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91.
We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate. 相似文献
92.
Light Harvesting and Directional Energy Transfer in Long‐Lived Homo‐ and Heterotrimetallic Complexes of FeII,RuII, and OsII 下载免费PDF全文
Dinesh Maity Chanchal Bhaumik Sourav Mardanya Srikanta Karmakar Dr. Sujoy Baitalik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13242-13252
A new family of trimetallic complexes of the form [(bpy)2M(phen‐Hbzim‐tpy)M′(tpy‐Hbzim‐phen)M(bpy)2]6+ (M=RuII, Os; M′=FeII, RuII, Os; bpy=2,2′‐bipyridine) derived from heteroditopic phenanthroline–terpyridine bridge 2‐{4‐[2,6‐di(pyridin‐2‐yl) pyridine‐4‐yl]phenyl}‐1H‐imidazole[4,5‐f][1,10]phenanthroline (phen‐Hbzim‐tpy) were prepared and fully characterized. Zn2+ was used to prepare mixed‐metal trimetallic complexes in situ by coordinating with the free tpy site of the monometallic precursors. The complexes show intense absorptions throughout the UV/Vis region and also exhibit luminescence at room temperature. The redox behavior of the compounds is characterized by several metal‐centered reversible oxidation and ligand‐centered reduction processes. Steady‐state and time‐resolved luminescence data show that the potentially luminescent RuII‐ and OsII‐based triplet metal‐to‐ligand charge‐transfer (3MLCT) excited states in the triads are quantitatively quenched, most likely by intercomponent energy transfer to the lower lying 3MLCT (for Ru and Os) or triplet metal‐centered (3MC) excited states of the FeII subunit (nonluminescent). Interestingly, iron did not adversely affect the photophysics of the respective systems. This suggests that the multicomponent molecular‐wire‐like complexes investigated here can behave as efficient light‐harvesting antennas, because all the light absorbed by the various subunits is efficiently channeled to the subunit(s) in which the lowest‐energy excited states are located. 相似文献
93.
94.
2,4‐Dinitroimidazole (2,4‐DNI), an important starting material for nitroimidazooxazole and nitroimidazooxazine types of antitubercular agents was synthesized by rearrangement of 1,4‐dinitroimidazole (1,4‐DNI) under microwave irradiation. Various new nitroimidazooxazoles analogues were prepared using 2,4‐DNI and were tested preliminarily against Mycobacterium tuberculosis, H37Rv strain. Some were found to be active. 相似文献
95.
We prove that the power function of the likelihood ratio test for MANOVA attains its minimum when the rank of the location parameter matrix Θ decreases from s to 1. This provides a theoretical justification of a result that is known in the literature based only on numerical studies. 相似文献
96.
Krishnan S Bagdanoff JT Ebner DC Ramtohul YK Tambar UK Stoltz BM 《Journal of the American Chemical Society》2008,130(41):13745-13754
Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described. 相似文献
97.
Uttam Bhaumik Animesh Ghosh Uttam Mandal Bappaditya Chatterjee Amlan Kanti Sarkar Anirbandeep Bose Kamala Kanta Ray Tapan Kumar Pal 《Chromatographia》2008,68(9-10):713-720
A bioanalytical method has been developed and validated for determination of drospirenone in human plasma. The analytical method consists in the extraction of plasma sample with dichloromethane, followed by determination of drospirenone by LC–MS–MS using levonorgestrel as internal standard. Separation was achieved on a Peerless cyano column with an isocratic mobile phase consisting of methanol and ammonium formate buffer. Protonated ions formed by a Turboionspray in the positive mode were used to detect analyte and IS. The MS–MS detection was by monitoring the fragmentation for drospirenone and for levonorgestrel on a triple quadrupole mass spectrometer. The assay was calibrated over the range 5–100 ng mL?1 with a correlation coefficient of 0.9998. Validation data showed intra-batch (n = 6) CV% ≤ 5.58 and RE (%) between ?3.34 and +6.27 and inter-batch (n = 18) CV% < 6.08 and RE (%) between ?1.84 and +6.73. Mean extraction recovery were 83.31–92.58% for three QC samples and 89.32% for IS. Plasma samples were stable for three freeze-thaw cycles, or 24 h ambient storage, or 1 and 3 months storage at ?20 °C. Processed samples (ready for injection) were stable up to 72 h at autosampler (4 °C). This method has been used for analyzing plasma samples from a bioequivalence study with 12 volunteers. 相似文献
98.
A library of eight 5-F(2)-isoprostanes was prepared through a ring-opening metathesis/cross-metathesis protocol between functionalized bicyclo[3.2.0]heptenes, ethylene, and alpha,beta-unsaturated ketones. This sequence provided racemic enones in a regio- and stereoselective fashion that could be converted to enantiomerically enriched allylic alcohols through a catalyst-controlled asymmetric reduction. Completion of the sidechains, followed by global deprotection, resulted in a stereodivergent route to eight enantiomerically enriched 5-F(2)-isoprostanes. Overall, the synthesis of this library of known and anticipated lipid oxidation metabolites was achieved in 10 steps from commercially available 4-hydroxy-2-cyclopentenone. 相似文献
99.
(+)-Amberketal (1) and its analog (2) have been synthesized from commercially available l-abietic acid (3) by a selective reduction of an unsaturated aldehyde in the presence of a ketone and simultaneous reduction of an iodide using an aqueous suspension of Raney Ni as the key step. 相似文献
100.
Arindam Modak Akshay R. Mankar Kamal Kishore Pant Asim Bhaumik 《Molecules (Basel, Switzerland)》2021,26(9)
Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N2 sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m2/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research. 相似文献