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ZnO nanoparticle-embedded Gellan Gum Based Sponge for Accelerated Wound Healing: An in vitro Study on Physicochemical, Antibacterial and Hemostatic Properties 纳米氧化锌包埋结冷胶海绵促进伤口愈合:理化、抗菌和止血性能的体外研究
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-08 DOI: 10.1007/s10924-024-03418-y
Başak Kurin Atasoyu, Gülşen Bayrak, Selen Öztürk, Aysun Kılıç Süloğlu, Bengi Özkahraman, Işık Perçin

In the current study, a biocompatible zinc oxide (ZnO) nanoparticle embedded gellan gum (GG) (GG-ZnNP) sponge with excellent antibacterial activity, enhanced wound healing and hemostatic properties was presented. Firstly, ZnO nanoparticles were synthesized by co-precipitation methods and characterized through Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) analysis. The size distribution and morphology of the ZnO nanoparticles were investigated by applying dynamic light scattering (DLS) and transmission electron microscopy (TEM). Presence and distribution of the ZnO nanoparticles in GG sponges were examined with Energy-dispersive x-ray spectroscopy (EDX) Thermogravitational Analysis (TGA) conducted to evaluate the thermal stability of GG-ZnO sponges. Following that, ZnO nanoparticles were embedded into GG sponges to enhance their antimicrobial properties. The physicochemical properties of GG-ZnNP sponges were characterized by FTIR, Scanning Electron Microscopy (SEM), swelling and degradation tests. The agar disk diffusion test and colony-forming unit assay findings showed that all GG-ZnNP sponges had a strong antibacterial activity against Escherichia coli (E.coli) and Staphylococcus aureus (S. aureus) bacteria. Furthermore, in vitro blood absorption tests indicated that GG-ZnNP sponges could effectively shorten bleeding time and increase blood absorption capacity. Cell viability studies conducted by MTT and scratch assay with L929 fibroblast cells. MTT assay were performed to found applicable ZnO dose of the sponges to be use as a wound dressings. In vitro scratch assays showed that GG-ZnNP sponges promoted wound closure and re-epithelialization in L929 fibroblast cells at increasing incubation time. GG-ZnNP sponges have a significant and improvable potential for wound dressing applications with their antibacterial and superior hemostatic properties.

Graphical Abstract

本研究提出了一种生物相容性氧化锌(ZnO)纳米颗粒包埋结冷胶(GG) (GG- znnp)海绵,具有良好的抗菌活性,促进伤口愈合和止血性能。首先,采用共沉淀法合成了ZnO纳米颗粒,并通过傅里叶变换红外光谱(FTIR)和x射线衍射(XRD)分析对其进行了表征。利用动态光散射(DLS)和透射电子显微镜(TEM)研究了ZnO纳米颗粒的尺寸分布和形貌。利用能量色散x射线能谱(EDX)和热重分析(TGA)对ZnO纳米颗粒在GG-ZnO海绵中的存在和分布进行了表征。然后,将ZnO纳米颗粒包埋在GG海绵中,以增强其抗菌性能。采用红外光谱(FTIR)、扫描电镜(SEM)、溶胀和降解实验对GG-ZnNP海绵的理化性质进行了表征。琼脂盘扩散试验和菌落形成单位试验结果表明,所有g - znnp海绵对大肠杆菌(E.coli)和金黄色葡萄球菌(S. aureus)具有较强的抗菌活性。此外,体外血液吸收试验表明,GG-ZnNP海绵可以有效缩短出血时间,提高血液吸收能力。用MTT法和划痕法研究L929成纤维细胞的细胞活力。采用MTT法确定了用于伤口敷料的海绵氧化锌的合适剂量。体外划伤实验表明,随着培养时间的延长,GG-ZnNP海绵可促进L929成纤维细胞伤口愈合和再上皮化。GG-ZnNP海绵在伤口敷料方面具有显著的改进潜力,具有抗菌和优越的止血性能。图形抽象
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引用次数: 0
Yarn Production from the Offshore Industry Mooring rope Waste: A Circular Textile Economy Opportunity 利用近海工业系泊绳废料生产纱线:循环纺织经济的机遇
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-08 DOI: 10.1007/s10924-024-03414-2
Thaiane Nolasco da Silva, Ana Maria Furtado de Sousa, Ana Lucia Nazareth da Silva, Adriano Alves Passos, Elen Beatriz Acordi Vasques Pacheco

Offshore platform decommissioning is a complex process that can cause marine damage. The circular economy can be used to implement sustainable initiatives in the decommissioning process. Mooring ropes, which commonly consist of poly(ethylene terephthalate) (PET) fiber, are one type of waste generated during offshore platform decommissioning. This study aims to demonstrate that the ring spinning process is a sustainable solution to recycling PET fibers from post-industrial mooring ropes (PMR-PET) by producing yarns containing 70–60% PMR-PET. One-way ANOVA and the Cochran test demonstrated that the yarns made with PMR-PET exhibit better tensile properties than those made with 100% commercial PET. Addition of PMR-PET produces a yarn with a higher crystallinity. The lower degradation temperatures of PMR-PET yarns are not enough to limit their use in textile products. This study demonstrates that recycling PMR-PET provides an opportunity to promote the circular economy and develop new yarns in the textile industry.

海上平台退役是一个复杂的过程,可能会对海洋造成损害。循环经济可用于在退役过程中实施可持续举措。系泊绳通常由聚对苯二甲酸乙二醇酯(PET)纤维组成,是海上平台退役过程中产生的一种废物。本研究旨在通过生产含有70-60% PMR-PET的纱线,证明环锭纺丝工艺是回收后工业系缆(PMR-PET)中PET纤维的可持续解决方案。单因素方差分析和Cochran检验表明,用PMR-PET制成的纱线比100%商用PET制成的纱线具有更好的拉伸性能。PMR-PET的加入使纱线具有更高的结晶度。PMR-PET纱线较低的降解温度不足以限制其在纺织产品中的应用。该研究表明,回收PMR-PET为纺织工业促进循环经济和开发新纱线提供了机会。
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引用次数: 0
Synergistic Effects of Polyethylene Glycol and Cellulose Nanofibers on the Isothermal and Non-isothermal Crystallization Behaviors of Polylactide 聚乙二醇和纤维素纳米纤维对聚丙交酯等温和非等温结晶行为的协同作用
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03412-4
Feng-jiao Li, Xi-tong Yu, Man-feng Gong, Xing-zao Ma, Xiao-jun Chen, Jun Xu, Bao-hua Guo

To significantly improve the crystallinity and crystallization rate of polylactide (PLA), plasticizer (polyethylene glycol, PEG) and nucleating agent (cellulose nanofibers, CNFs) were melt-blended with PLA to prepare PLA/PEG/CNF nanocomposites. The effects of PEG and/or CNFs and cooling rate on the crystallization kinetics of PLA were investigated by HS-POM, DSC, and WAXD. The non-isothermal crystallization kinetics of modified PLA samples were evaluated by the Jeziorny’s, Ozawa’s, and Mo’s models, while their non-isothermal crystallization activation energies were determined by Friedman’s method. The polarized optical micrographs showed that CNFs served as effective nucleating agents, increasing the nucleation density of PLA spherulites, but reducing their spherulite sizes; PEG improved the mobility of PLA chains and accelerated the growth rate of PLA spherulites, thus leading to larger spherulite sizes. The non-isothermal crystallization kinetics revealed that the crystallization temperature (Tc), crystallinity (XC), and crystallization half-time (t1/2) of all PLA-based samples decreased with increasing cooling rate. At the same cooling rate, the incorporation of 15 wt% PEG or 3 wt% CNFs increased Tc and XC but decreased t1/2 of PLA by enhancing spherulite growth rate and providing more crystal nuclei, respectively. Moreover, SEM micrographs showed that the addition of PEG improved the dispersion of CNFs within the PLA matrix, and the synergistic effect of PEG and CNFs more significantly increased Tc and XC, but reduced t1/2. The above results demonstrated that the combination of PEG and CNFs significantly enhanced the crystallization performance of PLA, providing insights for the design of high-performance PLA-based materials.

为了显著提高聚乳酸(PLA)的结晶度和结晶速率,将增塑剂(聚乙二醇,PEG)和成核剂(纤维素纳米纤维,CNF)与PLA熔融共混制备PLA/PEG/CNF纳米复合材料。采用HS-POM、DSC和WAXD研究了聚乙二醇和/或CNFs以及冷却速率对聚乳酸结晶动力学的影响。改性PLA样品的非等温结晶动力学采用Jeziorny’s、Ozawa’s和Mo’s模型进行评价,其非等温结晶活化能采用Friedman’s方法测定。极化光学显微照片表明,CNFs作为有效的成核剂,增加了聚乳酸球晶的成核密度,但减小了其球晶尺寸;PEG提高了PLA链的迁移率,加速了PLA球晶的生长速度,从而导致球晶尺寸增大。非等温结晶动力学表明,随着冷却速率的增加,所有pla基样品的结晶温度(Tc)、结晶度(XC)和结晶半衰期(t1/2)均降低。在相同的冷却速率下,15 wt%的PEG和3 wt%的CNFs分别通过提高球晶生长速率和提供更多的晶核而增加了Tc和XC,但减少了t1/2的PLA。此外,SEM显微图显示,PEG的加入改善了CNFs在PLA基体内的分散,PEG和CNFs的协同效应更显著地提高了Tc和XC,但降低了t1/2。上述结果表明,PEG和CNFs的结合显著增强了PLA的结晶性能,为高性能PLA基材料的设计提供了见解。
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引用次数: 0
Enhanced Flame-retardant Performance of Undervalued Polyethylene Terephthalate Waste as a Potential use in Foamed Materials 低估的聚对苯二甲酸乙二醇酯废物在泡沫材料中的潜在应用
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03424-0
Mercedes Santiago-Calvo, Andreas Himmelsbach, Carlos Alonso, Maria-Teresa Fernández, Esteban Cañibano, Christian Brütting, Tobias Standau, Holger Ruckdäschel

Nowadays, the post-consumer polyethylene terephthalate (PET) waste from the packaging industry is one of the largest plastic waste streams worldwide. While clear PET waste is commonly recycled and is reused for textile and packaging applications (even with food contact), coloured PET waste`s degraded state limits its reusing potential. This highlights the urgent need to upgrade low-value PET waste. This study focuses on enhancing coloured recycled PET (rPET) quality by introducing an epoxide chain extender (CE) from 0 to 1 wt%, to improve rheological behaviour. Simultaneously, upcycling opportunities are explored by incorporating an eco-friendly phosphorous-based flame retardant (FR) from 0 to 10 wt%, to reduce flammability and thus enabling electrical and electronic applications, among others. The impact of each additive, as well as their combination, is evaluated on the chemical structure, thermal, rheological and burning behaviour of undervalued rPET. The optimal CE content is determined at 0.8 wt%, promoting branched and higher molecular weight polymer chains. Regarding FR, 6, 8 and 10 wt% highly enhance the fire resistance. Furthermore, the combination CE/FR enables a synergistic effect, notably improving burning behaviour. Additionally, the foaming potential of the resulting high-value rPET is assessed for the first time through one-step batch foaming using supercritical CO2 as foaming agent, aiming to develop lightweight materials endowed with superior burning behaviour. The material containing 0.8 wt% CE reaches the lowest density (200 kg/m3) and a closed cellular structure with smaller cell diameters (8 ± 3 μm). Meanwhile, the combination of 0.8 wt% CE and 6 wt% FR gives rise to a foamed material with density of 659 kg/m3 and cell diameter of 7 μm. Thus, this batch procedure in one-step enables the formation of microcellular foams based on coloured rPET (cell size below 10 μm).

如今,来自包装行业的消费后聚对苯二甲酸乙二醇酯(PET)废物是全球最大的塑料废物流之一。虽然透明的PET废物通常被回收再利用,并用于纺织和包装应用(即使与食品接触),但彩色PET废物的降解状态限制了其再利用潜力。这凸显了对低价值PET废物进行升级的迫切需要。本研究的重点是提高彩色再生PET (rPET)的质量,通过引入环氧化物扩链剂(CE)从0到1 wt%,以改善流变性能。同时,通过将环保型磷基阻燃剂(FR)从0 wt%添加到10 wt%,探索升级回收的机会,以降低可燃性,从而实现电气和电子应用等。评估了每种添加剂及其组合对低估的rPET的化学结构、热、流变和燃烧行为的影响。最佳CE含量确定为0.8 wt%,促进支链和高分子量聚合物链。在阻燃系数方面,6、8、10 wt%的阻燃系数均能显著提高阻燃性能。此外,CE/FR的组合实现了协同效应,显著改善了燃烧性能。此外,本研究还首次以超临界CO2为发泡剂,通过一步间歇发泡的方法,对制备的高值rPET的发泡潜力进行了评估,旨在开发具有优异燃烧性能的轻质材料。含有0.8 wt% CE的材料密度最低(200 kg/m3),胞孔直径较小(8±3 μm),具有封闭的胞孔结构。同时,0.8 wt% CE和6 wt% FR的组合产生的泡沫材料密度为659 kg/m3,孔直径为7 μm。因此,该批处理过程可以一步形成基于彩色rPET的微孔泡沫(细胞尺寸小于10 μm)。
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引用次数: 0
A Highly Sensitive Test System for Measuring the Phenolic Index of Wastewater Based on a Biocompatible Composite Material with Carbon Nanotubes 基于碳纳米管生物相容性复合材料的高灵敏度废水酚指数测试系统
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03421-3
Tatyana Lavrova, Anna Kharkova, Roman Perchikov, Maria Gertsen, Andrey Shadrin, Vyacheslav Arlyapov

A biosensor for the determination of the phenol index in water bodies has been developed using enzymes immobilized on the redox-active polymer surface of a graphite paste electrode. Tyrosinase, laccase, and bacterial cell membrane fractions were used as biological materials. Redox polymers based on bovine serum albumin (BSA) and various electron transport mediators were synthesized for immobilization. It has been shown that a redox polymer based on ferrocene (FC) combined with single-walled carbon nanotubes (SWCNTs) is more promising for use in biosensors than a polymer based on safranin (SAF) based on electrochemical and analytical parameters. The best results were obtained with the “BSA-FC-SWCNT-tyrosinase” bioanalytical system, which has a lower limit of detectable concentrations of 1 × 10⁻³ mg/L, indicating the possibility of monitoring water environments with a phenol concentration corresponding to the maximum permissible concentration (MPC). The maximum analytical signal was generated at a temperature of 30 °С and a pH of 6.8. The biosensor was stable at concentrations of heavy metal ions up to 100 times the MPC, as well as at NaCl concentrations up to 5%. The system was tested on river water samples containing phenol. A statistical analysis of the results showed no significant difference between the biosensor results and those of standard analytical methods. The proposed approach will significantly reduce the analysis time, its labor intensity and cost.

将酶固定在石墨糊电极的氧化还原活性聚合物表面,研制了一种测定水体中苯酚指数的生物传感器。以酪氨酸酶、漆酶和细菌细胞膜组分作为生物材料。合成了基于牛血清白蛋白(BSA)和多种电子传递介质的氧化还原聚合物用于固定化。研究表明,基于二茂铁(FC)结合单壁碳纳米管(SWCNTs)的氧化还原聚合物比基于红花素(SAF)的基于电化学和分析参数的聚合物更有希望用于生物传感器。“bsa - fc - swcnt -酪氨酸酶”生物分析系统的检测结果最好,其检测浓度下限为1 × 10⁻³mg/L,表明用最大允许浓度(MPC)对应的苯酚浓度监测水环境是可能的。在温度为30°С和pH为6.8时产生最大的分析信号。该生物传感器在高达100倍MPC的重金属离子浓度和高达5%的NaCl浓度下都是稳定的。该系统在含酚的河水样品中进行了测试。统计分析结果表明,生物传感器的结果与标准分析方法的结果无显著差异。该方法将大大减少分析时间、劳动强度和成本。
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引用次数: 0
Biogenic Synthesis of Ag NPs Adorned Gellan Gum Modified Fe3O4 NPs Towards the Catalytic Reduction of Nitroarenes and the Investigation of Anti-breast Cancer Potential 结冷胶修饰Fe3O4 NPs的生物合成及其对硝基芳烃的催化还原及抗乳腺癌潜力的研究
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03380-9
Shi Qiu, Xiaofang Hu, Yun Zhao, Attalla F. El-kott, Sally Negm, Ali G. Alkhathami

In the realm of nanobiotechnology the bio-inspired and bioengineered nanoparticles have immense impetus in view of their unique and diverse implications. This research describes an eco-friendly method for the in situ synthesis of an Ag NP fabricated over gellan gum functionalized Fe3O4 NPs (Fe3O4@gellan gum-Ag) and its subsequent catalytic and biological uses. The morphological and physicochemical properties of this material were evaluated applying a variety of instrumental methods, including FT-IR, FE-SEM, TEM, EDS, elemental mapping, XRD, and ICP. The as synthesized Fe3O4@gellan gum-Ag NPs was used as a nanocatalyst in the catalytic application to reduce nitrobenzene derivatives. A UV–Vis spectrophotometer was used to track the reduction process. Through eight additional cycles, we assessed the sustainability of this catalyst based on its recyclable qualities. Furthermore, the nanocomposite’s bioapplication for in vitro anticancer research against the breast cell lines MCF-7 and SKBR3 was expanded through the use of the MTT assay. The material caused a dose-dependent reduction in the malignant breast cell line’s cell survival. Regarding the MCF-7 (Michigan Cancer Foundation-7) and SKBR3 (Sloan–Kettering breast cancer) cell lines, the nanocomposite was found to have IC50 values of 41.2 and 39 µg/mL. In the near future, cancer management may appear extremely promising, considering the amazing results the developed nanocomposite demonstrated.

在纳米生物技术领域,生物启发和生物工程纳米粒子由于其独特和多样的含义而具有巨大的推动力。本研究描述了在结冷胶功能化Fe3O4 NPs (Fe3O4@gellan gum-Ag)上原位合成银NP的环保方法及其后续的催化和生物用途。采用FT-IR、FE-SEM、TEM、EDS、元素映射、XRD和ICP等多种仪器方法对该材料的形态和物理化学性质进行了评价。将合成的Fe3O4@gellan胶银NPs作为纳米催化剂用于硝基苯衍生物的还原。采用紫外可见分光光度计对还原过程进行跟踪。通过八个额外的循环,我们根据催化剂的可回收性评估了其可持续性。此外,通过使用MTT试验,纳米复合材料在体外抗乳腺癌细胞系MCF-7和SKBR3的生物应用得到了扩展。该物质导致恶性乳腺细胞系细胞存活率呈剂量依赖性降低。对于MCF-7(密歇根癌症基金会-7)和SKBR3(斯隆-凯特琳乳腺癌)细胞系,纳米复合材料的IC50值分别为41.2和39µg/mL。在不久的将来,考虑到开发的纳米复合材料所展示的惊人结果,癌症治疗可能会显得非常有希望。
{"title":"Biogenic Synthesis of Ag NPs Adorned Gellan Gum Modified Fe3O4 NPs Towards the Catalytic Reduction of Nitroarenes and the Investigation of Anti-breast Cancer Potential","authors":"Shi Qiu,&nbsp;Xiaofang Hu,&nbsp;Yun Zhao,&nbsp;Attalla F. El-kott,&nbsp;Sally Negm,&nbsp;Ali G. Alkhathami","doi":"10.1007/s10924-024-03380-9","DOIUrl":"10.1007/s10924-024-03380-9","url":null,"abstract":"<div><p>In the realm of nanobiotechnology the bio-inspired and bioengineered nanoparticles have immense impetus in view of their unique and diverse implications. This research describes an eco-friendly method for the in situ synthesis of an Ag NP fabricated over gellan gum functionalized Fe<sub>3</sub>O<sub>4</sub> NPs (Fe<sub>3</sub>O<sub>4</sub>@gellan gum-Ag) and its subsequent catalytic and biological uses. The morphological and physicochemical properties of this material were evaluated applying a variety of instrumental methods, including FT-IR, FE-SEM, TEM, EDS, elemental mapping, XRD, and ICP. The as synthesized Fe<sub>3</sub>O<sub>4</sub>@gellan gum-Ag NPs was used as a nanocatalyst in the catalytic application to reduce nitrobenzene derivatives. A UV–Vis spectrophotometer was used to track the reduction process. Through eight additional cycles, we assessed the sustainability of this catalyst based on its recyclable qualities. Furthermore, the nanocomposite’s bioapplication for in vitro anticancer research against the breast cell lines MCF-7 and SKBR3 was expanded through the use of the MTT assay. The material caused a dose-dependent reduction in the malignant breast cell line’s cell survival. Regarding the MCF-7 (Michigan Cancer Foundation-7) and SKBR3 (Sloan–Kettering breast cancer) cell lines, the nanocomposite was found to have IC50 values of 41.2 and 39 µg/mL. In the near future, cancer management may appear extremely promising, considering the amazing results the developed nanocomposite demonstrated.</p></div>","PeriodicalId":659,"journal":{"name":"Journal of Polymers and the Environment","volume":"33 1","pages":"570 - 580"},"PeriodicalIF":4.7,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of Epoxy Chain Extender and Multiple Processing on Poly-(R)-3-Hydroxybutyrate’s Properties 环氧扩链剂及复合工艺对聚(R)-3-羟基丁酸酯性能的影响
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03425-z
Klaus Hinterberger, Priyanka Main, Christoph Waly, Thomas Lucyshyn

The semi-crystalline poly-(R)-3-hydroxybutyrate (PHB) is a biobased and biodegradable polymer. This makes it a promising alternative to polypropylene (PP), especially for packaging applications. PHB has excellent barrier properties to O2, CO2, and H2O, but is susceptible to degradation from heat and hydrolysis. The epoxy chain extender Joncryl® was added to PHB in a simulated recycling process to reverse the degradation due to processing. The effects of the chain extender and the degradation due to processing were investigated with thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), small strain oscillatory plate-plate rheometry, tensile tests, and notched Charpy impact tests. With the addition of the chain extender, a decrease in peak crystallization temperature and tensile modulus, and an increase in zero-shear viscosity and elongation at break were observed. For each additional processing step the zero-shear viscosity, the elongation at break, and the notched impact strength decreased, while the tensile modulus increased. The effect of the thermal load during processing on the material properties is significantly higher compared to the effect of the addition of the chain extender. Therefore, the practical application of the investigated chain extender alone in a multi-stage recycling process seems limited. This is due to the low processing temperature of PHB, which seems to limit the full potential of Joncryl® due to the slow reaction speed at this temperature.

半结晶聚-(R)-3-羟基丁酸酯(PHB)是一种生物基可生物降解聚合物。这使其成为聚丙烯(PP)的有前途的替代品,特别是用于包装应用。PHB对O2、CO2和H2O具有优异的阻隔性能,但易因热和水解而降解。在模拟回收过程中,将环氧扩链剂Joncryl®添加到PHB中,以逆转由于加工而导致的降解。通过热重分析(TGA)、差示扫描量热法(DSC)、小应变振荡板-板流变法、拉伸试验和缺口Charpy冲击试验,研究了扩链剂的影响和加工降解。扩链剂的加入降低了结晶峰温度和拉伸模量,提高了零剪切粘度和断裂伸长率。每增加一个加工步骤,零剪切粘度、断裂伸长率和缺口冲击强度降低,而拉伸模量增加。加工过程中的热负荷对材料性能的影响明显高于添加扩链剂的影响。因此,所研究的扩链剂在多阶段回收过程中的实际应用似乎有限。这是由于PHB的处理温度低,这似乎限制了Joncryl®的全部潜力,因为在这个温度下反应速度慢。
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引用次数: 0
Utilization of Lignin-derived Methoxybisphenols for the Preparation of Bio-based Polyesters for Packaging Applications 利用木质素衍生的甲氧基双酚制备包装用生物基聚酯
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03405-3
Haoming Xu, Zhengzai Cheng, Lesly Dasilva Wandji Djouonkep, Mario Gauthier, Yingzi Zuo, Wei Tang, Leyang Xiang

The packaging industry faces a shortage of high-strength bio-derived polyesters that can rival polyethylene derivatives, resulting in the overexploitation of fossil resources. By condensing lignin-derived 2-methoxyhydroquinone with methyl 4-chloromethyl benzoate, the diester dimethyl 4,4’-(((2-methoxy-1,4-phenylene)bis(oxy))bis(methylene))dibenzoate (M) was synthesized. Using monomer M and hydroquinone hydroxyethyl ether, aliphatic-aromatic copolyesters P1-P4 were prepared via melt polycondensation reaction employing various aliphatic diacids (1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, and 1,12-dodecanedioic acid). The chemical structures of the copolyesters were elucidated using FTIR and 1H NMR, while their properties were characterized through gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, tensile testing, and dynamic mechanical analysis. GPC analysis revealed that the average molecular weight (Mw) of copolyesters P1–P4 ranged from 4.22 to 5.03 × 104 g/mol, while thermal property analysis indicated that the copolyesters thermal stability decreased with increasing aliphatic diacid spacer length unit. Also, the glass transition temperature (Tg) and melting point (Tm) decreased from 90 to 68 °C and 182–158 °C, respectively. Mechanical analysis showed a decrease in tensile modulus from 1740 to 1010 MPa, as well as yield strength from 76 to 54 MPa, but indicated an increase in elongation at break from 236 to 295%, owed to the growth of carbon chains which increases the proportion of flexible units in the polymer chain. The degradability study indicated a modest degradation rate from 3.9 to 5.1% after 30 weeks from P1–P4, with low ecotoxicity in all cases. P4, consisting of 1,12-dodecanedioic acid, exhibited the highest degradation rate, due to its low proportion of benzene units. These findings provide insights into the structure-property relationships of aliphatic-aromatic copolyesters while contributing to the advancement of high Mw polyesters with performance comparable to conventional petroleum-derived polyesters, aligning with the strategy of green low-carbon, energy-saving, reduction, and sustainable development of polymeric materials.

包装行业面临着可以与聚乙烯衍生物相媲美的高强度生物衍生聚酯的短缺,导致化石资源的过度开发。通过木质素衍生的2-甲氧基对苯二酚与4-氯甲基苯甲酸甲酯缩合,合成了二甲酯4,4′-((2-甲氧基-1,4-苯基)双(氧)双(亚甲基))二苯甲酸酯(M)。以单体M和对苯二酚羟基乙醚为原料,以不同的脂肪二酸(1,4-丁二酸、1,6-己二酸、1,8-辛二酸和1,12-十二烯二酸)为原料,通过熔融缩聚反应制备了脂肪族-芳香族共聚酯P1-P4。利用FTIR和1H NMR对共聚酯的化学结构进行了表征,并通过凝胶渗透色谱、差示扫描量热、热重分析、拉伸测试和动态力学分析对其性能进行了表征。GPC分析表明,共聚酯p1 ~ p4的平均分子量(Mw)在4.22 ~ 5.03 × 104 g/mol之间,热性能分析表明,随着脂肪二酸间隔段长度单位的增加,共聚酯的热稳定性降低。玻璃化转变温度(Tg)和熔点(Tm)分别从90℃降低至68℃和182℃至158℃。力学分析表明,拉伸模量从1740降低到1010 MPa,屈服强度从76降低到54 MPa,但断裂伸长率从236增加到295%,这是由于碳链的增长增加了聚合物链中柔性单元的比例。可降解性研究表明,从P1-P4 30周后,降解率为3.9 - 5.1%,所有病例的生态毒性都很低。由1,12-十二烷二酸组成的P4,由于其苯单元比例低,表现出最高的降解率。这些发现为研究脂肪族-芳烃共聚酯的结构-性能关系提供了新的思路,同时也为开发性能与传统石油衍生聚酯相当的高毫瓦聚酯做出了贡献,符合高分子材料绿色低碳、节能、减量化和可持续发展的战略。
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引用次数: 0
Plasticization of Polylactide Using Biobased Epoxidized Isobutyl Esters Derived from Waste Soybean Oil Deodorizer Distillate 废大豆油脱臭馏出物生物基环氧化异丁基酯塑化聚丙交酯
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03415-1
L. Najera-Losada, P. C. Narváez-Rincón, A. Orjuela, J. Gomez-Caturla, O. Fenollar, R. Balart

A series of epoxidized isobutyl esters (EIE) derived from soybean oil deodorizing distillate (SODD) were synthesized via esterification with isobutanol followed by epoxidation. Epoxidized isobutyl soyate (EIS), epoxidized isobutyl soyate distillate (EISD), as well as the epoxidized esters of the main fatty acids contained in SODD, namely, epoxidized isobutyl linoleate (EIL), and epoxidized isobutyl oleate (EIO) were also synthesized and assessed as environmentally friendly plasticizers for polylactide (PLA). A comparison of the plasticizing efficiency of 10 wt.% of these EIE on PLA properties is addressed in this work. The effects of the different EIE on mechanical properties (tensile and impact tests) at 21 ºC, thermal transitions and thermal degradation, dynamic-mechanical thermal properties and dimensional change with temperature, and morphology are evaluated and compared with commercial epoxidized soybean oil (ESBO), and acetyl tributyl citrate (ATBC). Tensile tests indicate that EIE provide increased elongation at break from 8.8% (neat PLA), up to 10–32%, depending on the EIE. EIE seem to be more compatible with PLA as observed by field emission scanning electron microscopy (FESEM) since they do not give evidence of phase separation, or plasticizer saturation, which is clearly observed with ESBO. Regarding thermal properties, all EIE provide a noticeable decrease in the glass transition temperature (Tg) from 61.6 ºC (neat PLA), down to values ranging from 42 to 48 ºC, remarkably lower than the decrease provided by ESBO with a Tg value of 56.6 ºC. These findings reveal that EIE are promising plasticizers for PLA with balanced properties and contribute to improve its intrinsic brittleness by increasing the impact toughness.

以大豆油脱臭馏出物(SODD)为原料,经异丁醇酯化和环氧化反应,合成了一系列环氧化异丁基酯(EIE)。合成了环氧化大豆异丁酯(EIS)、环氧化大豆异丁酯馏出物(EISD)以及SODD中主要脂肪酸的环氧化酯,即环氧化亚油酸异丁酯(EIL)和环氧化油酸异丁酯(EIO),并对其作为聚乳酸(PLA)的环保型增塑剂进行了评价。比较了10% eee的塑化效率对PLA性能的影响。研究了不同eee对21℃下机械性能(拉伸和冲击试验)、热转变和热降解、动态-机械热性能、尺寸随温度变化以及形貌的影响,并与商品环氧大豆油(ESBO)和柠檬酸乙酰三丁酯(ATBC)进行了比较。拉伸试验表明,根据不同的EIE, EIE的断裂伸长率从8.8%(纯PLA)增加到10-32%。通过场发射扫描电子显微镜(FESEM)观察到,eee似乎与PLA更相容,因为它们没有提供相分离或增塑剂饱和的证据,而ESBO则清楚地观察到这一点。在热性能方面,所有eee的玻璃化转变温度(Tg)从61.6℃(纯PLA)显著降低至42 ~ 48℃,显著低于ESBO的56.6℃。这些发现表明,EIE是一种有前途的PLA增塑剂,具有平衡的性能,并有助于通过增加冲击韧性来改善其固有脆性。
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引用次数: 0
Functionalization of Chitosan-Chitin Nanowhiskers Films By Impregnation With Essential Oils Via Supercritical CO2 超临界CO2精油浸渍壳聚糖-几丁质纳米晶须膜的功能化研究
IF 4.7 3区 工程技术 Q2 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-04 DOI: 10.1007/s10924-024-03413-3
C. Muñoz-Núñez, V. Hevilla, J. Zágora, D. Plachá, A. Muñoz-Bonilla, M. Fernández-García

Herein, we prepared functional chitosan films reinforced with chitin nanocrystals by supercritical solvent impregnation with a variety of essential oils, i.e. mentha, clove, and cinnamon. Two different chitosan film structures were evaluated, smooth and compact films obtained by casting; and highly porous films prepared by lyophilization process. The effect of the film morphology, essential oil impregnation and the presence of chitin nanowhiskers on the properties of the films were extensively investigated by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and tensile testing; while the bioactive functions were evaluated by measuring the antioxidant and antimicrobial activities. It was found that the impregnation of essential oils is much higher in porous films, confering notable antioxidant and antimicrobial activity. The incorporation of chitin nanocrystal does not influence on the impregnation process, and only improves slightly the antioxidant performance, which is clearly appreciable in the case of films obtained by casting with an increase of ca. 35% from chitosan without to samples with 5 wt% of chitin nanowhiskers. Nevertheless, an important enhancement of the mechanical properties, particularly in elastic modulus, is clearly appreciated with the incorporation of chitin nanowhisker into the films, with values of 50% higher in comparison with chitosan without nanowishers. However, the elongation at break and tensile strength values suffer a slight decrease.

Graphical Abstract

本研究以薄荷、丁香、肉桂等多种精油为溶剂,通过超临界浸渍法制备甲壳素纳米晶增强壳聚糖功能膜。对两种不同壳聚糖薄膜结构进行了评价,采用铸造法制备了光滑致密的壳聚糖薄膜;以及采用冻干工艺制备的高多孔膜。采用扫描电镜、x射线衍射、傅里叶变换红外光谱和拉伸测试等方法研究了甲壳素纳米晶须的存在、精油浸渍和薄膜形貌对薄膜性能的影响;通过测定其抗氧化和抗菌活性来评价其生物活性。发现精油在多孔膜中的浸渍率高得多,具有显著的抗氧化和抗菌活性。几丁质纳米晶的掺入对浸渍过程没有影响,只略微提高了抗氧化性能,这在不含5 wt%的几丁质纳米晶须的情况下,壳聚糖增加约35%的浇铸膜的情况下是明显明显的。然而,在薄膜中加入几丁质纳米晶须后,其机械性能,特别是弹性模量有了显著的提高,与不加入纳米晶须的壳聚糖相比,其力学性能提高了50%。然而,断裂伸长率和抗拉强度值略有下降。图形抽象
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引用次数: 0
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Journal of Polymers and the Environment
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