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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 -
International Journal of Biological... Apr 2024The mechanical properties of ionic conductive hydrogels (ICHs) are generally inadequate, leading to their susceptibility to breakage under external forces and...
The mechanical properties of ionic conductive hydrogels (ICHs) are generally inadequate, leading to their susceptibility to breakage under external forces and consequently resulting in the failure of flexible electronic devices. In this work, a simple and convenient strategy was proposed based on the synergistic effect of ion cross-linking and salting out, in which the hydrogels consisting of polyvinyl alcohol (PVA) and xanthan gum (XG) were immersed in zinc sulfate (ZnSO) solution to obtain ICHs with exceptional mechanical properties. The salt-out effects between PVA chains and SO ions along with the cross-linked network of XG chains and Zn ions contribute to the desirable mechanical properties of ICHs. Notably, the mechanical properties of ICHs can be adjusted by changing the concentration of ZnSO solution. Consequently, the optimum fracture stress and the fracture energy can reach 3.38 MPa and 12.13 KJ m, respectively. Moreover, the ICHs demonstrated a favorable sensitivity (up to 2.05) when utilized as a strain sensor, exhibiting an accurate detection of human body movements across various amplitudes.
Topics: Humans; Polyvinyl Alcohol; Hydrogels; Ethanol; Sodium Chloride; Electric Conductivity; Ions; Poly A; Polyvinyl Chloride; Polysaccharides, Bacterial
PubMed: 38423443
DOI: 10.1016/j.ijbiomac.2024.130511 -
Marine Pollution Bulletin Apr 2024Microplastics (MPs) were analyzed in seven shrimp species Tiger shrimp (Penaeus monodon), Red tiger shrimp (Caridina cantonensis), Indian shrimp (Penaeus indicus), Red...
Microplastics (MPs) were analyzed in seven shrimp species Tiger shrimp (Penaeus monodon), Red tiger shrimp (Caridina cantonensis), Indian shrimp (Penaeus indicus), Red shrimp (Metapenaeus dobsoni), White shrimp (Penaeus merguiensis), Brown shrimp (Metapenaeus monoceros), and Roshna shrimp (Palaemon styliferus) collected from the Bay of Bengal. The abundance and characteristics of MPs were assessed in the gastrointestinal tract (GIT), which certainly translocated to the muscle of shrimp species. The highest MP abundance was found in C. cantonensis with 7.2 items/individual (25.3 items/g in the GIT and 6.3 items/g in muscle). The prominent types of MPs in shrimp samples were fibers (30 %) and fragments (29 %). The ingestion rate of MPs of black and transparent color was comparatively higher, with 64 % of the ingested MPs were < 100 μm. The primary polymer types detected based on Fourier Transform Infrared (FTIR) analysis were Low-Density Polyethylene (LDPE), High-Density Polyethylene (HDPE), Polymethyl Methacrylate (PMMA), Polyvinyl Chloride (PVC), Polypropylene (PP), and Ethylene Vinyl Acetate (EVA). Results from Scanning Electron Microscopy (SEM) showed rough surface textures and adhered particles on the MPs isolated from shrimps. The margin of exposure for females was 71.42, and for males, it was 80.64, indicating that women in Bangladesh are more likely to be exposed to MPs and face a higher risk than men. Sensitivity analysis revealed that MPs particle size was the most sensitive parameter. These findings provide a comprehensive understanding of MP ingestion, human exposure, and contamination in shrimps of Bangladesh, which can help future monitoring efforts.
Topics: Male; Animals; Humans; Female; Plastics; Microplastics; Bays; Decapoda; Penaeidae; Polyethylene; Environmental Monitoring; Water Pollutants, Chemical
PubMed: 38412798
DOI: 10.1016/j.marpolbul.2024.116185 -
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 -
Water Research Apr 2024Chromium and organochlorine solvents, particularly trichloroethene (TCE), are pervasive co-existing contaminants in subsurface aquifers due to their extensive industrial...
Chromium and organochlorine solvents, particularly trichloroethene (TCE), are pervasive co-existing contaminants in subsurface aquifers due to their extensive industrial use and improper disposal practices. In this study, we investigated the microbial dechlorination kinetics under different TCE-Cr(Ⅲ/VI) composite pollution conditions and elucidated microbial response mechanisms based on community shift patterns and metagenomic analysis. Our results revealed that the reductive dechlorinating consortium had high resistance to Cr(III) but extreme sensitivity to Cr(VI) disturbance, resulting in a persistent inhibitory effect on subsequent dechlorination. Interestingly, the vinyl chloride-respiring organohalide-respiring bacteria (OHRB) was notably more susceptible to Cr(III/VI) exposure than the trichloroethene-respiring one, possibly due to inferior competition for growth substrates, such as electron donors. In terms of synergistic non-OHRB populations, Cr(III/VI) exposure had limited impacts on lactate fermentation but significantly interfered with H-producing acetogenesis, leading to inhibited microbial dechlorination due to electron donor deficiencies. However, this inhibition can be effectively mitigated by the amendment of exogenous H supply. Furthermore, being the predominant OHRB, Dehalococcoides have inherent Cr(VI) resistance defects and collaborate with synergistic non-OHRB populations to achieve concurrent bio-detoxication of Cr(VI) and TCE. Our findings expand the understanding of the response patterns of different functional populations towards Cr(III/VI) stress, and provide valuable insights for the development of in situ bioremediation strategies for sites co-contaminated with chloroethene and chromium.
Topics: Chloroflexi; Trichloroethylene; Bacteria; Chromium; Biodegradation, Environmental
PubMed: 38382292
DOI: 10.1016/j.watres.2024.121328 -
Nature Chemistry Apr 2024The distribution, metabolism and ultimate fate of molecules within the body is central to the activity of pharmaceuticals. However, the introduction of radioisotopes...
The distribution, metabolism and ultimate fate of molecules within the body is central to the activity of pharmaceuticals. However, the introduction of radioisotopes into the metabolically stable carbon sites on drugs to probe these features typically requires toxic, radioactive gases such as [C]CO and [C]CO. Here we describe an approach to directly carbon-label carboxylic-acid-containing pharmaceuticals via a metal-catalysed functional group exchange reaction, forming C-labelled carboxylic-acid-containing drugs without radioactive gases, in one pot, using an easily available and handled carboxylic acid C source. To enable this process, a functional group metathesis of carbon-carbon covalent bonds in acid chloride functionalities is developed, exploiting the ability of nickel catalysts to both reversibly activate carbon-chloride bonds and exchange functionalities between organic molecules. The drug development applicability is illustrated by the direct incorporation of the C label or C label into an array of complex aryl, alkyl, vinyl and heterocyclic carboxylic acid drugs or drug candidates without gases or a special apparatus, at ambient conditions and without loss of the radiolabel.
PubMed: 38374455
DOI: 10.1038/s41557-024-01447-7 -
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