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941.
Hitoshi Tamiaki Rie Monobe Shun Koizumi Tomohiro Miyatake Yusuke Kinoshita 《Tetrahedron: Asymmetry》2013,24(11):677-682
Regioselective reduction of the 13-carbonyl group on the five-membered exo-ring of methyl pyropheophorbide-a, one of the chlorophyll-a derivatives, with sodium borohydride gave an epimeric mixture of (131R/S)-hydroxy-chlorins. The stereoselectivity was controlled by the steric effect of the (17S)-methoxycarbonylethyl group to afford the (131S)-rich secondary alcohol (25% de). The use of sterically large lithium tri(sec-butyl)borohydride as the reductant enhanced the stereoselectivity to 55% de. The regio- and stereoselective methylation and phenylation of the 13-CO of pyropheophorbide-a were observed using methyl and phenyl lithium, respectively. The major diastereomer of the tertiary alcohols obtained had the same configuration at the 131-stereogenic center as in the reduced product. All of the anion species (H?, CH3?, and C6H5?) favorably attacked the 131-carbon atom from the reverse side of the 17-propionate residue, that is, the less sterically crowded face of the 13-CO plane. 相似文献
942.
Tsutomu Kawai Yoichi Kodera Shigeru Oae Masahiro Ishida Takashi Takeda Shoji Wakabayashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):139-148
Abstract Ligand coupling reactions take place not only between benzyl and 2-pyridyl groups and two 2-pyridyl groups in the treatment of benzyl, alkyl and aryl 2-pyridyl sulfoxides with Grignard reagents, but also between such groups as p-benzenesulfonylphenyl, 4-pyridyl, 2-quinolyl and 2-pyrimidyl, and the benzyl group. There are cases in which ligand exchange precedes ligand coupling, especially with 2-heteroaryl groups. In addition, even some alkyl groups were found to couple with the 2-pyridyl group. The ease of coupling seems to be associated with the electronegativity of the coupling carbon atom of the ligand, when one compares the 13C NMR chemical shifts. 相似文献
943.
Hiroaki Ishida Kiyoharu Tadanaga Akitoshi Hayashi Masahiro Tatsumisago 《Journal of Sol-Gel Science and Technology》2013,65(1):41-45
Lithium silicate particles were prepared by the sol–gel process based on the Stöber method using tetraethoxysilane and lithium ethoxide as starting materials; lithium dodecyl sulfate (LDS) was used as a surfactant. Lithium ion concentration of the obtained particles increased with an increase of Li/Si ratios from 1 to 4. Scanning electron microscope images showed that the obtained particles were rather monodispersed with diameter of 100–300 nm, and the particle size was not influenced by the amount of added LDS but the Li/Si ratios. Fourier-transform infrared spectra of the particles showed that the intensity of the peaks due to CO3 2? increased with an increase of the Li/Si ratios. X-ray diffraction patterns and 29Si magic-angle spinning-nuclear magnetic resonance spectra of the particles indicated that Q3 and Q2 units were present as amorphous state in the particles prepared with Li/Si ratios of 1 and 2, respectively. In the case of Li/Si ratios of more than 3, lithium metasilicate crystals formed, and Q1 and Q2 units were dominant. 相似文献
944.
Dr. Akitaka Ito Akihiro Shimizu Noriaki Kishida Yusuke Kawanaka Dr. Daisuke Kosumi Prof. Dr. Hideki Hashimoto Prof. Dr. Yoshio Teki 《Angewandte Chemie (International ed. in English)》2014,53(26):6715-6719
The excited‐state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited‐state characteristics of the derivatives. 相似文献
945.
Shin‐ichiro Ishida Tomohiro Higashino Dr. Shigeki Mori Hirotaka Mori Dr. Naoki Aratani Dr. Takayuki Tanaka Dr. Jong Min Lim Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2014,53(13):3427-3431
Protonation of meso‐aryl [28]hexaphyrins(1.1.1.1.1.1) triggered conformational changes. Whereas protonation with trifluoroacetic acid led to the formation of monoprotonated Möbius aromatic species, protonation with methanesulfonic acid led to the formation of diprotonated triangular antiaromatic species. A peripherally hexaphenylated [28]hexaphyrin was rationally designed and prepared to undergo diprotonation to favorably afford a triangular‐shaped antiaromatic species. 相似文献
946.
Dr. Shintaro Ishida Fumiya Hirakawa Prof. Dr. Ko Furukawa Dr. Kenji Yoza Prof. Dr. Takeaki Iwamoto 《Angewandte Chemie (International ed. in English)》2014,53(42):11172-11176
Stibinyl and bismuthinyl radicals are recognized as representative intermediates of antimony and bismuth compounds, but still elusive in the condensed phase. We successfully synthesized persistent stibinyl and bismuthinyl radicals in solution by facile dissociation of the corresponding dimers with bulky substituents. We characterized the radicals by NMR and UV/Vis spectroscopy and estimated the thermodynamic parameters for the dissociation equilibria. The radicals show n→p (HOMO→SOMO) transition bands at 497 nm (stibinyl) and 543 nm (bismuthinyl) in 3‐methylpentane and react with a stable nitroxyl radical to give the cross‐radical coupling products in good yields. 相似文献
947.
Silylation Improves the Photodynamic Activity of Tetraphenylporphyrin Derivatives In Vitro and In Vivo 下载免费PDF全文
Prof. Hiroaki Horiuchi Prof. Masahiro Hosaka Hiroyuki Mashio Motoki Terata Prof. Shintaro Ishida Prof. Soichiro Kyushin Prof. Tetsuo Okutsu Prof. Toshiyuki Takeuchi Prof. Hiroshi Hiratsuka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6054-6060
The effects of silyl and hydrophilic groups on the photodynamic properties of tetraphenylporphyrin (TPP) derivatives have been studied in vitro and in vivo. Silylation led to an improvement in the quantum yield of singlet oxygen sensitization for both sulfo and carboxy derivatives, although the silylation did not affect other photophysical properties. Silylation also improved the cellular uptake efficiency for both sulfo and carboxy derivatives, enhancing the in vitro photodynamic activity of the photosensitizer in U251 human glioma cells. The carboxy derivative (SiTPPC4) was found to show higher cellular uptake efficiency and in vitro photodynamic activity than the corresponding sulfo derivative (SiTPPS4), which indicates that the carboxy group is a more promising hydrophilic group than the sulfo group in the silylated porphyrin. SiTPPC4 was found to show high selective accumulation efficiency in tumors, although almost no tumor selectivity was observed for the nonsilylated porphyrin. The concentration of SiTPPC4 in tumors was 13 times higher than that in muscle 12 h after drug administration. We also studied tumor response after treatment and found that silylation enhanced in vivo photodynamic activity significantly. SiTPPC4 shows higher photodynamic activity than NPe6 with white light irradiation. 相似文献
948.
Shota Ooi Takayuki Tanaka Takahisa Ikeue Kazuhisa Yamasumi Kento Ueta Daiki Shimizu Masatoshi Ishida Hiroyuki Furuta Atsuhiro Osuka 《化学:亚洲杂志》2019,14(10):1771-1776
Copper complexes of corroles have recently been a subject of keen interest due to their ligand non‐innocent character and unique redox properties. Here we investigated bis‐copper complex of a triply‐linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply‐linked corrole dimer 2 with Cu(acac)2 (acac=acetylacetonate) gave bis‐copper(II) complex 2Cu as a highly planar molecule with a mean‐plane deviation value of 0.020 Å, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF4 gave complex 3Cu , which was characterized as a bis‐copper(II) complex of a dicationic triply‐linked corrole dimer not as the corresponding bis‐copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu . Importantly, the magnetic spin–spin interaction differs depending on the redox‐state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu . 相似文献
949.
Poornenth Pushpanandan Dong‐Hoon Won Shigeki Mori Yuhsuke Yasutake Susumu Fukatsu Masatoshi Ishida Hiroyuki Furuta 《化学:亚洲杂志》2019,14(10):1729-1736
Triplet photosensitizers that generate singlet oxygen efficiently are attractive for applications such as photodynamic therapy (PDT). Extending the absorption band to a near‐infrared (NIR) region (700 nm≈) with reasonable photostability is one of the major demands in the rational design of such sensitizers. We herein prepared a series of mono‐ and bis‐palladium complexes ( 1‐Pd‐H2 , 2‐Pd‐H2 , 1‐Pd‐Pd , and 2‐Pd‐Pd ) based on modified calix[6]phyrins as photosensitizers for singlet oxygen generation. These palladium complexes showed intense absorption profiles in the visible‐to‐NIR region (500–750 nm) depending on the number of central metals. Upon photoirradiation in the presence of 1,5‐dihydroxynaphthalene (DHN) as a substrate for reactive oxygen species, the bis‐palladium complexes generated singlet oxygen with high efficiency and excellent photostability. Singlet oxygen generation was confirmed from the characteristic spectral feature of the spin trapped complex in the EPR spectrum and the intact 1O2 emission at 1270 nm. 相似文献
950.
Saito T Nishihara S Kataoka Y Nakanishi Y Kitagawa Y Kawakami T Yamanaka S Okumura M Yamaguchi K 《The journal of physical chemistry. A》2010,114(45):12116-12123
In the present study, the concerted and stepwise reaction mechanisms for 1,3-dipole cycloaddition of ozone with ethylene (1) and acrylonitrile (2) are investigated. The stationary points are optimized by using four hybrid R(U)DFT methods. A geometry optimization method based on an approximate spin projection (AP-opt method) is applied to eliminate a spin contamination from the broken-symmetry (BS) solution. The AP-opt method reveals that a diradical intermediate for the stepwise pathway is spurious due to the spin contamination. The revised reaction profile with no diradical intermediate supports the stereospecificity. On the basis of the experimental data, the RCCSD(T) method outperforms AP-UCCSD(T), AP-UBD(T), and MkMRCCSD(4e,4o) for the systems, indicating that the RCCSD(T) method can describe the diradical character of ozone within a framework of single reference wave function. The subsequent single point energy calculations show that the highly synchronous transition state is much more favorable than the asynchronous one for 1. In the case of 2, there is not much difference between two transition states because of its asymmetric structure and charge separations in the transition states. 相似文献