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M13 bacteriophages serve as a versatile foundation for nanobiotechnology due to their unique biological and chemical properties. The polypeptides that comprise their coat proteins, specifically pVIII, can be precisely tailored through genetic engineering. This enables the customized integration of various functional elements through specific interactions, leading to the development of innovative hybrid materials for applications such as energy storage, biosensing, and catalysis. Notably, a certain genetically engineered M13 bacteriophage variant, referred to as DSPH, features a pVIII with a repeating DSPHTELP peptide sequence. This sequence facilitates specific adhesion to single-walled carbon nanotubes (SWCNTs), primarily through π-π and hydrophobic interactions, though the exact mechanism remains unconfirmed. In this study, we synthesized the DSPHTELP peptide (an 8-mer peptide) and analyzed its interaction forces with different functional groups across various pH levels using surface forces apparatus (SFA). Our findings indicate that the 8-mer peptide binds most strongly to CH3 groups (Wad = 13.74 ± 1.04 mJ m-2 at pH 3.0), suggesting that hydrophobic interactions are indeed the predominant mechanism. These insights offer both quantitative and qualitative understanding of the molecular interaction mechanisms of the 8-mer peptide and clarify the basis of its specific interaction with SWCNTs through the DSPHTELP M13 bacteriophage.
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Bacteriófago M13 , Interacciones Hidrofóbicas e Hidrofílicas , Nanotubos de Carbono , Péptidos , Nanotubos de Carbono/química , Bacteriófago M13/química , Bacteriófago M13/genética , Bacteriófago M13/metabolismo , Péptidos/química , Péptidos/metabolismo , Concentración de Iones de Hidrógeno , Proteínas de la Cápside/química , Proteínas de la Cápside/metabolismoRESUMEN
Polyhexamethylene guanidine (PHMG) is a guanidine-based chemical that has long been used as an antimicrobial agent. However, recently raised concerns regarding the pulmonary toxicity of PHMG in humans and aquatic organisms have led to research in this area. Along with PHMG, there are concerns about the safety of non-guanidine 5-chloro-2-methylisothiazol-3(2H)-one/2-methylisothiazol-3(2H)-one (CMIT/MIT) in human lungs; however, the safety of such chemicals can be affected by many factors, and it is difficult to rationalize their toxicity. In this study, we investigated the adsorption characteristics of CMIT/ MIT on a model pulmonary surfactant (lung surfactant, LS) using a Langmuir trough attached to a fluorescence microscope. Analysis of the π-A isotherms and lipid raft morphology revealed that CMIT/MIT exhibited minimal adsorption onto the LS monolayer deposited at the air/water interface. Meanwhile, PHMG showed clear signs of adsorption to LS, as manifested by the acceleration of the L o phase growth with increasing surface pressure. Consequently, in the presence of CMIT/MIT, the interfacial properties of the model LS monolayer exhibited significantly fewer changes than PHMG.
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Antiinfecciosos , Desinfectantes , Surfactantes Pulmonares , Humanos , Adsorción , Pulmón , Guanidinas/química , GuanidinaRESUMEN
Pendant groups in acrylic adhesive polymers (Ads) have a profound influence on adhesive and cohesive properties and additionally on encapsulant application. However, a systematic investigation to assess the impact of the pendant groups' length and bulkiness is rare, and there is not even a single report on applying Ads as interfacial adhesion promotors and encapsulation materials simultaneously. Herein, we have developed a series of multifunctional methacrylic polymers, namely, R-co-Ads, with varying pendant length and bulkiness (R = methyl (C1), ethyl (C2), propyl (C3), butyl (C4), pentyl (C5), hexyl (C6), isobutyl (iC4), and 2-ethylhexyl (2EH)). The adhesion-related experimental results reveal that R-co-Ads have high transparency, strong adhesion strength to the various contact surfaces, and a fast cure speed. In particular, C1-co-Ad shows a superior adhesion performance with an improved cross-cut index of 4B and a shear bonding strength of 1.56 MPa. We also have adopted C1-co-Ad for encapsulation of various emerging optoelectronic applications (e.g., perovskite solar cell-, charge transport-, and conductivity-related characteristics), demonstrating its excellent edge encapsulant served to improve the device stability against ambient air conditions. Our study establishes the structure-adhesion-surface relationships, advancing the better design of adhesives and encapsulants for various research fields.
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Ion interactions with interfaces and transport in confined spaces, where electric double layers overlap, are essential in many areas, ranging from crevice corrosion to understanding and creating nano-fluidic devices at the sub 10 nm scale. Tracking the spatial and temporal evolution of ion exchange, as well as local surface potentials, in such extreme confinement situations is both experimentally and theoretically challenging. Here, we track in real-time the transport processes of ionic species (LiClO4) confined between a negatively charged mica surface and an electrochemically modulated gold surface using a high-speed in situ sensing Surface Forces Apparatus. With millisecond temporal and sub-micrometer spatial resolution we capture the force and distance equilibration of ions in the confinement of D ≈ 2-3 nm in an overlapping electric double layer (EDL) during ion exchange. Our data indicate that an equilibrated ion concentration front progresses with a velocity of 100-200 µm s-1 into a confined nano-slit. This is in the same order of magnitude and in agreement with continuum estimates from diffusive mass transport calculations. We also compare the ion structuring using high resolution imaging, molecular dynamics simulations, and calculations based on a continuum model for the EDL. With this data we can predict the amount of ion exchange, as well as the force between the two surfaces due to overlapping EDLs, and critically discuss experimental and theoretical limitations and possibilities.
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Owing to the rise in global population and living standards, waste treatment has inevitably become a critical issue for a sustainable environment. In particular, for an effective recycling process, it is vital to disassemble different types of materials by removing adhesives used in the packaging. However, this removal process requires harsh solvents (acidic and organic) that are unfriendly to nature and may cause additional pollution. To address this issue, functional adhesive materials that can be removed without the use of harsh solvents have drawn significant attention. One promising approach is to utilize the stimuli-responsive polymers to synthesize pressure sensitive adhesives (PSAs); however, it is technically challenging to simultaneously satisfy (i) strong initial adhesion (without stimulus), (ii) stimuli-responsive sufficient reduction of adhesion, and (iii) reversibility. In this study, thermo-switchable PSAs were synthesized by copolymerizing N-isopropylacrylamide (NIPAM), which possesses thermal-responsive properties; acrylic acid, which endows adhesive properties; and 2-ethylhexyl acrylate, which has a low glass transition temperature to attain sufficient flexibility. The synthesized NIPAM-based thermo-switchable PSAs exhibited significantly high peel strength at room temperature (â¼15.41 N/25 mm at 20 °C), which decreased by â¼97% upon heating (â¼0.46 N/25 mm at 80 °C). Importantly, no residues remained due to the cohesive nature of NIPAM at high temperature. The reversible adhesion behaviour of the thermo-switchable PSAs was retained during repeated heating and cooling cycles. Therefore, the developed thermo-switchable PSA can enhance the reusability and recyclability of valuable materials and minimize the use of toxic chemicals for adhesive removal, contributing to a more sustainable future.
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Recently, the desire for a safe and effective method for skin whitening has been growing in the cosmetics industry. Commonly used tyrosinase-inhibiting chemical reagents exhibit side effects. Thus, recent studies have focused on performing melanin decolorization with enzymes as an alternative due to the low toxicity of enzymes and their ability to decolorize melanin selectively. Herein, 10 different isozymes were expressed as recombinant lignin peroxidases (LiPs) from Phanerochaete chrysosporium (PcLiPs), and PcLiP isozyme 4 (PcLiP04) was selected due to its high stability and activity at pH 5.5 and 37 °C, which is close to human skin conditions. In vitro melanin decolorization results indicated that PcLiP04 exhibited at least 2.9-fold higher efficiency than that of well-known lignin peroxidase (PcLiP01) in a typical human skin-mimicking environment. The interaction force between melanin films measured by a surface forces apparatus (SFA) revealed that the decolorization of melanin by PcLiP04 harbors a disrupted structure, possibly interrupting π-π stacking and/or hydrogen bonds. In addition, a 3D reconstructed human pigmented epidermis skin model showed a decrease in melanin area to 59.8% using PcLiP04, which suggests that PcLiP04 exhibits a strong potential for skin whitening.
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Melaninas , Phanerochaete , Humanos , Peroxidasas , Piel , Epidermis , LigninaRESUMEN
The remarkable underwater adhesion of mussel foot proteins has long been an inspiration in the design of peptidomimetic materials. Although the synergistic wet adhesion of catechol and lysine has been recently highlighted, the critical role of the polymeric backbone has remained largely underexplored. Here, we present a peptidomimetic approach using poly(ethylene glycol) (PEG) as a platform to evaluate the synergistic compositional relation between the key amino acid residues (i.e., DOPA and lysine), as well as the role of the polyether backbone in interfacial adhesive interactions. A series of PEG-based peptides (PEGtides) were synthesized using functional epoxide monomers corresponding to catechol and lysine via anionic ring-opening polymerization. Using a surface force apparatus, highly synergistic surface interactions among these PEGtides with respect to the relative compositional ratio were revealed. Furthermore, the critical role of the catechol-amine synergy and diverse hydrogen bonding within the PEGtides in the superior adhesive interactions was verified by molecular dynamics simulations. Our study sheds light on the design of peptidomimetic polymers with reduced complexity within the framework of a polyether backbone.
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Bivalvos , Peptidomiméticos , Adhesivos/química , Animales , Enlace de Hidrógeno , Lisina/química , Polímeros/química , Proteínas/químicaRESUMEN
The quantification of supramolecular host-guest interactions is important for finely modulating supramolecular systems. Previously, most host-guest interactions quantified using force spectroscopic techniques have been reported in force units. However, accurately evaluating the adhesion energies of host-guest pairs remains challenging. Herein, using a surface forces apparatus, we directly quantify the interaction energies between cyclodextrin (CD)-modified surfaces and ditopic adamantane (DAd) molecules in water as a function of the DAd concentration and the CD cavity size. The adhesion energy of the ß-CD-DAd complex drastically increased with increasing DAd concentration and reached saturation. Moreover, the molecular adhesion energy of a single host-guest inclusion complex was evaluated to be ~9.51 kBT. This approach has potential for quantifying fundamental information toward furthering the understanding of supramolecular chemistry and its applications, such as molecular actuators, underwater adhesives, and biosensors, which require precise tuning of specific host-guest interactions.
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Transition metal layered oxides (LiNixCoyMn1-x-yO2, NCM) have been considered as one of the most promising cathodes for lithium-ion batteries used in long-mileage electric vehicles and energy storage systems. Despite its potential interest, dissolved transition metal (TM) ions toward anode sides can catalyze parasitic reactions such as electrolytic decomposition and dendritic Li growth, ultimately leading to catastrophic safety hazards. In this study, we demonstrate that Prussian Blue (PB) nanoparticles anchored to a commercial PE separator significantly reduce cell resistance and effectively suppress TM crossover during cycling, even under harsh conditions that accelerate Ni dissolution. Therefore, using a PB-coated separator in a harsh condition to intentionally dissolve Ni2+ ions at a high cutoff potential of 4.6 V, NCM||graphite full cells maintain 50.8% of their initial capacity at the 150th cycle. Scalable production of PB-coated separator through the facile synthetic methods can help establish a new research direction for the design of high-energy-density batteries.
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Lignin has been spotlighted as an abundant renewable bioresource for use in material technologies and applications such as biofuels, binders, composites, and nanomaterials for drug delivery. However, owing to its complex and irregular structure, it is difficult to investigate its fundamental interaction mechanism, which is necessary to promote its use. In this study, a surface forces apparatus (SFA) was used to investigate the pH-dependent molecular interactions between a lignin nanofilm and five functionalized self-assembled monolayers (SAMs). The lignin nanofilm adhered most strongly to the amine-functionalized SAM, indicating that the molecular interactions with lignin were mainly electrostatic and cation-π interactions. The force-distance profile between lignin and a methyl-functionalized SAM revealed pH-dependent interactions similar to those between two lignin nanofilms. This finding indicates that the dominant cohesion mechanism is hydrophobic interactions. A quartz crystal microbalance with dissipation was used to investigate the adsorption of free lignin molecules on functionalized SAMs. Lignin molecules, which were free in solution, were most effectively adsorbed to the phenyl-functionalized SAM. To investigate whether the nanoscopic interaction forces could be extended to macroscopic properties, the compressive strength of activated carbon-lignin composites prepared at different pH values was evaluated. As the pH increased, the compressive strength decreased owing to the reduced hydrophobic interactions between the activated carbon and lignin, consistent with the SFA results. These quantitative results regarding lignin interactions can advance the potential use of lignin as an eco-friendly biomaterial.
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Lignina , Adsorción , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Propiedades de SuperficieRESUMEN
Despite the widespread use of polymers for antifouling coatings, the effect of the polymeric topology on the antifouling property has been largely underexplored. Unlike conventional brush polymers, a loop conformation often leads to strong steric stabilization of surfaces and antifouling and lubricating behavior owing to the large excluded volume and reduced chain ends. Herein, we present highly antifouling multiloop polyethers functionalized with a mussel-inspired catechol moiety with varying loop dimensions. Specifically, a series of polyethers with varying catechol contents were synthesized via anionic ring-opening polymerization by using triethylene glycol glycidyl ether (TEG) and catechol-acetonide glycidyl ether (CAG) to afford poly(TEG-co-CAG)n. The versatile adsorption and antifouling effects of multiloop polyethers were evaluated using atomic force microscopy and a quartz crystal microbalance with dissipation. Furthermore, the crucial role of the loop dimension in the antifouling properties was analyzed via a surface force apparatus and a cell attachment assay. This study provides a new platform for the development of versatile antifouling polymers with varying topologies.
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Incrustaciones Biológicas , Adsorción , Incrustaciones Biológicas/prevención & control , Microscopía de Fuerza Atómica , Polímeros/química , Propiedades de SuperficieRESUMEN
The degree of acetylation (DA), which determines as the molar proportion of N-acetyl-D-glucosamine units on chitosan, characterizes the physical, chemical, and biological properties of chitosan. Thus, DA can be a critical factor in the utilization of chitosan. Nevertheless, quantitative studies on the molecular interactions of chitosan as a function of DA are lacking. Here, we directly measured the molecular interaction (adhesion and cohesion) of molecularly thin chitosan films, dependent on the molecular weight and DA, using a surface forces apparatus. Using low molecular weight (LMW, â¼5 kDa) and high molecular weight (HMW, â¼135 kDa) chitosan, we obtained several DA ranges through a reacetylation method. The interactions of LMW chitosan were greatly influenced by the intrinsic charge of the chitosan units, whereas for HMW chitosan, chain flexibility was found to be the major factor affecting molecular interaction Taken together, our comprehensive data provides a holistic understanding of the interaction mechanism of chitosan.
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Many studies on the deformation of soft films by liquids confirmed the increase in the radius of the deformation and the decrease in the apparent contact angle. However, due to the thinness, the dynamics of the deformation could not be observed until the thermodynamic equilibrium. Thus, the dynamics on thick soft materials was studied until equilibrium to contrast the effect of different interfacial energy between different soft materials and water. Therefore, we prepared two different polymeric fluids with similar rheology by cross-linking monomers, yet with different contact angles with water. Sometime after water droplets were placed on these thick polymers, 3D profiles of the deformation were recorded. Though the effect of the surface tension was not verified, the same trend in the dynamics was observed as with thin films, except for the decrease in the radius after the initial increase. The three-phase boundaries (TPBs) were found not at the apex of the ridges formed during the transition to equilibrium. By calculating the surface tensions and angles of each interface at the equilibrium, we found that the temporary imbalance among surface tensions induced the slip of the TPBs toward the center of water droplets, thus dislocating the TPBs and decreasing the radius.
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The efficient removal of gas bubbles in (photo)electrochemical gas evolution reactions is an important but underexplored issue. Conventionally, researchers have attempted to impart bubble-repellent properties (so-called superaerophobicity) to electrodes by controlling their microstructures. However, conventional approaches have limitations, as they are material specific, difficult to scale up, possibly detrimental to the electrodes' catalytic activity and stability, and incompatible with photoelectrochemical applications. To address these issues, we report a simple strategy for the realization of superaerophobic (photo)electrodes via the deposition of hydrogels on a desired electrode surface. For a proof-of-concept demonstration, we deposited a transparent hydrogel assembled from M13 virus onto (photo)electrodes for a hydrogen evolution reaction. The hydrogel overlayer facilitated the elimination of hydrogen bubbles and substantially improved the (photo)electrodes' performances by maintaining high catalytic activity and minimizing the concentration overpotential. This study can contribute to the practical application of various types of (photo)electrochemical gas evolution reactions.
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In polymer electrolyte fuel cells (PEFCs), protons from the anode are transferred to the cathode through the ionomer membrane. By impregnating the ionomer into the electrodes, proton pathways are extended and high proton transfer efficiency can be achieved. Because the impregnated ionomer mechanically binds the catalysts within the electrode, the ionomer is also called a binder. To yield good electrochemical performance, the binder should be homogeneously dispersed in the electrode and maintain stable interfaces with other catalyst components and the membrane. However, conventional binder materials do not have good dispersion properties. In this study, a facile approach based on using a supercritical fluid is introduced to prepare a homogeneous nanoscale dispersion of the binder material in aqueous alcohol. The prepared binder exhibited high dispersion characteristics, crystallinity, and proton conductivity. High performance and durability were confirmed when the binder material was applied to a PEFC cathode electrode.
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Poly(methyl methacrylate) (PMMA) is widely used as a transparent material for optical applications, owing to its high light transmittance. However, it exhibits poor heat resistance and high moisture absorption, leading to distortion and deformation upon exposure to elevated temperatures and/or moisture. These structural changes decrease the transparency of PMMA, critically limiting its applicability. In this study, we synthesized poly(methyl methacrylate-co-styrene-co-acrylamide) (PMSAm) as a reference polymer and introduced one of four different comonomers [N-phenylmaleimide (PMI), N-cyclohexylmaleimide (CHMI), allyltrimethylsilane (ATMS), or 2,2,2-trifluoroethyl methacrylate (TF)] as a means to improve heat resistance and reduce moisture absorption. Four series of PMMA-based random copolymers (PMSAm-PMI, PMSAm-CHMI, PMSAm-ATMS, and PMSAm-TF) were synthesized by conventional thermal radical polymerization. All of the polymers synthesized exhibited improved heat resistance, with PMSAm-CHMI exhibiting the highest glass transition temperature (Tg = 122.54 °C) and 5% weight loss thermal decomposition temperature (T5d = 343.40 °C) as well as the lowest thermal expansion coefficient (90.3 µm m-1 °C-1). The highest hydrophobicity was exhibited by PMSAm-TF, with a water contact angle of 78.9°, indicating higher hydrophobicity compared to that of pure PMMA (69.4°). More importantly, high transparency (â¼90%) was exhibited by all of the synthesized polymers. Thus, our copolymerization strategy successfully addresses the limitations, i.e., low heat resistance and high moisture absorption, of conventional PMMA-based materials.
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Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the surface forces apparatus-the µSFA-that has been designed for ease of use and multimodal capabilities with the retention of the capabilities of other SFA models including accurate measurements of the surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, and biospecific). The small physical size of the µSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the µSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Because of the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied to calculate the intersurface separation distance based on Newton's rings. The introduction of the µSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, the determination of surface species and morphology, and (bio)molecular binding kinetics.
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In this review, previous researches that measured intermembrane forces using the Surface Forces Apparatus are recapitulated. Different types of interaction forces are reported between two lipid bilayers including non-specific interactions (e.g., van der Waals, electrostatic, steric hydration, thermal undulation, and hydrophobic) and specific interactions (e.g., ligand-receptor). By measuring absolute distance and interaction forces at the sub-angstrom level and at a few nano-Newtons resolution, respectively, magnitudes, working ranges, and decay lengths of interaction between lipid bilayers are investigated. Utilizing recently developed fluorescence microscopy attachments, simultaneous fluorescence imaging of membrane proteins and lipid phases can be performed during approach/separation cycles of two lipid bilayer deposited surfaces, which can reveal cooperative effects between lipid phases and various types of membrane proteins.
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Técnicas Electroquímicas/instrumentación , Membrana Dobles de Lípidos/química , Interacciones Hidrofóbicas e Hidrofílicas , Fenómenos Mecánicos , Microscopía Fluorescente , Imagen Molecular/instrumentación , Electricidad Estática , Propiedades de Superficie , TermodinámicaRESUMEN
Understanding the fundamental wetting behavior of liquids on surfaces with pores or cavities provides insights into the wetting phenomena associated with rough or patterned surfaces, such as skin and fabrics, as well as the development of everyday products such as ointments and paints, and industrial applications such as enhanced oil recovery and pitting during chemical mechanical polishing. We have studied, both experimentally and theoretically, the dynamics of the transitions from the unfilled/partially filled (Cassie-Baxter) wetting state to the fully filled (Wenzel) wetting state on intrinsically hydrophilic surfaces (intrinsic water contact angle <90°, where the Wenzel state is always the thermodynamically favorable state, while a temporary metastable Cassie-Baxter state can also exist) to determine the variables that control the rates of such transitions. We prepared silicon wafers with cylindrical cavities of different geometries and immersed them in bulk water. With bright-field and confocal fluorescence microscopy, we observed the details of, and the rates associated with, water penetration into the cavities from the bulk. We find that unconnected, reentrant cavities (i.e., cavities that open up below the surface) have the slowest cavity-filling rates, while connected or non-reentrant cavities undergo very rapid transitions. Using these unconnected, reentrant cavities, we identified the variables that affect cavity-filling rates: (i) the intrinsic contact angle, (ii) the concentration of dissolved air in the bulk water phase (i.e., aeration), (iii) the liquid volatility that determines the rate of capillary condensation inside the cavities, and (iv) the presence of surfactants.
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Interacciones Hidrofóbicas e Hidrofílicas , Termodinámica , Humectabilidad , Aire , Fluoresceína/química , Menisco/química , Transición de Fase , Presión , Silicio/química , Solubilidad , Propiedades de Superficie , Tensoactivos/química , Volatilización , Agua/químicaRESUMEN
Various xenobiotics interact with biological membranes, and precise evaluations of the molecular interactions between them are essential to foresee the toxicity and bioavailability of existing or newly synthesized molecules. In this study, surface forces apparatus (SFA) measurement and Langmuir trough based tensiometry are performed to reveal nanomechanical interaction mechanisms between potential toxicants and biological membranes for ex vivo toxicity evaluation. As a toxicant, polyhexamethylene guanidine (PHMG) was selected because PHMG containing humidifier disinfectant and Vodka caused lots of victims in both S. Korea and Russia, respectively, due to the lack of holistic toxicity evaluation of PHMG. Here, we measured strong attraction (Wad â¼4.2â¯mJ/m2) between PHMG and head group of biological membranes while no detectable adhesion force between the head group and control molecules was measured. Moreover, significant changes in π-A isotherm of 1,2-Dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) monolayers were measured upon PHMG adsorption. These results indicate PHMG strongly binds to hydrophilic group of lipid membranes and alters the structural and phase behavior of them. More importantly, complementary utilization of SFA and Langmuir trough techniques are found to be useful to predict the potential toxicity of a chemical by evaluating the molecular interaction with biological membranes, the primary protective barrier for living organisms.