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1.
Anal Chem ; 96(28): 11455-11462, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38968402

RESUMO

Efficient, mild, and reversible adsorption of nucleic acids onto nanomaterials represents a promising analytical approach for medical diagnosis. However, there is a scarcity of efficient and reversible nucleic acid adsorption nanomaterials. Additionally, the lack of comprehension of the molecular mechanisms governing their interactions poses significant challenges. These issues hinder the rational design and analytical applications of the nanomaterials. Herein, we propose an ultra-efficient nucleic acid affinity nanomaterial based on programmable lanthanide metal-organic frameworks (Ln-MOFs). Through experiments and density functional theory calculations, a rational design guideline for nucleic acid affinity of Ln-MOF was proposed, and a modular and flexible preparation scheme was provided. Then, Er-TPA (terephthalic acid) MOF emerged as the optimal candidate due to its pore size-independent adsorption and desorption capabilities for nucleic acids, enabling ultra-efficient adsorption (about 150% mass ratio) within 1 min. Furthermore, we elucidate the molecular-level mechanisms underlying the Ln-MOF adsorption of single- and double-stranded DNA and G4 structures. The affinity nanomaterial based on Ln-MOF exhibits robust nucleic acid extraction capability (4-fold higher than commercial reagent kits) and enables mild and reversible CRISPR/Cas9 functional regulation. This method holds significant promise for broad application in DNA/RNA liquid biopsy and gene editing, facilitating breakthroughs in analytical chemistry, pharmacy, and medical research.


Assuntos
DNA , Elementos da Série dos Lantanídeos , Estruturas Metalorgânicas , Estruturas Metalorgânicas/química , Elementos da Série dos Lantanídeos/química , Adsorção , DNA/química , DNA/isolamento & purificação , Ácidos Ftálicos/química , Nanoestruturas/química , Teoria da Densidade Funcional , Humanos
2.
J Sep Sci ; 47(14): e2400314, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39034893

RESUMO

In this work, a novel electrospun nanofiber (PAN/TpBD; 2,4,6-triformylphloroglucinol [Tp] and benzidine [BD]; polyacrylonitrile [PAN]) was fabricated via a facile electrospinning method and utilized as adsorbent in thin film microextraction (TFME) of phthalate esters (PAEs) (dimethyl phthalate, diethyl phthalate, diallyl phthalate, dibutyl phthalate, and dioctyl phthalate) in biodegradable plastics. The prepared PAN/TpBD combines the strong stability of nanofibers with increased exposure sites for covalent organic frameworks and enhanced interactions with the target, thus improving the enrichment effect on the target. The extraction efficiency of PAN/TpBD reached above 80%. Based on PAN/TpBD, a TFME-high-performance liquid chromatography method was established, and the experimental parameters were optimized. Under the optimal extraction conditions, the PAEs of this method varied linearly in the range of 10-10 000 µg/L with low detection limits (0.69-2.72 µg/L). The intra-day and inter-day relative standard deviation values of the PAEs were less than 8.04% and 8.73%, respectively. The adsorbent can achieve more than 80% recovery of the five targets after six times reuse. The developed method was successfully applied for the determination of trace PAEs in biodegradable plastics with recoveries ranging from 80.1% to 113.4% and relative standard deviations were less than 9.45%. The as-synthesized PAN/TpBD adsorbent exhibited great potential in PAE analysis.


Assuntos
Ésteres , Nanofibras , Ácidos Ftálicos , Nanofibras/química , Ácidos Ftálicos/isolamento & purificação , Ácidos Ftálicos/química , Ácidos Ftálicos/análise , Ésteres/química , Ésteres/isolamento & purificação , Ésteres/análise , Plásticos/química , Cromatografia Líquida de Alta Pressão , Tamanho da Partícula , Adsorção , Microextração em Fase Sólida/métodos , Propriedades de Superfície , Resinas Acrílicas
3.
Int J Biol Macromol ; 273(Pt 2): 133057, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38866295

RESUMO

Poly (butylene adipate-co-terephthalate)/poly (L-lactic acid) (PBAT/PLLA) is one of the most important biodegradable polymer combinations; however, they are flammable with heavy melt dripping and incompatible. To achieve the objective of flame retardation and compatibility, a hybrid polyurethane (PU) with multiple flame retardation elements is synthesized via a new ring-opening polymerization (ROP) method and integrated into PBAT/PLLA film. The PU not only dissolves in different organic solvents at mild temperature but also improves the compatibility of PBAT/PLLA. As PU with respect to PBAT/PLLA is 20 wt%, the limiting oxygen index (LOI) and UL-94 reach 25.5 % and V-0 rating, respectively. In cone calorimeter test, the peak heat release rate (pHRR) of PU/PBAT/PLLA is ahead of PBAT/PLLA, and the total heat release (THR) decreases to 25.85 MJ/m2. The fire safety is achieved successfully. The initial pyrolysis of PU promotes the formation of a seed carbon layer; it continuously breaks down into a series of phosphorus­oxygen radicals and generates different inert gases, while the pyrolytic solid products accelerate the carbonization to form the carbon/silicon composite layer. Then the polymeric combustion is braked completely. Besides, the PU can also tune the mechanical properties of PBAT/PLLA film and enhance its hydrophobicity. This work opens a new window for developing multifunctional flame retardant and paves the way for the richening engineering application of PBAT/PLLA.


Assuntos
Retardadores de Chama , Poliésteres , Poliuretanos , Poliuretanos/química , Poliésteres/química , Ácidos Ftálicos/química , Polimerização
4.
J Hazard Mater ; 474: 134776, 2024 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-38852255

RESUMO

Phthalate esters (PAEs) are widely used as plasticizers and cause serious complex pollution problem in environment. Thus, strains with efficient ability to simultaneously degrade various PAEs are required. In this study, a newly isolated strain Rhodococcus sp. AH-ZY2 can degrade 500 mg/L Di-n-octyl phthalate completely within 16 h and other 500 mg/L PAEs almost completely within 48 h at 37 °C, 180 rpm, and 2 % (v/v) inoculum size of cultures with a OD600 of 0.8. OD600 = 0.8, 2 % (v/v). Twenty genes in its genome were annotated as potential esterase and four of them (3963, 4547, 5294 and 5359) were heterogeneously expressed and characterized. Esterase 3963 and 4547 is a type I PAEs esterase that hydrolyzes PAEs to phthalate monoesters. Esterase 5294 is a type II PAEs esterase that hydrolyzes phthalate monoesters to phthalate acid (PA). Esterase 5359 is a type III PAEs esterase that simultaneously degrades various PAEs to PA. Molecular docking results of 5359 suggested that the size and indiscriminate binding feature of spacious substrate binding pocket may contribute to its substrate versatility. AH-ZY2 is a potential strain for efficient remediation of PAEs complex pollution in environment. It is first to report an esterase that can efficiently degrade mixed various PAEs.


Assuntos
Biodegradação Ambiental , Esterases , Ésteres , Simulação de Acoplamento Molecular , Ácidos Ftálicos , Rhodococcus , Rhodococcus/metabolismo , Rhodococcus/genética , Rhodococcus/enzimologia , Ácidos Ftálicos/metabolismo , Ácidos Ftálicos/química , Esterases/metabolismo , Esterases/genética , Ésteres/metabolismo , Ésteres/química , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Plastificantes/metabolismo
5.
J Hazard Mater ; 474: 134797, 2024 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-38865921

RESUMO

Poly(butylene adipate-co-terephthalate) (PBAT) is widely utilized in the production of food packaging and mulch films. Its extensive application has contributed significantly to global solid waste, posing numerous environmental challenges. Recently, enzymatic recycling has emerged as a promising eco-friendly solution for the management of plastic waste. Here, we systematically investigate the depolymerization mechanism of PBAT catalyzed by cutinase TfCutSI with molecular docking, molecular dynamics simulations, and quantum mechanics/molecular mechanics calculations. Although the binding affinities for acid ester and terephthalic acid ester bonds are similar, a regioselective depolymerization mechanism and a "chain-length" effect on regioselectivity were proposed and evidenced. The regioselectivity is highly associated with specific structural parameters, namely Substrate@O4-Met@H7 and Substrate@C1-Ser@O1 distances. Notably, the binding mode of BTa captured by X-ray crystallography does not facilitate subsequent depolymerization. Instead, a previously unanticipated binding mode, predicted through computational analysis, is confirmed to play a crucial role in BTa depolymerization. This finding proves the critical role of computational modelling in refining experimental results. Furthermore, our results revealed that both the hydrogen bond network and enzyme's intrinsic electric field are instrumental in the formation of the final product. In summary, these novel molecular insights into the PBAT depolymerization mechanism offer a fundamental basis for enzyme engineering to enhance industrial plastic recycling.


Assuntos
Simulação de Acoplamento Molecular , Poliésteres , Polimerização , Poliésteres/química , Poliésteres/metabolismo , Simulação de Dinâmica Molecular , Ácidos Ftálicos/química , Ácidos Ftálicos/metabolismo , Estereoisomerismo , Hidrolases de Éster Carboxílico
6.
Biochemistry ; 63(13): 1663-1673, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38885634

RESUMO

The mono(2-hydroxyethyl) terephthalate hydrolase (MHETase) from Ideonella sakaiensis carries out the second step in the enzymatic depolymerization of poly(ethylene terephthalate) (PET) plastic into the monomers terephthalic acid (TPA) and ethylene glycol (EG). Despite its potential industrial and environmental applications, poor recombinant expression of MHETase has been an obstacle to its industrial application. To overcome this barrier, we developed an assay allowing for the medium-throughput quantification of MHETase activity in cell lysates and whole-cell suspensions, which allowed us to screen a library of engineered variants. Using consensus design, we generated several improved variants that exhibit over 10-fold greater whole-cell activity than wild-type (WT) MHETase. This is revealed to be largely due to increased soluble expression, which biochemical and structural analysis indicates is due to improved protein folding.


Assuntos
Burkholderiales , Burkholderiales/enzimologia , Burkholderiales/genética , Burkholderiales/metabolismo , Ácidos Ftálicos/metabolismo , Ácidos Ftálicos/química , Hidrolases/metabolismo , Hidrolases/genética , Hidrolases/química , Solubilidade , Polietilenotereftalatos/metabolismo , Polietilenotereftalatos/química , Proteínas Recombinantes/metabolismo , Proteínas Recombinantes/genética , Proteínas Recombinantes/química , Engenharia de Proteínas/métodos , Dobramento de Proteína , Escherichia coli/genética , Escherichia coli/metabolismo , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Proteínas de Bactérias/química , Modelos Moleculares
7.
J Hazard Mater ; 472: 134493, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38696960

RESUMO

Environmental pollution caused by plastic waste has become global problem that needs to be considered urgently. In the pursuit of a circular plastic economy, biodegradation provides an attractive strategy for managing plastic wastes, whereas effective plastic-degrading microbes and enzymes are required. In this study, we report that Blastobotrys sp. G-9 isolated from discarded plastic in landfills is capable of depolymerizing polyurethanes (PU) and poly (butylene adipate-co-terephthalate) (PBAT). Strain G-9 degrades up to 60% of PU foam after 21 days of incubation at 28 â„ƒ by breaking down carbonyl groups via secretory hydrolase as confirmed by structural characterization of plastics and degradation products identification. Within the supernatant of strain G-9, we identify a novel cutinase BaCut1, belonging to the esterase family, that can reproduce the same effect. BaCut1 demonstrates efficient degradation toward commercial polyester plastics PU foam (0.5 mg enzyme/25 mg plastic) and agricultural film PBAT (0.5 mg enzyme/10 mg plastic) with 50% and 18% weight loss at 37 â„ƒ for 48 h, respectively. BaCut1 hydrolyzes PU into adipic acid as a major end-product with 42.9% recovery via ester bond cleavage, and visible biodegradation is also identified from PBAT, which is a beneficial feature for future recycling economy. Molecular docking, along with products distribution, elucidates a special substrate-binding modes of BaCut1 with plastic substrate analogue. BaCut1-mediated polyester plastic degradation offers an alternative approach for managing PU plastic wastes through possible bio-recycling.


Assuntos
Biodegradação Ambiental , Hidrolases de Éster Carboxílico , Poliuretanos , Reciclagem , Poliuretanos/química , Hidrolases de Éster Carboxílico/metabolismo , Hidrolases de Éster Carboxílico/química , Burkholderiales/enzimologia , Burkholderiales/metabolismo , Ácidos Ftálicos/metabolismo , Ácidos Ftálicos/química , Plásticos/química , Plásticos/metabolismo , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/química , Poliésteres
8.
Environ Res ; 253: 119167, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38762006

RESUMO

Phthalate esters (PAEs) have become one of the most concerned emerging organic pollutants in the world, due to the toxicity to human health, and hard to remove it efficiently. In this study, the degradation performance of DBP and DEHP in the soil by water bath heating activated sodium persulfate (PS) method under different factors were studied, in which the degradation rate of DBP and DEHP were improved with the increasing of temperature, PS concentration and water/soil ratio, and higher diffusion efficiency treatments methods, due to the improved mass transfer from organic phase to aqueous media. However, the degradation rate of DEHP was much lower than that of DBP, because DEHP in the soil was more difficult to contact with SO4•- for reaction on soil surface, and the degradation rate of PAEs in soil was significantly lower than that in water. Redundancy analysis of degradation rate of DBP and DEHP in water demonstrated that the key factors that determine the degradation rate is time for DBP, and cosolvent dosage for DEHP, indicating that the solubility and diffusion rate of PAEs from soil to aqueous are predominance function. This study provides comprehensive scenes in PAEs degradation with persulfate oxidation activated by thermal in soil, reveal the difference of degradation between DBP and DEHP is structure-dependent. So that we provide fundamental understanding and theoretical operation for subsequent filed treatment of various structural emerging pollutants PAEs contaminated soil with thermal activated persulfate.


Assuntos
Oxirredução , Ácidos Ftálicos , Poluentes do Solo , Solo , Sulfatos , Sulfatos/química , Ácidos Ftálicos/química , Poluentes do Solo/química , Solo/química , Ésteres/química , Compostos de Sódio/química , Temperatura Alta
9.
Biosens Bioelectron ; 258: 116356, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38705073

RESUMO

In this work, the dual-ligand lanthanide metal-organic framework (MOF)-based electrochemiluminescence (ECL) sensor was constructed for the detection of miRNA-128 in glioblastoma (GBM) diagnosis. The luminescent Eu-MOF (EuBBN) was synthesized with terephthalic acid (BDC) and 2-amino terephthalic acid (BDC-NH2) as dual-ligand. Due to the antenna effect, EuBBN with conjugated-π structure exhibited strong luminescent signal and high quantum efficiency, which can be employed as ECL nanoprobe. Furthermore, the novel plasmonic CuS@Au heterostructure array has been prepared. The localized surface plasmon resonance coupling effect of the CuS@Au heterostructure array can amplify the ECL signal of EuBBN significantly. The EuBBN/CuS@Au heterostructure array-based sensing system has been prepared for the detection of miRNA-128 with a wide linear range from 1 fM to 1 nM and a detection limit of 0.24 fM. Finally, miRNA-128 in the clinic GBM tissue sample has been analysis for the distinguish of tumor grade successfully. The results demonstrated that the dual-ligand MOF/CuS@Au heterostructure array-based ECL sensor can provide important support for the development of GBM diagnosis.


Assuntos
Técnicas Biossensoriais , Európio , Glioblastoma , Ouro , Estruturas Metalorgânicas , MicroRNAs , MicroRNAs/análise , Glioblastoma/diagnóstico , Humanos , Estruturas Metalorgânicas/química , Técnicas Biossensoriais/métodos , Ouro/química , Európio/química , Limite de Detecção , Medições Luminescentes/métodos , Ligantes , Técnicas Eletroquímicas/métodos , Neoplasias Encefálicas/diagnóstico , Ácidos Ftálicos/química , Nanopartículas Metálicas/química , Cobre/química
10.
ACS Nano ; 18(20): 13117-13129, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38727027

RESUMO

The complexity, heterogeneity, and drug resistance of diseases necessitate a shift in therapeutic paradigms from monotherapy to combination therapy, which could augment treatment efficiency. Effective treatment of advanced osteoarthritis (OA) requires addressing three key factors contributing to its deterioration: chronic joint inflammation, lubrication dysfunction, and cartilage-tissue degradation. Herein, we present a supramolecular nanomedicine of multifunctionality via molecular recognition and self-assembly. The employed macrocyclic carrier, zwitterion-modified cavitand (CV-2), not only accurately loads various drugs but also functions as a therapeutic agent with lubricating properties for the treatment of OA. Kartogenin (KGN), a drug for articular cartilage regeneration and protection, and flurbiprofen (FP), an anti-inflammatory agent, were coloaded onto CV-2 assembly, forming a supramolecular nanomedicine KGN&FP@CV-2. The three-in-one combination therapy of KGN&FP@CV-2 addresses the three pathological features for treating OA collectively, and thus provides long-term therapeutic benefits for OA through sustained drug release and intrinsic lubrication in vivo. The multifunctional integration of macrocyclic delivery and therapeutics provides a simple, flexible, and universal platform for the synergistic treatment of diseases involving multiple drugs.


Assuntos
Flurbiprofeno , Osteoartrite , Osteoartrite/tratamento farmacológico , Osteoartrite/patologia , Animais , Flurbiprofeno/química , Flurbiprofeno/administração & dosagem , Flurbiprofeno/farmacologia , Ácidos Ftálicos/química , Ácidos Ftálicos/farmacologia , Sistemas de Liberação de Medicamentos , Humanos , Portadores de Fármacos/química , Lubrificação , Liberação Controlada de Fármacos , Camundongos , Masculino , Anilidas
11.
Int J Mol Sci ; 25(10)2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38791471

RESUMO

Given the widespread use of esters and polyesters in products like cosmetics, fishing nets, lubricants and adhesives, whose specific application(s) may cause their dispersion in open environments, there is a critical need for stringent eco-design criteria based on biodegradability and ecotoxicity evidence. Our approach integrates experimental and computational methods based on short oligomers, offering a screening tool for the rapid identification of sustainable monomers and oligomers, with a special focus on bio-based alternates. We provide insights into the relationships between the chemical structure and properties of bio-based oligomers in terms of biodegradability in marine environments and toxicity in benchmark organisms. The experimental results reveal that the considered aromatic monomers (terephthalic acid and 2,5-furandicarboxylic acid) accumulate under the tested conditions (OECD 306), although some slight biodegradation is observable when the inoculum derives from sites affected by industrial and urban pollution, which suggests that ecosystems adapt to non-natural chemical pollutants. While clean seas are more susceptible to toxic chemical buildup, biotic catalytic activities offer promise for plastic pollution mitigation. Without prejudice to the fact that biodegradability inherently signifies a desirable trait in plastic products, nor that it automatically grants them a sustainable "license", this study is intended to facilitate the rational design of new polymers and materials on the basis of specific uses and applications.


Assuntos
Biodegradação Ambiental , Poliésteres/química , Organismos Aquáticos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade , Ácidos Ftálicos/química , Ácidos Ftálicos/toxicidade , Ácidos Ftálicos/metabolismo
12.
J Hazard Mater ; 472: 134603, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38749243

RESUMO

Polybutylene adipate terephthalic acid (PBAT) is an emerging biodegradable material in food packaging. However, concerns have been raised regarding the potential hazards it could pose to food safety. In this study, the changes of PBAT films during food contact and the release of small molecules were inestigated by a multiscale approach. On a macro-scale, the surface roughness of the films increased with the reduction in the concentration of food simulants and the increase in contact temperatures, especially after immersion in acidic food environments. On a micro-scale, the crystallinity (Xc) and degradation indexes (DI) of the films increased by 5.7-61.2% and 7.8-48.6%, respectively, which led to a decrease in thermal stability. On a scale approaching the molecular level, 2,4-di-tert-butylphenol (2,4-DTBP) was detected by gas chromatography-mass spectrometry (GC-MS/MS) with the highest migration content, and the release behavior of 2,4-DTBP was further investigated by migration kinetics. In addition, terephthalic acid (TPA), a hydrolysis product of PBAT, was detected in acidic food environments by liquid chromatography-mass spectrometry (LC-MS/MS). The results of this study could provide practical guidance and assistance to promote sustainable development in the field of food packaging.


Assuntos
Embalagem de Alimentos , Ácidos Ftálicos , Ácidos Ftálicos/química , Poliésteres/química , Adipatos/química , Contaminação de Alimentos/análise , Cromatografia Gasosa-Espectrometria de Massas
13.
J Agric Food Chem ; 72(21): 12045-12056, 2024 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-38753963

RESUMO

The gene-encoding carboxylesterase (TM1022) from the hyperthermophilic bacterium Thermotoga maritima (T. maritima) was cloned and expressed in Escherichia coli Top10 and BL21 (DE3). Recombinant TM1022 showed the best activity at pH 8.0 and 85 °C and retained 57% activity after 8 h cultivation at 90 °C. TM1022 exhibited good stability at pH 6.0-9.0, maintaining 53% activity after incubation at pH 10.0 and 37 °C for 6 h. The esterase TM1022 exhibited the optimum thermo-alkali stability and kcat/Km (598.57 ± 19.97 s-1mM-1) for pN-C4. TM1022 hydrolyzed poly(ethylene terephthalate) (PET) degradation intermediates, such as bis(2-hydroxyethyl) terephthalate (BHET) and mono(2-hydroxyethyl) terephthalate (MHET). The Km, kcat, and kcat/Km values for BHET were 0.82 ± 0.01 mM, 2.20 ± 0.02 s-1, and 2.67 ± 0.02 mM-1 s-1, respectively; those for MHET were 2.43 ± 0.07 mM, 0.04 ± 0.001 s-1, and 0.02 ± 0.001 mM-1 s-1, respectively. When purified TM1022 was added to the cutinase BhrPETase, hydrolysis of PET from drinking water bottle tops produced pure terephthalic acids (TPA) with 166% higher yield than those obtained after 72 h of incubation with BhrPETase alone as control. The above findings demonstrate that the esterase TM1022 from T. maritima has substantial potential for depolymerizing PET into monomers for reuse.


Assuntos
Proteínas de Bactérias , Estabilidade Enzimática , Ácidos Ftálicos , Thermotoga maritima , Thermotoga maritima/enzimologia , Thermotoga maritima/genética , Hidrólise , Concentração de Íons de Hidrogênio , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/química , Cinética , Ácidos Ftálicos/metabolismo , Ácidos Ftálicos/química , Especificidade por Substrato , Esterases/metabolismo , Esterases/genética , Esterases/química , Polietilenotereftalatos/metabolismo , Polietilenotereftalatos/química , Temperatura
14.
Molecules ; 29(9)2024 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-38731608

RESUMO

In this paper, Cu-BTC derived mesoporous CuS nanomaterial (m-CuS) was synthesized via a two-step process involving carbonization and sulfidation of Cu-BTC for colorimetric glutathione detection. The Cu-BTC was constructed by 1,3,5-benzenetri-carboxylic acid (H3BTC) and Cu2+ ions. The obtained m-CuS showed a large specific surface area (55.751 m2/g), pore volume (0.153 cm3/g), and pore diameter (15.380 nm). In addition, the synthesized m-CuS exhibited high peroxidase-like activity and could catalyze oxidation of the colorless substrate 3,3',5,5'-tetramethylbenzidine to a blue product. Peroxidase-like activity mechanism studies using terephthalic acid as a fluorescent probe proved that m-CuS assists H2O2 decomposition to reactive oxygen species, which are responsible for TMB oxidation. However, the catalytic activity of m-CuS for the oxidation of TMB by H2O2 could be potently inhibited in the presence of glutathione. Based on this phenomenon, the colorimetric detection of glutathione was demonstrated with good selectivity and high sensitivity. The linear range was 1-20 µM and 20-300 µM with a detection limit of 0.1 µM. The m-CuS showing good stability and robust peroxidase catalytic activity was applied for the detection of glutathione in human urine samples.


Assuntos
Colorimetria , Cobre , Glutationa , Peróxido de Hidrogênio , Nanoestruturas , Glutationa/análise , Glutationa/química , Colorimetria/métodos , Cobre/química , Nanoestruturas/química , Catálise , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/análise , Porosidade , Oxirredução , Ácidos Ftálicos/química , Humanos , Benzidinas/química , Limite de Detecção
15.
Waste Manag ; 183: 21-31, 2024 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-38714119

RESUMO

Poly(vinyl chloride) (PVC) is one of the most widely used plastics. However, a major challenge in recycling PVC is that there is no economical method to separate and remove its toxic phthalate plasticizers. This research made a breakthrough by extracting PVC with liquefied dimethyl ether (DME) and successfully separating the plasticizer components. Nearly all (97.1 %) of the di(2-ethylhexyl) phthalate plasticizer was extracted within 30 min by passing liquefied DME (285 g) through PVC at 25 °C. The compatibility of PVC with organic solvents, including liquefied DME, was derived theoretically from their Hansen solubility parameters (HSP), and actual dissolution experiments were conducted to determine the optimal PVC solvents. A liquefied DME mixture was used to dissolve PVC, and the extract was diluted with ethanol to precipitate the dissolved PVC. We demonstrated that liquefied DME is a promising method for producing high quality recycled products and that the process retains the fundamental properties of plasticizers and PVC without inducing degradation or depolymerization. Because of its low boiling point, DME can be easily separated from the solute after extraction, allowing for efficient reuse of the solvent, extracted plasticizer, and PVC. DME does not require heat and produces little harmful wastewater, which significantly reduces the energy consumption of the plasticizer additive separation process.


Assuntos
Dietilexilftalato , Éteres Metílicos , Plastificantes , Cloreto de Polivinila , Reciclagem , Cloreto de Polivinila/química , Dietilexilftalato/química , Reciclagem/métodos , Éteres Metílicos/química , Éteres Metílicos/análise , Solventes/química , Ácidos Ftálicos/química
16.
Inorg Chem ; 63(21): 9801-9808, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38743640

RESUMO

Enzyme immobilization within metal-organic frameworks (MOFs) is a promising solution to avoid denaturation and thereby utilize the desirable properties of enzymes outside of their native environments. The biomimetic mineralization strategy employs biomacromolecules as nucleation agents to promote the crystallization of MOFs in water at room temperature, thus overcoming pore size limitations presented by traditional postassembly encapsulation. Most biomimetic crystallization studies reported to date have employed zeolitic imidazole frameworks (ZIFs). Herein, we expand the library of MOFs suitable for biomimetic mineralization to include zinc(II) MOFs incorporating functionalized terephthalic acid linkers and study the catalytic performance of the enzyme@MOFs. Amine functionalization of terephthalic acids is shown to accelerate the formation of crystalline MOFs enabling new enzyme@MOFs to be synthesized. The structure and morphology of the enzyme@MOFs were characterized by PXRD, FTIR, and SEM-EDX, and the catalytic potential was evaluated. Increasing the linker length while retaining the amino moiety gave rise to a family of linkers; however, MOFs generated with the 2,2'-aminoterephthalic acid linker displayed the best catalytic performance. Our data also illustrate that the pH of the reaction mixture affects the crystal structure of the MOF and that this structural transformation impacts the catalytic performance of the enzyme@MOF.


Assuntos
Ácidos Carboxílicos , Cristalização , Estruturas Metalorgânicas , Temperatura , Água , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/síntese química , Ácidos Carboxílicos/química , Água/química , Ácidos Ftálicos/química , Materiais Biomiméticos/química , Materiais Biomiméticos/síntese química , Estrutura Molecular , Zinco/química , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Aminas/química , Catálise
17.
Sci Rep ; 14(1): 7944, 2024 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-38575598

RESUMO

In recent years, the presence and migration of PAEs in packaging materials and consumer products has become a serious concern. Based on this concern, the aim of our study is to determine the possible migration potential and speed of PAEs in benthic fish stored in vacuum packaging, as well as to monitor the storage time and type as well as polyethylene (PE) polymer detection.As a result of the analysis performed by µ-Raman spectroscopy, 1 microplastic (MP) of 6 µm in size was determined on the 30th day of storage in whiting fish muscle and the polymer type was found to be Polyethylene (PE) (low density polyethylene: LDPE). Depending on the storage time of the packaging used in the vacuum packaging process, it has been determined that its chemical composition is affected by temperature and different types of polymers are formed. 10 types of PAEs were identified in the packaging material and stored flesh fish: DIBP, DBP, DPENP, DHEXP, BBP, DEHP, DCHP, DNOP, DINP and DDP. While the most dominant PAEs in the packaging material were determined as DEHP, the most dominant PAEs in fish meat were recorded as BBP and the lowest as DMP. The findings provide a motivating model for monitoring the presence and migration of PAEs in foods, while filling an important gap in maintaining a safe food chain.


Assuntos
Dietilexilftalato , Ácidos Ftálicos , Animais , Dietilexilftalato/análise , Plásticos , Vácuo , Ácidos Ftálicos/química , Polietileno/análise , Polímeros , Dibutilftalato , Ésteres/análise , China
18.
Environ Pollut ; 349: 123917, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38583794

RESUMO

Phthalate esters (PAEs) are plasticizers widely used in the industry and easily released into the environment, posing a serious threat to human health. Molecularly imprinted polymers (MIPs) are important as selective adsorbents for the removal of PAEs. In this study, three kinds of mussel-inspired MIPs for the removal of PAEs were first prepared with gallic acid (GA), hexanediamine (HD), tannic acid (TA), and dopamine (DA) under mild conditions. The adsorption results showed that the MIP with low cost derived from GA and HD (GAHD-MIP) obtained the highest adsorption capacity among these materials. Furthermore, 97.43% of equilibrium capacity could be reached within the first 5 min of adsorption. Especially, the dummy template of diallyl phthalate (DAP) with low toxicity was observed to be more suitable to prepare MIPs than dibutyl phthalate (DBP), although DBP was the target of adsorption. The adsorption process was in accordance with the pseudo-second-order kinetics model. In the isotherm analysis, the adsorption behavior agreed with the Freundlich model. Additionally, the material maintained high adsorption performance after 7 cycles of regeneration tests. The GAHD-MIP adsorbents in this study, with low cost, rapid adsorption equilibrium, green raw materials, and low toxicity dummy template, provide a valuable reference for the design and development of new MIPs.


Assuntos
Dibutilftalato , Ácido Gálico , Polímeros Molecularmente Impressos , Poluentes Químicos da Água , Adsorção , Dibutilftalato/química , Poluentes Químicos da Água/química , Ácido Gálico/química , Polímeros Molecularmente Impressos/química , Ácidos Ftálicos/química , Cinética , Purificação da Água/métodos
19.
ACS Appl Mater Interfaces ; 16(17): 21450-21462, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38649157

RESUMO

Osteoarthritis (OA) is a common joint disease characterized by progressive cartilage degeneration. Unfortunately, currently available clinical drugs are mainly analgesics and cannot alleviate the development of OA. Kartogenin (KGN) has been found to promote the differentiation of bone marrow mesenchymal stem cells (BMSCs) into chondrocytes for the treatment of cartilage damage in early OA. However, KGN, as a small hydrophobic molecule, is rapidly cleared from the synovial fluid after intra-articular injection. This study synthesized a KGN-loaded nanocarrier based on PLGA/polydopamine core/shell structure to treat OA. The fluorescence signal of KGN@PLGA/PDA-PEG-E7 nanoparticles lasted for 4 weeks, ensuring long-term sustained release of KGN from a single intra-articular injection. In addition, the polyphenolic structure of PDA enables it to effectively scavenge reactive oxygen species, and the BMSC-targeting peptide E7 (EPLQLKM) endows KGN@PLGA/PDA-PEG-E7 NPs with an effective affinity for BMSCs. As a result, the KGN@PLGA/PDA-PEG-E7 nanoparticles could effectively induce cartilage in vitro and protect the cartilage and subchondral bone in a rat ACLT model. This therapeutic strategy could also be extended to the delivery of other drugs, targeting other tissues to treat joint diseases.


Assuntos
Anilidas , Indóis , Células-Tronco Mesenquimais , Nanopartículas , Osteoartrite , Copolímero de Ácido Poliláctico e Ácido Poliglicólico , Polímeros , Ratos Sprague-Dawley , Osteoartrite/tratamento farmacológico , Osteoartrite/patologia , Animais , Ratos , Injeções Intra-Articulares , Copolímero de Ácido Poliláctico e Ácido Poliglicólico/química , Nanopartículas/química , Polímeros/química , Células-Tronco Mesenquimais/efeitos dos fármacos , Células-Tronco Mesenquimais/metabolismo , Indóis/química , Indóis/farmacologia , Ácidos Ftálicos/química , Ácidos Ftálicos/farmacologia , Masculino , Portadores de Fármacos/química , Humanos
20.
Environ Sci Pollut Res Int ; 31(23): 33443-33453, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38683426

RESUMO

A new type of titanium phthalate (Ti-PA) catalyst was prepared by exchange method of phthalic acid and isopropyl titanate, which is never been reported before. The Ti-PA catalyst was characterized by FT-IR, TG, Uv-vis, BET, SEM, and EDS. The Ti-PA catalyst shows good catalytic activity in the alcoholysis reaction of polyethylene terephthalate (PET) and optimal experimental conditions for the alcoholysis process were optimized by response surface methodology; the Ti-PA catalyst provided a BHET yield of 81.98% for reaction lasting 3.98 h at 191 °C of 0.86% catalyst and 13.7 ml ethylene glycol; the model has good reliability. The kinetics and reaction mechanism of the process were explored and apparent activation energy is 75.52 kJ/mol. Finally, the good catalytic activity of Ti-PA was illustrated by comparing it with currently reported catalysts.


Assuntos
Ácidos Ftálicos , Polietilenotereftalatos , Titânio , Titânio/química , Polietilenotereftalatos/química , Catálise , Ácidos Ftálicos/química , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier
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