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31.
This work duly investigates the recovery of Pd (II) chlorocomplexes from industrial wastewater. Chemical structures and thermodynamic stabilities of the complex formed are evaluated via density functional theory (DFT). By applying synergistic solutions of thiourea mixed with hydrochloric acid (HCl), the stripping reaction of Pd (II) in the loaded Aliquat 336 occurs and Pd (II) chlorocomplexes coordinated thiourea ligands are formed, thus 80.19% of Pd (II) chlorocomplexes can be recovered. The aim of this study is to gain a better understanding of the stripping mechanisms and the structure of the complexes formed via the synergistic system. Such an understanding is still limited since little research has been conducted in this field. Owing to their molecular geometry, ligand coordination and donor groups play a vital role in the reactivity of palladium (II) complex. Quantum models have been developed to evaluate the chemical structure and thermodynamics stability of ((NH2)2CS·PdCl2) namely: (i) DFT with B3LYP/6-31g(d,p) and MP2/6-31g(d,p) basis set, (ii) MP2 with cc-pVTZ basis set and (iii) CCSD(T)/cc-pVTZ. Results demonstrate that the highest geometric stability exhibited is the structure of Pd-S bonding with 180° Cl-Pd-Cl. The distance (r) and angle (a) of the selected geometrical parameters for (NH2)2CS·PdCl2 complex are reported. Additionally, FTIR and UV–vis spectroscopies have been conducted to analyze the sampling solutions. Further, the calculated vibrational frequencies and experimental spectroscopic results show good agreement with the optimized geometry. 相似文献
32.
Dr. Manuela Leticia Kim Dr. Deicy Barrera Dr. Mutsumi Kimura Prof. Dr. Juan P. Hinestroza Prof. Dr. Karim Sapag Dr. Eugenio Hernán Otal 《化学:亚洲杂志》2021,16(9):1086-1091
We report on a detailed textural analysis of mechanochemically synthesized MOF-199 including N2 adsorption-desorption and CO2 adsorption isotherms data at 77 K and 273 K (up to atmospheric pressure), respectively, and CH4 adsorption data at 298 K (up to 35 bar). We used the isotherm adsorption data to determine the micropore volume of the MOF-199 structures, to establish their methane uptake capacity and to understand how these properties depended on the Ethanol/BTC ratio used during the synthesis. The maximum methane uptake capacity for our specimens was recorded at 130 v/v at 35 bars. These results open an avenue for a better understanding of alternative manufacturing processes of MOF structures for gas storage applications. 相似文献
33.
Dipl.‐Chem. Günther Thiele Thomas Krüger Prof. Dr. Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2014,53(18):4699-4703
The first inorganic lead(IV) compound without oxygen, nitrogen or halogen ligands attached to the lead atom was obtained as the potassium salt of the tetraselenidoplumbate(IV) anion [PbIVSe4]4?. It is stable under inert conditions which may enable the transfer of the chemistry of chalcogenidogermanate(IV) or chalcogenidostannate(IV) materials, to the lead homologues. 相似文献
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在没有溶剂介质参与的高分子聚合反应中,高分子凝聚态的变化与化学反应之间的作用关系变得更加直接。以熔融聚合、反应挤出、固相聚合为代表的高分子树脂无溶剂生产技术是集高分子树脂合成、材料加工制备及工程一体化的新兴科学与技术,是当代材料科学领域发展的前沿领域,代表着高分子树脂生产技术发展的必然趋势。本文将上述这三种典型的树脂工业合成技术及相应机理进行了简要的介绍,并分别以聚对苯二甲酸乙二醇酯(PET)和聚乳酸(PLA)的实际生产研究情况为例,展示三种生产技术之间的相互联系,揭示这三种无溶剂型高分子制备技术过程中出现的高分子凝聚态变化与化学反应之间的基本问题,为广大科研工作提供一些有价值的参考。 相似文献
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利用双水平直接动力学方法对反应CH3SH+H的微观机理和动力学性质进行了理论研究.对于此反应的三个反应通道,即—SH和—CH3基团上的两个氢提取通道及一个取代通道,在MP2/6-311+G(d,p)水平上优化得到了各稳定点的结构及振动频率,并在G3(MP2)水平上进行了单点能量计算以获得更精确的能量信息;在此基础上运用结合小曲率隧道效应校正的变分过渡态理论(CVT/SCT)计算了各反应通道在220-1000 K温度区间的速率常数.计算结果表明提取—SH基团上H的反应通道R1在整个反应温度区间都是主要通道,而随着温度的升高,低温下的次要反应通道——取代通道R3变得越来越重要,并且在高温下将成为一个竞争的反应通道;提取—CH3基团上H的反应通道(R2)由于具有较高的反应能垒,因而,其对总反应速率常数的贡献可以忽略.计算得到的总反应速率常数与已有的实验值符合得很好,进而我们预测了该反应在220-1000 K温度范围内速率常数的表达式为:k=5.00×10-18T2.39exp(-119.81/T),为将来的实验研究提供参考. 相似文献
38.
对单电子溴键复合物H3C…Br—Y(Y=H,CCH,CN,NC,C2H3)的结构与性质进行了理论研究.在B3LYP/6-311++G**水平上计算了稳定构型并做了频率分析.BSSE矫正的相互作用能(EBSSE)和NBO及AIM分析输入的波函数在MP2/6-311++G**水平下完成.复合物H3C…Br—Y中,CH3(供电子体)自由基均提供一未成对电子与Br—Y中Br(受电子体)形成了单电子溴键,此单电子溴键也具有三电子键的特征.单电子溴键的形成导致甲基H的背向Y弯曲和Br—Y键的拉长及红移单电子溴键复合物的产生.考察了电子受体中不同取代基,C(spn)-Br杂化及溶剂的存在对复合物作用的影响,将单电子氢键,单电子卤键和单电子锂键的作用强度做了对比,进一步对Popelier提出的氢键体系中的前三个重要拓扑指标在单电子溴键体系中的重现性进行了探讨. 相似文献
39.
Fast and sensitive high performance liquid chromatography analysis of cosmetic creams for hydroquinone, phenol and six preservatives 总被引:1,自引:0,他引:1
A fast and sensitive HPLC method for analysis of cosmetic creams for hydroquinone, phenol and six preservatives has been developed. The influence of sample preparation conditions and the composition of the mobile phase and elution mode were investigated to optimize the separation of the eight studied components. Final conditions were 60% methanol and 40% water (v/v) extraction of the cosmetic creams. A C18 column (100 mm × 2.1 mm) was used as the separation column and the mobile phase consisted of methanol and 0.05 mol/L ammonium formate in water (pH=3.0) with gradient elution. The results showed that complete separation of the eight studied components was achieved within 10 min, the linear ranges were 1.0-200 μg/mL for phenol, 0.1-150 μg/mL for sorbic acid, 2.0-200 μg/mL for benzoic acid, 0.5-200 μg/mL for hydroquinone, methyl paraben, ethyl paraben and propyl paraben, butyl paraben, and good linear correlation coefficient (≥0.9997) were obtained, the detection limit was in the range of 0.05-1.0 μg/mL, the average recovery was between 86.5% and 116.3%, and the relative standard deviation (RSD) was less than 5.0% (n=6). The method is easy, fast and sensitive, it can be employed to analyze component residues in cosmetic creams especially in a quality control setting. 相似文献
40.
选取氮甲基乙酰胺(N-Methylacetamide,NMA)和DNA碱基为研究对象,应用ABEEMσπ/MM方法研究了NMA与碱基之间形成的二聚体的几何构型、电荷分布及结合能等性质,并进行了相应的从头算(abinitio)MP2水平研究,在B3LYP/6-311 ++G(d,p)水平下对结构进行了优化.将2种方法的研... 相似文献