全文获取类型
收费全文 | 226篇 |
免费 | 58篇 |
国内免费 | 10篇 |
专业分类
化学 | 138篇 |
力学 | 5篇 |
综合类 | 12篇 |
数学 | 23篇 |
物理学 | 116篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 4篇 |
2016年 | 3篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 8篇 |
2012年 | 4篇 |
2011年 | 5篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 1篇 |
2007年 | 6篇 |
2006年 | 3篇 |
2004年 | 11篇 |
2003年 | 47篇 |
2002年 | 65篇 |
2001年 | 56篇 |
2000年 | 22篇 |
1999年 | 12篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
排序方式: 共有294条查询结果,搜索用时 78 毫秒
1.
靳玲侠 《原子与分子物理学报》2019,36(6)
采用CCSD(T)/cc-pVTZ//B3LYP/6-311++G(2df,2p)水平上对CH3CHOH + HO2和CH3CH2O + HO2反应体系的单、三重态反应机理进行了详细的理论研究.计算结果表明,CH3CHOH + HO2反应主要发生在单重态势能面上,其中四条通道均为快速自发过程;CH3CH2O + HO2反应在三重态势能面上的通道CH3CH2O + HO2 → 3IM11 → 3TS11 → P11 (CH3CH2OH + 3O2)为动力学和热力学的优势路径. 大气中CH3CHOH比CH3CH2O更容易稳定存在. 相似文献
2.
In this paper, an unstable linear time invariant (LTI) ODE system is stabilized exponentially by the PDE compensato—a wave equation with Kelvin‐Voigt (K‐V) damping. Direct feedback connections between the ODE system and wave equation are established: The velocity of the wave equation enters the ODE through the variable vt(1,t); meanwhile, the output of the ODE is fluxed into the wave equation. It is found that the spectrum of the system operator is composed of two parts: point spectrum and continuous spectrum. The continuous spectrum consists of an isolated point , and there are two branches of asymptotic eigenvalues: the first branch approaches to , and the other branch tends to ?∞. It is shown that there is a sequence of generalized eigenfunctions, which forms a Riesz basis for the Hilbert state space. As a consequence, the spectrum‐determined growth condition and exponential stability of the system are concluded. 相似文献
3.
Tissue distribution and excretion study of neopanaxadiol in rats by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry 下载免费PDF全文
Cong Geng Jian‐yuan Yin Xiu‐hua Yu Jing‐yan Liu Yu‐xia Yang De‐ya Sun Qin Meng Zhong‐lin Wei Ji‐hua Liu 《Biomedical chromatography : BMC》2015,29(3):333-340
Neopanaxadiol (NPD), a major ginsenoside in Panax ginseng C. A. Meyer (Araliaceae), was reported to have neuroprotective effect. In this study, a method of ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry (UPLC/QTOF‐MS) was developed and validated for quantitative analysis of NPD in tissues, urine and feces, using liquid–liquid extraction (LLE) to isolate NPD from different biological samples, and chromatographic separation was performed on an Agilent Zorbax Stable Bond C18 (2.1 × 50 mm, 1.8 µm) column with 0.1% formic acid in water and acetonitrile. All standard calibration curves were linear (all r2 > 0.995) within the test range. After oral administration, NPD was extensively distributed to most of the tissues without long‐term accumulation. The higher levels were observed in stomach and intestine, followed by kidney and liver. Approximately 64.56 ± 20.32% of administered dose in feces and 0.0233 ± 0.0356% in urine were found within 96 h, which indicated that the major elimination route was fecal excretion. This analytical method was applied to the study of NPD distribution and excretion in rats after oral intake for the first time. The results we found here are helpful for us to understand the pharmacological effects of NPD, as well as its toxicity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
4.
考虑核间相互作用,利用修正的库仑玻恩模型(MCB-PT)计算了入射能量为16 MeV 的O7+碰撞氦单电离的全微分截面,并将计算结果与最近的实验数据和三体库仑波(3C)模型及含核间相互作用的连续扭曲波程函初态 (CDW-EIS-PT)模型所得结果进行了比较,发现MCB-PT理论结果在中间动量转移条件下binary峰的位置与实验结果符合得很好,且位于动量转移的方向上。此外,分析了扭曲效应对全微分截面的影响,表明随着动量转移的增加,扭曲效应更加明显。 相似文献
5.
Temperature-depended handedness inversion in chiral mesoporous silica was investigated by diffuse-reflectance circular dichroism spectra. 相似文献
6.
The enhanced biological activities of three Zn (II) complexes based on different 1,2,4‐triazole fungicides 下载免费PDF全文
Guo‐yu Ren Jie Li Xu‐zhan Wei Jin‐hua Zhou Biao Yan Zhao‐qi Guo Ying‐hui Ren Xiao‐hong Sun Hai‐xia Ma 《应用有机金属化学》2018,32(9)
In order to screen effective fungicides, three Zn (II) complexes, [Zn L 1 4 (NO3)2]·2H2O·2EtOH ( 1 ), [Zn L 2 4 (NO3)2] ( 2 ), and [Zn L 3 4 (DMF)2](NO3)2 ( 3 ), ( L 1 = paclobutrazol, L 2 = diniconazole, and L 3 = hexaconazole), were synthesized and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all the complexes show the enhanced antifungal activities than the corresponding ligand and mixtures. And, the interactions between the metal salt and ligands in the three complexes seem to be synergistic. According to the study of the influence of the structures on the activity, complex 2 with C=C linkage and 2,4‐dichlorophenyl moieties enhances the bioactivity significantly, especially against Wheat gibberellic ( II ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity of the Zn (II) complexes. Meanwhile, all complexes are excellent grow‐regulators, especially complex 3 . The resulting data show that the complexes based on triazole fungicides have the potential applications in agriculture. 相似文献
7.
8.
The steric effect of an aryloxido group on the synthesis and molecular structures of ytterbium aryloxides supported by β‐diketiminato ligand L (L = [N(2,6‐Me2C6H3)C(Me)]2CH?) is reported. Reactions of β‐diketiminatoytterbium dichloride, LYbCl2(THF)2, with NaOAr1 in THF (Ar1 = [2,6‐tBu2‐4‐MeC6H2], THF = tetrahydrofuran) at 60°C gave the corresponding ytterbium complexes LYb(OAr1)Cl(THF) ( 1 ) and LYb(OAr1)2 (1), depending on the molar ratio of dichloride to sodium aryloxide, respectively, while the same reactions with NaOAr2 and NaOAr3 (Ar2 = [2,6‐iPr2C6H3], Ar3 = [2,6‐Me2C6H3]) in 1:1 or 1:2 molar ratio in THF afforded only bisaryloxide complexes LYb(OAr2)2(THF) (1) and LYb(OAr3)2(THF) ( 4 ) in good yields, respectively. Complexes 1 , 2 , 3 , 4 were fully characterized, including X‐ray crystal structure analyses. All the complexes are efficient pre‐catalysts for the catalytic addition of amines to carbodiimides giving guanidines. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
9.
Łukasz Wiśniewski Katarína Vaňková Pavel Ačai Milan Polakovič 《Chemical Papers》2014,68(12):1649-1655
Galacto-oligosaccharides are typically produced by an enzymatic reaction when the post-reaction mixture contains considerable amounts of lactose and glucose and a smaller amount of galactose. In order to develop a process of chromatographic removal of saccharide impurities, adsorption equilibria and kinetics of these di- and monosaccharides were investigated for Diaion UBK 530, an industrialgrade strong cation-exchanger in the Na+ form. Frontal chromatographic experiments were carried out in the temperature range of 30–70°C and a broad interval of saccharide concentrations up to 350 g L?1. Breakthrough curves were described using the equilibrium-dispersive model with the linear adsorption isotherm. Both the distribution and the axial dispersion coefficient values depended on the saccharide molecule type and size. No significant effect of temperature or concentration on the distribution coefficient was observed. The apparent dispersion coefficients of all saccharides exhibited some decrease with the temperature, which was caused by the decrease of the intraparticle mass transfer resistance. An analysis showed that both the intraparticle mass transfer and the axial dispersion had a significant influence on the front dispersion. 相似文献
10.
Yan‐mei Shi Lin Mei Jun‐xia Zhang Kai Hu Xi Zhang Zhu‐zhu Li Ming‐san Miao Xiu‐min Li 《Electroanalysis》2020,32(7):1507-1515
A new electrochemical sensor material has been fabricated via the non‐covalent functionalization of reduced graphene oxide (rGO) and soluble tetramino zincphthalocyanines (ZnPc‐NH2). Immobilization of uricase onto the synthesized nanohybrids can evidently improve the electrocatalytic activity and selectivity. The obtained composite membrane possesses a great enhancement of electron transfer rate and excellent synergistic electrocatalytic effect toward uric acid (UA) oxidation under the working potential at 0.620 V vs. Ag/AgCl with a scan rate of 0.125 V/s. The effects of the experimental parameters on the electrochemical oxidation responses of UA were investigated and optimized in detail. Under the optimized conditions, the peak currents were proportional to the UA concentration in a range from 0.5 to 100 μmol/L with detection limit of 0.15 μmol/L. Moreover, the developed sensor was applied for UA determination in human urine samples with high accuracy and satisfactory recovery, which is envisioned to have promising applications in monitoring UA in clinical research. 相似文献