Pub Date : 2024-06-27DOI: 10.1021/acs.langmuir.4c01561
Georgios Karchilakis, Spyridon Varlas, Edwin C Johnson, Oleta Norvilaite, Matthew A H Farmer, George Sanderson, Graham J Leggett, Steven P Armes
Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that cis-diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C). Quartz crystal microbalance studies indicated an adsorbed amount, Γ, of 158 mg m-2 for vesicle adsorption onto such brushes, whereas negligible adsorption (Γ = 0.1 mg m-2) was observed for a control experiment conducted using a cis-diol-functionalized brush. Scanning electron microscopy and ellipsometry studies indicated a mean surface coverage of around 30% at the brush surface, which suggests reasonably efficient chemical adsorption. Importantly, such vesicles can be conveniently loaded with a model enzyme (horseradish peroxidase, HRP) using an aqueous polymerization-induced self-assembly formulation. Moreover, the immobilized vesicles remained permeable toward small molecules while retaining their enzyme payload. The enzymatic activity of such HRP-loaded vesicles was demonstrated using a well-established colorimetric assay. In principle, this efficient vesicle-on-brush strategy can be applied to a wide range of enzymes and functional proteins for the design of next-generation immobilized nanoreactors for enzyme-mediated catalysis.
{"title":"Capturing Enzyme-Loaded Diblock Copolymer Vesicles Using an Aldehyde-Functionalized Hydrophilic Polymer Brush.","authors":"Georgios Karchilakis, Spyridon Varlas, Edwin C Johnson, Oleta Norvilaite, Matthew A H Farmer, George Sanderson, Graham J Leggett, Steven P Armes","doi":"10.1021/acs.langmuir.4c01561","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01561","url":null,"abstract":"<p><p>Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that <i>cis</i>-diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C). Quartz crystal microbalance studies indicated an adsorbed amount, Γ, of 158 mg m<sup>-2</sup> for vesicle adsorption onto such brushes, whereas negligible adsorption (Γ = 0.1 mg m<sup>-2</sup>) was observed for a control experiment conducted using a <i>cis</i>-diol-functionalized brush. Scanning electron microscopy and ellipsometry studies indicated a mean surface coverage of around 30% at the brush surface, which suggests reasonably efficient chemical adsorption. Importantly, such vesicles can be conveniently loaded with a model enzyme (horseradish peroxidase, HRP) using an aqueous polymerization-induced self-assembly formulation. Moreover, the immobilized vesicles remained permeable toward small molecules while retaining their enzyme payload. The enzymatic activity of such HRP-loaded vesicles was demonstrated using a well-established colorimetric assay. In principle, this efficient vesicle-on-brush strategy can be applied to a wide range of enzymes and functional proteins for the design of next-generation immobilized nanoreactors for enzyme-mediated catalysis.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453717","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 : 2024-06-27DOI: 10.1021/acs.langmuir.4c01633
Haidong Jia, Han Jia, Qiuxia Wang, Yingbiao Xu, Bowen Wang, Qiang Wang, Xu Li, Zhe Wang, Kaihe Lv, Pan Huang
A novel polymeric ionic liquid (PDBA-IL-NH2) using imidazolium ionic liquids with short alkyl chains as monomers and two control ionic liquids (PDBA-IL-OH and PIL-NH2) were synthesized. Their inhibition properties and mechanisms were explored via surface analysis, weight loss tests, electrochemical studies, and adsorption isotherm analysis. The corrosion inhibition efficiency (CIE) of PDBA-IL-NH2 gradually increased with increasing concentration, and the largest efficiency was 94.67% at 100 ppm. At the same concentration (50 ppm), the corrosion inhibition abilities of inhibitors were in the order of PDBA-IL-NH2 > PDBA-IL-OH > PIL-NH2 > IL-NH2. Based on the experimental investigation, the synergistic effect of electrostatic interaction, protonation, and electron donor-acceptor interaction facilitated the intensive entanglement and coverage of PDBA-IL-NH2 with the reticulated form on the metal, and the generated densest films protected the metal from the corrosive media. Ultimately, the theoretical results of molecular dynamics simulations and quantum chemical study were in high agreement with the experimental data, which confirmed the proposed inhibition mechanisms on the microscopic scale. This study contributed valuable perspectives to the design of efficient and ecofriendly corrosion inhibitors.
{"title":"Imidazolium-Based Polymeric Ionic Liquids with Short Alkyl Chains as Green Corrosion Inhibitors for Mild Steel in 1 M HCl: Experimental and Theoretical Investigations.","authors":"Haidong Jia, Han Jia, Qiuxia Wang, Yingbiao Xu, Bowen Wang, Qiang Wang, Xu Li, Zhe Wang, Kaihe Lv, Pan Huang","doi":"10.1021/acs.langmuir.4c01633","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01633","url":null,"abstract":"<p><p>A novel polymeric ionic liquid (PDBA-IL-NH<sub>2</sub>) using imidazolium ionic liquids with short alkyl chains as monomers and two control ionic liquids (PDBA-IL-OH and PIL-NH<sub>2</sub>) were synthesized. Their inhibition properties and mechanisms were explored via surface analysis, weight loss tests, electrochemical studies, and adsorption isotherm analysis. The corrosion inhibition efficiency (CIE) of PDBA-IL-NH<sub>2</sub> gradually increased with increasing concentration, and the largest efficiency was 94.67% at 100 ppm. At the same concentration (50 ppm), the corrosion inhibition abilities of inhibitors were in the order of PDBA-IL-NH<sub>2</sub> > PDBA-IL-OH > PIL-NH<sub>2</sub> > IL-NH<sub>2</sub>. Based on the experimental investigation, the synergistic effect of electrostatic interaction, protonation, and electron donor-acceptor interaction facilitated the intensive entanglement and coverage of PDBA-IL-NH<sub>2</sub> with the reticulated form on the metal, and the generated densest films protected the metal from the corrosive media. Ultimately, the theoretical results of molecular dynamics simulations and quantum chemical study were in high agreement with the experimental data, which confirmed the proposed inhibition mechanisms on the microscopic scale. This study contributed valuable perspectives to the design of efficient and ecofriendly corrosion inhibitors.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453738","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 : 2024-06-27DOI: 10.1021/acs.langmuir.3c03274
Sai Sateesh Sagiri, Malick Samateh, George John
The emulsifying mechanism of supramolecular stereoisomeric sugar fatty acyl molecular gelators was evaluated. In-house-synthesized mannitol dioctanoate (M8) and sorbitol dioctanoate (S8) were tested. The stereoisomeric difference between the sugar groups significantly affected the gelation and emulsifying properties of the gelators. M8 and S8 formed oleogels at 2 and 3.5% (w/v) and emulsified water up to 30 and 60% (v/v), respectively. Microscopy showed that the gelator fibers are at the W/O interfaces, demonstrating a solid particle or network mode of stabilization. The long fibers of M8 were unable to completely encompass the water droplets, resulting in poor emulsification. Small, hair-like fibers of S8 showed better emulsification. When sunflower wax (SFW, 1% w/v) was added as a coemulsifier, synergetic action between the wax and S8 improved the stability of emulsions. Such synergy was not seen between SFW and M8, henceforth emulsion stability was not improved. This study proved that a subtle stereoisomeric difference at the molecular level can greatly alter the supramolecular and emulsifying properties of sugar-fatty acyl compounds.
{"title":"Investigating the Emulsifying Mechanism of Stereoisomeric Sugar Fatty Acyl Molecular Gelators.","authors":"Sai Sateesh Sagiri, Malick Samateh, George John","doi":"10.1021/acs.langmuir.3c03274","DOIUrl":"https://doi.org/10.1021/acs.langmuir.3c03274","url":null,"abstract":"<p><p>The emulsifying mechanism of supramolecular stereoisomeric sugar fatty acyl molecular gelators was evaluated. In-house-synthesized mannitol dioctanoate (M8) and sorbitol dioctanoate (S8) were tested. The stereoisomeric difference between the sugar groups significantly affected the gelation and emulsifying properties of the gelators. M8 and S8 formed oleogels at 2 and 3.5% (w/v) and emulsified water up to 30 and 60% (v/v), respectively. Microscopy showed that the gelator fibers are at the W/O interfaces, demonstrating a solid particle or network mode of stabilization. The long fibers of M8 were unable to completely encompass the water droplets, resulting in poor emulsification. Small, hair-like fibers of S8 showed better emulsification. When sunflower wax (SFW, 1% w/v) was added as a coemulsifier, synergetic action between the wax and S8 improved the stability of emulsions. Such synergy was not seen between SFW and M8, henceforth emulsion stability was not improved. This study proved that a subtle stereoisomeric difference at the molecular level can greatly alter the supramolecular and emulsifying properties of sugar-fatty acyl compounds.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464368","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 : 2024-06-27DOI: 10.1021/acs.langmuir.3c03218
Oscar Siles Brügge, Christopher A Hunter, Graham J Leggett
Lifshitz theory is widely used to calculate interfacial interaction energies and underpins established approaches to the interpretation of measurement data from experimental methods including the surface forces apparatus and the atomic force microscope. However, a significant limitation of Lifshitz theory is that it uses the bulk dielectric properties of the medium to predict the work of adhesion. Here, we demonstrate that a different approach, in which the interactions between molecules at surfaces and in the medium are described by a set of surface site interaction points (SSIPs), yields interaction free energies that are correlated better with experimentally determined values. The work of adhesion W(Lifshitz) between hydrocarbon surfaces was calculated in 260 liquids using Lifshitz theory and compared with interaction free energies ΔΔG calculated using the SSIP model. The predictions of these models diverge in significant ways. In particular, ΔΔG values for hydrocarbon surfaces are typically small and vary little, but in contrast, W(Lifshitz) values span 4 orders of magnitude. Moreover, the SSIP model yields significantly different ΔΔG values in some liquids for which Lifshitz theory predicts similar values of W(Lifshitz). These divergent predictions were tested using atomic force microscopy. Experimentally determined works of adhesion were closer to the values predicted using the SSIP model than Lifshitz theory. In mixtures of methanol and benzyl alcohol, even greater differences were found in the interaction energies calculated using the two models: the value of ΔΔG calculated using the SSIP model declines smoothly as the benzyl alcohol concentration increases, and values are well correlated with experimental data; however, W(Lifshitz) decreases to a minimum and then increases, reaching a larger value for benzyl alcohol than for methanol. We conclude that the SSIP model provides more reliable estimates of the work of adhesion than Lifshitz theory.
{"title":"Transcending Lifshitz Theory: Reliable Prediction of Adhesion Forces between Hydrocarbon Surfaces in Condensed Phases Using Molecular Contact Thermodynamics.","authors":"Oscar Siles Brügge, Christopher A Hunter, Graham J Leggett","doi":"10.1021/acs.langmuir.3c03218","DOIUrl":"https://doi.org/10.1021/acs.langmuir.3c03218","url":null,"abstract":"<p><p>Lifshitz theory is widely used to calculate interfacial interaction energies and underpins established approaches to the interpretation of measurement data from experimental methods including the surface forces apparatus and the atomic force microscope. However, a significant limitation of Lifshitz theory is that it uses the bulk dielectric properties of the medium to predict the work of adhesion. Here, we demonstrate that a different approach, in which the interactions between molecules at surfaces and in the medium are described by a set of surface site interaction points (SSIPs), yields interaction free energies that are correlated better with experimentally determined values. The work of adhesion <i>W</i>(Lifshitz) between hydrocarbon surfaces was calculated in 260 liquids using Lifshitz theory and compared with interaction free energies ΔΔ<i>G</i> calculated using the SSIP model. The predictions of these models diverge in significant ways. In particular, ΔΔ<i>G</i> values for hydrocarbon surfaces are typically small and vary little, but in contrast, <i>W</i>(Lifshitz) values span 4 orders of magnitude. Moreover, the SSIP model yields significantly different ΔΔ<i>G</i> values in some liquids for which Lifshitz theory predicts similar values of <i>W</i>(Lifshitz). These divergent predictions were tested using atomic force microscopy. Experimentally determined works of adhesion were closer to the values predicted using the SSIP model than Lifshitz theory. In mixtures of methanol and benzyl alcohol, even greater differences were found in the interaction energies calculated using the two models: the value of ΔΔ<i>G</i> calculated using the SSIP model declines smoothly as the benzyl alcohol concentration increases, and values are well correlated with experimental data; however, <i>W</i>(Lifshitz) decreases to a minimum and then increases, reaching a larger value for benzyl alcohol than for methanol. We conclude that the SSIP model provides more reliable estimates of the work of adhesion than Lifshitz theory.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453740","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 : 2024-06-27DOI: 10.1021/acs.langmuir.4c01570
Jingbin Yang, Lijun Yang, Ruo-Yu Dong
The complex diffusion behaviors of rod-shaped nanoparticles near the solid–liquid interface are closely related to various biological processes and technological applications. Despite recent advancements in understanding the diffusion dynamics of nanoparticles near some specific solid–liquid interfaces, systematical studies to tune the interfacial interaction or fabricating nonuniform wall to see their effects on the nanorod (NR) diffusion are still lacking. This work utilized molecular dynamics simulations to investigate the rotational and translational diffusion dynamics of a single NR near the solid–liquid interface. We constructed a patterned wall featuring adjustable nonuniformity, which was accomplished by modifying the interaction between NR and the wall, noting that the resulting nonuniformity limits both the translational and rotational diffusion of NR, evident from decreases in diffusion coefficients and exponents. By trajectory analysis, we categorized the diffusion modes of NRs near the patterned wall with varied nonuniformities into three types: Fickian diffusion, desorption-mediated flight, and in-plane diffusion. Furthermore, energy analysis based on the adsorption–desorption mechanism has demonstrated that the three diffusion states are driven by interactions between the NR and the wall, which are primarily influenced by rotational diffusion. These results could significantly deepen the understanding of anisotropic nanoparticle interfacial diffusion and would provide new insights into the transport mechanisms of nanoparticles within confined environments.
杆状纳米粒子在固液界面附近的复杂扩散行为与各种生物过程和技术应用密切相关。尽管近年来人们对某些特定固液界面附近纳米粒子的扩散动力学有了更深入的了解,但仍缺乏系统的研究来调整界面相互作用或制造非均匀壁来观察它们对纳米棒(NR)扩散的影响。这项研究利用分子动力学模拟来研究单个 NR 在固液界面附近的旋转和平移扩散动力学。我们构建了一个具有可调节不均匀性的图案化壁,通过改变 NR 与壁之间的相互作用来实现这一目标,并注意到由此产生的不均匀性限制了 NR 的平移和旋转扩散,这一点从扩散系数和指数的下降中可见一斑。通过轨迹分析,我们将图案壁附近不同不均匀度的 NR 扩散模式分为三种类型:菲克扩散、解吸介导的飞行和平面内扩散。此外,基于吸附-解吸机制的能量分析表明,这三种扩散状态是由 NR 与壁之间的相互作用驱动的,而这种相互作用主要受旋转扩散的影响。这些结果可以大大加深对各向异性纳米粒子界面扩散的理解,并为纳米粒子在密闭环境中的传输机制提供新的见解。
{"title":"Nanorod Diffusion near the Solid–Liquid Interface with Varied Wall Nonuniformity","authors":"Jingbin Yang, Lijun Yang, Ruo-Yu Dong","doi":"10.1021/acs.langmuir.4c01570","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01570","url":null,"abstract":"The complex diffusion behaviors of rod-shaped nanoparticles near the solid–liquid interface are closely related to various biological processes and technological applications. Despite recent advancements in understanding the diffusion dynamics of nanoparticles near some specific solid–liquid interfaces, systematical studies to tune the interfacial interaction or fabricating nonuniform wall to see their effects on the nanorod (NR) diffusion are still lacking. This work utilized molecular dynamics simulations to investigate the rotational and translational diffusion dynamics of a single NR near the solid–liquid interface. We constructed a patterned wall featuring adjustable nonuniformity, which was accomplished by modifying the interaction between NR and the wall, noting that the resulting nonuniformity limits both the translational and rotational diffusion of NR, evident from decreases in diffusion coefficients and exponents. By trajectory analysis, we categorized the diffusion modes of NRs near the patterned wall with varied nonuniformities into three types: Fickian diffusion, desorption-mediated flight, and in-plane diffusion. Furthermore, energy analysis based on the adsorption–desorption mechanism has demonstrated that the three diffusion states are driven by interactions between the NR and the wall, which are primarily influenced by rotational diffusion. These results could significantly deepen the understanding of anisotropic nanoparticle interfacial diffusion and would provide new insights into the transport mechanisms of nanoparticles within confined environments.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464061","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 : 2024-06-27DOI: 10.1021/acs.langmuir.4c01554
Chao Pang, Benjamin T Karlinsey, Megan Ward, Roger G Harrison, Robert C Davis, Adam T Woolley
DNA-templated nanofabrication presents an innovative approach to creating self-assembled nanoscale metal-semiconductor-based Schottky contacts, which can advance nanoelectronics. Herein, we report the successful fabrication of metal-semiconductor Schottky contacts using a DNA origami scaffold. The scaffold, consisting of DNA strands organized into a specific linear architecture, facilitates the competitive arrangement of Au and CdS nanorods, forming heterojunctions, and addresses previous limitations in low electrical conductance making DNA-templated electronics with semiconductor nanomaterials. Electroless gold plating extends the Au nanorods and makes the necessary electrical contacts. Tungsten electrical connection lines are further created by electron beam-induced deposition. Electrical characterization reveals nonlinear Schottky barrier behavior, with electrical conductance ranging from 0.5 × 10-4 to 1.7 × 10-4 S. The conductance of these DNA-templated junctions is several million times higher than with our prior Schottky contacts. Our research establishes an innovative self-assembly approach with applicable metal and semiconductor materials for making highly conductive nanoscale Schottky contacts, paving the way for the future development of DNA-based nanoscale electronics.
以 DNA 为模板的纳米制造是一种创新方法,可用于制造自组装的纳米级金属半导体肖特基触点,从而推动纳米电子学的发展。在此,我们报告了利用 DNA 折纸支架成功制造金属半导体肖特基触点的情况。该支架由组织成特定线性结构的 DNA 链组成,有利于金纳米棒和镉硅纳米棒的竞争性排列,形成异质结,并解决了以往使用半导体纳米材料制造 DNA 模板电子元件在低电导率方面的局限性。无电解镀金可延长金纳米棒并形成必要的电接触。通过电子束诱导沉积,进一步形成了钨电连接线。电学表征显示了非线性肖特基势垒行为,电导范围为 0.5 × 10-4 到 1.7 × 10-4 S。我们的研究利用适用的金属和半导体材料建立了一种创新的自组装方法,用于制造高导电性纳米级肖特基触点,为未来开发基于 DNA 的纳米级电子器件铺平了道路。
{"title":"DNA-Templated Nanofabrication of CdS-Au Nanoscale Schottky Contacts and Electrical Characterization.","authors":"Chao Pang, Benjamin T Karlinsey, Megan Ward, Roger G Harrison, Robert C Davis, Adam T Woolley","doi":"10.1021/acs.langmuir.4c01554","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01554","url":null,"abstract":"<p><p>DNA-templated nanofabrication presents an innovative approach to creating self-assembled nanoscale metal-semiconductor-based Schottky contacts, which can advance nanoelectronics. Herein, we report the successful fabrication of metal-semiconductor Schottky contacts using a DNA origami scaffold. The scaffold, consisting of DNA strands organized into a specific linear architecture, facilitates the competitive arrangement of Au and CdS nanorods, forming heterojunctions, and addresses previous limitations in low electrical conductance making DNA-templated electronics with semiconductor nanomaterials. Electroless gold plating extends the Au nanorods and makes the necessary electrical contacts. Tungsten electrical connection lines are further created by electron beam-induced deposition. Electrical characterization reveals nonlinear Schottky barrier behavior, with electrical conductance ranging from 0.5 × 10<sup>-4</sup> to 1.7 × 10<sup>-4</sup> S. The conductance of these DNA-templated junctions is several million times higher than with our prior Schottky contacts. Our research establishes an innovative self-assembly approach with applicable metal and semiconductor materials for making highly conductive nanoscale Schottky contacts, paving the way for the future development of DNA-based nanoscale electronics.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453718","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 : 2024-06-27DOI: 10.1021/acs.langmuir.4c01499
Ragini Rai, Deepak Kumar, Anjali A. Dhule, Binny A. Rudani, Sanjay Tiwari
In spite of the widespread use of alkanols as penetration enhancers, their effect on vesicular formulations remains largely unexplored. These can affect the stability and integrity of the phospholipid bilayers. In this study, we have investigated the interaction of linear (ethanol, butanol, hexanol, octanol) and branched alkanols (t-amylol and t-butanol) with three phospholipids (soya lecithin, SL; soy L-α-phosphatidylcholine, SPC; and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC). Thermodynamic and structural aspects of these interactions were studied as a function of the alkanol concentration and chain length. Our interpretations are based on isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) experiments. We observed one-site interactions wherein hydroxyl and acyl groups interacted with the polar and nonpolar regions of the phospholipid, respectively. The stability and structural integrity of bilayers appeared to be dependent upon (a) the hydrocarbon chain length and concentration of alcohols, and (b) the degree of unsaturation in the phospholipid molecule. We found that these interactions triggered a reduction in the enthalpy which was compensated by increased entropy, keeping free energy negative. Drop in enthalpy indicates reversible disordering of the bilayer which enables the diffusion of alcohol without triggering destabilization. Ethanol engaged predominantly with the interface, and it resulted in higher enthalpic changes. Interactions became increasingly unfavorable with longer alcohols – a cutoff point was recorded with hexanol. The overall sequence of membrane disordering capability was recorded as follows: ethanol < butanol < octanol < hexanol. Octanol’s larger size restricted its penetration in the bilayer, and hence it caused less enthalpic changes relative to hexanol. This could also be verified from the trends in the area ratio of these vesicles obtained from the DLS data. Branched alkanols displayed a lower binding affinity with the phospholipids relative to their linear counterparts. These data are useful while contemplating the inclusion of short-chain alcohols as penetration enhancers in phospholipid vesicles.
{"title":"Alkanols Regulate the Fluidity of Phospholipid Bilayer in Accordance to Their Concentration and Polarity","authors":"Ragini Rai, Deepak Kumar, Anjali A. Dhule, Binny A. Rudani, Sanjay Tiwari","doi":"10.1021/acs.langmuir.4c01499","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01499","url":null,"abstract":"In spite of the widespread use of alkanols as penetration enhancers, their effect on vesicular formulations remains largely unexplored. These can affect the stability and integrity of the phospholipid bilayers. In this study, we have investigated the interaction of linear (ethanol, butanol, hexanol, octanol) and branched alkanols (t-amylol and t-butanol) with three phospholipids (soya lecithin, SL; soy L-α-phosphatidylcholine, SPC; and 1,2-dipalmitoyl-<i>sn</i>-glycero-3-phosphocholine, DPPC). Thermodynamic and structural aspects of these interactions were studied as a function of the alkanol concentration and chain length. Our interpretations are based on isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) experiments. We observed one-site interactions wherein hydroxyl and acyl groups interacted with the polar and nonpolar regions of the phospholipid, respectively. The stability and structural integrity of bilayers appeared to be dependent upon (a) the hydrocarbon chain length and concentration of alcohols, and (b) the degree of unsaturation in the phospholipid molecule. We found that these interactions triggered a reduction in the enthalpy which was compensated by increased entropy, keeping free energy negative. Drop in enthalpy indicates reversible disordering of the bilayer which enables the diffusion of alcohol without triggering destabilization. Ethanol engaged predominantly with the interface, and it resulted in higher enthalpic changes. Interactions became increasingly unfavorable with longer alcohols – a cutoff point was recorded with hexanol. The overall sequence of membrane disordering capability was recorded as follows: ethanol < butanol < octanol < hexanol. Octanol’s larger size restricted its penetration in the bilayer, and hence it caused less enthalpic changes relative to hexanol. This could also be verified from the trends in the area ratio of these vesicles obtained from the DLS data. Branched alkanols displayed a lower binding affinity with the phospholipids relative to their linear counterparts. These data are useful while contemplating the inclusion of short-chain alcohols as penetration enhancers in phospholipid vesicles.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464068","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 : 2024-06-26DOI: 10.1021/acs.langmuir.4c01338
Jiawei Liu, Guo Du, Tiehong Chen
Ordered mesoporous silica is widely used in catalysis, adsorption, and biomedicine, among which SBA-15 (Santa Barbara Amorphous-15) is one of the most widely studied. However, the synthesis of SBA-15 often requires strong acid (hydrochloric acid or sulfuric acid), which will not only corrode industrial equipment but also pollute the environment with the wastewater containing strong acid and halogen (sulfur). Here, we demonstrate a green synthetic strategy for SBA-15 under weakly acidic conditions through an anionic assembly route. With the assistance of poly(acrylic acid) (PAA) and 3-aminopropyltrimethoxysilane (APMS), the pH value of the synthesis system can be increased to 4-5, which is a mild near-neutral condition. In addition, halogen-free synthesis using organic acids is also achieved. The powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N2 sorption characterizations show that the obtained SBA-15 has good texture properties, with a specific surface area of 430-500 m2/g and ordered 6-8 nm mesopores, which is similar to SBA-15 synthesized in traditional strong acid. This strategy provides a facile and environmentally friendly route for the large-scale production of ordered mesoporous materials.
{"title":"Synthesis of Ordered Mesoporous Silica with Nonionic Surfactant/Anionic Polyelectrolyte as Template under Near-Neutral pH Conditions.","authors":"Jiawei Liu, Guo Du, Tiehong Chen","doi":"10.1021/acs.langmuir.4c01338","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01338","url":null,"abstract":"<p><p>Ordered mesoporous silica is widely used in catalysis, adsorption, and biomedicine, among which SBA-15 (Santa Barbara Amorphous-15) is one of the most widely studied. However, the synthesis of SBA-15 often requires strong acid (hydrochloric acid or sulfuric acid), which will not only corrode industrial equipment but also pollute the environment with the wastewater containing strong acid and halogen (sulfur). Here, we demonstrate a green synthetic strategy for SBA-15 under weakly acidic conditions through an anionic assembly route. With the assistance of poly(acrylic acid) (PAA) and 3-aminopropyltrimethoxysilane (APMS), the pH value of the synthesis system can be increased to 4-5, which is a mild near-neutral condition. In addition, halogen-free synthesis using organic acids is also achieved. The powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N<sub>2</sub> sorption characterizations show that the obtained SBA-15 has good texture properties, with a specific surface area of 430-500 m<sup>2</sup>/g and ordered 6-8 nm mesopores, which is similar to SBA-15 synthesized in traditional strong acid. This strategy provides a facile and environmentally friendly route for the large-scale production of ordered mesoporous materials.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453739","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 : 2024-06-26DOI: 10.1021/acs.langmuir.4c01566
Xinchun Li, Pengtao Wang, Kun Xie, Chao Zhang, Xiao Liu, Long Lin
With the wide application of lithium-ion batteries (LIBs) in different fields, safety accidents occur frequently. Therefore, it is necessary to monitor the thermal runaway gas for an early warning. In this article, the adsorption properties of the characteristic gases of LIBs thermal runaway gases are studied by density functional theory (DFT). The adsorption structure of TM (Co/Rh/Ir)-decorated HfS2 (TM@HfS2) is established, and its adsorption properties for C2H4, CH4, and CO are studied. The adsorption energy, charge transfer, band, DOS, charge difference density, work function, and recovery time are discussed in detail. The results show that Ir@HfS2 has the strongest adsorption performance for C2H4 and CO, so C2H4 and CO can be stably adsorbed on the surface of the Ir@HfS2 monolayer. The adsorption energy of CH4 on Co@HfS2 is stronger than those of Rh@HfS2 and Ir@HfS2, but the adsorption energy is still very small. By applying biaxial strain to Co@HfS2, we found that the adsorption energy increases with the increase in negative strain. This study provides a theoretical basis for the regulation of the adsorption properties of HfS2 by different transition metals.
随着锂离子电池(LIB)在不同领域的广泛应用,安全事故频发。因此,有必要对热失控气体进行监测以提前预警。本文利用密度泛函理论(DFT)研究了锂离子电池热失控气体特征气体的吸附特性。建立了 TM(Co/Rh/Ir)装饰 HfS2(TM@HfS2)的吸附结构,并研究了其对 C2H4、CH4 和 CO 的吸附特性。详细讨论了吸附能、电荷转移、带、DOS、电荷差密度、功函数和恢复时间。结果表明,Ir@HfS2 对 C2H4 和 CO 的吸附性能最强,因此 C2H4 和 CO 可以稳定地吸附在 Ir@HfS2 单层表面。CH4在Co@HfS2上的吸附能要强于Rh@HfS2和Ir@HfS2,但吸附能仍然很小。通过对 Co@HfS2 施加双轴应变,我们发现吸附能随着负应变的增加而增加。这项研究为不同过渡金属调节 HfS2 的吸附特性提供了理论依据。
{"title":"Adsorption of LIBs Thermal Runaway Gases on TM-Decorated HfS<sub>2</sub> Surface: A DFT Study.","authors":"Xinchun Li, Pengtao Wang, Kun Xie, Chao Zhang, Xiao Liu, Long Lin","doi":"10.1021/acs.langmuir.4c01566","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01566","url":null,"abstract":"<p><p>With the wide application of lithium-ion batteries (LIBs) in different fields, safety accidents occur frequently. Therefore, it is necessary to monitor the thermal runaway gas for an early warning. In this article, the adsorption properties of the characteristic gases of LIBs thermal runaway gases are studied by density functional theory (DFT). The adsorption structure of TM (Co/Rh/Ir)-decorated HfS<sub>2</sub> (TM@HfS<sub>2</sub>) is established, and its adsorption properties for C<sub>2</sub>H<sub>4</sub>, CH<sub>4</sub>, and CO are studied. The adsorption energy, charge transfer, band, DOS, charge difference density, work function, and recovery time are discussed in detail. The results show that Ir@HfS<sub>2</sub> has the strongest adsorption performance for C<sub>2</sub>H<sub>4</sub> and CO, so C<sub>2</sub>H<sub>4</sub> and CO can be stably adsorbed on the surface of the Ir@HfS<sub>2</sub> monolayer. The adsorption energy of CH<sub>4</sub> on Co@HfS<sub>2</sub> is stronger than those of Rh@HfS<sub>2</sub> and Ir@HfS<sub>2</sub>, but the adsorption energy is still very small. By applying biaxial strain to Co@HfS<sub>2</sub>, we found that the adsorption energy increases with the increase in negative strain. This study provides a theoretical basis for the regulation of the adsorption properties of HfS<sub>2</sub> by different transition metals.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449085","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 : 2024-06-26DOI: 10.1021/acs.langmuir.4c01582
Chiara Perrino, Seunghwan Lee, Nicholas D Spencer
We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(l-lysine)-graft-dextran (PLL-g-dex) and poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG), respectively. The copolymers were attached to a negatively charged silica-titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-g-PEG(5) and PLL(20)-g-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as g decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the -CH2CH2O- units that make up the PEG chains form a cage-like structure with 2-3 water molecules, these "strongly bound" water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.
{"title":"Quantitative Comparison of the Hydration Capacity of Surface-Bound Dextran and Polyethylene Glycol.","authors":"Chiara Perrino, Seunghwan Lee, Nicholas D Spencer","doi":"10.1021/acs.langmuir.4c01582","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01582","url":null,"abstract":"<p><p>We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(l-lysine)-<i>graft</i>-dextran (PLL-<i>g</i>-dex) and poly(l-lysine)-<i>graft</i>-poly(ethylene glycol) (PLL-<i>g</i>-PEG), respectively. The copolymers were attached to a negatively charged silica-titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-<i>g</i>-PEG(5) and PLL(20)-<i>g</i>-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as <i>g</i> decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the -CH<sub>2</sub>CH<sub>2</sub>O- units that make up the PEG chains form a cage-like structure with 2-3 water molecules, these \"strongly bound\" water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449053","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}