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Chemical Science Jun 2024Full dechlorination of poly(vinyl chloride) (PVC) in a controlled manner to yield useful polymeric and chlorinated products is of great interest for the processing of...
Full dechlorination of poly(vinyl chloride) (PVC) in a controlled manner to yield useful polymeric and chlorinated products is of great interest for the processing of PVC waste. Forming polyethylene (PE) without corrosive by-products would allow for a pre-treatment of PE wastes that are often contaminated with PVC. Herein, full dechlorination of PVC has been achieved generation of silylium ions , to furnish PE products. Complete dechlorination of PVC can be achieved in 2 hours, yielding organic polymer that has similar spectroscopic and thermal signatures of branched PE, with no observable chlorine. The degree of branching can be tuned between 31 and 57 branches per 1000 carbons, with melting temperatures ranging from 51 to 93 °C. This method is applicable to not only pure PVC, but also commercial PVC products. Depending on if the PVC products are separated from plasticizers, different melting points of the resulting PE are observed. PVC dechlorination in the presence of PE waste is also shown. This is the first report of being able to cleanly convert PVC waste to PE in high yields and tune the thermal properties of the PE product, highlighting the remarkable control that silylium ion mediated transformations enables compared to past chemical methods.
PubMed: 38873082
DOI: 10.1039/d4sc00130c -
The ISME Journal Jan 2024Isolate studies have been a cornerstone for unraveling metabolic pathways and phenotypical (functional) features. Biogeochemical processes in natural and engineered...
Isolate studies have been a cornerstone for unraveling metabolic pathways and phenotypical (functional) features. Biogeochemical processes in natural and engineered ecosystems are generally performed by more than a single microbe and often rely on mutualistic interactions. We demonstrate the rational bottom-up design of synthetic, interdependent co-cultures to achieve concomitant utilization of chlorinated methanes as electron donors and organohalogens as electron acceptors. Specialized anaerobes conserve energy from the catabolic conversion of chloromethane or dichloromethane to formate, H2, and acetate, compounds that the organohalide-respiring bacterium Dehalogenimonas etheniformans strain GP requires to utilize cis-1,2-dichloroethenene and vinyl chloride as electron acceptors. Organism-specific qPCR enumeration matched the growth of individual dechlorinators to the respective functional (i.e. dechlorination) traits. The metabolite cross-feeding in the synthetic (co-)cultures enables concomitant utilization of chlorinated methanes (i.e. chloromethane and dichloromethane) and chlorinated ethenes (i.e. cis-1,2-dichloroethenene and vinyl chloride) without the addition of an external electron donor (i.e. formate and H2). The findings illustrate that naturally occurring chlorinated C1 compounds can sustain anaerobic food webs, an observation with implications for the development of interdependent, mutualistic communities, the sustenance of microbial life in oligotrophic and energy-deprived environments, and the fate of chloromethane/dichloromethane and chlorinated electron acceptors (e.g. chlorinated ethenes) in pristine environments and commingled contaminant plumes.
Topics: Coculture Techniques; Hydrocarbons, Chlorinated; Methane; Chloroflexi; Halogenation; Metabolic Networks and Pathways; Dichloroethylenes; Anaerobiosis
PubMed: 38818735
DOI: 10.1093/ismejo/wrae090 -
Analytical and Bioanalytical Chemistry Jul 2024An environmentally conscious methodology is investigated for the precise and discerning identification of trace concentrations of gold ions in diverse matrices. A novel...
Eco-friendly optical sensor for precise detection of gold ions in diverse matrices through the integration of β-2-hydroxybenzyl-3-methoxy-2-hydroxyazastyrene in a PVC membrane.
An environmentally conscious methodology is investigated for the precise and discerning identification of trace concentrations of gold ions in diverse matrices. A novel optical sensor membrane is proposed for the determination of Au ions, utilizing the immobilization of β-2-hydroxybenzyl-3-methoxy-2-hydroxyazastyrene (HMHS) entrapped in polyvinyl chloride (PVC). The sensor incorporates sodium tetraphenylborate (Na-TPB) as the ionic additive and dibutyl phthalate (DBP) as a plasticizer. Under optimal conditions, the suggested sensor exhibits a linear calibration response to Au ions within a concentration range of 5.0 to 165 ng mL. Detection and quantification limits are specified as 1.5 and 4.8 ng mL, respectively, with a rapid response time of 5.0 min. Upon presentation, this optical sensor not only affirms high reproducibility, stability, and an extended operational lifespan but also showcases exceptional selectivity for Au ions. Notably, no discernible interference is observed when assessing the potential influence of other cations and anions on Au ion detection. The adaptability of this optical sensor is validated through its successful application in determining Au ion concentrations across various sample types, including water, environmental, cosmetics, and soil matrices.
PubMed: 38809460
DOI: 10.1007/s00216-024-05324-7 -
Polymers May 2024Dual networks formed by entangled polymer chains and wormlike surfactant micelles have attracted increasing interest in their application as thickeners in various fields...
Dual networks formed by entangled polymer chains and wormlike surfactant micelles have attracted increasing interest in their application as thickeners in various fields since they combine the advantages of both polymer- and surfactant-based fluids. In particular, such polymer-surfactant mixtures are of great interest as novel hydraulic fracturing fluids with enhanced properties. In this study, we demonstrated the effect of the chemical composition of an uncharged polymer poly(vinyl alcohol) (PVA) and pH on the rheological properties and structure of its mixtures with a cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride already exploited in fracturing operations. Using a combination of several complementary techniques (rheometry, cryo-transmission electron microscopy, small-angle neutron scattering, and nuclear magnetic resonance spectroscopy), we showed that a small number of residual acetate groups (2-12.7 mol%) in PVA could significantly reduce the viscosity of the mixed system. This result was attributed to the incorporation of acetate groups in the corona of the micellar aggregates, decreasing the molecular packing parameter and thereby inducing the shortening of worm-like micelles. When these groups are removed by hydrolysis at a pH higher than 7, viscosity increases by five orders of magnitude due to the growth of worm-like micelles in length. The findings of this study create pathways for the development of dual semi-interpenetrating polymer-micellar networks, which are highly desired by the petroleum industry.
PubMed: 38794623
DOI: 10.3390/polym16101430 -
Gels (Basel, Switzerland) May 2024In recent years, the quest to advance fuel cell technologies has intensified, driven by the imperative to reduce reliance on hydrocarbon-derived fuels and mitigate...
In recent years, the quest to advance fuel cell technologies has intensified, driven by the imperative to reduce reliance on hydrocarbon-derived fuels and mitigate pollutant emissions. Proton exchange membranes are a critical material of fuel cell technologies. The potential of ionic liquid-based polymer inclusion membranes or ionogels for proton exchange membrane fuel cells (PEMFCs) has recently appeared. Thermal stability, SEM-EDX characterization, NMR and IR characterization, thermogravimetric analysis, ion exchange capacity, and water uptake are key properties of these membranes which need to be investigated. In this work, ionogel based on quaternary ammonium salts, such as [N][Cl], [N][Br], and [N][Cl] in various compositions with poly(vinyl chloride) are extensively studied and characterized based on those key properties. The best properties were obtained when a quaternary ammonium cation was combined with a bromide anion. Finally, ionogels are tested in microbial fuel cells. Microbial fuel cells based on the ionogel reach a maximum of 147 mW/m, which represents 55% of the reference membrane (Nafion 212). These results indicate that we still have the possibility of improvement through the appropriate selection of the cation and anion of the ionic liquid. Overall, the promise of ionogel membranes as a viable alternative in fuel cell applications has been demonstrated.
PubMed: 38786225
DOI: 10.3390/gels10050308 -
The Science of the Total Environment Jun 2024Carbonaceous materials catalyze reductive dechlorination of chlorinated ethylenes (CEs) by iron(II) materials providing a new approach for the remediation of CE polluted...
Carbonaceous materials catalyze reductive dechlorination of chlorinated ethylenes (CEs) by iron(II) materials providing a new approach for the remediation of CE polluted groundwater. While most CEs are reduced via β-elimination, vinyl chloride (VC), the most toxic and recalcitrant CE, degrades by hydrogenolysis. The significance of carbon catalysts for reduction of VC is well documented for iron(0) systems, but hardly investigated with iron(II) materials as reductants. In this study, a layered iron(II)‑iron(III) hydroxide sulfate (green rust) was used as reductant for VC, with an N-doped graphene (NG), prepared by co-pyrolysis of graphene and urea, as catalyst. VC (80 μM) was completely reduced to ethylene within 336 h in the presence of 5 g Fe/L GR and 5 g/L NG pyrolyzed at 950 °C, following pseudo-first-order kinetics with a rate constant of 0.017 h. Dosing experiments demonstrated that dechlorination of VC takes place on the NG phase. Monitoring of hydrogen formation, cyclic voltammetry, and quenching experiments demonstrated that atomic hydrogen contributes significantly to the dehalogenation reaction, where NG is critical for formation of atomic hydrogen. CE competition experiments demonstrated the presence of specific VC reduction sites with hydrogenolysis being unaffected by concurrent β-elimination reactions. The system exhibited excellent performance in natural groundwaters and in comparison with iron(0) systems. This study demonstrates that GR + NG is a promising system for remediation of VC contaminated groundwater, and the mechanistic part of the study can be used as a reference for subsequent studies.
PubMed: 38692311
DOI: 10.1016/j.scitotenv.2024.172825 -
Chemical Science Apr 2024Poly(vinyl chloride) (PVC) is one of the highest production volume polymers due to its many applications, and it is one of the least recycled due to its chemical... (Review)
Review
Poly(vinyl chloride) (PVC) is one of the highest production volume polymers due to its many applications, and it is one of the least recycled due to its chemical structure and frequent formulation with additives. Developing efficient PVC recycling techniques would enable PVC waste to be reused or repurposed in other processes. Within this context, the literature on PVC modification offers considerable insight into versatile reaction pathways, potentially inspiring new approaches for repurposing PVC waste into value-added products. This perspective provides an overview of PVC functionalization through a lens of chemical recycling, discussing various PVC reactivity trends and their applications with a critical assessment and future outlook of their recycling implications.
PubMed: 38665509
DOI: 10.1039/d3sc06758k -
Heliyon Apr 2024In this work, magnetic molecularly imprinted polymers (MIPs) for specific recognition of Hydroxytyrosol (HT) were designed by vinyl-modified magnetic particles...
In this work, magnetic molecularly imprinted polymers (MIPs) for specific recognition of Hydroxytyrosol (HT) were designed by vinyl-modified magnetic particles (FeO@SiO@VTEOs) as carrier, ternary deep eutectic solvent (DES) as functional monomer, while ethylene glycol dimethacrylate (EGDMA) as crosslinker. The optimum amount of DES was obtained by adsorption experiments (molar ratio, caffeic acid: choline chloride: formic acid = 1:6:3) which were 140 μL in total. Under the optimized amount of DES, the maximum adsorption capacity of the MIPs particles was 42.43 mg g, which was superior to non-imprinted polymer (4.64 mg g) and the imprinting factor (IF) is 9.10. Syringin and Oleuropicrin were used as two reference molecules to test the selectivity of the DES-MIPs particles. The adsorption capacity of HT was 40.11 mg g. Three repeated experiments show that the polymer has high stability and repeatability (RSD = 5.50).
PubMed: 38655314
DOI: 10.1016/j.heliyon.2024.e28257 -
Molecules (Basel, Switzerland) Mar 2024To date, there has been limited information in the literature on the application of carbon fibre-carbon nanotube systems for the modification of poly(vinyl chloride)...
To date, there has been limited information in the literature on the application of carbon fibre-carbon nanotube systems for the modification of poly(vinyl chloride) (PVC) matrixes by micro- and nanometric fillers and an evaluation of the properties of the unique materials produced. This paper presents the results of newly designed unique multiscale composites. The advantages of the simultaneous use of carbon fibres (CFs) and carbon nanotubes (CNTs) in PVC modification are discussed. To increase the dispersibility of the nanofiller, CFs together with nanotubes were subjected to a sonication process. The resulting material was introduced into PVC blends, which were processed by extrusion. The ratio of components in the hybrid filler with CF_CNT was 20:1, and its proportion in the PVC matrix was 1, 5, and 10 wt.%, respectively. Comparatively, PVC composites modified only with carbon fibres were obtained. The structure, thermal, electrical, and mechanical properties and swelling resistance of the composites were studied. The study showed a favourable homogeneous dispersion of nanotubes in the PVC matrix. This enabled effective modification of the structure at the nanometric level and the formation of an interpenetrating network of well-dispersed hybrid filler, as evidenced by a decrease in volume resistivity and improvement in swelling resistance, as well as an increase in glass transition temperature in the case of PVC/CF_CNT composites.
PubMed: 38611759
DOI: 10.3390/molecules29071479 -
International Journal of Hygiene and... Jun 2024A growing literature has reported associations between traffic-related air pollution and breast cancer, however there are fewer investigations into specific ambient...
BACKGROUND
A growing literature has reported associations between traffic-related air pollution and breast cancer, however there are fewer investigations into specific ambient agents and any putative risk of breast cancer development, particularly studies occurring in populations residing in higher pollution areas such as Los Angeles.
OBJECTIVES
To estimate breast cancer risks related to ambient air toxics exposure at residential addresses.
METHODS
We examined the relationships between ambient air toxics and breast cancer risk in the Multiethnic Cohort among 48,665 California female participants followed for cancer from 2003 through 2013. We obtained exposure data on chemicals acting as endocrine disruptors or mammary gland carcinogens from the National-Scale Air Toxics Assessment. Cox proportional hazards models were used to estimate breast cancer risk per one interquartile range (IQR) increase in air toxics exposure lagged by 5-years. Stratified analyses were conducted by race, ethnicity, and hormone receptor types.
RESULTS
Among all women, increased risks of invasive breast cancer were observed with toxicants related to industries [1,1,2,2-tetrachloroethane (hazard ratio [HR] = 4.22, 95% confidence interval [95% CI] 3.18-5.60), ethylene dichloride (HR = 2.81, 95% CI 2.20-3.59), and vinyl chloride (HR = 2.27, 95% CI 1.81, 2.85); these 3 agents were correlated (r2 = 0.45-0.77)]. Agents related to gasoline production or combustion were related to increased breast cancer risk [benzene (HR = 1.32, 95% CI 1.24, 1.41), ethylbenzene (HR = 1.20, 95% CI 1.13-1.28), toluene (HR = 1.29, 95% CI 1.20-1.38), naphthalene (HR = 1.11, 95% CI 1.02-2.22), acrolein (HR = 2.26, 95% CI 1.92, 2.65)]. Higher hazard ratios were observed in African Americans and Whites compared to other racial and ethnic groups (p-heterogeneity <0.05 for traffic-related air toxics, acrolein, and vinyl acetate).
CONCLUSIONS
Our findings suggest that specific toxic air pollutants may be associated with increase breast cancer risk.
Topics: Humans; Breast Neoplasms; Female; Middle Aged; Air Pollutants; Aged; Cohort Studies; Environmental Exposure; California; Adult; Risk Factors; Los Angeles; Proportional Hazards Models
PubMed: 38574449
DOI: 10.1016/j.ijheh.2024.114362