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91.
Sung KE Vanapalli SA Mukhija D McKay HA Millunchick JM Burns MA Solomon MJ 《Journal of the American Chemical Society》2008,130(4):1335-1340
We report a technique for continuous production of microparticles of variable size with new forms of anisotropy including alternating bond angles, configurable patchiness, and uniform roughness. The sequence and shape of the anisotropic particles are configured by exploiting a combination of confinement effects and microfluidics to pack precursor colloids with different properties into a narrow, terminal channel. The width and length of the channel relative to the particle size fully specify the configuration of the anisotropic particle that will be produced. The precursor spheres packed in the production zone are then permanently bonded into particles by thermal fusing. The flow in the production zone is reversed to release the particles for collection and use. Particles produced have linear chain structure with precisely configured, repeatable bond angles. With software programmable microfluidics, sequence and shape anisotropy are combined to yield synthesized homogeneous (type "A"), surfactantlike (type "A-B") or triblock (type "A-B-A") internal sequences in a single device. By controlling the dimensions of the microfluidic production zone, triangular prisms and particles with controlled roughness and patchiness are produced. The fabrication method is performed with precursors spheres with diameter as small as 3.0 microm. 相似文献
92.
Carcinogenic Chromium(VI) Compounds Formed by Intracellular Oxidation of Chromium(III) Dietary Supplements by Adipocytes
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Dr. Lindsay E. Wu Dr. Aviva Levina Prof. Hugh H. Harris Dr. Zhonghou Cai Dr. Barry Lai Dr. Stefan Vogt Prof. David E. James Prof. Peter A. Lay 《Angewandte Chemie (International ed. in English)》2016,55(5):1742-1745
Chromium(III) nutritional supplements are widely consumed for their purported antidiabetic activities. X‐ray fluorescence microscopy (XFM) and X‐ray absorption near‐edge structure (XANES) studies have now shown that non‐toxic doses of [Cr3O(OCOEt)6(OH2)3]+ ( A ), a prospective antidiabetic drug that undergoes similar H2O2 induced oxidation reactions in the blood as other Cr supplements, was also oxidized to carcinogenic CrVI and CrV in living cells. Single adipocytes treated with A had approximately 1 μm large Cr hotspots containing CrIII, CrV, and CrVI (primarily CrVI thiolates) species. These results strongly support the hypothesis that the antidiabetic activity of CrIII and the carcinogenicity of CrVI compounds arise from similar mechanisms involving highly reactive CrVI and CrV intermediates, and highlight concerns over the safety of CrIII nutritional supplements. 相似文献
93.
W. Hugh Woodin 《Archive for Mathematical Logic》2016,55(1-2):319-351
94.
Thominet O Baker JR Britton H Etheridge ZC Soscia MG Caddick S 《Organic & biomolecular chemistry》2007,5(22):3703-3712
We present herein our recent efforts towards the synthesis of epoxydiynes which represent an unusual structural feature of the neocarzinostatin chromophore. A number of different routes to these epoxydiynes have been explored with varying success. Ultimately a concise and convergent approach was developed, which involved the addition of an allenyl zinc bromide to propargylic ketones/aldehydes followed by epoxide formation. This new protocol enabled us to synthesise a fully elaborated epoxydiyne which will find application for our studies towards the total synthesis of the NCS chromophore. 相似文献
95.
García-Zubiri IX Burrows HD Seixas de Melo JS Pina J Monteserín M Tapia MJ 《Photochemistry and photobiology》2007,83(6):1455-1464
The complexation of beta-carboline-3-carboxylic acid N-methylamide (betaCMAM) with the sodium salts of the nucleotides polyadenylic (Poly A), polycytidylic (Poly C), polyguanylic (Poly G), polythymidylic (Poly T) and polyuridylic (Poly U) acids, and with double stranded (dsDNA) and single stranded deoxyribonucleic acids (ssDNA) was studied at pH 4, 6 and 9. Predominant 1:1 complex formation is indicated from Job plots. Association constants were determined using the Benesi-Hildebrand equation. BetaCMAM-sensitized singlet oxygen quantum yields were determined at pH 4, 6 and 9, and the effects on this of adding oligonucleotides, dsDNA and ssDNA were studied at the three pH values. With dsDNA, the effect on betaCMAM triplet state formation was also determined through triplet-triplet transient absorption spectra. To evaluate possible oxidative damage of DNA following singlet oxygen betaCMAM photosensitization, we used thiobarbituric acid-reactivity assays and electrophoretic separation of DNA assays. The results showed no oxidative damage at the level of DNA degradation or strand break. 相似文献
96.
Pina J de Melo JS Burrows HD Batista RM Costa SP Raposo MM 《The journal of physical chemistry. A》2007,111(35):8574-8578
A comprehensive study has been made in solution at room temperature (293 K), low temperature (77 K), and in thin films (Zeonex matrixes) of the spectral and photophysical properties of six arylthienyl- and bithienyl-benzothiazole derivatives functionalized with different donor groups. Similar experiments have been carried out with two related precursors (containing the arylthienyl and aryl-bithienyl conjugated systems), and results are compared. Singlet-singlet and triplet-triplet absorption spectra, emission spectra together with lifetimes and quantum yields have been obtained, and from these data the rates for all the radiative and nonradiative processes determined, providing information on the dominant decay processes. The arylthienyl-benzothiazole derivatives show high fluorescence quantum yields (phi(F)) with negligible internal conversion (phi(IC)), whereas the bithienyl-benzothiazoles display lower but still significant phi(F) values, but now radiationless processes (phi(IC) and phi(ISC)) are competitive. A comparison with the analogous oligothiophenes is made. Singlet oxygen yields were also determined and the triplet energy transfer to (3)O2 to produce (1)O2 was found to be highly efficient with values of S(Delta)(= phi(Delta)/phi(T)) varying from 0.4 to 1. 相似文献
97.
Urade VN Bollmann L Kowalski JD Tate MP Hillhouse HW 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4268-4278
The double-gyroid phase of nanoporous silica films has been shown to possess facile mass-transport properties and may be used as a mold to fabricate a variety of highly ordered inverse double-gyroid metal and semiconductor films. This phase exists only over a very small region of the binary phase diagram for most surfactants, and it has been very difficult to synthesize metal oxide films with this structure by evaporation-induced self-assembly (EISA). Here, we show the interplay of the key parameters needed to synthesize these structures reproducibly and show that the interfacial curvature may be systematically controlled. Grazing angle of incidence small-angle X-ray scattering (GISAXS) is used to determine the structure and orientation of nanostructured silica films formed by EISA from dilute silica/(poly(ethylene oxide)-b-poly(propylene oxide)-b-alkyl) surfactant solutions. Four different highly ordered film structures are observed by changing only the concentration of the surfactant, the relative humidity during dip-coating, and the aging time of the solution prior to coating. The highly ordered films progress from rhombohedral (Rm) to 2D rectangular (c2m) to double-gyroid (distorted Iad) to lamellar systematically as interfacial curvature decreases. Under all experimental conditions investigated, increasing the aging time of the coating solution was found to decrease the interfacial curvature. In particular, this parameter was critical to being able to synthesize highly ordered, pure-phase double-gyroid films. The key role of the aging time is shown via processing diagrams that map out the interplay between the aging time, composition, and relative humidity. 29Si nuclear magnetic resonance (NMR) spectroscopy and solution-phase small-angle X-ray scattering (SAXS) of the aged coating solutions presented in part I of this series are then used to interpret the effects of aging prior to dip-coating. Specifically, it was found that a predictive model based on volume fractions and the silica cluster stoichiometry obtained from 29Si NMR qualitatively explains the trends observed with composition and aging. However, apart from the effects of relative humidity, a quantitative comparison of the predicted phase with the experimental processing diagram suggests that less-condensed silica clusters are more effective at swelling the EO blocks at early aging times. This enhanced swelling decreases with aging time and results in lower-curvature nanostructures such as the double-gyroid. The decrease in swelling is attributed to the decreased thermodynamic driving force for the more-condensed silica clusters to mix with the EO block of the surfactant. 相似文献
98.
An opinion function on a graph G = (V, E) is a function f: V → {−1, +1}. The vote of a vertex v is the sum of these function values over the closed neighborhood of v. A strict majority function on a graph G is an opinion function for which more than half of the vertices have a positive vote. The strict majority number of G is the minimum sum of the values in a strict majority function of G. We prove the conjecture of Cockayne and Mynhardt (Ars. Combin. 43 (1996), 235–245) that every tree has strict majority number at most 2. We also prove that every graph has strict majority number at most 4. Both bounds are sharp. © 1998 John Wiley & Sons, Inc. J Graph Theory 28: 49–56, 1998 相似文献
99.
Hugh W. Thompson Roger A. Lalancette 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(10):o580-o582
In the title compound, C15H24O3, derived from a naturally occurring sesquiterpenoid, the asymmetric unit consists of two molecules differing by 167.4 (8)° in the rotational conformation of the carboxyl group. Each molecule aggregates separately with its own type as carboxyl‐to‐ketone hydrogen‐bonding catemers [O⋯O = 2.715 (6) and 2.772 (6) Å, and O—H⋯O = 169 and 168°]. This generates two crystallographically independent single‐strand hydrogen‐bonding helices passing through the cell in the b direction, with opposite end‐to‐end orientations. One intermolecular C—H⋯O=C close contact exists for the carboxyl group of one of the molecules. The structure is isostructural with that of a closely related unsaturated keto acid reported previously. 相似文献
100.
Single-phase permeability k has intensively been investigated over the past several decades by means of experiments, theories and simulations. Although the effect of surface roughness on fluid flow and permeability in single pores and fractures as well as networks of fractures was studied previously, its influence on permeability in a random mass fractal porous medium constructed of pores of different sizes remained as an open question. In this study, we, therefore, address the effect of pore–solid interface roughness on single-phase flow in random fractal porous media. For this purpose, we apply a mass fractal model to construct porous media with a priori known mass fractal dimensions \(2.579 \le D_{\mathrm{m}} \le 2.893\) characterizing both solid matrix and pore space. The pore–solid interface of the media is accordingly roughened using the Weierstrass–Mandelbrot approach and two parameters, i.e., surface fractal dimension \(D_{\mathrm{s}}\) and root-mean-square (rms) roughness height. A single-relaxation-time lattice Boltzmann method is applied to simulate single-phase permeability in the corresponding porous media. Results indicate that permeability decreases sharply with increasing \(D_{\mathrm{s}}\) from 1 to 1.1 regardless of \(D_{\mathrm{m}}\) value, while k may slightly increase or decrease, depending on \(D_{\mathrm{m}}\), as \(D_{\mathrm{s}}\) increases from 1.1 to 1.6. 相似文献