Langmuir Monolayers Research Articles

On the relationship between the properties of planar structures of non-ionic surfactants and their vesicular analogues – Niosomes

In recent years, the study of niosomes as nanocarriers alternative to liposomes has received increasing attention. In contrast to well-studied liposome membranes, many aspects of the behavior of analogous niosome bilayers have not been studied. This paper considers one of these aspects related to the communication between the physicochemical properties of planar and vesicular objects. We present the first results of comparative studies of Langmuir monolayers of binary and ternary (with cholesterol) mixtures of non-ionic surfactants based on sorbitan esters and niosomal structures assembled from the same materials. The Thin-Film Hydration (TFH) method in the gentle shaking version was used to produce the particles of large sizes, while small unilamellar high quality vesicles with a unimodal distribution of particles were prepared by TFH using ultrasonic treatment and extrusion. An analysis of the structural organization and phase state of monolayers based on compression isotherms and supplemented by thermodynamic calculations, as well as the results of determining the particle morphology, polarity and microviscosity of niosome shells, made it possible to obtain fundamental data on the intermolecular interactions of the components and their packing in shells and to relate these data to the properties of niosomes. This relationship can be used to optimize the composition of niosome membranes and predict the behavior of these vesicular systems. It was shown that cholesterol excess creates regions of bilayers with increased rigidity (like “lipid rafts”), which hinders the process of folding film fragments into small niosomes.

Site of the Hydroxyl Group Determines the Surface Behavior of Bipolar Chain-Oxidized Cholesterol Derivatives─Langmuir Monolayer Studies Supplemented with Theoretical Calculations.

Cholesterol oxidation products (called oxysterols) are involved in many biological processes, showing both negative (e.g., neurodegenerative) and positive (e.g., antiviral and antimicrobial) effects. The physiological activity of oxysterols is undoubtedly closely related to their structure (i.e., the type and location of the additional polar group in the cholesterol skeleton). In this paper, we focus on determining how a seemingly minor structural change (introduction of a hydroxyl moiety at C(24), C(25), or C(27) in the isooctyl chain of cholesterol) affects the organization of the resulting molecules at the phase boundary. In our research, we supplemented the classic Langmuir monolayer technique, based on the surface pressure and electric surface potential isotherms, with microscopic (BAM) and spectroscopic (PM-IRRAS) techniques, as well as theoretical calculations (DFT and MD). This allowed us to show that 24-OH behaves more like cholesterol and forms stable, rigid monolayers. On the other hand, 27-OH, similar to 25-OH, undergoes the phase transition from monolayer to bilayer structures. Theoretical calculations enabled us to conclude that the formation of bilayers from 27-OH or 25-OH is possible due to the hydrogen bonding between adjacent oxysterol molecules. This observation may help to understand the factors responsible for the unique biological activity (including antiviral and antimicrobial) of 27-OH and 25-OH compared to other oxysterols.

Study of Interactions between Saponin Biosurfactant and Model Biological Membranes: Phospholipid Monolayers and Liposomes

The aim of this study was to determine the effect of saponins-rich plant extract on two model biological membranes: phospholipid monolayers and liposomes. The Langmuir monolayer technique was used to study the interactions of model phospholipid membranes with saponins. The π-A isotherms were determined for DPPE (1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine) monolayer with the addition of various concentrations of licorice saponins extracts and subjected to qualitative as well as quantitative analysis. Additionally, relaxation studies of the obtained monolayers were carried out and morphological changes were examined using Brewster angle microscopy. Moreover, changes in the structure of phospholipid vesicles treated with solutions of saponins-rich plant extracts were assessed using the FTIR technique. The size and zeta potential of the liposomes were estimated based on DLS methods. The obtained results indicated that the saponins interact with the phospholipid membrane formed by DPPE molecules and that the stability of the mixed DPPE/saponins monolayer strongly depends on the presence of impurities in saponins. Furthermore, it was found that the plant extract rich in saponins biosurfactant interacts mainly with the hydrophilic part of liposomes.

Effect of partial O-methylation in dehydrodieugenol on its antitrypanosomal activity - correlation with the toxicity using cell membrane models

Biseugenol (1), a neolignan with antiprotozoal activity against Trypanosoma cruzi, was partially methylated, and the compound obtained – methyl biseugenol (2) – had its activity evaluated against the extracellular (trypomastigotes) and intracellular (amastigotes) forms of T. cruzi. It was observed that both compounds 1 and 2 exhibited similar effects against trypomastigotes (IC50 of 11.7 and 16.2 μM, respectively), whereas compound 2 displayed higher activity against amastigotes (IC50 = 8.2 μM) in comparison with biseugenol (IC50 = 15.4 μM). Additionally, reduced toxicity against NCTC cells for compound 2 was observed (CC50 > 200 μM), differently from compound 1 with CC50 = 58.0 μM. Aiming to understand better the molecular mechanism of the biological action of compound 2, the prodrug was incorporated into cellular membrane models constituted of Langmuir monolayers of the lipids dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylethanolamine (DPPE), dipalmitoylphosphatidylserine (DPPS), and dipalmitoylphosphatidylglycerol (DPPG). The lipid-drug interaction was inferred through tensiometry, surface potential, infrared spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). The prodrug expanded DPPC and DPPG monolayers and condensed DPPE ones, as well as presented characteristic behaviors regarding the chemical structure of the lipid considering expansion-compression curves, surface potential-area isotherms, and stability of previously compressed monolayers to relevant-biological surface pressures. PM-IRRAS indicated a molecular disorder for DPPC and DPPS alkyl chains in the presence of the drug. BAM revealed the presence of domains in the DPPG and DPPE monolayers, which was probably induced by the prodrug. These data suggest, in general, that the lipid composition modulates the interaction of compound 2, whose results are expected to correlate to its trypanocidal activity, which involves the plasma membrane of T. cruzi as the primary target, i.e., the first barrier that the compound should encounter to interact with the microorganism.

In-situ construction of magnetic raspberry-like ZnO/C supporting different transition metal (Fe, Co, Ni) species with high adsorption-photocatalysis efficiency

Organic pollutants that are difficult to degrade with potential biological toxicity are challenges in the environmental field. Magnetic raspberry microspheres of three transition metal (Fe, Co, Ni) nitrate sources were prepared by simple chemical route using zinc gluconate aqueous solution as precursor, the adsorption-catalytic efficiency of which was studied in detail. The effects of the types of transition metal sources, zinc sources, carbon sources and addition amount on the phase composition, structure and properties were investigated. The specific surface area of the products under the optimal conditions is 531, 687 and 592 m2/g, which are 28, 36 and 31 times higher than that of the products with glucose porous carbon alone. In addition, the products also show excellent photoelectric, paramagnetic properties and stability. Interestingly, the phase compositions are Fe/ZnO/ZnFe2O4, Co/ZnO and ZnO/Ni3ZnC0.7 coated with carbon substrate, quite different when the same amount of Fe, Co and Ni nitrates introduced into hydrothermal system, demonstrating heterojunction/doping, doping and heterojunction effects, respectively. Within 40 min, the microspheres could rapidly remove 65.6 mg/g, 146.1 mg/g and 114.6 mg/g of Rhodamine B, respectively, higher than the adsorption of glucose carbon (18.8 mg/g), of which the adsorption processes were in accordance with Pseudo second kinetics and Langmuir monolayer adsorption. These findings not only provide a strategy for the construction of magnetic raspberry microspheres ZnO/C composites with transition metal nitrate salts, but also contribute to the analysis of adsorption-photocatalysis mechanism, which has practical application in the environmental field.

Formation behavior of monolayers on the water surface of water-soluble thermoplastic and insoluble-thermosetting copolymers with hyperbranched units containing s-benzenetricarbamide cores

The formation and structure of Langmuir monolayers and Langmuir-Blodgett films were studied using water-soluble polymers, which have difficulty forming monolayers on the water surface, and polymers that are insoluble in all solvents. The network copolymers consisting of hyperbranched units with an s-benzenetricarbamide core used in this study can be freely controlled by azidation/non-azidation of both ends of the hard segment. The water-soluble copolymer, which exhibits the properties of a thermoplastic resin, can form a monolayer when spread on the water surface at a low temperature at which the solubility decreases. Even when the subphase temperature increased, no significant change in the monolayer behavior of the thermoplastic copolymer was observed. This behavior was attributed to the formation of an insoluble single-particle layer with hydrophilic groups facing inward on the water surface. The insoluble copolymer, which exhibits thermosetting properties, forms a tablet that floats on the water surface for an extended period. The surface pressure-time isotherms showed the formation of a monolayer from the tablet over time, and it was possible to measure the surface pressure-area isotherms by two-dimensional compression after a certain period of time.

Reversible Dehydration-Hydration of Poly(ethylene glycol) in Langmuir Monolayers of a Diblock Copolymer Inferred from Changes in Filament Curvature.

We investigated changes in the hydration state of poly(ethylene glycol) (PEG) through morphological changes in Langmuir monolayers of a PEG-poly(l-lactide) (PlLA) (PEG-b-PlLA) diblock copolymer. When the PEG blocks were hydrated, we observed a remarkable morphology of bundles of ring-like filaments, arranged concentrically, yielding densely packed disk-like objects with a hollow center. We attribute the uniform curvature of these filaments to a strong mismatch between the molecular volumes occupied by PlLA blocks and hydrated PEG blocks. Under the constraint that each hydrated PEG block is attached to a hydrophobic PlLA block anchored to the air-water interface, this mismatch of molecular volumes caused strong repulsion within the PEG layer, in particular when the PlLA blocks packed tightly. Induced by a transition in the ordering of the PlLA blocks, the PEG blocks lost their hydration shell and packed into a dense polymer brush, accompanied by a reduction of the pressure within the PEG layer. During this packing process, the curvature of the filaments was eliminated and the ring-like filaments fractured into small linear pieces. Upon compression, the linear pieces coalesced and formed long filaments aligned in parallel. Importantly, upon expansion of the Langmuir film, these changes in morphology were reversible, and the PEG blocks could be rehydrated and bundles of concentrically arranged ring-like filaments were reformed. We conclude that the change in curvature of the filaments provides a means for distinguishing between the hydrated and dehydrated states of PEG.

The effects of size and surface functionalization of polystyrene nanoplastics on stratum corneum model membranes: An experimental and computational study

Nanoplastics are mainly generated from the decomposition of plastic waste and artificial production and have attracted much attention due to their wide distribution in the environment and the potential risk for humans. As the largest organ of the human body, the skin is inevitably in contact with nanoplastics. Stratum corneum is the first barrier when the skin is exposed to nanoplastics. However, little is known about the interactions between nanoplastics and stratum corneum. Here, the effects of particle size and surface functionalization (amino-modified and carboxy-modified) of polystyrene nanoplastics on the stratum corneum models were studied by Langmuir monolayer and molecular dynamics simulations. An equimolar mixture of ceramide/cholesterol/free fatty acid was used to mimic stratum corneum intercellular lipids. The Langmuir monolayer studies demonstrated that the larger size and surface functionalization of polystyrene nanoplastics significantly reduced the stability of stratum corneum lipid monolayer in a concentration-dependent fashion. Simulation results elucidated that functionalized polystyrene oligomers had a stronger interaction with lipid components of the stratum corneum model membrane. The cell experiments also indicated that functionalized polystyrene nanoplastics, especially for amino-modified polystyrene nanoplastics, had significant cytotoxicity on normal human dermal fibroblast cells. Our results provide fundamental information and the basis for a deeper understanding of the health risks of nanoplastics to humans.

Solubilization of free β-sitosterol in milk sphingomyelin and polar lipid vesicles as carriers: Structural characterization of the membranes and sphingosome morphology

High consumption of plant sterols reduces the risk of cardiovascular diseases in humans and provides health benefits. Increasing the amount of plant sterols in the diet is therefore necessary to reach the recommended daily dietary intake. However, food supplementation with free plant sterols is challenging because of their low solubility in fats and water. The objectives of this study were to investigate the capacity of milk-sphingomyelin (milk-SM) and milk polar lipids to solubilise β-sitosterol molecules in bilayer membranes organised as vesicles called sphingosomes. The thermal and structural properties of milk-SM containing bilayers composed of various amounts of β-sitosterol were examined by differential scanning calorimetry (DSC) and temperature-controlled X-ray diffraction (XRD), the molecular interactions were studied using the Langmuir film technique, the morphologies of sphingosomes and β-sitosterol crystals were observed by microscopy. We showed that the milk-SM bilayers devoid of β-sitosterol exhibited a gel to fluid Lα phase transition for Tm = 34.5 °C and formed facetted spherical sphingosomes below Tm. The solubilisation of β-sitosterol within milk-SM bilayers induced a liquid-ordered Lo phaseabove 25 %mol (1.7 %wt) β-sitosterol and a softening of the membranes leading to the formation of elongated sphingosomes. Attractive molecular interactions revealed a condensing effect of β-sitosterol on milk-SM Langmuir monolayers. Above 40 %mol (25.7 %wt) β-sitosterol, partitioning occured with the formation of β-sitosterol microcrystals in the aqueous phase. Similar results were obtained with the solubilization of β-sitosterol within milk polar lipid vesicles. For the first time, this study highlighted the efficient solubilization of free β-sitosterol within milk-SM based vesicles, which opens new market opportunities for the formulation of functional foods enriched in non-crystalline free plant sterols.

The interdependence of thermodynamic, mechanical, and structural properties in saturated phospholipid membranes.

Lipid membranes undergo conformational and structural changes when they transition from the gel phase to the fluid phase. These phase transitions are accompanied by changes in the lipid packing and the membrane mechanical properties, as previously reported in experimental studies and molecular dynamics simulations. Here, we report a simple direct approach for calculating the mechanical properties of single-component lipid membranes using size-dependent calorimetry measurements, performed on lipid vesicles with different mean diameters. Using differential scanning calorimetry (DSC), we find that the melting temperature, associated with the gel-to-fluid phase transition, increases with the vesicle diameter until it approaches an asymptotic value representative of uncurved membranes. More importantly, fits of the transition temperature as a function of vesicle size show a clear dependence on the structural and mechanical properties of the membranes, i.e., the area-per-lipid and the area compressibility modulus. Our method is validated by comparing the obtained parameters against results from small-angle X-ray scattering measurements and Langmuir monolayer compression studies. The findings indicate that the thermodynamic properties of vesicular lipid membranes depend on their nanoscale curvature and corresponding energetic contributions for membrane stretching and bending. When combined with measurements of the bending rigidity modulus by neutron spin-echo spectroscopy, our approach yields the interleaflet coupling constant, a sought-after quantity describing the extent of interactions between the two membrane leaflets. The application of this approach to saturated phospholipid membranes with molecular additives (e.g., cholesterol) provides a platform to assess the resultant effects on interleaflet interactions.

Magnetic MOF composite material for decontamination of direct red 81 from polluted water

Herewith, magnetic Zn MOF composite material was utilized as an efficient adsorbent for direct red 81 “DR81” dye from wastewater. The synthesized magnetic MOF was characterized using X-ray diffraction (XRD), field emission transmission electron microscopy (FETEM), Fourier-transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), thermal gravimetrical analysis (TGA), and Brunauer-Emmett-Teller (BET) surface area analysis. The adsorption profile of DR81 anionic dye onto the prepared magnetic MOF was investigated with various processing parameters such as contact time, dosage, and initial dye concentrations. The optimum dosage from the fabricated magnetic Zn MOF for decontamination of DR81 was 1.0 g l−1 at pH = 7 after 30 min. The maximum Langmuir monolayer adsorption capacity of the DR81 decontamination via the synthesized magnetic MOF was recorded 67.35 mg g−1. These promising data confirmed the availability of the synthesized magnetic MOF composite as an excellent adsorbent material for the adsorption of DR81 from aqueous media.

Interaction between Pharmaceutical Drugs and Polymer-Coated Fe3O4 Magnetic Nanoparticles with Langmuir Monolayers as Cellular Membrane Models

Surface modification of magnetic nanoparticles (MNPs) has been reported to play a significant role in determining their interactions with cell membranes. In this research, the interactions between polymer functionalized (chitosan, CHI or diethylamino-ethyl dextran, DEAE-D) Fe3O4 MNPs, pharmaceutical drugs and model cell membranes were investigated by Langmuir isotherms and adsorption measurements. In this study, 1,2-distearoyl-sn-glycerol-3-phosphate (DSPA) phospholipid monolayers were used as cell membrane models. Insertion experiments demonstrate that diclofenac (DCFN) is not absorbed at the air-water interface, whereas triflupromazine (TFPZ) has a MIP (maximum insertion pressure) of 35 m Nm-1. The insertion of composites MNPs:TFPZ or DCFN has larger MIP values, indicating that the MNPs are adsorbed on the monolayer with the drugs. An Fe3O4@CHI:DCFN composite presented an MIP of 39 m Nm-1 and Fe3O4@DEAE-D:DCFN presented an impressive MIP of 67 mNm-1. In the case of TFPZ, the enhancement in the MIP values is also evident, being 42 mNm-1 for Fe3O4@CHI:TFPZ and 40 mNm-1 for Fe3O4@DEAE-D:DCFN composite. All MNPs:drugs composites have MIP values greater than commonly accepted membrane pressure values, indicating that MNPs:drugs can penetrate a cellular membrane. The fact that the composite MNPs:drugs present greater MIP values than separated compounds indicates that polymer-coated MNPs can act as good drug delivery systems.

Insight into the anti-corrosion mechanism of Pisum sativum L leaves extract as the degradable inhibitor for Q235 steel in sulfuric acid medium

BackgroundIn this work, we obtained Pisum sativum L leaf extract by soaking in sulfuric acid solution. Using sulfuric acid solution as solvent, the prepared Pisum sativum L leaf extract (PSLLE) has good solvent property and can be effectively dissolved in H2SO4 solution. Pisum sativum L leaf was selected as the research object, which is attributed to the large amount of Pisum sativum L cultivated in many countries and regions on the earth. Pisum sativum L leaf as a corrosion inhibitor, it can greatly realize the transformation of waste into treasure. MethodsThe Tafel curve data manifest that PSLLE is mixed-type inhibitor, which concurrently delaying the anodic and cathodic reactions of working electrode in sulfuric acid environment. Surface topography test results prove that PSLLE can form the stabilized isolation film after adsorption of Q235 steel, and the corrosion of Q235 steel is significantly descend. Theoretical results indicate that the active ingredient in PSLLE can emerge high standard anti-corrosion nature. Significant findingsWhen the concentration of PSLLE is 600 mg/L, its corrosion inhibition efficiency can reach 95.9% at 298 K. With the increase of temperature, PSLLE can still show high anti-corrosion performance. The adsorption isotherm model data showed that there was chemical and physical co-adhesion of PSLLE onto the Q235 steel surface. The PSLLE adhesion at Q235 steel surface is consistent with Langmuir monolayer model.

Investigation on the relationship between lipid composition and structure in model membranes composed of extracted natural phospholipids

HypothesisUnravelling the structural diversity of cellular membranes is a paramount challenge in life sciences. In particular, lipid composition affects the membrane collective behaviour, and its interactions with other biological molecules. ExperimentsHere, the relationship between membrane composition and resultant structural features was investigated by surface pressure-area isotherms, Brewster angle microscopy and neutron reflectometry on in vitro membrane models of the mammalian plasma and endoplasmic-reticulum-Golgi intermediate compartment membranes in the form of Langmuir monolayers. Natural extracted yeast lipids were used because, unlike synthetic lipids, the acyl chain saturation pattern of yeast and mammalian lipids are similar. FindingsThe structure of the model membranes, orthogonal to the plane of the membrane, as well as their lateral packing, were found to depend strongly on their specific composition, with cholesterol having a major influence on the in-plane morphology, yielding a coexistence of liquid-order and liquid-disorder phases.

The effective Ni(II) removal of red mud modified chitosan from aqueous solution.

This study used red mud modified with chitosan (RM/CS) as a novel adsorbent to remove Ni(II) ions from an aqueous solution. The adsorbent was characterized by the techniques of the BET method, X-ray diffraction (XRD), and scanning electron microscopy (SEM) analysis. According to the findings, the surface area of RM/CS is nearly doubled compared to CS, from 68.6 to 105.7 m2.g-1. The Ni(II) batch adsorption of RM/CS was performed as a function of pH value, contact time, and volume of adsorbent. Three isotherm adsorption models (Langmuir, Freundlich, and Sips) and three kinetic models (the pseudo-first-order, the pseudo-second-order, and the intra-diffusion models) were fitted with the experimental data to calculate the maximum adsorption capacity and to estimate the uptake in nature. The Langmuir monolayer adsorption capacity for Nickel (II) is 31.66mg.g-1 at a pH of 6.0, with an adsorption time of 180min and a temperature of 323K. The Ni(II) adsorption on RM/CS is the exothermic process and is controlled by the intra-diffusion model.

Cross-linking reactions in Langmuir monolayers of specially designed aminolipids - a toolbox for the customized production of amphiphilic nanosheets.

Synthetic amino lipids, already known as highly efficient gene therapy tool, are used in a novel way to create cross-linked stable one-molecule-thin films envisioned for future (bio)-materials applications. The films are prepared as Langmuir monolayers at the air/water interface and cross-linked 'in situ' via dynamic imine chemistry. The cross-linking process and the film characteristics are monitored by various surface-sensitive techniques such as grazing incidence X-ray diffraction, X-ray reflectivity, and infrared reflection-absorption spectroscopy. After transfer onto carbon grids, the cross-linked films are investigated by transmission and scanning electron microscopy. The obtained micrographs display mechanically self-supported nanosheets with area dimensions over several micrometers and, thus, an undeniable visual proof of successful cross-linking. The cross-linking process at the air/water interface allows to obtain Janus-faced sheets with a hydrophobic side characterized by aliphatic alkyl chains and a hydrophilic side characterized by nucleophilic groups like amines, hydroxyl groups and imine.

Chitin-Based Magnesium Oxide Biocomposite for the Removal of Methyl Orange from Water.

In this work, a cost-effective chitin-based magnesium oxide (CHt@MgO) biocomposite with excellent anionic methyl orange (MO) dye removal efficiency from water was developed. The CHt@MgO biocomposite was characterized by FT-IR, XRD, SEM-EDX, and TGA/DTG. Results proved the successful synthesis of CHt@MgO biocomposite. Adsorption of MO on the CHt@MgO biocomposite was optimized by varying experimental conditions such as pH, amount of adsorbent (m), contact time (t), temperature (T), and initial MO concentration (Co). The optimized parameters for MO removal by CHt@MgO biocomposite were as follows: pH, 6; m, 2 g/L; t, 120 min. Two common isotherm models (Langmuir and Freundlich) and three kinetic models (pseudo-first-order (PFO), pseudo-second-order (PSO), and intraparticle diffusion (IPD)) were tested for experimental data fitting. Results showed that Langmuir and PFO were the most suitable to respectively describe equilibrium and kinetic results on the adsorption of MO adsorption on CHt@MgO biocomposite. The maximum Langmuir monolayer adsorption capacity (qm) on CHt@MgO biocomposite toward MO dye was 252 mg/g at 60 °C. The reusability tests revealed that CHt@MgO biocomposite possessed high (90.7%) removal efficiency after the fifth regeneration cycle.

Langmuir monolayer of lysozyme at variable subphase pH conditions: a comprehensive study on structure, morphology and hysteresis behaviour.

Formation of a pure Langmuir monolayer of lysozyme at the air-water interface and its investigation by means of a surface pressure (π)-mean molecular area (A) isotherm has been accomplished under different subphase pH conditions. A normalized area-time curve confirms the stable nature of the lysozyme monolayer whose compressibility variation with an increased surface pressure at specific subphase pH has also been studied from π-A isotherms. The monolayers exhibit irreversible hysteresis behaviour irrespective of subphase pH conditions, as evidenced from successive compression-expansion π-A isotherm cycles. Comparison of surface thermodynamics under hysteresis with subphase pH variation confirms that the monolayer at subphase pH ≈ 4.0 involves a greater amount of energy to attain and retain the ordered and compact monolayer than the other two pH conditions (pH ≈ 7.0 and 9.5). In situ visualization of lysozyme monolayers by Brewster angle microscopy suggests the homogeneous and stripe-like pattern formation at lower and higher surface pressure respectively. Further investigations of lysozyme films at solid surfaces have been carried out with atomic force microscopy and X-ray reflectivity (XRR) analysis. Structural reversibility of lysozyme molecules under compression-expansion-compression of the monolayer is revealed from the comparison of height profiles of AFM images and electron density profiles as extracted from XRR analysis of the films deposited during both first and second compressions of the monolayer. The mechanism of the structural rearrangement of lysozyme molecules with surface pressure variation at different subphase pH is explored, correlating macroscopic and microscopic information.

Surface Properties of the Polyethylene Terephthalate (PET) Substrate Modified with the Phospholipid-Polypeptide-Antioxidant Films: Design of Functional Biocoatings.

Surface properties of polyethylene terephthalate (PET) coated with the ternary monolayers of the phospholipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), the immunosuppressant cyclosporine A (CsA), and the antioxidant lauryl gallate (LG) were examined. The films were deposited, by means of the Langmuir-Blodgett (LB) technique, on activated by air low temperature plasma PET plates (PETair). Their topography and surface chemistry were determined with the help of atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS), respectively, while wettability was evaluated by the contact angle measurements. Then, the surface free energy and its components were calculated from the Lifshitz-van der Waals/Acid-Base (LWAB) approach. The AFM imaging showed that the Langmuir monolayers were transferred effectively and yielded smoothing of the PETair surface. Mass spectrometry confirmed compatibility of the quantitative and qualitative compositions of the monolayers before and after the transfer onto the substrate. Moreover, the molecular arrangement in the LB films and possible mechanisms of DOPC-CsA-LG interactions were determined. The wettability studies provided information on the type and magnitude of the interactions that can occur between the biocoatings and the liquids imitating different environments. It was found that the changes from open to closed conformation of CsA molecules are driven by the hydrophobic environment ensured by the surrounding DOPC and LG molecules. This process is of significance to drug delivery where the CsA molecules can be released directly from the biomaterial surface by passive diffusion. The obtained results showed that the chosen techniques are complementary for the characterization of the molecular organization of multicomponent LB films at the polymer substrate as well as for designing biocompatible coatings with precisely defined wettability.

Removal of Co(II) from aqueous solutions with amino acid-modified hydrophilic metal-organic frameworks

Adsorbents capable of rapidly and efficiently adsorbing specific metal ions in solution are critical in emergency disposal and waste minimization of radioactive effluents. A microporous zeolitic imidazole framework-90 belonging to metal-organic frameworks (MOFs) was synthesized and functionalized with methionine and lysine to obtain ZIF-90-Met and ZIF-90-Lys with efficient and selective adsorption of cobalt ions. The synthesized materials were characterized by means of SEM, TGA, N2 adsorption–desorption, XRD and FTIR. The adsorption properties of two materials for Co(II) in simulated waste liquid were investigated. Under the conditions of pH = 6.69, T = 303 K and initial concentration of 500.00 mg·L−1, the maximum adsorption capacity of Co(II) on ZIF-90-Met and ZIF-90-Lys were 136.83 mg·g−1 and 164.40 mg·g−1, respectively. Two materials exhibit high selectivity in the adsorption of Co(II) and Ni(II) in multimetal ion solutions. Kinetic and adsorption isotherm analysis showed that the adsorption of Co(II) by ZIF-90-Met and ZIF-90-Lys was consistent with pseudo-second-order chemisorption and Langmuir monolayer adsorption. Thermodynamic analysis shows that the adsorption process of Co(II) by ZIF-90-Met and ZIF-90-Lys is spontaneous and endothermic.