全文获取类型
收费全文 | 2994篇 |
免费 | 87篇 |
国内免费 | 15篇 |
专业分类
化学 | 2084篇 |
晶体学 | 26篇 |
力学 | 44篇 |
数学 | 196篇 |
物理学 | 746篇 |
出版年
2021年 | 23篇 |
2020年 | 40篇 |
2019年 | 33篇 |
2018年 | 28篇 |
2017年 | 29篇 |
2016年 | 62篇 |
2015年 | 42篇 |
2014年 | 67篇 |
2013年 | 128篇 |
2012年 | 149篇 |
2011年 | 166篇 |
2010年 | 81篇 |
2009年 | 88篇 |
2008年 | 167篇 |
2007年 | 174篇 |
2006年 | 175篇 |
2005年 | 158篇 |
2004年 | 121篇 |
2003年 | 114篇 |
2002年 | 95篇 |
2001年 | 74篇 |
2000年 | 65篇 |
1999年 | 46篇 |
1998年 | 31篇 |
1997年 | 30篇 |
1996年 | 30篇 |
1995年 | 32篇 |
1994年 | 28篇 |
1993年 | 36篇 |
1992年 | 55篇 |
1991年 | 51篇 |
1990年 | 35篇 |
1989年 | 37篇 |
1988年 | 46篇 |
1987年 | 37篇 |
1986年 | 34篇 |
1985年 | 58篇 |
1984年 | 44篇 |
1983年 | 34篇 |
1982年 | 34篇 |
1981年 | 26篇 |
1980年 | 26篇 |
1979年 | 32篇 |
1978年 | 22篇 |
1977年 | 24篇 |
1976年 | 26篇 |
1975年 | 19篇 |
1974年 | 19篇 |
1973年 | 22篇 |
1969年 | 14篇 |
排序方式: 共有3096条查询结果,搜索用时 250 毫秒
61.
The existence of a 2‐factor in K1, n‐free graphs with large connectivity and large edge‐connectivity
R. E. L. Aldred Yoshimi Egawa Jun Fujisawa Katsuhiro Ota Akira Saito 《Journal of Graph Theory》2011,68(1):77-89
In this article, we study the existence of a 2‐factor in a K1, n‐free graph. Sumner [J London Math Soc 13 (1976), 351–359] proved that for n?4, an (n?1)‐connected K1, n‐free graph of even order has a 1‐factor. On the other hand, for every pair of integers m and n with m?n?4, there exist infinitely many (n?2)‐connected K1, n‐free graphs of even order and minimum degree at least m which have no 1‐factor. This implies that the connectivity condition of Sumner's result is sharp, and we cannot guarantee the existence of a 1‐factor by imposing a large minimum degree. On the other hand, Ota and Tokuda [J Graph Theory 22 (1996), 59–64] proved that for n?3, every K1, n‐free graph of minimum degree at least 2n?2 has a 2‐factor, regardless of its connectivity. They also gave examples showing that their minimum degree condition is sharp. But all of them have bridges. These suggest that the effects of connectivity, edge‐connectivity and minimum degree to the existence of a 2‐factor in a K1, n‐free graph are more complicated than those to the existence of a 1‐factor. In this article, we clarify these effects by giving sharp minimum degree conditions for a K1, n‐free graph with a given connectivity or edge‐connectivity to have a 2‐factor. Copyright © 2010 Wiley Periodicals, Inc. J Graph Theory 68:77‐89, 2011 相似文献
62.
Microbial biosynthesis of hydrocarbon from CO2 reduction driven by electron uptake process from the cathodic electrode has gained intensive attention in terms of potential industrial application. However, a lack of a model system for detailed studies on the mechanism of the CO2 reduction hinders the improvement in efficiency for microbial electrosynthesis. Here, we examined the mechanism of microbial CO2 reduction at the cathode by a well‐described microbe for extracellular electron uptake, Shewanella oneidensis MR‐1, capable of reducing gaseous CO2 to produce formic acid. Using whole‐cell electrochemical assay, we observed stable cathodic current production at ?0.65 V vs Ag/AgCl KCl sat. associated with the introduction of CO2. The observed cathodic current was enhanced by the addition of 4 μM riboflavin, which specifically accelerates the electron uptake process of MR‐1 by the interaction to its outer‐membrane c‐type cytochromes. The significant impact of an uncoupler agent and a mutant strain of MR‐1 lacking sole F‐type ATPase suggested the importance of proton import to the cytoplasm for the cathodic CO2 reduction. The present data suggest that MR‐1 potentially serves as a model system for microbial electrosynthesis from CO2. 相似文献
63.
Ryota Kudo Masahiro Sonobe Yoshiaki Chino Yu Kitazawa Mutsumi Kimura 《Molecules (Basel, Switzerland)》2020,25(23)
The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid. 相似文献
64.
Ryo Kimura Hikaru Kuramochi Pengpeng Liu Takuya Yamakado Atsuhiro Osuka Tahei Tahara Shohei Saito 《Angewandte Chemie (International ed. in English)》2020,59(38):16430-16435
Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S1 excited state. The S1 planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM). 相似文献
65.
Hayate Saito Keita Yamamoto Yosuke Sumiya Ling‐Jun Liu Keisuke Nogi Satoshi Maeda Hideki Yorimitsu 《化学:亚洲杂志》2020,15(16):2442-2446
C?H iodination of aromatic compounds has been accomplished with the aid of sulfinyl directing groups under palladium catalysis. The reaction proceeds selectively at the peri‐position of polycyclic aryl sulfoxides or at the ortho‐position of phenyl sulfoxides. The iodination products can be further converted via iterative catalytic cross‐coupling at the expense of the C?I and C?S bonds. Computational studies suggest that peri‐C?H palladation would proceed via a non‐directed pathway, wherein neither of the sulfur nor oxygen atom of the sulfinyl group coordinates to the palladium before and at the transition state. 相似文献
66.
Application of plug–plug technique to ACE experiments for discovery of peptides binding to a larger target protein: A model study of calmodulin‐binding fragments selected from a digested mixture of reduced BSA 下载免费PDF全文
Kazuki Saito Mamiko Nakato Takaaki Mizuguchi Shinji Wada Hiromasa Uchimura Hiroshi Kataoka Shigeyuki Yokoyama Hiroshi Hirota Yoshiaki Kiso 《Electrophoresis》2014,35(6):846-854
To discover peptide ligands that bind to a target protein with a higher molecular mass, a concise screening methodology has been established, by applying a “plug–plug” technique to ACE experiments. Exploratory experiments using three mixed peptides, mastoparan‐X, β‐endorphin, and oxytocin, as candidates for calmodulin‐binding ligands, revealed that the technique not only reduces the consumption of the protein sample, but also increases the flexibility of the experimental conditions, by allowing the use of MS detection in the ACE experiments. With the plug–plug technique, the ACE–MS screening methodology successfully selected calmodulin‐binding peptides from a random library with diverse constituents, such as protease digests of BSA. Three peptides with Kd values between 8–147 μM for calmodulin were obtained from a Glu‐C endoprotease digest of reduced BSA, although the digest showed more than 70 peaks in its ACE–MS electropherogram. The method established here will be quite useful for the screening of peptide ligands, which have only low affinities due to their flexible chain structures but could potentially provide primary information for designing inhibitors against the target protein. 相似文献
67.
Synthesis, π‐Face‐Selective Aggregation,and π‐Face Chiral Recognition of Configurationally Stable C3‐Symmetric Propeller‐Chiral Molecules with a π‐Core 下载免费PDF全文
Dr. Nozomi Saito Dr. Ryo Terakawa Prof. Dr. Masahiko Yamaguchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5601-5607
The C3‐symmetric propeller‐chiral compounds (P,P,P)‐ 1 and (M,M,M)‐ 1 with planar π‐cores perpendicular to the C3‐axis were synthesized in optically pure states. (P,P,P)‐ 1 possesses two distinguishable propeller‐chiral π‐faces with rims of different heights named the (P/L)‐face and (P/H)‐face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π‐core. (P,P,P)‐ 1 formed dimeric aggregates in organic solutions as indicated by the results of 1H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single‐crystal X‐ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of 1H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)‐ 1 /(M,M,M)‐ 1 interactions were much weaker than the homochiral (P,P,P)‐ 1 /(P,P,P)‐ 1 interactions. The results indicated that the propeller‐chiral (P/L)‐face interacts with the (P/L)‐face more strongly than with the (P/H)‐face, (M/L)‐face, and (M/H)‐face. The study showed the π‐face‐selective aggregation and π‐face chiral recognition of the configurationally stable propeller‐chiral molecules. 相似文献
68.
Facile Synthesis of Dibenzopentalene Dianions and Their Application as New π‐Extended Ligands 下载免费PDF全文
Takuya Kuwabara Dr. Kazuya Ishimura Prof. Dr. Takahiro Sasamori Prof. Dr. Norihiro Tokitoh Prof. Dr. Masaichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7571-7575
Reduction of phenyl(silyl)ethynes with potassium followed by quenching with iodine gave dibenzopentalenes in moderate yields. The intermediates of the reactions, dipotassium dibenzopentalenides, were isolated. The first dibenzopentalene–transition‐metal complex was successfully synthesized. The ruthenium atoms are located above the six‐membered rings. However, X‐ray diffraction analysis and theoretical calculations revealed that the aromatic nature of the five‐membered rings was retained. The cyclic voltammetry of the Ru complex revealed two oxidation waves with relatively large separation. 相似文献
69.
Chiral Phosphoric‐Acid‐Catalyzed Transfer Hydrogenation of Ethyl Ketimine Derivatives by Using Benzothiazoline 下载免费PDF全文
Dr. Kodai Saito Kosaku Horiguchi Yukihiro Shibata Prof. Dr. Masahiro Yamanaka Prof. Takahiko Akiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7616-7620
Chiral phosphoric acid catalyzed transfer hydrogenation of ketimines derived from propiophenone derivatives and reductive amination of alkyl ethyl ketone derivatives were extensively examined in the presence of two representative hydrogen donors. The excellent enantioselective transfer hydrogenation was achieved by use of benzothiazoline as a hydrogen donor. The theoretical studies elucidated that the unsymmetrical structure of benzothiazoline plays an important role in high enantioselective hydrogenation. 相似文献
70.