全文获取类型
收费全文 | 392篇 |
免费 | 29篇 |
国内免费 | 1篇 |
专业分类
化学 | 312篇 |
力学 | 15篇 |
数学 | 35篇 |
物理学 | 60篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 14篇 |
2020年 | 21篇 |
2019年 | 25篇 |
2018年 | 21篇 |
2017年 | 21篇 |
2016年 | 42篇 |
2015年 | 24篇 |
2014年 | 21篇 |
2013年 | 53篇 |
2012年 | 38篇 |
2011年 | 34篇 |
2010年 | 18篇 |
2009年 | 23篇 |
2008年 | 13篇 |
2007年 | 13篇 |
2006年 | 6篇 |
2005年 | 4篇 |
2004年 | 5篇 |
2003年 | 3篇 |
2002年 | 2篇 |
2001年 | 1篇 |
1999年 | 1篇 |
1997年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有422条查询结果,搜索用时 15 毫秒
31.
Mohammad A. Khalilzadeh Hassan Karimi-Maleh Azra Amiri Fathali Gholami Robabeh Motaghed mazhabi 《中国化学快报》2010,21(12):1467-1470
<正>In this work,we describe a new strategy for the electrochemical determination of captopril(CA) using ferrocenemonocarboxylic acid as a mediator and multiwall carbon nanotubes as sensors in aqueous solution at pH 7.0.The diffusion coefficient(D),and the kinetic parameters such as electron transfer coefficient(α).and heterogeneous rate constant(k_h),for CA were also determined using electrochemical approaches.Under the optimized conditions,the electrocatalytic oxidation peak current of captopril showed two linear dynamic ranges with a detection limit of 0.3×10~(-6) mol L~(-1) captopril.The linear calibration range was 0.8×10~(-6) to 65×10~(-6) mol L~(-1) using cyclic voltammetry.Finally,this modified electrode was also examined as a selective,simple and precise new electrochemical sensor for the determination of captopril in real samples such as drug and patient human urine. 相似文献
32.
N. Azizi A. Khajeh Amiri M. Bolourtchian M. R. Saidi 《Journal of the Iranian Chemical Society》2009,6(4):749-753
An environmentally benign and efficient process for the preparation of thioethers was developed by simple and practical reactions of alkyl halides and thiols in water in the presence of K2CO3 or Et3N in very high yields. The reaction of aryl, alkyl, aliphatic and hindered thiols with various alkyl halides gave the corresponding products with significant advantages such as high conversions, short reaction time, mild reaction conditions, and low cost, simple workup with good to quantitative yields. 相似文献
33.
Golnaz Parhizkar Ahmad Reza Khosropour Iraj Mohammadpoor-Baltork Elahehnaz Parhizkar Hadi Amiri Rudbari 《Tetrahedron》2017,73(11):1397-1406
1-Azabicyclo[3.3.0]oct-3-en-2-one derivatives were synthesized efficiently through the facile cascade reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with arylidene azlactones. This research provides a straightforward procedure for the synthesis of a novel class of multicyclic semi-alkaloids which shows good antimicrobial activity. Under catalyst-free, mild, and solventless condition, a wide range of fused tricyclic derivatives was obtained in high yields. 相似文献
34.
Amiri S Reisenauer HP Schreiner PR 《Journal of the American Chemical Society》2010,132(45):15902-15904
We present the first generation and spectroscopic identification of the higher-lying E conformer of the simplest aromatic carboxylic acid, benzoic acid (1a), as its O-deuterated isotopologue (E)-d(1)-1a using matrix-isolation techniques; the parent (E)-1a could not be observed because of fast H-tunneling to the more stable conformer (Z)-1a. Even deuterated (E)-d(1)-1a converts quickly back to (Z)-d(1)-1a through D-tunneling with a half-life (τ) of ~12 min in Ar at 11 K. Tunneling computations using an Eckart barrier in conjunction with a CCSD(T)/cc-pVTZ//MP2/cc-pVDZ + ZPVE intrinsic reaction path revealed that τ of (E)-1a is only ~10(-5) min, in marked contrast to those of simple aliphatic acids, which are in the range of minutes. The electronic substituent effects on D-tunneling in para-substituted benzoic acid derivatives (p-X-PhCOOD, d(1)-1) were systematically studied in Ar matrices at 11 K to derive the first Hammett relationships for atom tunneling. σ-Electron donors (X = alkyl) increase the half-life of d(1)-1, while σ-acceptor/π-donor groups (X = OD, NH(2), halogen) and to an even greater extent a σ-/π-acceptor group (X = NO(2)) decrease τ. The latter finding is in line with the smaller E-to-Z reaction barriers and narrower reaction widths for the isomerization. Tunneling substituent constants (σ(t)) for this conformational isomerization were derived experimentally and computationally. 相似文献
35.
Crispin Lichtenberg 《Journal of organometallic chemistry》2010,695(17):2000-2006
Ph2P(C5HMe4) (1) was found to undergo a prototropic rearrangement contrary to previous reports. The first detailed investigation of a cyclopentadienylphosphane to undergo such a reaction is presented. One of the two tautomers of 1 which were observed represents the kinetic product, the other one is the thermodynamic product. The two isomers exhibit pronounced differences with respect to their chemical reactivity. Thermodynamic and kinetic data of the isomerisation process were determined. A novel, electron rich cyclopentadienylphosphane, the phosphorus diamide (Me2N)2P(C5HMe4) (2), was synthesised and was also found to undergo a prototropic rearrangement. The characteristics of the isomerisation process are fully consistent with the findings on 1. The molecular structure of the kinetic product of 2 was established by means of single crystal X-ray diffraction analysis. Me2P(C5H4tBu) (3) is presented as another novel cyclopentadienylphosphane. The mixture of isomers of 3 in thermodynamic equilibrium was investigated in detail with respect to the molecular structures of the tautomers. The results of this study suggested a reinvestigation of the parent compound Ph2P(C5H4tBu) (4) and findings differing from an earlier report in some details are presented. 相似文献
36.
Soraia Meghdadi Kurt Mereiter Ahmad Amiri Narges S. Mohammadi Fahimeh Zamani Mehdi Amirnasr 《Polyhedron》2010
A novel and highly efficient approach for the synthesis of H2Me2bqb and H2Me2bpb using ionic liquid as an environmentally benign reaction medium has been developed, eliminating the need for the pyridine as a toxic solvent. The Ni(II) complex of the dianionic ligand Me2bqb2−, [Me2bqb2− = 1,2-bis(quinoline-2-carboxamide)-4,5-dimethyl-benzene dianion], has been synthesized and characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structure of [Ni(Me2bqb)] (1), has been determined by X-ray crystallography. The complex exhibits distorted square-planar NiN4 coordination geometry with two short and two long Ni–N bonds (Ni–N ∼1.85 and ∼1.96 Å, respectively). The electrochemical behavior of [Ni(Me2bqb)] (1), has been studied by cyclic voltammetry and compared with the analogous complex, [Ni(Me2bpb)] (2). 相似文献
37.
Quantum annealing extends simulated annealing by introducing artificial quantum fluctuations. The path-integral Monte Carlo version chosen is population-based and designed to be implemented on a classical computer. Its first application to the graph coloring problem is presented in this paper. It is shown by experiments that quantum annealing can outperform classical thermal simulated annealing for this particular problem. Moreover, quantum annealing proved competitive when compared with the best algorithms on most of the difficult instances from the DIMACS benchmarks. The quantum annealing algorithm has even found that the well-known benchmark graph dsjc1000.9 has a chromatic number of at most 222. This is an improvement on its best upper-bound from a large body of literature. 相似文献
38.
Lizbet Le��n Angel Bustamante Ana Osorio G. S. Olarte Luis De Los Santos Valladares Crispin H. W. Barnes Yutaka Majima 《Hyperfine Interactions》2011,202(1-3):131-137
In this work we report the preparation of magnetic hematite hollow sub-micron spheres (??-Fe2O3) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO3)3·9H2O) particles in citric acid solution by following the sol?Cgel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM). 相似文献
39.
40.
Martin Rides Crispin Allen Huub Omloo Kazuo Nakayama Gianpiero Cancelli 《Polymer Testing》2009,28(6):572-591
The current standard for melt flow rate testing, ISO 1133, does not adequately cover the measurement of materials that degrade or further polymerise at the melt flow rate test conditions. Materials such as PET, PBT and PA tend to degrade, sometimes rapidly, at melt temperatures if they contain absorbed water. This results in poor repeatability and reproducibility of melt flow rate results. The ISO Plastics Melt Rheology Working Group (TC61/SC5/WG9) is currently developing a modified melt flow rate test method for reliable measurement of moisture sensitive materials, thereby providing an alternative to intrinsic viscosity measurements. The modified method controls more tightly the time–temperature history experienced by the material during testing and, thus, the resultant variability in measured properties due to degradation.The results of an intercomparison of testing of moisture sensitive polymers using the melt volume flow rate (MVR) and melt mass flow rate (MFR) methods are reported. A polypropylene (PP), used as a benchmark material, and five moisture sensitive materials were tested by a number of laboratories measuring either MVR or MFR, or both. For standard testing of the PP material, the repeatability and reproducibility of measurements of MVR were up to 5% and 11%, respectively, and for MFR were 7% and 21%, respectively (95% confidence level, outliers excluded). For the moisture sensitive materials the repeatability and reproducibility of measurements varied significantly, with repeatability values up to 26% and reproducibility values up to 114% being obtained. By imposing moisture and temperature control criteria in accordance with the proposed testing standard, the repeatability and reproducibility limits were significantly reduced to approximately 10% and 60%, respectively. The results suggest that both the moisture and temperature criteria were important for improving the repeatability of MVR measurements. However, the moisture content criterion was more important for improving the reproducibility of MVR measurements.The need to tightly control the sample preparation, in particular the drying and subsequent sample handing procedures, and the time–temperature history of the sample throughout the test is considered critical to further improve the precision of measurements of such materials. 相似文献