Tailoring the draw solution chemistry in the integrated electro-Fenton and forward osmosis for enhancing emerging contaminants removal: Performance, DFT calculation and degradation pathway.

Integrated electro-Fenton and forward osmosis is capable to simultaneously separate emerging contaminants and degrade accumulated ones. Thus, an understanding of how draw solution chemistry in forward osmosis influences electro-Fenton is vital for maximizing overall treatment. Therefore, this study aimed to determine the transport behavior of four trace organic contaminants (TrOCs) including Diuron, Atrazine, DEET and Sulfamethoxazole under several influencing factors. Alkalic NaCl severely deteriorated degradation because of the less generation of OH caused by the interfered iron redox cycle. pH-neutral NaCl resulted in the highest reverse salt flux, namely possible largest production of active chlorine, therefore leading to the highest degradation. Compared to NaCl, Na2SO4 presented a significant lower reverse diffusion due to the larger hydrated radius of SO42- than Cl-. Meanwhile, the large consumption of OH by SO42- decreased degradation. Dissolved organic matters in the secondary effluent acted as the scavenger for OH and resulted in a degradation decline. Water extraction resulted from forward osmosis deteriorated degradation kinetics of all compounds except Sulfamethoxazole. On the other hand, Density functional theory calculations and identified intermediates contributed to propose the possible degradation pathways for each TrOC in terms of understanding TrOCs removal mechanism.

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.

Towards understanding the binding affinity of lipid drug carriers to serum albumin.

In the past several years there has been a rapid rise in the use of lipid-based drug formulations. In the case of intravenous drug administration the interaction of lipid carrier with serum albumin is crucial for the distribution of the bioactive molecules in the bloodstream and reaching the target tissue. In this work, we have explored the interaction of serum albumin with three-component lipid monolayer build of palmitoyloleoylphosphatidylcholine (POPC), sphingomyelin (SM), and cholesterol (Chol). Using wide range of lipid compositions and various concentrations of serum albumin we identified the factors governing the lipid-protein binding. Our study revealed that albumin can penetrate selectively the monolayers of POPC/SM/Chol depending on the lipid composition in the mixture. Moreover, the interaction of albumin with monolayer can be controlled by the molecular density of the film and the concentration of protein. The adsorbed albumin exists in the film on the top of lipid monolayer. This behavior may lead to the increase of the size and charge of the lipid carrier and affect the drug transport throughout the bloodstream. The results of this work provide essential physicochemical data that can be used for predicting the pharmacokinetic profile of lipid-based formulations.

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.

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.

Mindfulness-based cognitive therapy reduces clinical symptoms, but do not change frontal alpha asymmetry in people with major depression disorder.

OBJECTIVES: Mindfulness-based cognitive therapy (MBCT) has demonstrated to be successful in the reduction of relapse rates in patients with recurrent major depressive disorder (MDD). Little is known if MBCT is effective for treating individuals with current MDD episode and about underlying psychophysiological mechanisms of symptoms reduction. The aim of the present study was to assess effects of MBCT on depressed individuals in terms of reduction of depressive and anxiety symptoms and to evaluate if this therapeutic improvement would be reflected on neurophysiological level by shift in frontal alpha asymmetry (FAA). PARTICIPANTS: We studied 20 individuals with current MDD. DESIGN: Participants were randomly assigned either to waiting list or 8-week MBCT. Before and after the treatment we have assessed depression, anxiety, and FAA in resting-state electroencephalogram (EEG) - an indicator of approach vs. withdrawal-related response dispositions and a vulnerability factor of MDD. RESULTS: In line with previous findings, reduction of depressive and anxiety symptoms, but no change in mean values of FAA in MBCT group was found. CONCLUSIONS: These results provide a support for the beneficial effects of MBCT in current MDD treatment, however, they do not support the hypothesis on alpha asymmetry change as a neural correlate of MDD improvement.

Physicochemical Characterization of Oleanolic Acid-Human Serum Albumin Complexes for Pharmaceutical and Biosensing Applications.

Among numerous compounds found in marine organisms, triterpenes have attracted considerable research interest due to a beneficial impact on health including anti-inflammatory, antitumor, antiviral, and antioxidation effects. Specifically, new functionalities of oleanolic acid (OLA) have been revealed recently, indicating possible applications in nutrition and pharmaceuticals. However, this bioactive material has limited value due to low water solubility and stability. Therefore, oleanolic acid needs a carrier that protects it and enables controlled release in the human body. Innovative drug delivery systems provide a promising strategy for overcoming these problems. However, the development of those systems requires a comprehensive understanding of the physicochemical properties of triterpenes and their carriers as well as the interactions between them. Among numerous substances, human serum albumin (HSA) has been widely studied as a drug carrier. In addition, human serum albumin is the main blood plasma protein responsible for the transport of drugs and metabolites; therefore, the interactions between that protein and other substances are of physiological and pharmaceutical importance. Moreover, sensing the HSA level in blood plasma is an important challenge that requires binding studies on a molecular scale. The aim of this study was to investigate the properties of oleanolic acid in the presence of human serum albumin in terms of thermodynamics, morphology, and viscoelasticity at the air/water interface. Moreover, the wettability, surface free energy, and topography of the films after deposition on the solid substrate were determined. The results have been discussed in terms of providing physicochemical insight into the interfacial behavior of the OLA-HSA complex, which is crucial for pharmaceutical and bioanalytical applications.

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.

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.