Carboxymethyl Starch Films as Enteric Coatings: Processing and Mechanistic Insights.

This study proposes the application of carboxymethyl starch derivatives as tablet coatings affording gastro-protection. Carboxymethyl starch (CMS) films were obtained by casting of aqueous filmogenic starch solutions with or without plasticizers and their structural organization was followed using Fourier transform infrared (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD). Together with data from mechanical tests (tensile strength, elongation, Young's modulus) the results were used to select filmogenic formulations adapted for coatings of tablets. The behaviour of these films was evaluated in simulated gastric and intestinal fluids. The effect of plasticizers (glycerol and sorbitol) on the starch organization, on the rate of drying of the films and on the water vapor absorption was also analyzed. Various types of starch have been compared and the best results were found with high amylose starch (HAS) that was carboxymethylated in an aqueous phase to obtain carboxymethyl high amylose starch (CMHAS). The CMHAS coating solutions containing sorbitol or glycerol as plasticizers have been applied with an industrial pan coater and the final tablets exhibited a good gastro-resistance (up to 2h) in simulated gastric fluid followed by disintegration in simulated intestinal fluid (SIF). The CMHAS derivatives present a high potential as coatings for nutraceutical and pharmaceutical solid dosage forms.

Anionic and Ampholytic High-Amylose Starch Derivatives as Excipients for Pharmaceutical and Biopharmaceutical Applications: Structure-Properties Correlations.

Many chemical modifications of starch are realized in organic (mostly methanol) phase, allowing high degrees of substitution (DS). Some of these materials are used as disintegrants. To expand the usage of starch derivative biopolymers as drug delivery system, various starch derivatives obtained in aqueous phase were evaluated with the aim to identify materials and procedures which would generate multifunctional excipients providing gastro-protection for controlled drug delivery. Chemical, structural and thermal characteristics of anionic and ampholytic High Amylose Starch (HAS) derivatives under powder (P), tablet (T) and film (F) forms were evaluated by X-ray Diffraction (XRD), Fourier Transformed Infrared (FTIR) and thermogravimetric analysis (TGA) methods and correlated with the behavior of tablets and films in simulated gastric and intestinal media. At low DS, the HAS carboxymethylation (CMHAS) in aqueous phase, generated tablets and films that were insoluble at ambient conditions. The CMHAS filmogenic solutions, with a lower viscosity, were easier to cast and gave smooth films without the use of plasticizer. Correlations were found between structural parameters and the properties of starch excipients. Compared to other starch modification procedures, the aqueous modification of HAS generated tunable multifunctional excipients that may be recommended for tablets and functional coatings for colon-targeted formulations.

Synthesis of Metal-Loaded Carboxylated Biopolymers with Antibacterial Activity through Metal Subnanoparticle Incorporation.

Carboxymethyl starch (CMS) and carboxymethyl cellulose (CMC) loaded by highly dispersed metal subnanoparticles (MSNPs) showed antibacterial activity against E. coli and B. subtilis strains. Copper and silver were found to act in both cationic and zero-valence forms. The antibacterial activity depends on the metal species content but only up to a certain level. Silver cation (Ag+) showed higher antibacterial activity as compared to Ag0, which was, however, more effective than Cu0, due to weaker retention. The number of carboxyl groups of the biopolymers was found to govern the material dispersion in aqueous media, the metal retention strength and dispersion in the host-matrices. Cation and metal retention in both biopolymers was found to involve interactions with the oxygen atoms of both hydroxyl and carboxyl groups. There exists a ternary interdependence between the Zeta potential (ZP), pH induced by the biocidal agent and its particle size (PS). This interdependence is a key factor in the exchange processes with the surrounding species, including bacteria. Clay mineral incorporation was found to mitigate material dispersion, due to detrimental competitive clay:polymer interaction. This knowledge advancement opens promising prospects for manufacturing metal-loaded materials for biomedical applications.

In vivo evaluation of targeted delivery of biological agents using barium sulfate.

This study was aimed to monitor the transit through the intestine by X-ray imaging using barium sulfate (BS) as tracer. The in vitro features of monolithic tablets were correlated with their in vivo behavior in order to provide a tool for the development of targeted formulations containing macromolecular bioactive agents. The impact of BS on various matrices (neutral, ionic) was studied in simulated fluids using the disintegration time (DT) as main parameter. Dry tablets were characterized by spectroscopic methods (X-ray diffraction and Infra-Red) and scanning electron microscopy (SEM). The selected formulations were followed in a beagle dog model. The in vivo and in vitro DT of tablets formulated with BS were compared. Results: anionic excipients carboxymethylcellulose (CMC) and carboxymethylstarch (CMS) protected the active ingredient from the gastric acidity, ensuring its targeted delivery in the intestine. The SEM analysis, before and after transit in simulated fluids, showed that BS remained in the tablets allowing their good follow-up in vivo. The incorporation of 30% protein in tablets with 40% BS had no impact on their behavior. In conclusion, BS and X-ray imagery could be a good alternative to scintigraphy for development of targeted formulations containing high molecular weight bioactive agents.

Effect of ozonation on anaerobic digestion sludge activity and viability.

The effect of ozonation of anaerobic digested sludge on methane production was studied as a means of increasing the capacity of municipal anaerobic digesters. Ozone doses ranging from 0 to 192 mg O3/g sludge COD were evaluated in batch tests with a bench scale ozonation unit. Ozonation initially, and temporarily, reduced biomass viability and acetoclastic methanogenic activity, resulting in an initial lag phase ranging from 0.8 to 10 days. Following this lag phase, ozonation enhanced methane production with an optimal methane yield attained at 86 mg O3/g COD. Under these conditions, the yield of methane and the rate of its formation were 52% and 95% higher, respectively, than those factors measured without ozonation. A required optimal ozone dose could be feasible to improve the anaerobic digestion performance by increasing the methane production potential with a minimum impact on microbial activity; thus, an optimal ozone dose would enable an increase in the capacity of anaerobic digesters.

Activated Sludge Production Parameters and Nutrient Content of Organic Sludge Components.

An important part of biological treatment system design is quantifying the sludge production and the nutrient removal capacity. Influent wastewater COD fractionation, biomass growth and endogenous respiration directly impacts the composition of the mixed liquor solids in activated sludge systems. The objectives of this project were to determine the model kinetic and stoichiometric parameters associated with activated sludge production and the nutrient content (N and P) of unbiodegradable organic matter components. A complete sludge retention experiment was conducted over 70 days in a pilot-scale membrane bioreactor fed with a real municipal wastewater, and operated with alternating growth and famine periods. Experimental results were simulated and compared using the default values from two well-accepted model parameter sets. The General ASDM parameter set was found to better fit the experimental data than the Metcalf and Eddy parameter set, mainly to characterize endogenous respiration and the heterotrophic biomass concentration. An influent unbiodegradable organic particulate fraction (fXU,Inf) value of 0.16 g COD/g COD was determined by calibration of the accumulated sludge total COD, suspended solids and heterotrophic biomass concentrations. The nutrient content of the accumulated endogenous residue (XE) and influent unbiodegradable organic particulate (XU,Inf) components were calibrated to 0.030 and 0.100 g N/g COD and 0.035 and 0.008 g P/g COD, respectively. These values are in the range of those reported in the literature except for the high P content found in the endogenous residue, possibly due to the presence of coagulants added for P removal in the accumulated sludge. These results were consistent under the wide range of dynamic conditions tested and could improve model prediction of sludge production and composition.

Compact secondary treatment train combining a lab-scale moving bed biofilm reactor and enhanced flotation processes.

High-rate wastewater processes are receiving a renewed interest to obtain energy positive/efficient water resource recovery facilities. An innovative treatment train combining a high-rate moving bed biofilm reactor (HR-MBBR) with an enhanced flotation process was studied. The two objectives of this work were 1) to maximize the conversion of soluble organics to particulate matter in an HR-MBBR and 2) to maximize the particulate matter recovery from the HR-MBBR effluent by green chemicals to enhance biogas production by anaerobic digestion. To achieve these objectives, lab-scale MBBRs fed with synthetic soluble wastewater were operated at organic loading rates (OLRs) between 4 and 34 kg COD m-3 reactor d-1 corresponding to hydraulic retention times (HRTs) between 6 and 54 min. Colloidal and soluble chemical oxygen demand (COD) removal efficiency in the HR-MBBR increased with HRT to reach a plateau of 85% at an HRT longer than 27 min. Carrier clogging observed at an OLR higher than 16 kg COD m-3 d-1 (HRT < 13 min) resulted in about 23% loss in colloidal and soluble COD removal efficiency. Thus, the recommended parameters were between 22 and 37 min and between 6 and 10 kg COD m-3 d-1 for the HRT and the OLR, respectively, to maximize the conversion of soluble organics to particulate matter. Total suspended solids (TSS) recovery of 58-85% and 90-97% were achieved by enhanced flotation using green and unbiodegradable chemicals, respectively, corresponding to a TSS effluent concentration below 14 and 7 mg TSS/L. Among the synthetic polymers tested, a high molecular weight and low charge density cationic polyacrylamide was found to give the best results with less than 2 mg TSS/L in the clarified effluent (97% TSS recovery). Green chemicals, although performing slightly less for solids separation than unbiodegradable chemicals, achieved a mean TSS concentration of 10 ± 3 mg/L in the clarified effluent.

Mechanisms for Reduced Excess Sludge Production in the Cannibal Process.

Reducing excess sludge production is increasingly attractive as a result of rising costs and constraints with respect to sludge treatment and disposal. A technology in which the mechanisms remain not well understood is the Cannibal process, for which very low sludge yields have been reported. The objective of this work was to use modeling as a means to characterize excess sludge production at a full-scale Cannibal facility by providing a long sludge retention time and removing trash and grit by physical processes. The facility was characterized by using its historical data, from discussion with the staff and by conducting a sampling campaign to prepare a solids inventory and an overall mass balance. At the evaluated sludge retention time of 400 days, the sum of the daily loss of suspended solids to the effluent and of the waste activated sludge solids contributed approximately equally to the sum of solids that are wasted daily as trash and grit from the solids separation module. The overall sludge production was estimated to be 0.14 g total suspended solids produced/g chemical oxygen demand removed. The essential functions of the Cannibal process for the reduction of sludge production appear to be to remove trash and grit from the sludge by physical processes of microscreening and hydrocycloning, respectively, and to provide a long sludge retention time, which allows the slow degradation of the "unbiodegradable" influent particulate organics (XU,Inf) and the endogenous residue (XE). The high energy demand of 1.6 kWh/m³ of treated wastewater at the studied facility limits the niche of the Cannibal process to small- to medium-sized facilities in which sludge disposal costs are high but electricity costs are low.

Modelling the degradation of endogenous residue and 'unbiodegradable' influent organic suspended solids to predict sludge production.

Activated sludge models have assumed that a portion of organic solids in municipal wastewater influent is unbiodegradable. Also, it is assumed that solids from biomass decay cannot be degraded further. The paper evaluates these assumptions based on data from systems operating at higher than typical sludge retention times (SRTs), including membrane bioreactor systems with total solids retention (no intentional sludge wastage). Data from over 30 references and with SRTs of up to 400 d were analysed. A modified model that considers the possible degradation of the two components is proposed. First order degradation rates of approximately 0.007 d(-1) for both components appear to improve sludge production estimates. Factors possibly influencing these degradation rates such as wastewater characteristics and bioavailability are discussed.

Seawater denitrification in a closed mesocosm by a submerged moving bed biofilm reactor.

The performance of a submerged moving bed biofilm reactor (MBBR) for the denitrification of seawater in a 3.25 million closed circuit mesocosm was investigated at pilot scale, using methanol as a carbon source at various C/N ratios. Nitrate accumulation in closed systems where water changes are expensive and problematic may cause toxicity problems to marine life. Seawater was pretreated in a recirculated fixed bed to remove oxygen prior to the denitrification step. The 110l MBBR was partly filled (25%) with spherical positively buoyant polyethylene carriers with an effective surface area of approximately 100 m2 m(-3), which represents 35% of the total surface area. Carriers were maintained submerged by a conical grid and circulated by the downflow jet of an eductor. The MBBR mixing system was designed to prevent dead mixing zones and carrier fouling to avoid sulfate reduction while treating seawater containing as high as 2150 mg SO4-Sl(-1). NO3-N reduction from 53 to as low as 1.7+/-0.7 mg l(-1) and a maximum denitrification rate of 17.7+/-1.4 g Nm(-2) d(-1) were achieved at 4.2-4.3 applied COD/N (w/w) ratio. Methanol consumption corresponded to denitrification stoichiometric values, indicating the absence of sulfate reduction. Denitrification rates and effluent residual dissolved organic carbon were proportional to the C/N ratio. Such reactors could be scaled up in closed systems where water changes must be minimized.