全文获取类型
收费全文 | 243篇 |
免费 | 12篇 |
专业分类
化学 | 199篇 |
晶体学 | 4篇 |
力学 | 5篇 |
数学 | 11篇 |
物理学 | 36篇 |
出版年
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 4篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 2篇 |
2014年 | 11篇 |
2013年 | 16篇 |
2012年 | 15篇 |
2011年 | 18篇 |
2010年 | 14篇 |
2009年 | 11篇 |
2008年 | 23篇 |
2007年 | 16篇 |
2006年 | 12篇 |
2005年 | 6篇 |
2004年 | 15篇 |
2003年 | 12篇 |
2002年 | 14篇 |
2001年 | 1篇 |
1998年 | 2篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1971年 | 2篇 |
1967年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有255条查询结果,搜索用时 46 毫秒
1.
Kazuhiro Yamamoto Haruhiko Ito Kouki Totsuka Tomohiro Sato 《Optics Communications》2006,265(2):692-695
We consider a new scheme of optically ionizing atoms with 10-nm-order spatial resolution. In this method, two-color near-field lights are generated on a narrow slit illuminated by two-color evanescent lights via total-internal reflection of two-wavelength light beams. In order to illustrate the feasibility, we first obtain the ionization cross section from two-step photionization of cold Rb atoms by two-color evanescent lights on a plane surface of a prism. Then, we numerically estimate the ionization efficiency as a function of the slit width using Bethe formula. The scheme is useful for detecting ground-state atoms under less perturbation by scattered light. 相似文献
2.
Tetsuji Kametani Hideo Lida Shinzo Kano Sadao Tanaka Keiichiro Fukumoto Shiroshi Shibuya Haruhiko Yagi 《Journal of heterocyclic chemistry》1967,4(1):85-92
Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination. 相似文献
3.
[structure: see text] The first total synthesis of gambierol, a marine polycyclic ether toxin, has been achieved. The synthesis features the Pd(PPh3)4/CuCl/LiCl-promoted Stille coupling for the stereoselective construction of the sensitive triene side chain that includes a conjugated (Z,Z)-diene moiety. 相似文献
4.
Takashima H Mimura N Ohkubo T Yoshida T Tamaoki H Kobayashi Y 《Journal of the American Chemical Society》2004,126(14):4504-4505
Distributed computing has been implemented to the solution structure determination of endothelin-1 to evaluate efficiency of the method for NMR constraint-based structure calculations. A key target of the investigation was determination of the C-terminal folding of the peptide, which had been dispersed in previous studies of NMR, despite its pharmacological significances. With use of tens of thousands of random initial structures to explore the conformational space comprehensively, we determined high-resolution structures with good convergences of C-terminal as well as previously defined N-terminal structures. The previous studies had missed the C-terminal convergence because of initial structure dependencies trapped in localized folding of the N-terminal region, which are strongly constricted by two disulfide bonds. 相似文献
5.
Yagi H Ramesha AR Kalena G Sayer JM Kumar S Jerina DM 《The Journal of organic chemistry》2002,67(19):6678-6689
We describe a novel and efficient synthesis (62-84% yields) of the eight possible, diastereomerically pure, cis and trans, R and S O(6)-allyl-protected N(2)-dGuo phosphoramidite building blocks derived through cis and trans opening of (+/-)-3alpha,4beta-dihydroxy-1beta,2beta-epoxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene [BcPh DE-1 (1)] and (+/-)-3alpha,4beta-dihydroxy-1alpha,2alpha-epoxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene [BcPh DE-2 (2)] by hexafluoropropan-2-ol (HFP)-mediated addition of O(6)-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine (3) at C-1 of the epoxides. Simply changing the relative amount of HFP used in the reaction mixture can achieve a wide ratio of cis/trans addition products. Thus, the observed cis/trans adduct ratio for the reaction of DE-1 (1) in the presence of 5 equiv of 3 varied from 17/83 to 91/9 over the range of 5-532 equiv of HFP. The corresponding ratios for DE-2 (2) varied from 2/98 to 61/39 under the same set of conditions. When 1 or 2 was fused with a 20-fold excess of 3 at 140 degrees C in the absence of solvent HFP, almost exclusive trans addition (>95%) was observed for the both DEs. Through the use of varying amounts of HFP in the reaction mixture as described above, each of the eight possible phosphoramidite oligonucleotide building blocks (DE-1/DE-2, cis/trans, R/S) of the BcPh DE N(2)-dGuo adducts can be prepared in an efficient fashion. To rationalize the varying cis-to-trans ratio, we propose that the addition of 3 to 1 or 2 in the absence of solvent or in the presence of small amounts of HFP proceeds primarily via an S(N)2 mechanism to produce mainly trans-opened adducts. In contrast, increasing amounts of HFP promote increased participation of an S(N)1 mechanism involving a relatively stable carbocation with two possible conformations. One of these conformations reacts with 3 to give mostly trans adduct, while the other conformation reacts with 3 to give mostly cis adduct. 相似文献
6.
Haruhiko Aoi Michihiro Ishimori Sadao Yoshikawa Teiji Tsuruta 《Journal of organometallic chemistry》1975,85(2):241-248
An optically active Co(I)(salen) type complex, lithium N,N′-bis(salicylaldehyde)-1(R), 2(R)-1,2-trans-cyclohexanediiminatocobalt(I), was prepared by reducing the CoII complex, N,N′-bis(salicylaldehyde)-1(R),2(R)-1,2-trans-cyclohexanediiminatocobalt(II), with LiAlH4. The structure of the CoI complex was determined on the basis of the structure of the corresponding CoII complex and was confirmed by usual physicochemical methods. Furthermore, characteristics of the absorption and circular dichroism(CD) spectra of the CoI complex were compared with those of the reported structure of Na+[Co(I)(salen)]?. Highly asymmetric selectivity was found in a resolution reaction of DL-propylene oxide by use of the above optically active lithium cobalt(I) complex as a catalyst. 相似文献
7.
The general synthesis and a novel intramolecular nucleophilic aromatic substitution (SNAr) reaction of 2-carboxamido-3-arylquinazolin-4-ones, a potentially useful scaffold in the field of medicinal chemistry, are described. The synthetic utility of the SNAr reaction as a tool for the synthesis of secondary aryl amines, including diaryl amines, is also demonstrated. 相似文献
8.
Haruhiko Watanabe Masao Murano 《Journal of polymer science. Part A, Polymer chemistry》1971,9(4):911-918
The γ-ray induced polymerizations of α-chloroacrylic acid, mp 66°C, and α-bromo-acrylic acid, mp 72°C, were investigated in the temperature range from 35°C to 85°C. An analysis of polymerization kinetics was made, and results were similar to those reported in the literature for other vinyl monomers. On heating of the polymer obtained, elimination of hydrogen halide takes place, and intramolecular lactone formation is observed. The rate of lactone formation of poly(α-chloroacrylic acid) obtained in the solid-state polymerization was found to be higher than that in the liquid state, because a highly isotactic configuration of polymers, tends to be formed in the solid-state polymerization, and elimination of hydrogen chloride is facilitated with an isotactic 52 helix structure. 相似文献
9.
Synthesis of the ABCDE ring fragment of ciguatoxins has been achieved in a highly stereocontrolled and convergent manner via the B-alkyl Suzuki-Miyaura coupling-based approach. 相似文献
10.
The kinetics of the thermal decompositions of CaCO3, SrCO3 and BaCO3 into their oxides were studied by thermogravimetry at constant and linearly increasing temperatures. The kinetics of the isothermal decompositions of calcium and strontium carbonates were described by the lawR
n
=1–(1–)1/n
, wheren=1.8 and 1.2, respectively. The kinetics of the non-isothermal decompositions of the two carbonates, analysed by the Ozawa and Coats-Redfern methods, were in keeping with the isothermal kinetics. True kinetic compensation laws were established for each decomposition of the two carbonates, including the data under both isothermal and non-isothermal conditions.As concerns the decompositions of BaCO3, however, there was some difference between the kinetic features relating the isothermal and non-isothermal conditions. A true kinetic compensation law was not established in this case.
Zusammenfassung Die Kinetik der thermischen Zersetzung von CaCO3, SrCO3 und BaCO3 zu den Oxiden wurden durch Thermogravimetrie bei konstanter und linear ansteigender Temperatur untersucht. Die Kinetik der isothermen Zersetzung von Calcium- und Strontium-carbonat folgt dem GesetzR n =1–(1 –)1/n, won=1,8 bzw. 1,2. Die Kinetik der nichtisothermen nach den Methoden von Ozawa und Coats-Redfern analysierten Zersetzung der zwei Carbonate ist in Übereinstimmung mit der isothermen Zersetzung. Wahre kinetische Kompensationsgesetze wurden für die Zersetzung der beiden Carbonate erhalten, einschließlich der sich sowohl auf isotherme als auch auf nichtisotherme Bedingungen beziehenden Daten. Was die Zersetzung von Bariumcarbonat betrifft, so wurden einige Unterschiede im kinetischen Verhalten bei der Zersetzung unter isothermen und nichtisothermen Bedingungen festgestellt. Ein wahres kinetisches Kompensationsgesetz konnte in diesem Falle nicht ermittelt werden.
, . R n =1–(1–)1/n , , , 1,8 1,2. , -, . « » , . , , . - «» .相似文献