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41.
42.
Christine De Brauer Patrick Germain Marie Pierre Merlin 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):197-201
The heat capacities of solid -CD, 8.1 H2O and -CD, 6.0 H2O have been measured between 10 and 300 K by adiabatic calorimetry. Using earlier results obtained in similar experiments with anhydrous cyclodextrins and with -CD, 9.7 H2O, a comparative analysis has been developed. The energetic behaviours of anhydrous and hydrated cyclodextrins (CDs) have been compared in order to investigate the role of water molecules in the stabilization of the cyclodextrin's rings and on their reactivities. Calculations, based on the additivity of thermodynamic properties, provide the energetic and entropic average contributions of water molecules in each cyclodextrin. From these results, we assumed that the water–water and water–CD interactions are rather different according to the cyclodextrin. In the (-CD, 9.7 H2O) structure, the water molecules seem to be better organised in a relatively independent network. Concerning hydrated -CD and -CD, stronger water–CD interactions probably prevent an optimal organisation of the water–water bonds network. Differential scanning calorimetry was also used to follow the evolution of the thermal behaviour of -CD, nH2O versus hydration ratio between 170 and 300 K. Our results indicate that the -CD ring needs at least 1.6 water molecules to be stabilized in the solid state. 相似文献
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44.
Effect of meta-tetra(hydroxyphenyl)chlorin (mTHPC)-mediated photodynamic therapy on sensitive and multidrug-resistant human breast cancer cells 总被引:1,自引:0,他引:1
Teiten MH Bezdetnaya L Merlin JL Bour-Dill C Pauly ME Dicato M Guillemin F 《Journal of photochemistry and photobiology. B, Biology》2001,62(3):146-152
Meta-tetra(hydroxyphenyl)chlorin (mTHPC) is in clinical trials for the photodynamic therapy (PDT) of localized-stage cancer. The PDT susceptibility of cells expressing multidrug resistance (MDR) phenotype is an attractive possibility to overcome the resistance to cytotoxic drugs observed during cancer chemotherapy. The accumulation, photocytotoxicity and intracellular localization of mTHPC were examined using the doxorubicin selected MCF-7/DXR human breast cancer cells, expressing P-glycoprotein (P-gp), and the wild-type parental cell line, MCF-7. No significant difference in mTHPC accumulation was observed between the two cell lines up to 3 h contact. The photodynamic activity of mTHPC, measured 24 h after irradiation with red laser light (lambda=650 nm), was significantly greater in MCF-7/DXR as compared to MCF-7 cells. A light dose of 2.5 J cm(-2) inducing 50% of cytotoxicity in MCF-7, resulted in 85% cytotoxicity in MCF-7/DXR. The presence of P-gp inhibitors SDZ-PSC-833 and cyclosporin A did not modify the mTHPC-induced cytotoxicity. The difference in intracellular mTHPC distribution pattern between two cell lines may contribute to different photocytotoxicity. Our results indicate that mTHPC mediated PDT could be useful in killing cells expressing MDR phenotype. 相似文献
45.
C. De Brauer M. P. Merlin P. Germain T. Guerandel 《Journal of inclusion phenomena and macrocyclic chemistry》2000,37(1-4):75-82
Heat capacities of anhydrous -and -cyclodextrin were measured by adiabaticcalorimetry between 10 K and 300 K. The thermalbehaviour of the two compounds exhibits significantdifferences. -Cyclodextrin shows an anomalousexcess heat capacity in the entire region between 70 Kand 210 K. In the case of -cyclodextrin, anendothermic effect is observed at 240K. This effect isanalysed through the study of the correspondingentropy change and discussed in terms ofintramolecular organization.Using the known heat capacity values of anhydrous-CD, a comparative analysis has been developed.For each cyclodextrin, the average behaviour of abound -D-glucopyranose has been calculated andcompared. From a thermodynamic point of view, thedegree of organization of the dehydrated macrocycliccompounds could be expressed as-CD -CD -CD. 相似文献
46.
Edgar Ocando-mavarez Merlin Rosales Ninoska Silva 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Addition of four equivalents of tButyldiallylphosphine to a solution of one equivalent of [(COE)2Cl]2 in CHCl3 at low temperature produced two isomers of the metallated complex 2, formed by C-H activation. 2 evolve at 40°C to 3, by a hydride transfer from iridium to the cyclooctene (COE) ligand. 相似文献
47.
48.
Jean-Louis Santailler Claire Audoin Guy Chichignoud Rémy Obrecht Belkhiri Kaouache Pascal Marotel Denis Pelenc Stéphane Brochen Jérémy Merlin Isabelle Bisotto Carole Granier Guy Feuillet François Levy 《Journal of Crystal Growth》2010,312(23):3417-3424
A chemically assisted vapour phase transport (CVT) method is proposed for the growth of bulk ZnO crystals. Thermodynamic computations have confirmed the possibility of using CO as a sublimation activator for enhancing the sublimation rate of the feed material in a large range of pressures (10−3 to 1 atm) and temperatures (800–1200 °C). Growth runs in a specific and patented design yielded single ZnO crystals up to 46 mm in diameter and 8 mm in thickness, with growth rates up to 400 μm/h. These values are compatible with an industrial production rate. N type ZnO crystals (μ=182 cm2/(V s) and n=7 1015 cm−3) obtained by this CVT method (Chemical Vapour Transport) present a high level of purity (10–30 times better than hydrothermal ZnO crystals), which may be an advantage for obtaining p-type doped layers ([Li] and [Al] <10+15 cm−3). Structural (HR-XRD), defect density (EPD), electrical (Hall measurements) and optical (photoluminescence) properties are presented. 相似文献
49.
Johan Urdaneta Yaneth Bermúdez Federico Arrieta Merlin Rosales Néstor Cubillán Javier Hernández Olga Castellano Humberto Soscún 《Theoretical chemistry accounts》2010,126(1-2):27-37
The linear (α), and nonlinear (β, γ) optical NLO properties of ortho-, meta- and para-nitrophenol (ONP, MNP and PNP) isomers have been calculated in gas phase by using ab initio (HF, MP2 and MP4) and density functional theory (DFT) (B3LYP, CAM-B3LYP) methods, with the 6-31+G(d,p) and 6-311+G(3d,3p) standard and the Sadlej specialized basis sets. These properties were evaluated both at static and at dynamic regime within the finite field FF numerical techniques and the time-dependent-Hartree–Fock approach at 1,910 nm, respectively. Additional calculations were performed for the β static hyperpolarizability of these isomers in presence of p-dioxane solvent with the Onsager Model and the SCRF-PCM approach, using B3LYP/6-31+G(d,p) and MP2/6-31+G(d,p) levels of theory. Additionally, CCSD/6-31+G(d,p) calculations were performed for the α, β and γ properties of PNP isomer. The B3LYP and MP2 α ave results of the nitrophenol isomers are comparable to the experimental α ave reports; while the tendency for the β v calculated values (β v PNP > β v MNP > β v ONP), that can be explained in terms of the O x atomic charge of the –NO2 group, does not follow exactly the experimental ones. The B3LYP γ ave results are in correspondence to the experimental measurements, the correlation of which is r 2 = 0.99. The use of FF methodology in conjunction with the B3LYP and MP2 methods and the 6-31+G(d,p) basis set show to be appropriate approaches to predict qualitative optical properties of Push–Pull like organic molecules, provided are considered the solvent effects or frequency dependence. However, to have a clear picture of the NLO properties of an isolated molecule, higher order correlation effects combined with specialized basis sets, frequency and solvent effects should be employed. We have demonstrated that MP4/Sadlej level of theory is able to reproduce NLO properties that can be considered equivalent to those from more sophisticated approaches, such as CCSD together with extended basis sets. 相似文献
50.
Dai J Bao Z Sun L Hong SU Baker GL Bruening ML 《Langmuir : the ACS journal of surfaces and colloids》2006,22(9):4274-4281
Polymeric coatings with high protein-binding capacities are important for increasing the output of affinity-based protein purification and decreasing the detection limits of antibody microarrays. This report describes the use of thick poly(acrylic acid) (PAA) brushes to immobilize as much as 80 monolayers of protein. The brushes were prepared using a recently developed procedure that allows polymerization of 100-nm-thick poly(tert-butyl acrylate) films from a surface in just 5 min along with hydrolysis of these films to PAA in 15 min. Covalent binding of bovine serum albumin (BSA) to PAA brushes that were activated using standard coupling agents, however, resulted in immobilization of less than two monolayers of BSA because of competitive hydrolysis of the esters in the activated film. In contrast, derivatization of PAA with nitrilotriacetate (NTA)-Cu2+ complexes yielded films capable of binding many monolayers of protein via metal-ion affinity interactions. For example, derivatization of 55-nm-thick PAA films with NTA-Cu2+ allowed immobilization of about 15 monolayers (5.8 microg/cm2 or 58 nm) of BSA. The binding capacity was even higher for myoglobin (7.7 microg/cm2) and anti-IgG (9.6 microg/cm2). Remarkably, electrostatic adsorption of lysozyme in 55-nm-thick, underivatized PAA resulted in as much as 80 monolayers (16.2 microg/cm2 or 162 nm) of adsorbed protein. Polymer synthesis, derivatization, and swelling, as well as BSA immobilization kinetics and thermodynamics were characterized using reflectance FT-IR spectroscopy, ellipsometry, and protein assays. 相似文献