Pub Date : 2024-07-03DOI: 10.1021/acs.langmuir.4c01165
Kumi Semba, Kazunori Kadota, Tero Kämäräinen, Yuzuki Nakayama, Yuta Hatanaka, Hiromasa Uchiyama, Hiroshi Arima-Osonoi, Kazumasa Sugiyama, Yuichi Tozuka
We fabricated porous particles incorporating sugars (mannitol, sucrose, or dextran) and fenofibrate nanoparticles (FNPs) by using spray-freeze-drying (SFD). The type of sugar significantly influenced the pore architecture of the resulting SFD particles. Rapid freezing of droplets containing dextran produced ice encapsulation within a dextran matrix, forming porous dextran particles. In the presence of FNPs, the particle size (approximately 4 μm) and pore volume (0.3 cm3/g) of SFD dextran were barely affected. In contrast, SFD particles derived from mannitol and sucrose exhibited denser structures with a lower pore volume than dextran. SFD mannitol incorporating FNPs produced porous structures. FNPs containing surfactant and polymer, which reduced surface tension and increased viscosity, promoted the formation of small droplets with a polymeric structure and porous particles with a relatively sharp size distribution with a median around 5 μm. FNPs were uniformly distributed in SFD dextran, which featured large pore structures, whereas in SFD mannitol, the Raman signal of FNPs was more broadly distributed across the powder samples. Both morphologies contributed to enhancing the FNP dispersibility within a redispersed suspension of SFD particles. FNPs in SFD mannitol and dextran matrices maintained their particle size distribution from before SFD, showing no aggregation upon redispersion. Dextran formed a highly porous network irrespective of the presence of FNPs, whereas mannitol tended to alter the particle attributes upon FNP inclusion. In conclusion, SFD particles derived from dextran and mannitol might help to increase FNP dispersibility by increasing the formation of porous architectures.
{"title":"Tailored Sugar-Mediated Porous Particle Structures for Improved Dispersion of Drug Nanoparticles in Spray-Freeze-Drying.","authors":"Kumi Semba, Kazunori Kadota, Tero Kämäräinen, Yuzuki Nakayama, Yuta Hatanaka, Hiromasa Uchiyama, Hiroshi Arima-Osonoi, Kazumasa Sugiyama, Yuichi Tozuka","doi":"10.1021/acs.langmuir.4c01165","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01165","url":null,"abstract":"<p><p>We fabricated porous particles incorporating sugars (mannitol, sucrose, or dextran) and fenofibrate nanoparticles (FNPs) by using spray-freeze-drying (SFD). The type of sugar significantly influenced the pore architecture of the resulting SFD particles. Rapid freezing of droplets containing dextran produced ice encapsulation within a dextran matrix, forming porous dextran particles. In the presence of FNPs, the particle size (approximately 4 μm) and pore volume (0.3 cm<sup>3</sup>/g) of SFD dextran were barely affected. In contrast, SFD particles derived from mannitol and sucrose exhibited denser structures with a lower pore volume than dextran. SFD mannitol incorporating FNPs produced porous structures. FNPs containing surfactant and polymer, which reduced surface tension and increased viscosity, promoted the formation of small droplets with a polymeric structure and porous particles with a relatively sharp size distribution with a median around 5 μm. FNPs were uniformly distributed in SFD dextran, which featured large pore structures, whereas in SFD mannitol, the Raman signal of FNPs was more broadly distributed across the powder samples. Both morphologies contributed to enhancing the FNP dispersibility within a redispersed suspension of SFD particles. FNPs in SFD mannitol and dextran matrices maintained their particle size distribution from before SFD, showing no aggregation upon redispersion. Dextran formed a highly porous network irrespective of the presence of FNPs, whereas mannitol tended to alter the particle attributes upon FNP inclusion. In conclusion, SFD particles derived from dextran and mannitol might help to increase FNP dispersibility by increasing the formation of porous architectures.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496364","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}
MXene has attracted considerable attention for supercapacitor applications in the past decade owing to its exceptional electrochemical properties. Although major research interests are focused on composite-based MXene, doping engineering of MXene has recently emerged as a promising alternative. This work unveils the potential of doped MXene for supercapacitor applications with a critical perspective. Various doping engineering strategies and synthesis methods adopted are explicitly delineated. Detailed discussions on the optimization of lattice, functionalization, substitution, and interface modification are provided. Further, it sheds light on recent developments with the asssociated mechanism of doped MXene supercapacitors, followed by the associated challenges. Finally, a roadmap for further progress of doped MXene for the realization of advanced and high-performing energy storage systems has been described. We envision that this Perspective will open up new avenues for the further exploration of this domain.
{"title":"Can Doped-MXene-Based Supercapacitors Be the Game-Changer for Future Energy Landscape? A Critical Perspective.","authors":"Ritik Mohanty, Amtul Nashim, Kaushik Parida, Kulamani Parida","doi":"10.1021/acs.langmuir.4c01242","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01242","url":null,"abstract":"<p><p>MXene has attracted considerable attention for supercapacitor applications in the past decade owing to its exceptional electrochemical properties. Although major research interests are focused on composite-based MXene, doping engineering of MXene has recently emerged as a promising alternative. This work unveils the potential of doped MXene for supercapacitor applications with a critical perspective. Various doping engineering strategies and synthesis methods adopted are explicitly delineated. Detailed discussions on the optimization of lattice, functionalization, substitution, and interface modification are provided. Further, it sheds light on recent developments with the asssociated mechanism of doped MXene supercapacitors, followed by the associated challenges. Finally, a roadmap for further progress of doped MXene for the realization of advanced and high-performing energy storage systems has been described. We envision that this Perspective will open up new avenues for the further exploration of this domain.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489987","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 : 2024-07-03DOI: 10.1021/acs.langmuir.4c00910
Xinyi Zhao, Qian Sang, Mingzhe Dong, Jun Yao
Carbon dioxide (CO2) has been widely used to enhance the recovery of adsorbed hydrocarbons from the organic matter (OM) in shale formations. To reveal the driving force of replacing adsorbed hydrocarbons from OM by CO2, we performed molecular dynamics (MD) simulations of the replacement process and calculated the interaction forces between CO2 and hydrocarbons. In addition, based on the umbrella sampling method, steered MD simulations were performed, and the free energy profiles of hydrocarbons were obtained using the weighted histogram analysis method. Results show that the condition of the hydrocarbon replacement by CO2 requires the hydrocarbon to have sufficient kinetic energy or to have a sufficiently large attractive force exerted to ensure that the hydrocarbon escapes the potential well of the OM. The attractive forces exerted on hydrocarbon molecules by CO2 can significantly decrease the energy barrier associated with hydrocarbon movement away from the OM surface. Furthermore, both CO2 and supercritical CO2 can effectively displace adsorbed hydrocarbon gas (methane) on the OM, while supercritical CO2 is required to enhance the recovery of adsorbed hydrocarbon oil (n-dodecane). The results obtained in this study provide guidance for enhancing the recovery of adsorbed hydrocarbons by CO2 in shale formations.
二氧化碳(CO2)已被广泛用于提高页岩层中有机物(OM)吸附碳氢化合物的回收率。为了揭示 CO2 取代 OM 中吸附的碳氢化合物的驱动力,我们对取代过程进行了分子动力学(MD)模拟,并计算了 CO2 与碳氢化合物之间的相互作用力。此外,基于伞状采样方法,我们还进行了转向 MD 模拟,并利用加权直方图分析方法获得了碳氢化合物的自由能曲线。结果表明,碳氢化合物被二氧化碳置换的条件要求碳氢化合物具有足够的动能或施加足够大的吸引力,以确保碳氢化合物逃离 OM 的势阱。二氧化碳对碳氢化合物分子施加的吸引力可大大降低碳氢化合物远离 OM 表面的能量障碍。此外,二氧化碳和超临界二氧化碳都能有效地置换 OM 上吸附的烃类气体(甲烷),而要想提高吸附的烃类石油(正十二烷)的采收率,则需要超临界二氧化碳。本研究获得的结果为利用二氧化碳提高页岩层中吸附烃的采收率提供了指导。
{"title":"Investigation of the Driving Force of Replacing Adsorbed Hydrocarbons by CO<sub>2</sub> in Organic Matter from an Energy Perspective.","authors":"Xinyi Zhao, Qian Sang, Mingzhe Dong, Jun Yao","doi":"10.1021/acs.langmuir.4c00910","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00910","url":null,"abstract":"<p><p>Carbon dioxide (CO<sub>2</sub>) has been widely used to enhance the recovery of adsorbed hydrocarbons from the organic matter (OM) in shale formations. To reveal the driving force of replacing adsorbed hydrocarbons from OM by CO<sub>2</sub>, we performed molecular dynamics (MD) simulations of the replacement process and calculated the interaction forces between CO<sub>2</sub> and hydrocarbons. In addition, based on the umbrella sampling method, steered MD simulations were performed, and the free energy profiles of hydrocarbons were obtained using the weighted histogram analysis method. Results show that the condition of the hydrocarbon replacement by CO<sub>2</sub> requires the hydrocarbon to have sufficient kinetic energy or to have a sufficiently large attractive force exerted to ensure that the hydrocarbon escapes the potential well of the OM. The attractive forces exerted on hydrocarbon molecules by CO<sub>2</sub> can significantly decrease the energy barrier associated with hydrocarbon movement away from the OM surface. Furthermore, both CO<sub>2</sub> and supercritical CO<sub>2</sub> can effectively displace adsorbed hydrocarbon gas (methane) on the OM, while supercritical CO<sub>2</sub> is required to enhance the recovery of adsorbed hydrocarbon oil (<i>n</i>-dodecane). The results obtained in this study provide guidance for enhancing the recovery of adsorbed hydrocarbons by CO<sub>2</sub> in shale formations.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489994","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}
Surface enhanced Raman spectroscopy (SERS) is a highly sensitive analytical detection method commonly employed in biochemical and environmental analysis. Nevertheless, the rapid movement of analytes and interfering components in flow systems can impact the real-time, online detection capability of Raman spectroscopy. To address this issue, we developed an innovative approach utilizing covalent organic framework (COF), a robust porous material with excellent water stability, to coat the surface of Ag nanowire (AgNW) for synthesizing AgNW@COF hybrid. The regular pores of the COF serve to effectively eliminate large interfering molecules while facilitating the efficient transport of specific analytes to SERS hot spots. Additionally, the fluid flow-induced scouring effect aids in excluding interfering molecules from the surface of AgNW. By incorporating AgNW@COF into a bifunctional filter membrane with simultaneous filtration and sensing capabilities, we had achieved efficient purification of organic pollutants as well as real-time identification of pollutant species and concentration.
{"title":"A Dual-Function AgNW@COF SERS Membrane for Organic Pollutant Removal and Simultaneous Concentration Determination.","authors":"Qian Niu, Weitao Li, Ruiling Yuan, Qianqian Li, Haozhe Tang, Zhenyuan Yang, Yongqi Yang, Xuezhi Qiao","doi":"10.1021/acs.langmuir.4c01780","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01780","url":null,"abstract":"<p><p>Surface enhanced Raman spectroscopy (SERS) is a highly sensitive analytical detection method commonly employed in biochemical and environmental analysis. Nevertheless, the rapid movement of analytes and interfering components in flow systems can impact the real-time, online detection capability of Raman spectroscopy. To address this issue, we developed an innovative approach utilizing covalent organic framework (COF), a robust porous material with excellent water stability, to coat the surface of Ag nanowire (AgNW) for synthesizing AgNW@COF hybrid. The regular pores of the COF serve to effectively eliminate large interfering molecules while facilitating the efficient transport of specific analytes to SERS hot spots. Additionally, the fluid flow-induced scouring effect aids in excluding interfering molecules from the surface of AgNW. By incorporating AgNW@COF into a bifunctional filter membrane with simultaneous filtration and sensing capabilities, we had achieved efficient purification of organic pollutants as well as real-time identification of pollutant species and concentration.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496355","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 : 2024-07-03DOI: 10.1021/acs.langmuir.4c00649
Li Ma, Yilong Yao, Xiong Zhao, Junsheng Hou, Lei Huang, Zihan Ding, Xinlan Lu, Jinjia Wei, Nanjing Hao
Hydrogel microspheres are biocompatible materials widely used in biological and medical fields. Emulsification and stirring are the commonly used methods to prepare hydrogels. However, the size distribution is considerably wide, the monodispersity and the mechanical intensity are poor, and the stable operation conditions are comparatively narrow to meet some sophisticated applications. In this paper, a T-shaped stepwise microchannel combined with a simple side microchannel structure is developed to explore the liquid-liquid dispersion mechanism, interfacial evolution behavior, satellite droplet formation mechanism and separation, and the eventual successful synthesis of dextran hydrogel microspheres. The effect of the operation parameters on droplet and microsphere size is comprehensively studied. The flow pattern and the stable operation condition range are given, and mathematical prediction models are developed under three different flow regimes for droplet size prediction. Based on the stable operating conditions, a microdroplet-based method combined with UV light curing is developed to synthesize the dextran hydrogel microsphere. The highly uniform and monodispersed dextran microspheres with good mechanical intensity are synthesized in the developed microfluidic platform. The size of the microsphere could be tuned from 50 to 300 μm with a capillary number in the range of 0.006-0.742. This work not only provides a facile method for functional polymeric microsphere preparation but also offers important design guidelines for the development of a robust microreactor.
水凝胶微球是一种生物相容性材料,广泛应用于生物和医疗领域。乳化和搅拌是制备水凝胶的常用方法。但其粒度分布较广,单分散性和机械强度较差,稳定操作条件相对狭窄,难以满足一些复杂的应用。本文开发了一种结合简单侧微通道结构的 T 型阶梯式微通道,以探索液-液分散机理、界面演化行为、卫星液滴形成机理和分离,并最终成功合成右旋糖酐水凝胶微球。全面研究了操作参数对液滴和微球尺寸的影响。给出了流动模式和稳定操作条件范围,并建立了三种不同流动状态下的液滴粒度预测数学模型。在稳定操作条件的基础上,开发了一种基于微液滴并结合紫外光固化的方法来合成葡聚糖水凝胶微球。在所开发的微流控平台上合成了高度均匀、单分散且具有良好机械强度的葡聚糖微球。微球的尺寸可在 50 到 300 μm 之间调节,毛细管数在 0.006-0.742 之间。这项工作不仅为功能性聚合物微球的制备提供了简便的方法,还为开发坚固耐用的微反应器提供了重要的设计指南。
{"title":"Rational Design of Liquid-Liquid Microdispersion Droplet Microreactors for the Controllable Synthesis of Highly Uniform and Monodispersed Dextran Microspheres.","authors":"Li Ma, Yilong Yao, Xiong Zhao, Junsheng Hou, Lei Huang, Zihan Ding, Xinlan Lu, Jinjia Wei, Nanjing Hao","doi":"10.1021/acs.langmuir.4c00649","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00649","url":null,"abstract":"<p><p>Hydrogel microspheres are biocompatible materials widely used in biological and medical fields. Emulsification and stirring are the commonly used methods to prepare hydrogels. However, the size distribution is considerably wide, the monodispersity and the mechanical intensity are poor, and the stable operation conditions are comparatively narrow to meet some sophisticated applications. In this paper, a T-shaped stepwise microchannel combined with a simple side microchannel structure is developed to explore the liquid-liquid dispersion mechanism, interfacial evolution behavior, satellite droplet formation mechanism and separation, and the eventual successful synthesis of dextran hydrogel microspheres. The effect of the operation parameters on droplet and microsphere size is comprehensively studied. The flow pattern and the stable operation condition range are given, and mathematical prediction models are developed under three different flow regimes for droplet size prediction. Based on the stable operating conditions, a microdroplet-based method combined with UV light curing is developed to synthesize the dextran hydrogel microsphere. The highly uniform and monodispersed dextran microspheres with good mechanical intensity are synthesized in the developed microfluidic platform. The size of the microsphere could be tuned from 50 to 300 μm with a capillary number in the range of 0.006-0.742. This work not only provides a facile method for functional polymeric microsphere preparation but also offers important design guidelines for the development of a robust microreactor.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489995","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}
Understanding mass transfer kinetics within individual porous particles is crucial for theoretically explaining the retention and elution behaviors in chromatography and drug delivery. Using laser trapping and fluorescence microspectroscopy, we investigated the diffusion mechanism of coumarin 102 (C102) into single octadecylsilyl particle in acetonitrile (ACN)/water, N,N-dimethylformamide (DMF)/water, and 1-butanol (BuOH)/water solutions. The intraparticle diffusion behavior of C102 was evaluated using the spherical diffusion equation, allowing us to determine the intraparticle diffusion coefficients (Dintra): (8-10) × 10-9 cm2 s-1 for ACN, (10-16) × 10-9 cm2 s-1 for DMF, and (4-6) × 10-9 cm2 s-1 for BuOH. The obtained Dintra values were further analyzed using a pore and surface diffusion model. Thus, we revealed that the diffusion mechanism of C102 differed depending on the organic solvent: surface diffusion for ACN and DMF and pore and surface diffusions for BuOH were observed. This difference is attributed to the formation of a concentrated liquid phase of ACN and DMF at the interface of the alkyl chain and the bulk solution in the pore.
{"title":"Effect of Organic Solvent on the Mass Transfer Mechanism of Coumarin 102 in a Single Octadecylsilyl Silica Gel/Organic Solvent-Water System by Laser Trapping and Fluorescence Microspectroscopy.","authors":"Kazuki Yamada, Akihisa Miyagawa, Ren Honma, Shigenori Nagatomo, Kiyoharu Nakatani","doi":"10.1021/acs.langmuir.4c00878","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00878","url":null,"abstract":"<p><p>Understanding mass transfer kinetics within individual porous particles is crucial for theoretically explaining the retention and elution behaviors in chromatography and drug delivery. Using laser trapping and fluorescence microspectroscopy, we investigated the diffusion mechanism of coumarin 102 (C102) into single octadecylsilyl particle in acetonitrile (ACN)/water, <i>N</i>,<i>N</i>-dimethylformamide (DMF)/water, and 1-butanol (BuOH)/water solutions. The intraparticle diffusion behavior of C102 was evaluated using the spherical diffusion equation, allowing us to determine the intraparticle diffusion coefficients (<i>D</i><sub>intra</sub>): (8-10) × 10<sup>-9</sup> cm<sup>2</sup> s<sup>-1</sup> for ACN, (10-16) × 10<sup>-9</sup> cm<sup>2</sup> s<sup>-1</sup> for DMF, and (4-6) × 10<sup>-9</sup> cm<sup>2</sup> s<sup>-1</sup> for BuOH. The obtained <i>D</i><sub>intra</sub> values were further analyzed using a pore and surface diffusion model. Thus, we revealed that the diffusion mechanism of C102 differed depending on the organic solvent: surface diffusion for ACN and DMF and pore and surface diffusions for BuOH were observed. This difference is attributed to the formation of a concentrated liquid phase of ACN and DMF at the interface of the alkyl chain and the bulk solution in the pore.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489990","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 : 2024-07-03DOI: 10.1021/acs.langmuir.4c00907
Nitesh Kumar, Uvinduni I Premadasa, Dengpan Dong, Santanu Roy, Ying-Zhong Ma, Benjamin Doughty, Vyacheslav S Bryantsev
Amino acids make up a promising family of molecules capable of direct air capture (DAC) of CO2 from the atmosphere. Under alkaline conditions, CO2 reacts with the anionic form of an amino acid to produce carbamates and deactivated zwitterionic amino acids. The presence of the various species of amino acids and reactive intermediates can have a significant effect on DAC chemistry, the role of which is poorly understood. In this study, all-atom molecular dynamics (MD) based computational simulations and vibrational sum frequency generation (vSFG) spectroscopy studies were conducted to understand the role of competitive interactions at the air-aqueous interface in the context of DAC. We find that the presence of potassium bicarbonate ions, in combination with the anionic and zwitterionic forms of amino acids, induces concentration and charge gradients at the interface, generating a layered molecular arrangement that changes under pre- and post-DAC conditions. In parallel, an enhancement in the surface activity of both anionic and zwitterionic forms of amino acids is observed, which is attributed to enhanced interfacial stability and favorable intermolecular interactions between the adsorbed amino acids in their anionic and zwitterionic forms. The collective influence of these competitive interactions, along with the resulting interfacial heterogeneity, may in turn affect subsequent capture reactions and associated rates. These effects underscore the need to consider dynamic changes in interfacial chemical makeup to enhance DAC efficiency and to develop successful negative emission and storage technologies.
{"title":"Adsorption, Orientation, and Speciation of Amino Acids at Air-Aqueous Interfaces for the Direct Air Capture of CO<sub>2</sub>.","authors":"Nitesh Kumar, Uvinduni I Premadasa, Dengpan Dong, Santanu Roy, Ying-Zhong Ma, Benjamin Doughty, Vyacheslav S Bryantsev","doi":"10.1021/acs.langmuir.4c00907","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00907","url":null,"abstract":"<p><p>Amino acids make up a promising family of molecules capable of direct air capture (DAC) of CO<sub>2</sub> from the atmosphere. Under alkaline conditions, CO<sub>2</sub> reacts with the anionic form of an amino acid to produce carbamates and deactivated zwitterionic amino acids. The presence of the various species of amino acids and reactive intermediates can have a significant effect on DAC chemistry, the role of which is poorly understood. In this study, all-atom molecular dynamics (MD) based computational simulations and vibrational sum frequency generation (vSFG) spectroscopy studies were conducted to understand the role of competitive interactions at the air-aqueous interface in the context of DAC. We find that the presence of potassium bicarbonate ions, in combination with the anionic and zwitterionic forms of amino acids, induces concentration and charge gradients at the interface, generating a layered molecular arrangement that changes under pre- and post-DAC conditions. In parallel, an enhancement in the surface activity of both anionic and zwitterionic forms of amino acids is observed, which is attributed to enhanced interfacial stability and favorable intermolecular interactions between the adsorbed amino acids in their anionic and zwitterionic forms. The collective influence of these competitive interactions, along with the resulting interfacial heterogeneity, may in turn affect subsequent capture reactions and associated rates. These effects underscore the need to consider dynamic changes in interfacial chemical makeup to enhance DAC efficiency and to develop successful negative emission and storage technologies.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489986","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}
Phase behavior in protein-nanoparticle systems in light of protein corona formation has been investigated. We report the formation of HSA thin films following the addition of a solid protein to a solution of CTAB-capped gold nanorods (AuNRs) via phase separation. The phase separation behavior was observed through UV-vis spectroscopy, turbidity assays, and DLS studies. UV-vis spectra for the protein-AuNR solution indicated a possible self-assembly formation by CTAB-HSA complexes and AuNR-HSA conjugates. The turbidity was found to increase linearly up to 30-50% v/v for each component. The growth phase slope is proportional to the concentration of the components, AuNRs, and HSA, with no lag phase. Dynamic light scattering (DLS) shows the formation of larger aggregates with time, implying a segregated phase of AuNR-HSA and a CTAB-HSA-AuNR network. ζ-potential values confirm surface modification, implying protein corona formation on nanorods. The thin films were also characterized using SEM, AFM, SAXS, XPS, FTIR, and TGA studies. SEM images show a smooth surface with a reduced number of pores, indicating the compactness of the deposited structure. AFM shows two different structural pattern formations with the deposition, indicating possible self-assembly of the protein-conjugated nanoparticles. FTIR studies indicate a change in the hydrogen bonding network and confirm the CTAB-HSA-AuNR complex network formation. The XPS studies indicate Au-S bond formation, along with Au-S-S-Au interactions. SAXS studies indicate the formation of aggregates (oligomers), as well as the presence of dominant attractive intermolecular interactions in the thin films.
{"title":"Thin Film Formation of HSA in the Presence of CTAB-Capped Gold Nanorods through Phase Separation.","authors":"Krishna Halder, Kabira Sabnam, Abhirup Das, Dipak K Goswami, Swagata Dasgupta","doi":"10.1021/acs.langmuir.4c00694","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00694","url":null,"abstract":"<p><p>Phase behavior in protein-nanoparticle systems in light of protein corona formation has been investigated. We report the formation of HSA thin films following the addition of a solid protein to a solution of CTAB-capped gold nanorods (AuNRs) via phase separation. The phase separation behavior was observed through UV-vis spectroscopy, turbidity assays, and DLS studies. UV-vis spectra for the protein-AuNR solution indicated a possible self-assembly formation by CTAB-HSA complexes and AuNR-HSA conjugates. The turbidity was found to increase linearly up to 30-50% v/v for each component. The growth phase slope is proportional to the concentration of the components, AuNRs, and HSA, with no lag phase. Dynamic light scattering (DLS) shows the formation of larger aggregates with time, implying a segregated phase of AuNR-HSA and a CTAB-HSA-AuNR network. ζ-potential values confirm surface modification, implying protein corona formation on nanorods. The thin films were also characterized using SEM, AFM, SAXS, XPS, FTIR, and TGA studies. SEM images show a smooth surface with a reduced number of pores, indicating the compactness of the deposited structure. AFM shows two different structural pattern formations with the deposition, indicating possible self-assembly of the protein-conjugated nanoparticles. FTIR studies indicate a change in the hydrogen bonding network and confirm the CTAB-HSA-AuNR complex network formation. The XPS studies indicate Au-S bond formation, along with Au-S-S-Au interactions. SAXS studies indicate the formation of aggregates (oligomers), as well as the presence of dominant attractive intermolecular interactions in the thin films.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475434","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 : 2024-07-02DOI: 10.1021/acs.langmuir.4c01394
Jingdong Yang, Rong Li, Jinxing Wang, Jiaxin Wen, Junliu Ye, Guangsheng Huang, Jingfeng Wang, Fusheng Pan
The electrochemical properties of TiB4 and TiB5 monolayers in Na-ion batteries (NIBs) were studied by using the first-principles calculation method based on density functional theory. The TiB4/TiB5 monolayer showed excellent Na storage capacity, capable of adsorbing two layers of Na with theoretical capacities of 1176.77 and 1052.05 mA g-1, respectively. The average operating voltages of the TiB4 and TiB5 monolayers are 0.073 and 0.042 eV, respectively, indicating that they can be used as anode materials for NIBs. More interestingly, the exposed B surface not only brings a high theoretical capacity but also provides a relatively small diffusion barrier of 0.16 (for TiB4) and 0.33 eV (for TiB5), enhancing their rate capability in NIBs.
通过基于密度泛函理论的第一性原理计算方法,研究了 TiB4 和 TiB5 单层在钠离子电池(NIB)中的电化学特性。TiB4/TiB5 单层显示出优异的贮纳能力,能够吸附两层 Na,理论容量分别为 1176.77 mA g-1 和 1052.05 mA g-1。TiB4 和 TiB5 单层的平均工作电压分别为 0.073 和 0.042 eV,这表明它们可用作 NIB 的阳极材料。更有趣的是,裸露的 B 表面不仅带来了较高的理论容量,还提供了相对较小的扩散势垒,分别为 0.16(TiB4)和 0.33 eV(TiB5),从而提高了它们在 NIB 中的速率能力。
{"title":"First-Principles Calculations of TiB<sub>4</sub> and TiB<sub>5</sub> as Anodes with High Capacity for Na-Ion Batteries.","authors":"Jingdong Yang, Rong Li, Jinxing Wang, Jiaxin Wen, Junliu Ye, Guangsheng Huang, Jingfeng Wang, Fusheng Pan","doi":"10.1021/acs.langmuir.4c01394","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01394","url":null,"abstract":"<p><p>The electrochemical properties of TiB<sub>4</sub> and TiB<sub>5</sub> monolayers in Na-ion batteries (NIBs) were studied by using the first-principles calculation method based on density functional theory. The TiB<sub>4</sub>/TiB<sub>5</sub> monolayer showed excellent Na storage capacity, capable of adsorbing two layers of Na with theoretical capacities of 1176.77 and 1052.05 mA g<sup>-1</sup>, respectively. The average operating voltages of the TiB<sub>4</sub> and TiB<sub>5</sub> monolayers are 0.073 and 0.042 eV, respectively, indicating that they can be used as anode materials for NIBs. More interestingly, the exposed B surface not only brings a high theoretical capacity but also provides a relatively small diffusion barrier of 0.16 (for TiB<sub>4</sub>) and 0.33 eV (for TiB<sub>5</sub>), enhancing their rate capability in NIBs.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489992","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 : 2024-07-02DOI: 10.1021/acs.langmuir.4c00922
Huiping Song, Zheng Cheng, Ran Qin, Ziyu Chen, Tianxiao Wang, Yuli Wang, Huijun Jiang, Yifei Du, Fan Wu
The issue of bacterial infectious diseases remains a significant concern worldwide, particularly due to the misuse of antibiotics, which has caused the emergence of antibiotic-resistant strains. Fortunately, the rapid development of nanomaterials has propelled significant progress in antimicrobial therapy, offering promising solutions. Among them, the utilization of nanoenzyme-based chemodynamic therapy (CDT) has become a highly hopeful approach to combating bacterial infectious diseases. Nevertheless, the application of CDT appears to be facing certain constraints for its low efficiency in the Fenton reaction at the infected site. In this study, we have successfully synthesized a versatile nanozyme, which was a composite of molybdenum sulfide (MoS2) and iron sulfide (FeS2), through the hydrothermal method. The results showed that iron/molybdenum sulfide nanozymes (Fe/Mo SNZs) with desirable peroxidase (POD) mimic activity can generate cytotoxic reactive oxygen species (ROS) by successfully triggering the Fenton reaction. The presence of MoS2 significantly accelerates the conversion of Fe2+/Fe3+ through a cocatalytic reaction that involves the participation of redox pairs of Mo4+/Mo6+, thereby enhancing the efficiency of CDT. Additionally, based on the excellent photothermal performance of Fe/Mo SNZs, a near-infrared (NIR) laser was used to induce localized temperature elevation for photothermal therapy (PTT) and enhance the POD-like nanoenzymatic activity. Notably, both in vitro and in vivo results demonstrated that Fe/Mo SNZs with good broad-spectrum antibacterial properties can help eradicate Gram-negative bacteria like Escherichia coli and Gram-positive bacteria like Staphylococcus aureus. The most exciting thing is that the synergistic PTT/CDT exhibited astonishing antibacterial ability and can achieve complete elimination of bacteria, which promoted wound healing after infection. Overall, this study presents a synergistic PTT/CDT strategy to address antibiotic resistance, providing avenues and directions for enhancing the efficacy of wound healing treatments and offering promising prospects for further clinical use in the near future.
{"title":"Iron/Molybdenum Sulfide Nanozyme Cocatalytic Fenton Reaction for Photothermal/Chemodynamic Efficient Wound Healing","authors":"Huiping Song, Zheng Cheng, Ran Qin, Ziyu Chen, Tianxiao Wang, Yuli Wang, Huijun Jiang, Yifei Du, Fan Wu","doi":"10.1021/acs.langmuir.4c00922","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00922","url":null,"abstract":"The issue of bacterial infectious diseases remains a significant concern worldwide, particularly due to the misuse of antibiotics, which has caused the emergence of antibiotic-resistant strains. Fortunately, the rapid development of nanomaterials has propelled significant progress in antimicrobial therapy, offering promising solutions. Among them, the utilization of nanoenzyme-based chemodynamic therapy (CDT) has become a highly hopeful approach to combating bacterial infectious diseases. Nevertheless, the application of CDT appears to be facing certain constraints for its low efficiency in the Fenton reaction at the infected site. In this study, we have successfully synthesized a versatile nanozyme, which was a composite of molybdenum sulfide (MoS<sub>2</sub>) and iron sulfide (FeS<sub>2</sub>), through the hydrothermal method. The results showed that iron/molybdenum sulfide nanozymes (Fe/Mo SNZs) with desirable peroxidase (POD) mimic activity can generate cytotoxic reactive oxygen species (ROS) by successfully triggering the Fenton reaction. The presence of MoS<sub>2</sub> significantly accelerates the conversion of Fe<sup>2+</sup>/Fe<sup>3+</sup> through a cocatalytic reaction that involves the participation of redox pairs of Mo<sup>4+</sup>/Mo<sup>6+</sup>, thereby enhancing the efficiency of CDT. Additionally, based on the excellent photothermal performance of Fe/Mo SNZs, a near-infrared (NIR) laser was used to induce localized temperature elevation for photothermal therapy (PTT) and enhance the POD-like nanoenzymatic activity. Notably, both <i>in vitro</i> and <i>in vivo</i> results demonstrated that Fe/Mo SNZs with good broad-spectrum antibacterial properties can help eradicate Gram-negative bacteria like <i>Escherichia coli</i> and Gram-positive bacteria like <i>Staphylococcus aureus</i>. The most exciting thing is that the synergistic PTT/CDT exhibited astonishing antibacterial ability and can achieve complete elimination of bacteria, which promoted wound healing after infection. Overall, this study presents a synergistic PTT/CDT strategy to address antibiotic resistance, providing avenues and directions for enhancing the efficacy of wound healing treatments and offering promising prospects for further clinical use in the near future.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489780","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}