Daunomycin binding to detergent micelles: A model system for evaluating the hydrophobic contribution to drug-DNA interactions

The interaction of daunomycin with sodium dodecyl sulfate and Triton X-100 micelles was investigated as a model for the hydrophobic contribution to the free energy of DNA intercalation reactions. Measurements of visible absorbance, fluorescence lifetime, steady-state fluorescence emission intensity, and fluorescence anisotropy indicate that the anthraquinone ring partitions into the hydrophobic micelle interior. Fluorescence quenching experiments using both steady-state and lifetime measurements demonstrate reduced accessibility of daunomycin in sodium dodecyl sulfate micelles to the anionic quencher iodide and to the neutral quencher acrylamide. Quenching of daunomycin fluorescence by iodide in Triton X-100 micelles was similar to that seen with free daunomycin. Studies of the energetics of the interaction of daunomycin with micelles by fluorescence and absorbance titration methods and by isothermal titration calorimetry in the presence of excess micelles revealed that association with sodium dodecyl sulfate and Triton X-100 micelles is driven by a large negative enthalpy. Association of the drug with both types of micelles also has a favorable entropic contribution, which is larger in magnitude for Triton X-100 micelles than for sodium dodecyl sulfate micelles.

Chemical effects of cationic surfactant and anionic surfactant used in organically modified montmorillonites on degradation and fire retardancy of polyamide 12 nanocomposites

Three kinds of organically modified Na+-montmorillonites (OMMTs), including two kinds of octadecylammonium modified montmorillonite with different contents of octadecylammonium and a kind of sodium dodecylsulfonate (SDSo) modified montmorillonite, were used to prepare polyamide 12 (PA12)/OMMT nanocomposites. Effects of the modifiers on degradation and fire retardancy of PA12/OMMT nanocomposites were investigated. Acid sites formed in cationic surfactant modified MMT via Hoffman decomposition could accelerate degradation of PA12 at high temperature. However, catalytic effect of the acid sites on carbonization of the degradation products promoted char barrier formation, which reduced heat release rate (HRR). Higher content of cationic surfactant in OMMT is beneficial to fire retardancy of PA12 nanocomposites and the dispersion states of OMMT have assistant effects. In contrast, Na+-montmorillonite (Na-MMT) and anionic surfactant modified MMT (a-MMT) could not form acid sites on the MMT layers; in this case, fire retardancy of PA12/Na-MMT appears to have no improvement and PA12/a-MMT appears to have limited improvement.

Mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and a catalyst in catalytic degradation of polyethylene

The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene (PE) catalytic degradation was investigated. Here, HMCM- 41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves (SAPO1 and SAPO2) were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.

Synthesis and characterization of photo-cross-linked hydrogels based on biodegradable polyphosphoesters and poly(ethylene glycol) copolymers

Novel biodegradable hydrogels by photo-cross-linking macromers based on polyphosphoesters and poly(ethylene glycol) (PEG) are reported. Photo-cross-linkable macromers were synthesized by ring-opening polymerization of the cyclic phosphoester monomer 2-(2-oxo-1,3,2-dioxaphospholoyloxy) ethyl methacrylate (OPEMA) using PEG as the initiator and stannous octoate as the catalyst. The macrorners were characterized by H-1 NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography measurements. The content of polyphosphoester in the macromer was controlled by varying the feed ratio of OPEMA to PEG. Hydrogels were fabricated by exposing aqueous solutions of macromers with 0.05% (w/w) photoinitiator to UV light irradiation, and their swelling kinetics as well as degradation behaviors were evaluated. The results demonstrated that cross-linking density and pH values strongly affected the degradation rates. The macromers was compatible to osteoblast cells, not exhibiting significant cytotoxicity up to 0.5 mg/mL. "Live/dead" cell staining assay also demonstrated that a large majority of the osteoblast cells remained viable after encapsulation into the hydrogel constructs, showing their potential as tissue engineering scaffolds.

Drug-human serum albumin binding studied by capillary electrophoresis with electrochemiluminescence detection

A new technique for investigating drug-protein binding was developed employing capillary electrophoresis (CE) coupled with tris(2,2'-bipyridyl) ruthenium(II) [Ru(bPY)(3)(2+)] electrochemiluminescence (ECL) (CE-ECL) detection after equilibrium dialysis. Three basic drugs, namely pridinol, procyclidine and its analogue trihexyphenidyl, were successfully separated by capillary zone electrophoresis with end-column Ru(bPY)(3)(2+) ECL detection. The relative drug binding to human serum albumin (HSA) for each single drug as well'as for the three drugs binding simultaneously was calculated. It was found that the three antiparkinsonian drugs compete for the same binding site on HSA. This work demonstrated that Ru(bPY)(3)(2+) CE-ECL can be a suitable technique for studying drug-protein binding.

Enzymatic degradation of poly(L-lactide) and poly (epsilon-caprolactone) electrospun fibers

Poly(L-lactide) (PLLA) and poly(epsilon-caprolactone) (PCL) ultrafine fibers were prepared by electrospinning. The influence of cationic and anionic surfactants on their enzymatic degradation behavior was investigated by measuring weight loss, molecular weight, crystallinity, and melting temperature of the fibers as a function of degradation time. Under the catalysis of proteinase K, the PLLA fibers containing the anionic surfactant sodium docecyl sulfate (SDS) exhibited a faster degradation rate than those containing cationic surfactant triethylbenzylammonium chloride (TEBAC), indicating that surface electric charge on the fibers is a critical factor for an enzymatic degradation. Similarly, TEBAC-containing PCL fibers exhibited a 47% weight loss within 8.5 h whereas SDS-containing PCL fibers showed little degradation in the presence of lipase PS. By analyzing the charge status of proteinase K and lipase PS under the experimental conditions, the importance of the surface charges of the fibers and their interactions with the charges on the enzymes were revealed. Consequently, a "two-step" degradation mechanism was proposed: (1) the enzyme approaches the fiber surface; (2) the enzyme initiates hydrolysis of the polymer.

Characterization of prolidase activity using capillary electrophoresis with tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence detection and application to evaluate collagen degradation in diabetes mellitus

A new method for prolidase (PLD, EC 3.4.13.9) activity assay was developed based on the determination of proline produced from enzymatic reaction through capillary electrophoresis (CE) with tris(2,2'-bipyridyl)ruthenium(11) [Ru(bpy)(3)(2+)] electrochemiluminescence detection (ECL). A detection limit of 12.2 fmol (S/N = 3) for proline, corresponding to 1.22 x 10(-8) units of prolidase catalyzing for 1 min was achieved. PLD activity determined by CE-ECL method was in agreement with that obtained from the classical Chinard's one. CE-ECL showed its powerful resolving ability and selectivity as no sample pretreatmentwas needed and no interference existed. The clinical utility of this method was successfully demonstrated by its application to assay PLD activity in the serum of diabetic patients in order to evaluate collagen degradation in diabetes mellitus (DM). The results indicated that enhanced collagen degradation occurred in DM.

Compositional differences of propylene-ethylene block copolymers manufactured by degradation and hydrogenation techniques

The purpose of the present work is to investigate the compositional difference of polypropylene-polyethylene block copolymers (PP-b-PE) manufactured industrially by the process of degradation and hydrogenation, respectively. Each of the PP-b-PE copolymers was fractionated into three fractions with heptane and chloroform. The compositions of the three fractions were characterized by C-13 nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy, as well as differential scanning calorimetry (DSC) and thermal fractionation. The results showed that the Chloroform-soluble fraction was amorphous ethylene-propylene rubber, and the content of the rubber in PP-b-PE manufactured by hydrogenation was less than that by degradation. The degree of crystallinity of the chloroform-insoluble fraction of the PP-b-PE manufactured by hydrogenation is higher than that of by degradation.

Thermal degradation kinetics of uncapped and end-capped poly(propylene carbonate)

In order to improve its thermal stability, poly(propylene carbonate)(PPC) was end-capped by different active agents. Thermogravimetric data show that the degradation temperature of uncapped PPC was lower than that of end-capped PPC. The kinetic parameters of thermal degradation of uncapped and end-capped PPC were calculated according to Chang's method. The results show that different mechanisms operate during the whole degradation temperature range for uncapped PPC. In the first stage, chain unzipping dominates the degradation. With increasing temperature, competing multi-step reactions occur. In the last stage, random chain scission plays an important role in degradation. For end-capped PPC, random chain scission dominates the whole degradation process.

Thermal degradation kinetics of poly(propylene carbonate) obtained from the copolymerization of carbon dioxide and propylene oxide

The kinetics of the thermal degradation of poly(propylene carbonate) (PPC) were investigated with different kinetic methods with data from thermogravimetric analysis under dynamic conditions. The apparent activation energies obtained with different integral methods (Ozawa-Flynn-Wall and Coats-Redfern) were consistent with the values obtained with the Kinssinger method (99.93 kJ/mol). The solid-state decomposition process was a sigmoidal A(3) type in terms of the Coats-Redfern and Phadnis-Deshpande results. The influence of the heating rate on the thermal decomposition temperature was also studied. The derivative thermogravimetry curves of PPC confirmed only one weight-loss step.

Synthesis and characterization of PCL/PEG/PCL triblock copolymers by using calcium catalyst

Triblock copolymer PCL-PEG-PCL was prepared by ring-opening polymerization of epsilon-caprolactone (CL) in the presence of poly(ethylene glycol) catalyzed by calcium ammoniate at 60 degreesC in xylene solution. The copolymer composition and triblock structure were confirmed by H-1 NMR and C-13 WR measurements. The differential scanning calorimetry and wide-angle X-ray diffraction analyses revealed the micro-domain structure in the copolymer. The melting temperature T-c and crystallization temperature T-c of the PEG domain were influenced by the relative length of the PCL blocks. This was caused by the strong covalent interconnection between the two domains. Aqueous micelles were prepared from the triblock copolymer. The critical micelle concentration was determined to be 0.4-1.2 mg/l by fluorescence technique using pyrene as probe, depending on the length of PCL blocks, and lower than that of corresponding PCL-PEG diblock copolymers. The H-1 NMR spectrum of the micelles in D2O demonstrated only the -CH2CH2O- signal and thus confirmed. the PCL-core/PEG-shell structure of the micelles.