全文获取类型
收费全文 | 728篇 |
免费 | 40篇 |
国内免费 | 8篇 |
专业分类
化学 | 461篇 |
晶体学 | 5篇 |
力学 | 48篇 |
数学 | 105篇 |
物理学 | 157篇 |
出版年
2023年 | 5篇 |
2022年 | 15篇 |
2021年 | 22篇 |
2020年 | 17篇 |
2019年 | 27篇 |
2018年 | 18篇 |
2017年 | 26篇 |
2016年 | 42篇 |
2015年 | 19篇 |
2014年 | 23篇 |
2013年 | 81篇 |
2012年 | 55篇 |
2011年 | 56篇 |
2010年 | 38篇 |
2009年 | 35篇 |
2008年 | 45篇 |
2007年 | 52篇 |
2006年 | 29篇 |
2005年 | 37篇 |
2004年 | 37篇 |
2003年 | 22篇 |
2002年 | 12篇 |
2001年 | 4篇 |
2000年 | 7篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有776条查询结果,搜索用时 31 毫秒
81.
Tetrakis(bicyclo[2.2.2]oct‐2‐ene)‐fused calix[4]pyrrole, 5 , was obtained starting from (E)‐1,2‐bis(phenylsulfonyl)ethylene. This new calixpyrrole derivative is the prospective precursor of tetrabenzocalix[4]pyrrole, a potential ion‐pair receptor and an attractive species as a possible deep‐walled ‘molecular container’. 相似文献
82.
Synthesis of Spirocyclic and Tricyclic Isoxazoline via 1,3‐Dipolar Cycloaddition Reactions
下载免费PDF全文
![点击此处可从《Journal of heterocyclic chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
1,3‐Dipolar cycloadditions of the bicyclic monoterpenes (S)‐(?)‐camphene ( 1 ), (R)‐(+)‐a‐pinene ( 2 ), and (S)‐(?)‐b‐pinene ( 3 ) with aryl and heteroaryl nitrile oxides afforded new spirocyclic and tricyclic isoxazoline derivatives 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 whose biological activities were evaluated in bioassay studies. 相似文献
83.
In this study, new xanthine biosensors, XO/Au/PVF/Pt and XO/Pt/PVF/Pt, based on electroless deposition of gold(Au) and platinum(Pt) nanoparticles on polyvinylferrocene(PVF) coated Pt electrode for detection of xanthine were presented. The amperometric responses of the enzyme electrodes were measured at the constant potential, which was due to the electrooxidation of enzymatically produced H2O2. Compared with XO/PVF/Pt electrode, XO/Au/PVF/Pt and XO/Pt/PVF/Pt exhibited excellent electrocatalytic activity towards the oxidation of the analyte. Effect of Au and Pt nanoparticles was investigated by monitoring the response currents at the different deposition times and the different concentrations of KAuCl4 and PtBr2. Under the optimal conditions, the calibration curves of XO/Au/PVF/Pt and XO/Pt/PVF/Pt were obtained over the range of 2.5 × 10?3 to 0.56 mM and 2.0 × 10?3 to 0.66 mM, respectively. The detection limits were 7.5 × 10?4 mM for XO/Au/PVF/Pt and 6.0 × 10?4 mM for XO/Pt/PVF/Pt. The effects of interferents, the operational and the storage stabilities of the biosensors and the applicabilities of the proposed biosensors to the drug samples analysis were also evaluated. 相似文献
84.
Chang TY Huang M Yanik AA Tsai HY Shi P Aksu S Yanik MF Altug H 《Lab on a chip》2011,11(21):3596-3602
Microarrays allowing simultaneous analysis of thousands of parameters can significantly accelerate screening of large libraries of pharmaceutical compounds and biomolecular interactions. For large-scale studies on diverse biomedical samples, reliable, label-free, and high-content microarrays are needed. In this work, using large-area plasmonic nanohole arrays, we demonstrate for the first time a large-scale label-free microarray technology with over one million sensors on a single microscope slide. A dual-color filter imaging method is introduced to dramatically increase the accuracy, reliability, and signal-to-noise ratio of the sensors in a highly multiplexed manner. We used our technology to quantitatively measure protein-protein interactions. Our platform, which is highly compatible with the current microarray scanning systems can enable a powerful screening technology and facilitate diagnosis and treatment of diseases. 相似文献
85.
Cell–cell communication is often achieved via granular exocytosis, as in neurons during synaptic transmission or neuroendocrine
cells during blood hormone control. Owing to its critical role in membrane properties and SNARE function, cholesterol is expected
to play an important role in the highly conserved process of exocytosis. In this work, membrane cholesterol concentration
is systematically varied in primary culture mouse chromaffin cells, and the change in secretion behavior of distinct vesicle
pools as well as pool recovery following stimulation is measured using carbon-fiber microelectrode amperometry. Amperometric
traces obtained from activation of the younger readily releasable and slowly releasable pool (RRP/SRP) vesicles at depleted
cholesterol levels showed fewer sustained fusion pore features (6.1 ± 1.1% of spikes compared with 11.2 ± 1.0% for control),
revealing that cholesterol content influences fusion pore formation and stability during exocytosis. Moreover, subsequent
stimulation of RRP/SRP vesicles showed that cellular cholesterol level influences both the quantal recovery and kinetics of
the later release events. Finally, diverging effects of cholesterol on RRP and the older reserve pool vesicle release suggest
two different mechanisms for the release of these two vesicular pools. 相似文献
86.
Panda SK Al-Hajji AA Müller H Koseoglu OR 《Analytical and bioanalytical chemistry》2011,400(5):1231-1239
In the present study, we established a statistical distribution pattern of indigenous sulfur, nitrogen, and oxygen species in Arabian Heavy crude oil and its distilled fractions: naphtha, gas oil, and vacuum gas oil (VGO) using chemical derivatization with methyl iodide and subsequent characterization by positive electrospray Fourier transform mass spectrometry. It was observed that sulfur species for naphtha and gas oil were accumulated at lower double bond equivalent values and at lower carbon numbers compared to VGO, whereas crude oil encompassed a complete range of the sulfur species detected in all distilled fractions. Moreover, the use of alumina column chromatography and ligand exchange chromatography (LEC) on a palladium-bonded silica stationary phase revealed additional structural features of sulfur heterocycles in terms of condensed and non-condensed thiophenes. During LEC separation, in addition to sulfur heterocycles, interesting results were obtained for oxygen-containing compounds. Ortho-substituted alkyl phenols were separated from meta- and para-substituted alkyl phenols on a palladium-bonded silica stationary phase. 相似文献
87.
88.
A new N-TEMPO-3,5-di-tert-butylsalicylaldimine radical (1) has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis, and EPR spectroscopy and temperature dependent magnetic susceptibility. X-ray diffraction revealed that H-atoms of γ-CH in TEMPO and CH3 in salicylaldimine moieties, are located in close contact with the neighboring N–O radical group in crystal 1. The temperature dependence of the magnetic susceptibility (χm) of 1 has been fitted by the Curie–Weiss law with θ = −0.3 K within 10–300 K, suggesting the presence of a weak intermolecular antiferromagnetic interaction between radical centers at T < 10 K. It has been demonstrated that radical 1 possesses crystal structure involving co-existence of antiferromagnetic and ferromagnetic interactions through C–H?O–N contacts of γ-CH and tBu groups hydrogen atoms, in which the former path dominates over the latter. 相似文献
89.
Ataç A Yurdakul Ş Berber S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,81(1):684-689
We report synthesis of six new bis-nicotinamide metal(II) dihalide complexes [M(nia)(2)Cl(2); M = Mn, Co; nia:nicotinamide, M(nia)(2)Br(2); M = Mn, Hg; M(nia)(2)I(2); M = Cd, Cu], and their characterization by combining infrared spectroscopy with density functional theory (DFT) calculations. Infrared spectra indicate that ring-nitrogen is the active donor cite, and the atomic structure of the complexes is determined to be polymeric octahedral or distorted polymeric octahedral. Spin polarized electronic ground state is obtained for Mn, Co, and Cu halide complexes. The colors of the complexes also support the conclusion of octahedral coordination around the metal atoms, in agreement with DFT results. 相似文献
90.
Tokatlı A Ozen E Ucun F Bahçeli S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(3):1201-1211
The optimized molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) (1)H and (13)C NMR shift values of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester have been calculated by using Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31G(d), 6-31G(d,p) and LANL2DZ basis sets. The optimized molecular geometric parameters were presented and compared with the data obtained from X-ray diffraction. In order to fit the calculated harmonic wavenumbers to the experimentally observed ones, scaled quantum mechanics force field (SQM FF) methodology was proceeded. Correlation factors between the experimental and calculated (1)H chemical shift values of the title compound in vacuum and in CHCl(3) solution by using the conductor-like screening continuum solvation model (COSMO) were reported. The calculated results showed that the optimized geometry well reproduces the crystal structure. The theoretical vibrational frequencies and chemical shifts are in very good agreement with the experimental data. In solvent media the energetic behavior of the title compound was also examined by using the B3LYP method with the 6-31G(d) basis set, applying the COSMO model. The obtained results indicated that the total energy of the title compound decreases with increasing polarity of the solvent. Furthermore, molecular electrostatic potential (MEP), natural bond orbital (NBO) and frontier molecular orbitals (FMOs) of the title compound were performed by the B3LYP/LANL2DZ method, and also thermodynamic parameters for the title compound were calculated at all the HF and B3LYP levels. 相似文献