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Journal of Colloid and Interface Science May 2024The desalination performance of thin film nanocomposite (TFN) membranes is significantly influenced by the nature of nanofillers and the structure of the polyamide (PA)...
The desalination performance of thin film nanocomposite (TFN) membranes is significantly influenced by the nature of nanofillers and the structure of the polyamide (PA) layer. Herein, a micelles regulated interfacial polymerization (MRIP) strategy is reported for the preparation of TFN membranes with enhanced nanofiltration (NF) performance. Specially, stable and ultrafine micelles, synthesized from the poly(ethylene oxide)-b-poly(4-vinyl pyridine)-b-polystyrene (PEO-PVP-PS) triblock copolymers, were utilized as regulators in the aqueous phase during the interfacial polymerization (IP) process. TFN membranes were fabricated with varying concentrations of micelles to improve their properties and performances. The structure of the PA layer was further regulated by modulating the content of trimesoyl chloride (TMC), which significantly enhances the performance of the TFN membrane with micelles. Attributable to the homogeneously dispersed micelles and the modified PA layer, the optimized membrane denoted as TFN-2-0.3 exhibits an improved separation performance of 20.7 L mh bar and 99.3 % NaSO rejection, demonstrating nearly twice the permeance and 2.7 % higher rejection than that of the original control membrane, respectively. The mechanism of this MRIP strategy was investigated through the diffusion experiments of piperazine (PIP) and interfacial tension tests. The incorporated micelles effectively lower the interfacial tension, promote the diffusion of PIP and accelerate the IP reaction, resulting in a denser and thinner PA layer. Collectively, these findings demonstrate that TFN membranes with micelles exhibit increased roughness, enhanced hydrophilicity, superior rejection to divalent salts, and better acid-base resistance, highlighting their potential applications in the design of TFN membranes.
PubMed: 38364479
DOI: 10.1016/j.jcis.2024.02.102 -
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 -
The Journal of Physical Chemistry. B Feb 2024The redox-active properties of a series of ferrocene-containing vinyl polymers were investigated in aqueous and organic media. Each metallopolymer contained...
The redox-active properties of a series of ferrocene-containing vinyl polymers were investigated in aqueous and organic media. Each metallopolymer contained vinylferrocene (VFc) and a non-redox-active species (X), and was combined with carbon nanotubes (CNT) to generate P(VFc--X)-CNT composites for heterogeneous electrochemical analysis. Tunable pseudocapacitances spanning ca. 0.03-280 F/g VFc in aqueous solution were achieved by varying the copolymer composition, with P(VFc--HEMA) producing standardized values at ca. 160-180 F/g VFc even for differently hydrated anions. Additionally, the polymer-bound ferrocene/ferrocenium redox potential was seen to depend prominently on its electrolyte anion's Gibbs free energy of hydration. Although the hydrophilic chloride anion negatively influenced the electrochemical stability of the VFc units when in their PVFc homopolymer, copolymerizing them with 2-hydroxyethyl methacrylate (HEMA) and introducing perchlorate anions ameliorated their overall capacity retention by 64% and 38%, respectively. Lastly, the electrodes' responses in aprotic and protic solvents were examined for correlations with numerous solvent polarity metrics and solubility measures, with a notable observation being the stability and pseudocapacitive increase of the styrene (St)-containing P(VFc--St)-CNT from 5 to ca. 190 F/g VFc when in methanol instead of water. This study can help provide insight regarding material design considerations for redox moiety implementation in electrochemical applications.
PubMed: 38331399
DOI: 10.1021/acs.jpcb.3c06140 -
Chemistry (Weinheim An Der Bergstrasse,... Apr 2024Poly(vinyl chloride) undergoes dechlorination in the presence of triethylsilane (EtSiH) and a catalytic amount of [CpZr(NPh)][CHB(CF)] (1 b) at 40-80 °C, with up to...
Poly(vinyl chloride) undergoes dechlorination in the presence of triethylsilane (EtSiH) and a catalytic amount of [CpZr(NPh)][CHB(CF)] (1 b) at 40-80 °C, with up to 91 % efficiency. Stoichiometric reactivity studies conducted on cyclohexyl chloride as a model suggest that 1 b dechlorinates PVC by initial chloride abstraction, followed by hydride transfer to the cationic PVC chain from EtSiH. Consumer items such as pipe fitting, vinyl disc or electric cable insulation undergo either dechlorination or hydrosilylation of the carbonyl-containing copolymer (polyvinyl acetate) or plasticizer (phthalate).
PubMed: 38314958
DOI: 10.1002/chem.202304005 -
ACS Sensors Feb 2024Ketone bodies (KBs), especially β-hydroxybutyrate (BHB), have gained tremendous attention as potential biomarkers as their presence in bodily fluids is closely...
Ketone bodies (KBs), especially β-hydroxybutyrate (BHB), have gained tremendous attention as potential biomarkers as their presence in bodily fluids is closely associated with health and wellness. While a variety of blood fingerstick test strips are available for self-testing of BHB, there are major needs for wearable devices capable of continuously tracking changing BHB concentrations. To address these needs, we present here the first demonstration of a wearable microneedle-based continuous ketone monitoring (CKM) in human interstitial fluid (ISF) and illustrate its ability to closely follow the intake of ketone drinks. To ensure highly stable and selective continuous detection of ISF BHB, the new enzymatic microneedle BHB sensor relies on a gold-coated platinum working electrode modified with a reagent layer containing toluidine blue O (TBO) redox mediator, β-hydroxybutyrate dehydrogenase (HBD) enzyme, a nicotinamide adenine dinucleotide (NAD) cofactor, along with carbon nanotubes (CNTs), chitosan (Chit), and a poly(vinyl chloride) (PVC) outer protective layer. The skin-worn microneedle sensing device operates with a miniaturized electrochemical analyzer connected wirelessly to a mobile electronic device for capturing, processing, and displaying the data. Cytotoxicity and skin penetration studies indicate the absence of potential harmful effects. A pilot study involving multiple human subjects evaluated continuous BHB monitoring in human ISF, against gold standard BHB meter measurements, revealing the close correlation between the two methods. Such microneedle-based CKM offers considerable promise for dynamic BHB tracking toward the management of diabetic ketoacidosis and personal nutrition and wellness.
Topics: Humans; Ketones; Nanotubes, Carbon; Pilot Projects; Ketone Bodies; 3-Hydroxybutyric Acid; Wearable Electronic Devices
PubMed: 38300831
DOI: 10.1021/acssensors.3c02677 -
Journal of the American Chemical Society Feb 2024Interlocked molecular assemblies constitute a captivating ensemble of chemical topologies, comprising two or more separate components that exhibit remarkably intricate...
Interlocked molecular assemblies constitute a captivating ensemble of chemical topologies, comprising two or more separate components that exhibit remarkably intricate structures. The interlocked molecular assemblies are typically identical, and heterointerlocked systems that comprise structurally distinct assemblies remain unexplored. Here, we demonstrate that metal-templated synthesis can be exploited to afford not only a homointerlocked cage but also a heterointerlocked cage. Treatment of a carboxylated 2,9-dimethyl-1,10-phenanthroline (dmp) or Cu(I) bis-dmp linker with a Ni---butylsulfonylcalix[4]arene cluster affords noninterlocked octahedron and quadruply interlocked double cages consisting of two identical tetragonal pyramids, respectively. In contrast, when a mixture of dmp and Cu(I) bis-dmp linkers is used, a quadruply heterointerlocked cage is produced, consisting of a tetragonal pyramid and an octahedron. With photoredox-active [Cu(dmp)] in the structures, both interlocked cages exhibit remarkable performance as photocatalysts for atom transfer radical addition (ATRA) reactions of trifluoromethanesulfonyl chloride with alkenes or oxo-azidations of vinyl arenes. These interlocked structures serve the dual purpose of stabilizing photocatalytically active components against deactivation and encapsulating substrates within the cavity, resulting in yields comparable to or even surpassing those of their molecular counterparts. This work thus provides a new strategy that combines metal templating and nontemplating approaches to design new types of interlocked assemblies with intriguing architectures and properties.
PubMed: 38279915
DOI: 10.1021/jacs.3c10734 -
International Journal of Molecular... Jan 2024The spin theory of fullerenes is taken as a basis concept to virtually exhibit a peculiar role of C fullerene in the free radical polymerization of vinyl monomers.... (Review)
Review
The spin theory of fullerenes is taken as a basis concept to virtually exhibit a peculiar role of C fullerene in the free radical polymerization of vinyl monomers. Virtual reaction solutions are filled with the initial ingredients (monomers, free radicals, and C fullerene) as well as with the final products of a set of elementary reactions, which occurred in the course of the polymerization. The above objects, converted to the rank of digital twins, are considered simultaneously under the same conditions and at the same level of the theory. In terms of the polymerization passports of the reaction solutions, a complete virtual picture of the processes considered is presented.
Topics: Fullerenes; Polymerization; Free Radicals; Polyvinyl Chloride
PubMed: 38279316
DOI: 10.3390/ijms25021317 -
Toxics Dec 2023Poly(vinyl chloride) (PVC) is widely used to produce various consumer goods, including food packaging, toys for children, building materials, and cosmetic products....
Poly(vinyl chloride) (PVC) is widely used to produce various consumer goods, including food packaging, toys for children, building materials, and cosmetic products. However, despite their widespread use, phthalate plasticizers have been identified as endocrine disruptors, which cause adverse health effects, thus leading to increasing concerns regarding their migration from PVC products to the environment. This study proposed a method for rapidly measuring the migration of phthalates, particularly di(2-ethylhexyl) phthalate (DEHP), from PVC products to commonly encountered liquids. The release of DEHP under various conditions, including exposure to aqueous and organic solvents, different temperatures, and household microwaves, was investigated. The amount of DEHP released from both laboratory-produced PVC films and commercially available PVC products was measured to elucidate the potential risks associated with its real-world applications. Furthermore, tests were performed to evaluate cytotoxicity using estrogen-dependent and -independent cancer cell lines. The results revealed a dose-dependent impact on estrogen-dependent cells, thus emphasizing the potential health implications of phthalate release. This comprehensive study provides valuable insights into the migration patterns of DEHP from PVC products and forms a basis for further research on the safety of PVC and plasticizers.
PubMed: 38276720
DOI: 10.3390/toxics12010007 -
Gels (Basel, Switzerland) Dec 2023Natural fibers have attracted increasing interest as an alternative to produce environmentally friendly and sustainable materials. Particularly, hemp fibers have been...
Natural fibers have attracted increasing interest as an alternative to produce environmentally friendly and sustainable materials. Particularly, hemp fibers have been widely used in various industrial applications due to their extremely unique properties. However, hemp can generate a large amount of agro-waste, and it results in an attractive source of biopolymers for the development of low-cost materials as an alternative to the raw materials and conventional petroleum-based plastics. In addition, deep eutectic solvents (DESs), a new type of truly green solvents, have been shown to remove gums, lignin, and other non-cellulosic components from hemp fibers. Reusing these components dissolved into the DESs to fabricate new materials directly by electrospinning is a very attractive but still unexplored endeavor. Thus, this innovative research to venture new upcycling pathways is focused on the fabrication of composite nanofibers by electrospinning of a gel-based blend of Poly(vinyl alcohol) (PVA) and hemp agro-waste (HW) dissolved into choline chloride (ChCl):Glycerol (1:2) and ChCl:Urea (1:2) DES mixtures. The results obtained revealed that the produced nanofibers displayed uniform appearance with diameters ranging from 257.7 ± 65.6 nm to 380.8 ± 134.0 nm. In addition, the mechanical properties of the electrospun composite nanofibers produced from the gel-based blends of HW dissolved in DESs and PVA (HW-DESs_PVA) were found to be superior, resulting in an enhanced tensile strength and Young's modulus. Furthermore, the incorporation of HW into the nanofibers was able to provide bioactive antioxidant and antibacterial properties. Overall, this study demonstrated a promising, more sustainable, and eco-friendly way to produce electrospun composite nanofibers using HW in a circular economy perspective.
PubMed: 38275839
DOI: 10.3390/gels10010001