aminolysis

氨解
  • 文章类型: Journal Article
    为聚碳酸酯的解聚/上循环开发的无添加剂氨解方法。我们在这里报告聚碳酸酯在环境条件下的化学回收以获得其单体双酚A,单氨基氨基甲酸酯和双氨基甲酸酯的比例分别为1:2:1。通过使用仲胺作为胺化试剂,促进解聚在无添加剂/催化剂条件下工作。所开发的方法涉及废聚碳酸酯的解聚,甚至可以使用晚期胺衍生物,例如阿莫沙平和地氯雷他定,它们是已知分别治疗神经症和过敏的药物分子。该反应可以按比例放大并以类似的效力工作,其描述了寿命终止的聚碳酸酯塑料废物的解聚效率。将双氨基甲酸酯和双酚-A进一步进行后官能化,从而以良好的产率获得酰胺和苯酚。
    Additive free aminolysis method developed for the depolymerization/upcycling of polycarbonates. We report here chemical recycling of polycarbonate under ambient conditions to get its monomer bisphenol A, monoaminocarbamate and biscarbamates in 1:2:1 ratio respectively. By employing the secondary amine as the aminating reagent, facilitates the depolymerization to work under additive/catalyst free conditions. The developed method deals with depolymerization of waste polycarbonates and works even with late-stage amine derivatives such as amoxapine and desloratadine which are drugs molecules known to treat neurotic disorders and allergies respectively. The reaction can be scaled up and works with similar efficacy which depicts the efficiency of the depolymerization of end-of-life polycarbonate plastic waste. The biscarbamate and bisphenol-A was further subjected for the post functionalization to obtain amides and phenol in good yields.
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  • 文章类型: Journal Article
    聚氨酯(PU)有各种各样的定制物理,化学,机械,和结构特征,使其成为生物医学应用的绝佳选择。当前的研究涉及通过氨解过程(氨解聚氨酯;PU-A)改性聚氨酯表面,然后利用席夫碱化学共价固定羧甲基纤维素(CMC)聚合物。CMC的氧化周期性地导致沿着CMC链产生二醛基团。当OCMC上的醛基与改性PU表面上的胺基接触时,它们形成一个亚胺键。扫描电子显微镜(SEM),接触角,采用X射线光电子能谱(XPS)技术分析和确认OCMC在氨解PU膜(PU-O)上的固定。OCMC凝胶包含呋喃妥因(NF)并将其固定在PU表面(PU-ON),创造一个抗菌PU表面。使用EDX分析实现药物掺入的确认。不同剂量的NF对革兰氏阳性和革兰氏阴性细菌均具有浓度依赖性的抑菌和杀菌作用。除了持续释放。所提出的聚氨酯(PU-ON)表面在体内测试中表现出优异的抗感染性。该材料表现出生物相容性,非常适合生物医学应用。
    Polyurethane (PU) has a diverse array of customized physical, chemical, mechanical, and structural characteristics, rendering it a superb option for biomedical applications. The current study involves modifying the polyurethane surface by the process of aminolysis (aminolyzed polyurethane; PU-A), followed by covalently immobilizing Carboxymethyl cellulose (CMC) polymer utilizing Schiff base chemistry. Oxidation of CMC periodically leads to the creation of dialdehyde groups along the CMC chain. When the aldehyde groups on the OCMC contact the amine group on a modified PU surface, they form an imine bond. Scanning electron microscopy (SEM), contact angle, and X-ray photoelectron spectroscopy (XPS) techniques are employed to analyze and confirm the immobilization of OCMC on aminolyzed PU film (PU-O). The OCMC gel incorporates Nitrofurantoin (NF) and immobilizes it on the PU surface (PU-ON), creating an antibacterial PU surface. The confirmation of medication incorporation is achieved using EDX analysis. The varying doses of NF have demonstrated concentration-dependent bacteriostatic and bactericidal effects on both Gram-positive and Gram-negative bacteria, in addition to sustained release. The proposed polyurethane (PU-ON) surface exhibited excellent infection resistance in in vivo testing. The material exhibited biocompatibility and is well-suited for biomedical applications.
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  • 文章类型: Journal Article
    透析膜与人体血液不兼容,因为患者正在遭受血膜相互作用的副作用。两性离子结构显示出改善的血液相容性;然而,它们复杂的合成阻碍了它们的商业化。该研究的目的是实现羧基甜菜碱和磺基甜菜碱两性离子固定在PES膜上的快速功能化,同时比较稳定性和目标血液相容性。化学改性方法基于氨解反应。表征,计算模拟,并进行了临床分析以研究改性膜。原子力显微镜(AFM)图案显示,与纯膜(52.61nm)相比,羧基甜菜碱修饰(6.3nm)和磺基甜菜碱修饰(7.7nm)膜的平均粗糙度较低。膜的孔径从纯PES的高于50nm的值减小到两性离子膜的2至50nm之间的值。使用Brunauer-Emmett-Teller(BET)分析。更亲水的表面导致羧基甜菜碱的生长平衡水含量(EWC)为近6%,磺基甜菜碱改性膜的生长平衡水含量为10%。差示扫描量热法(DSC)测量值分别为羧基甜菜碱和磺基甜菜碱改性膜的12%和16%稳定水,分别。关于C5a,磺基甜菜碱膜显示出与血液更好的相容性,IL-1a,和IL-6生物标志物。发现基于氨基分解的两性离子适合于改善血液透析膜。本文介绍的方法可用于在生产设施变化最小的情况下修改当前的透析膜。
    Dialysis membranes are not hemocompatible with human blood, as the patients are suffering from the blood-membrane interactions\' side effects. Zwitterionic structures have shown improved hemocompatibility; however, their complicated synthesis hinders their commercialization. The goal of the study is to achieve fast functionalization for carboxybetaine and sulfobetaine zwitterionic immobilization on PES membranes while comparing the stability and the targeted hemocompatibility. The chemical modification approach is based on an aminolysis reaction. Characterization, computational simulations, and clinical analysis were conducted to study the modified membranes. Atomic force microscopy (AFM) patterns showed a lower mean roughness for carboxybetaine-modified (6.3 nm) and sulfobetaine-modified (7.7 nm) membranes compared to the neat membrane (52.61 nm). The pore size of the membranes was reduced from values above 50 nm for the neat PES to values between 2 and 50 nm for zwitterionized membranes, using Brunauer-Emmett-Teller (BET) analysis. More hydrophilic surfaces led to a growth equilibrium water content (EWC) of nearly 6% for carboxybetaine and 10% for sulfobetaine-modified membranes. Differential scanning calorimetry (DSC) measurements were 12% and 16% stable water for carboxybetaine- and sulfobetaine-modified membranes, respectively. Sulfobetaine membranes showed better compatibility with blood with respect to C5a, IL-1a, and IL-6 biomarkers. Aminolysis-based zwitterionization was found to be suitable for the improvement of hemodialysis membranes. The approach introduced in this paper could be used to modify the current dialysis membranes with minimal change in the production facilities.
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  • 文章类型: Journal Article
    基于生物材料的药物携带系统在生物医学领域得到了极大的关注。在这种情况下,聚(乳酸)(PLA)是通用材料。多孔和亲水的PLA表面可以更好地完成这项工作。我们旨在合成pH响应的PLA基多孔膜,用于在水介质中吸收和释放硫酸阿米卡星。天然PLA缺乏用于所述目的的功能/极性位点。所以,我们倾向于对其进行氨基分解以获得定制的物理化学和表面特性。使用九三酮测定法检查经处理的膜上的氨基(-NH2)基团密度。电子显微镜分析表明,氨解后保留了多孔形态。表面润湿性和FTIR结果表明,氨解后所得薄膜变得亲水。热分析表明了氨解膜的合理热稳定性。制备的薄膜分别在pH5.5和7.4时表现出pH响应性,可加载和释放硫酸阿米卡星药物。药物释放数据基于Akaike信息和模型选择标准最佳拟合了一级动力学模型。所制备的基于PLA的氨解膜符合作为pH响应性药物递送应用的潜在候选物的资格。这项研究可能是关于pH响应性硫酸阿米卡星在可溶胀的氨解PLA基多孔膜上吸收和释放的有效药物递送应用的首次报道。
    Biomaterial-based drug-carrying systems have scored enormous focus in the biomedical sector. Poly(lactic acid) (PLA) is a versatile material in this context. A porous and hydrophilic PLA surface can do this job better. We aimed to synthesize pH-responsive PLA-based porous films for uptaking and releasing amikacin sulfate in the aqueous media. The native PLA lacks functional/polar sites for the said purpose. So, we tended to aminolyze it for tailored physicochemical and surface properties. The amino (-NH2) group density on the treated films was examined using the ninhydrin assay. Electron microscopic analyses indicated the retention of porous morphology after aminolysis. Surface wettability and FTIR results expressed that the resultant films became hydrophilic after aminolysis. The thermal analysis expressed reasonable thermal stability of the aminolyzed films. The prepared films expressed pH-responsive behaviour for loading and releasing amikacin sulfate drug at pH 5.5 and 7.4, respectively. The drug release data best-fitted the first-order kinetic model based on Akaike information and model selection criteria. The prepared PLA-based aminolyzed films qualified as potential candidates for pH-responsive drug delivery applications. This study could be the first report on pH-responsive amikacin sulfate uptake and release on the swellable aminolyzed PLA-based porous films for effective drug delivery application.
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  • 文章类型: Journal Article
    抗癌药物递送系统中的一个显著挑战是开发可改善化疗效果的可植入系统。聚氨酯是一种优良的可植入基材,具有疏水性缺陷。我们通过化学氨解技术对聚氨酯进行改性,以增强润湿性和蛋白质相互作用。产生的孔可以释放掺入聚氨酯基质中的芦丁复合物。在这项工作中,混合聚合物基质由Mxene组成,该Mxene通过引入无毒的MAX相和蚀刻剂通过可持续且简单的方法合成。Mxene和PCL的掺入可以增强物理化学和生物相容性。可持续Mxene增加氧化应激,细胞死亡,和抗菌活性,这也导致了Mxene@APU/PCL薄膜。同时,在pH敏感性方面的药物释放被证明,其中Mxene和Mxene@APU/PCL膜在pH5.2时显示出最高的释放;这表明制备的Mxene和氨基分解聚氨酯可以根据生物系统起作用,并在缓慢降解和溶胀性下从聚合物基质中释放药物。Mxene和Mxene@APU/PCL膜对THP-1细胞显示出93.2%的药物释放与氧化应激,导致癌细胞破裂和凋亡。Mxene@APU/PCL膜可以在未来的可植入抗癌药物递送系统中显示出巨大的潜力。
    A remarkable challenge in the anticancer drug delivery system is developing an implantable system that can improve the chemotherapeutic effect. Polyurethane is an excellent implantable substrate, with flaws in hydrophobicity. We modified polyurethane via the chemical aminolysis technique to enhance the wettability and protein interaction. The created pores can release the rutin complex incorporated in the polyurethane matrix. In this work, the hybrid polymer matrix consists of Mxene synthesized via a sustainable and simple method by introducing a toxic-free MAX phase and etchants. The incorporation of Mxene and PCL can enhance physicochemical and biological compatibility. Sustainable Mxene increases oxidative stress, cell death, and antibacterial activity, which also resulted in the Mxene@APU/PCL film. Meanwhile, the drug release with respect to pH sensitivity was demonstrated in which Mxene and Mxene@APU/PCL films showed the highest release at pH 5.2; this indicates that the prepared Mxene and aminolyzed polyurethane can function according to the biological system and release the drug from the polymer matrix on slow degradation and swellability. The Mxene and Mxene@APU/PCL films showed 93.2% drug release with oxidative stress on THP-1 cells, which causes rupturing and apoptosis of cancerous cells. The Mxene@APU/PCL film can show great potential in future implantable anticancer drug delivery systems.
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  • 文章类型: Journal Article
    氨解被广泛认为是解聚含酯的聚合材料的有价值的化学途径,酰胺,或氨基甲酸酯官能团,包括聚氨酯泡沫。生物基聚氨酯泡沫,原始和用40重量%的可持续填料增强,在生物衍生的丁烷-1,4-二胺的存在下解聚,BDA.使用化石衍生的乙烷-1,2-二胺进行了工艺比较,EDA,通过改变胺/聚氨酯比(F/A,1:1和1:0.6)。通过FTIR和NMR表征分析获得的解聚体系,以了解两种二胺对降解途径的影响。与传统的EDA相比,生物基BDA的使用似乎更有效,由于其更强的碱性(因此更高的亲核性),对应于更快的解聚速率。然后采用基于BDA的解聚体系,通过部分替代异氰酸酯组分(20wt%)来制备第二代生物基复合聚氨酯泡沫。形态学,机械,并对第二代聚氨酯泡沫塑料的导热性能进行了评价。最佳性能(σ10%=71±9kPa,λ=0.042±0.015W·m-1·K-1)通过采用最低的F/A比(1:0.6)获得;这表明它们在包装或建筑等不同领域的潜在应用,实现循环经济的范式。
    Aminolysis is widely recognized as a valuable chemical route for depolymerizing polymeric materials containing ester, amide, or urethane functional groups, including polyurethane foams. Bio-based polyurethane foams, pristine and reinforced with 40 wt% of sustainable fillers, were depolymerized in the presence of bio-derived butane-1,4-diamine, BDA. A process comparison was made using fossil-derived ethane-1,2-diamine, EDA, by varying amine/polyurethane ratio (F/A, 1:1 and 1:0.6). The obtained depolymerized systems were analyzed by FTIR and NMR characterizations to understand the effect of both diamines on the degradation pathway. The use of bio-based BDA seemed to be more effective with respect to conventional EDA, owing to its stronger basicity (and thus higher nucleophilicity), corresponding to faster depolymerization rates. BDA-based depolymerized systems were then employed to prepare second-generation bio-based composite polyurethane foams by partial replacement of isocyanate components (20 wt%). The morphological, mechanical, and thermal conductivity properties of the second-generation polyurethane foams were evaluated. The best performances (σ10 %=71 ± 9 kPa, λ = 0.042 ± 0.015 W∙ m-1 ∙K-1) were attained by employing the lowest F/A ratio (1:0.6); this demonstrates their potential application in different sectors such as packaging or construction, fulfilling the paradigm of the circular economy.
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  • 文章类型: Journal Article
    基于生物的药物递送装置由于其生物相容性而在生物医学领域获得了极大的兴趣。正在对用于药物递送应用的基于壳聚糖的装置进行广泛的研究。壳聚糖在中性条件下是疏水性的,使得难以与姜黄素的极性药物相互作用。我们倾向于通过溶胶-凝胶合成和通过聚乙二醇化改性使其具有极性,碱性水解,和氨解。这种改变可以使基于壳聚糖的支架多孔,亲水性,氨基官能化,和pH响应。进行了三三酮测定,证实了成功的氨解发生,并在红外光谱下解释了前驱体之间的化学相互作用。最佳氨解膜的扫描形态似乎是多孔的,平均孔径为320±20nm。发现氨基分解的壳聚糖膜在高达310°C的温度下是热稳定的,亲水,水接触角为23.4°,中等流动性,多孔(97±5%,w/w)对乙醇。负载姜黄素的壳聚糖膜表现出99%的UV防护行为。发现姜黄素负载和释放现象具有pH响应性。通过特定的动力学模型评估姜黄素释放结果。这项研究可能是关于两亲性的第一份报告,多孔,和可溶胀的载药明胶/壳聚糖膜,具有pH响应性负载和姜黄素的释放,用于潜在的药物递送应用。
    Bio-based drug delivery devices have gained enormous interest in the biomedical field due to their biocompatible attributes. Extensive research is being conducted on chitosan-based devices for drug delivery applications. Chitosan being hydrophobic under neutral conditions makes it difficult to interact with a polar drug of curcumin. We tended to make it polar through sol-gel synthesis and modification via PEGylation, alkaline hydrolysis, and aminolysis. Such alterations could make the chitosan-based scaffolds porous, hydrophilic, amino-functionalized, and pH-responsive. The ninhydrin assay confirmed that a successful aminolysis occurred, and the chemical interaction among the precursors was explained under infrared spectroscopy. The scanning morphology of the optimum aminolyzed membrane appeared to be porous with an average pore size of 320 ± 20 nm. The aminolyzed chitosan membrane was found thermally stable up to 310 °C, hydrophilic with a water contact angle of 23.4°, moderate flowablity, and porous (97 ± 5 %, w/w) against ethanol. The curcumin-loaded chitosan membrane expressed the UV-protection behavior of 99 %. The curcumin-loading and release phenomena were found pH-responsive. The curcumin release results were evaluated through specific kinetic models. This study could be the first report on the amphiphilic, porous, and swellable drug-loaded gelatin/chitosan membrane with pH-responsive loading and release of curcumin for potential drug delivery applications.
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  • 文章类型: Journal Article
    尽管在从塑料废物中开发功能材料以促进其回收利用方面取得了巨大进展,仅报道了来自塑料废物的水凝胶材料的几个例子。在这项研究中,使用多胺对废PET塑料进行微波辅助解聚,以制备短的氨基苯二胺低聚物,然后化学交联成水凝胶材料。PET的无催化剂微波辅助氨解在30-40s内完成,证明了解聚反应的高效率。随后的低聚物的环氧交联产生了溶胀度大约为10的水凝胶。纯净水中的92.1倍。证明了所获得的水凝胶用于从水中去除铜离子(Cu2+)的应用。水凝胶的NH2基团与Cu2的有效络合导致水凝胶材料对Cu2去除的高吸附能力,在中性pH下最高,达到约。213mg/g。所提出的环境材料的类型是有益的,因为其废物来源的性质和功能可用于高效去除广泛范围的已知环境污染物。
    Despite the tremendous progress in the development of functional materials from plastic waste to promote its recycling, only a few examples of hydrogel materials from plastic waste were reported. In this study, microwave-assisted depolymerization of waste PET plastic using polyamine was performed to prepare short aminophthalamide oligomers followed by chemically cross-linking into a hydrogel material. Catalyst-free microwave-assisted aminolysis of PET was completed within 30-40 s, demonstrating high efficiency of the depolymerization reaction. Subsequent epoxy cross-linking of the oligomers yielded a hydrogel with a swelling degree of ca. 92.1 times in pure water. The application of the obtained hydrogel for the removal of copper ions (Cu2+) from water was demonstrated. Efficient complexation of NH2 groups of the hydrogel with Cu2+ resulted in high adsorption capacities of the hydrogel material toward Cu2+ removal, which were the highest at neutral pHs and reached ca. 213 mg/g. The proposed type of environmental material is beneficial owing to its waste-derived nature and functionality that can be applied for the high-efficiency removal of a broad scope of known environmental pollutants.
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  • 文章类型: Journal Article
    人造细胞的构建需要开发模拟天然磷脂膜形成的直接方法。在这里,我们描述了使用直接氨解连接从水溶性起始材料自发产生仿生磷脂膜。此外,我们探讨了这种仿生方法是否适合驱动天然磷脂膜的原位形成。我们的研究表明,在生命起源期间,非酶连接反应可能对磷脂样膜的合成很重要。并可能被用作简化的方法,以在人造细胞中产生脂质隔室。
    Construction of artificial cells requires the development of straightforward methods for mimicking natural phospholipid membrane formation. Here we describe the use of direct aminolysis ligations to spontaneously generate biomimetic phospholipid membranes from water-soluble starting materials. Additionally, we explore the suitability of such biomimetic approaches for driving the in situ formation of native phospholipid membranes. Our studies suggest that non-enzymatic ligation reactions could have been important for the synthesis of phospholipid-like membranes during the origin of life, and might be harnessed as simplified methods to enable the generation of lipid compartments in artificial cells.
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  • 文章类型: Journal Article
    聚对苯二甲酸乙二醇酯(PET)衍生聚酯(PES)纺织品的废物管理是一个全球性的问题,通过化学回收进行材料回收可以恢复循环经济。在我们的调查中,已经提出了使用Ag掺杂的ZnO纳米颗粒对PES纺织废物进行微波诱导的催化氨解和糖酵解。通过溶胶-凝胶法制备了Ag掺杂的ZnO,并通过XRD表征,FT-IR,UV-Vis,SEM-EDX和TEM。反应参数,如PET与催化剂的比例,微波功率和辐照时间,温度和催化剂回收已得到优化。发现该催化剂更稳定并且可以再循环多达6次而不损失其活性。PES的氨解和糖酵解均显示出100%的转化率,并提供了双(2-羟基亚乙基)对苯二甲酰胺(BHETA)和双(2-羟基亚乙基)对苯二甲酸酯(BHET),分别。PES废物的解聚使用Ag掺杂的ZnO提供BHETA和BHET约95%和90%,分别。通过FT-IR确认单体BHET和BHETA,1HNMR和质谱。根据调查结果,2mol%Ag掺杂的ZnO具有较高的催化活性。
    The waste management of polyethylene terephthalate (PET)-derived polyester (PES) textile is a global issue, and material recovery through chemical recycling can restore a circular economy. In our investigation, microwave-induced catalytic aminolysis and glycolysis of PES textile wastes using Ag-doped ZnO nanoparticles have been proposed. Ag-doped ZnO is prepared by the sol-gel method and characterised by XRD, FT-IR, UV-Vis, SEM-EDX and TEM. The reaction parameters such as PET-to-catalyst ratio, microwave power and irradiation time, temperature and catalyst recycling have been optimised. The catalyst was found to be more stable and could be recycled up to six times without losing its activity. Both the aminolysis and glycolysis of PES showed 100% conversion and afforded of bis (2-hydroxy ethylene) terephthalamide (BHETA) and bis (2-hydroxy ethylene) terephthalate (BHET), respectively. The depolymerisation of PES wastes using Ag-doped ZnO afforded BHETA and BHET for about 95 and 90%, respectively. The monomers BHET and BHETA confirmed by FT-IR, 1H NMR and mass spectroscopy. According to the findings, 2 mol% Ag-doped ZnO has higher catalytic activity.
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