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Fabrication of an Antibacterial/Anticoagulant Dual-Functional Surface for Left Ventricular Assist Devices via Mussel-Inspired Polydopamine Chemistry. 通过贻贝启发的聚多巴胺化学,为左心室辅助装置制造抗菌/抗凝血双功能表面。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-19 Epub Date: 2024-11-05 DOI: 10.1021/acs.langmuir.4c02619
Chuangxin Huang, Xin Liu, Lingwei Meng, Hongyi Qu, Qi Chen, Qiuliang Wang

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。
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引用次数: 0
Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation. 绿色合成的导电聚合物纳米隧洞与氢氧化金属纳米束,用于无缓和水氧化。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-19 Epub Date: 2024-11-06 DOI: 10.1021/acs.langmuir.4c02586
Kuppusamy Rajan, Dhanasingh Thiruvengadam, Krishnan Umapathy, Murugan Muthamildevi, Muthukumaran Sangamithirai, Jayaraman Jayabharathi, Manoharan Padmavathy

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.

电化学水分离需要高效的电催化剂来生产清洁的氢燃料。在此,我们采用绿色通道共沉淀(GC)法合成了附着有腔体-腔体CoNi氢氧化物(GC-CoNiCP)的导电聚合物(CP)纳米通道网络,即GC-Co1Ni2CP、GC-Co1.5Ni1.5CP和GC-Co2Ni1CP。与 IrO2(125 mV dec-1)相比,活性催化剂 GC-Co2Ni1CP/GC 的氧进化反应(OER)过电位(307 mV)较低,塔菲尔斜率(47 mV dec-1)较小。电化学活性表面积(EASA)归一化线性扫描伏安法(LSV)曲线显示,GC-Co2Ni1CP 具有出色的内在活性,需要 285 mV 才能达到 10 mA cm-2。在 1.54 V 电压下,GC-Co2Ni1CP/GC 的估计周转频率(TOF)(0.017337 s-1)比 IrO2(0.0014 s-1)高出 3 倍。此外,GC-Co2Ni1CP/NF 消耗的过电位很低(281 mV),塔菲尔斜率很小,为 121 mV dec-1。GC-Co2Ni1CP 在 10 和 100 mA cm-2 下的 OER(GC/NF-8 h,2.0%/100 h,2.2%)和整体水分裂(100 h,3.8%)的耐久性证实了其在工业应用中的超稳定性,这意味着 GC-Co2Ni1CP 具有足够的动力学性能来解决水氧化率升高的问题。pH 值和添加四甲基铵阳离子(TMA+)的影响表明,GC-Co2Ni1CP 遵循晶格氧机制(LOM)。在 1.55 V 的电压下进行的太阳能水电解证明了 GC-Co2Ni1CP 在太阳能转化为氢气方面的功效。环境影响研究和太阳能驱动的水电解分别证明了 GC-CoNiCP 具有优异的绿色性和效率。
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引用次数: 0
Galvanic Interaction between Galena and Pyrite in the Presence of Sodium Lignosulfonate and Its Effects on Flotation. 方铅矿和黄铁矿在木质素磺酸钠存在下的电化作用及其对浮选的影响。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-19 DOI: 10.1021/acs.langmuir.4c03312
Zhicheng Liu, Yanfang Cui, Fen Jiao, Wenqing Qin, Qian Wei

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.

在浮选过程中,硫化矿物颗粒之间会发生电化学腐蚀,这增加了矿物之间分离的难度。因此,选择合适的试剂来削弱这种腐蚀具有重要意义。本文采用大分子有机试剂木质素磺酸钠(SLC)来削弱方铅矿和黄铁矿之间的电化学腐蚀。同时,研究了 SLC 对矿物浮选行为的影响,并通过离子溶解试验、接触角试验、红外光谱试验和密度泛函理论(DFT)计算进一步研究了 SLC 的作用机理。SLC 在矿物电极上的吸附增加了矿物电极表面的电荷转移电阻,阻碍了电阻的传递,从而削弱了方铅矿和黄铁矿之间的电化学腐蚀。在低碱度条件下,SLC 可以选择性地抑制黄铁矿。CaOH+ 促进了 SLC 在黄铁矿表面的吸附。用石灰调节矿浆的 pH 值时,SLC 更容易吸附在黄铁矿表面,从而阻碍了黄铁矿表面对捕收剂的吸附。
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引用次数: 0
Photoanode/Electrolyte Interface Modification for Efficient Hydrogen Evolution in Cu2SnS3 Dots-Sensitized Solar PEC Cells 光阳极/电解质界面改性促进 Cu2SnS3 点敏化太阳能 PEC 电池中的高效氢气进化
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-19 DOI: 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.
通过透射电子显微镜(TEM)分析证明,通过热注入路线制备的太阳能敏化剂 Cu2SnS3(CTS)点是非球形的多面体纳米晶体,大小为 11 纳米。将 CTS 点沉积到多孔的 TiO2 层中形成 CTS/TiO2,这是一种有效的光阳极 II 型异质结。利用基于密度泛函理论(DFT)的平面波超软伪势法研究了 TiO2 和 CTS 的电子和能带结构,并通过紫外-可见(UV-vis)光谱进行了验证。紫外可见光谱和光致发光(PL)光谱显示,CTS/TiO2 光阳极具有更广泛的可见光吸收和更低的电荷重组。通过原位连续离子层吸附和反应(SILAR)方法在 CTS/TiO2 光阳极上沉积 ZnS 量子点(QDs)作为钝化层,可以在 CTS/TiO2 光阳极和电解质界面上建立势垒,从而抑制载流子反向转移,提高光电流密度。当沉积 2 层 ZnS QD 时,由 ZnS/CTS/TiO2 光阳极、铂对电极和 Na2SO4 溶液电解质组成的光电化学(PEC)电池的最大光电流密度为 8.43 mA/cm2,最大外加偏压光子对电流效率(ABPE)为 7.79%。在阳光(AM 1.5,100 mW/cm2)照射下,偏压为 0.6 V,4 小时后氢气产率达到 125.7 μmol-cm-2,速率为 31.4 μmol-cm-2-h-1,而 CTS/TiO2 光阳极的产率为 107.86 μmol-cm-2,速率为 21.3 μmol-cm-2-h-1。
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引用次数: 0
Maximizing Blue Energy via Densely Grafted Soft Layers in Nanopores 通过纳米孔中密集接枝的软层最大化蓝光能量
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-19 DOI: 10.1021/acs.langmuir.4c03192
Md Ismayeel, Sumit Kumar Mehta, Pranab Kumar Mondal
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。
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引用次数: 0
Investigation on the Moisture Absorption Behaviors of Palm Leaves (Corypha umbraculifera) and Their Variation Mechanism. 棕榈叶吸湿行为及其变化机制研究
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-18 DOI: 10.1021/acs.langmuir.4c03368
Zirui Zhu, Yuqing Jia, Hanwei Yu, Shuang Yu, Yangxin Zhou, Peng Liu, Hongbin Zhang, Yuliang Yang

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.

棕榈叶是一种传统的记录媒介,广泛分布于南亚和东南亚地区,具有悠久的历史。然而,棕榈叶对环境波动非常敏感,尤其是水分,这可能会严重影响其保存状况。本研究通过智能重量分析法(IGA)和保水值(WRV)研究了不同状态下棕榈叶的吸湿行为,包括生叶、处理过的棕榈叶、自然老化的棕榈叶和人工老化的棕榈叶,以分析其吸湿特性。采用数学模型对它们的吸水曲线进行拟合和分析,旨在探索单层和多层中吸附水的含量和分布。然后,通过化学成分分析、傅立叶变换红外光谱(FT-IR)、X 射线衍射(XRD)、氮吸附、扫描电子显微镜(SEM)和低场核磁共振(low-field NMR)研究了不同棕榈叶片的化学和物理特性,并分析了吸湿特性与其化学成分和物理结构之间的关系。结果表明,处理和老化过程都会对棕榈叶的吸湿性产生明显影响,表现为高相对湿度(RH)下的平衡含水率(EMC)降低,多层吸水率降低,单层吸水率略有上升。此外,棕榈叶在 30-50% 相对湿度下的吸湿率较低,这有利于其长期保存。化学和物理分析结果表明,亲水基团含量减少是棕榈叶吸湿性降低的主要原因。此外,棕榈叶经处理或老化引起的纤维结构变化也会对其吸湿性,特别是单层吸附水含量产生不同的影响。
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引用次数: 0
High-Efficiency Enrichment of Metallic Particles in Lubricating Oil Based on Filter-Free Acoustic Manipulation Chip. 基于免滤波器声学操纵芯片的润滑油中金属颗粒高效富集技术。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-18 DOI: 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.

润滑油中金属颗粒的富集是基于状态的机械维护应用中磨损碎片分析的重要预处理。目前使用物理过滤清洁和磁性附着来富集金属颗粒的技术在效率和选择性方面存在局限性。本研究提出了一种创新的声学操纵芯片,用于高效富集润滑油中的金属颗粒。该平台利用混合声学力在微通道中进行高通量颗粒富集,即使在高强度流动环境中也是如此。关于润滑油的粘度效应,探讨了颗粒富集的温度依赖性,并采用了功勋值来从捕获的显微图像量化富集性能。实验结果表明,所提议的平台在富集磁性和非磁性粒子方面都表现出了极大的非选择性。该方法为开发自动免滤器预处理工具打开了一扇新的大门,可对润滑油中的颗粒进行高效富集,在高级磨损碎片分析、油质监测等许多应用场景中具有巨大潜力。
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引用次数: 0
High-Resolution Atomic Force Microscopy Investigation of Alginate Hydrogel Materials in Aqueous Media. 水介质中藻酸盐水凝胶材料的高分辨率原子力显微镜研究
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-18 DOI: 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.

藻酸盐水凝胶常用于三维生物打印、组织修复和再生。在水环境中进行从分子水平到连续的高分辨率结构表征,将大大有利于建立这些材料的结构-性能相关性。本研究克服了技术难题,实现了水合藻酸盐水凝胶在水介质中的高分辨率原子力显微镜(AFM)成像。通过将新的样品制备方案与极其温和的轻敲模式原子力显微镜成像相结合,我们确定了水合藻酸盐的形态和区域机械特性。交联后,这些水凝胶材料的基本单元由蛋盒二聚体组成,并组合成长纤维。这些纤维聚集堆积,形成海绵状结构,其孔隙大小和分布取决于交联条件。在外部,表面张力会影响纤维的堆积,从而形成条纹状特征。这些结构特征有助于局部、区域和宏观力学。研究结果为我们提供了从纳米到数十微米(即与生物材料和水凝胶-细胞相互作用相关的尺寸)的结构特征的新见解。总之,这些成果增进了我们对从纳米到连续的结构和力学的了解,促进了水凝胶生物材料的先进应用。
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引用次数: 0
Revealing the Effect of Ce on Pitting Corrosion Induced by Inclusions in Low Alloy Steel: Induction by CaS·C12A7 and Inhibition by CeAlO3. 揭示 Ce 对低合金钢中夹杂物引起的点蚀的影响:CaS-C12A7 的诱导和 CeAlO3 的抑制。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-18 DOI: 10.1021/acs.langmuir.4c03491
Leru Zhang, Yanchong Yu, Wangwang Mao, Jinling Zhang, Cong Chang, Shaohua Zhang, Wei Yan

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.

低合金钢在使用环境中面临局部腐蚀问题,主要是由于夹杂物引起的点腐蚀。传统的保护措施无法显著提高钢的耐腐蚀性。本研究提出了一种有效的工业方法来提高低合金钢的耐腐蚀性。在精炼过程中添加铈(Ce)以改变夹杂物,改变夹杂物引起局部腐蚀的机理,从而提高基体抑制点蚀的能力。研究了 Ce 处理对钢水洁净度的影响,并根据热力学计算建立了夹杂物演变动力学模型。通过不同持续时间的浸泡实验研究了 CaS-C12A7 和 CeAlO3 包裹体诱导的点腐蚀。浸泡 20 分钟后的腐蚀程度明显不同。CeAlO3 夹杂物诱发的点蚀坑的大小和深度远远小于 CaS-C12A7 夹杂物诱发的点蚀坑。电子背散射衍射测试证实,与 CeAlO3 相比,CaS-C12A7 包裹体表现出更高的腐蚀敏感性,从而促进了点蚀的形成。电化学测试表明,腐蚀电位发生了正向移动,电流密度降低。这意味着 CeAlO3 包裹体能显著抑制点蚀的发生。根据 CaS-C12A7 和 CeAlO3 夹杂物的溶解行为,建立了一个动力学模型来描述这些夹杂物引起的点蚀的引发和扩展。
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引用次数: 0
Sialic Acid-Targeted Ru(II)/Ir(III)/Re(I) Complexes for Ferroptosis Induction in Triple-Negative Breast Cancer. 用于诱导三阴性乳腺癌铁突变的茜草酸靶向 Ru(II)/Ir(III)/Re(I) 复合物
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-18 DOI: 10.1021/acs.langmuir.4c02043
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

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.

铁凋亡被认为是一种基于铁的非凋亡调控细胞死亡过程。为了抵御三阴性乳腺癌(TNBC)不屈不挠的攻势,我们在本文中展示了诱导铁变态反应的异极[LIrcRu]、[LIrcIrh]和[LIrcRe]复合物,使它们能够选择性地靶向 "硅铝酸"(一种过度表达的癌细胞表面标志物)。在活癌细胞中进行的开路电位(OCP)测量显示了 TNBC 与复合物之间的特异性相互作用,而用正常细胞进行的对照实验则未显示出这种相互作用。在使用这些复合物处理癌细胞时,对GSH耗竭、GPx4抑制、NADH/NADPH氧化、脂质过氧化、COX-2激活和Nrf2失活进行了细致的研究,从而为铁变态反应奠定了坚实的基础。在所有复合物中,[LIrcIrh]复合物(IC50 = 25 ± 2.17 μM)已被证实是一种强效的铁变态反应诱导剂,它与具有最高结合常数(Kb = 0.71 × 105 M-1,ΔG = -279345.8026 kcal/mol)以及最高的血清白蛋白结合亲和力(KHSA = 0.67 × 106 M-1)和显著的 DNA 插层(Kb = 0.56 × 105 M-1,Kapp = 1.06 × 106 M-1,插层 C50 为 76.56 μM),在差分脉冲伏安法(DPV)中显示出电流强度的下降。此外,[LIrcIrh] 复合物在 MDA-MB-231 细胞线粒体中大量积累后,通过产生大量活性氧(ROS),表现出线粒体功能障碍和膜损伤(MMP 减少,ΔΨm)(皮尔逊系数 = 0.842)。场发射扫描电子显微镜(FE-SEM)图像分析显示,[LIrcIrh]复合物诱导了生动的膜损伤,展示了 TNBC 细胞通过铁变态反应遭到破坏的有力证据。
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