全文获取类型
收费全文 | 2452篇 |
免费 | 106篇 |
国内免费 | 20篇 |
专业分类
化学 | 2003篇 |
晶体学 | 21篇 |
力学 | 15篇 |
数学 | 155篇 |
物理学 | 384篇 |
出版年
2023年 | 18篇 |
2021年 | 26篇 |
2020年 | 35篇 |
2019年 | 53篇 |
2018年 | 32篇 |
2017年 | 29篇 |
2016年 | 59篇 |
2015年 | 71篇 |
2014年 | 66篇 |
2013年 | 133篇 |
2012年 | 179篇 |
2011年 | 206篇 |
2010年 | 127篇 |
2009年 | 108篇 |
2008年 | 191篇 |
2007年 | 174篇 |
2006年 | 132篇 |
2005年 | 150篇 |
2004年 | 146篇 |
2003年 | 115篇 |
2002年 | 105篇 |
2001年 | 19篇 |
2000年 | 21篇 |
1999年 | 17篇 |
1998年 | 16篇 |
1997年 | 15篇 |
1996年 | 19篇 |
1995年 | 29篇 |
1994年 | 23篇 |
1993年 | 25篇 |
1992年 | 20篇 |
1991年 | 17篇 |
1990年 | 16篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 10篇 |
1986年 | 23篇 |
1985年 | 25篇 |
1984年 | 24篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 5篇 |
1970年 | 3篇 |
排序方式: 共有2578条查询结果,搜索用时 16 毫秒
1.
Naoto Sato Taiki Hayashi Kazuma Tochigi Prof. Hiroaki Wada Prof. Atsushi Shimojima Prof. Kazuyuki Kuroda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7860-7865
Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials. 相似文献
2.
3.
Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion‐Channel‐Forming 48‐mer Peptides with Potent Cytotoxicity 下载免费PDF全文
Atsushi Hayata Dr. Hiroaki Itoh Shoko Matsutaka Prof.Dr. Masayuki Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3370-3377
Polytheonamide B ( 1 ) is a natural peptide that displays potent cytotoxicity against P388 mouse leukemia cells (IC50=0.098 nm ). Linear 48‐mer 1 is known to form monovalent cation channels on binding to lipid bilayers. We previously developed a fully synthetic route to 1 , and then achieved the design and synthesis of a structurally simplified analogue of 1 , namely, dansylated polytheonamide mimic 2 . Although the synthetically more accessible 2 was found to emulate the channel function of 1 , its cytotoxicity was decreased 120‐fold. Herein, the chemical preparation and biological evaluation of seven analogues 3 – 9 of 2 are reported. Compounds 3 – 9 were modified at their N terminus and/or the side chain of residue 44 of 2 to alter their physicochemical properties. The total synthesis of 3 – 9 was accomplished in a unified fashion by a combination of solid‐phase and solution‐phase chemistry. Systematic evaluation of the hydrophobicities, single‐channel currents, ion‐exchange activities, and cytotoxicities of 3 – 9 revealed that their hydrophobicities are correlated with the total magnitude of ion exchange and determine their cytotoxic potency. Consequently, the most hydrophobic analogue 9 exhibited the lowest IC50 value, which is comparable to that of 1 . Therefore, these results clarified that the bioactivity of the polytheonamide‐based peptides can be rationally controlled by changing their hydrophobicity at the N and C termini of the 48‐amino‐acid sequence. 相似文献
4.
A new periodic pattern with five‐neighbored domain packing from ABC triblock terpolymer/B homopolymer blend 下载免费PDF全文
Yuki Izumi Mutsuhiko Yamada Atsushi Takano Yushu Matsushita 《Journal of Polymer Science.Polymer Physics》2015,53(13):907-911
Self‐assembled structures from poly(isoprene‐b‐styrene‐b‐2‐vinylpyridine)(ISP)/styrene homopolymer blend were investigated. Five terpolymers whose total molecular weight, M, is in the narrow range of 121k < M < 214k, and volume fractions of the center block polystyrenes, ?S, are similar at around 0.55, were prepared as parent block terpolymers. Their ?P/?I ratios, used as an indicator of asymmetry, are varied in the range 0.32 < ?P/?I < 2.46. Three low‐molecular weight styrene homopolymers with molecular weights of 3k, 9k, and 12k, respectively, were mixed with those block terpolymers to produce blends with almost constant styrene content within the range 0.65 < ?S < 0.68. Both ISP/S(3k) and ISP/S(12k) blend series show a morphological transition from tetragonally packed cylinders (TPC) to double hexagonal structure (DHS) with hexagonally arrayed polyisoprene cylinders, each surrounded by six thin cylinders as satellites. If one focuses on ISP‐III(150k)/S blends whose ?P/?I is 0.88, TPC for ISP‐III/S(3k) was transformed to DHS for ISP‐III/S(12k), evidently due to the molecular weight effect of the added homopolymer. Finally a new periodic pattern, having P cylinders surrounded by five I cylinders each, has been discovered from ISP‐III/S(9k) at overall composition of ?I/?S/?P = 0.17/0.68/0.15 and polystyrene block/styrene homopolymer ratio of wS(b)/wS(h) = 1.4. This structure was confirmed to possess hexagonal symmetry with larger unit cell than regular patterns ever known by X‐ray diffraction experiment. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 907–911 相似文献
5.
A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis 下载免费PDF全文
Atsushi Sudo Shou Sugita 《Journal of polymer science. Part A, Polymer chemistry》2016,54(21):3436-3443
A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443 相似文献
6.
Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene 下载免费PDF全文
Tatsuya Hirofuji Dr. Toshiaki Ikeda Prof. Dr. Takeharu Haino Prof. Dr. Yohsuke Yamamoto Prof. Dr. Atsushi Kawachi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9734-9739
A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 . 相似文献
7.
Daisuke Saito Dr. Tomasz Galica Prof. Dr. Eiji Nishibori Dr. Masaki Yoshida Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200703
The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N-heterocyclic carbene [Pt(CN)2(tBu-impy)] (tBu-impyH+=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor. 相似文献
8.
Multiple ionization process of a rare gas dimer BC collided with a slow highly charged ion Aq+ is investigated with the three-center Coulombic over-barrier model previously developed by the present authors. To reveal stereodynamical effects, we calculate asymmetric ion-pair formation cross sections σ(QB,QC) as a function of the orientation angle. We introduce a pair of atomic impact parameters bB and bC with which we distinguish the near and far sites. Furthermore, we distinguish the forward and backward emitted ions produced as a result of Coulomb explosion. Partial screening effects are also considered. 相似文献
9.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
10.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献