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Science Advances Apr 2024Hydrogen chloride is produced as a by-product in industrial processes on a million-ton scale. Since HCl is inherently dangerous, its storage and transport are avoided...
Hydrogen chloride is produced as a by-product in industrial processes on a million-ton scale. Since HCl is inherently dangerous, its storage and transport are avoided by, e.g., on-site electrolysis providing H and Cl which usually requires complex cell designs and PFAS-based membranes. Here we report a complementary approach to safely store 0.61 kilogram HCl per kilogram storage material [NEtMe]Cl forming the bichloride [NEtMe][Cl(HCl)]. Although HCl release is possible from this ionic liquid by heat or vacuum, the bichloride can be used directly to produce base chemicals like vinyl chloride. Alternatively, [NEtMe][Cl(HCl)] is electrolyzed under anhydrous conditions using a membrane-free cell to generate H and the corresponding chlorination agent [NEtMe][Cl(Cl)], enabling the combination of these ionic liquids for the production of base chemicals.
PubMed: 38569024
DOI: 10.1126/sciadv.adn5353 -
ACS Applied Engineering Materials Mar 2024One of the challenges preventing wide use of inorganic salt hydrate phase change materials (PCMs) is their low viscosity above their melting point, leading to leakage,... (Review)
Review
One of the challenges preventing wide use of inorganic salt hydrate phase change materials (PCMs) is their low viscosity above their melting point, leading to leakage, phase segregation, and separation from heat exchanger surfaces in thermal management applications. The development of a broad strategy for using polymers that provide tunable, temperature-reversible shape stabilization of a variety of salt hydrates by using the lowest possible polymer concentrations is hindered by differences in solubility and gelation behavior of polymers with change in the type of ion. This work addressed the challenge of creating robust, temperature-responsive shape-stabilizing polymer gels (i.e., salogels) using a low cost PCM, calcium chloride hexahydrate (CaCl·6HO, CCH). Due to the extremely high (9 M) concentration of chloride ions and the tendency to salting-out polymer chains, the previous strategy of using single-polymer salogels was not successful. Thus, this work introduced a strategy of using two polymers, poly(vinyl alcohol) and ultrahigh molecular weight polyacrylamide (PVA and PAAm, respectively), along with borax as a cross-linker to achieve temperature-reversible, shape-stable salogels. This system resulted in robust salogels whose gel-to-sol transition temperature () was tunable within an application-relevant range of gelation temperature (30-80 °C). This behavior was enabled by a synergistic combination of dynamic covalent cross-links between PVA units and entanglements of PAAm chains which were combined into a single hybrid network. The hybrid salogels had <5 wt % polymer content, maintaining ∼95% of the heat of fusion of the pure PCM. Importantly, the noncovalent nature of gelation supported thermo-reversibility of gelation, shape stability, and retention of thermal properties over 50 melting/crystallization cycles.
PubMed: 38544947
DOI: 10.1021/acsaenm.3c00522 -
The Journal of Physical Chemistry. C,... Mar 2024Mg nanoparticles are an emerging plasmonic material due to Mg's abundance and ability to sustain size- and shape-dependent localized surface plasmon resonances across a...
Mg nanoparticles are an emerging plasmonic material due to Mg's abundance and ability to sustain size- and shape-dependent localized surface plasmon resonances across a broad range of wavelengths from the ultraviolet to the near infrared. However, Mg nanoparticles are colloidally unstable due to their tendency to aggregate and sediment. Nanoparticle aggregation can be inhibited by the addition of capping agents that impart surface charges or steric repulsion. Here, we report that the common capping agents poly(vinyl) pyrrolidone (PVP), polyethylene glycol (PEG), cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS) interact differently and have varied effects on the aggregation and colloidal stability of Mg nanoparticles. Nanoparticles synthesized in the presence of PVP showed improvements in colloidal stability and reduced aggregation, as observed by electron microscopy and optical spectroscopy. The binding of PVP was confirmed through infrared and X-ray photoelectron spectroscopy. The influence of PVP on the reduction of di--butyl magnesium was evaluated through analysis of particle size distribution and Mg yield as a function of reaction time, reducing agent, and temperature. Furthermore, the presence of PVP drastically changes the growth pattern of metallic Mg structures obtained from the reduction of the Grignard reagents butylmagnesium chloride and phenylmagnesium chloride by lithium naphthalenide: large polycrystalline aggregates and well-separated faceted nanoparticles grow without and with PVP, respectively. This study provides new synthetic routes that generate colloidally stable and well-dispersed Mg nanoparticles for plasmonic and other applications.
PubMed: 38533241
DOI: 10.1021/acs.jpcc.4c00366 -
Journal of Chromatography. A Apr 2024Successive multiple ionic-polymer layers (SMILs) have long since proved their worth in capillary electrophoresis as they ensure stable electroosmotic flow (EOF) and...
Successive multiple ionic-polymer layers (SMILs) have long since proved their worth in capillary electrophoresis as they ensure stable electroosmotic flow (EOF) and relatively high separation efficiency. Recently, we demonstrated that plotting the plate height (H) against the solute migration velocity (u) enabled a reliable quantitative evaluation of the coating performances in terms of separation efficiency. In this work, various physicochemical and chemical parameters of the SMIL coating were studied and optimized in order to decrease the slope of the ascending part of the H vs u curve, which is known to be controlled by the homogeneity in charge of the coating surface and by the possible residual solute adsorption onto the coating surface. SMILs based on poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium styrene sulfonate) (PSS) were formed and the effect of each polyelectrolyte molar mass and of the number of polyelectrolyte layers (up to 21 layers) was studied. The use of polyethylene imine as an anchoring first layer was considered. More polyelectrolyte couples based on PDADMAC, polybrene, PSS, poly(vinyl sulfate), and poly(acrylic acid) were tested. Finally, zwitterionic polymers based on the poly(α-l-lysine) scaffold were synthesized and used as the last layer of SMILs, illustrating their ability to finetune the EOF, while maintaining good separation efficiency.
Topics: Polymers; Polyelectrolytes; Cations; Electrophoresis, Capillary; Proteins; Polyethyleneimine; Quaternary Ammonium Compounds; Polyethylenes
PubMed: 38507871
DOI: 10.1016/j.chroma.2024.464802 -
ACS Applied Materials & Interfaces Apr 2024The endotracheal tube (ETT) affords support for intubated patients, but the increasing incidence of ventilator-associated pneumonia (VAP) is jeopardizing its...
The endotracheal tube (ETT) affords support for intubated patients, but the increasing incidence of ventilator-associated pneumonia (VAP) is jeopardizing its application. ETT surfaces promote (poly)microbial colonization and biofilm formation, with a heavy burden for VAP. Devising safe, broad-spectrum antimicrobial materials to tackle the ETT bioburden is needful. Herein, we immobilized ciprofloxacin (CIP) and/or chlorhexidine (CHX), through polydopamine (pDA)-based functionalization, onto poly(vinyl chloride) (PVC) surfaces. These surfaces were characterized regarding physicochemical properties and challenged with single and polymicrobial cultures of VAP-relevant bacteria (, , , , ) and fungi (). The coatings imparted PVC surfaces with a homogeneous morphology, varied wettability, and low roughness. The antimicrobial immobilization via pDA chemistry was still evidenced by infrared spectroscopy. Coated surfaces exhibited sustained CIP/CHX release, retaining prolonged (10 days) activity. CIP/CHX-coated surfaces evidencing no A549 lung cell toxicity displayed better antibiofilm outcomes than CIP or CHX coatings, preventing bacterial attachment by 4.1-7.2 Log CFU/mL and modestly distressing. Their antibiofilm effectiveness was endured toward polymicrobial consortia, substantially inhibiting the adhesion of the bacterial populations (up to 8 Log CFU/mL) within the consortia in dual- and even in// triple-species biofilms while affecting fungal adhesion by 2.7 Log CFU/mL (dual consortia) and 1 Log CFU/mL (triple consortia). The potential of the dual-drug coating strategy in preventing triple-species adhesion and impairing bacterial viability was still strengthened by live/dead microscopy. The pDA-assisted CIP/CHX co-immobilization holds a safe and robust broad-spectrum antimicrobial coating strategy for PVC-ETTs, with the promise laying in reducing VAP incidence.
Topics: Humans; Chlorhexidine; Vinyl Chloride; Ciprofloxacin; Staphylococcus aureus; Anti-Infective Agents; Intubation, Intratracheal; Pneumonia, Ventilator-Associated; Bacteria; Biofilms; Pseudomonas aeruginosa
PubMed: 38507790
DOI: 10.1021/acsami.4c01334 -
Biomacromolecules Apr 2024Postpolymerization modification of highly defined "scaffold" polymers is a promising approach for overcoming the existing limitations of controlled radical...
Postpolymerization modification of highly defined "scaffold" polymers is a promising approach for overcoming the existing limitations of controlled radical polymerization such as batch-to-batch inconsistencies, accessibility to different monomers, and compatibility with harsh synthesis conditions. Using multiple physicochemical characterization techniques, we demonstrate that poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) scaffolds can be efficiently modified with a coumarin derivative, doxorubicin, and camptothecin small molecule drugs. Subsequently, we show that coumarin-modified PVDMA has a high cellular biocompatibility and that coumarin derivatives are liberated from the polymer in the intracellular environment for cytosolic accumulation. In addition, we report the pharmacokinetics, biodistribution, and antitumor efficacy of a PVDMA-based polymer for the first time, demonstrating unique accumulation patterns based on the administration route (i.e., intravenous vs oral), efficient tumor uptake, and tumor growth inhibition in 4T1 orthotopic triple negative breast cancer (TNBC) xenografts. This work establishes the utility of PVDMA as a versatile chemical platform for producing polymer-drug conjugates with a tunable, stimuli-responsive delivery.
Topics: Humans; Tissue Distribution; Polymers; Polyvinyls; Polyvinyl Chloride; Neoplasms; Doxorubicin; Lactones
PubMed: 38457653
DOI: 10.1021/acs.biomac.4c00181 -
Environmental Science & Technology Mar 2024Electrification and clean hydrogen are promising low-carbon options for decarbonizing industrial process heat, which is an essential target for reducing sector-wide...
Electrification and clean hydrogen are promising low-carbon options for decarbonizing industrial process heat, which is an essential target for reducing sector-wide emissions. However, industrial processes with heat demand vary significantly across industries in terms of temperature requirements, capacities, and equipment, making it challenging to determine applications for low-carbon technologies that are technically and economically feasible. In this analysis, we develop a framework for evaluating life cycle emissions, water use, and cost impacts of electric and clean hydrogen process heat technologies and apply it in several case studies for plastics and petrochemical manufacturing industries in the United States. Our results show that industrial heat pumps could reduce emissions by 12-17% in a typical poly(vinyl chloride) (PVC) facility in certain locations currently, compared to conventional natural gas combustion, and that other electric technologies in PVC and ethylene production could reduce emissions by nearly 90% with a sufficiently decarbonized electric grid. Life cycle water use increases significantly in all low-carbon technology cases. The levelized cost of heat of viable low-carbon technologies ranges from 15 to 100% higher than conventional heating systems, primarily due to energy costs. We discuss results in the context of relevant policies that could be useful to manufacturing facilities and policymakers for aiding the transition to low-carbon process heat technologies.
Topics: United States; Vinyl Chloride; Hot Temperature; Carbon; Manufacturing and Industrial Facilities; Ethylenes; Hydrogen; Water
PubMed: 38446013
DOI: 10.1021/acs.est.3c05880 -
Gels (Basel, Switzerland) Jan 2024An inhibitor that can effectively inhibit shale hydration is necessary for the safe and efficient development of shale gas. In this study, a novel ionic liquid copolymer...
An inhibitor that can effectively inhibit shale hydration is necessary for the safe and efficient development of shale gas. In this study, a novel ionic liquid copolymer shale inhibitor (PIL) was prepared by polymerizing the ionic liquid monomers 1-vinyl-3-aminopropylimidazolium bromide, acrylamide, and methacryloyloxyethyl trimethyl ammonium chloride. The chemical structure was characterized using fourier transform infrared spectroscopy (FT-IR) and hydrogen-nuclear magnetic resonance (H-NMR), and the inhibition performance was evaluated using the inhibition of slurrying test, bentonite flocculation test, linear expansion test, and rolling recovery test. The experimental results showed that bentonite had a linear expansion of 27.9% in 1 wt% PIL solution, 18% lower than that in the polyether amine inhibitor. The recovery rate of shale in 1 wt% PIL was 87.4%. The ionic liquid copolymer could work synergistically with the filtrate reducer, reducing filtration loss to 7.2 mL with the addition of 1%. Mechanism analysis showed that PIL adsorbed negatively charged clay particles through cationic groups, which reduced the electrostatic repulsion between particles. Thus, the stability of the bentonite gel systems was destroyed, and the hydration dispersion and expansion of bentonite were inhibited. PIL formed a hydrophobic film on the surface of clay and prevented water from entering into the interlayer of clay. In addition, PIL lowered the surface tension of water, which prevented the water from intruding into the rock under the action of capillary force. These are also the reasons for the superior suppression performance of PIL.
PubMed: 38391426
DOI: 10.3390/gels10020096 -
Polymers Jan 2024Herein, a bio-based plasticizer ketalized tung oil butyl levulinate (KTBL) was developed using methyl eleostearate, a derivative of tung oil, and butyl levulinate. KTBL...
Herein, a bio-based plasticizer ketalized tung oil butyl levulinate (KTBL) was developed using methyl eleostearate, a derivative of tung oil, and butyl levulinate. KTBL can be used as an auxiliary plasticizer to partially replace traditional plasticizer. The plasticizer has a ketone structure, an ester base, and a long linear chain. It was mixed with dioctyl phthalate (DOP), and the effect of the plasticizer KTBL as an auxiliary plasticizer on the plasticization of poly(vinyl chloride) (PVC) was studied. Their compatibility and plasticizing effect were evaluated using dynamic-mechanical thermal analysis (DMA), mechanical property analysis, and thermogravimetric analysis (TGA). The results demonstrate that when the KTBL to DOP ratio is 1:1, the blended sample with KTBL exhibits superior mechanical performance compared to pure DOP, resulting in an increased elongation at break from 377.47% to 410.92%. Moreover, with the increase in KTBL content, the durability is also significantly improved. These findings suggest that KTBL can serve as an effective auxiliary plasticizer for PVC, thereby reducing the reliance on DOP.
PubMed: 38337249
DOI: 10.3390/polym16030361 -
RSC Advances Feb 2024Nowadays, ductile and conducting polymeric materials are highly utilizable in the realm of stretchable organic electronics. Here, mechanically ductile and electrically...
Nowadays, ductile and conducting polymeric materials are highly utilizable in the realm of stretchable organic electronics. Here, mechanically ductile and electrically conducting free-standing films are fabricated by blending different solvents such as dimethyl sulfoxide (DMSO), diethylene glycol (DEG) and ,-dimethylformamide (DMF), and salts such as silver nitrate (AgNO), zinc chloride (ZnCl), copper chloride (CuCl) and indium chloride (InCl) with the homogeneous solution of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) and poly(vinyl alcohol) (PVA) through solution casting method. The presence of salt modifies the PEDOT conformation from benzoid to quinoid, and induces the evolution of different morphologies. ZnCl or AgNO blended films have lower surface roughness and good miscibility with polymers, while CuCl or InCl blended films have relatively higher surface roughness as well as irregularly distributed surface morphology. Some crystalline domains are also formed due to the salt agglomeration. The presence of salt inside PEDOT:PSS/PVA/solvent system changes the current-voltage response from non-linear to linear. Among all the films, zinc salt blended PEDOT:PSS/PVA/DMSO, PEDOT:PSS/PVA/DEG and PEDOT:PSS/PVA/DMF films have higher conductivity, and zinc salt blended PEDOT:PSS/PVA/DEG film shows the highest conductivity of 0.041 ± 0.0014 S cm, while silver salt blended PEDOT:PSS/PVA/DMSO, PEDOT:PSS/PVA/DEG and PEDOT:PSS/PVA/DMF films have higher elongation at break, and silver salt blended PEDOT:PSS/PVA/DMSO film shows the highest elongation at break of 670 ± 31%. Both the charge carriers, , electrons and ions, contribute to the electrical conduction, and the presence of hydrogen bonds and ionic interactions among PEDOT, PSS, PVA, residual solvent, salt cations and anions modifies the film behaviours. Among all the films, ZnCl blended PEDOT:PSS/PVA/DMSO film offers relatively superior behaviours having higher conductivity (0.025 ± 0.0013 S cm) and elongation at break (517 ± 15%), and therefore can have potential applications in the fields of wearable devices, bioelectronics,
PubMed: 38332796
DOI: 10.1039/d3ra08260a