全文获取类型
收费全文 | 391篇 |
免费 | 19篇 |
国内免费 | 1篇 |
专业分类
化学 | 263篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 40篇 |
物理学 | 83篇 |
出版年
2023年 | 1篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 13篇 |
2019年 | 18篇 |
2018年 | 13篇 |
2017年 | 12篇 |
2016年 | 30篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 35篇 |
2012年 | 34篇 |
2011年 | 29篇 |
2010年 | 40篇 |
2009年 | 30篇 |
2008年 | 39篇 |
2007年 | 19篇 |
2006年 | 15篇 |
2005年 | 9篇 |
2004年 | 10篇 |
2003年 | 11篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1995年 | 2篇 |
1985年 | 1篇 |
1976年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有411条查询结果,搜索用时 15 毫秒
51.
We studied the synthesis and characterization of polymeric coordination complexes of Co(II) and Ni(II) ions with pyrazine-2,3-dicarboxylic acid and 1-vinylimidazole. The e lemental analysis, infrared spectroscopy, powder X-ray diffraction, magnetic susceptibility, thermal analysis and X-ray single crystal techniques were used in the characterization. The X-ray single crystal analysis suggests that the pyrazine-2,3-dicarboxylato ligand acts as a bridging ligand through the oxygen atoms of the carboxylate groups and the nitrogen atoms on the pyrazine ring. The 1-vinylimidazole ligand behaves as a monodentate ligand via the ring nitrogen atom. Further, the H2 adsorption studies were carried out at 75 K for various increasing pressures and the highest H2 adsorption performances for Co(II) and Ni(II) complexes were estimated as 2.66 and 2.99 wt% at 87 bar. The theoretical calculations using the crystal data were also performed to determine the voids in the structure of Co(II) complex. 相似文献
52.
Hakan Arslan Donald VanDerveer Ismail Ozdemir Bekir Cetinkaya Serpil Demir 《Journal of chemical crystallography》2005,35(6):491-495
Two imidazolidin ruthenium complexes, [RuCl2{[N-(2,4,6-trimethyl-benzyl)-N-(n-butyl)]-imidazolidin-2-ylidene}], 1, and [RuCl2{[N-(2,4,6-trimethyl-benzyl)-N-(2-methoxyethyl)]-imidazolidin-2-ylidene}], 2, have been synthesised and their crystal structures have been determined from single crystal X-ray diffraction data. Compound 1 is monoclinic, of space group C2/c with a = 18.466(4) Å, b = 14.816(3) Å, c = 15.413(3) Å, β = 118.067(2)∘, and V = 3720.9(12) Å3 with Z = 8 for dcalc = 1.536 g/cm3. Compound 2 is monoclinic, of space group P21/c with a = 8.1800(5) Å, b = 14.344(8) Å, c = 14.809(9), β = 91.604(10)∘, and V = 1736.7(18) Å3 with Z = 4 for dcalc = 1.653 g/cm3. In each complex the ligand functions as an arene and carbene, occupying four coordination sites. The two chlorines in each compound complete a distorted octahedron. 相似文献
53.
The molecular mechanism playing a role in the development of prostate cancer (PCA) is not well defined. We decided to determine the changes in gene expression in PCA tissues and to compare them to those in non-cancerous samples. Prostate tissue samples were collected by needle biopsy from 21 PCA and 10 benign prostate hyperplasic (BPH) patients. Total RNA was isolated, cDNA was synthesized, and gene expression levels were determined by microarray method. In the progression to PCA, 738 up-regulated and 515 down-regulated genes were detected in samples. Analysis using Ingenuity Pathway Analysis (IPA) software revealed that 466 network and 423 functions-pathways eligible genes were up-regulated, and 363 network and 342 functions-pathways eligible genes were down-regulated. Up-regulated networks were identified around IL-1beta and insulin-like growth factor-1 (IGF-1) genes. The NFKB gene was centered around two up- and down-regulated networks. Up-regulated canonical pathways were assigned and four of them were evaluated in detail: acute phase response, hepatic fibrosis, actin cytoskeleton, and coagulation pathways. Axonal guidance signaling was the most significant down-regulated canonical pathway. Our data provide not only networks between the genes for understanding the biologic properties of PCA but also useful pathway maps for future understanding of disease and the construction of new therapeutic targets. 相似文献
54.
Olcay Bekircan Zekeriya Bıyıklıoğlu Irfan Acar Hakan Bektas Halit Kantekin 《Journal of organometallic chemistry》2008,693(21-22):3425-3429
The synthesis of metallophthalocyanines [6–9; M = Ni(II), Zn(II), Co(II) and Cu(II)] with four 1,2,4-triazole units obtained from 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-methylphenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile (5) in the presence of dimethylaminoethanol and the corresponding anhydrous metal salts is described. The thermal stabilities of the Pc compounds were determined by thermogravimetric analysis. The new compounds were characterized by a combination of IR, 1H NMR, 13C NMR, UV–Vis, elemental analysis. 相似文献
55.
Hakan Demirtas Robab Ahmadian Sema Atis Fatma Ezgi Can Ilker Ercan 《Computational Statistics》2016,31(4):1385-1401
Two algorithms for establishing a connection between correlations before and after ordinalization under a wide spectrum of nonnormal underlying bivariate distributions are developed by extending the iteratively found normal-based results via the power polynomials. These algorithms are designed to compute the polychoric correlation when the ordinal correlation is specified, and vice versa, along with the distributional properties of latent, continuous variables that are subsequently ordinalized through thresholds dictated by the marginal proportions. The method has broad applicability in the simulation and random number generation world where modeling the relationships between these correlation types is of interest. 相似文献
56.
Ertürk H Hofmann A Puchta R van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2007,(22):2295-2301
A series of dinuclear Pt(II) complexes of the type [Pt2(N,N,N',N'-tetrakis(2-pyridylmethyl)diamine(H2O)2]4+ were synthesized. Acid-base titrations, and concentration and temperature dependent stopped-flow measurements of the reaction with chloride were performed to study the thermodynamic and kinetic behaviour of the dinuclear bridged complexes. The results indicate that there is a clear interaction between the two Pt(II) centres, which becomes weaker as the aliphatic chain increases in length. From a certain chain length onwards, the Pt(II) centres become independent of each other and exhibit identical thermodynamic and kinetic properties. The experimental results are discussed in reference to structures obtained by DFT (BP86/LACVP*) calculations. 相似文献
57.
Serpil Ylmaztürk Hüseyin Deligz Mesut Ylmazolu Hakan Damyan Faruk
ksüzmer S. Naci Ko Ali Durmu M. Ali Gürkaynak 《Journal of membrane science》2009,343(1-2):137-146
A series of highly proton conductive electrolyte membranes with improved methanol barrier properties are prepared from polyallylamine hydrochloride (PAH) and polystyrene sulfonic acid (PSS) including salt by Layer-by-Layer (LbL) method. The effects of added salt type (NaCl, MgCl2) and salt concentration (1.0 M, 0.1 M) on proton conductivity (σ) and methanol barrier properties of the LbL self-assembled composite membranes are discussed in terms of controlled layer thickness and charge density. Furthermore, the influences of ion type in the multilayered composite membranes are studied in conjunction with physicochemical and thermal properties.The deposition of the self-assembly of PAH/PSS film on Nafion is followed by UV–Vis spectroscopy and it is observed that the polyelectrolyte layers growth on both sides of Nafion membrane regularly. (PAH/PSS)5–Na+ and (PAH/PSS)5–H+ with 1.0 M NaCl exhibits 49.6 and 27.8% reduction in lower methanol permittivity in comparison with the pristine Nafion®117, respectively, while the proton conductivities are 12.97 and 74.69 mS cm−1. Promisingly, it is found that the membrane selectivity values (Φ) of all multilayered membranes in H+ form are much higher than that of salt form (Na+ and Mg2+) and perfluorosulfonated ionomers reported in the literature. Also, we find out that the use of polyelectrolytes with high charge density causes a further improvement in proton conductivity and methanol barrier properties simultaneously. These encouraging results indicate that upon a suitable choice of LbL deposition conditions, composite membranes exhibiting both high proton conductivity and improved methanol barrier properties can be tailored for fuel cells. 相似文献
58.
Seyyed Javad Sabounchei Parisa Shahriary Zabiholla Bolboli Nojini Hamid Reza Khavasi Cengiz Arici Hakan Dal 《Heteroatom Chemistry》2010,21(7):475-485
Stable phosphoranes, Ar3P = CHCOR (R = C6H5, C6H4NO2, C6H4OCH3, CH3, OCH2C6H5; Ar = p‐tolyl or phenyl), have been C‐acylated by acetic anhydride to obtain new types of phosphorus ylides. Synthesis and characterization of six phosphorus ylides of the type Ar3PC(COCH3)(COR) are reported. The reaction of {(p‐tolyl)3PCHCOC6H5} ( I ), {(p‐ tolyl)3PCHCOC6H4NO2} ( II ), {Ph3PCHCOC6H4NO2} ( III ), {Ph3PCHCOC6H4OCH3} ( IV ), {(p‐tolyl)3PCHCOCH3} ( V ), and {Ph3PCHCOOCH2C6H5} ( VI ) with acetic anhydride in dry chloroform as solvent gives (p‐tolyl)3PC(COMe)(COC6H5), α‐acetyl‐α‐benzoylmethy‐lenetriphenylphosphorane ( 1 ), {(p‐tolyl)3PC(COMe) (COC6H4NO2)} ( 2 ), {Ph3PC(COMe)(COC6H4NO2)} ( 3 ), {Ph3PC(COMe)(COC6H4OCH3)} ( 4 ), {(p‐tolyl)3 PC(COCH3)2} ( 5 ), and {Ph3PC(COMe)(COOCH2 C6H5)} ( 6 ). Single crystal X‐ray analyses for ylides 2 , 5 , and 6 reveal the monoclinic ( 2, 5 ) and triclinic ( 6 ) crystal systems. Characterization of the obtained compounds was also performed by elemental analysis, IR, 1H, 31P, and 13C NMR. The geometries of these compounds have been investigated using density functional theory (DFT). In addition, electronic parameters of these compounds such as HOMO and LUMO energy, Mulliken partial charge, and dipole moment were obtained. In this paper, the reactivity of these ylides is discussed in regard to the aforementioned data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:475–485, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20633 相似文献
59.
Shafqat Hussain Hakan F. Öztop Khalid Mehmood Nidal Abu-Hamdeh 《Chinese Journal of Physics (Taipei)》2018,56(2):484-501
A computational analysis has been performed on mixed convection in a double sided lid-driven cavity in the presence of volumetric heat generation or absorption. Effects of inclined magnetic field are also studied. The governing parameters are solved via Galerkin weighted residual finite element method in space and the Crank–Nicolson in time. Governing parameters are nanoparticle volume fraction (0.0?≤???≤?0.04), Richardson number (0.01?≤?Ri?≤?10), internal heat generation or absorption parameter inclination angle of magnetic field (0°?≤?γ?≤?90°) and Hartmann number (0?≤?Ha?≤?100). It is observed that the highest heat transfer is obtained in case of the maximum value of heat absorption. As a further finding, heat transfer decreases with increasing of Hartmann number and increases with increasing of nanoparticle volume fraction. 相似文献
60.
The crystal structure of 2-((5-amino-1,3,4-thiadiazol-2-yl)thio)-1-phenylethanone was determined by X-ray diffraction method. The compound crystallizes in orthorhombic crystal system, sp. gr. Pbca. The atoms that constitute thiadiazole and phenyl rings do not form any significant deviation from the ring planes. Compound has two intermolecular N–H···N hydrogen bonds and one C–H···π interaction. Using DFT/B3LYP method with 6-31G(d), 6-311G(d), 6-311G(d, p), and 6-311++G(d, p) basis sets, the molecular geometry of the compound was optimised. Bond lenghts, bond angles, torsion angles, dihedral angles, and HOMO–LUMO were calculated from the optimised geometry of the compound. The results obtained by X-ray diffraction method were compared with the results obtained through four different basis sets. Total energy of the molecule was calculated for four different basis sets. 相似文献