排序方式: 共有182条查询结果,搜索用时 31 毫秒
171.
Faraji AH Cui JJ Guy Y Li L Gavigan CA Strein TG Weber SG 《Langmuir : the ACS journal of surfaces and colloids》2011,27(22):13635-13642
Electroosmosis is the bulk fluid flow initiated by application of an electric field to an electrolyte solution in contact with immobile objects with a nonzero ζ-potential such as the surface of a porous medium. Electroosmosis may be used to assist analytical separations. Several gel-based systems with varying electroosmotic mobilities have been made in this context. A method was recently developed to determine the ζ-potential of organotypic hippocampal slice cultures (OHSC) as a representative model for normal brain tissue. The ζ-potential of the tissue is significant. However, determining the role of the ζ-potential in solute transport in tissue in an electric field is difficult because the tissue's ζ-potential cannot be altered. We hypothesized that mass transport properties, namely the ζ-potential and tortuosity, could be modulated by controlling the composition of a set of hydrogels. Thus, poly(acrylamide-co-acrylic acid) gels were prepared with three compositions (by monomer weight percent): acrylamide/acrylic acid 100/0, 90/10, and 75/25. The ζ-potentials of these gels at pH 7.4 are distinctly different, and in fact vary approximately linearly with the weight percent of acrylic acid. We discovered that the 25% acrylic acid gel is a respectable model for brain tissue, as its ζ-potential is comparable to the OHSC. This series of gels permits the experimental determination of the importance of electrokinetic properties in a particular experiment or protocol. Additionally, tortuosities were measured electrokinetically and by evaluating diffusion coefficients. Hydrogels with well-defined ζ-potential and tortuosity may find utility in biomaterials and analytical separations, and as a surrogate model for OHSC and living biological tissues. 相似文献
172.
Dr. June S. Lum Dr. Laleh Tahsini Prof. Dr. James A. Golen Dr. Curtis Moore Prof. Dr. Arnold L. Rheingold Prof. Dr. Linda H. Doerrer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6374-6384
Seven E[Cu(OR)2] copper(I) complexes (E=K+, {K(18C6)}+ (18C6=[18]crown‐6), or Ph4P+; R=C4F9, CPhMeF2, and CMeMeF2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper‐concentration‐dependent manner such that 2:1 and 3:1 Cu/O2 adducts are observed manometrically at ?78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}+ or Ph4P+ derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K+ ions induce aggregation of multiple [Cu(OR)2]? units through K???F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K+ ions. Intramolecular hydroxylation of ligand aryl and alkyl C? H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a CuII carbonate has been isolated and characterized. 相似文献
173.
Quantum Chemical Study of the Enzymatic Repair of T(6‐4)C/C(6‐4)T UV‐Photolesions by DNA Photolyases
Several strategies have evolved to repair one of the abundant UV radiation‐induced damages caused to DNA, namely the mutagenic pyrimidine (6‐4) pyrimidone photolesions. DNA (6‐4)‐photolyases are enzymes repairing these lesions by a photoinitiated electron transfer. An important aspect of a possible repair mechanism is its generality and transferability to different (6‐4) lesions. Therefore, previously suggested mechanisms for the repair of the T(6‐4)T lesion are here transferred to the T(6‐4)C and C(6‐4)T lesions and investigated theoretically using quantum chemical methods. Despite the different functional groups of the pyrimidine bases involved, a general valid molecular mechanism was identified, in which the initial step is an electron transfer coupled to a proton transfer from the protonated HIS365 to the N3′ nitrogen of the 3′ pyrimidine, followed by an intramolecular OH/NH2 transfer in one concerted step, which does not require an oxetane/azetidine or isolated water/ammonia intermediate. 相似文献
174.
Hossein Reza Darabi Khosrow Jadidi Ali Reza Mohebbi Laleh Faraji Kioumars Aghapoor Shant Shahbazian 《Supramolecular chemistry》2013,25(3):327-333
The bromination/dehydrobromination of stilbenophanes as a practical, simple and efficient strategy is applied to the synthesis of tolanophanes 1a (n = 2) and 1b (n = 4). The method is significantly superior to the reported methods. A careful conformational study on a novel tolanophane 1b showed that the relative stability of its conformers is directly linked to both twist angle between the two arene rings and the orientation of the alkoxy groups. The strong interaction between 1b and CDCl3 at ? 60°C is an unusual feature that is attributed to high restriction in its molecular motion. 相似文献
175.
Silver nanoparticles in chitosan medium were prepared by the chemical reduction method. Silver nitrate and hydrazine were used as the precursor and reducing agent in the present of chitosan as a natural host polymer. The samples are characterized by UV–visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The measurements of nonlinear optical properties were defined by Z-scan technique using green CW laser beam operated at 532 nm wavelengths. Thermal effect has a dominant role in the overall material nonlinearity with CW laser. It is shown that the synthesized samples have a negative nonlinear refractive index. 相似文献
176.
A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions. 相似文献
177.
Seyed Majid Hashemianzadeh Shirin Faraji Amir Hossein Amin Sepideh Ketabi 《Monatshefte für Chemie / Chemical Monthly》2008,139(2):89-100
Summary. Interactions of the DNA bases adenine (A), guanine (G), cytosine (C), and thymine (T) with various metal ions (M) of groups IA and IIA of the periodic table of the elements were studied at the HF, MP2, and DFT levels of theory. The structures and thermodynamic stabilities of these species were studied at the gas phase. The calculations
uphold that there exist two active sites in G and one in A, C, and T. The calculations also show that the O2 atom in T is a more active site for metal ion bindings than that in C. The stability energies for G … M complexes are larger than those for A … M complexes and the stability energies for T … M complexes are larger than those for C … M complexes. As z/r ratio for the metal ion increases, the interaction energy for the complex increases systematically. Thermodynamic quantities
such as ΔH, ΔG, ΔS, and ln K were determined for each complexation reaction, [Base+M
n+ →(Base … M)
n+]. A, G, and C complexation reactions except for C … Rb+ are exothermic. The situation is quite different for T complexation reactions and all except for T … Be2+ and T … Mg2+ are endothermic. 相似文献
178.
Counterfeiting is an ever-growing global problem challenging companies, governments, and customers. In recent decades, as a potential remedy, anticounterfeiting technology and information security have gained a great deal of attention from academia and industry. In this work and for the first time, Rhodamine B (RhB), an efficient and enticing fluorescent material, was modified and used as a reactive stimuli-responsive component in the formulation of an eco-friendly ink. Additionally, a UV-curable polyurethane dispersion (UCPUD) with zero volatile organic compound was synthesized and employed as the matrix for the fluorescent ink. The modified RhB and UCPUD were thoroughly characterized using Fourier-transform infrared and proton nuclear magnetic resonance analyses. Exploiting the fluorescent monomer in the ink formulations could enhance the absorption intensity (λmax = 552 nm) of the prepared ink up to 7 with respect to its solution (λmax = 519 nm). The printed pattern was immediately illuminated with brilliant red-pink fluorescence emission upon UV irradiation. It has been shown that the prepared fluorescent ink has potential applications in the encryption, security marking, and optical authentication of confidential cellulose substrates. 相似文献
179.
Tahsini L Kotani H Lee YM Cho J Nam W Karlin KD Fukuzumi S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(4):1084-1093
The four-electron reduction of dioxygen by decamethylferrocene (Fc*) to water is efficiently catalyzed by a binuclear copper(II) complex (1) and a mononuclear copper(II) complex (2) in the presence of trifluoroacetic acid in acetone at 298 K. Fast electron transfer from Fc* to 1 and 2 affords the corresponding Cu(I) complexes, which react at low temperature (193 K) with dioxygen to afford the η(2):η(2)-peroxo dicopper(II) (3) and bis-μ-oxo dicopper(III) (4) intermediates, respectively. The rate constants for electron transfer from Fc* and octamethylferrocene (Me(8)Fc) to 1 as well as electron transfer from Fc* and Me(8)Fc to 3 were determined at various temperatures, leading to activation enthalpies and entropies. The activation entropies of electron transfer from Fc* and Me(8)Fc to 1 were determined to be close to zero, as expected for outer-sphere electron-transfer reactions without formation of any intermediates. For electron transfer from Fc* and Me(8)Fc to 3, the activation entropies were also found to be close to zero. Such agreement indicates that the η(2):η(2)-peroxo complex (3) is directly reduced by Fc* rather than via the conversion to the corresponding bis-μ-oxo complex, followed by the electron-transfer reduction by Fc* leading to the four-electron reduction of dioxygen to water. The bis-μ-oxo species (4) is reduced by Fc* with a much faster rate than the η(2):η(2)-peroxo complex (3), but this also leads to the four-electron reduction of dioxygen to water. 相似文献
180.
In this work, gas diffusion electrodes were fabricated from Nafion and polyaniline (PANI) nanofibers. The goal of this work was to find the optimal combination of Nafion and polyaniline in gas diffusion electrodes. The electrodes were evaluated for oxygen reduction reaction effectiveness, and their electrochemical properties were investigated by using electrochemical techniques, and PEM single cell. The results revealed that electrodes containing both Nafion and polyaniline worked more efficiently than electrodes containing either Nafion or polyaniline only. The optimum combination is noted as 0.6 mg/cm2 PANI and 0.4 mg/cm2 Nafion. 相似文献