全文获取类型
收费全文 | 325篇 |
免费 | 28篇 |
国内免费 | 1篇 |
专业分类
化学 | 249篇 |
晶体学 | 4篇 |
力学 | 6篇 |
数学 | 16篇 |
物理学 | 79篇 |
出版年
2023年 | 9篇 |
2022年 | 10篇 |
2021年 | 11篇 |
2020年 | 9篇 |
2019年 | 12篇 |
2018年 | 6篇 |
2017年 | 17篇 |
2016年 | 15篇 |
2015年 | 14篇 |
2014年 | 6篇 |
2013年 | 17篇 |
2012年 | 18篇 |
2011年 | 30篇 |
2010年 | 18篇 |
2009年 | 13篇 |
2008年 | 23篇 |
2007年 | 20篇 |
2006年 | 16篇 |
2005年 | 12篇 |
2004年 | 5篇 |
2003年 | 13篇 |
2002年 | 11篇 |
2001年 | 5篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1967年 | 1篇 |
1966年 | 5篇 |
1965年 | 1篇 |
排序方式: 共有354条查询结果,搜索用时 15 毫秒
1.
The angular variations of the five-fold differential cross section obtained by using different wave functions of helium are
compared with experimental data. It is found that in the coplanar geometry two kinematical arrangements, (i) equal energy
sharing between the two ejected electrons with one of them ejected along the momentum transfer direction and the other along
varying direction and (ii) the Bethe ridge condition with fixed sum of ejected electron energies and varying angle between
them, are very sensitive to e-e correlations contained in the target wave function. This comparison has been used to show
that open-shell class of wave functions better incorporate e-e correlations than the closed-shell class. 相似文献
2.
Arup Baksi Bidyut Kumar Roy Rasajit Kumar Bera 《Mathematical and Computer Modelling》2006,44(11-12):1069-1079
The fundamental equations of the problems of generalized thermoelasticity with one relaxation parameter including heat sources in infinite rotating magneto-thermo-viscoelastic media have been derived in the form of a vector matrix differential equation in the Laplace transform domain for a one dimensional problem. These equations have been solved by the eigenvalue approach to determine deformations, stress, and temperature. The results have been compared to those available in the existing literature. The graphs have been drawn to show the effect of rotation in the medium. 相似文献
3.
From flash photolysis data of benzil and 2,2′-dichlorobenzil, the role of conformeric triplets in the formation of hydrogen
adduct radicals has been discussed. The planar relaxed triplet absorbing at 470 nm is less efficient in forming a hydrogen
adduct radical as compared to its puckered conformeric partner. Among the hydrogen donors, triethyl amine and isopropanol,
the former is more efficient in converting puckered triplets and less efficient in the case of planar conformers. Absorptions
of radicals and radical anions of 2,2′-dichlorobenzil appear at 355 nm and 460 nm respectively. These are blue-shifted as
compared to those of the parent compound benzil appearing at 370 nm and 540 nm, respectively. This blue-shift has been discussed
in terms of steric hindrance due to ortho-substitution. 相似文献
4.
The first enantiospecific approach to garsubellin A and related phloroglucin natural product nemorosone, of contemporary interest from (−)-α-pinene, has been delineated. Through a series of stereospecific operations, the requisite stereochemistry of the prenyl groups has been secured. Kende cyclization has been employed as the key step to construct the functionalized bicyclo[3.3.1]nonane core. 相似文献
5.
Silver-palladium nanodispersions in silicate matrices: highly uniform, stable, bimetallic structures
Ag-Pd nanobimetallic colloidal particles are prepared in a single step by a chemical reduction method. Organically modified aminosilicate is used as a supporting matrix as well as a stabilizing agent, to obtain very uniform, well-distributed bimetallic particles. These nanoparticles are found to be stable for several months in both the solid and the liquid phases. The structure of the bimetallic particles has been followed by X-ray photoelectron spectroscopy and ultraviolet-visible spectroscopy. The distribution and the particle size are determined by transmission electron microscope and X-ray diffraction studies. Polymerization and condensation of the support silicate material have been confirmed by Fourier transform infrared spectroscopy. 相似文献
6.
Reaction of Mo(2)Cl(4)(dppm)(2) (dppm = bis(diphenylphosphino)methane) with 6 equiv of [n-Bu(4)N][CN] or [Et(4)N][CN] in dichloromethane yields [n-Bu(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (1) and [Et(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (2), respectively. The corresponding one- and two-electron oxidation products [n-Bu(4)N][Mo(2)(CN)(6)(dppm)(2)] (3) and Mo(2)(CN)(6)(dppm)(2) (4)were prepared by reactions of 1 with the oxidant NOBF(4). Single-crystal X-ray structures of 2.2CH(3)CN, 3.2CH(3)CN.2H(2)O, and 4.2CH(3)NO(2) were performed, and the results confirmed that all three complexes contain identical ligand sets with trans dppm ligands bisecting the Mo(2)(mu-CN)(2)(CN)(4) equatorial plane. The binding of the bridging cyanide ligands is affected by the oxidation state of the dimolybdenum core as evidenced by an increase in side-on pi-bonding overlap of the mu-CN in going from 1 to 4. The greater extent of pi-donation into Mo orbitals is accompanied by a lengthening of the Mo-Mo distance (2.736(1) A in Mo(2)(II,II) (2), 2.830(1) A in Mo(2)(II,III) (3), and 2.936(1) A in Mo(2)(III,III) (4)). A computational study of the closed-shell members of this homologous series, [Mo(2)(CN)(6)(dppm)(2)](n)() (n = 2-, 0), indicates that the more pronounced side-on pi-donation evident in the X-ray structure of 4 leads to significant destabilization of the delta orbital and marginal stabilization of the delta() orbitals with respect to nearly degenerate delta and delta orbitals in the parent compound, 2. The loss of delta contributions combined with the reduced orbital overlap due to higher charges on molybdenum centers in oxidized complexes 3 and 4 is responsible for the observed increase in the length of the Mo-Mo bond. 相似文献
7.
Kritika Keshari Moumita Bera Lucía Velasco Sandip Munshi Geetika Gupta Dooshaye Moonshiram Sayantan Paria 《Chemical science》2021,12(12):4418
A terminal FeIIIOH complex, [FeIII(L)(OH)]2− (1), has been synthesized and structurally characterized (H4L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at −45 °C results in the formation of a FeIIIOH ligand radical complex, [FeIII(L˙)(OH)]− (2), which is hereby characterized by UV-visible, 1H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pKa value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.One-electron oxidation of an FeIII–OH complex (1) results in the formation of a FeIII–OH ligand radical complex (2). Its reaction with (C6H5)3C˙ results in the formation of (C6H5)3COH, which is a functional mimic of compound II of cytochrome P450. 相似文献
8.
Adiabatic electron affinities, optimized molecular geometries, and IR-active vibrational frequencies have been predicted for small cyclic hydrocarbon radicals C(n)H(2)(n)(-)(1) (n = 3-6) and their perfluoro counterparts C(n)F(2)(n)(-)(1) (n = 3-6). Total energies and optimized geometries of the radicals and corresponding anions have been obtained using carefully calibrated (Chem. Rev. 2002, 102, 231) density functional methods, namely, the B3LYP, BLYP, and BP86 functionals in conjunction with the DZP++ basis set. The predicted electron affinities show that only the cyclopropyl radical tends to bind electrons among the hydrocarbon radicals studied. The trend for the perfluorocarbon (PFC) radicals is quite different. The electron affinities increase with expanding ring size until n = 5 and then slightly decrease at n = 6. Predicted electron affinities of the hydrocarbon radicals using the B3LYP hybrid functional are 0.24 eV (C(3)H(5)/C(3)H(5)(-)), -0.19 eV (C(4)H(7)/C(4)H(7)(-)), -0.15 eV (C(5)H(9)/C(5)H(9)(-)), and -0.11 eV (C(6)H(11)/C(6)H(11)(-)). Analogous electron affinities of the perflurocarbon radicals are 2.81 eV (C(3)F(5)/C(3)F(5)(-)), 3.18 eV (C(4)F(7)/C(4)F(7)(-)), 3.34 eV (C(5)F(9)/C(5)F(9)(-)), and 3.21 eV (C(6)F(11)/C(6)F(11)(-)). 相似文献
9.
Shyam Sundar Mondal Namita Jaiswal Partha Sarathi Bera Ranjay K. Tiwari Jogendra Nath Behera Nripen Chanda Subhas Ghosal Tanmoy Kumar Saha 《应用有机金属化学》2021,35(1)
A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH 2 (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH 2 = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC50 values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished. 相似文献
10.
Parnajyoti Karmakar Sumon Ray Debabrata Nandi Arup Mandal Subala Mondal Subhasis Mallick Biplab K. Bera Alak K. Ghosh 《Journal of solution chemistry》2013,42(2):441-458
The kinetics of the substitution reactions of [Pt(dach)(H2O)2]2+ and [Pt(en)(H2O)2]2+ (where ‘dach’ and ‘en’ are cis-1,2-diaminocyclohexane and ethylenediamine, respectively) with excess N,N′-diethylthiourea have been studied in aqueous solution by UV–Vis spectrophotometry. The effect of different N–N spectator ligands on the reactivity of platinum(II) complexes was investigated by studying the water lability of the reactant complexes. The kinetic study has been substantiated by product isolation, IR, NMR and ESI-MS spectral analysis and DFT calculations. The reactions follow normal square-planar substitution mainly in an associative way. Rate parameters have been evaluated under different conditions. The substitution rates of the complexes studied can be tuned through the nature of the N–N chelates, which is important in the development of new active compounds for cancer therapy. 相似文献