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81.
Structure-Photodynamic Activity Relationships of a Series of 4-Substituted Zinc Phthalocyanines 总被引:1,自引:0,他引:1
Philippe Margaron Marie-Josée Grégoire Vladimir asnár † Hasrat Ali Johan E. van Lier ‡ 《Photochemistry and photobiology》1996,63(2):217-223
Abstract— Radioiodinated zinc phthalocyanine including [125I]ZnPcI4 and differently sulfonated [65Zn]ZnPcS (ZnPcS4, ZnPcS3, ZnPcS2 and ZnPcS1.75, a mixture of adjacent di and 25% mono) were prepared in order to study cell uptake and release kinetics in EMT-6 cells. The same compounds were evaluated for their in vitro phototoxicity and the biological parameters were compared to partition coefficients to arrive at quantitative structure-activity relationships (QSAR). At 1 μM in 1% serum, at 37°C, all dyes showed rapid cell uptake during the first hour followed by a slow accumulation phase. After 24 h, the highest cellular concentration was observed with the lipophilic ZnPcI4, followed by the amphiphilic ZnPcS2 and ZnPcS1.75. The hydrophilic ZnPcS4 and ZnPcS3 showed lower uptake. Dye release from dyeloaded cells during incubation in dye-free medium could reach up to 60% and was shown to depend mainly on the amount of drug incorporated rather than the type of compound. These results suggest that care should be taken in interpreting dye toxicity data, which involve in vitro cell manipulations in dye-free medium, particularly during in vitro/in vivo protocols. The EMT-6 cell survival after 1 h or 24 h incubation with 1 μM dye in 1% serum followed by exposure to red light was assessed by means of the colorimetric 3-(4,5-dimethylthiazol-2-yl)-diphenyl-tetrazolium bromide (MTT) assay. Photocytotoxicities correlated inversely with the tendencies of the dyes to aggregate. Increased dye uptake by the cells also correlated with their activities, except for the lipophilic ZnPcI4, which showed the highest cell uptake but little phototoxicity. The QSAR between phototoxicity and the log of the partition coefficients (phosphate-buffered saline and n-octanol) gave a parabola with optimal partition values corresponding to the adjacent sulfonated ZnPcS2. 相似文献
82.
Wim Goettsch Johan Garssen Arja de Klerk Tineke M. P. T. Herremans Paul Dortant Frank R. de Gruijl Henk Van Loveren 《Photochemistry and photobiology》1996,63(5):672-679
A rat infection model using the bacterial pathogen Listeria monocytogenes was employed to analyze the im-munosuppressive activity of UVB radiation. Rats were exposed to suberythemal doses of UVB radiation for 5 or 7 consecutive days, using Kromayer or FS40 lamps respectively. Subsequently, the rats were infected subcuta-neously or intravenously with Listeria . Exposure to UVB resulted in an increased number of bacteria in the spleen 4 days after infection. Listeria -specific lymphocyte proliferation assays as well as delayed-type hypersensitivity reactions demonstrated that T cell-mediated immunity to Listeria was impaired by UVB as measured 4 and 8 days after infection. In addition, UVB exposure decreased phagocytotic activity of peripheral blood macrophages. This study demonstrated that suberythemal doses of UVB radiation caused a delay in the clearance of Listeria bacteria from the spleen of the rats and that this was probably caused by impaired nonspecific phagocytosis of Listeria by macrophages in addition to an impaired activity of Listeria -specific T cells. 相似文献
83.
Allen CM Langlois R Sharman WM La Madeleine C Van Lier JE 《Photochemistry and photobiology》2002,76(2):208-216
Photodynamic therapy (PDT) is a promising treatment modality that has recently been accepted in clinics as a curative or palliative therapy for cancer and other nonmalignant conditions. Phthalocyanines (Pc) are attractive photosensitizers for PDT because of their enhanced photophysical and photochemical properties. The overall charge and solubility of Pc play a major role in their potential usefulness for PDT. A series of amphiphilic derivatives of tetrasulfonated aluminum Pc (AlPcS4) was prepared by substituting one of the four sulfonate groups with aliphatic side chains of 4, 8, 12 and 16 carbon atoms. The photodynamic properties of the derivatives were compared with those of AlPcS4 and the adjacent disulfonated aluminum Pc. Parameters studied included reversed-phase high-performance liquid chromatography (HPLC) retention times, capacity to generate singlet oxygen (1O2), in vitro cell uptake and phototoxicity, as well as PDT response of transplantable EMT-6 tumors in mice. The monomerized AlPcS4 derivatives showed similar or higher capacities to generate 1O2 as compared with the parent AlPcS4 as measured from relative L-tryptophan photooxidation yields. A549 cell uptake of the AlPcS4 derivatives decreased in the following order: AlPcS4(C16) > AlPcS4(C12) > AlPcS4(C8) > AlPcS4(C4). Human low-density lipoprotein at high concentrations (40 micrograms/mL) completely prevented uptake, whereas at 4 micrograms/mL uptake was decreased for the more lipophilic compounds and yet remained unaffected for the more hydrophilic dyes. Using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, A549 cell survival was assessed; it showed that photocytotoxic activity varied directly with the HPLC retention times, i.e. more hydrophilic compounds were less phototoxic. As 1O2 yields were similar for the four substituted AlPcS4 derivatives, it was postulated that the increased cytotoxic activity was caused by enhanced subcellular localization as a result of the long aliphatic side chains. These amphiphilic compounds proved to be photodynamically potent against the EMT-6 mouse mammary tumor model implanted in Balb/c mice. At dye doses of 0.2 mumol/kg and a fluence of 400 J/cm2 complete tumor regression was observed with no morbidity. The substitution of AlPcS4 with long aliphatic chains on the macrocycle greatly enhances its photodynamic efficacy both in vitro and in vivo. 相似文献
84.
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86.
In this paper, we present a finite element method with a residual‐based artificial viscosity for simulation of turbulent compressible flow, with adaptive mesh refinement based on a posteriori error estimation with sensitivity information from an associated dual problem. The artificial viscosity acts as a numerical stabilization, as shock capturing, and as turbulence capturing for large eddy simulation of turbulent flow. The adaptive method resolves parts of the flow indicated by the a posteriori error estimates but leaves shocks and turbulence under‐resolved in a large eddy simulation. The method is tested for examples in 2D and 3D and is validated against experimental data. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
87.
Dr. Peter Wick Dr. Anna E. Louw‐Gaume Dr. Melanie Kucki Prof. Harald F. Krug Prof. Kostas Kostarelos Prof. Bengt Fadeel Prof. Kenneth A. Dawson Dr. Anna Salvati Prof. Ester Vázquez Dr. Laura Ballerini Dr. Mauro Tretiach Dr. Fabio Benfenati Dr. Emmanuel Flahaut Dr. Laury Gauthier Prof. Maurizio Prato Dr. Alberto Bianco 《Angewandte Chemie (International ed. in English)》2014,53(30):7714-7718
88.
Likelihood-based procedures are a common way to estimate tail dependence parameters. They are not applicable, however, in non-differentiable models such as those arising from recent max-linear structural equation models. Moreover, they can be hard to compute in higher dimensions. An adaptive weighted least-squares procedure matching nonparametric estimates of the stable tail dependence function with the corresponding values of a parametrically specified proposal yields a novel minimum-distance estimator. The estimator is easy to calculate and applies to a wide range of sampling schemes and tail dependence models. In large samples, it is asymptotically normal with an explicit and estimable covariance matrix. The minimum distance obtained forms the basis of a goodness-of-fit statistic whose asymptotic distribution is chi-square. Extensive Monte Carlo simulations confirm the excellent finite-sample performance of the estimator and demonstrate that it is a strong competitor to currently available methods. The estimator is then applied to disentangle sources of tail dependence in European stock markets. 相似文献
89.
Johan Sjöblom Hege Ebeltoft Alf Bjørseth Stig E. Friberg Chris Brancewicz 《Journal of Dispersion Science and Technology》2013,34(1):21-34
Hydrolysis and condensation of monomolecular alkyloxysilane films by the Langmuir technique is presented. Octadecyltrimethoxysilane formed monolayers on aqueous subphases with different properties depending on the bulk pH. At pH 1 a solid condensed film was directly formed with a molecular area of 23 Å2 and a surface pressure/surface area variation similar to that on non-ionized stearic acid. At pH 5.6 and 11 several phase transitions were observed during the compression of the monolayer with a final collapse at a molecular area of 20 Å2. Relaxation measurements confirmed the stability of the films for longer than 12 hours at different surface pressures below a critical value. 相似文献
90.
Monique A. Mballa Mballa Johan P. A. Heuts Alex M. van Herk 《Colloid and polymer science》2013,291(6):1419-1427
The effect of montmorrilonite clay (MMT) platelets on the morphology of polystyrene/poly(methyl methacrylate) (PMMA) composite latex particles prepared via PMMA-seeded (semi-) batch emulsion polymerization of styrene was studied. It was found that the particle morphology obtained greatly depended on the ability of the clay platelets to diffuse through the polymer particle. Indeed, when the reactions were strictly under kinetic control, i.e., where the clay platelets were unable to diffuse during polymerization, anisotropic core-shell-like morphologies with split core were observed. A better mobility of the clay platelets could more or less restrict the diffusion of the second-stage polymers within the host polymer, leading to original kinetically controlled morphologies. In the case of a full migration of the clay platelets to the particle surface, the penetration of the second-stage polymer species in the seed latex was found to be more limited, enhancing the formation of secondary particles. 相似文献