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81.
The chemo-enzymatic synthesis of (R)-5-hydroxymethyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate, a potential chiral building block for polycyclic terpenoids containing a five–membered ring having isopropyl and angular methyl substituents, such as erinacin A and dolatriol, was achieved over 11 steps from ethyl 2-oxocyclopentane-1-carboxylate. The key synthetic precursor for this triflate was ethyl (1S,2R)-2-hydroxycyclopentanecarboxylate (>99% ee), which was prepared by a lipase-catalyzed enantioselective hydrolysis of the corresponding racemic acetate. The antipodal (S)-triflate is expected to be the synthetic intermediate for another group of terpenoids involving hamigeran B and stolonidiol. Enantiomerically pure (1R,2S)-hydroxyester (>99% ee) was prepared in high yield using the asymmetric reduction of the oxoester with commercially available carbonyl reductase, “Chiralscreen® OH”-E001. 相似文献
82.
Symmetry‐Driven Strategy for the Assembly of the Core Tetracycle of (+)‐Ryanodine: Synthetic Utility of a Cobalt‐Catalyzed Olefin Oxidation and α‐Alkoxy Bridgehead Radical Reaction 下载免费PDF全文
Dr. Masanori Nagatomo Dr. Koji Hagiwara Kengo Masuda Masaki Koshimizu Takahiro Kawamata Yuki Matsui Dr. Daisuke Urabe Prof. Dr. Masayuki Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):222-229
Ryanodine ( 1 ) is a potent modulator of intracellular calcium release channels, designated as ryanodine receptors. The exceptionally complex molecular architecture of 1 comprises a highly oxygenated pentacyclic system with eleven contiguous stereogenic centers, which makes it a formidable target for organic synthesis. We identified the embedded C2‐symmetric tricyclic substructure within 1 . This specific recognition permitted us to design a concise synthetic route to enantiopure tricycle 9 by utilizing a series of pairwise functionalizations. The four tetrasubstituted carbon centers of 9 were effectively constructed by three key reactions, a dearomatizing Diels–Alder reaction, the kinetic resolution of the obtained racemic 14 through asymmetric methanolysis, and the transannular aldol reaction of the eight‐membered diketone 10 . A new combination of cobalt‐catalyzed hydroperoxidation and NfF‐promoted elimination enabled conversion of the hindered olefin of 9 into the corresponding ketone, thus realizing the desymmetrization. Finally, the tetrasubstituted carbon was stereospecifically installed by utilizing the α‐alkoxy bridgehead radical to deliver the core tetracycle 7 with the six contiguous tetrasubstituted carbon centers. Consequently, the present work not only accomplishes efficient assembly of four out of the five fused rings of 1 , but also develops two new powerful methodologies: two‐step ketone formation and bridgehead radical reaction. 相似文献
83.
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85.
Wong CP Shimada M Nagakura Y Nugroho AE Hirasawa Y Kaneda T Awang K Hadi AH Mohamad K Shiro M Morita H 《Chemical & pharmaceutical bulletin》2011,59(3):407-411
Five new limonoids, ceramicines E-I (1-5), have been isolated from the bark of Chisocheton ceramicus. The structures and relative stereochemistry of them were fully elucidated based on 1D- and 2D-NMR data. Ceramicines E-I (1-5) exhibited moderate cell growth inhibitory activities on a range of cell lines (HL-60, A549, MCF7, and HCT116). The absolute structure of previously isolated ceramicine B (6) was also elucidated by circular dichroism (CD) and X-ray analysis. 相似文献
86.
Yutaka Hitomi Kengo Arakawa Masahito Kodera 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14697-14701
We have reported previously that an iron(III) complex supported by an anionic pentadentate monoamido ligand, dpaqH (dpaqH=2‐[bis(pyridin‐2‐ylmethyl)]amino‐N‐quinolin‐8‐yl‐acetamido), promotes selective C? H hydroxylation with H2O2 with high regioselectivity. Herein, we report on the preparation of FeIII–dpaq derivatives that have a series of substituent groups at the 5‐position of a quinoline moiety in the parent ligand dpaqH (dpaqR, R: OMe, H, Cl, and NO2), and examine them with respect to their catalytic activity in C? H hydroxylation with H2O2. As the substituent group becomes more electron‐withdrawing, both the selectivity and the turnover number increase, but the selectivity of epoxidation shows the opposite trend. 相似文献
87.
Superconducting Double Perovskite Bismuth Oxide Prepared by a Low‐Temperature Hydrothermal Reaction 下载免费PDF全文
Mirza H. K. Rubel Prof. Akira Miura Prof. Takahiro Takei Prof. Nobuhiro Kumada M. Mozahar Ali Prof. Masanori Nagao Prof. Satoshi Watauchi Prof. Isao Tanaka Prof. Kengo Oka Prof. Masaki Azuma Prof. Eisuke Magome Prof. Chikako Moriyoshi Prof. Yoshihiro Kuroiwa Prof. A. K. M. Azharul Islam 《Angewandte Chemie (International ed. in English)》2014,53(14):3599-3603
Perovskite‐type structures (ABO3) have received significant attention because of their crystallographic aspects and physical properties, but there has been no clear evidence of a superconductor with a double‐perovskite‐type structure, whose different elements occupy A and/or B sites in ordered ways. In this report, hydrothermal synthesis at 220 °C produced a new superconductor with an A‐site‐ordered double perovskite structure, (Na0.25K0.45)(Ba1.00)3(Bi1.00)4O12, with a maximum Tc of about 27 K. 相似文献
88.
18π‐Electron Tautomeric Benziphthalocyanine: A Functional Near‐Infrared Dye with Tunable Aromaticity 下载免费PDF全文
Naoyuki Toriumi Dr. Atsuya Muranaka Dr. Keiichi Hirano Kengo Yoshida Dr. Daisuke Hashizume Prof. Dr. Masanobu Uchiyama 《Angewandte Chemie (International ed. in English)》2014,53(30):7814-7818
Dihydroxybenziphthalocyanine 1 , with bulky aryloxy groups, has been synthesized and characterized by X‐ray crystallography, NMR and UV/Vis‐NIR spectroscopy, and theoretical calculations. Macrocycle 1 is the first example of an aromatic benziphthalocyanine with an 18π‐electron structure, and was found to exist as an equilibrium mixture of weakly aromatic and strongly aromatic tautomers. The aromaticity and near‐IR absorption can be controlled by chemical modification at the reactive resorcinol moiety and by variation of the solvent. 相似文献
89.
Let G=(V,E) be an undirected graph with a node set V and an arc set E. G has k pairwise disjoint subsets T1,T2,…,Tk of nodes, called resource sets, where |Ti| is even for each i. The partition problem with k resource sets asks to find a partition V1 and V2 of the node set V such that the graphs induced by V1 and V2 are both connected and |V1∩Ti|=|V2∩Ti|=|Ti|/2 holds for each i=1,2,…,k. The problem of testing whether such a bisection exists is known to be NP-hard even in the case of k=1. On the other hand, it is known that if G is (k+1)-connected for k=1,2, then a bisection exists for any given resource sets, and it has been conjectured that for k?3, a (k+1)-connected graph admits a bisection. In this paper, we show that for k=3, the conjecture does not hold, while if G is 4-connected and has K4 as its subgraph, then a bisection exists and it can be found in O(|V|3log|V|) time. Moreover, we show that for an arc-version of the problem, the (k+1)-edge-connectivity suffices for k=1,2,3. 相似文献
90.
Shinichi Yano Hitoshi Yamamoto Kenji Tadano Eisaku Hirasawa 《Journal of Polymer Science.Polymer Physics》1989,27(13):2647-2655
This article describes dielectric properties of complex Zn(II) salts of ethylene-methacrylic acid copolymer (5.4 mol% methacrylic acid) with n-hexylamine. In all samples, the β′ relaxation near 340 K and γ relaxation near 170 K are observed. These are assigned, respectively, to micro-Brownian molecular motion of long segments above Tg and to local molecular motion of short segments below Tg. The dielectric results indicate that ionic clusters are not formed in these systems. 相似文献