Infections and thrombosis remain unsolved problems for implanted cardiovascular devices, such as left ventricular assist devices. Hence, the development of surfaces with improved blood compatibility and antimicrobial properties is imperative to reduce complications after artificial heart implantation. In this work, we report a novel approach to fabricate multifunctional surfaces for left ventricular transplanted ventricular assist devices (LVADs) by immobilizing nitric oxide (NO) generation catalysts and heparin and reducing silver nanoparticles in situ. The general view, structure, and chemical compositions of the pure/modified surfaces were characterized using digital imaging, scanning electron microscope (SEM), atomic force microscope (AFM), water contact angle (WCA), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma (ICP). All of the results demonstrated that the AgNPs and heparin were successfully immobilized on the surface. The Cu ions and NO release experimental results showed that the immobilized copper ions could catalyze the production of NO from S-nitrosothiols within the biological system. Meanwhile, due to the synergistic anticoagulant effect of NO and surface-immobilized heparin, the fabricated modified surfaces exhibited antiplatelet adhesion activities and good hemocompatibility. Finally, the antimicrobial activity of the samples was evaluated by Escherichia coli and Staphylococcus aureus, and cytocompatibility was measured using human umbilical vein endothelial cells (HUVECs). The results demonstrated that silver nanoparticles (AgNPs) immobilized by surface reduction reaction did not cause any significant inhibition of cell proliferation while providing stable and effective antimicrobial properties. We envision that this simple surface modification strategy with bifunctional activities of antimicrobial and anticoagulant will find widespread use in clinically used indwelling left ventricular assist devices.
感染和血栓形成仍是左心室辅助装置等植入式心血管装置尚未解决的问题。因此,为了减少人工心脏植入后的并发症,开发具有更好的血液相容性和抗菌性能的表面势在必行。在这项工作中,我们报告了一种新方法,即通过固定一氧化氮(NO)生成催化剂和肝素以及原位还原银纳米粒子来制造左心室移植心室辅助装置(LVAD)的多功能表面。利用数字成像、扫描电子显微镜(SEM)、原子力显微镜(AFM)、水接触角(WCA)、X射线光电子能谱(XPS)和电感耦合等离子体(ICP)对纯表面/改性表面的总体外观、结构和化学成分进行了表征。所有结果都表明,AgNPs 和肝素成功地固定在了表面。铜离子和 NO 释放实验结果表明,固定化的铜离子可以催化生物系统中的 S-亚硝硫醇产生 NO。同时,由于 NO 和表面固定肝素的协同抗凝作用,制备的改性表面具有抗血小板粘附活性和良好的血液相容性。最后,用大肠杆菌和金黄色葡萄球菌评估了样品的抗菌活性,并用人脐静脉内皮细胞(HUVECs)测量了细胞相容性。结果表明,通过表面还原反应固定的银纳米粒子(AgNPs)不会明显抑制细胞增殖,同时具有稳定有效的抗菌特性。我们预计,这种具有抗菌和抗凝双重功能的简单表面修饰策略将在临床使用的留置左心室辅助装置中得到广泛应用。
{"title":"Fabrication of an Antibacterial/Anticoagulant Dual-Functional Surface for Left Ventricular Assist Devices via Mussel-Inspired Polydopamine Chemistry.","authors":"Chuangxin Huang, Xin Liu, Lingwei Meng, Hongyi Qu, Qi Chen, Qiuliang Wang","doi":"10.1021/acs.langmuir.4c02619","DOIUrl":"10.1021/acs.langmuir.4c02619","url":null,"abstract":"<p><p>Infections and thrombosis remain unsolved problems for implanted cardiovascular devices, such as left ventricular assist devices. Hence, the development of surfaces with improved blood compatibility and antimicrobial properties is imperative to reduce complications after artificial heart implantation. In this work, we report a novel approach to fabricate multifunctional surfaces for left ventricular transplanted ventricular assist devices (LVADs) by immobilizing nitric oxide (NO) generation catalysts and heparin and reducing silver nanoparticles in situ. The general view, structure, and chemical compositions of the pure/modified surfaces were characterized using digital imaging, scanning electron microscope (SEM), atomic force microscope (AFM), water contact angle (WCA), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma (ICP). All of the results demonstrated that the AgNPs and heparin were successfully immobilized on the surface. The Cu ions and NO release experimental results showed that the immobilized copper ions could catalyze the production of NO from <i>S</i>-nitrosothiols within the biological system. Meanwhile, due to the synergistic anticoagulant effect of NO and surface-immobilized heparin, the fabricated modified surfaces exhibited antiplatelet adhesion activities and good hemocompatibility. Finally, the antimicrobial activity of the samples was evaluated by <i>Escherichia coli</i> and <i>Staphylococcus aureus</i>, and cytocompatibility was measured using human umbilical vein endothelial cells (HUVECs). The results demonstrated that silver nanoparticles (AgNPs) immobilized by surface reduction reaction did not cause any significant inhibition of cell proliferation while providing stable and effective antimicrobial properties. We envision that this simple surface modification strategy with bifunctional activities of antimicrobial and anticoagulant will find widespread use in clinically used indwelling left ventricular assist devices.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":"24306-24317"},"PeriodicalIF":3.7,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142575192","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}
Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co1Ni2CP, GC-Co1.5Ni1.5CP, and GC-Co2Ni1CP. The active catalyst, GC-Co2Ni1CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec-1) than IrO2 (125 mV dec-1). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co2Ni1CP, which required 285 mV to attain 10 mA cm-2. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co2Ni1CP/GC (0.017337 s-1) was found to be 3-fold higher than that of IrO2 (0.0014 s-1). Furthermore, the GC-Co2Ni1CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec-1. The ultrastability of GC-Co2Ni1CP for industrial application was confirmed by durability at 10 and 100 mA cm-2 for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co2Ni1CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA+) reveal that GC-Co2Ni1CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co2Ni1CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.
{"title":"Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation.","authors":"Kuppusamy Rajan, Dhanasingh Thiruvengadam, Krishnan Umapathy, Murugan Muthamildevi, Muthukumaran Sangamithirai, Jayaraman Jayabharathi, Manoharan Padmavathy","doi":"10.1021/acs.langmuir.4c02586","DOIUrl":"10.1021/acs.langmuir.4c02586","url":null,"abstract":"<p><p>Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co<sub>1</sub>Ni<sub>2</sub>CP, GC-Co<sub>1.5</sub>Ni<sub>1.5</sub>CP, and GC-Co<sub>2</sub>Ni<sub>1</sub>CP. The active catalyst, GC-Co<sub>2</sub>Ni<sub>1</sub>CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec<sup>-1</sup>) than IrO<sub>2</sub> (125 mV dec<sup>-1</sup>). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co<sub>2</sub>Ni<sub>1</sub>CP, which required 285 mV to attain 10 mA cm<sup>-2</sup>. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co<sub>2</sub>Ni<sub>1</sub>CP/GC (0.017337 s<sup>-1</sup>) was found to be 3-fold higher than that of IrO<sub>2</sub> (0.0014 s<sup>-1</sup>). Furthermore, the GC-Co<sub>2</sub>Ni<sub>1</sub>CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec<sup>-1</sup>. The ultrastability of GC-Co<sub>2</sub>Ni<sub>1</sub>CP for industrial application was confirmed by durability at 10 and 100 mA cm<sup>-2</sup> for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co<sub>2</sub>Ni<sub>1</sub>CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA<sup>+</sup>) reveal that GC-Co<sub>2</sub>Ni<sub>1</sub>CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co<sub>2</sub>Ni<sub>1</sub>CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":"24292-24305"},"PeriodicalIF":3.7,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580870","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}
In the flotation process, there is galvanic corrosion between sulfide mineral particles, which increases the difficulty of separation between minerals. Therefore, the selection of suitable reagents to weaken this corrosion is of great significance. In this article, macromolecular organic reagent sodium lignosulfonate (SLC) was used to weaken the galvanic corrosion between galena and pyrite. Meanwhile, the effect of SLC on the mineral flotation behavior was studied, and the mechanism of SLC was further studied through ion dissolution tests, contact angle tests, infrared spectrum tests, and density functional theory (DFT) calculation. The adsorption of SLC on the mineral electrode increased the charge transfer resistance on the surface of the mineral electrode and hindered the resistance transfer; therefore, it could weaken the galvanic corrosion between galena and pyrite. SLC could selectively depress pyrite at low alkalinity. CaOH+ promoted the adsorption of SLC on the pyrite surface. When the pH of the slurry was adjusted by lime, SLC was more easily adsorbed on the pyrite surface, which hindered the adsorption of the collector on the surface of pyrite.
{"title":"Galvanic Interaction between Galena and Pyrite in the Presence of Sodium Lignosulfonate and Its Effects on Flotation.","authors":"Zhicheng Liu, Yanfang Cui, Fen Jiao, Wenqing Qin, Qian Wei","doi":"10.1021/acs.langmuir.4c03312","DOIUrl":"10.1021/acs.langmuir.4c03312","url":null,"abstract":"<p><p>In the flotation process, there is galvanic corrosion between sulfide mineral particles, which increases the difficulty of separation between minerals. Therefore, the selection of suitable reagents to weaken this corrosion is of great significance. In this article, macromolecular organic reagent sodium lignosulfonate (SLC) was used to weaken the galvanic corrosion between galena and pyrite. Meanwhile, the effect of SLC on the mineral flotation behavior was studied, and the mechanism of SLC was further studied through ion dissolution tests, contact angle tests, infrared spectrum tests, and density functional theory (DFT) calculation. The adsorption of SLC on the mineral electrode increased the charge transfer resistance on the surface of the mineral electrode and hindered the resistance transfer; therefore, it could weaken the galvanic corrosion between galena and pyrite. SLC could selectively depress pyrite at low alkalinity. CaOH<sup>+</sup> promoted the adsorption of SLC on the pyrite surface. When the pH of the slurry was adjusted by lime, SLC was more easily adsorbed on the pyrite surface, which hindered the adsorption of the collector on the surface of pyrite.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666434","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}
Pub Date : 2024-11-19DOI: 10.1021/acs.langmuir.4c03364
Ao Chen, Chuang Chen, Jinshan Cao, Xiufen Chen, Shuai Shao, Yang Lian, Wei Zheng
It is proven through transmission electron microscope (TEM) analysis that solar sensitizer Cu2SnS3 (CTS) dots prepared via the hot-injection route are nonspherical, polyhedral nanocrystals with the size of ∼11 nm. CTS dots were deposited into a porous TiO2 layer to form CTS/TiO2, an effective type II heterojunction in photoanodes. The electronic and energy band structures of TiO2 and CTS were studied by the plane-wave ultrasoft pseudopotential method based on density functional theory (DFT) and verified by ultraviolet–visible (UV–vis) spectroscopy. UV–vis and Photoluminescence (PL) spectra show that the CTS/TiO2 photoanode exhibits wider visible-light absorption as well as lower charge recombination. ZnS quantum dots (QDs) deposited on the CTS/TiO2 photoanode through the in situ successive ion layer adsorption and reaction (SILAR) method as the passivation layer can inhibit the reverse carrier transfer and increase the photocurrent density by building a potential barrier on the CTS/TiO2 photoanode and electrolyte interface. When 2-layer ZnS QDs are deposited, the maximum photocurrent density of the photoelectrochemical (PEC) cell composed of a ZnS/CTS/TiO2 photoanode, a Pt counter electrode, and Na2SO4 solution electrolyte is 8.43 mA/cm2 and the maximum applied bias photon-to-current efficiency (ABPE) is 7.79%. Under 1 sun (AM 1.5, 100 mW/cm2) with 0.6 V bias, its hydrogen yield reached 125.7 μmol·cm–2 after 4 h with the rate of 31.4 μmol·cm–2·h–1 in contrast to the yield of 107.86 μmol·cm–2 with the rate of 21.3 μmol·cm–2·h–1 for the CTS/TiO2 photoanode.
{"title":"Photoanode/Electrolyte Interface Modification for Efficient Hydrogen Evolution in Cu2SnS3 Dots-Sensitized Solar PEC Cells","authors":"Ao Chen, Chuang Chen, Jinshan Cao, Xiufen Chen, Shuai Shao, Yang Lian, Wei Zheng","doi":"10.1021/acs.langmuir.4c03364","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03364","url":null,"abstract":"It is proven through transmission electron microscope (TEM) analysis that solar sensitizer Cu<sub>2</sub>SnS<sub>3</sub> (CTS) dots prepared via the hot-injection route are nonspherical, polyhedral nanocrystals with the size of ∼11 nm. CTS dots were deposited into a porous TiO<sub>2</sub> layer to form CTS/TiO<sub>2</sub>, an effective type II heterojunction in photoanodes. The electronic and energy band structures of TiO<sub>2</sub> and CTS were studied by the plane-wave ultrasoft pseudopotential method based on density functional theory (DFT) and verified by ultraviolet–visible (UV–vis) spectroscopy. UV–vis and Photoluminescence (PL) spectra show that the CTS/TiO<sub>2</sub> photoanode exhibits wider visible-light absorption as well as lower charge recombination. ZnS quantum dots (QDs) deposited on the CTS/TiO<sub>2</sub> photoanode through the in situ successive ion layer adsorption and reaction (SILAR) method as the passivation layer can inhibit the reverse carrier transfer and increase the photocurrent density by building a potential barrier on the CTS/TiO<sub>2</sub> photoanode and electrolyte interface. When 2-layer ZnS QDs are deposited, the maximum photocurrent density of the photoelectrochemical (PEC) cell composed of a ZnS/CTS/TiO<sub>2</sub> photoanode, a Pt counter electrode, and Na<sub>2</sub>SO<sub>4</sub> solution electrolyte is 8.43 mA/cm<sup>2</sup> and the maximum applied bias photon-to-current efficiency (ABPE) is 7.79%. Under 1 sun (AM 1.5, 100 mW/cm<sup>2</sup>) with 0.6 V bias, its hydrogen yield reached 125.7 μmol·cm<sup>–2</sup> after 4 h with the rate of 31.4 μmol·cm<sup>–2</sup>·h<sup>–1</sup> in contrast to the yield of 107.86 μmol·cm<sup>–2</sup> with the rate of 21.3 μmol·cm<sup>–2</sup>·h<sup>–1</sup> for the CTS/TiO<sub>2</sub> photoanode.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673661","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}
We investigate energy generation from salinity gradients inside a nanopore that is connected to reservoirs at both ends. We consider that the inner wall surfaces are grafted with a densely grafted polyelectrolyte layer (PEL). We developed the PEL grafting density-dependent correlation of dielectric permittivity, molecular diffusivity, and dynamic viscosity in this endeavor. Using these correlations, we employ the finite element framework to solve the equations describing the ionic and fluidic transport. We use a partially hydrolyzed polyacrylamide polymer solution, which exhibits a shear-thinning fluid, in combination with the KCl electrolyte for energy-harvesting analysis. To describe the shear-rate-dependent apparent viscosity of non-Newtonian liquid, we have employed the Carreau model. For a window of right-side reservoir concentration, we investigate the effects of ion-partitioning in conjugation with the change in PEL grafting density on the ionic field, ionic selectivity, pore current, osmotic power, energy conversion efficiency, and flow field. The findings of this endeavor demonstrate how the ion-partitioning effect lowers the screening effect and raises the electrical double layer (EDL) potential by reducing the counterions in PEL. We show that the unique distribution of the ionic field leads to a higher prediction of generated osmotic power and power density due to the ion-parting effect. Additionally, we establish that the augmentation in PEL space charge density leads to improvement in average flow velocity, osmotic power, and consequently energy conversion efficiency. We establish that the generated osmotic power density and the energy conversion efficiency become very high at the higher grafting density. In summary, inferences of this analysis are deemed pertinent in designing the nanoscale device intended for high and efficient osmotic energy generation.
我们研究了在一个两端与储层相连的纳米孔内利用盐度梯度产生能量的问题。我们认为内壁表面接枝了致密的聚电解质层(PEL)。在此过程中,我们开发出了 PEL 接枝密度与介电常数、分子扩散率和动态粘度的相关性。利用这些相关性,我们采用有限元框架来求解描述离子和流体传输的方程。我们使用部分水解的聚丙烯酰胺聚合物溶液(表现为剪切稀化流体)与 KCl 电解质结合进行能量收集分析。为了描述非牛顿液体随剪切速率变化的表观粘度,我们采用了 Carreau 模型。对于右侧储层浓度窗口,我们研究了离子分区与 PEL 接枝密度变化对离子场、离子选择性、孔隙电流、渗透功率、能量转换效率和流场的影响。这项研究结果表明了离子分隔效应如何通过减少 PEL 中的反离子来降低屏蔽效应并提高电双层(EDL)电位。我们表明,由于离子分区效应,离子场的独特分布导致了对所产生的渗透力和功率密度的更高预测。此外,我们还确定,PEL 空间电荷密度的增加会导致平均流速、渗透功率以及能量转换效率的提高。我们发现,接枝密度越高,产生的渗透功率密度和能量转换效率就越高。总之,本分析的推论被认为有助于设计用于高效渗透能生成的纳米级装置。
{"title":"Maximizing Blue Energy via Densely Grafted Soft Layers in Nanopores","authors":"Md Ismayeel, Sumit Kumar Mehta, Pranab Kumar Mondal","doi":"10.1021/acs.langmuir.4c03192","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03192","url":null,"abstract":"We investigate energy generation from salinity gradients inside a nanopore that is connected to reservoirs at both ends. We consider that the inner wall surfaces are grafted with a densely grafted polyelectrolyte layer (PEL). We developed the PEL grafting density-dependent correlation of dielectric permittivity, molecular diffusivity, and dynamic viscosity in this endeavor. Using these correlations, we employ the finite element framework to solve the equations describing the ionic and fluidic transport. We use a partially hydrolyzed polyacrylamide polymer solution, which exhibits a shear-thinning fluid, in combination with the KCl electrolyte for energy-harvesting analysis. To describe the shear-rate-dependent apparent viscosity of non-Newtonian liquid, we have employed the Carreau model. For a window of right-side reservoir concentration, we investigate the effects of ion-partitioning in conjugation with the change in PEL grafting density on the ionic field, ionic selectivity, pore current, osmotic power, energy conversion efficiency, and flow field. The findings of this endeavor demonstrate how the ion-partitioning effect lowers the screening effect and raises the electrical double layer (EDL) potential by reducing the counterions in PEL. We show that the unique distribution of the ionic field leads to a higher prediction of generated osmotic power and power density due to the ion-parting effect. Additionally, we establish that the augmentation in PEL space charge density leads to improvement in average flow velocity, osmotic power, and consequently energy conversion efficiency. We establish that the generated osmotic power density and the energy conversion efficiency become very high at the higher grafting density. In summary, inferences of this analysis are deemed pertinent in designing the nanoscale device intended for high and efficient osmotic energy generation.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"80 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673663","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}
Palm leaves serve as a traditional recording medium and are widespread in south and southeast Asia, and they have a long history. However, they are sensitive to environmental fluctuations, especially moisture, which may severely affect their conservation status. In this research, the moisture absorption behaviors of palm leaves in different states, including raw, treated, naturally aged, and artificially aged ones, were investigated by intelligent gravimetric analysis (IGA) and water retention value (WRV) to analyze their moisture absorption characteristics. Mathematical model was employed to fit and analyze their water adsorption curves, aiming to explore the content and distribution of the adsorbed water in monolayered and multilayered. Then, the chemical and physical properties of different palm leaves were studied by chemical composition analysis, Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM), and low-field nuclear magnetic resonance (low-field NMR), and the relationship between moisture absorption characteristics and their chemical composition and physical structures was analyzed. The results demonstrated that both treatment and aging processes could have a noticeable impact on the moisture absorption of palm leaves, as evidenced by reduced equilibrium moisture content (EMC) at high relative humidity (RH), decreased multilayer water adsorption content, and slightly increased monolayer water adsorption content. Besides, palm leaves exhibit a lower rate of moisture adsorption, at ∼30-50% RH, which facilitates their long-term conservation. The results of chemical and physical analyses revealed that the reduced content of hydrophilic groups was the primary reason for a decrease in palm leaves moisture absorption. Additionally, the fiber structure changes of palm leaves caused by treatment or aging may have different influences on their moisture adsorption, especially the content of monolayer adsorbed water.
{"title":"Investigation on the Moisture Absorption Behaviors of Palm Leaves (<i>Corypha umbraculifera</i>) and Their Variation Mechanism.","authors":"Zirui Zhu, Yuqing Jia, Hanwei Yu, Shuang Yu, Yangxin Zhou, Peng Liu, Hongbin Zhang, Yuliang Yang","doi":"10.1021/acs.langmuir.4c03368","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03368","url":null,"abstract":"<p><p>Palm leaves serve as a traditional recording medium and are widespread in south and southeast Asia, and they have a long history. However, they are sensitive to environmental fluctuations, especially moisture, which may severely affect their conservation status. In this research, the moisture absorption behaviors of palm leaves in different states, including raw, treated, naturally aged, and artificially aged ones, were investigated by intelligent gravimetric analysis (IGA) and water retention value (WRV) to analyze their moisture absorption characteristics. Mathematical model was employed to fit and analyze their water adsorption curves, aiming to explore the content and distribution of the adsorbed water in monolayered and multilayered. Then, the chemical and physical properties of different palm leaves were studied by chemical composition analysis, Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM), and low-field nuclear magnetic resonance (low-field NMR), and the relationship between moisture absorption characteristics and their chemical composition and physical structures was analyzed. The results demonstrated that both treatment and aging processes could have a noticeable impact on the moisture absorption of palm leaves, as evidenced by reduced equilibrium moisture content (EMC) at high relative humidity (RH), decreased multilayer water adsorption content, and slightly increased monolayer water adsorption content. Besides, palm leaves exhibit a lower rate of moisture adsorption, at ∼30-50% RH, which facilitates their long-term conservation. The results of chemical and physical analyses revealed that the reduced content of hydrophilic groups was the primary reason for a decrease in palm leaves moisture absorption. Additionally, the fiber structure changes of palm leaves caused by treatment or aging may have different influences on their moisture adsorption, especially the content of monolayer adsorbed water.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646471","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}
Pub Date : 2024-11-18DOI: 10.1021/acs.langmuir.4c02884
Xiaolong Lu, Shuting Zhang, Xinhai Chen, Ying Wei, Long Cao, Bincheng Zhao, Jun Yin
Enrichment of metal particles in lubricating oil is a crucial pretreatment for wear debris analyses in applications of condition-based machinery maintenance. Current techniques using physical filter cleaning and magnetic attachment to enrich metal particles have limitations in terms of efficiency and selectivity. This work presents an innovative acoustic manipulation chip for efficiently enriching metallic particles from lubricating oil. The platform utilizes the hybrid acoustic forces to perform high throughput particle enrichment in microchannels, even in an intensive flow environment. Regarding the viscosity effect of lubricating oil, the temperature dependence upon the particle enrichment is explored, and the figure of merit is employed to quantify the enrichment performance from the captured microscopic images. Experimental results demonstrate the proposed platform shows great nonselectivity for enriching both magnetic and nonmagnetic particles. This method opens a new door for developing automatic filter-free pretreatment tools to perform efficient particle enrichment in lubricating oil, which have great potential in many application scenarios, such as advanced wear debris analyses, oil quality monitoring, etc.
{"title":"High-Efficiency Enrichment of Metallic Particles in Lubricating Oil Based on Filter-Free Acoustic Manipulation Chip.","authors":"Xiaolong Lu, Shuting Zhang, Xinhai Chen, Ying Wei, Long Cao, Bincheng Zhao, Jun Yin","doi":"10.1021/acs.langmuir.4c02884","DOIUrl":"10.1021/acs.langmuir.4c02884","url":null,"abstract":"<p><p>Enrichment of metal particles in lubricating oil is a crucial pretreatment for wear debris analyses in applications of condition-based machinery maintenance. Current techniques using physical filter cleaning and magnetic attachment to enrich metal particles have limitations in terms of efficiency and selectivity. This work presents an innovative acoustic manipulation chip for efficiently enriching metallic particles from lubricating oil. The platform utilizes the hybrid acoustic forces to perform high throughput particle enrichment in microchannels, even in an intensive flow environment. Regarding the viscosity effect of lubricating oil, the temperature dependence upon the particle enrichment is explored, and the figure of merit is employed to quantify the enrichment performance from the captured microscopic images. Experimental results demonstrate the proposed platform shows great nonselectivity for enriching both magnetic and nonmagnetic particles. This method opens a new door for developing automatic filter-free pretreatment tools to perform efficient particle enrichment in lubricating oil, which have great potential in many application scenarios, such as advanced wear debris analyses, oil quality monitoring, etc.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666445","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}
Pub Date : 2024-11-18DOI: 10.1021/acs.langmuir.4c03554
Yunbo Zheng, Umit Celik, Charlotte Vorwald, J Kent Leach, Gang-Yu Liu
Alginate hydrogels are frequently used in 3D bioprinting and tissue repair and regeneration. Establishing the structure-property-performance correlation of these materials would benefit significantly from high-resolution structural characterization in aqueous environments from the molecular level to continuum. This study overcomes technical challenges and enables high-resolution atomic force microscopy (AFM) imaging of hydrated alginate hydrogels in aqueous media. By combining a new sample preparation protocol with extremely gentle tapping mode AFM imaging, we characterized the morphology and regional mechanical properties of the hydrated alginate. Upon cross-linking, basic units of these hydrogel materials consist of egg-box dimers, which assemble into long fibrils. These fibrils congregate and pile up, forming a sponge-like structure, whose pore size and distribution depend on the cross-linking conditions. At the exterior, surface tension impacts the piling of fibrils, leading to stripe-like features. These structural features contribute to local, regional, and macroscopic mechanics. The outcome provides new insights into its structural characteristics from nanometers to tens of micrometers, i.e., at the dimensions pertaining to biomaterial and hydrogel-cell interactions. Collectively, the results advance our knowledge of the structure and mechanics from the nanometer to continuum, facilitating advanced applications in hydrogel biomaterials.
{"title":"High-Resolution Atomic Force Microscopy Investigation of Alginate Hydrogel Materials in Aqueous Media.","authors":"Yunbo Zheng, Umit Celik, Charlotte Vorwald, J Kent Leach, Gang-Yu Liu","doi":"10.1021/acs.langmuir.4c03554","DOIUrl":"10.1021/acs.langmuir.4c03554","url":null,"abstract":"<p><p>Alginate hydrogels are frequently used in 3D bioprinting and tissue repair and regeneration. Establishing the structure-property-performance correlation of these materials would benefit significantly from high-resolution structural characterization in aqueous environments from the molecular level to continuum. This study overcomes technical challenges and enables high-resolution atomic force microscopy (AFM) imaging of hydrated alginate hydrogels in aqueous media. By combining a new sample preparation protocol with extremely gentle tapping mode AFM imaging, we characterized the morphology and regional mechanical properties of the hydrated alginate. Upon cross-linking, basic units of these hydrogel materials consist of egg-box dimers, which assemble into long fibrils. These fibrils congregate and pile up, forming a sponge-like structure, whose pore size and distribution depend on the cross-linking conditions. At the exterior, surface tension impacts the piling of fibrils, leading to stripe-like features. These structural features contribute to local, regional, and macroscopic mechanics. The outcome provides new insights into its structural characteristics from nanometers to tens of micrometers, i.e., at the dimensions pertaining to biomaterial and hydrogel-cell interactions. Collectively, the results advance our knowledge of the structure and mechanics from the nanometer to continuum, facilitating advanced applications in hydrogel biomaterials.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666473","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}
Low alloy steel faces localized corrosion issues in service environments, primarily due to pitting corrosion induced by inclusions. Conventional protective measures cannot significantly improve the corrosion resistance of the steel. In this study, an effective industrial approach was proposed to enhance the corrosion resistance of low alloy steels. Cerium (Ce) was added during the refining process to modify inclusions and alter the mechanism of inclusion-induced localized corrosion, thereby improving the substrate's ability to inhibit pitting corrosion. The effect of Ce treatment on the cleanliness of molten steel was investigated, and a kinetic model of inclusion evolution was established based on thermodynamic calculations. The pitting corrosion induced by CaS·C12A7 and CeAlO3 inclusions was studied through immersion experiments over different durations. The degree of corrosion after being soaked for 20 min was significantly different. The size and depth of pitting pits induced by CeAlO3 inclusions were much smaller than those induced by CaS·C12A7 inclusions. The electron back scatter diffraction tests confirmed that CaS·C12A7 inclusions exhibited a higher corrosion sensitivity compared to CeAlO3, thus promoting the initiation of pitting. Electrochemical tests demonstrated a positive shift in the corrosion potential and a reduction in current density. This implies that CeAlO3 inclusions can significantly inhibit pitting occurrences. Based on the dissolution behaviors of CaS·C12A7 and CeAlO3 inclusions, a kinetic model was established to describe the initiation and propagation of pitting induced by these inclusions.
{"title":"Revealing the Effect of Ce on Pitting Corrosion Induced by Inclusions in Low Alloy Steel: Induction by CaS·C<sub>12</sub>A<sub>7</sub> and Inhibition by CeAlO<sub>3</sub>.","authors":"Leru Zhang, Yanchong Yu, Wangwang Mao, Jinling Zhang, Cong Chang, Shaohua Zhang, Wei Yan","doi":"10.1021/acs.langmuir.4c03491","DOIUrl":"10.1021/acs.langmuir.4c03491","url":null,"abstract":"<p><p>Low alloy steel faces localized corrosion issues in service environments, primarily due to pitting corrosion induced by inclusions. Conventional protective measures cannot significantly improve the corrosion resistance of the steel. In this study, an effective industrial approach was proposed to enhance the corrosion resistance of low alloy steels. Cerium (Ce) was added during the refining process to modify inclusions and alter the mechanism of inclusion-induced localized corrosion, thereby improving the substrate's ability to inhibit pitting corrosion. The effect of Ce treatment on the cleanliness of molten steel was investigated, and a kinetic model of inclusion evolution was established based on thermodynamic calculations. The pitting corrosion induced by CaS·C<sub>12</sub>A<sub>7</sub> and CeAlO<sub>3</sub> inclusions was studied through immersion experiments over different durations. The degree of corrosion after being soaked for 20 min was significantly different. The size and depth of pitting pits induced by CeAlO<sub>3</sub> inclusions were much smaller than those induced by CaS·C<sub>12</sub>A<sub>7</sub> inclusions. The electron back scatter diffraction tests confirmed that CaS·C<sub>12</sub>A<sub>7</sub> inclusions exhibited a higher corrosion sensitivity compared to CeAlO<sub>3</sub>, thus promoting the initiation of pitting. Electrochemical tests demonstrated a positive shift in the corrosion potential and a reduction in current density. This implies that CeAlO<sub>3</sub> inclusions can significantly inhibit pitting occurrences. Based on the dissolution behaviors of CaS·C<sub>12</sub>A<sub>7</sub> and CeAlO<sub>3</sub> inclusions, a kinetic model was established to describe the initiation and propagation of pitting induced by these inclusions.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646474","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}
Ferroptosis has been recognized as an iron-based nonapoptotic-regulated cell death process. In the quest of resisting the unyielding vehemence of triple-negative breast cancer (TNBC), herein we have showcased the ferroptosis-inducing heteroleptic [LIrcRu], [LIrcIrh], and [LIrcRe] complexes, enabling them to selectively target "sialic acid", an overexpressed cancer cell-surface marker. The open-circuit potential (OCP) measurements in live cancer cells revealed the specific interaction between TNBC and the complexes, whereas control experiments with normal cells did not exhibit such interactions. GSH depletion, GPx4 inhibition, NADH/NADPH oxidation, lipid peroxidation, COX-2 activation, and Nrf2 inactivation were meticulously investigated upon treatment with these complexes to establish a strong basis for ferroptosis. Among all complexes, the complex [LIrcIrh] (IC50 = 25 ± 2.17 μM) has been well-documented as a potent ferroptosis inducer, which unveils the sturdy interaction with sialic acid possessing the highest binding constant (Kb = 0.71 × 105 M-1, ΔG = -279345.8026 kcal/mol) along with the highest serum albumin binding affinity (KHSA = 0.67 × 106 M-1) and significant DNA intercalation (Kb = 0.56 × 105 M-1, Kapp = 1.06 × 106 M-1, and C50 of intercalation is 76.56 μM), displaying the decreased current intensity in differential pulse voltammetry (DPV). Moreover, the complex [LIrcIrh] exhibited mitochondrial dysfunction and membrane damage (diminished MMP, ΔΨm) through the production of copious reactive oxygen species (ROS) in MDA-MB-231 cells upon considerable accumulation in mitochondria (Pearson's coefficient = 0.842). The analysis of the field emission scanning electron microscopy (FE-SEM) image has marked the vivid membrane damage induced by the complex [LIrcIrh], exhibiting ablaze evidence for the destruction of TNBC cells through ferroptosis.
{"title":"Sialic Acid-Targeted Ru(II)/Ir(III)/Re(I) Complexes for Ferroptosis Induction in Triple-Negative Breast Cancer.","authors":"Nilmadhab Roy, Tiasha Dasgupta, Sreejani Ghosh, Meena Jayaprakash, Maynak Pal, Shanooja Shanavas, Surja Kanta Pal, Venkatesan Muthukumar, Annamalai Senthil Kumar, Ramasamy Tamizhselvi, Mithun Roy, Bipasha Bose, Debashis Panda, Rinku Chakrabarty, Priyankar Paira","doi":"10.1021/acs.langmuir.4c02043","DOIUrl":"10.1021/acs.langmuir.4c02043","url":null,"abstract":"<p><p>Ferroptosis has been recognized as an iron-based nonapoptotic-regulated cell death process. In the quest of resisting the unyielding vehemence of triple-negative breast cancer (TNBC), herein we have showcased the ferroptosis-inducing heteroleptic [<b>LIr</b><sub><b>c</b></sub><b>Ru</b>], [<b>LIr</b><sub><b>c</b></sub><b>Ir</b><sub><b>h</b></sub>], and [<b>LIr</b><sub><b>c</b></sub><b>Re</b>] complexes, enabling them to selectively target \"sialic acid\", an overexpressed cancer cell-surface marker. The open-circuit potential (OCP) measurements in live cancer cells revealed the specific interaction between TNBC and the complexes, whereas control experiments with normal cells did not exhibit such interactions. GSH depletion, GPx4 inhibition, NADH/NADPH oxidation, lipid peroxidation, COX-2 activation, and Nrf2 inactivation were meticulously investigated upon treatment with these complexes to establish a strong basis for ferroptosis. Among all complexes, the complex [<b>LIr</b><sub><b>c</b></sub><b>Ir</b><sub><b>h</b></sub>] (IC<sub>50</sub> = 25 ± 2.17 μM) has been well-documented as a potent ferroptosis inducer, which unveils the sturdy interaction with sialic acid possessing the highest binding constant (<i>K</i><sub>b</sub> = 0.71 × 10<sup>5</sup> M<sup>-1</sup>, Δ<i>G</i> = -279345.8026 kcal/mol) along with the highest serum albumin binding affinity (<i>K</i><sub>HSA</sub> = 0.67 × 10<sup>6</sup> M<sup>-1</sup>) and significant DNA intercalation (<i>K</i><sub>b</sub> = 0.56 × 10<sup>5</sup> M<sup>-1</sup>, <i>K</i><sub>app</sub> = 1.06 × 10<sup>6</sup> M<sup>-1</sup>, and <i>C</i><sub>50</sub> of intercalation is 76.56 μM), displaying the decreased current intensity in differential pulse voltammetry (DPV). Moreover, the complex [<b>LIr</b><sub><b>c</b></sub><b>Ir</b><sub><b>h</b></sub>] exhibited mitochondrial dysfunction and membrane damage (diminished MMP, ΔΨ<sub>m</sub>) through the production of copious reactive oxygen species (ROS) in MDA-MB-231 cells upon considerable accumulation in mitochondria (Pearson's coefficient = 0.842). The analysis of the field emission scanning electron microscopy (FE-SEM) image has marked the vivid membrane damage induced by the complex [<b>LIr</b><sub><b>c</b></sub><b>Ir</b><sub><b>h</b></sub>], exhibiting ablaze evidence for the destruction of TNBC cells through ferroptosis.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666478","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}