The formation of mixed adsorption layers of amyloid fibrils of a plant protein, oat globulin (OG), and a strong polyelectrolyte, sodium polystyrene sulfonate (PSS), at the liquid–gas interface was studied by measurements of the kinetic dependencies of surface tension, dynamic surface elasticity, and ellipsometric angle. The micromorphology of the layers was determined by atomic force microscopy. A strong increase in the surface elasticity was discovered when both components had similar concentrations and formed a network of threadlike aggregates at the interface, thereby explaining the high foam stability in this concentration range. The sequential adsorption of PSS and OG resulted in the formation of thick mixed multilayers and the surface elasticity increased with the number of duplex layers.
Interactions between a zwitterionic phospholipid, 1, 2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and four anionic phospholipids dihexadecyl phosphate (DHP), 1, 2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG), 1, 2-dipalmitoyl-sn-glycero-3-phosphate (DPP) and 1, 2-dipalmitoyl-sn-glycero-3-phospho ethanol (DPPEth) in combination with an additional amount of 30 mol% cholesterol were separately investigated at air-buffer interface through surface pressure (π) - area (A) measurements. π-A isotherm derived parameters revealed maximum negative deviation from ideality for the mixtures comprising 30 mol% anionic lipids. Besides the film functionality, structural changes of the monomolecular films at different surface pressures in the absence and presence of polyamidoamine (PAMAM, generation 4), a cationic dendrimer, were visualised through Brewster angle microscopy and fluorescence microscopic studies. Fluidity/rigidity of monolayers were assessed by surface dilatational rheology studies. Effect of PAMAM on the formation of adsorbed monolayer, due to bilayer disintegration of liposomes (DPPC:anionic lipids= 7:3 M/M, and 30 mol% cholesterol) were monitored by surface pressure (π) - time (t) isotherms. Bilayer disintegration kinetics were dependent on lipid head group and chain length, besides dendrimer concentration. Such studies are considered to be an in vitro cell membrane model where the alteration of molecular orientation play important roles in understanding the nature of interaction between the dendrimer and cell membrane. Liposome-dendrimer aggregates were nontoxic to breast cancer cell line as well as in doxorubicin treated MDA-MB-468 cell line suggesting their potential as drug delivery systems.
Self-assembly gives rise to the versatile strategies of smart material design but requires precise control on the supramolecular level. Here, inorganic-organic synthons (conjugates) are produced by covalently grafting stearic acid tails to giant polyoxometalate (POM) Keplerate-type {Mo-132} through an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS). Using the liposome production approach, the synthons self-assemble to form hollow nanosized vesicles (100-200 nm in diameter), which can be loaded with organic dyes & horbar;eriochrome black T (ErChB) and fluorescein (FL)& horbar;where the POM layer serves as a membrane with subnanopores for cell-like communication. The dye structure plays an essential role in embedding dyes into the vesicle's shell, which opens the way to control the colloidal stability of the system. The produced vesicles are moved by an electric field and used for the creation of an infochemistry scheme with three types of logic gates (AND, OR, and IMP). To design 2D materials, synthons can form spread films, from simple addition on the water-air interface to lateral compression in the Langmuir bath, and highly ordered structures appear, demonstrating electron diffraction in Langmuir-Schaefer (LS) films. These results show the significant potential of POM-based synthons and nanosized vesicles to supramolecular design the diversity of smart materials.
The formation of beta-lactoglobulin (BLG)/sodium polystyrene sulfonate (PSS) complexes decelerates the change in the surface properties of the mixed solutions with the surface age and increases the steady-state dilational surface elasticity in a narrow PSS concentration range. At the same time, the changes in the surface properties are accelerated in the dispersions of BLG fibrils with and without PSS due to the influence of small peptides coexisting with fibrils. A decrease in the peptide concentration as a result of the dispersion purification leads to slower changes in the surface properties at low PSS concentrations. The increase in the polyelectrolyte concentration results in an increase in the steady-state surface elasticity due to the fibril/PSS complex formation and in very slow changes in the surface properties if the polyelectrolyte exceeds a certain critical value. The latter effect is a consequence of the formation of large aggregates and of an increase in the electrostatic adsorption barrier. The consecutive adsorption of BLG fibrils and PSS leads to the formation of regular multilayers at the liquid–gas interface. The multilayer properties change noticeably with an increase in the number of layers from four to six in agreement with previous results on the multilayers of PSS with an oppositely charged synthetic polyelectrolyte, presumably due to the heterogeneity of the first PSS layer. The dynamic elasticity of the multilayers approaches 250 mN/m, indicating that they can effectively stabilize foams and emulsions.
Основной компонент легочного сурфактанта дипальмитоил фосфатидилхолин (ДПФХ) позволяет снижать поверхностное натяжение практически до нуля при сжатии поверхности легких, что препятствует коллапсу альвеол на выдохе. В данной работе с помощью методов поверхностной реологии было определено влияние шести липидов, входящих в состав легочного сурфактанта, на динамические поверхностные свойства нанесенного монослоя ДПФХ в широкой области поверхностных натяжений и при различных температурах. Особое внимание было уделено области низких поверхностных натяжений (менее 25 мН/м) при температурах 25 и 35°С, что близко к физиологическому состоянию на внутренней поверхности легких. Добавление к ДПФХ липидов с близкой молекулярной структурой не оказывало значительного влияния на динамические поверхностные свойства при температуре 25°С. В то же время при температуре 35°С позволяло увеличивать поверхностную упругость в области малых поверхностных натяжений. Однако в этих условиях присутствие в поверхностном слое липидов с ненасыщенными углеводородными радикалами приводило к противоположному эффекту и препятствовало достижению низких поверхностных натяжений при медленном сжатии. Полученные результаты демонстрируют возможность управления свойствами смешанного слоя, который можно рассматривать в качестве модели легочного сурфактанта.
Amphiphilic silk fibroin (SF) forms stable adsorption layers at the air–water interface. The range of the investigated protein concentrations can be divided into two parts according to the peculiarities of the surface layer properties. At protein concentrations from 0.0005 to 0.01 mg/mL, the dynamic surface elasticity monotonically increases with the concentration and surface age and reaches values of up to 220 mN/m. In this range, the adsorption layer compression leads to a fast increase of the surface pressure. In the second part (>0.01 mg/mL), the surface elasticity decreases again and the kinetic dependences of the film thickness and adsorbed amount change only a little. In this case, the layer compression leads only to a slight increase of the surface pressure. These two types of behavior can be attributed to the distinctions in the protein aggregation in the surface layer. Atomic force microscopy (AFM) investigations of the layers transferred from the liquid surface onto a mica surface by the Langmuir–Schaefer method show some peculiarities of the layer morphology in the intermediate concentration range (~0.02 mg/mL).
Layers of pulmonary lipids on an aqueous substrate at non-equilibrium conditions can decrease the surface tension of water to quite low values. This is connected with different relaxation processes occurring at the interface and the associated changes in the surface layer structure. Results of measurements by the combination of methods like surface rheology, ellipsometry, Brewster angle microscopy, and IRRAS for spread layers of lipid mixtures open a possibility to specify the dynamics of structural changes at conditions close to the physiological state. At sufficiently low surface tension values (below 5 mN/m) significant changes in the ellipsometric signal were observed for pure DPPC layers, which can be related to a transition from 2D to 3D structures caused by the layer folding. The addition of other lipids can accelerate the relaxation processes connected with squeezing-out of molecules or multilayer stacks formation hampering thereby a decrease of surface tension down to low values corresponding to the folding of the monolayer.
Self-assembly gives rise to the versatile strategies of smart material design but requires precise control on the supramolecular level. Here, inorganic-organic synthons (conjugates) are produced by covalently grafting stearic acid tails to giant polyoxometalate (POM) Keplerate-type {Mo132} through an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS). Using the liposome production approach, the synthons self-assemble to form hollow nanosized vesicles (100-200 nm in diameter), which can be loaded with organic dyes─eriochrome black T (ErChB) and fluorescein (FL)─where the POM layer serves as a membrane with subnanopores for cell-like communication. The dye structure plays an essential role in embedding dyes into the vesicle's shell, which opens the way to control the colloidal stability of the system. The produced vesicles are moved by an electric field and used for the creation of an infochemistry scheme with three types of logic gates (AND, OR, and IMP). To design 2D materials, synthons can form spread films, from simple addition on the water-air interface to lateral compression in the Langmuir bath, and highly ordered structures appear, demonstrating electron diffraction in Langmuir-Schaefer (LS) films. These results show the significant potential of POM-based synthons and nanosized vesicles to supramolecular design the diversity of smart materials.
Physicochemical investigations on the inclusion of anionic polyamidoaminesuccinamic acid dendrimer, generation 5 (PAMAM-SA, G5) with positively charged hybrid vesicles (HCV), prepared using soylecithin, ion pair amphiphile (IPA), cholesterol and dihexadecyldimethylammonium bromide, were investigated by dynamic light scattering, transmission electron/atomic force microscopy (TEM/AFM), differential scanning calorimetry, fluorescence spectroscopy and surface pressure-time isotherm studies. Adsorption of dendrimer onto vesicle surface and subsequent bilayer disruption strongly depends on the bilayer composition and dendrimer concentration. Change in the zeta potential value with increasing dendrimer concentration suggests the dendrimer-vesicle interaction to be electrostatic in nature. AFM studies also confirm the adsorption of dendrimer as well as hole formation in the bilayer. Impact of the inclusion of dendrimer into the bilayer were further investigated through differential scanning calorimetry by monitoring the chain melting temperature and enthalpy of the chain melting processes. Dendrimer at low concentration does not alter bilayer integrity, while hole formations are noted at higher dendrimer concentration. Fluorescence anisotropy studies confirm the adsorption and subsequent bilayer disruption due to dendrimer inclusion. Dendrimer induced vesicle disintegration kinetics conclusively illustrate the transformation of cationic bilayer to monolayer and thereby exposing the role of IPA. In vitro cytotoxicity studies on PAMAM-SA, G5 and HCVs mixtures against human breast cancer cell line suggest that dendrimer-liposome aggregates (dendriosomes) exhibit substantial anticancer activities with insignificant side effects. It is expected that the dendriosomes may have application to host and deliver anticancer drug in the field of targeted drug delivery.
The main component of pulmonary surfactant is dipalmitoyl phosphatidylcholine (DPPC), which reduces the surface tension almost to zero when the lung surface is compressed, thus preventing the alveolus from collapse in the course of exhalation. In this work the methods of the surface rheology have been employed to determine the influence of six pulmonary lipids on the dynamic surface properties of a DPPC monolayer at different temperatures and in a wide range of surface tensions. Particular attention has been paid to the region of low surface tensions (lower than 25 mN/m) at temperatures of 25 and 35°С, with these conditions being close to the physiological state on the internal surface of lungs. The addition of lipids with similar molecular structures to DPPC does not affect significantly the dynamic surface properties at a temperature of 25°C. At the same time, the addition of these lipids increases the surface elasticity in the region of low surface tensions at 35°С. However, under these conditions, the presence of lipids with unsaturated hydrocarbon radicals in the surface layer leads to the opposite effect and hinders the achievement of low surface tensions during slow compression. The results obtained have shown the possibility to control the properties of the lipid/DPPC mixed monolayer, which can be considered which can be considered as a model of pulmonary surfactant.
Dicarboxylate metallosurfactants (AASM), synthesized by mixing N -dodecyl aminomalonate, -aspartate and -glutamate with CaCl 2 , MnCl 2 and CdCl 2 , were characterized by XRD, FTIR, and NMR spectroscopy. Layered structures, formed by metallosurfactants, were evidenced from differential scanning calorimetry and thermogravimetric analyses. Solvent-spread monolayer of AASM in combination with soyphosphatidylcholine (SPC) and cholesterol (CHOL) were studied using Langmuir surface balance. With increasing mole fraction of AASM mean molecular area increased and passed through maxima at ~60 mol% of AASMs, indicating molecular packing reorganization. Systems with 20 and 60 mol% AASM exhibited positive deviations from ideal behavior signifying repulsive interaction between the AASM and SPC, while synergistic interactions were established from the negative deviation at other combinations. Dynamic surface elasticity increased with increasing surface pressure signifying formation of rigid monolayer. Transition of monolayer from gaseous to liquid expanded to liquid condensed state was established by Brewster angle microscopic studies. Stability of the hybrid vesicles, formed by AASM+SPC+CHOL, were established by monitoring their size, zeta potential and polydispersity index values over 100 days. Size and spherical morphology of hybrid vesicles were confirmed by transmission electron microscopic studies. Biocompatibility of the hybrid vesicles were established by cytotoxicity studies revealing their possible applications in drug delivery and imaging.
Viruses significantly impact global health because they are the leading cause of death everywhere they are found. Despite the rapid development of human healthcare, more effective viricidal or antiviral therapies must be developed. The need to find safe, novel, and effective alternatives against viral diseases is heightened by the rapid emergence of resistance to, and the high cost of, synthetic antiviral drug(s). The development of novel multi-target antiviral compounds that affect multiple steps of the viral life cycle and host proteins has benefited tremendously from looking to nature for guidance and inspiration. Hundreds of natural molecules are preferred over synthetic drugs because of concerns regarding efficacy and safety and a high resistance rate to conventional therapies. In addition, naturally occurring antiviral agents have demonstrated reasonable antiviral value in both animal and human studies. Therefore, finding new antiviral drugs is crucial, and natural products provide an excellent opportunity. This brief review examines the evidence of antiviral effects exhibited by various plants and herbs.
The non-constancy of the bulk resistance of solvent-polymeric ion-selective membranes containing ionophores is semi-quantitatively explained in view of micro-heterogeneity of membranes due to water uptake. Membranes are considered containing a dispersed aqueous sub-phase (water droplets) within the organic sub-phase (plasticized polymer). It is assumed that charged species in the membrane (ion-ionophore complexes and ion-exchanger ions) are confined in the organic sub-phase owing to their lipophilicity. This entails two inferences: (1) part of the membrane volume is excluded from the transportation of charged species, and (2) the average path length of the charged species transfer across membranes increases because these species have to circumvent water droplets. Because of this, the membrane bulk resistance increases along with the increase of water uptake. The presented results of the theoretical account based on this conjecture are consistent with experimental data. The increase of water uptake alongside the dilution of the external aqueous solution is considered thermodynamically. It is shown that the increase of water uptake from diluted solutions with almost constant chemical potential of water is caused by an interplay between the osmotic pressure, surface tension at the water - polymer matrix curved interface and the elasticity of the membrane matrix.
In many modern technologies, surface-active compounds, such as surfactants, polymers, proteins, particles and their mixtures, are essential components. They change the dynamic and equilibrium properties of the inherent interfaces, which is mostly visible in foams and emulsions. The interfacial dilational visco-elasticity is probably the most informative quantity due to its direct interrelation to the equation of state of the corresponding interfacial layers as well as the mechanisms governing the interfacial molecular dynamics. The scientific field of interfacial visco-elasticity, although quite young, has been inspired by the pioneering work of Marangoni, Levich, Lucassen, Lucassen-Reynders, Hansen, van den Tempel and Krotov, and during the last decades, also significantly by Boris Noskov. His contributions to the theoretical foundation and experimental analysis of polymer and mixed surfactant–polymer interfacial layers in particular are essential.
Pulmonary surfactant, which is a complex mixture of lipids and proteins, plays a key role in the functional properties of the respiratory system. Lipids form complexes with proteins to maintain low values of surface tension at continuous compression/expansion deformations. However, interactions that lead to the complexation still remain to be unknown thus significantly hampering the development of synthetic analogs of the natural pulmonary surfactant. In this work, the methods of surface rheology and ellipsometry have been employed to study the dynamic properties of model phospholipid monolayers applied onto the surfaces of synthetic polyelectrolyte solutions. It has been shown, that electrostatic or hydrophobic interactions between lipids and macromolecules are insufficient for the efficient complexation and maintenance of low surface tension values.
The dynamic surface properties of aqueous dispersions of α-lactalbumin (ALA) amyloid fibrils differ noticeably from the properties of the fibril dispersions of other globular proteins. As a result, the protocol of the application of ALA fibrils to form stable foams and emulsions has to be deviate from that of other protein fibrils. Unlike the fibrils of β-lactoglobulin and lysozyme, ALA fibrils can be easily purified from hydrolyzed peptides and native protein molecules. The application of the oscillating barrier method shows that the dynamic surface elasticity of ALA fibril dispersions exceeds the surface elasticity of native protein solutions at pH 2. ALA fibrils proved to be stable at this pH, but the stability breaks at higher pH levels when the fibrils start to release small peptides of high surface activity. As a result, the dynamic surface properties of ALA coincide with those of native protein solutions. The ionic strength strongly influences the adsorption kinetics of both fibril dispersions and native protein solutions but have almost no impact on the structure of the adsorption layers.
The dynamic surface properties of native κ-casein solutions and aqueous dispersions of its fibrils differ significantly from the corresponding properties of the systems with globular proteins. The dependence of the dynamic surface elasticity of κ-casein solutions on surface pressure has a local maximum, indicating partial displacement of macromolecules from the proximal region of the surface layer to the distal one. This dependence becomes monotonic for fibril dispersions, similar to the results for dispersions of globular protein fibrils, but unlike the latter case, the surface elasticity close to the steady state reaches values that are approximately four times higher than the data for native protein solutions at the same concentrations.
The input of chemical and physical sciences to life sciences is increasingly important. Surface science as a complex multidisciplinary research area provides many relevant practical tools to support research in medicine. The tensiometry and surface rheology of human biological liquids as diagnostic tools have been very successfully applied. Additionally, for the characterization of pulmonary surfactants, this methodology is essential to deepen the insights into the functionality of the lungs and for the most efficient administration of certain drugs. Problems in ophthalmology can be addressed using surface science methods, such as the stability of the wetting films and the development of artificial tears. The serious problem of obesity is fast-developing in many industrial countries and must be better understood, while therapies for its treatment must also be developed. Finally, the application of fullerenes as a suitable system for detecting cancer in humans is discussed.
The properties of adsorbed layers of protein fibrils differ significantly from the properties of fibril spread layers on an aqueous subphase. If the dependencies of the dynamic surface elasticity on surface pressure of Lysozyme (LYS) and β-lactoglobulin (BLG) aqueous dispersions proved to be close to the results for native protein solutions, LYS and BLG spread layers on the surface of 0.1 M NaCl solution exhibited the surface elasticity more than two times higher than the values for protein solutions with the same NaCl concentatration, presumably due to lower surface concentrations of hydrolysed peptides in the latter case. The properties of fibril spread and adsorbed layers and also their morphology, unlike the surface properties of protein solutions, depend noticeably on the ionic strength of the aqueous bulk phase. This dependence is stronger in case of LYS layers, which are also more prone to the formation of macroscopic and mesoscopic surface aggregates as compared with BLG layers.