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101.
102.
Recently, we have developed novel Eu(III) complexes with three beta-diketonates and one asymmetric bis(phosphine) oxide whose light emission intensity is drastically increased. In this paper, one of these complexes is investigated by the density functional theory calculation. Sixteen isomers of this complex have been considered. The ratio of the existence for the most stable isomer (B1_1a) is found to be about 51%, and the sum of the ratio of the existence for the six most stable isomers (B1_1a, B1_3a, B1_8a, B1_2a, B1_1b, and B1_5a) is about 100%, assuming the Boltzmann distribution (T = 300 K). The coordination structures of the six most stable isomers in the ground states are similar, and we can expect asymmetric ligand fields for them, favorable for the efficient light emission. Vertical excitation energies and oscillator strengths for each isomer have been obtained by the time-dependent density functional theory. With the red-shift of the wavelength and the interpolation by Gaussian convolution, both the calculated absorption spectra for the most stable isomer B1_1a and the calculated absorption spectra for the ensemble average of the isomers are found to be similar to the experimental fluorescence excitation spectra. The efficiency of energy transfer from the triplet excited state to the Eu(III) ion is considered by calculating DeltaEET (difference between the adiabatic excitation energy of the complex for the lowest triplet state and the emission energy of the Eu(III) ion for 5D0 to 7F2). The characters for the lowest triplet states for the isomers are investigated by the spin density distributions of the triplet states. 相似文献
103.
Specific isolation of N-terminal fragments from proteins and their high-fidelity de novo sequencing 总被引:1,自引:0,他引:1
Yamaguchi M Obama T Kuyama H Nakayama D Ando E Okamura TA Ueyama N Nakazawa T Norioka S Nishimura O Tsunasawa S 《Rapid communications in mass spectrometry : RCM》2007,21(20):3329-3336
A new method to determine N-terminal amino acid sequences of multiple proteins at low pmol level by a parallel processing has been developed. The method contains the following five steps: (1) reduction, S-alkylation and guanidination for targeted proteins; (2) coupling with sulfosucccimidyl-2-(biotinamido)ethyl-1,3-dithiopropionate(sulfo-NHS-SS-biotin) to N(alpha)-amino groups of proteins; (3) digestion of the modified proteins by an appropriate protease; (4) specific isolation of N-terminal fragments of proteins by affinity capture using the biotin-avidin system; (5) de novo sequence analysis of peptides by MALDI-TOF-/MALDI-TOF-PSD mass spectrometry with effective utilization of the CAF (chemically assisted fragmentation) method.1 This method is also effective for N-terminal sequencing of each protein in a mixture of several proteins, and for sequencing components of a multiprotein complex. It is expected to become an essential proteomics tool for identifying proteins, especially when used in combination with a C-terminal sequencing method. 相似文献
104.
Masashi Yokoya Kimiko Shinada-Fujino Saiko Yoshida Masahiro Mimura Hiroki Takada Naoki Saito 《Tetrahedron》2012,68(22):4166-4181
An improved total synthesis of (±)-renieramycin G (1g) from readily available 2-hydroxy-3-methyl-4,5-dimethoxybenzaldehyde (7) in 21 steps (6.3% overall yield) is described. The synthesis features the concise construction of a pentacyclic framework using the stereoselective Pictet–Spengler type cyclization reaction of lactam (25) with ethyl diethoxyacetate, followed by the base-catalyzed epimerization of the C-1 stereo center of aldehyde (30a). The results of cytotoxicity studies are also presented. 相似文献
105.
Akutsu H Akutsu-Sato A Turner SS Le Pevelen D Day P Laukhin V Klehe AK Singleton J Tocher DA Probert MR Howard JA 《Journal of the American Chemical Society》2002,124(42):12430-12431
Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs. 相似文献
106.
Generation of Aryl(2‐lithiophenyl)methanone O‐Methyl Oximes and Their Use for the Synthesis of N‐(3‐Alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines via the Reaction with Nitriles 下载免费PDF全文
Kazuhiro Kobayashi Kota Matsumoto Yuu Shirai Hiroaki Ishikawa Hiroki Inouchi Miyuki Tanmatsu 《Helvetica chimica acta》2014,97(7):915-922
An efficient two‐step procedure for the preparation of a new type of 1H‐isoindoles, i.e., N‐(3‐alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines 5 , from readily available aryl(2‐bromophenyl)methanones 1 has been developed. Aryl(2‐bromophenyl)methanone O‐methyloximes 2 , derived from the corresponding ketones, were treated with BuLi in Et2O at 0° to generate novel lithium compounds, aryl(2‐lithiophenyl)methanone O‐methyloximes 3 , which were allowed to react with nitriles to give the desired products 5 in moderate‐to‐fair yields. 相似文献
107.
Feroza Begum Yoshinori Namihira S. M. Abdur Razzak Shubi F. Kaijage Nguyen H. Hai Kazuya Miyagi Hiroki Higa Nianyu Zou 《Optical Review》2009,16(2):54-58
This research presents a simple index-guiding square photonic crystal fibers (SPCFs) that has a silica core surrounded by
air hole with two different diameters. It is demonstrated that the designed two-different-size hole-arrayed index-guiding
SPCFs has a ultra-flattened chromatic dispersion of 0 ± 0.9 ps/(nm·km) in a wavelength range of 1.34 to 1.61 μm and low confinement
loss of less than 10−7 dB/m in a wavelength range of 1.2 to 1.7 μm. It has also been shown that the proposed SPCFs show reasonable dispersion tolerance. 相似文献
108.
109.
Koichi KikuchiHiroyuki Nishikawa Isao IkemotoTakashi Toita Hiroki AkutsuShin'ichi Nakatsuji Jun-ichi Yamada 《Journal of solid state chemistry》2002,168(2):503-508
Three FeCl4 salts based on non-tetrathiafulvalene (TTF) donors, 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) and 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), have been prepared and characterized as κ-(BDH-TTP)2FeCl4, β-(BDA-TTP)2FeCl4, and (BDA-TTP)3FeCl4 · PhCl. The κ-(BDH-TTP)2FeCl4 salt, with a room-temperature conductivity (σrt) of 39 S cm−1, is metallic down to 1.5 K, and its magnetic susceptibility obeys the Curie-Weiss law with a Curie constant (C) of 4.25 emu K mol−1 and a Weiss constant (θ) of 0.041 K. β-(BDA-TTP)2FeCl4 exhibits metallic behavior (σrt=9.4 S cm−1) with a sharp metal-to-insulator (MI) transition (TMI=113 K) and antiferromagnetic ordering with the Néel temperature of near 8.5 K, whereas the solvated (BDA-TTP)3FeCl4 · PhCl salt is a semiconductor with a thermal activation energy of 0.11 eV (σrt=2.0× 10−2 S cm−1) and exhibits Curie-Weiss behavior (C=4.42 emu K mol−1, θ=−0.35 K). 相似文献
110.
The pendant E-ring moiety of the podophyllotoxin aza-analogue 1 that is a potent inhibitor of microtubule assembly was modified in order to acquire inhibitory activity of DNA topoisomerase II. The monophenolic analogue 2 did not exhibit human topoisomerase II inhibition, while the ortho-quinone 3 that was obtained by oxidation of 2 inhibited its catalytic activity (decatenation) in a dose-dependent manner and stimulated double strand DNA breaks in supercoiled circular plasmid DNA, resulting in the production of linear DNA. These results showed that the topoisomerase II inhibition of the ortho-quinone 3 is due to stabilization of the topoisomerase II-DNA covalent binary complex. On the other hand, the ortho-quinone 3 did not inhibit the relaxation process of supercoiled DNA by topoisomerase I at concentrations up to 400 microM, nor was intercalation observed in unwinding measurements of 3. Therefore, the ortho-quinone 3 was shown to be a novel nonintercalative topoisomerase II specific inhibitor that stabilizes the cleavable complex. The present results suggest that the 4'-free hydroxyl group on the E-ring and the sugar moiety on the C-ring are not a prerequisite for topoisomerase II inhibition by podophyllotoxin derivatives. 相似文献