New Derivatives of Modified Starch for Food Technology.

The food industry extensively uses chemically modified starches and their hydrolysates, which is mainly due to their emulsification ability. Therefore, it becomes inevitable to develop new starch derivatives, including modified starch hydrolysates, and effective preparation methods to meet the increasing demands of producers, consumers, and technology. This study comprehensively researches the physical, chemical, and functional properties (such as the water-binding capacity, swelling power, solubility, and fat absorption capacity) of chemically modified biopolymers and their enzymatic hydrolysis products. We utilized oxidized and acetylated potato and waxy-corn starches with varying degrees of substitution by carboxyl and acetyl groups in our research. The process of enzymatic hydrolysis was performed in a recirculated membrane reactor (CRMR). Our findings indicated that the physicochemical properties of starch derivatives and their hydrolysates depended on the biological origin of the biopolymer and the type and degree of modification. However, the presence of carboxyl groups in the modified starch molecules is critical and affects the rheological properties and water-binding capacity of the starch preparations. For example, in the case of waxy-corn starch preparations with a lower content of carboxyl groups (i.e., derivatives with a low degree of oxidation), the water-binding capacity (WBC) increases when compared to native starch. The highest WBC value of 206.3% was noted for the doubly modified waxy-corn starch with an oxidation degree of 0.2% and an acetylation degree of 2.5%, while native waxy-corn starch shows a WBC of 161.4%. In contrast, it was observed that preparations with a higher content of carboxyl groups, i.e., derivatives with an oxidation degree of 2.5%, show a lower swelling power compared to native waxy starch.

Adsorption Properties and Wettability of Ethoxy- and Propoxy- Derivatives of 2-Ethylhexanol as Sterically Specific Surfactant Structures.

2-ethylhexanol, an oxo alcohol competitively priced on the global market, has not been explored intensively as a raw material for surfactants, due to its weak hydrophobic character. However, its sequenced propoxylation and ethoxylation yield an innovative amphiphilic structure, which exhibits unique interfacial activity. The paper presents the differences in the fractional composition of innovative surfactants derived from 2-EH alcohol prepared using alkali and dimetalcyanide catalysts, as well as examples of excellent adsorption and interfacial properties of the latter. The adsorption behavior of the synthesized compounds was explored using equilibrium surface tension (the du Noüy ring method), dynamic surface tension (the maximum gas bubble pressure method) and static/dynamic contact angle (the sessile drop method). The results from the adsorption tests conducted at the air/aqueous surfactant solution interface underwent comprehensive qualitative and quantitative analyses. Moreover, based on the experimentally obtained dynamic surface tension isotherms and the developed algorithm, the diffusion coefficients for these preparations were estimated, and it was shown that the diffusivity of these surfactants is higher compared to the commercial formulations. The study's outcomes in the testing of wettability indicate that new synthesized nonionic and anionic surfactants constitute an interesting group of amphiphiles with a wide application potential as effective wetting agents, especially in relation to the polymer surface. It should therefore be emphasized that the innovative surfactants described in this article, derived from 2-EH alcohol and prepared using dimetalcyanide catalysts, can successfully compete with conventional preparations such as ABS (Dodecylbenzenesulfonic Acid) or AES (Alcohol Ethoxysulphate) acid salts.

Preparation of Thin Films Containing Modified Hydroxyapatite Particles and Phospholipids (DPPC) for Improved Properties of Biomaterials.

The main aims of thin biofilm synthesis are to either achieve a new form to promote the transport of drugs in oral delivery systems or as a coating to improve the biocompatibility of the implant's surface. In this study, the Langmuir monolayer technique was employed to obtain films containing Mg-doped hydroxyapatite with 0.5%, 1.0%, and 1.5% Mg(II). The obtained modified HA particles were analysed via the FT-IR, XRD, DLS, and SEM methods. It was shown that the modified hydroxyapatite particles were able to form thin films at the air/water interface. BAM microscopy was employed to characterized the morphology of these films. In the next step, the mixed films were prepared using phospholipid (DPPC) molecules and modified hydroxyapatite particles (HA-Mg(II)). We expected that the presence of phospholipids (DPPC) in thin films improved the biocompatibility of the preparing films, while adding HA-Mg(II) particles will promote antibacterial properties and enhance osteogenesis processes. The films were prepared in two ways: (1) by mixing DPPC and HA-Mg (II) and spreading this solution onto the subphase, or (2) by forming DPPC films, dropping the HA-Mg (II) dispersion onto the phospholipid monolayer. Based on the obtained π-A isotherms, the surface parameters of the achieved thin films were estimated. It was observed that the HA-Mg(II) films can be stabilized with phospholipid molecules, and a more stable structure was obtained from films synthesied via method (2).

Surface Functionalization of Poly(lactic acid) via Deposition of Hydroxyapatite Monolayers for Biomedical Applications.

The surface modification of poly(lactic acid) (PLA) using hydroxyapatite (HAP) particles via Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) approaches has been reported. The HAP monolayer was characterized at the air/water interface and deposited on three-dimensional (3D) printed poly(lactic acid). The deposition of HAP particles using the LS approach led to a larger surface coverage in comparison to the LB method, which produces a less uniform coating because of the aggregation of the particles. After the transfer of HAP on the PLA surface, the wettability values remained within the desired range. The presence of HAP on the surface of the polymer altered the topography and roughness in the nanoscale, as evidenced by the atomic force microscopy (AFM) images. This effect can be beneficial for the osteointegration of polymeric implants at an early stage, as well as for the reduction of the adherence of the microbial biofilm. Overall, the results suggest that the LS technique could be a promising approach for surface modification of PLA by hydroxyapatite with respective advantages in the biomedical field.

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.

Morphology-Dependent Aggregation-Induced Emission of Janus Emulsion Surfactants.

We report a novel stimuli-responsive fluorescent material platform that relies on an evocation of aggregation-induced emission (AIE) from tetraphenylethylene (TPE)-based surfactants localized at one hemisphere of biphasic micro-scale Janus emulsion droplets. Dynamic alterations in the available interfacial area were evoked through surfactant-induced dynamic changes of the internal droplet morphology that can be modulated as a function of the balance of interfacial tensions of the droplet constituent phases. Thus, by analogy with a Langmuir-Blodgett trough that enables selective concentration of surfactants at a liquid-gas interface, we demonstrate here a method for controllable modulation of the available interfacial area of surfactant-functionalized liquid-liquid interfaces. We show that a morphology-dependent alteration of the interfacial area can be used to evoke an optical signal, by selectively assembling synthesized TPE-based surfactants on the respective droplet interfaces. A trigger-induced increase in the concentration of TPE-based surfactants at the liquid-liquid interfaces results in an evocation of aggregation-induced emission (AIE), inducing an up to 3.9-fold increase in the measured emission intensity of the droplets.

The Biomimetic System of Oleanolic Acid and Oleic Acid at the Air-Water Interface-Interactions in Terms of Nanotechnology-Based Drug Delivery Systems.

Oleanolic acid (OLA) and oleic acid (OA) are ubiquitous in the plant kingdom, exhibiting a therapeutic effect on human health, and are components of novel pharmaceutical formulations. Since OLA has limited solubility, the utilization of nanotechnology-based drug delivery systems enhancing bioavailability is highly advantageous. We report on the interfacial behavior of the OLA:OA system at various molar ratios, using the Langmuir technique to assess the dependence of the molar composition on miscibility and rheological properties affecting film stability. Specifically, we evaluate the interfacial properties (morphology, thermodynamics, miscibility, and viscoelasticity) of the OLA:OA binary system in various molar ratios, and indicate how the OLA:OA system exhibits the most favorable molecular interactions. We apply the Langmuir monolayer technique along with the complementary techniques of Brewster angle microscopy, dilatational interfacial rheology, and excess free energy calculations. Results demonstrate that the properties of mixed monolayers depend on OLA:OA molar ratio. Most of the systems (OLA:OA 2:1, 1:1, 1:5) are assumed to be immiscible at surface pressures >10 mN/m. Moreover, the OLA:OA 1:2 is immiscible over the entire surface pressure range. However, the existence of miscibility between molecules of OLA and OA in the 5:1 for every surface pressure tested suggests that OA molecules incorporate into the OLA lattice structure, improving the stability of the mixed film. The results are discussed in terms of providing physicochemical insights into the behavior of the OLA:OA systems at the interface, which is of high interest in pharmaceutical design.

Effect of Silica Microparticles on Interactions in Mono- and Multicomponent Membranes.

Advancing our understanding of the mechanism of the interaction between inhaled pollutant microparticles and cell membrane components is useful to study the impact of fine particulate matter on human health. In this paper, we focus on the effect of cholesterol (Chol) molecules on the surface properties of a model membrane in the presence of silica microparticles (MPs). Mixed monolayers containing phospholipid-dipalmitoylphosphatidylcholine (DPPC), Chol and silica particle dispersions (MPs; 0.033% w/w, 0.33% w/w and 0.83% w/w) were formed and studied using the Langmuir monolayer technique complemented by Brewster Angle Microscopy (BAM) images. It was shown that Chol caused a condensation of the DPPC monolayer, which influenced the penetration of MPs and their interactions with the model membrane. The relaxation experiments of the lipid-MP monolayer proved that the presence of Chol molecules in the monolayer led to the formation of lipid and MP complexes. Strong interactions between Chol and MPs contributed to the formation of more stable monolayers. The presented results can be useful to better comprehend the interaction between particulate materials and the lipid components of biomembranes.

Concentration-Dependent Effect of the Steroid Drug Prednisolone on a Lung Surfactant Monolayer.

The lung surfactant monolayer (LSM) is the main barrier for particles entering the lung, including steroid drugs used to treat lung diseases. The present study combines Langmuir experiments and coarse-grained (CG) molecular dynamics simulations to investigate the concentration-dependent effect of steroid drug prednisolone on the structure and morphology of a model LSM. The surface pressure-area isotherms for the Langmuir monolayers reveal a concentration-dependent decrease in area per lipid (APL). Results from simulations at a fixed surface tension, representing inhalation and exhalation conditions, suggest that at high drug concentrations, prednisolone induces a collapse of the LSM, which is likely caused by the inability of the drug to diffuse into the bilayer. Overall, the monolayer is most susceptible to drug-induced collapse at surface tensions representing exhalation conditions. The presence of cholesterol also exacerbates the instability. The findings of this investigation might be helpful for better understanding the interaction between steroid drug prednisolone and lung surfactants in relation to off-target effects.

Langmuir Monolayer Techniques for the Investigation of Model Bacterial Membranes and Antibiotic Biodegradation Mechanisms.

The amounts of antibiotics of anthropogenic origin released and accumulated in the environment are known to have a negative impact on local communities of microorganisms, which leads to disturbances in the course of the biodegradation process and to growing antimicrobial resistance. This mini-review covers up-to-date information regarding problems related to the omnipresence of antibiotics and their consequences for the world of bacteria. In order to understand the interaction of antibiotics with bacterial membranes, it is necessary to explain their interaction mechanism at the molecular level. Such molecular-level interactions can be probed with Langmuir monolayers representing the cell membrane. This mini-review describes monolayer experiments undertaken to investigate the impact of selected antibiotics on components of biomembranes, with particular emphasis on the role and content of individual phospholipids and lipopolysaccharides (LPS). It is shown that the Langmuir technique may provide information about the interactions between antibiotics and lipids at the mixed film surface (π-A isotherm) and about the penetration of the active substances into the phospholipid monolayer model membranes (relaxation of the monolayer). Effects induced by antibiotics on the bacterial membrane may be correlated with their bactericidal activity, which may be vital for the selection of appropriate bacterial consortia that would ensure a high degradation efficiency of pharmaceuticals in the environment.

Combined Effect of Nitrofurantoin and Plant Surfactant on Bacteria Phospholipid Membrane.

Due to the increasing use of antibiotics, measures are being taken to improve their removal from the natural environment. The support of biodegradation with natural surfactants that increase the bioavailability of impurities for microorganisms that degrade them, raises questions about their effect on bacterial cells. In this paper we present analysis of the interaction of nitrofurantoin (NFT) and saponins from the Saponaria officinalis on the environmental bacteria membrane and the model phospholipid membrane mimicking it. A wide perspective of the process is provided with the Langmuir monolayer technique and membrane permeability test with bacteria. The obtained results showed that above critical micelle concentration (CMC), saponin molecules are incorporated into the POPE monolayer, but the NFT impact was ambiguous. What is more, differences in membrane permeability between the cells exposed to NFT in comparison to that of the non-exposed cells were observed above 1.0 CMC for Achromobacter sp. KW1 or above 0.5 CMC for Pseudomonas sp. MChB. In both cases, NFT presence lowered the membrane permeability. Moreover, the Congo red adhesion to the cell membrane also decreased in the presence of a high concentration of surfactants and NFT. The results suggest that saponins are incorporated into the bacteria membrane, but their sugar hydrophilic part remains outside, which modifies the adsorption properties of the cell surface as well as the membrane permeability.

Thermodynamic, viscoelastic and electrical properties of lipid membranes in the presence of astaxanthin.

Among numerous compounds found in marine organisms, astaxathin has received considerable research interest due to beneficial impact on health such as anti-inflammatory, antioxidant and neuroprotective activity. Recently new functionalities of this xanthophyll have been revealed indicating important applications in nutrition and pharmacy. However, astaxanthin, as the bioactive, has limited value without a protecting carrier that provides controlled release in a human body. Fabrication of liposomes as efficient drug delivery systems is promising strategy that may overcome these problems. However, the development of new delivery systems requires comprehensive understanding of physicochemical properties of carotenoids and their carriers as well as the interactions between them. The aim of this study was to investigate the mixed lipid-sterol monolayer in the presence of astaxanthin in terms of thermodynamic, morphological and viscoelastic behaviour. The results have been discussed in relation to pure lipid-sterol films. In addition we determined the surface charge density of the liposomes built of these components. The results are helpful in better understanding the role of interfacial viscoelasticity in the quality of liposomal drug delivery forms.

Lipid-Protein Interactions in Langmuir Monolayers under Dynamically Varied Conditions.

In the Langmuir monolayer technique, a single layer of molecules is formed on a water subphase. This approach was used to mimic the antitumoricidal lipid-protein complex of oleic acid and bovine α-lactalbumin called the BAMLET complex. Our previous studies have shown that at the interface, the BAMLET complex is stabilized by the hydrophobic forces supported by the hydrogen bonds. This study provides an insight into the influence of calcium ions and the experimental conditions (temperature and subphase pH) on the stability of the complex at the interface. The Langmuir technique was expanded using a dosing pump to exchange the subphase and deliver additional substances to the system. We investigated the interactions between oleic acid monolayer and α-lactalbumin in the presence of Ca2+ in the bulk and the effect of varied experimental conditions on the complex stability. The role of calcium ions in this system is important because (in addition to low pH and relatively high temperature) it affects the conformational changes within the protein molecule and facilitates the transition of α-lactalbumin into the molten globule state. A partially unfolded state is required to form the BAMLET complex. We found that the mixed monolayer spread at the interface is stable despite drastic changes in the process conditions and remains stable even after the subphase exchange. This study of molecular interactions explored by the Langmuir technique with peristaltic pump enabled to understand the role of Ca2+ in BAMLET complex formation.

Langmuir-Blodgett films of membrane lipid in the presence of hybrid silsesquioxane, a promising component of biomaterials.

Functionalized polyhedral oligomeric silsesquioxanes (POSS) derivatives have great potential in biomedical applications such as tissue engineering, drug delivery, biosensors, dental composites and biomedical devices. Having the above in mind, in this paper, the study of the surface characteristics of binary Langmuir-Blodgett films consisting of an open cage silsesquioxane POSS-poly (ethylene glycol) (POSS-PEG) and 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), as a representative of phospholipid was conducted based on contact angle measurements of three liquids. The measured values of the contact angle (with water, formamide and diiodomethane as the wetting liquids) allowed to calculate surface free energy of the films from van Oss et al. approach. The film structure of the deposited layers was evaluated using an atomic force microscope. Analysis of the obtained results led to the conclusion, that the pure DMPE molecules create agglomerates onto a solid substrate, whereas the POSS-PEG molecules form a homogenous monolayer. After an addition of POSS-PEG to lipid film, changes in the surface properties are visible. The wettability as well as surface free energy depend on the molar ratio of both components. The AFM images shed more light on the changes of the DMPE monolayer topography caused by the POSS-PEG addition.

Temperature, pH, and Molecular Packing Effects on the Penetration of Oleic Acid Monolayer by α-Lactalbumin.

Recently, we reported on the interfacial behavior of mixed oleic acid (OA)-α-lactalbumin monolayer and its relevance in the formation of tumoricidal HAMLET (human α-lactalbumin made lethal to tumor cells)-like complex. This complex is probably formed in the gastrointestinal tract, but it has not been proved so far. The molecular base and the underlying physicochemical forces leading to such complexation remain to be known as well. There are also several other issues related with the complex stoichiometry that need to be fully explained. This study provides insight into the mechanism of temperature, pH, and physical state of monolayer-dependent binding of OA by the milk protein- apo-α-lactalbumin. Using the Langmuir and Langmuir-Blodgett approaches, we investigated the interactions between the OA monolayer and the apo-bovine α-lactalbumin (BLA III) at different pH, temperatures, and molecular packing. We found that the most favorable conditions for the formation of mixed OA-BLA III film are relevant to the gastric environment. The stabilization of OA-BLA III at the interface is associated with the conformational changes of protein in the presence of fatty acids induced by low pH and high temperature in the expanded monolayer. Our approach helps to understand the molecular mechanism of HAMLET/bovine α-lactalbumin made lethal to tumor cells formation in vivo.

Detailed characterization of POSS-poly(ethylene glycol) interaction with model phospholipid membrane at the air/water interface.

Polyhedral oligomeric silsesquioxanes (POSS) derivatives have been receiving remarkable attention due to their potential biomedical application and therefore understanding molecular mechanism of their interaction with cell membranes should be studied at molecular level. Here we investigate the binary mixture of an open silsesquioxane cage POSS-poly(ethylene glycol) (POSS-PEG) and 1,2-myristoyl-sn-glycero-3-phosphoethanolamine (DMPE) as a representative of phospholipid located in biological membranes. The surface pressure-area and surface potential-area compression isotherms, as well as Brewster angle microscopy and interfacial shear rheology were used to study monolayers at the air/water interface. The results show that POSS-PEG exhibits an insoluble monolayer with side group chains anchored to the air/water interface. The outcomes of the conducted experiments show (i) the evidence of a stable incorporation of POSS molecule to the DMPE monolayer modifying its equilibrium and dynamic properties and (ii) squeezing the POSS-polymer out of the lipid monolayer at a higher molecular packing density. The results from the conducted experiments together with thermodynamic analysis suggest area condensation and mutual miscibility at the surface pressure relevant to a real biological membrane.

Surface properties and morphology of mixed POSS-DPPC monolayers at the air/water interface.

From the point of view of the possible medical applications of POSS (polyhedral oligomeric silsesquioxanes), it is crucial to analyse interactions occurring between POSS and model biological membrane at molecular level. Knowledge of the interaction between POSS and DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) allows prediction of the impact of POSS contained in biomaterials or cosmetics on a living organism. In the study presented, the surface properties and morphology of Langmuir monolayers formed by mixtures of POSS and the phospholipid (DPPC) at the air/water surface are examined. We selected two POSS derivatives, with completely different chemical structure of substituents attached to the corner of the silicon open cage, which allowed the analysis of the impact of the character of organic moieties (strongly hydrophobic or clearly hydrophilic) on the order of POSS molecules and their tendency to form self-aggregates at the air/water surface. POSS derivatives significantly changed the profile of the π-A isotherms obtained for DPPC but in different ways. On the basis of the regular solution theory, the miscibility and stability of the two components in the monolayer were analysed in terms of compression modulus (Cs-1), excess Gibbs free energy (ΔGexc), activity coefficients (γ) and interaction parameter (ξ). The results obtained indicate the existence of two different interaction mechanisms between DPPC and POSS which depend on the chemical character of moieties present in POSS molecules.

Synthesis of an Open-Cage Structure POSS Containing Various Functional Groups and Their Effect on the Formation and Properties of Langmuir Monolayers.

Recently, silsesquioxanes have been recognized as a new group of film-forming materials. This study has been aimed at determining the effect of the kind of functional groups present in two different open-cage structure POSS molecules on the possibility of the formation of Langmuir monolayers and their properties. To achieve this goal, two new POSS derivatives (of open-cage structures) containing polyether and fluoroalkyl functional groups have been synthesized on the basis of a hydrosilylation process. An optimization of the process was performed, which makes it possible to obtain the above-mentioned derivatives with high yields. In the next step, the Langmuir technique was applied to measurements of the surface pressure (π) - the mean molecular area (A) isotherms during the compression of monolayers formed by molecules of the two POSS derivatives considered. Subsequently, the monolayers were transferred onto quartz plates according to the Langmuir-Blodgett technique. Both derivatives are able to form insoluble Langmuir films at the air-water interface, which can be transferred onto a solid substrate and effectively change its wetting properties.

Interaction of polyhedral oligomeric silsesquioxane containing epoxycyclohexyl groups with cholesterol at the air/water interface.

Binary mixtures of cholesterol and fully-condensed octakis[{2-(3,4-epoxycyclohexyl) etyl}dimethyl-silyloxy]octasilsesquioxane (OE-POSS) were characterized using Langmuir trough for obtaining surface pressure-area isotherms. The most characteristic feature of the mixed films is the presence of two collapse points on the isotherms. The first one is attributed to the collapse of less stable OE-POSS and it occurs at similar surface pressures for all compositions, while the second one corresponds to cholesterol collapse. Brewster angle microscopy observations confirmed the collapse behavior of the mixed film. Strong condensing effect was observed for the mean molecular areas dependence on cholesterol content in the film. Moreover, formation of microdomains of each component in the matrix of the other one was confirmed by BAM images. For the reasons of molecular structures and interactions a true mixed and homogenous film did not form in the systems considered. Phase separation was observed for all the compositions experimented. The lack of the interactions of OE-POSS with biomembrane components represented by cholesterol is beneficial for applications of OE-POSS in biomedical devices.

Nanofiltration, bipolar electrodialysis and reactive extraction hybrid system for separation of fumaric acid from fermentation broth.

A novel approach based on a hybrid system allowing nanofiltration, bipolar electrodialysis and reactive extraction, was proposed to remove fumaric acid from fermentation broth left after bioconversion of glycerol. The fumaric salts can be concentrated in the nanofiltration process to a high yield (80-95% depending on pressure), fumaric acid can be selectively separated from other fermentation components, as well as sodium fumarate can be conversed into the acid form in bipolar electrodialysis process (stack consists of bipolar and anion-exchange membranes). Reactive extraction with quaternary ammonium chloride (Aliquat 336) or alkylphosphine oxides (Cyanex 923) solutions (yield between 60% and 98%) was applied as the final step for fumaric acid recovery from aqueous streams after the membrane techniques. The hybrid system permitting nanofiltration, bipolar electrodialysis and reactive extraction was found effective for recovery of fumaric acid from the fermentation broth.