Chemical degradation

  • 文章类型: Journal Article
    自从秦兵马俑出土以来,聚酰胺650交联的E-44环氧树脂粘合剂已用于粘合和恢复它们。在本文中,通过红外光谱研究了兵马俑在过去30年中在室内自然环境中使用的粘合剂的化学老化,X射线光电子能谱和热重分析。结果表明,在所有确定的粘合剂的红外光谱中,粘合剂在1700cm-1处均未出现羰基拉伸振动的特征峰,它们的热分解曲线没有出现任何异常变化,热分解主要发生在300℃以上。有明显的陶瓷颗粒附着在粘合剂的表面上,被剥离用于取样。这些结果表明,秦兵马俑中的粘合剂没有表现出可观察到的化学老化,并且仍然具有很强的粘附力。一般来说,由于自然老化和加速人工老化无法重现复杂天气条件的影响,因此在自然老化和加速人工老化之间存在差异。与人工加速衰老相比,评估结果是用于修复真人大小的秦兵马俑的粘合剂长期自然老化,在目前的调查中,在预测恢复的兵马俑的安全性方面更可靠。
    Since the Qin terracotta warriors were unearthed, polyamide 650 cross-linked E-44 epoxy resin binder has been employed to bond and restore them. In this paper, the chemical aging of the binders service in indoor natural environment during the past 30 years in the terracotta warriors was studied by means of infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. The results indicated that the binders did not emerge the characteristic peak of carbonyl stretching vibration at 1700 cm-1 in the IR spectra of all determined binders, and their thermal decomposition curves did not emerge any abnormal changes, and the thermal decomposition mainly occurred above 300 °C. There are evident ceramic grains attached to the surface of the binders being peeled off for sampling. These results that the binders service in the Qin terracotta warriors did not exhibit an observable chemical aging and still has strong adhesion. Generally, discrepancies were observed between natural aging and accelerated artificial aging due to the ineffectiveness of the latter to reproduce the effects of complex weather conditions. Compared to artificially accelerated aging, the evaluation results in a long-term natural aging of the binder which is used for restoration of the life-size Qin terracotta warriors, providing in the present investigation, are more reliable in terms of predicting the safety of restored terracotta warriors.
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  • 文章类型: Journal Article
    应对有害蓝藻水华(CyanoHAB)及其相关微囊藻毒素(MC)的威胁对于全球饮用水安全至关重要。在这次审查中,我们全面分析和比较了身体,化学,以及水生环境中MCs降解的生物学方法和基因工程。物理方法,如紫外线处理和光催化反应,在分解MC方面有很高的效率,具有进一步提高性能和减少危险副产品的潜力。使用二氧化氯和高锰酸钾的化学处理可以降低MC水平,但需要谨慎的剂量管理,以避免有毒副产物并保护水生生态系统。生物方法,包括微生物降解和植物修复技术,显示出MCs生物降解的希望,提供减少的环境影响和增加的可持续性。基因工程,例如微囊藻毒素酶A(MlrA)在大肠杆菌中的固定及其在集胞藻属中的表达。,已证明在分解MC如MC-LR方面是有效的。然而,与温度变化等特定环境条件相关的挑战,pH值,其他污染物的存在,营养可用性,氧气水平,和曝光,以及生物系统的可扩展性,需要进一步探索。我们提供了对MC降解技术的全面评估,深入研究它们的实用性,评估环境影响,并仔细检查它们的效率,以提供对这些方法在各种环境背景下的多面性的关键见解。整合各种方法以提高降解效率在水安全领域至关重要,强调持续创新的必要性。
    Addressing the threat of harmful cyanobacterial blooms (CyanoHABs) and their associated microcystins (MCs) is crucial for global drinking water safety. In this review, we comprehensively analyze and compares the physical, chemical, and biological methods and genetic engineering for MCs degradation in aquatic environments. Physical methods, such as UV treatments and photocatalytic reactions, have a high efficiency in breaking down MCs, with the potential for further enhancement in performance and reduction of hazardous byproducts. Chemical treatments using chlorine dioxide and potassium permanganate can reduce MC levels but require careful dosage management to avoid toxic by-products and protect aquatic ecosystems. Biological methods, including microbial degradation and phytoremediation techniques, show promise for the biodegradation of MCs, offering reduced environmental impact and increased sustainability. Genetic engineering, such as immobilization of microcystinase A (MlrA) in Escherichia coli and its expression in Synechocystis sp., has proven effective in decomposing MCs such as MC-LR. However, challenges related to specific environmental conditions such as temperature variations, pH levels, presence of other contaminants, nutrient availability, oxygen levels, and light exposure, as well as scalability of biological systems, necessitate further exploration. We provide a comprehensive evaluation of MCs degradation techniques, delving into their practicality, assessing the environmental impacts, and scrutinizing their efficiency to offer crucial insights into the multifaceted nature of these methods in various environmental contexts. The integration of various methodologies to enhance degradation efficiency is vital in the field of water safety, underscoring the need for ongoing innovation.
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  • 文章类型: Journal Article
    世界各地的木材种植园正遭受越来越频繁的野火的影响,可能会降解受影响树木的木材,取决于暴露温度和时间。然而,确定火灾的确切温度相当复杂,或木材暴露的温度。本研究旨在通过固态NMR分析回顾性确定木材的暴露温度。模型是从暴露于定义温度的软木和硬木样品开发的,它成功地将NMR信号与暴露温度联系起来。开发了各种拟合方程以将NMR信号的半宽度或峰面积与暴露温度联系起来。硬木和软木显示出明显的差异:线性函数最好地描述了松树和桉树在较高温度区域的半宽度,而桉树峰面积的抛物线函数与整个温度范围具有最佳相关性。这种非破坏性和直接的方法提供了一种有价值的评估方法来确定,如果烧焦的树木中的木材退化并且可以加工。在决定使用时可以做出明智的选择,或丢弃烧焦的木头。
    Timber plantations across the world are suffering from the effects of increasingly frequent wildfires, which potentially degrade the wood of affected trees, depending on the exposure temperature and time. However, it is rather complicated to determine the exact temperature of the fire, or the temperature to which the wood was exposed. This study aimed to determine the exposure temperature of wood retrospectively through solid-state NMR analysis. Models were developed from softwood and hardwood samples exposed to defined temperatures, which successfully linked the NMR signal to the exposure temperature. Various fit equations were developed to link the half-width or peak area of the NMR signal to the exposure temperatures. Hard- and softwoods displayed noticeable differences: a linear function best described the half-width in the higher temperature region for Pine and Eucalyptus, whereas a parabolic function for the peak area of Eucalyptus yielded the best correlation to the entire temperature range. This non-destructive and direct method offers a valuable evaluation method to determine, if wood in burnt trees is degraded and can be processed. An informed choice can be made on the decision to use, or discard burnt wood.
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  • 文章类型: Journal Article
    修饰的信使RNA(mRNA)代表一类迅速出现的治疗药物产品。因此,开发用于控制产品质量的稳定指示方法对于支持成功的药物开发至关重要。本文介绍了一种离子对反相液相色谱(IP-RPLC)方法,以表征暴露于多种应激诱导条件下的修饰mRNA,与mRNA药物产品的药物开发有关。优化后的方法可用于大RNA的分离和分析,大小为1000个核苷酸。柱温,流动相流速和离子对选择分别进行了研究和优化。使用所有检查的离子配对剂实现模型RNA梯样品的基线分离。我们确定了优化方法,使用100mM三乙胺,实现了RNA梯中最大片段(750/1000个核苷酸)的最高分辨率分离,除了选定的修饰mRNA化合物的最高整体分辨率(eGFPmRNA,996个核苷酸)。通过分析修饰的eGFPmRNA证明了该方法的稳定性指示能力,直接暴露在高温下,水解条件和核糖核酸酶处理。我们的结果表明,形成的降解产物,在主峰前表现为较短的RNA片段,可以很好地监控,使用优化方法,并且可以评估mRNA在各种应激条件下的相对稳定性。
    Modified messenger RNA (mRNA) represents a rapidly emerging class of therapeutic drug product. Development of robust stability indicating methods for control of product quality are therefore critical to support successful pharmaceutical development. This paper presents an ion-pair reversed-phase liquid chromatography (IP-RPLC) method to characterise modified mRNA exposed to a wide set of stress-inducing conditions, relevant for pharmaceutical development of an mRNA drug product. The optimised method could be used for separation and analysis of large RNA, sized up to 1000 nucleotides. Column temperature, mobile phase flow rate and ion-pair selection were each studied and optimised. Baseline separations of the model RNA ladder sample were achieved using all examined ion-pairing agents. We established that the optimised method, using 100 mM Triethylamine, enabled the highest resolution separation for the largest fragments in the RNA ladder (750/1000 nucleotides), in addition to the highest overall resolution for the selected modified mRNA compound (eGFP mRNA, 996 nucleotides). The stability indicating power of the method was demonstrated by analysing the modified eGFP mRNA, upon direct exposure to heat, hydrolytic conditions and treatment with ribonucleases. Our results showed that the formed degradation products, which appeared as shorter RNA fragments in front of the main peak, could be well monitored, using the optimised method, and the relative stability of the mRNA under the various stressed conditions could be assessed.
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  • 文章类型: Journal Article
    抗抑郁药物在精神疾病的治疗中起着至关重要的作用,但是它们的功效和安全性会受到药物降解的影响。最近的报告指出,在全球污水处理厂中发现了几种浓度从检测限(LOD)到数百ng/L的药物;因此,抗抑郁药可以被认为是对人类健康和福祉有潜在影响的新兴污染物。了解和实施有效的降解策略不仅对于确保这些药物的稳定性和效力至关重要,而且对于符合当前环境修复目标的安全处置至关重要。这篇综述概述了阿米替林的降解途径,典型的三环抗抑郁药,通过探索氧化等化学途径,水解,和光降解。Connex问题,例如通过配方和包装考虑来增强稳定性的方法,监管准则,并简要说明了质量控制措施。阿米替林降解途径的具体案例研究预测了该领域的未来前景和挑战,帮助研究人员和药品制造商为最有效的降解途径提供指导,以最大程度地减少对环境的影响。
    Antidepressant drugs play a crucial role in the treatment of mental health disorders, but their efficacy and safety can be compromised by drug degradation. Recent reports point to several drugs found in concentrations ranging from the limit of detection (LOD) to hundreds of ng/L in wastewater plants around the globe; hence, antidepressants can be considered emerging pollutants with potential consequences for human health and wellbeing. Understanding and implementing effective degradation strategies are essential not only to ensure the stability and potency of these medications but also for their safe disposal in line with current environment remediation goals. This review provides an overview of degradation pathways for amitriptyline, a typical tricyclic antidepressant drug, by exploring chemical routes such as oxidation, hydrolysis, and photodegradation. Connex issues such as stability-enhancing approaches through formulation and packaging considerations, regulatory guidelines, and quality control measures are also briefly noted. Specific case studies of amitriptyline degradation pathways forecast the future perspectives and challenges in this field, helping researchers and pharmaceutical manufacturers to provide guidelines for the most effective degradation pathways employed for minimal environmental impact.
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  • 文章类型: Journal Article
    研究的目的是生产新的弹性体材料,其中包含填充有二氧化硅和页硅酸盐的丁基橡胶(IIR)(蛭石,蒙脱石,珍珠岩或埃洛石管)具有增强的疏水性和阻隔性能,并减少了化学降解。发现填料类型对丁基橡胶的交联度及其硫化胶的性能有显着影响。对于填充有珍珠岩或埃洛石管的Arsil的IIR复合材料,可实现最高的交联度和最高的机械强度。对于具有Arsil和蒙脱石的IIR硫化橡胶,确认了最高的表面疏水性(119°)。由于气体扩散速率系数和渗透系数均达到低值,因此所有测试样品均显示出高阻隔性能。未填充和填充的IIR硫化橡胶在与甲醇接触480分钟时都保持耐化学性。极性溶剂(甲醇)与每种硫化橡胶长时间接触不会导致材料降解,而非极性溶剂(正庚烷)的存在使机械参数恶化多达80%。然而,填料的存在降低了硫化橡胶的化学降解(在用Arsil和埃洛石管填充的固化IIR的情况下,与没有填料的复合材料相比降低了40%)。
    The aim of the study was to produce new elastomeric materials containing butyl rubber (IIR) filled with silica and phyllosilicates (vermiculite, montmorillonite, perlite or halloysite tubes) with enhanced hydrophobicity and barrier properties and reduced chemical degradation. It was found that the filler type had a significant impact on the degree of cross-linking of butyl rubber and the properties of its vulcanizates. The highest degree of cross-linking and the highest mechanical strength were achieved for IIR composites filled with Arsil with perlite or halloysite tubes. The highest surface hydrophobicity (119°) was confirmed for the IIR vulcanizates with Arsil and montmorillonite. All tested samples showed high barrier properties because both the gas diffusion rate coefficient and the permeability coefficient reached low values. Both unfilled and filled IIR vulcanizates retained chemical resistance in contact with methanol for 480 min. Hour-long contact of a polar solvent (methanol) with each of the vulcanizates did not cause material degradation, while the presence of a non-polar solvent (n-heptane) worsened the mechanical parameters by up to 80%. However, the presence of fillers reduced the chemical degradation of vulcanizates (in the case of cured IIR filled with Arsil and halloysite tubes by 40% compared to the composite without fillers).
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  • 文章类型: Journal Article
    为了表征红酒聚合物对芳香化合物(气味剂)的结合性能,对不同化学处理后的化学降解产物进行定性和定量分析(硫解、酸性,和碱性解聚)进行了红葡萄酒的高分子量(HMW)馏分。使用1HNMR,LC-ToF-MS,LC-MS/MS,HPIC揭示了碳水化合物等关键结构特征,有机酸,酚类化合物,花青素,花青素,氨基酸,和黄烷-3-醇负责气味剂-聚合物相互作用。Further,所选芳香化合物3-甲基丁醇的基于NMR的相互作用研究,顺式威士忌内酯,3-甲基丁酸,和3-异丁基-2-甲氧基吡嗪与HMW聚合物在化学处理后,与天然HMW馏分相比,聚合物的相互作用亲和力降低。进一步,芳香族化合物如黄烷-3-醇对气味聚合物相互作用的形成的重要性。此外,这些观察结果可以通过人类感官实验得到证实。第一次,红葡萄酒聚合物的组成分析和基于NMR的相互作用研究与化学处理的HMW馏分相结合,可以直接分析聚合物结构的相关性及其与红葡萄酒中关键气味物质的相互作用亲和力。
    In order to characterize red wine polymers with regard to their binding properties to aroma compounds (odorants), a qualitative and quantitative analysis of chemical degradation products after different chemical treatments (thiolytic, acidic, and alkaline depolymerization) of high -molecular-weight (HMW) fractions of red wine was performed. Using 1H NMR, LC-ToF-MS, LC-MS/MS, and HPIC revealed key structural features such as carbohydrates, organic acids, phenolic compounds, anthocyanins, anthocyanidins, amino acids, and flavan-3-ols responsible for odorant-polymer interactions. Further, NMR-based interaction studies of the selected aroma compounds 3-methylbutanol, cis-whisky lactone, 3-methylbutanoic acid, and 3-isobutyl-2-methoxypyrazine with HMW polymers after chemical treatment demonstrated a reduced interaction affinity of the polymer compared to the native HMW fractions, and further, the importance of aromatic compounds such as flavan-3-ols for the formation of odorant polymer interactions. In addition, these observations could be verified by human sensory experiments. For the first time, the combination of a compositional analysis of red wine polymers and NMR-based interaction studies with chemically treated HMW fractions enabled the direct analysis of the correlation of the polymer\'s structure and its interaction affinity with key odorants in red wine.
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  • 文章类型: Journal Article
    双螺杆熔融造粒(TSMG)依赖于捏合区的分散和分布混合,以使颗粒生长发生,突显了捏合元素在TSMG中所起的关键作用。尽管对螺杆几何形状在熔体复合中的影响进行了广泛的研究,TSMG没有足够的文献。捏合元件的圆盘宽度为2mm,与标准的5毫米相反。这项研究的目的是评估不同的飞越间隙(OC)是否可以改变TSMG的范式。新的元件降低了捏合区的峰值剪切,然而需要更高的机筒温度和填充度(DoF)来补偿以获得类似的颗粒属性。DoF的变化通过改进的螺杆配置的组合来实现,以在较低的螺杆速度下捏合和加工之前预致密化粉末。尽管机筒温度较高,进行了热不稳定加巴喷丁的工艺优化。使用新的元素,尽管OC增加至0.4mm,但制造具有低%GABA-L含量的可压缩颗粒(拉伸强度>2MPa)。颗粒在40°C下的稳定性,6个月的环境湿度表明加巴喷丁是稳定的(%GABA-LØ0.4%),尽管120°C的高机筒温度。
    Twin-screw melt granulation (TSMG) relies on the dispersive and distributive mixing at the kneading zone for granule growth to happen highlighting the critical role played by the kneading elements in TSMG. Despite extensive research conducted on the impact of screw geometry in melt compounding, there is not enough literature for TSMG. Disc width for the kneading elements was 2 mm, contrary to the standard 5 mm. The objective of this study was to evaluate if varying overflight clearance (OC) can alter the paradigm for TSMG. The new elements reduce the peak shear at kneading zone however a higher barrel temperature and degree of fill (DoF) is required to compensate to attain similar granule attributes. The change in DoF was achieved through a combination of modified screw configuration to pre-densify powders before kneading and processing at a lower screw speed. Despite the higher barrel temperature, process optimization of thermally unstable gabapentin was carried out. Using the new elements, compressible granules (Tensile strength > 2 MPa) with low % GABA-L content were manufactured despite increasing OC to 0.4 mm. Granule stability at 40 °C, ambient humidity for 6 months indicated gabapentin was stable (% GABA-L ≪0.4 %) despite a high barrel temperature of 120 °C.
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  • 文章类型: Journal Article
    这项工作研究了与参考(未处理)样品相比,热改性温度(180、200和220°C)对六种热带木材物种Sp的选定光学特性的影响。雪松(雪松),iroko(Chlorophoraexcelsa),merbau(Intsiaspp.),美兰蒂(Shoreaspp。),padouk(Pterocarpussoyauxii),和柚木(Tectonagrandis)。主要目标是通过了解与发色结构的形成相关的降解机制来扩展木材热改性领域的现有知识,最重要的是,重点关注提取物质含量的变化。对于实木,CIELAB颜色空间参数(L*,a*,b*,和ΔE*),黄色(Y),ISO亮度,获得了紫外-可见漫反射光谱。随后,这些木材样品被提取到三种单独的溶剂(丙酮,乙醇,和乙醇-甲苯)。提取的化合物的产率,它们的吸收光谱,L*,a*,b*,ΔE*,和Yi参数进行了测定。随着温度的升高,样品失去亮度和变暗,而它们的总色差增加(除了Merbau)。最高收率的提取物(主要是酚类化合物,糖苷,和染料)通常使用乙醇从热改性样品中获得。新型提取物(例如,2-糠醛,内酯,甲酸,一些酚的单体衍生物,等。)已经在180°C左右的温度下产生,并且可能在更高的温度下发生缩合反应。对Padouk来说,Merbau,柚木,并在200和220°C的温度下对部分Iroko进行了改性,在与酚醛相对应的波长区域,其UV-VisDR光谱的强度存在检测到的相似性,不饱和酮,醌,二苯乙烯,和其他共轭羰基结构。总的来说,使用PCA的统计评估将样本分为五个簇。集群3由几乎所有在200和220°C下改性的样品组成,在其他四个中,在180°C下分配参考样品和热改性样品。木材(Y)的黄度对其亮度(L*)和丙酮Yi(Ac)中提取物的黄度指数有很高的依赖性(r=0.972),其关系由方程Y=-0.0951×Y(Ac)+23.3485描述。
    This work examines the effect of thermal modification temperature (180, 200, and 220 °C) in comparison with reference (untreated) samples on selected optical properties of six tropical wood species-Sp. cedar (Cedrala odorata), iroko (Chlorophora excelsa), merbau (Intsia spp.), meranti (Shorea spp.), padouk (Pterocarpus soyauxii), and teak (Tectona grandis). The main goal is to expand the existing knowledge in the field of wood thermal modification by understanding the related degradation mechanisms associated with the formation of chromophoric structures and, above all, to focus on the change in the content of extractive substances. For solid wood, the CIELAB color space parameters (L*, a*, b*, and ΔE*), yellowness (Y), ISO brightness, and UV-Vis diffuse reflectance spectra were obtained. Subsequently, these wood samples were extracted into three individual solvents (acetone, ethanol, and ethanol-toluene). The yields of the extracted compounds, their absorption spectra, and again L*, a*, b*, ΔE*, and Yi parameters were determined. With increasing temperatures, the samples lose brightness and darken, while their total color difference grows (except merbau). The highest yield of extractives (mainly phenolic compounds, glycosides, and dyes) from thermally modified samples was usually obtained using ethanol. New types of extractives (e.g., 2-furaldehyde, lactones, formic acid, some monomer derivatives of phenols, etc.) are already created around a temperature of 180 °C and may undergo condensation reactions at higher temperatures. For padouk, merbau, teak, and partially iroko modified at temperatures of 200 and 220 °C, there was a detected similarity in the intensities of their UV-Vis DR spectra at the wavelength regions corresponding to phenolic aldehydes, unsaturated ketones, quinones, stilbenes, and other conjugated carbonyl structures. Overall, a statistical assessment using PCA sorted the samples into five clusters. Cluster 3 consists of almost all samples modified at 200 and 220 °C, and in the other four, the reference and thermally modified samples at 180 °C were distributed. The yellowness of wood (Y) has a very high dependence (r = 0.972) on its brightness (L*) and the yellowness index of the extractives in acetone Yi(Ac), whose relationship was described by the equation Y = -0.0951 × Y(Ac) + 23.3485.
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  • 文章类型: Journal Article
    在这项研究中,通过双组分脱胶剂乙二醇和乙醇胺降解废PU泡沫后,获得了液态再生聚醚多元醇。通过添加不同比例的SiO2气凝胶通过自制备二氧化硅气凝胶(SiO2气凝胶)对再生多元醇基聚氨酯泡沫进行改性,制备了SiO2气凝胶改性再生聚氨酯复合材料的气凝胶/再生聚氨酯泡沫纳米复合材料。对自行制备的二氧化硅气凝胶和气凝胶改性的再生聚氨酯泡沫复合材料进行了一系列分析测试。试验结果分析表明,聚氨酯降解材料中SiO2气凝胶添加量为0.3%得到的再生硬质PU泡沫密度小,低热导率,和更高的抗压强度;因此,制备的二氧化硅气凝胶再生多元醇基聚氨酯纳米复合材料具有良好的保温性能和强度支撑性能。干净的,低碳,实现了废旧聚氨酯的高值利用。
    In this study, a liquid regenerated polyether polyol was obtained after the degradation of waste PU foam by the two-component decrosslinker agents ethylene glycol and ethanolamine. The regenerated polyol-based polyurethane foam was modified by adding different ratios of SiO2 aerogel through the self-preparation of silica aerogel (SiO2 aerogel) to prepare aerogel/regenerated polyurethane foam nanocomposites of SiO2 aerogel-modified regenerated polyurethane composites. A series of analytical tests on self-prepared silica aerogel and aerogel-modified recycled polyurethane foam composites were performed. The analysis of the test results shows that the regenerated rigid PU foam obtained with SiO2 aerogel addition of 0.3% in the polyurethane degradation material has a small density, low thermal conductivity, and higher compressive strength; hence, the prepared silica aerogel-regenerated polyol-based polyurethane nanocomposite has good thermal insulation and strength support properties. The clean, low-carbon, and high-value utilization of recycled waste polyurethane was achieved.
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