全文获取类型
收费全文 | 1438篇 |
免费 | 35篇 |
国内免费 | 7篇 |
专业分类
化学 | 1051篇 |
晶体学 | 24篇 |
力学 | 27篇 |
数学 | 89篇 |
物理学 | 289篇 |
出版年
2022年 | 11篇 |
2021年 | 18篇 |
2020年 | 16篇 |
2019年 | 20篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 24篇 |
2015年 | 24篇 |
2014年 | 35篇 |
2013年 | 56篇 |
2012年 | 67篇 |
2011年 | 98篇 |
2010年 | 46篇 |
2009年 | 47篇 |
2008年 | 79篇 |
2007年 | 81篇 |
2006年 | 80篇 |
2005年 | 82篇 |
2004年 | 70篇 |
2003年 | 56篇 |
2002年 | 68篇 |
2001年 | 20篇 |
2000年 | 25篇 |
1999年 | 16篇 |
1998年 | 17篇 |
1997年 | 19篇 |
1996年 | 18篇 |
1995年 | 11篇 |
1994年 | 17篇 |
1993年 | 9篇 |
1992年 | 22篇 |
1991年 | 15篇 |
1990年 | 17篇 |
1989年 | 24篇 |
1988年 | 9篇 |
1987年 | 14篇 |
1986年 | 20篇 |
1985年 | 27篇 |
1984年 | 17篇 |
1983年 | 12篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1980年 | 12篇 |
1979年 | 16篇 |
1978年 | 13篇 |
1977年 | 11篇 |
1976年 | 7篇 |
1975年 | 14篇 |
1974年 | 9篇 |
1966年 | 6篇 |
排序方式: 共有1480条查询结果,搜索用时 207 毫秒
91.
During the course of studies on butenolide synthesis1 we have investigated the utilities of 3-sulfur-functionalized propionic acid derivatives. We report the results with 3-carbanion species obtained from 3-phenylsulfiny1- and 3-phenylsulfonylpropionic acids (1) and (2). These compounds were easily prepared from 3-phenylthiopropionic acid. 相似文献
92.
Ayako Yano Nobuyuki Akai Hiroshi Ishii Chikahiro Satoh Takayuki Hironiwa Keith R. Millington Munetaka Nakata 《Polymer Degradation and Stability》2013
Thermal oxidative degradation of additive-free polypropylene pellets heated isothermally in dry air at 150 and 180 °C (below and above the melting point of 163 °C) was investigated by multichannel Fourier-transform chemiluminescence spectroscopy. The initial peak wavelength of chemiluminescence emission at 490 nm remained constant during the early stages of thermal degradation, but new emissions developed with time in the red spectral region over an extended oxidation period. The time-dependent luminescence spectra were deconvoluted into three emission bands by least-squares fitting using Gaussian curves. We concluded that at least three groups of luminescent species (luminophores), having different conjugation lengths, were generated by thermal oxidation over extended periods and show luminescence around 490, 660, and 740 nm. 相似文献
93.
Nobuyoshi Yamashita Yoshikuni Urushigawa Shigeki Masunaga Mohamed I. Walash Akira Miyazaki 《International journal of environmental analytical chemistry》2013,93(4):289-303
Abstract To assess the risks of organochlorine pesticides discharged into the hydrospheric environment of Egypt, river and lake water, drinking water, suspended solids, sediments and fish were collected during 1993—1994 from the Nile River and Manzala Lake in Egypt and were transported to Japan for chemical analysis. Among different organochlorine pesticides analyzed, p,p′-DDE was the most predominant in fish (7.6 to 67 ng/g wet wt.), sediments (3.2 to 432 ng/g dry wt.) and suspended solids (5.3 tc 138 pg/L). However, in the dissolved phase of water samples HCH compounds predominated (α-HCH, 71 to 2,815 pg/L). Concentrations of organochlorine pesticides, except chlordane, were higher in Manzala Lake than in the River Nile. Concentrations of organochlorine pesticides in fish corresponded with those in sediments from each location. Comparison of organochlorine concentrations in Nile River water with those reported in earlier studies suggested a decrease in concentrations during the last decade. However, concentrations of p,p′-DDE has increased in fish. It appears that the release of this metabolite from contaminated sediment is the major source of p,p′-DDE in fish during recent years. 相似文献
94.
Nobuyuki Ichinose Masahide Hagiri Jun-ichiro Kinugasa Nobuyuki Shichi Toshihiro Nakayama 《Research on Chemical Intermediates》2013,39(1):425-435
A charge-transfer (CT) complex of NOBF4 and hexamethoxybenzene (HMB), which gives out HMB?+ as a “fluorescent radical cation probe,” upon one-electron oxidation, has been designed to explore the excited state dynamics of contact radical ion pairs by laser-induced fluorescence and femtosecond transient absorption spectroscopic techniques. The acetonitrile solution of the CT complex showed weak fluorescence with a similar spectrum to that observed for free excited HMB radical cation (HMB?+*), suggesting the formation of HMB?+* upon the one-photonic excitation of the CT complex. The laser-power dependence of the fluorescence intensity supported the one-photonic excitation event. We have also observed a short-lived transient species but no long-lived species by femtosecond laser flash photolysis of the CT complex. The lifetime (6.5 ps) was in good accordance with its fluorescence quantum yield (2.5 × 10?5) and was able to assign the transient species to the fluorescent state, an excited radical ion pair [HMB ?+*/NO?]. All the events were completed within the inner sphere and the short lifetime of the transient species could be attributed to rapid back-electron transfer. It is concluded that the excited radical cation character in the excited state of the CT complex originates from the radical ion character in the CT complex in the ground state and that a relatively long lifetime of HMB?+* facilitates its observation even in the contact ion pair. 相似文献
95.
96.
Yasuo Kameda Takuya Miyazaki Toshiya Otomo Yuko Amo Takeshi Usuki 《Journal of solution chemistry》2014,43(9-10):1588-1600
Neutron diffraction measurements were carried out at 25 °C for aqueous LiNO3 heavy water solutions, (*LiNO3) x (D2O)1?x where x = 0.1, 0.05 and 0.01, in which the 6Li/7Li isotopic ratios were varied. Structural information on intermolecular nearest neighbor Li+···D2O interactions in the extensive concentration range was derived from the first-order difference function, ?Li(Q), obtained from the difference in scattering cross sections between 6Li- and 7Li-enriched sample solutions. The nearest neighbor Li+···O distance and coordination number for sample solution with x = 0.1 were determined to be r LiO = 1.969 (8) Å and n LiO = 4.12 (6), respectively, corresponding to the four-coordinated Li+ ion in the solution. On the other hand, those obtained for the solution with x = 0.01 are r LiO = 2.00 (2) Å and n LiO = 6.0 (2), respectively, indicating that hexaaqua Li+ is dominant in the dilute solution. These results clearly indicate that a concentration dependence of the hydration number of Li+ occurs in the aqueous solutions. 相似文献
97.
Ariaki Murata Ryota Akaike Tatsuya Kawahashi Ryo Tsuchiya Hiroyuki Takemoto Toshiyuki Ohnishi Yasushi Todoroki Nobuyuki Mase Mineyuki Yokoyama Kazuteru Takagi Peter Winterhalter Naoharu Watanabe 《Tetrahedron》2014
A flower-inducing compound, LDS1, was isolated from a free-floating aquatic plant, Lemna paucicostata. The chemical structure and the absolute stereochemistry of LDS1 were determined as (9R,13R,11E,15Z)-9,13-dihydroxy-10-oxooctadeca-11,15-dienoic acid for its most abundant diastereomer. LDS1 was enzymatically produced when the plant was exposed to drought stress, and induced flowering at a concentration of 10 nM. 相似文献
98.
Caffeine (1,3,7-trimethylxanthine) is a chemical substance associated with everyday human life. In order to recognize caffeine in water, six water-soluble acyclic phane compounds composed of three aromatic rings were examined as artificial receptors. 1H NMR titration experiments revealed that 6,6′-[1,3-phenylenebis(carbonylimino)]bis-1,3-naphthalenedisulfonate had the highest binding ability for caffeine, with a binding constant (Kb) of 127±5 M−1 at 300 K. While this phane compound also formed a complex with theophylline (1,3-dimethylxanthine) at around half the value of the binding constant for caffeine (Kb=64±4 M−1), it showed weak or little complexation for adenosine, guanosine, inosine, and their 5′-phosphates (sodium salts of adenylic acid, guanylic acid, and inosinic acid). 相似文献
99.
Dr. Santiago Alonso-Gil Dr. Kamil Parkan Dr. Jakub Kaminský Dr. Radek Pohl Dr. Takatsugu Miyazaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(14):e202200148
The conformational changes in a sugar moiety along the hydrolytic pathway are key to understand the mechanism of glycoside hydrolases (GHs) and to design new inhibitors. The two predominant itineraries for mannosidases go via OS2→B2,5→1S5 and 3S1→3H4→1C4. For the CAZy family 92, the conformational itinerary was unknown. Published complexes of Bacteroides thetaiotaomicron GH92 catalyst with a S-glycoside and mannoimidazole indicate a 4C1→4H5/1S5→1S5 mechanism. However, as observed with the GH125 family, S-glycosides may not act always as good mimics of GH's natural substrate. Here we present a cooperative study between computations and experiments where our results predict the E5→B2,5/1S5→1S5 pathway for GH92 enzymes. Furthermore, we demonstrate the Michaelis complex mimicry of a new kind of C-disaccharides, whose biochemical applicability was still a chimera. 相似文献
100.
Miyazaki Reona Sakaguchi Isao Hihara Takehiko 《Journal of Solid State Electrochemistry》2021,25(6):1927-1936
Journal of Solid State Electrochemistry - In the present work, the conduction ions in 15NaI∙LiBH4 are investigated by secondary ion mass spectroscopy (SIMS) and galvanostatic measurements. An... 相似文献