全文获取类型
收费全文 | 183篇 |
免费 | 23篇 |
国内免费 | 1篇 |
专业分类
化学 | 149篇 |
晶体学 | 2篇 |
力学 | 12篇 |
综合类 | 1篇 |
数学 | 7篇 |
物理学 | 36篇 |
出版年
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 11篇 |
2019年 | 9篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 17篇 |
2015年 | 6篇 |
2014年 | 13篇 |
2013年 | 12篇 |
2012年 | 12篇 |
2011年 | 14篇 |
2010年 | 3篇 |
2009年 | 9篇 |
2008年 | 11篇 |
2007年 | 8篇 |
2006年 | 4篇 |
2005年 | 3篇 |
2004年 | 3篇 |
2003年 | 3篇 |
2002年 | 3篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1991年 | 1篇 |
1988年 | 1篇 |
排序方式: 共有207条查询结果,搜索用时 31 毫秒
1.
A theoretical model of Dewangan, in which the total scattering wave function is approximated by a distorted wave containing
two Coulomb wave functions, is discussed and its relation with the Brauner-Briggs-Klar model for ionization is examined. An
important feature of the theory is that it includes a second Born amplitude naturally and in addition, contains, albeit approximately,
both real and imaginary parts of all higher order Born terms. The theory is applied to study the 1s→2s excitation of hydrogen by electrons in the energy range 54.4 to 400eV. The differential and integral cross sections predicted
by the theory are compared with the results of other theories and experimental data at 54.4eV and a good agreement is found. 相似文献
2.
Several cyanine dyes were found to protect K562 leukemia cells against toxicity mediated by cis-di(4-sulfonatophenyl)diphenylporphine (TPPS2) and light. Most cyanine dyes derived from dimethylindole were better photoprotectors than cyanine dyes with other structures. This correlated with the fact that cyanine dyes derived from dimethylindole were predominately monomeric at millimolar concentrations within K562 cells, while other cyanine dyes formed aggregates. For cyanine dyes that are derived from dimethylindole and have absorption band wavelengths greater than 700 nm, fluorescence-energy transfer from TPPS2 to the cyanine dye was the most important mechanism for photoprotection. There was no spectroscopic evidence for complex formation between the cyanine dyes and TPPS2. The dimethylindole derivative, 1,1',3,3,3',3'-hexamethylindodicarbocyanine, was an excellent photoprotector, but a poor quencher of TPPS2 fluorescence and a relatively poor singlet-oxygen quencher. This cyanine dye may act by quenching excited triplet TPPS2. Singlet-oxygen quenching may contribute to the photoprotection provided by cyanine dyes not derived from dimethylindole. Differences in the subcellular distribution of the various cyanine dyes studied may have contributed to the different apparent mechanisms of photoprotection. 相似文献
3.
催化褪色光度法测定痕量钴的研究 总被引:15,自引:2,他引:15
研究了在PH10.5的Na2B4O7-NaOH介质中,痕量钴(Ⅱ)对过氧化氢氧化桑色素初色反应的催化作用,建立了催化动力学光度法测定痕量钴的新方法。方法的线性范围为0-1.2μ/mL检出限为4.4*10^-18g/L。用于水和维生素B12中钴的测定,结果满意。 相似文献
4.
A renewable three-dimensional chemically modified carbon ceramic electrode containing Ru [(tpy)(bpy)Cl] PF6 was constructed by sol-gel technique. It exhibits an excellent electro-catalytic activity for oxidation of l-cysteine and glutathione at pH range 2-8. Cyclic voltammetry was employed to characterize the electrochemical behavior of the chemically modified electrode. The electrocatalytic behavior is further exploited as a sensitive detection scheme for l-cysteine and glutathione by hydrodynamic amperometry. Optimum pH value for detection is 2 for both l-cysteine and glutathione. The catalytic rate constants for l-cysteine and glutathione were determined, which were about 2.1×103 and 2.5×103 M−1 s−1, respectively. Under the optimized condition the calibration curves are linear in the concentration range 5-685 and 5-700 μM for l-cysteine and glutathione determination, respectively. The detection limit (S/N=3) and sensitivity is 1 μM, 5 nA/μM for l-cysteine and 1 μM, 7.8 nA/μM for glutathione. The relative standard deviation (RSD) for the amperogram's currents with five injections of l-cysteine or glutathione at concentration range of linear calibration is <1.5%. The advantages of this amperometric detector are: high sensitivity, good catalytic effect, short response time (t<3 s), remarkable long-term stability, simplicity of preparation and reproducibility of surface fouling (RSD for six successive polishing is 3.31%). This sensor can be used as a chromatographic detector for analysis of l-cysteine and glutathione. 相似文献
5.
A highly sensitive and fast responding sensor for the determination of thiosulfate, sulfite, sulfide and dithionite is described. It consists of a chemically modified carbon ceramic composite electrode (CCE) containing [Ru(bpy)(tpy)Cl]PF6 complex that was constructed by the sol-gel technique. A reversible redox couple of Ru(II)/Ru(III) was observed as a solute in acetonitrile solution and as a component of carbon based conducting composite electrode. Electrochemical behavior and stability of modified CCE were investigated by cyclic voltametry, the apparent electron transfer rate constant (kappa(S)) and transfer coefficient (a) were determined by cyclic voltametry which were about 28 s(-1) and 0.43 respectively. Electrocatalytic oxidation of S(2-), SO3(2-), S2O4(2-) and S2O3(2-) were effective at the modified electrode at significantly reduced overpotentials and in the pH range 1-11. Optimum pH values for amperometric detection of thiosulfate, dithionite, sulfide and sulfite are 7, 9, 2 and 2. Under the optimized conditions the calibration curves are linear in the concentration ranges 1-500, 3-80, 2-90 and 1-100 microM for S2O3(2-), SO3(2-), S2- and S2O4(2-) determination. The detection limit (signal to noise is 3) and sensitivity are 0.5 and 12, 2.8 and 6, 1.6 and 8, and 0.65 microM and 80 nA microM(-1) for thiosulfate, sulfite, sulfide and dithionite detection. The modified carbon ceramic electrode doped with Ru-complex shows good reproducibility, a short response time (t < 2 s), remarkable long term stability (> 6 month) and especially good surface renewability by simple mechanical polishing (RSD for eight successive polishing is 2%). The advantages of this sulfur compound amperometric detector based on ruthenium doped CCE are high sensitivity, inherent stability at a broader pH range, excellent catalytic activity, less expense and simplicity of preparation in comparison with recently published papers. This sensor can be used as a chromatographic detector for analysis of sulfur derivatives. 相似文献
6.
Abstract— Several ozone-biomolecule reactions have previously been shown to generate singlet oxygen in high yields. For some of these orone-biomolecule reactions, we now show that the apparent singlet-oxygen yields determined from measurements of 1270 nm chemiluminescence were artifactually elevated by production of gas-phase singlet oxygen. The gas-phase singlet oxygen results from the reaction of gas-phase ozone with biomolecules near the surface of the solution. Through the use of a flow system that excludes air from the reaction chamber, accurate singlet-oxygen yields can be obtained. The revised singlet-oxygen yields (mol 1 O2 per mol O3 ) for the reactions of ozone with cysteine, reduced glutathione, NADH, NADPH, human albumin, methionine, uric acid and oxidized glutathione are 0.23 ± 0.02, 0.26 ± 0.02, 0.48 ± 0.04, 0.41 ± 0.01, 0.53 ± 0.06, 1.11 ± 0.04, 0.73 ± 0.05 and 0.75 ± 0.01, respectively. These revised singlet-oxygen yields are still substantial. 相似文献
7.
Silver,iron, and nickel immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 MNPs catalyzed one‐pot five‐component reactions for the synthesis of tetrahydropyridines by tandem condensation of amines,aldehydes, and methyl acetoacetate
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
In this study, Ag, Ni2+, and Fe2+ immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 nanoparticles (γ‐Fe2O3@HAp‐Ag, γ‐Fe2O3@HAp‐Ni2+, and γ‐Fe2O3@HAp‐Fe2+) as a new and reusable Lewis acid magnetic nanocatalyst was successfully synthesized and reported for an atom economic, extremely facile, and environmentally benign procedure for the synthesis of highly functionalized tetrahydropyridines derivatives 4a‐t is described by one‐pot five‐component reaction of 2 equiv of aldehydes 1 , 2 equiv of amines 2 , and 1 equiv of methyl acetoacetate 3 in EtOH at room temperature in good to high yields and short reaction time. The presented methodology offers several advantages such as easy work‐up procedure, reusability of the magnetic nanocatalyst, operational simplicity, green synthesis avoiding toxic reagents and solvent, mild reaction conditions, and no tedious column chromatographic separation. 相似文献
8.
9.
Mengyuan Ge Guangwen Li Zibo Ni Ning Liu Yushan Liu Yuzhou Liu 《Journal of polymer science. Part A, Polymer chemistry》2020,58(21):3009-3017
Utilizing collective forces between reactant and multiple catalyst molecules has been unprecedented due to the difficulty in realizing high order catalysis. Inspired by the power of collective forces in enzymes and organic catalysts, herein we report a rare example of high order catalysis for ring opening reaction (ROR) of strained rings by methanol. ROR is an important way to produce various polysiloxanes, but usually suffers from serious side reactions especially at high conversion, and currently there is a need to design new reaction pathway to achieve low molecular dispersity. In our study, the judiciously designed strained spiral cyclosiloxanes enable a high order catalysis by methanol, and this new methodology leads to a cyclic polysiloxane with high molecular weight and low dispersity even at full conversion of reactants. Kinetic study indicates an extremely unusual high-order reaction involving multiple methanol molecules per reaction, also confirmed by quantum calculation which reveals the presence of zwitterionic ions stabilized by collecting force of hydrogen bonds by methanol molecules. The inherent driving force for this unusual phenomenon is dominated by enthalpy stabilization of the reactive intermediates through hydrogen bonding. The selective formation of Si O Si bonds, instead of silanol products, reflects the power of scientific design. 相似文献
10.
Dr. Lihui Chen Haifeng Hu Yuzhou Chen Yuan Li Prof. Jing Gao Prof. Guohua Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):1057-1065
For plasmonic copper-deficient Cu2−xS nanoparticles (NPs), accurate control of the crystal phase and morphology is highly desirable as both of which are known to determine the localized surface plasmon resonance (LSPR) wavelength and amplitude. Here, how the sulfur precursor reactivity in the synthesis of Cu2−xS NPs affects the resulting crystal phase and morphology is examined. Djurleite Cu1.94S, roxbyite Cu1.8S, digenite Cu1.8S as well as covellite CuS nanodisks were synthesized by using 1-dodecanethiol, N,N-dibutylthiourea, and crystal sulfur 1-octadecene/oleylamine solutions and their crystal phase dependent LSPR properties were exhaustively discussed. In addition, crystal phase interconversion between covellite CuS and djurleite/roxbyite Cu2−xS was realized in the presence of the above sulfur precursors. On the other hand, djurleite Cu1.94S nanorods rather than nanodisks were prepared by replacing 1-dodecanethiol with more reactive tert-dodecanethiol. The structural and morphological Cu2−xS NPs here holds great promise in the application of photothermal therapy, photocatalysis, surface-enhanced Raman scattering (SERS), and many others. 相似文献