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Alkali-Free Oxidation of 1,2-Propanediol to Lactic Acid over Intermetallic Cu1Pt Compounds 在金属间 Cu1Pt 化合物上将 1,2-丙二醇无碱氧化成乳酸
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c03138
Zixin Zhong, Yingdan Ye, Yibin Zhang, Weichen Du, Zhaoyin Hou
Polylactic acid (PLA) plastics are the most popular biodegradable and biocompatible materials; however, their monomer, lactic acid (LA), is currently produced via an inefficient fermentation process. Herein, activated carbon-supported Pt–Cu intermetallic compounds were synthesized and utilized in the selective oxidation of 1,2-propanediol (1,2-PDO) toward LA without the participation of homogeneous alkali or a basic support. It was found that rhombohedral intermetallic Cu1Pt compounds exhibited excellent performance and the calculated turnover frequency of each surface Pt atom reached 10 049 h–1. The yield of free LA reached 64.6% with a complete conversion of 1,2-PDO at 100 °C within 2 h. Diverse characterization and DFT calculations revealed that Pt–Cu intermetallic compounds were active for the adsorption and/or activation of molecular oxygen and 1,2-PDO. Raman analysis of adsorbed 1,2-PDO further disclosed that 1,2-PDO contacted with rhombohedral intermetallic Cu1Pt compounds strongly, and then the oxidation of the terminal hydroxyl group was performed preferentially, which promoted the formation of LA.
聚乳酸(PLA)塑料是最受欢迎的可生物降解和生物相容性材料;然而,其单体乳酸(LA)目前是通过低效发酵工艺生产的。本文合成了活性炭支撑的铂铜金属间化合物,并将其用于 1,2-丙二醇(1,2-PDO)向 LA 的选择性氧化,而无需均相碱或碱性支撑物的参与。研究发现,斜方金属间 Cu1Pt 化合物表现出优异的性能,每个表面铂原子的计算周转频率达到 10 049 h-1。多种表征和 DFT 计算显示,铂铜金属间化合物对分子氧和 1,2-PDO 的吸附和/或活化具有活性。对吸附的 1,2-PDO 的拉曼分析进一步表明,1,2-PDO 与斜方体金属间化合物 Cu1Pt 的接触很强,然后末端羟基优先被氧化,从而促进了 LA 的形成。
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引用次数: 0
Luteolin Functionalized Zinc Oxide Nanoparticles for Cancer Therapy Based on Autophagy Activation and EMT Inhibition 基于自噬激活和 EMT 抑制的用于癌症治疗的木犀草素功能化氧化锌纳米粒子
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c04194
Yan Gao, Jinwen Zhu, Xingye Zheng, Guanghui Lin, Peng Miao
Natural bioactive compounds have become increasingly important antitumor and antimicrobial agents due to their high therapeutic potential and low systemic toxicity. However, they also have significant drawbacks like nontumor targeting and low bioavailability, which limit their wide therapeutic applications. There is an urgent need for a safe and compatible nanoparticle-mediated drug delivery system for the efficient transport of drug candidates into tumor tissues. In this paper, amine-modified zinc oxide nanoparticles are synthesized to load luteolin. The functionalized nanoparticles exhibit good synergistic effects in terms of antitumor and antibacterial activities. They show significant induction of oxidative stress and antitumor effects, while no significant inhibitory effect on normal cells is observed, suggesting that the nanocomposites have good targeting of cancer cells. Autophagy activation and EMT inhibition effects are studied to explain the good antitumor performances. The prepared nanocomposites are demonstrated to be attractive candidates for cancer therapy.
天然生物活性化合物因其治疗潜力大、全身毒性低,已成为越来越重要的抗肿瘤和抗菌剂。然而,它们也有明显的缺点,如非肿瘤靶向性和生物利用度低,这限制了其广泛的治疗应用。目前迫切需要一种安全、兼容的纳米颗粒介导的给药系统,以便将候选药物高效地输送到肿瘤组织中。本文合成了负载木犀草素的胺修饰氧化锌纳米粒子。功能化纳米粒子在抗肿瘤和抗菌活性方面表现出良好的协同效应。它们具有明显的诱导氧化应激和抗肿瘤作用,而对正常细胞没有明显的抑制作用,这表明纳米复合材料对癌细胞具有良好的靶向性。对自噬激活和 EMT 抑制作用的研究解释了其良好的抗肿瘤性能。所制备的纳米复合材料被证明是具有吸引力的癌症治疗候选材料。
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引用次数: 0
Thermodynamically Dependent Behavior in Gas Transport in Two-Dimensional Graphene Nanochannels 二维石墨烯纳米通道中与热力学相关的气体传输行为
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c03572
Feifan Li, Yudong Zhang, Xiao Wu, Wei Peng, Mingfu Zhu, Tianshui Liang, Shijiao Li, Yilin Hao, Zheyuan Zhang, Ronghan Wei
Gas transport through nanochannels has aroused significant interest in many fields. Recently, “ballistic transport” of gas was observed through a two-dimensional graphene nanochannel, and it causes a peculiar enhancement compared to the predictions of the Knudson theory. Many studies attributed this effect to the specular reflection caused by the atomically smooth surface of the channel. Here, our molecular dynamics simulation, showing consistent results with previous experiments and simulations, reveals an interesting aspect: gas atoms with higher kinetic energies tend to pass the channel more easily. Extensive calculations of the tangential momentum accommodation coefficient considering different velocities on the graphene surface reveal that the attractive force between the gas and the surface atoms plays a more prominent role than the previous view, and gas atoms with more normal kinetic energies will overcome the attraction. Consequently, it indicates that a constant parameter used to balance the specular and diffuse reflection may not be adequate and should be replaced by a function considering the thermodynamic properties of gases.
气体在纳米通道中的传输引起了许多领域的浓厚兴趣。最近,人们观察到气体在二维石墨烯纳米通道中的 "弹道传输",与诺德森理论的预测相比,这种传输产生了奇特的增强效应。许多研究将这种效应归因于通道原子光滑表面引起的镜面反射。在这里,我们的分子动力学模拟结果与之前的实验和模拟结果一致,并揭示了一个有趣的方面:动能较高的气体原子往往更容易通过通道。考虑到石墨烯表面的不同速度,对切向动量容纳系数进行的大量计算显示,气体和表面原子之间的吸引力比以前的观点起着更加突出的作用,动能更正常的气体原子会克服吸引力。因此,这表明用于平衡镜面反射和漫反射的常数参数可能不够充分,应该用考虑气体热力学特性的函数来代替。
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引用次数: 0
Integrin Subtypes and Lamellipodia Mediate Spatial Sensing of RGD Ligands during Cell Adhesion. 整合素亚型和纤毛膜在细胞粘附过程中介导 RGD 配体的空间感应
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 Epub Date: 2024-11-15 DOI: 10.1021/acs.langmuir.4c02796
Xiaokai Pan, Juan Nie, Jiacheng Lei, Peng Wang, Kaikai Zheng, Qiang Wei, Xiaojing Liu

Understanding how the spatial distribution of adhesive ligands regulates cell behavior is crucial for designing biomaterials. This study investigates how precisely controlled ligand spacing affects cell spreading and integrin subtype engagement. Using engineered polyacrylamide hydrogels with gold nanoparticle arrays, we explored the impact of RGD ligand spacings (30 and 150 nm) on human mesenchymal stromal cells. Cells exhibited distinct morphological behaviors: smaller spacings promoted larger spreading areas, while larger spacings resulted in elongated shapes with reduced spreading. Mechanistically, we found that the α5β1 integrin, not the αvβ3 integrin, played a central role in mediating these responses, alongside lamellipodia formation. Our findings provide critical insights into the spatial sensing of ligands, highlighting the influence of ligand spacing on cellular mechanotransduction and integrin-specific responses. This work advances the understanding of cell-material interactions and offers potential strategies for designing biomaterials to guide cell behavior in tissue engineering.

了解粘附配体的空间分布如何调节细胞行为对设计生物材料至关重要。本研究探讨了精确控制的配体间距如何影响细胞扩散和整合素亚型参与。我们利用带有金纳米粒子阵列的工程聚丙烯酰胺水凝胶,探索了 RGD 配体间距(30 纳米和 150 纳米)对人间充质基质细胞的影响。细胞表现出不同的形态学行为:较小的间距能促进较大的扩散面积,而较大的间距则导致细胞形状拉长,扩散能力减弱。从机理上讲,我们发现α5β1整合素(而非αvβ3整合素)在介导这些反应以及形成片层的过程中发挥了核心作用。我们的发现为配体的空间感应提供了重要见解,突出了配体间距对细胞机械传导和整合素特异性反应的影响。这项工作加深了人们对细胞与材料相互作用的理解,并为设计生物材料提供了潜在的策略,以指导组织工程中的细胞行为。
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引用次数: 0
Rate-Controlled Washing of Surface-Modified Nanoparticles Using Rationally Designed Supercritical CO2 Media. 利用合理设计的超临界二氧化碳介质对表面修饰的纳米颗粒进行速率控制洗涤
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 Epub Date: 2024-11-15 DOI: 10.1021/acs.langmuir.4c02306
Yasuhiko Orita, Kai Ikeda, Aoi Muronosono, Thossaporn Wijakmatee, Taishi Kataoka, Yusuke Shimoyama

In practical applications of surface-modified nanoparticles (NPs), the washing stage has a number of challenges, such as insufficient washing, long treatment time, and various waste liquors. Cosolvent-enhanced supercritical CO2 (scCO2) is an appealing solvent system for complete, rapid, and eco-friendly washing owing to its high diffusivity and recyclability. In this paper, we report a rapid washing guideline for surface-modified NPs using ethanol-enhanced scCO2. Kinetic analysis was performed on the washing behavior of oleic acid-modified NPs mixed with various modifiers (C10 to C18 fatty acids) at 40 °C and 20.0 MPa while designing scCO2 media based on rationally estimated modifier solubilities. Notably, the scCO2 medium showed superior washing rates to that of ethanol for various modifiers with a wide range of solubilities in scCO2. The washing rate was dependent on solubility and could be organized into two regions, with a threshold value of 0.016 mol kg-1: solubility/diffusivity-controlled and diffusivity-controlled washing. These findings provide valuable guidelines for designing cosolvent-enhanced scCO2 media for the rapid washing of surface-modified NPs.

在表面修饰纳米粒子(NPs)的实际应用中,洗涤阶段面临着许多挑战,例如洗涤不充分、处理时间长以及产生各种废液。助溶剂增强型超临界二氧化碳(scCO2)具有高扩散性和可回收性,是一种具有吸引力的溶剂系统,可用于完整、快速和环保的洗涤。在本文中,我们报告了使用乙醇增强的 scCO2 对表面修饰的 NPs 进行快速洗涤的指南。在 40 °C 和 20.0 MPa 条件下,对油酸修饰的 NPs 与各种修饰剂(C10 至 C18 脂肪酸)混合的洗涤行为进行了动力学分析,同时根据合理估计的修饰剂溶解度设计了 scCO2 介质。值得注意的是,对于在 scCO2 中溶解度范围较宽的各种改性剂,scCO2 介质显示出优于乙醇的洗涤率。洗涤率取决于溶解度,以 0.016 mol kg-1 为临界值可分为两个区域:溶解度/扩散率控制的洗涤和扩散率控制的洗涤。这些发现为设计用于快速洗涤表面修饰 NPs 的共溶剂增强 scCO2 介质提供了宝贵的指导。
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引用次数: 0
Enhanced Biodiesel Production with Eversa Transform 2.0 Lipase on Magnetic Nanoparticles 利用磁性纳米颗粒上的 Eversa Transform 2.0 脂肪酶提高生物柴油生产效率
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c02542
Kaiany Moreira dos Santos, Juliana de França Serpa, Viviane de Castro Bizerra, Rafael Leandro Fernandes Melo, Paulo Gonçalves de Sousa Junior, Valdilane Santos Alexandre, Aluísio Marques da Fonseca, Pierre Basílio Almeida Fechine, Diego Lomonaco, José Cleiton Sousa dos Santos, Maria Cristiane Martins de Souza
This research investigated the usefulness of magnetic iron oxide nanoparticles (Fe3O4) as a support to immobilize the lipase Eversa Transform 2.0 (ET 2.0) to obtain an active and stable biocatalyst, easily recoverable from the reaction medium for applications in the production of biodiesel. Biodiesel was an alternative fuel composed mainly of fatty acid esters with strong transesterification and esterification capabilities. The study focused on the esterification of oleic acid with ethanol to synthesize ethyl oleate. Magnetic nanoparticles were prepared by coprecipitation, then activated with glutaraldehyde and functionalized with γ-aminopropyltriethoxysilane (APTES). The optimal conditions for immobilizing ET 2.0 were pH 10, 25 mM sodium carbonate buffer, an enzymatic load of 200 U/g, and 1 h of contact time, obtaining 78% yield and enzymatic activity of 205.9 U/g. Postimmobilization evaluation showed that the immobilized enzyme performed better than its free form. Kinetic studies were conducted under these optimized conditions (2–96 h at 150 rpm and 37 °C). The biocatalyst was tested for the synthesis of ethyl oleate using oleic acid as the substrate and ethanol, achieving a conversion of 88.1%. Subsequent recirculation tests maintained approximately 80% conversion until the fourth cycle, confirming the sustainability of ester production. Molecular docking studies revealed that the binding affinity for the enzyme-docked oil composition was estimated at −5.8 kcal/mol, suggesting that the combination of the substrate and lipase was stable and suitable for esterification.
本研究调查了磁性氧化铁纳米颗粒(Fe3O4)作为固定脂肪酶 Eversa Transform 2.0(ET 2.0)的载体的有用性,以获得一种活性稳定的生物催化剂,并易于从反应介质中回收,应用于生物柴油的生产。生物柴油是一种替代燃料,主要由脂肪酸酯组成,具有很强的酯交换和酯化能力。研究重点是油酸与乙醇的酯化反应,以合成油酸乙酯。通过共沉淀法制备了磁性纳米粒子,然后用戊二醛进行活化,并用γ-氨基丙基三乙氧基硅烷(APTES)进行功能化。固定 ET 2.0 的最佳条件是 pH 值为 10、25 mM 碳酸钠缓冲液、酶载量为 200 U/g、接触时间为 1 小时,从而获得了 78% 的产率和 205.9 U/g的酶活。固定化后的评估表明,固定化酶的性能优于游离态酶。在这些优化条件下(2-96 h,150 rpm,37 °C)进行了动力学研究。以油酸为底物和乙醇对生物催化剂进行了油酸乙酯合成试验,转化率达到 88.1%。随后进行的循环测试在第四个循环之前保持了约 80% 的转化率,证实了酯类生产的可持续性。分子对接研究表明,酶对接油成分的结合亲和力估计为-5.8 kcal/mol,这表明底物和脂肪酶的组合是稳定的,适合酯化。
{"title":"Enhanced Biodiesel Production with Eversa Transform 2.0 Lipase on Magnetic Nanoparticles","authors":"Kaiany Moreira dos Santos, Juliana de França Serpa, Viviane de Castro Bizerra, Rafael Leandro Fernandes Melo, Paulo Gonçalves de Sousa Junior, Valdilane Santos Alexandre, Aluísio Marques da Fonseca, Pierre Basílio Almeida Fechine, Diego Lomonaco, José Cleiton Sousa dos Santos, Maria Cristiane Martins de Souza","doi":"10.1021/acs.langmuir.4c02542","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c02542","url":null,"abstract":"This research investigated the usefulness of magnetic iron oxide nanoparticles (Fe<sub>3</sub>O<sub>4</sub>) as a support to immobilize the lipase Eversa Transform 2.0 (ET 2.0) to obtain an active and stable biocatalyst, easily recoverable from the reaction medium for applications in the production of biodiesel. Biodiesel was an alternative fuel composed mainly of fatty acid esters with strong transesterification and esterification capabilities. The study focused on the esterification of oleic acid with ethanol to synthesize ethyl oleate. Magnetic nanoparticles were prepared by coprecipitation, then activated with glutaraldehyde and functionalized with γ-aminopropyltriethoxysilane (APTES). The optimal conditions for immobilizing ET 2.0 were pH 10, 25 mM sodium carbonate buffer, an enzymatic load of 200 U/g, and 1 h of contact time, obtaining 78% yield and enzymatic activity of 205.9 U/g. Postimmobilization evaluation showed that the immobilized enzyme performed better than its free form. Kinetic studies were conducted under these optimized conditions (2–96 h at 150 rpm and 37 °C). The biocatalyst was tested for the synthesis of ethyl oleate using oleic acid as the substrate and ethanol, achieving a conversion of 88.1%. Subsequent recirculation tests maintained approximately 80% conversion until the fourth cycle, confirming the sustainability of ester production. Molecular docking studies revealed that the binding affinity for the enzyme-docked oil composition was estimated at −5.8 kcal/mol, suggesting that the combination of the substrate and lipase was stable and suitable for esterification.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"21 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Microneedles Constructed by Swellable Hydrogels Loaded with Celastrol for Efficient Treatment of Skin Infections Induced by Drug-Resistant Bacterial Strains 用载入塞拉斯特罗的可膨胀水凝胶构建微针,有效治疗耐药菌株引发的皮肤感染
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c03593
Jianbin Deng, Mengqi Liu, Shiqi Gao, Dongjie Lei, Zhicheng Su, Fuqing Liang, Songyun Tang, Huiyuan Yang, Yuan-Yuan Huang, Weiquan Xie, Guang-Yu Pan
The urgent need for new antimicrobial drugs arises from the limited efficacy of traditional antibiotics against emerging drug-resistant strains. Celastrol (CSL) demonstrates an exceptional antibacterial property that remains unaffected by bacterial resistance, but its poor water solubility limits its wide applications. This study uses the hydrophobic inner cavity of mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin (mβ-CD) (a derivative of cyclodextrin) to encapsulate CSL, constructing an inclusion complex (CSL@mβ-CD) to enhance the water solubility of CSL. The obtained inclusion complex is further incorporated into a swellable hydrogel microneedle (MN) to obtain CSL@mβ-CD/MN. The fabricated CSL@mβ-CD/MN can enable the sustained release of CSL, achieving effective bacterial eradication at infected sites. In vivo experiments demonstrate that CSL@mβ-CD/MN has a remarkable efficacy in the treatment of methicillin-resistant Staphylococcus aureus-induced subcutaneous abscesses and wound infections. Specifically, CSL@mβ-CD/MN can effectively penetrate the stratum corneum of the skin to realize rapid elimination of the bacteria in wounds. Moreover, CSL@mβ-CD/MN can efficiently scavenge reactive oxygen species, promote M2 polarization of macrophages, and relieve local inflammation at the wound sites. These results reveal that CSL@mβ-CD/MN holds great promise in the clinical treatment of acute skin infections induced by drug-resistant bacteria.
传统抗生素对新出现的耐药菌株的疗效有限,因此迫切需要新的抗菌药物。塞拉斯托(CSL)具有优异的抗菌性能,不受细菌耐药性的影响,但其较差的水溶性限制了它的广泛应用。本研究利用单(6-二乙烯三胺-6-脱氧)-β-环糊精(mβ-CD)(环糊精的一种衍生物)的疏水性内腔来包裹 CSL,构建出一种包合物(CSL@mβ-CD),以提高 CSL 的水溶性。将得到的包合物进一步与可溶胀水凝胶微针(MN)结合,得到 CSL@mβ-CD/MN。制成的 CSL@mβ-CD/MN 可实现 CSL 的持续释放,从而有效清除感染部位的细菌。体内实验证明,CSL@mβ-CD/MN 在治疗耐甲氧西林金黄色葡萄球菌引起的皮下脓肿和伤口感染方面具有显著疗效。具体来说,CSL@mβ-CD/MN 能有效穿透皮肤角质层,实现伤口细菌的快速清除。此外,CSL@mβ-CD/MN 还能有效清除活性氧,促进巨噬细胞的 M2 极化,缓解伤口处的局部炎症。这些结果表明,CSL@mβ-CD/MN 在临床治疗耐药细菌诱发的急性皮肤感染方面大有可为。
{"title":"Microneedles Constructed by Swellable Hydrogels Loaded with Celastrol for Efficient Treatment of Skin Infections Induced by Drug-Resistant Bacterial Strains","authors":"Jianbin Deng, Mengqi Liu, Shiqi Gao, Dongjie Lei, Zhicheng Su, Fuqing Liang, Songyun Tang, Huiyuan Yang, Yuan-Yuan Huang, Weiquan Xie, Guang-Yu Pan","doi":"10.1021/acs.langmuir.4c03593","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03593","url":null,"abstract":"The urgent need for new antimicrobial drugs arises from the limited efficacy of traditional antibiotics against emerging drug-resistant strains. Celastrol (CSL) demonstrates an exceptional antibacterial property that remains unaffected by bacterial resistance, but its poor water solubility limits its wide applications. This study uses the hydrophobic inner cavity of mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin (mβ-CD) (a derivative of cyclodextrin) to encapsulate CSL, constructing an inclusion complex (CSL@mβ-CD) to enhance the water solubility of CSL. The obtained inclusion complex is further incorporated into a swellable hydrogel microneedle (MN) to obtain CSL@mβ-CD/MN. The fabricated CSL@mβ-CD/MN can enable the sustained release of CSL, achieving effective bacterial eradication at infected sites. In vivo experiments demonstrate that CSL@mβ-CD/MN has a remarkable efficacy in the treatment of methicillin-resistant <i>Staphylococcus aureus</i>-induced subcutaneous abscesses and wound infections. Specifically, CSL@mβ-CD/MN can effectively penetrate the stratum corneum of the skin to realize rapid elimination of the bacteria in wounds. Moreover, CSL@mβ-CD/MN can efficiently scavenge reactive oxygen species, promote M2 polarization of macrophages, and relieve local inflammation at the wound sites. These results reveal that CSL@mβ-CD/MN holds great promise in the clinical treatment of acute skin infections induced by drug-resistant bacteria.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"19 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142712717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Experiment and Simulation Study on the Adsorption Interaction between a Fluorescent Tracer and a Montmorillonite Crystal in Drilling Fluid. 钻井液中荧光示踪剂与蒙脱石晶体吸附相互作用的实验与模拟研究
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 Epub Date: 2024-11-15 DOI: 10.1021/acs.langmuir.4c02848
Jie Fang, Ying Huang, Yangbing Li, Houfu Luo, Lihua Ma, Ming Duan, Xinliang Li, Run Zhang, Yan Xiong
<p><p>The adsorption interaction of oil field tracer in drilling fluid plays a significant role in tracer monitoring (TM) technology in the petroleum industry. In this work, the adsorption performances of Rhodamine B (RhB<sup>+</sup>) and fluorescein sodium (Fln<sup>-</sup>) tracers with montmorillonite (MMT) crystal in drilling fluid were investigated by both experimental and simulation methods. For the experimental aspect, the macroscopic results indicate thermodynamic monolayer adsorption by the Langmuir model and kinetic chemical adsorption by the pseudo-second-order (PSO) model. As a result, MMT shows a larger adsorption capacity (<i>q</i><sub>m</sub>) for RhB<sup>+</sup> than for Fln<sup>-</sup> with <math><msub><mrow><mi>q</mi></mrow><mrow><mi>m</mi><mrow><mo>(</mo><msup><mrow><mi>RhB</mi></mrow><mrow><mo>+</mo></mrow></msup><mo>)</mo></mrow></mrow></msub><mo>=</mo><mn>0.069</mn><mo>⁡</mo><mi>g</mi><mo>⁡</mo><msup><mrow><mi>g</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup><mo>></mo><msub><mrow><mi>q</mi></mrow><mrow><mi>m</mi><mrow><mo>(</mo><msup><mrow><mi>Fln</mi></mrow><mrow><mo>-</mo></mrow></msup><mo>)</mo></mrow></mrow></msub><mo>=</mo><mn>0.016</mn><mi>g</mi><mo>⁡</mo><msup><mrow><mi>g</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup></math> but stronger adsorption spontaneity (Δ<sub>r</sub><i>G</i><sub>m</sub><sup>θ</sup>) for Fln<sup>-</sup> than for RhB<sup>+</sup> with <math><msub><mrow><mi>Δ</mi></mrow><mrow><mi>r</mi></mrow></msub><msub><mrow><msubsup><mrow><mi>G</mi></mrow><mrow><mi>m</mi></mrow><mrow><mi>θ</mi></mrow></msubsup></mrow><mrow><mo>(</mo><msup><mrow><mi>Fln</mi></mrow><mrow><mo>-</mo></mrow></msup><mo>)</mo></mrow></msub><mo>=</mo><mo>-</mo><mn>7.92</mn></math> kJ mol<sup>-1</sup> < <math><msub><mrow><mi>Δ</mi></mrow><mrow><mi>r</mi></mrow></msub><msub><mrow><msubsup><mrow><mi>G</mi></mrow><mrow><mi>m</mi></mrow><mrow><mi>θ</mi></mrow></msubsup></mrow><mrow><mo>(</mo><msup><mrow><mi>RhB</mi></mrow><mrow><mo>+</mo></mrow></msup><mo>)</mo></mrow></msub><mo>=</mo><mo>-</mo><mn>6.90</mn></math> kJ mol<sup>-1</sup>. Meanwhile, the interaction rate (<i>k</i><sub>2</sub>) of Fln<sup>-</sup> was shown to be faster than that of RhB<sup>+</sup> with <math><msub><mrow><msub><mrow><mi>k</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow><mrow><mo>(</mo><msup><mrow><mi>Fln</mi></mrow><mrow><mo>-</mo></mrow></msup><mo>)</mo></mrow></msub><mo>=</mo><mn>1.07</mn><mo>⁡</mo><msup><mrow><mi>min</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup><mo>⁡</mo><mo>></mo><msub><mrow><msub><mrow><mi>k</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow><mrow><mo>(</mo><msup><mrow><mi>RhB</mi></mrow><mrow><mo>+</mo></mrow></msup><mo>)</mo></mrow></msub><mo>=</mo><mn>0.95</mn><mo>⁡</mo><msup><mrow><mi>min</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup><mo>⁡</mo></math>. For simulation insight, MMT shows much higher system stability (<i>E</i>) for Fln<sup>-</sup> than for RhB<sup>+</sup> with <math><msub><mrow><mi>E</mi></mrow><mrow><msup>
油田示踪剂在钻井液中的吸附相互作用在石油工业的示踪监测(TM)技术中发挥着重要作用。本文通过实验和模拟两种方法研究了钻井液中罗丹明 B(RhB+)和荧光素钠(Fln-)示踪剂与蒙脱石(MMT)晶体的吸附性能。在实验方面,宏观结果表明,热力学单层吸附采用 Langmuir 模型,动力学化学吸附采用伪二阶(PSO)模型。结果表明,MMT 对 RhB+ 的吸附容量(qm)大于对 Fln-的吸附容量(qm(RhB+)=0.069gg-1>qm(Fln-)=0.016gg-1),但对 Fln- 的吸附自发性(ΔrGmθ)强于对 RhB+的吸附自发性(ΔrGmθ(Fln-)=-7.92 kJ mol-1 < ΔrGmθ(RhB+)=-6.90 kJ mol-1)。同时,Fln- 的相互作用速率(k2)比 RhB+ 快,k2(Fln-)=1.07min-1>k2(RhB+)=0.95min-1。在模拟洞察方面,MMT 显示 Fln- 的系统稳定性(E)远高于 RhB+,EFln----MMTERhB+---MMT 和 ΔEFln----MMT>ΔERhB+---MMT。同时,微观模拟结果显示了 RhB+ 和 Fln- 与 MMT 晶体相互作用的构型变化和位点差异。通过提出力主导和位置定向的相互作用机制,解释了不同的吸附反应。具体来说,Fln- 与 MMT 晶体夹层中的金属(Al、Ca)和类金属(Si)元素的相互作用被推断为 "直立-插入 "取向,而 RhB+ 与 MMT 晶体表面的氧原子的相互作用被推断为 "平躺 "取向。结果表明,氢键、静电作用和配位效应在示踪剂吸附的相互作用中占主导地位。这项工作从性能和机理两方面研究了钻井液中荧光示踪剂与 MMT 晶体的吸附相互作用,对储层开采具有重要意义。
{"title":"Experiment and Simulation Study on the Adsorption Interaction between a Fluorescent Tracer and a Montmorillonite Crystal in Drilling Fluid.","authors":"Jie Fang, Ying Huang, Yangbing Li, Houfu Luo, Lihua Ma, Ming Duan, Xinliang Li, Run Zhang, Yan Xiong","doi":"10.1021/acs.langmuir.4c02848","DOIUrl":"10.1021/acs.langmuir.4c02848","url":null,"abstract":"&lt;p&gt;&lt;p&gt;The adsorption interaction of oil field tracer in drilling fluid plays a significant role in tracer monitoring (TM) technology in the petroleum industry. In this work, the adsorption performances of Rhodamine B (RhB&lt;sup&gt;+&lt;/sup&gt;) and fluorescein sodium (Fln&lt;sup&gt;-&lt;/sup&gt;) tracers with montmorillonite (MMT) crystal in drilling fluid were investigated by both experimental and simulation methods. For the experimental aspect, the macroscopic results indicate thermodynamic monolayer adsorption by the Langmuir model and kinetic chemical adsorption by the pseudo-second-order (PSO) model. As a result, MMT shows a larger adsorption capacity (&lt;i&gt;q&lt;/i&gt;&lt;sub&gt;m&lt;/sub&gt;) for RhB&lt;sup&gt;+&lt;/sup&gt; than for Fln&lt;sup&gt;-&lt;/sup&gt; with &lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;RhB&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mn&gt;0.069&lt;/mn&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;&gt;&lt;/mo&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;q&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;Fln&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mn&gt;0.016&lt;/mn&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;g&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;/math&gt; but stronger adsorption spontaneity (Δ&lt;sub&gt;r&lt;/sub&gt;&lt;i&gt;G&lt;/i&gt;&lt;sub&gt;m&lt;/sub&gt;&lt;sup&gt;θ&lt;/sup&gt;) for Fln&lt;sup&gt;-&lt;/sup&gt; than for RhB&lt;sup&gt;+&lt;/sup&gt; with &lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;G&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;θ&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;Fln&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;7.92&lt;/mn&gt;&lt;/math&gt; kJ mol&lt;sup&gt;-1&lt;/sup&gt; &lt; &lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;Δ&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;msub&gt;&lt;mrow&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;G&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;m&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;θ&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;RhB&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;6.90&lt;/mn&gt;&lt;/math&gt; kJ mol&lt;sup&gt;-1&lt;/sup&gt;. Meanwhile, the interaction rate (&lt;i&gt;k&lt;/i&gt;&lt;sub&gt;2&lt;/sub&gt;) of Fln&lt;sup&gt;-&lt;/sup&gt; was shown to be faster than that of RhB&lt;sup&gt;+&lt;/sup&gt; with &lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;Fln&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mn&gt;1.07&lt;/mn&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;min&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;mo&gt;&gt;&lt;/mo&gt;&lt;msub&gt;&lt;mrow&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;RhB&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/msub&gt;&lt;mo&gt;=&lt;/mo&gt;&lt;mn&gt;0.95&lt;/mn&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;msup&gt;&lt;mrow&gt;&lt;mi&gt;min&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mo&gt;⁡&lt;/mo&gt;&lt;/math&gt;. For simulation insight, MMT shows much higher system stability (&lt;i&gt;E&lt;/i&gt;) for Fln&lt;sup&gt;-&lt;/sup&gt; than for RhB&lt;sup&gt;+&lt;/sup&gt; with &lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;msup&gt;","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":"24901-24920"},"PeriodicalIF":3.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unraveling the Phase Behavior and Stability of Surfactant-Free Microemulsions: From Molecular Interactions to Macroscopic Properties 揭示无表面活性剂微乳液的相行为和稳定性:从分子相互作用到宏观特性
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1021/acs.langmuir.4c03761
Changsheng Chen, Yawen Gao, Mingbo Li, Chao Sun
Surfactant-free microemulsions (SFMEs), formed in mixed ternary systems such as water/ethanol/oil, have garnered substantial interest due to their unique properties and broad applications in areas such as enzyme-catalyzed reactions and nanoparticle synthesis. In this work, we conducted an in-depth investigation of the spontaneous nucleation and stabilization mechanisms of SFMEs, employing experimental techniques, molecular dynamics (MD) simulations, and Flory–Huggins (F–H) theory. The formation of multiscale nanostructures (characteristic scales of ∼1 and ∼100 nm) and their interfacial charging characteristics in SFMEs have been revealed experimentally. MD simulations investigated the structure and stability on the microscopic scale, enhancing our understanding of molecular interactions within these microemulsions. Our theoretical analysis revealed that the stability of mesoscopic nanodroplets within SFMEs hinges on a delicate balance between mixing entropy and internal energy. Equilibrium between these energies results in stable nanodroplet solutions, showcasing a delicate balance that can be manipulated by adjusting the volume fractions of the components and their interaction parameters. This research not only advances the theoretical understanding of SFMEs but also highlights their potential in industrial applications, emphasizing the importance of integrating theoretical and experimental approaches to develop functional nanostructured materials.
在水/乙醇/油等三元混合体系中形成的无表面活性剂微乳液(SFMEs)因其独特的性质以及在酶催化反应和纳米粒子合成等领域的广泛应用而备受关注。在这项工作中,我们采用实验技术、分子动力学(MD)模拟和弗洛里-哈金斯(F-H)理论,对 SFMEs 的自发成核和稳定机制进行了深入研究。实验揭示了 SFMEs 中多尺度纳米结构(特征尺度为 ∼1 和 ∼100 nm)的形成及其界面充电特性。MD 模拟研究了微观尺度上的结构和稳定性,加深了我们对这些微乳液中分子相互作用的理解。我们的理论分析表明,SFMEs 中介观纳米液滴的稳定性取决于混合熵和内能之间的微妙平衡。这些能量之间的平衡会产生稳定的纳米液滴溶液,展示了一种可以通过调整各组分的体积分数及其相互作用参数来操纵的微妙平衡。这项研究不仅推进了对 SFME 的理论理解,而且突出了其在工业应用中的潜力,强调了将理论与实验方法相结合开发功能性纳米结构材料的重要性。
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引用次数: 0
In Situ Preparation of MnO2 on the Catechol/Silane-Coated Polypropylene Nonwoven Fabrics for Effective Removal of Cationic Dyes. 在邻苯二酚/硅烷涂层聚丙烯无纺布上原位制备二氧化锰,以有效去除阳离子染料。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 Epub Date: 2024-11-14 DOI: 10.1021/acs.langmuir.4c03266
Jing Li, Hui Sun, Dewei Zhang, Xiaodong Yang, Zhuan Fu, Bin Yu

Previous studies have confirmed that MnOx removes heavy metal ions and organic pollutants from water with dual effects of adsorption and oxidation coupling, significantly improving the ability to remove impurities. Nanometal oxides have a highly reactive surface but tend to agglomerate during preparation and are challenging to recycle after use. A common method is to combine nano-MnO2 with Fe3O4 to prepare magnetic materials for easy recycling. Our previous research has confirmed that catechol (CA) and (3-aminopropyl) triethoxysilane (KH550) can be co-deposited on the surface of polypropylene nonwovens to form a stable CK coating under alkaline conditions. In addition, the coating has many active groups, including hydroxyl groups, amino groups, etc. This study further investigates the secondary reactivity of CK coatings. The coordination of catechol groups and metal ions was used to anchor manganese ions to the coating. Meanwhile, the hydroxyl and amino groups were used to reduce manganese ions to Mn4+ in situ to prepare PP-(CK-MnO2). We found that the sample had an excellent decolorization effect on cationic dyes but was limited to anionic dyes. The decolorization mechanism of cationic dyes was further discussed. The results showed that the decolorization of cationic dyes had a dual effect of adsorption and oxidative degradation. Under acidic conditions, its oxidation properties were enhanced. It can be used as a highly effective decolorizing agent for cationic dyes, and the decolorization behavior is consistent with the first-order kinetics. As the pH increases, its oxidation properties gradually decrease. Although the electrostatic adsorption effect was enhanced, the overall decolorization performance was significantly reduced. Recycling experiments have proved that it can maintain >90% removal rate after five cycles. This study also demonstrated that the CK coating has dopamine-like properties, which can coordinate with metal ions to prepare metal-organic hybrid materials.

以往的研究已经证实,氧化锰能以吸附和氧化耦合的双重效应去除水中的重金属离子和有机污染物,显著提高了去除杂质的能力。纳米金属氧化物具有高活性表面,但在制备过程中容易团聚,使用后难以回收。一种常见的方法是将纳米二氧化锰与 Fe3O4 结合起来制备磁性材料,以便于回收利用。我们之前的研究证实,在碱性条件下,儿茶酚(CA)和(3-氨基丙基)三乙氧基硅烷(KH550)可共同沉积在聚丙烯无纺布表面,形成稳定的 CK 涂层。此外,涂层还具有许多活性基团,包括羟基、氨基等。本研究进一步研究了 CK 涂层的二次反应性。利用邻苯二酚基团和金属离子的配位将锰离子锚定在涂层上。同时,利用羟基和氨基将锰离子原位还原为 Mn4+,制备出 PP-(CK-MnO2)。我们发现,该样品对阳离子染料有很好的脱色效果,但对阴离子染料的脱色效果有限。我们进一步讨论了阳离子染料的脱色机理。结果表明,阳离子染料的脱色具有吸附和氧化降解的双重作用。在酸性条件下,其氧化性能增强。它可用作阳离子染料的高效脱色剂,其脱色行为符合一阶动力学。随着 pH 值的升高,其氧化性能逐渐降低。虽然静电吸附效果增强,但整体脱色性能却明显下降。循环实验证明,经过五个循环后,其去除率仍能保持在 90% 以上。这项研究还证明,CK 涂层具有类似多巴胺的特性,可以与金属离子配位,制备金属有机杂化材料。
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引用次数: 0
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