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611.
Sato K Yokosuka S Takigami Y Hirakuri K Fujioka K Manome Y Sukegawa H Iwai H Fukata N 《Journal of the American Chemical Society》2011,133(46):18626-18633
Magnetic/fluorescent composite materials have become one of the most important tools in the imaging modality in vivo using magnetic resonance imaging (MRI) monitoring and fluorescence optical imaging. We report herein on a simplified procedure to synthesize hybrid nanoparticles (HNPs) that combine silicon and magnetic iron oxides consisting of magnetite (Fe(3)O(4)) and maghemite (γ-Fe(2)O(3)). Intriguingly, our unique synthetic approach can control magnetic and optical behaviors by reducing the particle size, demonstrating that the HNPs with the mean diameter of 3.0 nm exhibit superparamagnetic behavior and green fluorescence in an aqueous solution, ambient air, and a cellular environment, whereas the HNPs with the mean diameter more than 5.0 nm indicate ferromagnetic behavior without fluorescence. Additionally, both HNPs with different diameters possess excellent magnetic responsivity for external applied magnetic field and good biocompatibility due to the low cytotoxicity. Our biocompatible HNPs with the superparamagnetism can provide an attractive approach for diagnostic imaging system in vivo. 相似文献
612.
Higashi T Suzuki M Hanai J Inagaki S Min JZ Shimada K Toyo'oka T 《Journal of separation science》2011,34(7):725-732
Vitamin D deficiency in an infant is associated with a wide range of adverse health outcomes in later life. A method for the quantification of 25‐hydroxyvitamin D3 [25(OH)D3, the best‐established indicator of vitamin D status] in neonatal dried blood spots (DBSs) using LC/ESI‐MS/MS has been developed and validated. The method employed two steps of derivatization, a Diels–Alder reaction with 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione followed by acetylation, to enhance the detectability of 25(OH)D3 in ESI‐MS/MS and to separate 25(OH)D3 from 3‐epi‐25‐hydroxyvitamin D3 [3‐epi‐25(OH)D3], a potent interfering metabolite. 25(OH)D3 was extracted from two DBS punches (3 mm in diameter, equivalent to 5.3 μL of whole blood), purified using an Oasis HLB® cartridge, and subjected to derivatization prior to analysis with LC/ESI‐MS/MS. 25‐Hydroxyvitamin D4 was used as the internal standard. This method was reproducible (intra‐ and inter‐assay RSDs, <6.9%) and accurate (analytical recovery, 95.2–102.7%), and the LOQ was 3.0 ng/mL. The developed method enabled specific quantification of 25(OH)D3 in neonatal DBSs and detection of vitamin D deficiency without interference from 3‐epi‐25(OH)D3. 相似文献
613.
Shinsuke MarumotoMitsuo Miyazawa 《Tetrahedron》2011,67(2):495-500
Microbial transformation of coumarin, psoralen, and xanthyletin was performed with the fungus Glomerella cingulata. The main reaction pathways involved reduction at α,β-unsaturated δ-lactone ring on coumarin analogue. Coumarin was metabolized by G. cingulata to give the corresponding reduced acid, hydrocoumaric acid. In the biotransformation of psoralen, two reduced metabolites, 6,7-furano-hydrocoumaric acid, and 6,7-furano-o-hydrocoumaryl alcohol were isolated from the incubation of psoralen. Xanthyletin was converted to reduced products 9,9-dimethyl-6,7-pyrano-hydrocoumaric acid and 9,9-dimethyl-6,7-pyrano-o-hydrocoumaryl alcohol by G. cingulata. The structures of the new compounds were characterized using spectroscopic techniques. In addition, all of compounds including methyl ester derivatives of the metabolites were tested for the β-secretase (BACE1) inhibitory activity in vitro. 6,7-Furano-hydrocoumaric acid methyl ester was shown to possess BACE1 inhibitory activity, and an IC50 value was 0.84 ± 0.06 mM. 相似文献
614.
Egawa T Watanabe H Fujimura T Ishida Y Yamato M Masui D Shimada T Tachibana H Yoshida H Inoue H Takagi S 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10722-10729
Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, (27)Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. In the case of tetrakis(1-methylpyridinium-4-yl)porphyrin (H(2)TMPyP(4+)), the average intermolecular distances on the SS surface can be controlled from 2.3 to 3.0 nm on the basis of a hexagonal array. It was also found that absorption maxima of porphyrins depend on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported "size-matching rule". This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes. 相似文献
615.
A multiresidue analytical method for the determination of emerging pollutants belonging to personal care products (PCPs) (antimicrobials, preservatives), benzotriazole UV stabilizers (BUVSs) and organophosphorus compounds (OPCs) in fish has been developed using high speed solvent extraction (HSSE) followed by silica gel clean up and ultra fast liquid chromatography coupled with tandem mass spectrometry (UFLC–MS/MS) analysis. Developed extraction and clean up method yielded good recovery (>70%) for all the four groups of emerging pollutants, i.e. antimicrobials (78.5–85.6%), preservatives (85.0–89.4%), BUVSs (70.9–112%) and OPCs (81.6–114%; except for TEP – 68.9% and TPeP – 58.1%) with RSDs ranging from 0.7 to 15.4%. Intra- and inter-day repeatabilities were less than 19.8% and 19.0%, respectively at three spiked levels. The concentrations were given in lipid weight (lw) basis, and the method detection limits were achieved in the lowest range of 0.001–0.006 ng g−1 for two antimicrobials, 0.001–0.015 ng g−1 for four preservatives, 0.0002–0.009 ng g−1 for eight BUVSs and 0.001–0.014 ng g−1 for nine OPCs. Finally, the method was successfully validated as a simple and fast extraction method for the determination of 23 compounds belonging to PCPs, BUVSs and OPCs and applied to the analysis of three species of fish from Manila Bay, the Philippines. Concentrations ranged from 27 to 278 ng g−1 for antimicrobials, 6.61 to 1580 ng g−1 for paraben preservatives, −1 for BUVSs and ND (not detected) to 266 ng g−1 for OPCs suggesting the ubiquitous contamination by these emerging pollutants in Manila Bay. This is the first method developed for the determination of triclocarban, four paraben preservatives and four BUVSs, in fish. 相似文献
616.
Fujioka H Goto A Otake K Kubo O Sawama Y Maegawa T 《Chemical communications (Cambridge, England)》2011,47(35):9894-9896
An unusual and novel reaction of α-alkoxyphosphonium salts, generated from O,O-acetals and Ph(3)P, with Grignard reagents under an O(2) atmosphere afforded alcohols in moderate to high yields. It was clarified by isotopic labelling experiments that the reaction proceeded via a novel radical pathway. 相似文献
617.
Tetsuya Shimada Satoshi Hamatani Shingo Onodera Yohei Ishida Haruo Inoue Shinsuke Takagi 《Research on Chemical Intermediates》2013,39(1):269-278
Time-resolved fluorescence and steady-state spectroscopic measurements were performed with +4-charged cationic porphyrins adsorbed on an anionic-type clay (Sumecton SA; SSA) surface at a low molecular loading level (10 % vs. cation-exchange capacity of clay) corresponding to an occupied area of ca 50 nm2 per molecule. Absorption spectra indicated no interaction between transition moments of the porphyrins on the clay surface. An efficient energy-transfer process from donor to acceptor porphyrin was observed on the clay surface even under low porphyrin loading conditions. The efficiency of energy transfer obtained from the steady-state measurement was 65 %. Real-time behavior of the porphyrins was successfully captured during energy transfer. The rate constant of the energy transfer obtained from time-resolved fluorescence measurements was found to be 5.3 × 108 s?1. According to the efficiency and the rate constant, it is proposed that the adsorbed porphyrins did not have a uniform and fixed distribution. 相似文献
618.
Yi Shen Shinsuke Inagi Mahito Atobe Toshio Fuchigami 《Research on Chemical Intermediates》2013,39(1):89-99
The electrocatalytic reduction of open-chain and cyclic dibromides in ionic liquids, mediated by cobalt(II)salen, was investigated. Macro-scale constant-potential electrolysis in an undivided cell gave the corresponding debrominated products in moderate to good yields. The workup process after electrolysis proved to be much simpler in the ionic liquid than that in organic solvents. The possibility of reuse of the ionic liquid was demonstrated. 相似文献
619.
Dr. Shinsuke Nishida Dr. Junya Kawai Miki Moriguchi Tomohiro Ohba Naoki Haneda Dr. Kozo Fukui Prof. Akira Fuyuhiro Prof. Daisuke Shiomi Prof. Kazunobu Sato Prof. Takeji Takui Prof. Kazuhiro Nakasuji Prof. Yasushi Morita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):11904-11915
The tri‐tert‐butylphenalenyl (TBPLY) radical exists as a π dimer in the crystal form with perfect overlapping of the singly occupied molecular orbitals (SOMOs) causing strong antiferromagnetic exchange interactions. 2,5‐Di‐tert‐butyl‐6‐oxophenalenoxyl (6OPO) is a phenalenyl‐based air‐stable neutral π radical with extensive spin delocalization and is a counter analogue of phenalenyl in terms of the topological symmetry of the spin density distribution. X‐ray crystal structure analyses showed that 8‐tert‐butyl‐ and 8‐(p‐XC6H4)‐6OPOs (X=I, Br) also form π dimers in the crystalline state. The π‐dimeric structure of 8‐tert‐butyl‐6OPO is seemingly similar to that of TBPLY even though its SOMO–SOMO overlap is small compared with that of TBPLY. The 8‐(p‐XC6H4) derivatives form slipped stacking π dimers in which the SOMO–SOMO overlaps are greater than in 8‐tert‐butyl‐6OPO, but still smaller than in TBPLY. The solid‐state electronic spectra of the 6OPO derivatives show much weaker intradimer charge‐transfer bands, and SQUID measurements for 8‐(p‐BrC6H4)‐6OPO show a weak antiferromagnetic exchange interaction in the π dimer. These results demonstrate that the control of the spin distribution patterns of the phenalenyl skeleton switches the mode of exchange interaction within the phenalenyl‐based π dimer. The formation of the relevant multicenter–two‐electron bonds is discussed. 相似文献
620.
Masaaki Hori Satoshi Tsutsumi Yukimasa Yasumoto Masanori Ito Michimasa Suzuki Fumine S. Tanaka Shinsuke Kyogoku Masanobu Nakamura Takashi Tabuchi Issei Fukunaga Yuriko Suzuki Koji Kamagata Yoshitaka Masutani Shigeki Aoki 《Magnetic resonance imaging》2014