Application of Poly (Agar-Co-Glycerol-Co-Sweet Almond Oil) Based Organo-Hydrogels as a Drug Delivery Material

In this study, it was aimed to investigate the synthesis, characterization and drug release behaviors of organo-hydrogels containing pH-sensitive Agar (A), Glycerol (G), Sweet Almond oil (Wu et al. in J Mol Struct 882:107–115, 2008). Organo-hydrogels, which contained Agar, Glycerol and different amounts of Sweet Almond oil, were synthesized via the free-radical polymerization reaction with emulsion technique using glutaraldehyde or methylene bis acrylamide crosslinkers. Then, the degree of swelling, bond structures, blood compatibility and antioxidant properties of the synthesized organo-hydrogels were examined. In addition, Organo-hydrogels which loaded with Ceftriaxone and Oxaliplatin were synthesized with the same polymerization reaction and release kinetics were investigated. In vitro release studies were performed at media similar pH to gastric fluid (pH 2.0), skin surface (pH 5.5), blood fluid (pH 7.4) and intestinal fluid (pH 8.0), at 37 °C. The effects on release of crosslinker type and sweet almond oil amount were investigated. Kinetic parameters were determined using release results and these results were applied to zero and first-order equations and Korsmeyer-Peppas and Higuchi equations. Diffusion exponential was calculated for drug diffusion of organo-hydrogels and values consistent with release results were found.

     

Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

Determination of Kinetic Parameters for the Degradation of Chitosan/Silica Hybrid Nano Composites

The thermal degradation behavior of chitosan (CS) and chitosan–silica (CS–Si) nanocomposites were studied using a differential kinetic model. The influence of the heating rate in the non-isothermal degradation kinetics of CS and CS–Si nanocomposites are presented. Kinetic parameters, such as the activation energy (E) and pre-exponential factor (A), and thermodynamic parameters, such as the Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were determined using the modified Arrhenius equation. It was shown that the rate constant for degradation (k), activation energy and pre-exponential factor depend on the heating rates. The order of reaction was found to be one. The isothermal stability of CS and CS–Si was determined from non-isothermal kinetics and was also found to be dependent on the heating rate. Thermogravimetric studies revealed that neat CS was less thermally stable than the CS–Si nanocomposites.     

Palm Oleic Acid Based Alkyds: Effect of the Fatty Acid Content on the Polyesterification Kinetics

The kinetic behavior of polyesterification of the alkyd resins synthesized using glycerol and phthalic anhydride modified with oleic acid from the palm oil at temperatures between 120 and 240 °C was studied. Three alkyds having oleic acid contents of 28, 40, and 65% were prepared by employing fatty acid method. The extent of the polyesterification reaction and average degree of polymerization were monitored by determining the acid number of the aliquot of the reaction mixture at various intervals of time and by measuring the volume of water evolved. Kinetic studies revealed that initial reaction rates followed a second-order kinetics up to certain limit and thereafter deviations were observed. The extent of reaction varied from 77.4 to 86.3% before deviation for all the three samples and exhibited a considerable degree of conversion. The second-order rate constants calculated from the linear part were found to be of the order of 10⁻⁵ g (mg KOH)⁻¹ min⁻¹. Molecular weight of the alkyd samples was determined by GPC; number average molecular weight of the alkyds ranged from 980 to 2,070.     

Mathematical modelling of a composting process, and validation with experimental data

The present study aimed to develop a mathematical model of composting which, while not overlooking the fundamental principles of physical and microbiological chemistry, could be easily applied in practice and be validated by experimental data. The experimental results of the biological aerobic decomposition of a mixture consisting of rice and rice husks, could be explained in terms of the parameter aggregation model, assuming a set of pseudo-first-order reactions in series, in which a hydrolysis step is followed by a biochemical oxidative step with formation of compost, biomass and biological gases (CO2, O2). The corresponding kinetic parameters and their temperature dependence were determined. These parameters indicated that the hydrolysis step was always the slowest one, and, therefore, the overall rate-determining step. This is in substantial agreement with our experimental observations of a non-dependency of the overall rate on the oxygen concentration, and suggests that rather than using mesophilic and thermophilic bacteria and fungi for seeding or accelerating the process, adequate hydrolytic enzymes (or related micro-organisms) should be added, instead.     

Projection of landfill stabilization period by time series analysis of leachate quality and transformation trends of VOCs

The purpose of this study was to evaluate suitability of using the time series analysis for selected leachate quantity and quality parameters to forecast the duration of post closure period of a closed landfill. Selected leachate quality parameters (i.e., sodium, chloride, iron, bicarbonate, total dissolved solids (TDS), and ammonium as N) and volatile organic compounds (VOCs) (i.e., vinyl chloride, 1,4-dichlorobenzene, chlorobenzene, benzene, toluene, ethyl benzene, xylenes, total BTEX) were analyzed by the time series multiplicative decomposition model to estimate the projected levels of the parameters. These parameters were selected based on their detection levels and consistency of detection in leachate samples. In addition, VOCs detected in leachate and their chemical transformations were considered in view of the decomposition stage of the landfill. Projected leachate quality trends were analyzed and compared with the maximum contaminant level (MCL) for the respective parameters. Conditions that lead to specific trends (i.e., increasing, decreasing, or steady) and interactions of leachate quality parameters were evaluated. Decreasing trends were projected for leachate quantity, concentrations of sodium, chloride, TDS, ammonia as N, vinyl chloride, 1,4-dichlorobenzene, benzene, toluene, ethyl benzene, xylenes, and total BTEX. Increasing trends were projected for concentrations of iron, bicarbonate, and chlorobenzene. Anaerobic conditions in landfill provide favorable conditions for corrosion of iron resulting in higher concentrations over time. Bicarbonate formation as a byproduct of bacterial respiration during waste decomposition and the lime rock cap system of the landfill contribute to the increasing levels of bicarbonate in leachate. Chlorobenzene is produced during anaerobic biodegradation of 1,4-dichlorobenzene, hence, the increasing trend of chlorobenzene may be due to the declining trend of 1,4-dichlorobenzene. The time series multiplicative decomposition model in general provides an adequate forecast for future planning purposes for the parameters monitored in leachate. The model projections for 1,4-dichlorobenzene were relatively less accurate in comparison to the projections for vinyl chloride and chlorobenzene. Based on the trends observed, future monitoring needs for the selected leachate parameters were identified.     

Sensitivity analysis and literature review of parameters controlling local biodegradation processes in municipal solid waste landfills

The local gas production rate in municipal landfills is influenced by a large number of processes, which have been modelled by a local mechanistic reaction model based on Monod kinetics. This type of model, however, requires over 40 input parameters. The aim of this research was to review published values for these input parameters, and to analyse the sensitivity of the model to changes in each of them. Included were rate constants based on Monod kinetics, general rate-controlling variables, and parameters that influence the local pH and temperature of the waste. Mathematical functions that describe the influence of water content, temperature, and pH on biodegradation rates were calibrated on the basis of literature data. The results of the sensitivity analysis suggest that the parameters with the largest impact on model output are the hydrolysis constant k(Hy), the kinetic constants [Formula: see text] , [Formula: see text] , [Formula: see text] , K(i,ac,Hy), and [Formula: see text] , the water content, temperature, pH, initial concentration of X(me), the enthalpy of formation of the original organic matter, as well as the protein content and buffering capacity of the waste. These parameters, therefore, should be carefully selected when similar modelling studies are performed.     

Evaluation of natural attenuation at a 1,4‐dioxane‐contaminated site

1,4‐Dioxane entered the environment as a result of historic leaks and spills in the production area at an industrial facility in the southeastern coastal plain. The areal extent of the 1,4‐dioxane plume is several hundred acres and is largely contained on the site. Land use adjacent to the plant property is primarily undeveloped (wetlands or woods) or industrial, with a small area of mixed land use (commercial/residential) to the southwest and north. The surficial aquifer is a relatively simple hydrogeologic system with well‐defined boundaries and is comprised of a 50‐ to 70‐foot‐thick deposit of alluvial/fluvial sand and gravel that overlies an aquitard in excess of 100 feet thick. A groundwater flow model, developed and calibrated using field‐measured data, was used for the fate‐and‐transport modeling of 1,4‐dioxane. The flow‐and‐transport model, combined with the evaluation of other site geochemical data, was used to support the selection of monitored natural attenuation (MNA) as the proposed groundwater remedy for the site. Since the active sources of contamination have been removed and the modeling/field data demonstrated that the plume was stable and not expanding, the proposed MNA approach was accepted and approved by the regulatory agency for implementation in 2004. Subsequent accumulated data confirm that concentrations in the 1,4‐dioxane plume are declining as predicted by the fate‐and‐transport modeling. © 2008 Wiley Periodicals, Inc.     

The Removal of Acid Violet 90 from Aqueous Solutions Using PANI and PANI/Clinoptilolite Composites: Isotherm and Kinetics

Polyaniline (PANI) and polyaniline/Gördes-clinoptilolite (PANI/GC) composite materials were synthesized by the chemical oxidative polymerization technique and used in the adsorption of Acid Violet 90 metal-complex dye (AV 90). The samples were characterized by X-ray diffractions, nitrogen adsorption–desorption isotherms, scanning electron microscopes and Fourier transform infrared. The effect of initial pH (2–8), sorbent dosage (0.5–4.0 g/L) and initial dye concentrations (50–400 mg/L) on adsorption onto PANI and PANI/GC were examined in a batch system. Langmuir, Freundlich and Temkin isotherm models were used to investigate the adsorption mechanism of AV 90 on PANI and PANI/GC. Langmuir isotherm model for PANI/GC and Freundlich isotherm model for PANI were fitted well with the experimental data. The highest dye uptake capacities were obtained with Langmuir isotherm model as 153.85 mg/g and 72.46 mg/g for PANI and PANI/GC, respectively. In order to determine the adsorption kinetics, pseudo first-order and second-order kinetic models were studied. As a result, the adsorption of AV 90 dye on PANI and PANI/GC was better identified with Pseudo second-order kinetic model than the first one.     

Low NOx burners--prediction of emissions concentration based on design,measurements and modelling

This paper describes possible ways of prediction of nitrogen oxides formation during combustion of hydrocarbon fuels. Mathematical model based on experimental data acquired from the testing facility has been developed. The model enables to predict--at a high probability measure--the extent of nitrogen oxides emissions. The mathematical model of nitrogen oxide formation relies on the application of simplified kinetic equations describing the formation of nitrogen oxides at so-called equivalent temperature. It is a semi-empirical model that comes out of experimental knowledge. An important role played by the burner design itself has been emphasized and therefore an important supplementary parameter of the model is the characteristic of the burner design. It has been established that there was a good agreement between experimental data and those calculated by the application of the model to various conditions marked out by different combustion parameters in the combustion chamber. The results obtained by application of the model respect the influence of parameters validated by industrial practice that control the formation of nitrogen oxides in the course of fuel combustion. Such parameters-first of all-tare the temperature in the combustion chamber and the concentration of the substances taking part in the reaction. By application of the model, it is possible to assess the consequence of, for example the surplus of combustion air, the increase of temperature of combustion air, the supply of inert gas, etc. on the nitrogen oxides emissions of the operating burner under evaluation. Efficient combining of experience and sophisticated approach together with importance of thus access for an improved design are shown.     

Bio-Based Non-Isocyanate Urethane Derived from Plant Oil

A new bio-based non-isocyanate urethane was obtained by the reaction of a cyclic carbonate synthesized from a modified linseed oil and an alkylated phenolic polyamine (Phenalkamine) from cashew nut shell liquid. The incorporation of functional cyclic carbonate groups to the triglyceride units of the oil was done by reacting epoxidized linseed oil with carbon dioxide in the presence of a catalyst. Structural changes and changes in molar mass during the carbonation reaction were characterized using infrared spectrometry (FTIR) and chromatography. The aminolysis reaction of the cyclic carbonate with phenalkamine was monitored using real-time FTIR at 80 and 100?°C, respectively. The decay of the carbonate groups and the appearance of the newly built C=O groups of the urethane linkages were measured in situ through real-time FTIR spectra in dependence on the reaction time. Oscillatory time sweep measurements were used to monitor the viscoelastic properties of the system at 80 and 100?°C. The time of gelation was determined from rheometric measurements. Changes of the apparent activation energy with respect to the conversion of the reaction were calculated from isothermal measurements using Vyazovkin??s free kinetic model.     

The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

利用含铝废硫酸和废铝渣制备聚合硫酸铝

以含铝废硫酸和废铝渣为原料制备聚合硫酸铝（PAS）。优化了废铝渣的酸溶条件,确定了合适的稳定剂和碱化剂。实验结果表明：在酸溶反应温度为80 ℃、酸溶反应时间为40 min、以20 g/L Ca（OH）₂溶液为碱化剂、以加入量为60 mg/L的固体柠檬酸为稳定剂的条件下,制备的PAS比聚合氯化铝（PAC）和Al₂（SO₄）₃具有更优异的混凝性能。该工艺可回收利用废铝渣和含铝废硫酸,从而达到综合利用的目的。     

First-order kinetic gas generation model parameters for wet landfills

Landfill gas collection data from wet landfill cells were analyzed and first-order gas generation model parameters were estimated for the US EPA landfill gas emissions model (LandGEM). Parameters were determined through statistical comparison of predicted and actual gas collection. The US EPA LandGEM model appeared to fit the data well, provided it is preceded by a lag phase, which on average was 1.5 years. The first-order reaction rate constant, k, and the methane generation potential, L(o), were estimated for a set of landfills with short-term waste placement and long-term gas collection data. Mean and 95% confidence parameter estimates for these data sets were found using mixed-effects model regression followed by bootstrap analysis. The mean values for the specific methane volume produced during the lag phase (V(sto)), L(o), and k were 33 m(3)/Megagrams (Mg), 76 m(3)/Mg, and 0.28 year(-1), respectively. Parameters were also estimated for three full scale wet landfills where waste was placed over many years. The k and L(o) estimated for these landfills were 0.21 year(-1), 115 m(3)/Mg, 0.11 year(-1), 95 m(3)/Mg, and 0.12 year(-1) and 87 m(3)/Mg, respectively. A group of data points from wet landfills cells with short-term data were also analyzed. A conservative set of parameter estimates was suggested based on the upper 95% confidence interval parameters as a k of 0.3 year(-1) and a L(o) of 100 m(3)/Mg if design is optimized and the lag is minimized.     

Laccase-Assisted Grafting of Acrylic Acid onto Lignin for its Recovery from Wastewater

The acrylic acid (AA) in the wastewater from paint manufacturing could be recovered by grafting to lignosulfonate in the presence of laccase and tert-butyl hydroperoxide (t-BHP). The low concentration of t-BHP did not inhibit the laccase activity, but improved the radical formation on lignin by laccase reaction, then initiated AA polymerization on lignin. The results showed laccase took a significant role for AA grafting to lignin. 94 % of AA could be polymerized on lignin by laccase/t-BHP, while only 32 % of AA was grafted on lignin with the same condition without laccase. The ratio of lignin to acrylic acid also affected AA recovery, and higher concentration of acrylic acid led to high recovery rate of AA. In this reaction system, the suitable range of temperature was 30–40 °C for the chemo-enzymatic reaction. The AA grafted on lignin could be precipitated by calcium ion and recovered.     

Bisolute Equilibrium Studies for the Sorption of Basic Dyes on a GAC from Almond Shells: A Nonlinear Approach

Aqueous phase adsorption of three textile dyes onto a granular activated carbon produced from acid activation of almond shells is presented. Primarily, the sorption of three basic dyes, methylene blue, rhodamine b, and malachite green oxalate were studied. Four models, the Freundlich, the Langmuir, the Redlich-Peterson, and the Toth isotherms were compared for their quality of fit to the single-solute sorption data. Next, sorption of the three likely binary systems was examined. Four bi-solute models, the extended Langmuir with and without an interaction term, the extended Redlich-Peterson with an interaction term, and the empirical extended Freundlich model were used to predict sorption in the binary systems. Nonlinearly determined constants of the corresponding single-solute isotherms were used in the binary models to compare with experimental binary sorption data. For the single-solute system, the three-parameter models of the Redlich-Peterson and the Toth isotherms outperformed the Langmuir and Freundlich models. The empirical extended Freundlich model produced the closest comparison to the binary data in each system. In general, the nonlinear method provided a simple and computationally effective technique of producing optimal fitting parameters for the bi-solute sorption models.     

Characterization of a poly(3-hydroxybutyrate) depolymerase fromaureobacterium saperdae: Active site and kinetics of hydrolysis studies

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase was purified fromAureobacterium saperdae cultural medium by using hydrophobic interaction chromatography. The isolated enzyme was composed of a single polypeptide chain with a molecular mass of 42.7 kDa as determined by SDS-PAGE and by native gel filtration on TSK-HW-55S. The enzyme was not a glycoprotein. Its optimum activity occurred at pH 8.0 and it showed a broad pH stability, ranging from pH 3 to pH 11.N-Bromosuccinamide and 2-hydroxy-5-nitrobenzyl bromide completely inactivated the enzyme, suggesting the involvement of tryptophan residues at the active site of the protein. The enzyme was very sensitive to diisopropyl fluorophosphate and diazo-dl-norleucine methyl ester, showing the importance of serine and carboxyl groups. The modification of cysteine residues byp-hydroxy mercuricbenzoate did not cause a loss of activity, whereas dithiothreitol rapidly inactivated the enzyme, revealing the presence of disulfide bonds.A saperdae depolymerase acted on the surface layer of PHB films and the degradation proceeded by surface erosion releasing monomers and dimers of 3-hydroxybutric acid. The degradation of PHB films byA. saperdae depolymerase was partially inhibited in the presence of excess amounts of enzyme. This phenomenon, already observed by Mukaiet al. with poly(hydroxyalkanoates) depolymerases fromAlcaligenes faecalis, Pseudomonas pickettii, andComamonas testosteroni, was analyzed according to the kinetic model proposed by these authors. The experimental data evidenced a general agreement with the kinetic model, although higher initial degradation rates were found withA. saperdae depolymerase.     

Biosorption potential and kinetic studies of vegetable waste mixture for the removal of Nickel(II)

Biosorption potential of new low cost biosorbent prepared from vegetable waste, composed of 1:1 mixture of potato and carrot peels for the removal of Ni(II) from aqueous solution was determined. The residual metallic ion concentrations were determined using an atomic absorption spectrophotometric technique (AAS). Batch experiments were conducted to optimize parameters such as initial pH, temperature, contact time, initial metal ion concentration and biosorbent dose and the results showed that maximum adsorption of Nickel (79.32 %) occurs when the contents were stirred for 75 min with 3.0 g of biosorbent at 35 °C and pH 4. Kinetic studies of the reaction revealed that it follows a pseudo-second order reaction. The experimental results were analyzed in terms of Langmuir and Freundlich isotherms. The Langmuir isotherm model fits well to data of Ni(II) biosorption by the prepared biomass as compared to the model of Freundlich. Both neat and Ni loaded biosorbent samples were analyzed by AAS using a dry ashing process in a furnace and also by use of a FT-IR spectrophotometer and an X-Ray florescence spectrometer in order to confirm the biosorption of Ni(II) and the results have revealed that a significant amount of Ni is present in the spent biosorbent.     

Thermal Stabilization of Recycled PET Through Chain Extension and Blending with PBT

This study investigates the effect of using a multifunctional epoxide chain extender (Joncryl^® ADR 4468) on the thermal stabilization and rheological properties of recycled polyethylene terephthalate (R-PET) and its blends with polybutylene terephthalate (PBT). The R-PET samples were prepared without and with chain extender (CE) contents of 0.4 wt% and 0.8 wt%. R-PET/PBT blends with weight ratios of 75w/25w, 50w/50w and 25w/75w were also prepared without and with a given CE content of 0.2 wt%. The thermal stability of the melt blended samples was analyzed through small amplitude oscillatory shear (SAOS) rheological experiments. The structure of the samples was evaluated using a Fourier transform infrared (FTIR) spectrometer. While the dynamic rheological properties of R-PET were improved with the addition of Joncryl and by blending with PBT, during the SAOS rheological experiments, the complex viscosity of R-PET further increased due to the concurrent polycondensation of R-PET and the resumption of Joncryl reaction with R-PET molecules. These reactions during the rheological experiments were further expedited with increasing the testing temperature. On the other hand, in R-PET/PBT blends, the reactivity of Joncryl was more noticeable in blends with higher R-PET contents due to the higher available internal reactive sites of much shorter R-PET molecules. It was observed that the addition of only 0.2 wt% Joncryl to the blends of R-PET/PBT (75w/25w) dramatically improves the thermal stability and dynamic rheological properties of R-PET and most likely its processability.

     

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160?°C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (T_g) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.