全文获取类型
收费全文 | 593篇 |
免费 | 14篇 |
国内免费 | 4篇 |
专业分类
化学 | 432篇 |
晶体学 | 15篇 |
力学 | 7篇 |
数学 | 56篇 |
物理学 | 101篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 6篇 |
2019年 | 12篇 |
2018年 | 6篇 |
2017年 | 8篇 |
2016年 | 10篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 36篇 |
2012年 | 27篇 |
2011年 | 26篇 |
2010年 | 17篇 |
2009年 | 12篇 |
2008年 | 38篇 |
2007年 | 40篇 |
2006年 | 39篇 |
2005年 | 33篇 |
2004年 | 32篇 |
2003年 | 40篇 |
2002年 | 29篇 |
2001年 | 18篇 |
2000年 | 16篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 9篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1979年 | 8篇 |
1976年 | 3篇 |
1974年 | 6篇 |
1973年 | 2篇 |
1968年 | 2篇 |
1966年 | 2篇 |
1961年 | 1篇 |
排序方式: 共有611条查询结果,搜索用时 0 毫秒
21.
Ryosuke Matsui Erina Niijima Tomomi Imai Hiroyuki Kobayashi Akiko Hori Azusa Sato Yuko Nakamura Osamu Kitagawa 《Molecules (Basel, Switzerland)》2022,27(7)
The halogen bond has been widely used as an important supramolecular tool in various research areas. However, there are relatively few studies on halogen bonding related to molecular chirality. 3-(2-Halophenyl)quinazoline-4-thione derivatives have stable atropisomeric structures due to the rotational restriction around an N-C single bond. In X-ray single crystal structures of the racemic and optically pure N-C axially chiral quinazoline-4-thiones, we found that different types of intermolecular halogen bonds (C=S⋯X) are formed. That is, in the racemic crystals, the intermolecular halogen bond between the ortho-halogen atom and sulfur atom was found to be oriented in a periplanar conformation toward the thiocarbonyl plane, leading to a syndiotactic zig-zag array. On the other hand, the halogen bond in the enantiomerically pure crystals was oriented orthogonally toward the thiocarbonyl plane, resulting in the formation of a homochiral dimer. These results indicate that the corresponding racemic and optically pure forms in chiral molecules are expected to display different halogen bonding properties, respectively, and should be separately studied as different chemical entities. 相似文献
22.
23.
I. Shimizu H. Okabayashi N. Hattori K. Taga A. Yoshino C. J. O’Connor 《Colloid and polymer science》1997,275(3):293-297
Changes in the 13C and 1H NMR chemical shifts of the silane coupling agent (3-aminopropyltri-ethoxysilane, APTS) in toluene, which were detected as
the concentration of APTS increased, have been interpreted in terms of the formation of micelles and the presence of a critical
micelle concentration (CMC) equal to ca. 0.47 mol 1-1. For the protons of the n-propyl segment, 1H NMR splitting patterns have been analyzed and conformations of the propyl segment have been discussed. Plots of relative
absorbance of the two NH2 stretch IR bands at 3324 and 3384 cm-1 against concentration provided an inflection point (corresponding to the CMC) at a value equal to 0.46 mol 1-1. Thus, consideration of the interaction of APTS with a surface must take into account the presence of both APTS aggregates
as well as APTS monomers.
Received: 16 August 1996 Accepted: 26 September 1996 相似文献
24.
Yuichiro Hori Miyako Nishiura Tomomi Tao Reisuke Baba Steven D. Bull Kazuya Kikuchi 《Chemical science》2021,12(7):2498
Reversible enzymatic post-translational modification of the ε-amino groups of lysine residues (e.g. N-acylation reactions) plays an important role in regulating the cellular activities of numerous proteins. This study describes how enzyme catalyzed N-deprotection of lysine residues of non-fluorescent peptide-coumarin probes can be used to generate N-deprotected peptides that undergo spontaneous O- to N-ester transfer reactions (uncatalyzed) to generate a highly fluorescent N-carbamoyl peptide. This enables detection of enzyme catalyzed N-deacetylation, N-demalonylation, N-desuccinylation and N-demethylation reactions activities towards the N-modified lysine residues of these probes using simple ‘turn on’ fluorescent assays.We developed “turn-on” fluorescent probes that detect enzymatic lysine deacylation and demethylation critical for epigenetic and other cellular phenomena, using intramolecular O- to N-ester transfer reactions. 相似文献
25.
Matsumoto T Kominami T Ueda K Sugimoto T Tada T Noguchi S Yoshino H Murata K Shiro M Negishi E Toyota N Endo S Takahashi K 《Inorganic chemistry》2002,41(18):4763-4769
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1. 相似文献
26.
Two new acylated flavanone glycosides, (S)-eriodictyol 7-O-(6"-O-trans-p-coumaroyl)-beta-D-glucopyranoside (1) and (S)-eriodictyol 7-O-(6"-O-galloyl)-beta-D-glucopyranoside (2) were isolated from the leaves and branches of Phyllanthus emblica together with a new phenolic glycoside, 2-(2-methylbutyryl)phloroglucinol 1-O-(6"-O-beta-D-apiofuranosyl)-beta-D-glucopyranoside (3), as well as 22 known compounds. Their structures were determined by spectral and chemical methods. 相似文献
27.
Kazuo Mukai Kanae Nagai Aya Ouchi Tomomi Suzuki Katsuhiro Izumisawa Shin-Ichi Nagaoka 《国际化学动力学杂志》2019,51(9):643-656
Measurements of aroxyl radical (ArO•)-scavenging rate constants () of antioxidants (AOHs) (α-tocopherol (α-TocH) and three catechins (CatHs) (ie, epicatechin (EC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) were performed in ethanol solution, using stopped-flow spectrophotometry. values were measured not only for each AOH, but also for the mixtures of two AOHs (α-TocH and CatH). A notable synergistic effect that the value of α-TocH increases 1.29, 1.84, and 1.65 times under the coexistence of constant concentrations of EC, EGC, and EGCG, respectively, was observed for the solutions including α-TocH and CatH. Similarly, values of CatHs (EC, EGC, and EGCG) increased 1.72, 2.25, and 2.34 times under the coexistence of constant concentrations of α-TocH, respectively. UV-Vis absorption of α-tocopheroxyl radical (α-Toc•) (λmax = 428 nm), which had been produced by reaction of α-TocH with ArO•, decreased remarkably under the coexistence of α-TocH and CatHs due to the fast α-TocH-regeneration reaction by CatHs. The result suggests that the prooxidant reaction due to α-Toc• is suppressed by the coexistence of CatHs. By analyzing the formation and decay curves of α-Toc•, it has been ascertained that one molecule of EGCG having three OH groups at B-ring may rapidly regenerate three molecules of α-Toc• to α-TocH. 相似文献
28.
Novel silicon-based alternating copolymers: synthesis,photophysical properties,and tunable EL colors
Hwan Kyu Kim Kyung Lim Paik Nam Seob Baek Youngil Lee Katsumi Yoshino 《Macromolecular Symposia》2003,192(1):135-150
We synthesized novel silicon-based alternating copolymers for tunable electroluminescent (EL) colors by Heck synthetic method. Their thermal, photophysical and electroluminescent properties were studied. Most of them exhibited a blue-green EL color at the operating voltage of lower than 12 V. Unusually, we observed the white EL color from a EL device based on SiPhPVK. From photophysical studies and the time-resolved PL spectroscopies, it might be attributed to the formation of stabilized excited state in SiPhPVK. Furthermore, in order to reduce the operating voltage of their LED with increasing the electron affinity of the main chain in silicon-based alternating copolymers, we synthesized the silicon-based copolymers containing electron transporting oxadiazole units in main chain. We also studied their photophysical and electroluminescent properties. 相似文献
29.
Silicon substrate surface and silica particle surface were modified with five kinds of polymers, poly(2-methoxyethyl methacrylate) (pMEMA), poly(2-hydroxyethyl methacrylate) (pHEMA), poly(acrylamide) (pAAm), poly(methyl methacrylate) (pMMA), and poly(styrene) (pSt), using a combined polymerization of surface-initiated polymerization that gives dense polymer chain layers and atom transfer radical polymerization (ATRP) that yields polymers with a narrow molecular weight distribution. Measurements of water contact angle and polymer chain amount on the modified silicon substrate surface and adsorption amounts of proteins (albumin and fibrinogen) on the modified silica particle surface revealed that the amount of polymer on the modified surface greatly affects the suppression of protein adsorption on the surface. 相似文献