全文获取类型
收费全文 | 923篇 |
免费 | 45篇 |
国内免费 | 5篇 |
专业分类
化学 | 752篇 |
晶体学 | 11篇 |
力学 | 15篇 |
数学 | 33篇 |
物理学 | 162篇 |
出版年
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 5篇 |
2020年 | 15篇 |
2019年 | 20篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 17篇 |
2015年 | 28篇 |
2014年 | 28篇 |
2013年 | 51篇 |
2012年 | 59篇 |
2011年 | 64篇 |
2010年 | 35篇 |
2009年 | 30篇 |
2008年 | 63篇 |
2007年 | 51篇 |
2006年 | 61篇 |
2005年 | 53篇 |
2004年 | 46篇 |
2003年 | 36篇 |
2002年 | 23篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 16篇 |
1997年 | 8篇 |
1996年 | 12篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 17篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1972年 | 2篇 |
排序方式: 共有973条查询结果,搜索用时 296 毫秒
141.
Kanna Adachi Tomoshi Yamada Hayate Ishizuka Mana Oki Shunsuke Tsunogae Noriko Shimada Osamu Chiba Tatsuya Orihara Prof. Dr. Masafumi Hidaka Prof. Dr. Takatsugu Hirokawa Dr. Minami Odagi Prof. Dr. Keiichi Konoki Prof. Dr. Mari Yotsu-Yamashita Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(9):2025-2033
A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their NaV-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC50 and IC50 values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of NaV1.5, with an IC50 value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from NaV1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with NaV in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp1717. 相似文献
142.
Dr. Yoji Horii Prof. Dr. Keiichi Katoh Prof. Dr. Yuji Miyazaki Dr. Marko Damjanović Tetsu Sato Prof. Dr. Liviu Ungur Prof. Dr. Liviu F. Chibotaru Prof. Dr. Brian K. Breedlove Prof. Dr. Motohiro Nakano Prof. Dr. Wolfgang Wernsdorfer Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8076-8082
Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+–Gd3+ interactions and the other does not. It was found that the Gd3+–Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes. 相似文献
143.
144.
This paper describes two analytic models for the heat-transfer-controlled lateral growth of a clathrate-hydrate film along a planar interface between liquid water and an immiscible hydrate-forming fluid (or guest fluid), such as methane or carbon dioxide. The two models are different from each other only regarding the assumption of the film-front geometry. Either model assumes the film to be uniform and constant in thickness, ignoring possible changes in the thickness on a time scale relevant to its lateral growth. Another fundamental assumption employed in the model is that the film's hydrate-forming front is maintained at the hydrate/guest/water three-phase equilibrium temperature, thereby forming a two-dimensional temperature distribution in the surrounding three-phase space. Based on these assumptions, the transient, two-dimensional conductive heat transfer from the film front into the three phases is formulated and numerically solved to give the instantaneous rate of lateral film growth (i.e., the linear speed of the film-front) along the water/guest-fluid interface, while the film thickness is arbitrarily assumed as a fitting parameter. By comparing the predicted rates of film growth with the corresponding experimental data obtained with methane or carbon dioxide as the guest fluid, we estimated the film thickness to be about 10–20 μm for the methane hydrate at a pressure of 9.06 MPa and about 0.5 μm for the carbon-dioxide hydrate at a pressure of 5 MPa. 相似文献
145.
Okada S Arayama K Murayama R Ishizuka T Hara K Hirone N Hata T Urabe H 《Angewandte Chemie (International ed. in English)》2008,47(36):6860-6864
146.
147.
Hazra P Inoue K Laan W Hellingwerf KJ Terazima M 《The journal of physical chemistry. B》2008,112(5):1494-1501
A recently developed method for time-resolved thermodynamic measurements was used to study the photochemical reaction(s) of the BLUF domain of AppA (AppA-BLUF), which has a dimeric form in the ground state, in terms of the energetics and heat capacity changes (DeltaC(p)) in different time domains. The enthalpy change (DeltaH) of the first intermediate that forms within 1 ns after photoexcitation was 38 (+/-8) kJ mol(-1) at 298 K. The heat capacity change (DeltaC(p)) upon formation of this intermediate was positive [1.4 (+/-0.3) kJ mol(-1) K(-1)]. This positive DeltaC(p) suggests that the hydrophobic surface area of AppA-BLUF exposed to the bulk solvent increased. After this initial transition, a dimerization reaction with another ground-state dimer (i.e., tetramer formation) takes place. Upon this reaction, the energy was stabilized to 26 (+/-6) kJ mol(-1) at 298 K. Interestingly, the dimer formation was accompanied by a larger but negative DeltaC(p) [-6.0 (+/-1) kJ mol(-1) K(-1)]. This negative DeltaC(p) might indicate buried hydrophobic residues at the interface of the dimer and/or the existence of trapped water at the interface. We suggest that hydrophobic interactions are the main driving force for the formation of the dimer upon photoactivation of AppA-BLUF. 相似文献
148.
Toshinori Higashi Keiko Inami Masataka Mochizuki 《Journal of heterocyclic chemistry》2008,45(6):1889-1892
149.
Volatile acidic solutes were used to make dilute solutions, which were frozen by various methods. The concentration of solutes and the pH of the samples were measured before and after being frozen. When the sample solution is frozen from the bottom to the top, solutes are concentrated into the unfrozen solution (i.e., the upper part of the sample) due to the freeze concentration effect. Thereafter, concentrated anions combine with protons to form acids, and the amount of acids in the unfrozen solution increase as the ice formation progresses. At the end of freezing, the acid is saturated at the ice surface, and if the formed acid is volatile, then evaporation occurs. Frozen solutions were allowed to stand below 0 degrees C, where evaporation rates were obtained in the following order: formate > acetate > propionate > n-butyrate > chloride > nitrate. Except for nitrate, evaporation rates were enough to take place in frozen water of the natural environment (e.g., ice crystal, graupel, snow crystal, and frozen droplets). The relationship between the evaporation rate of volatile acids and their physical properties demonstrate that the evaporation rates of weak acids are faster than those of strong acids, and the evaporation rates among weak acids are the same as the volatility of weak acids. 相似文献
150.
Yokoyama A Katsumata K Ohba H Akagi H Saeki M Yokoyama K 《The journal of physical chemistry. A》2008,112(29):6571-6577
Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of 18O and the dissociation probability were measured at a laser frequency between 1033.5 and 1057.3 cm-1, the laser fluence of 2.2-2.3 J/cm2, and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm-1. On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of 18O increases with increasing the 2,3-dihydropyran pressure at the laser fluence of 2.7 J/cm2 or less and the laser frequency of 1033.5 cm-1, whereas the yield of 2-propenal decreases with increasing the pressure. A very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm2. Collisional effect of vibrationally excited molecules with ambient molecules on isotopic selectivity is discussed on the basis of a rate equation model including a collisional vibrational de-excitation process. 相似文献