Effect of Hydration Forms and Polymer Grades on Theophylline Controlled-Release Tablet: An Assessment and Evaluation.

BACKGROUND: Drug release from controlled release delivery systems is influenced by various factors, including the polymer's grade and the drug's hydration form. This study aimed to investigate the impact of these factors on the controlled release of theophylline (THN). This research compares the monohydrate form found in branded products with the anhydrous form in generic equivalents, each formulated with different polymer grades. METHODS: Quality control assessment was conducted alongside in vitro evaluation, complemented by various analytical techniques such as X-ray diffraction (XRD) and scanning electron microscopy (SEM). Additionally, thermal analyses using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed. RESULTS: Quality control assessments demonstrated that the generic tablets exhibited lower average weight and resistance force compared to the branded ones. In vitro tests revealed that generic tablets released contents within 120 min, compared to 720 min for the branded counterpart. Characterization using XRD and SEM identified disparities in crystallinity and particle distribution between the three samples. Additionally, the thermal analysis indicated consistent endothermic peaks across all samples, albeit with minor variations in heat flow and decomposition temperatures between the two products. CONCLUSIONS: This study demonstrated that variations in polymer grade and hydration form significantly impact THN release.

Predicting the Decomposition Mechanism of the Serine α-Amino Acid in the Gas Phase and Condensed Media.

Comprehending the nitrogen combustion chemistry during the thermal treatment of biomass demands acquiring a detailed mechanism for reaction pathways that dictate the degradation of amino acids. Serine (Ser) is an important α-amino acid that invariably exists in various categories of biomass, most notably algae. Based on density functional theory (DFT) coupled with kinetic modeling, this study presents a mechanistic overview of reactions that govern the fragmentation of the Ser compound in the gas phase as well as in the crystalline form. Thermokinetic parameters are computed for a large set of reactions and involved species. The initial decomposition of Ser is solely controlled by a dehydration channel that leads to the formation of a 2-aminoacrylic acid molecule. Decarboxylation and deamination routes are likely to be of negligible importance. The falloff window of the dehydration channel extends until the atmospheric pressure. Bimolecular reactions between two Ser compounds simulate the widely discussed cross-linking reactions that prevail in the condensed medium. It is demonstrated that the formation of the key experimentally observed products (NH3, CO2, and CO) may originate from direct bond fissions in the melted phase of Ser prior to evaporation. A constructed kinetic model (with 24 reactions) accounts for the primary steps in the degradation of the Ser molecule in the gas phase. These steps include dehydration, decarboxylation, deamination, and others. The kinetic model presents an onset decomposition temperature of 700 K with the complete conversion attained at ∼1090 K. Likewise, the model portrays the temperature-dependent increasing yields of CO2 and NH3. The results presented in this work offer a detailed analysis of the intricate chemical processes involved in nitrogen transformations, specifically in relation to amino acids. Amino acids play a crucial role as the primary nitrogen carriers in biomass, such as microalgae and protein-rich biomass.

Debromination of novel brominated flame retardants using Zn-based additives: A viable thermochemical approach in the mitigation of toxic effects during e-waste recycling.

Brominated flame retardants (BFRs) are bromine-bearing additives added to the polymeric fraction in various applications to impede fire ignition. The Stockholm Convention and various other legislations abolished legacy BFRs usage and hence, the so-called novel BFRs (NBFRs) were introduced into the market. Recent studies spotlighted their existence in household dust, aquifers and aquatic/aerial species. Co-pyrolysis of BFRs with metal oxides has emerged as a potent chemical recycling approach that produces a bromine-free stream of hydrocarbon. Herein, we investigate the debromination of two prominent two NBFRs; namely tetrabromobisphenol A 2,3-dibromopropyl ether (TD) and tetrabromobisphenol A diallyl ether (TAE) through their co-pyrolysis with zinc oxide (ZnO) and franklinite (ZnFe2O4). Most of the zinc content in electrical arc furnace dust (EAFD) exists in the form of these two metal oxides. Conversion of these metal oxides into their respective bromides could also assist in the selective extraction of the valuable zinc content in EAFD. The debromination potential of both oxides was unveiled via a multitude of characterization studies to analyze products (char, gas and condensates). The thermogravimetric analysis suggested a pyrolytic run up to 500 °C and the TAE treatment with ZnO produced only a trivial amount of brominated compounds (relative area, 0.83%). Phenol was the sole common compound in condensable products; potentially formed by the ß-scission debromination reaction from the parental molecular skeleton. Inorganic compounds and methane were the major constituents in the gaseous products. The pyrochar analyses confirmed the presence of metal bromides retained in the residue, averting the bromine release into the atmosphere. The ion chromatography analysis portrayed <8% of HBr gas release into the atmosphere upon pyrolysis with ZnO. The ZnO dominance herein envisaged further probes into other spinel ferrites in combating brominated polymers.

Prediction of Thermogravimetric Data in the Thermal Recycling of e-waste Using Machine Learning Techniques: A Data-driven Approach.

The release of bromine-free hydrocarbons and gases is a major challenge faced in the thermal recycling of e-waste due to the corrosive effects of produced HBr. Metal oxides such as Fe2O3 (hematite) are excellent debrominating agents, and they are copyrolyzed along with tetrabromophenol (TBP), a lesser used brominated flame retardant that is a constituent of printed circuit boards in electronic equipment. The pyrolytic (N2) and oxidative (O2) decomposition of TBP with Fe2O3 has been previously investigated with thermogravimetric analysis (TGA) at four different heating rates of 5, 10, 15, and 20 °C/min, and the mass loss data between room temperature and 800 °C were reported. The objective of our paper is to study the effectiveness of machine learning (ML) techniques to reproduce these TGA data so that the use of the instrument can be eliminated to enhance the potential of online monitoring of copyrolysis in e-waste treatment. This will reduce experimental and human errors as well as improve process time significantly. TGA data are both nonlinear and multidimensional, and hence, nonlinear regression techniques such as random forest (RF) and gradient boosting regression (GBR) showed the highest prediction accuracies of 0.999 and lowest prediction errors among all the ML models employed in this work. The large data sets allowed us to explore three different scenarios of model training and validation, where the number of training samples were varied from 10,000 to 40,000 for both TBP and TBP + hematite samples under N2 (pyrolysis) and O2 (combustion) environments. The novelty of our study is that ML techniques have not been employed for the copyrolysis of these compounds, while the significance is the excellent potential of enhanced online monitoring of e-waste treatment and extension to other characterization techniques such as spectroscopy and chromatography. Lastly, e-waste recycling could greatly benefit from ML applications since it has the potential to reduce total and operational costs and improve overall process time and efficiency, thereby encouraging more treatment plants to adopt these techniques, resulting in reducing the increasing environmental footprint of e-waste.

Combating toxic emissions from thermal recycling of polymeric fractions laden with novel brominated flame retardants (NBFRs) in e-waste: an in-situ approach using Ca(OH)2.

Legacy brominated flame retardants (BFRs) in printed circuit boards are gradually being replaced by novel BFRs (NBFRs). Safe disposal and recycling of polymeric constituents in the polymeric fractions of e-waste necessitate the removal of their toxic and corrosive bromine content. This is currently acquired through thermal recycling operations involving the pyrolysis of BFRs-containing materials with metal oxides. Nonetheless, the debromination capacity toward NBFRs is yet to be established. Thus, this study aims to address these two crucial gaps in the current knowledge pertaining to the plausible formation of brominated toxicants from the thermal decomposition of NBFRs and their thermal recycling potential. Herein, we investigate the pyrolysis of a mixture of 2,4,6-tribromophenol (TBP), allyl 2,4,6-tribromophenyl ether (ATE) and Tetrabromobisphenol A-bis (2,3-dibromo propyl ether) (TBBPA-DBPE) in the presence of acrylonitrile butadiene styrene (ABS) polymers at various loads. To demonstrate a viable debromination route, pyrolysis of NBFRs-ABS mixture with Ca(OH)2 was also investigated. The latter is a potent debromination agent for legacy BFRs. Upon pyrolysis with Ca(OH)2, the bromine content in the collected oil was reduced up to 80.49% between 25-500 °C. Products of the co-pyrolysis process generally feature non-brominated aromatic and aliphatic compounds; a finding that indicates an effective thermal recycling approach. As evident by IC measurements, no HBr emission could be detected when Ca(OH)2 is added to the mixture. As XRD patterns show, Ca(OH)2 is partially converted into CaBr2. DFT calculations provide pathways for the observed surface debromination characterized by surface-assisted fission of aromatic C-Br bonds and the formation of CaBr sites. Outcomes reported herein are instrumental to designing and operating a thermal recycling facility of polymeric materials contaminated with high loads of bromine, i.e., most notably during scenarios encountered in the thermal recycling of e-waste.

Mechanochemical debromination of allyl 2,4,6-tribromophenyl ether (TBP-AE): optimization of the operational conditions.

Allyl 2,4,6-tribromophenyl ether (TBP-AE) is a flame retardant that is added to plastics to improve their fire resistance. This kind of additive is hazardous to both human health and the environment. As any other BFRs, TBP-AE resists photo-degradation in the environment and hence materials laden with TBP-AE are to be dibrominated to avoid environmental pollution. Mechanochemical degradation of TBP-AE is a promising approach with potential industrial applications since it does not require high temperatures nor it generates any secondary pollutants. A planetary ball milling simulation experiment was designed to study TBP-AE's mechanochemical debromination. To report products from the mechanochemical process, a variety of characterization techniques were used. The characterization methods included gas chromatography-mass spectrometry (GC-MS), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX). The effects of various co-milling reagent types, co-milling reagent concentrations with raw material, time, and revolution speed on mechanochemical debromination efficiency have been thoroughly investigated. The Fe/Al2O3 mixture entails the highest debromination efficiency of 23%. However, when using a Fe/Al2O3 mixture, neither the reagent concentration nor the revolution speed influenced the debromination efficiency. In case of using only Al2O3, the next viable reagent, it was revealed that while increasing the revolution, speed improved debromination efficiency to a certain point, and increasing it any further left the debromination efficiency unchanged. In addition, the results showed that an equal mass ratio of TBP-AE to Al2O3 promoted degradation more than an increase in the ratio of Al2O3 to TBP-AE. The addition of ABS polymer largely inhibits the reaction between Al2O3 and TBP-AE, which hindered alumina's ability to capture organic bromine, causing a significant decrease in the debromination efficiency when model of waste printed circuit board (WPCB) is considered.

Prediction of Thermogravimetric Data in Bromine Captured from Brominated Flame Retardants (BFRs) in e-Waste Treatment Using Machine Learning Approaches.

The principal objective in the treatment of e-waste is to capture the bromine released from the brominated flame retardants (BFRs) added to the polymeric constituents of printed circuits boards (PCBs) and to produce pure bromine-free hydrocarbons. Metal oxides such as calcium hydroxide (Ca(OH)2) have been shown to exhibit high debromination capacity when added to BFRs in e-waste and capturing the released HBr. Tetrabromobisphenol A (TBBA) is the most commonly utilized model compound as a representative for BFRs. Our coauthors had previously studied the pyrolytic and oxidative decomposition of the TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C/min, using a thermogravimetric (TGA) analyzer and reported the mass loss data between room temperature and 800 °C. However, in the current work, we applied different machine learning (ML) and chemometric techniques involving regression models to predict the TGA data at different heating rates. The motivation of this work was to reproduce the TGA data with high accuracy in order to eliminate the physical need of the instrument itself, so that this could save significant experimental time involving sample preparation and subsequently minimizing human errors. The novelty of our work lies in the application of ML techniques to predict the TGA data from e-waste pyrolysis since this has not been conducted previously. The significance of our work lies in the fact that e-waste is ever increasing, and predicting the mass loss curves faster will enable better compositional analysis of the e-waste samples in the industry. Three ML models were employed in our work, namely Linear, random forest (RF), and support vector regression (SVR), out of which the RF method exhibited the highest coefficient of determination (R2) of 0.999 and least error of prediction as estimated by the root mean squared error (RMSEP) at all 4 heating rates for both pyrolysis and oxidation conditions. An 80:20 split was used for calibration and validation data sets. Furthermore, for showing versatility and robustness of the best-predicting RF model, it was also trained using all the data points in the lower heating rates of 5 and 10 °C/min and predicted on all the data points for the higher heating rates of 15 and 20 °C/min to again obtain a high R2 of 0.999. The excellent performance of the RF model showed that ML techniques can be used to eliminate the physical use of TGA equipment, thus saving experimental time and potential human errors, and can further be applied in other real-time e-waste recycling scenarios.

Degradation of tetrabromobisphenol A (TBBA) with calcium hydroxide: a thermo-kinetic analysis.

Thermal treatment of bromine-contaminated polymers (i.e., as in e-waste) with metal oxides is currently deployed as a mainstream strategy in recycling and resources recovery from these objects. The underlying aim is to capture the bromine content and to produce pure bromine-free hydrocarbons. Bromine originates from the added brominated flame retardants (BFRs) to the polymeric fractions in printed circuits boards, where tetrabromobisphenol A (TBBA) is the most utilized BFR. Among notable deployed metal oxides is calcium hydroxide, i.e., Ca(OH)2 that often displays high debromination capacity. Comprehending thermo-kinetic parameters that account for the BFRs:Ca(OH)2 interaction is instrumental to optimize the operation at an industrial scale. Herein, we report comprehensive kinetics and thermodynamics studies into the pyrolytic and oxidative decomposition of a TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C min-1, carried out using a thermogravimetric analyser. Fourier Transform Infrared Spectroscopy (FTIR) and a carbon, hydrogen, nitrogen, and sulphur (CHNS) elemental analyser established the vibrations of the molecules and carbon content of the sample. From the thermogravimetric analyser (TGA) data, the kinetic and thermodynamic parameters were evaluated using iso-conversional methods (KAS, FWO, and Starink), which were further validated by the Coats-Redfern method. The computed activation energies for the pyrolytic decomposition of pure TBBA and its mixture with Ca(OH)2 reside in the narrow ranges of 111.7-112.1 kJ mol-1 and 62.8-63.4 kJ mol-1, respectively (considering the various models). Obtained negative ΔS values suggest the formation of stable products. The synergic effects of the blend exhibited positive values in the low-temperature ranges (200-300 °C) due to the emission of HBr from TBBA and the solid-liquid bromination process occurring between TBBA and Ca(OH)2. From a practical point of view, data provided herein are useful in efforts that aim to fine-tune operational conditions encountered in real recycling scenarios, i.e., in co-pyrolysis of e-waste with Ca(OH)2 in rotary kilns.

Oxidative and pyrolytic decomposition of an evaporated stream of 2,4,6-tribromophenol over hematite: A prevailing scenario during thermal recycling of e-waste.

Brominated flame retardants (BFRs) constitute a major load in the polymeric fraction of e-waste. Degradation of BFRs-laden plastics over transition metal oxides is currently deployed as a mainstream strategy in the disposal and treatment of the non-metallic segment of e-waste. However, interaction of pyrolysis's products of BFRs with transition metal oxides is well-known to facilitate the formation of notorious pollutants. Despite recent progress to comprehend the germane chemistry of this interaction, several important pertinent aspects remain to be addressed. To fill in this gap, an integrated experimental and simulation account of the pyrolytic and oxidative decomposition of a gaseous stream of 2,4,6-tribromophenol (TBP) over hematite (Fe2O3) has been reported herein. TBP is utilized as a model compounds of BFRs as their most common formulations include brominated phenolic rings. Overall, hematite entails a rather low cracking capacity under pyrolytic conditions. Analysis of condensate products indicates that oxidative degradation of a gaseous stream of TBP results mainly in the formation of brominated alkanes such as bromoethane and bromo-pentane. Likewise, Ion chromatography (IC) measurements disclosed a noticeable reduction in the concentrations of escaped HBr. Transformation of iron oxides into iron bromides (possibly in the form of FeBr2) during pyrolysis and combustion operations is evident through XRD measurements. Density functional theory (DFT) calculations map out important reactions pathways that operate in the initial degradation of the TBP molecule. From a broader perspective, outlined results shall be instrumental to precisely assess the effectiveness of using iron oxides in thermal catalytic recycling of e-waste and the likely emission of brominated toxicants.

Removal of Bromine from the non-metallic fraction in printed circuit board via its Co-pyrolysis with alumina.

The effectiveness of a recycling approach of the printed circuit board (PCBs), and, thus, the quality of polymeric constituents, primarily rests on the capacity to eliminate the bromine content (mainly as HBr). HBr is emitted in appreciable quantities during thermal decomposition of PCB-contained brominated flame retardants (BFRs). The highly corrosive, yet relatively reactive HBr, renders recovery of bromine-free hydrocarbons streams from brominated polymers in PCBs very challenging. Via combined experimental and theoretical frameworks, this study explores the potential of deploying alumina (Al2O3) as a debromination agent of Br-containing hydrocarbon fractions in PCBs. A consensus from a wide array of characterization techniques utilized herein (ICP-OES, IC, XRD, FTIR, SEM-EDX, and TGA) clearly demonstrates the transformation of alumina upon its co-pyrolysis with the non-metallic fractions of PCBs, into aluminum bromides and oxy-bromides. ICP-OES measurements disclose the presence of high concentration of Cu in the non-metallic fraction of PCB, along with minor levels of selected valuable metals. Likewise, elemental ionic analysis by IC demonstrates an elevated concentration of bromine in washed alumina-PCBs pyrolysates, especially at 500 °C. The Coats-Redfern model facilitates the derivation of thermo-kinetic parameters underpinning the thermal degradation of alumina-PCB mixtures. Density functional theory calculations (DFT) establish an accessible reaction pathway for the HBr uptake by the alumina surface, thus elucidating chemical reactions governing the observed alumina debromination activity. Findings from this study illustrate the capacity of alumina as a HBr fixation agent during the thermal treatment of e-waste.