Karuvalam Ranjith Sivasubramanian Arvind Sathiah Thennarasu 《Journal of heterocyclic chemistry》2015,52(5):1321-1330
An efficient, solvent‐free and 18‐crown‐6 catalyzed method for the synthesis of N‐alkyl‐4‐(4‐(5‐(2‐(alkyl‐amino)thiazol‐4‐yl)pyridin‐3‐yl)phenyl)thiazol‐2‐amine, N‐alkyl‐4‐(5‐(2‐alkyamino)thiazol‐4‐yl)pyridine‐3‐yl)thiazol‐2‐amine, and 4,4′‐bis‐{2‐[amino]‐4‐thiazolyl}biphenyl bis‐heterocyclic derivatives via microwave accelerated cyclization is presented. 相似文献
55.
An efficient stereoselective synthesis of C4-12 fragment of the cembranoids, sarcophytonolides E-G and L and C5-11 fragment of sarcophytonolide L is described. The C4-12 building block is efficiently assembled starting from chiral pool material (R)-carvone employing the Baeyer-Villiger oxidation, modified Knoevenagel condensation and asymmetric dihydroxylation as the key steps. The synthesis of C5-11 fragment is based on orthoester Johnson-Claisen rearrangement as the key step. 相似文献
56.
A diethylpyrrole‐bridged dizinc(II) bisporphyrin (Zn2DEP) is reported that encapsulates fluorescent probe pyrene molecules through strong π–π interactions, which can relay information about the chemical environment in the interior of the host–guest supramolecular assembly. X‐ray structures of both Zn2DEP and the encapsulated pyrene complex are reported, which provides a rare opportunity to investigate the structural changes upon guest binding. A comparative structural analysis demonstrated the exceptional ability of this bisporphyrin platform to open its binding pocket for pyrene encapsulation by a vertical displacement of more than 2.45 Å, although both Zn2DEP and the pyrene complex have nearly parallel porphyrin ring orientations. The 1H NMR spectrum of the encapsulated pyrene complex in solution shows the upfield shifts of the pyrene protons due to a strong ring current effect, which demonstrates the retention of the solid‐state structure in solution. To further assess the extent to which pyrene guests remain encapsulated in solution, a known fluorescence quencher, dimethylaniline, was added to the host–guest assembly, which shows no exciplex formation for days in nonpolar solvents. Thus, the assembly also retained the structural integrity in solution for a long time. The association constant (Kasso) for such a complexation process in solution was observed to be 1.78×105 M ?2 for 1:2 binding. Steady‐state fluorescence and lifetime studies indicate significant photoinduced singlet–singlet energy transformation from the excited state of pyrene to zinc bisporphyrin. 相似文献
57.
A nanocomposite of Pd? TiO2? SiO2 is developed through a sol‐gel process from the reaction products of titanium isopropoxide followed by mixing the same with palladium linked 3‐glycidoxypropyltrimethoxysilane. The reaction product is sonicated and calcinated to obtain the nanocomposite of Pd? TiO2? SiO2. The calcination at 600 °C yielded an amorphous structure whereas at 900 °C it resulted into a nanocrystalline structure. The nanocomposite of palladium was further characterized by TEM, XRD, IR and EDS. The material acts as an efficient electrocatalyst. Electrocatalysis of ascorbic acid is observed at 0.1 V vs. Ag/AgCl, shows linearity between 1 µM and 1 mM in 0.1 M phosphate buffer (pH 7.0). 相似文献
58.
[2.2]Paracyclophanes, incorporating functional groups in the aliphatic bridges, suitable for elimination to give [2.2]paracyclophanedienes, are synthesized through a novel approach. It relies on a double Pummerer rearrangement on dithiacyclophane precursors, followed by ring contraction through a photochemical sulfur extrusion, and it is compatible with aryl moieties possessing very different electronic properties. 相似文献
59.
Retailers often conduct non-overlapping sequential online auctions as a revenue generation and inventory clearing tool. We build a stochastic dynamic programming model for the seller’s lot-size decision problem in these auctions. The model incorporates a random number of participating bidders in each auction, allows for any bid distribution, and is not restricted to any specific price-determination mechanism. Using stochastic monotonicity/stochastic concavity and supermodularity arguments, we present a complete structural characterization of optimal lot-sizing policies under a second order condition on the single-auction expected revenue function. We show that a monotone staircase with unit jumps policy is optimal and provide a simple inequality to determine the locations of these staircase jumps. Our analytical examples demonstrate that the second order condition is met in common online auction mechanisms. We also present numerical experiments and sensitivity analyses using real online auction data. 相似文献
60.
The synthesis of versatile fluorine compounds and monomers for conducting polymer research and cyclopolymerizations is presented. Semiprotected 2,3,5,6-tetrafluoroterephthaldehyde 1 could be elaborated through Wittig olefination chemistry, deprotection and reduction to the previously unknown 4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 in good yields. Compound 8 can be reacted to form the malonate ester, and then alkylation on the malonate moiety in mild conditions affords difunctional monomer 3. Through sequential esterifications on the malonate moiety, and subsequent alkylation, compound 4, a difunctional monomer for cyclopolymerization bearing one styrene and one perfluoroaryl styrene moiety, has been obtained. Preliminary experiments show that it is possible to cyclopolymerize 4 under free radical conditions. 相似文献