全文获取类型
收费全文 | 377篇 |
免费 | 23篇 |
国内免费 | 9篇 |
专业分类
化学 | 323篇 |
晶体学 | 2篇 |
力学 | 14篇 |
数学 | 29篇 |
物理学 | 41篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 6篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 10篇 |
2015年 | 15篇 |
2014年 | 11篇 |
2013年 | 24篇 |
2012年 | 29篇 |
2011年 | 46篇 |
2010年 | 33篇 |
2009年 | 25篇 |
2008年 | 21篇 |
2007年 | 21篇 |
2006年 | 26篇 |
2005年 | 22篇 |
2004年 | 21篇 |
2003年 | 12篇 |
2002年 | 7篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1966年 | 1篇 |
1964年 | 1篇 |
1937年 | 1篇 |
1933年 | 1篇 |
排序方式: 共有409条查询结果,搜索用时 562 毫秒
71.
The reaction of dimedone with various aromatic aldehydes produces 2,2'-arylmethylene bis (3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) in excellent yields. The reactions occur in water as solvent at room temperature and avoiding the addition of any catalyst. The workup procedure is very simple and the products do not required further purification. 相似文献
72.
Photodissociation mechanisms of nitrosamine (NH2NO) have been studied at the complete active space self-consistent field level of theory in conjunction with atomic-natural-orbital-type basis sets. In addition, the energies of all the critical points and the potential energy curves connecting them have been recomputed with the multiconfigurational second-order perturbation method. Ground state minimum of nitrosamine has a C1 nonplanar structure with the hydrogen atoms of the amino moiety out of the plane defined by the N-N-O bonds. Electronic transitions to the three lowest states are allowed by selection rules: (i) S0-->S3 (7.41 eV) has an oscillator strength of f=0.0006 and it is assigned as an (npO)0-->(piNO*)2 transition, (ii) S0-->S2 (5.86 eV) has an oscillator strength of f=0.14 and it is assigned as an npN-->piNO* transition, and (iii) S0-->S1 (2.98 eV) has an oscillator strength of f=0.002 and it is assigned as an npO-->piNO* transition. It is found that N-N bond cleavage is the most likely process in all the photochemical relevant states, namely, S1 (1 1A"), S2 (2 1A'), and T1 (1 3A"). While S1 and T1 yield exclusively homolytic dissociation: NH2NO-->NH2 (1 2B1)+NO(X 2Pi), on S2 the latter process constitutes the major path, but two additional minor channels are also available: adiabatic homolytic dissociation: NH2NO-->NH2 (1 2A1)+NO(X 2Pi), and adiabatic oxygen extrusion: NH2NO-->NH2N (1 3A1)+O(3P). The excited species NH2 (1 2A1) experiences a subsequent ultrafast decay to the ground state, the final products in all cases the fragments being in their lowest electronic state. We have not found a unimolecular mechanism connecting excited states with the ground state. In addition, homolytic dissociation in the ground state, tautomerizations to NHNOH and NHNHO, and intersystem crossings to T1 are considered. The most favorable process on this state is the isomerization to NHNOH. 相似文献
73.
Antonio Antiñolo Antonio Otero Sanjiv Prashar Ana M. Rodríguez 《Journal of organometallic chemistry》2006,691(13):2924-2932
The dialkyl complexes, (R = Pri, R′ = Me (2a), CH2Ph (3a); R = Bun, R′ = Me (2b), CH2Ph (3b); R = But, R′ = Me (2c), CH2Ph (3c); R = Ph, R′ = Me (2d), CH2Ph (3d)), have been synthesized by the reaction of the ansa-metallocene dichloride complex, [Zr{R(H)C(η5-C5Me4)(η5-C5H4)}Cl2] (R = Pri (1a), Bun (1b), But (1c), Ph (1d)), and two molar equivalents of the alkyl Gringard reagent. The insertion reaction of the isocyanide reagent, CNC6H3Me2-2,6, into the zirconium-carbon σ-bond of 2 gave the corresponding η2-iminoacyl derivatives, [Zr{R(H)C(η5-C5Me4)(η5-C5H4)}{η2-MeCNC6H3Me2-2,6}Me] (R = Pri (4a), Bun (4b), But (4c), Ph (4d)). The molecular structures of 1b, 1c and 3b have been determined by single-crystal X-ray diffraction studies. 相似文献
74.
R. Rodríguez-Ramos R. Guinovart-Díaz J. C. López-Realpozo J. Bravo-Castillero J. A. Otero F. J. Sabina H. Berger M. Würkner U. Gabbert 《Archive of Applied Mechanics (Ingenieur Archiv)》2014,84(9-11):1565-1582
In this work, two-phase parallel fiber-reinforced periodic piezoelectric composites are considered wherein the constituents exhibit transverse isotropy and the cells have different configurations. Mechanical imperfect contact at the interface of the piezoelectric composites is studied via linear spring model. The statement of the problem for two-phase piezoelectric composites with mechanical imperfect contact is given. The local problems are formulated by means of the asymptotic homogenization method, and their solutions are found using complex variable theory. Analytical formulae are obtained for the effective properties of the composites with spring imperfect type of contact and different rhombic cells. Using the concept of a representative volume element (RVE), a finite element model is created, which combines the angular distribution of fibers and imperfect contact conditions (spring type) between the phases. Periodic boundary conditions are applied to the RVE, so that effective material properties can be derived. The fibers are distributed in such a way that the microstructure is characterized by a rhombic cell. The presented numerical homogenization technique is validated by comparing results with theoretical approach reported in the literature. Some studies of particular cases, numerical examples, and comparisons between the two aforementioned methods with other theoretical results illustrate that the model is efficient for the analysis of composites with presence of rhombic cells and the aforementioned imperfect contact. 相似文献
75.
The reaction of electrochemically generated anthradiquinone as a Michael acceptor with 2-mercaptobenzothiazole and 2- mercaptobenzoxazole,as nucleophiles in ethanol/water mixtures has been studied by means of cyclic voltammetry.Our voltammetric data indicate that produced anthradiquinone participates in Michael addition reaction with nucleophiles and via an ECEC mechanism converts to the new anthraquinonethioether derivatives.Based on an EC mechanism,the observed homogeneous rate constant of the Michael reaction of anthradiquinone with nucleophiles were estimated by comparing the experimental cyclic voltammograms with the digital simulated results. 相似文献
76.
Jose Luis Castro Maria Rosa Lopez‐Ramirez Juan Francisco Arenas Juan Carlos Otero 《Journal of Raman spectroscopy : JRS》2012,43(7):857-862
The Surface‐enhanced Raman scattering of benzenesulfonamide and sulfanilamide adsorbed on silver sols was studied. On the basis of the noticeable shifts observed for wavenumbers of the νs(OSO), ν(CS), and ν(SN) vibrations with respect to the Raman spectra of the solids and the ionic solutions, we conclude that these molecules are adsorbed on silver nanoclusters at pH ≥ 7 with the aminosulfonyl groups partially deprotonated. The benzenesulfonamide links to the metal through the nitrogen atom of the corresponding azanion, while the sulfanilamide interacts in turn through the nitrogen atoms of the –NH2 and –SO2NH– groups in the para‐position. Additionally, it was found that the most enhanced surface‐enhanced Raman scattering bands, especially the 8a;νring mode, are related to the presence of the charge transfer mechanism. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
77.
Iran Sheikhshoaie Tayebeh Shamspur S. Yousef Ebrahimipur 《Arabian Journal of Chemistry》2012,5(2):201-205
Manganese(II) complex of (E)-2-(hydroxyl-5-methoxybenzylideneamino) phenol was synthesized and used as a suitable Mn(II) – selective membrane in PVC matrix. The plasticized membrane sensor exhibits a nersian response for Mn(II) ions over a wide concentration range of 6 × 10?6–2 × 10?2 M with slope of 29 ± 1 mV per decade. It has a response time of <11 s and can be used for 2 months without any measurable divergence in potential. The response of the proposed sensor is independent of pH between 4 and 9.5. The proposed sensor shows a fairly good discriminating ability towards Mn(II) in comparison with some hard and soft metals. The electrode was used in the determination of Mn(II) in aqueous solutions and as an indicator electrode in potentiometer titration of manganese ions against EDTA. 相似文献
78.
Iran Sheikhshoaie Najmeh Lotfi Joachim Sieler Harald Krautscheid Moj Khaleghi 《Transition Metal Chemistry》2018,43(6):555-562
Three Ni(II) and Zn(II) complexes [Ni(L1)], [Ni(L2)], and [Zn(L3)(DMSO)] (L1 = 2,3-bis(2-hydroxybenzylideneimino)-2,3-butenedinitrile, L2 = 2,3-bis(2-hydroxy-3-methoxybenzylideneimino)-2,3-butenedinitrile, L3 = 2,3-bis(2-hydroxy-1-naphthylideneimino)-2,3-butenedinitrile) were obtained in DMSO by one-pot syntheses. The complexes were characterized by physicochemical and spectroscopic methods. Also, their solid-state structures were determined by single-crystal X-ray diffraction. The geometries of the Ni(II) and Zn(II) complexes were square planar and square pyramidal, respectively. The complexes were screened in vitro against a fungal species and eight species of bacteria, revealing their antimicrobial activity. 相似文献
79.
Vimont A Lavalley JC Sahibed-Dine A Otero Arean C Rodríguez Delgado M Daturi M 《The journal of physical chemistry. B》2005,109(19):9656-9664
By hydrolysis of an ethanolic gallium nitrate solution, gamma-Ga2O3 was prepared as a single-phase polymorph having a specific surface area of 160 m2 g(-1). Surface acidity and basicity of this material was studied by IR spectroscopy, using pyridine, 2,6-dimethylpyridine, acetonitrile, and carbon dioxide as spectroscopic probe molecules. For comparison, a gamma-Al2O3 sample having a surface area of 290 m2 g(-1) was also studied. On partially hydroxylated gamma-Ga2O3, the main O-H stretching bands were found at 3693 (sharp) and at 3660-3630 cm(-1) (broad), and the material proved (by adsorbed dimethylpyridine) to have a weak Br?nsted acidity. Surface Lewis acidity of gamma-Ga2O3 was revealed (mainly) by adsorbed pyridine, which gave the characteristic IR absorption bands of Lewis-type adducts at 1612, 1579, 1488, and 1449 cm(-1) (values noted under an equilibrium pressure of 1 Torr at room temperature); the corresponding Lewis acid centers (coordinatively unsaturated Ga3+ ions) were found to be weaker, although more abundant, than those present on the surface of gamma-Al2O3 (unsaturated Al3+ ions). Another significant difference between gamma-Ga2O3 and gamma-Al2O3 is the smaller thermal stability of pyridine and 2,6-dimethylpyridine Lewis adducts formed on the gallium oxide. The surface basicity of gamma-Ga2O3 was studied by using carbon dioxide and deuterated acetonitrile as IR probe molecules. Adsorbed CO2 gave carbonate and hydrogen-carbonate surface species similar to those formed by gamma-Al2O3. Adsorbed acetonitrile gave rise to acetamide species, which revealed the basic character of surface O2- ions. These acetamide species were found to be more abundant on gamma-Ga2O3 than on gamma-Al2O3. 相似文献
80.
Otero A Fernández-Baeza J Antiñolo A Tejeda J Lara-Sánchez A Sánchez-Barba L Rodríguez AM Maestro MA 《Journal of the American Chemical Society》2004,126(5):1330-1331
An efficient method for the preparation of the first hybrid scorpionate/cyclopentadienyllithium compound as a new class of tridentate ligand is described. This compound is an excellent reagent for the introduction of this ligand into transition metal complexes. 相似文献