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The Journal of Organic Chemistry Jun 2024A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and...
A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and styrenes including 1,1-, 1,2-disubstituted alkenes can be subjected to the protocol, and a wide range of vinyl sulfones was obtained in high to excellent yields with good functional group compatibility. Notably, the process did not allow the desulfonylation of sulfonyl chloride or chlorosulfonylation of alkenes. Radical-trapping experiment supported that a sulfonyl free-radical was likely produced and triggered subsequent transformation in the process.
PubMed: 38935873
DOI: 10.1021/acs.joc.4c00094 -
Water Research Jun 2024The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant...
The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant named PRL-VAc-DMC was synthesized using pulp reject as the raw material, with vinyl acetate (VAc) and methacryloxyethyltrimethyl ammonium chloride (DMC) as the grafting monomers. A series of modern characterization methods were used to confirm the successful preparation of PRL-VAc-DMC and elucidate its polymerization mechanism. It was found that the Ph-OH group and its contiguous carbon atoms of lignin served as the primary active sites to react with grafting monomers. Flocculation experiments revealed that PRL-VAc-DMC could react with tetracycline (TC) through π-π* interaction, hydrophobic interaction, hydrogen bonding, and electrostatic attraction. With the coexistence of humic acid (HA) and Kaolin, the aromatic ring, hydroxyl, and amide group of TC could react with the benzene ring, hydroxyl group, and carboxyl group of HA, forming TC@HA@Kaolin complexes with Kaolin particles acting as the hydrophilic shell. The increase in particle size, electronegativity, and hydrophily of TC@HA@Kaolin complexes facilitated their interaction with PRL-VAc-DMC through strong interfacial interactions. Consequently, the presence of HA and Kaolin promoted the removal of TC. The synergistic removal mechanism of TC, HA, and Kaolin by PRL-VAc-DMC was systematically analyzed from the perspective of muti-interface interactions. This paper is of great significance for the comprehensive utilization of pulp reject and provides new insights into the flocculation mechanism at the molecular scale.
PubMed: 38908312
DOI: 10.1016/j.watres.2024.121966 -
Langmuir : the ACS Journal of Surfaces... Jun 2024The structure-property relationship of poly(vinyl chloride) (PVC)/CaCO nanocomposites is investigated by all-atom molecular dynamics (MD) simulations. MD simulation...
The structure-property relationship of poly(vinyl chloride) (PVC)/CaCO nanocomposites is investigated by all-atom molecular dynamics (MD) simulations. MD simulation results indicate that the dispersity of nanofillers, interfacial bonding, and chain mobility are imperative factors to improve the mechanical performance of nanocomposites, especially toughness. The tensile behavior and dissipated work of the PVC/CaCO model demonstrate that 12 wt % CaCO modified with oleate anion and dodecylbenzenesulfonate can impart high toughness to PVC due to its good dispersion, favorable interface interaction, and weak migration of PVC chains. Under the guidance of MD simulation, we experimentally prepared a transparent PVC/CaCO nanocomposite with good mechanical properties by polymerization of monodispersed CaCO in vinyl chloride monomers. Interestingly, experimental tests indicate that the optimum toughness of a nanocomposite (a 368% increase in the elongation at break and 204% improvement of the impact strength) can be indeed realized by adding 12 wt % CaCO modified with oleic acid and dodecylbenzenesulfonic acid, which is remarkably consistent with the MD simulation prediction. In short, this work provides a proof-of-concept of using MD simulation to guide the experimental synthesis of PVC/CaCO nanocomposites, which can be considered as an example to develop other functional nanocomposites.
PubMed: 38902198
DOI: 10.1021/acs.langmuir.4c01435 -
Journal of Biomaterials Applications Jun 2024The release of antibiotics or anions by traditional bacteriostatic agents led to the development of bacterial drug resistance and environmental pollution. Ionic liquids...
The release of antibiotics or anions by traditional bacteriostatic agents led to the development of bacterial drug resistance and environmental pollution. Ionic liquids (ILs) have become important choices for antibacterial agents because of their excellent physical, chemical and biological properties. In this paper, the bioactivities of 1-vinyl-3-butylimidazolium chloride ([VBIM]Cl, IL) and poly (1-vinyl-3-butylimidazolium chloride) (P[VBIM]Cl, PIL) were evaluated, and the potential antibacterial material was used to synthesize hydrogels. Using the colony formation assay and the Oxford cup method, antibacterial effect of IL and PIL were tested. Cell-Counting-Kit-8 (CCK-8) experiments were used to study the IC (half maximal inhibitory concentration) values of IL and showed 1.47 mg/mL, 0.35 mg/mL and 0.33 mg/mL at 24 h, 48 h and 72 h, respectively. The IC value of PIL were 12.15 μg/mL, 12.06 μg/mL and 11.76 μg/mL at 24 h, 48 h and 72 h, respectively. The PIL is further crosslinked with polyvinyl alcohol (PVA) to form a novel hydrogel through freeze-thaw cycles. The newly fabricated hydrogel exhibited a high water content, excellent water absorption properties and outstanding mechanical performance. Using the colony formation assay and the inhibition zone assay, the hydrogels exhibited favorable antibacterial effects (against and ) such that nearly 100% of the bacteria were killed in liquid medium while cultivating with H4 (synthesized by 0.5 g PIL and 1g PVA). In addition, the cytotoxicity of PIL was significantly reduced through hydrogen bond crosslinking. H4 showed the highest antibacterial activity and a good biocompatibility. The results indicated that the PVA&PIL hydrogels had great potential for wound dressing.
PubMed: 38901419
DOI: 10.1177/08853282241264095 -
The Science of the Total Environment Jun 2024Field determination of the metal adsorption capacity of microplastics (MPs) by using a passive sampler had been done in typical subtropical mariculture area in China....
Field determination of the metal adsorption capacity of microplastics (MPs) by using a passive sampler had been done in typical subtropical mariculture area in China. The adsorption of eight metals (Fe, Mn, Cu, Zn, As, Pb, Cr and Cd) by five types of MPs (low-density polyethylene, polypropylene, polystyrene, poly(ethylene terephthalate) and poly(vinyl chloride) (PVC) was compared, including metal types, mariculture types (cage and longline culture), metal residue content in ambient environment, polymer types and particle sizes of MPs. The results showed that Cu, Zn, As, Cd, Pb and Cr in the mariculture environment were contaminated compared with the quality criteria. The concentrations of these six metals adsorbed on five MPs increased linearly with those in seawater. More enriched Cu and As in MPs in marine cage culture than in longline culture, due to the obvious endogenous pollution emissions for the artificial diets, fish medicine and disinfectants. Aged PVC with more cracks and pores showed higher metal adsorption capacity than any other polymers. MPs with a smaller size range of 50-74 μm tended to accumulate higher amounts of metals than those with a larger size range of 74-178 μm, consisting with the surface characteristics of MPs. The significant positive relationship between the concentrations of nutrients in seawater and the adsorption amounts of Cu, Zn and As on MPs implies that the eutrophication would promote their pollution. Based on the ecological risk assessment, the occurrence of MPs could aggravate the potential risk of metals to marine organisms in intensive mariculture areas. This is the first time to reveal the impacts of the adsorption of metals on aged MPs on the potential ecological risks of metals to organisms under the realistic environmental condition.
PubMed: 38876355
DOI: 10.1016/j.scitotenv.2024.173964 -
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 -
International Journal of Biological... Jun 2024Here, a polysaccharide derivative acryloyl chitosan (AcCS) is exploited as macro-crosslinker to synthesize a novel ionogel poly (acrylic acid-co-1-Vinyl-3-butyl...
Here, a polysaccharide derivative acryloyl chitosan (AcCS) is exploited as macro-crosslinker to synthesize a novel ionogel poly (acrylic acid-co-1-Vinyl-3-butyl imidazolium chloride) (AA-IL/AcCS) via a one-pot method. AcCS provides abundant physical and chemical crosslinking sites contributing to the high mechanical stretchability (elongation at break 600 %) and strength (tensile strength 137 kPa) of AA-IL/AcCS. The high-density of dynamic bonds (hydrogen bonds and electrostatic interactions) in the network of ionogels enables self-healing and self-adhesive features of AA-IL/AcCS. Meanwhile, AA-IL/AcCS exhibits high ionic conductivity (0.1 mS/cm) at room temperature and excellent antifreeze ability (-58 °C). The AA-IL/AcCS-based sensor shows diverse sensory capabilities towards temperature and humidity, moreover, it could precisely detect human motions and handwritings signals. Furthermore, AA-IL/AcCS exhibits excellent bactericidal properties against both gram-positive and gram-negative bacteria. This work opens the possibility of polysaccharides as a macro-crosslinkers for preparing ionogel-based sensors for wearable electronics.
PubMed: 38851613
DOI: 10.1016/j.ijbiomac.2024.133002 -
Nature Chemistry Jun 2024Halogenated organic pollutants (HOPs) are causing a significant environmental and human health crisis due to their high levels of toxicity, persistence and...
Halogenated organic pollutants (HOPs) are causing a significant environmental and human health crisis due to their high levels of toxicity, persistence and bioaccumulation. Urgent action is required to develop effective approaches for the reduction and reuse of HOPs. Whereas current strategies focus primarily on the degradation of HOPs, repurposing them is an alternative approach, albeit a challenging task. Here we discover that alkyl bromide can act as a catalyst for the transfer of chlorine using alkyl chloride as the chlorine source. We demonstrate that this approach has a wide substrate scope, and we successfully apply it to reuse HOPs that include dichlorodiphenyltrichloroethane, hexabromocyclododecane, chlorinated paraffins, chloromethyl polystyrene and poly(vinyl chloride) (PVC). Moreover, we show that the synthesis of essential non-steroidal anti-inflammatory drugs can be achieved using PVC and hexabromocyclododecane, and we demonstrate that PVC waste can be used directly as a chlorinating agent. Overall, this methodology offers a promising strategy for repurposing HOPs.
PubMed: 38844635
DOI: 10.1038/s41557-024-01551-8 -
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