全文获取类型
收费全文 | 449篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 327篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 128篇 |
出版年
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 2篇 |
2016年 | 2篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 15篇 |
2012年 | 16篇 |
2011年 | 16篇 |
2010年 | 14篇 |
2009年 | 21篇 |
2008年 | 19篇 |
2007年 | 15篇 |
2006年 | 21篇 |
2005年 | 15篇 |
2004年 | 15篇 |
2003年 | 25篇 |
2002年 | 8篇 |
2001年 | 10篇 |
2000年 | 9篇 |
1999年 | 4篇 |
1997年 | 4篇 |
1996年 | 11篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 2篇 |
1991年 | 9篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 12篇 |
1985年 | 16篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 8篇 |
1981年 | 15篇 |
1980年 | 17篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 7篇 |
1972年 | 3篇 |
1969年 | 2篇 |
1968年 | 3篇 |
排序方式: 共有470条查询结果,搜索用时 874 毫秒
381.
Kano K Itoh Y Kitagishi H Hayashi T Hirota S 《Journal of the American Chemical Society》2008,130(25):8006-8015
A per-O-methylated beta-cyclodextrin dimer, Py2CD, was conveniently prepared via two steps: the Williamson reaction of 3,5-bis(bromomethyl)pyridine and beta-cyclodextrin (beta-CD) yielding 2A,2'A-O-[3,5-pyridinediylbis(methylene)bis-beta-cyclodextrin (bisCD) followed by the O-methylation of all the hydroxy groups of the bisCD. Py2CD formed a very stable 1:1 complex (Fe(III)PCD) with [5,10,15,20-tetrakis(p-sulfonatophenyl)porphinato]iron(III) (Fe(III)TPPS) in aqueous solution. Fe(III)PCD was reduced with Na2S2O4 to afford the Fe (II)TPPS/Py2CD complex (Fe(II)PCD). Dioxygen was bound to Fe(II)PCD, the P(1/2)(O2) values being 42.4 +/- 1.6 and 176 +/- 3 Torr at 3 and 25 degrees C, respectively. The k(on)(O2) and k(off)(O2) values for the dioxygen binding were determined to be 1.3 x 10(7) M(-1) s(-1) and 3.8 x 10(3) s(-1), respectively, at 25 degrees C. Although the dioxygen adduct was not very stable (K(O2) = k(on)(O2)/k(off)(O2) = 3.4 x 10(3) M(-1)), no autoxidation of the dioxygen adduct of Fe(II)PCD to Fe(III)PCD was observed. These results suggest that the encapsulation of Fe (II)TPPS by Py2CD strictly inhibits not only the extrusion of dioxygen from the cyclodextrin cage but also the penetration of a water molecule into the cage. The carbon monoxide affinity of Fe(II)PCD was much higher than the dioxygen affinity; the P(1/2)(CO), k(on)(CO), k(off)(CO), and K(CO) values being (1.6 +/- 0.2) x 10(-2) Torr, 2.4 x 10(6) M(-1) s(-1), 4.8 x 10(-2) s(-1), and 5.0 x 10(7) M(-1), respectively, at 25 degrees C. Fe(II)PCD also bound nitric oxide. The rate of the dissociation of NO from (NO)Fe(II)PCD ((5.58 +/- 0.42) x 10(-5) s(-1)) was in good agreement with the maximum rate ((5.12 +/- 0.18) x 10(-5) s(-1)) of the oxidation of (NO)Fe(II)PCD to Fe(III)PCD and NO3(-), suggesting that the autoxidation of (NO)Fe(II)PCD proceeds through the ligand exchange between NO and O2 followed by the rapid reaction of (O2)Fe(II)PCD with released NO, affording Fe(II)PCD and the NO3(-) anion inside the cyclodextrin cage. 相似文献
382.
Teruyuki Hakoda Kanae Matsumoto Akira Mizuno Takuji Kojima Koichi Hirota 《Plasma Chemistry and Plasma Processing》2008,28(1):25-37
The oxidation of xylene and its irradiation byproducts in air using TiO2 was studied under electron beam (EB) irradiation for the purification of ventilation gases emitted from paint factories.
EB irradiation experiments were mainly performed under two different conditions: a TiO2 pellet layer was placed in an irradiation or a non-irradiation space. The results revealed that xylene was decomposed and
CO was formed in the gas phase of the irradiation space irrespective of the presence of TiO2 pellets, while CO2 was produced in the gas phase of the irradiation space and on the surface of TiO2 pellets. The total CO2 concentration increased when the pellet layer was in the non-irradiation space. On the other hand, the concentration of CO2 produced on the surface of the TiO2 pellets in the irradiation space was higher than that in a non-irradiation space. 相似文献
383.
Nurshazliana Othman Vuanghao Lim Muggundha Raoov Ramachandran Mohd Marsin Sanagi Sazlinda Kamaruzaman Yuichiro Hirota Norikazu Nishiyama Noorfatimah Yahaya 《Chromatographia》2017,80(10):1553-1562
A rapid, simple, and efficient method using ultrasound-assisted emulsification microextraction combined with dispersive micro-solid phase extraction (USAE-D-µ-SPE) was developed for detection and quantification of three azole antifungals in milk samples by high-performance liquid chromatography diode array detector. In this study, mesoporous carbon, COU-2, was used as sorbent in USAE-D-µ-SPE for the extraction and preconcentration of analytes. Several important experimental parameters, including type of deproteinized solvents, desorption time, type of extraction solvents, volume of extraction solvent, extraction time, emulsification time, sample pH, salt addition, and mass of COU-2 sorbent, were optimized using spiked milk samples. Under the optimum extraction and detection conditions, three azole antifungals, namely ketoconazole, clotrimazole, and miconazole, were determined within 20 min, with good linearity of matrix-matched calibration in the range of 0.5–5000.0 µg L?1 with coefficient of determination, r 2 ≥ 0.9943. The method showed limits of detection and limits of quantification of all analytes in the range of 0.15–3.0 and 0.5–10.0 µg L?1, respectively. Good repeatability with RSDs <15% (n = 3) and satisfactory relative recoveries (83.3–111.1%) were obtained for spiked azole antifungal drugs in milk. The results reveal that the developed USAE-D-µ-SPE method was a simple, rapid, efficient, environmentally friendly, and practicable method for the determination of azole antifungals in milk samples. 相似文献
384.
Synthesis and NMR Spectroscopic Elucidation of Four Diastereoisomers of Oxygenated Bisabolane Side Chain 下载免费PDF全文
Misaki Hirai Rurina Miyazaki Kana Mitsui Kota Kiuchi Hiroyuki Onuki Hiroshi Hirota Chiaki Kuroda 《Helvetica chimica acta》2015,98(8):1035-1060
Four possible stereoisomers of a model compound of highly O‐bearing bisabolane sesquiterpenes were synthesized and their NMR spectra were compared. Starting from isopulegol, allylic oxidation and Grignard reaction afforded a mixture of alcohols at C(8), which was separated. After metathesis reaction, both α‐ and β‐epoxides were obtained via non‐stereoselective epoxidation, while VO(OiPr)3‐catalyzed epoxidation afforded a single diastereoisomer selectively. NMR Spectra of twelve synthesized compounds, four stereoisomers of acetates, isobutyrates, and tiglates, were measured. A difference between C(8α)‐ and C(8β)‐acyloxy isomers was observed in the δ‐values of H? C(8) in CDCl3. Within the 8β‐acyloxy compounds, the α‐ and the β‐epoxides were distinguished by either the J‐value of H? C(8) or the chemical shift of CH2(9). Within the 8α‐acyloxy compounds, two epoxide isomers were distinguished by the J‐value of H? C(10) in C6D6 or in CD3OD. 相似文献
385.
Polycyclic N‐Heterocyclic Compounds. Part 84: Reaction of N‐(pyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidin‐4‐yl)amidines or N‐(pyrido[2′,3′:4,5]furo[3,2‐d]pyrimidin‐4‐yl)amidines with Hydroxylamine Hydrochloride 下载免费PDF全文
Kensuke Okuda Ryota Ide Naoto Uramaru Takashi Hirota 《Journal of heterocyclic chemistry》2015,52(3):880-887
The reactions of nine N‐(pyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidin‐4‐yl)amidines ( 3 ) with hydroxylamine hydrochloride produced new cyclization products. These were formed via ring cleavage of the pyrimidine component followed by a 1,2,4‐oxadiazole‐forming ring closure to give N‐[2‐([1,2,4]oxadiazol‐5‐yl)thieno[2,3‐b]pyridin‐3‐yl]formamide oximes ( 11 ). Reaction of six N‐(pyrido[2′,3′:4,5]furo[3,2‐d]pyrimidin‐4‐yl)amidines ( 12 ) with hydroxylamine hydrochloride gave similar results. Effects of the newly synthesized compounds on pentosidine formation were also evaluated. 相似文献
386.
Kensuke Okuda Shigeki Takarada Takashi Hirota Kenji Sasaki 《Journal of heterocyclic chemistry》2015,52(3):780-792
Libraries of tricyclic 2‐substituted 4‐alkylamino‐9‐chloro‐5,6‐dihydropyrimido[5,4‐d]benzazepines and tetracyclic 12‐substituted 8‐chloro‐1,2,5,6‐tetrahydro‐4H‐imidazo[1′,2′:1,6]pyrimido[5,4‐d]benzazepines were synthesized as part of our research to develop new effective antiplatelet drugs. Several alkyl and aryl groups were used as substituents at the 2‐position. Evaluation of the effects of the newly synthesized compounds on collagen‐induced platelet aggregation revealed several promising antiplatelet candidates with potencies superior to aspirin. 相似文献
387.
Prof. Ying‐Wu Lin Dr. Satoshi Nagao Mohan Zhang Dr. Yasuhito Shomura Prof. Yoshiki Higuchi Prof. Shun Hirota 《Angewandte Chemie (International ed. in English)》2015,54(2):511-515
Protein design is a useful method to create novel artificial proteins. A rational approach to design a heterodimeric protein using domain swapping for horse myoglobin (Mb) was developed. As confirmed by X‐ray crystallographic analysis, a heterodimeric Mb with two different active sites was produced efficiently from two surface mutants of Mb, in which the charges of two amino acids involved in the dimer salt bridges were reversed in each mutant individually, with the active site of one mutant modified. This study shows that the method of constructing heterodimeric Mb with domain swapping is useful for designing artificial multiheme proteins. 相似文献
388.
CH Activation Generates Period‐Shortening Molecules That Target Cryptochrome in the Mammalian Circadian Clock 下载免费PDF全文
Tsuyoshi Oshima Dr. Iori Yamanaka Dr. Anupriya Kumar Dr. Junichiro Yamaguchi Dr. Taeko Nishiwaki‐Ohkawa Kei Muto Rika Kawamura Dr. Tsuyoshi Hirota Prof. Dr. Kazuhiro Yagita Prof. Dr. Stephan Irle Prof. Dr. Steve A. Kay Prof. Dr. Takashi Yoshimura Prof. Dr. Kenichiro Itami 《Angewandte Chemie (International ed. in English)》2015,54(24):7193-7197
The synthesis and functional analysis of KL001 derivatives, which are modulators of the mammalian circadian clock, are described. By using cutting‐edge C? H activation chemistry, a focused library of KL001 derivatives was rapidly constructed, which enabled the identification of the critical sites on KL001 derivatives that induce a rhythm‐changing activity along with the components that trigger opposite modes of action. The first period‐shortening molecules that target the cryptochrome (CRY) were thus discovered. Detailed studies on the effects of these compounds on CRY stability implicate the existence of an as yet undiscovered regulatory mechanism. 相似文献
389.
Shinji Hasegawa Kyuya Yakushi Hiroo Inokuchi Koji Kamiya-Okudaira Nobuo Ueno Kazuhiko Seki Eizi Morikawa Volker Saile 《Journal of Electron Spectroscopy and Related Phenomena》2001,120(1-3):121-129
Photoelectron angular distributions from ω-(n-pyrrolyl)alkanethiol self-assembled monolayers (SAMs) were calculated within a single-scattering approximation of the photoemission process. The calculations were carried out on two different surface structures with face-stacked and herringbone arrangements of the pyrrole groups, which were deduced from molecular dynamics calculations. The characteristic angular patterns calculated for the molecular orbital originating from the pyrrole group involve information on the orientations of the pyrrole groups, which allows distinction between these arrangements. The photoelectron angular distributions from substituted SAMs can be used as a clue for studying the surface structures of the substituent groups. 相似文献
390.
Procyanidins are contained in various foods, and their effects on starch hydrolysis have been reported. In Japan, black soybeans, which contain a trimeric procyanidin, procyanidin C1 (proC1), are cooked with rice and used to prepare dumplings. In this study, the effects of proC1 on the pancreatin-induced formation of reducing sugars and starch hydrolysis were studied using potato starch and corn starch. ProC1 inhibited both reactions; the inhibition was greater in potato starch than corn starch when added to heated potato starch and corn starch. When heated with proC1, its inhibitory effects decreased, especially in potato starch, suggesting the important role of proC1 itself for the inhibition of potato starch hydrolysis. ProC1 also inhibited the hydrolysis when added to heated, longer amylose (average molecular weight: 31,200), and the inhibition decreased when heated with the amylose. On the other hand, proC1 could not inhibit the hydrolysis when added to heated, shorter amylose (average molecular weight: 4500), but could when heated with the amylose, suggesting the important role of the degradation products of proC1 for the inhibition. We discuss the mechanism of the proC1-dependent inhibition of amylose hydrolysis, taking the molecular weight into account. 相似文献