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The search for protective substances that can be used during red blood cell thawing and the study of their effects on red blood cells contribute to increasing the number and quality of viable cells after the cryopreservation cycle. We studied the effect of posthypertonic shock and amphiphilic compounds on the shape and eryptosis of human erythrocytes. The method of flow cytometry was used, this allows analyzing two parameters simultaneously, which increases the efficiency of research. The shape was assessed by the sphericity index (SphI), and eryptosis by the redistribution of phosphatidylserine to the membrane outer surface. It has been shown that sodium decylsulfate and chlorpromazine reduce erythrocyte damage in posthypertonic shock by 3.6 and 4.2 times, respectively. Sodium decylsulfate helps to preserve the shape of cells (SphI coefficient remains the same), while when chlorpromazine is used, the shape changes towards spherical (SphI coefficient changes 2 times). The study of the level of Annexin V FITC binding to phosphatidylserine in outer layer of membrane revealed a concentration-dependent increase in fluorescence when sodium decylsulfate was used, indicating a disorder of the bilayer asymmetry. In contrast, chlorpromazine did not change the distribution of phosphatidylserine. Comparison of two parameters of cell viability - the sphericity coefficient and anexin binding - allowed us to choose the conditions that are optimal for the use of the studied protective substances. Namely, it is advisable to use the lowest effective concentration of sodium decylsulfate (200 mcmol/l) for protective purposes. This ensures the preservation of the cell shape and minimal impact on the membrane asymmetry [ABSTRACT FROM AUTHOR]

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Ru-based chemotherapy is emerging as an effective alternative to the well-established Pt-based one, typically associated with high toxicity. In this context, our recent efforts were devoted to the preparation of nucleolipid-based Ru(III) complexes able to form, under physiological conditions, supramolecular aggregates which can efficiently prevent metal deactivation and convey Ru(III) inside the cells where it exerts its activity. Within an interdisciplinary program for the development of multifunctional nanoparticles for theranostic applications, we here report the design, synthesis, and characterization of a novel functionalized Ru(III) salt, carrying a lipoic acid moiety in the nucleolipid-based scaffold to allow its incorporation onto metal-based nanoparticles. [ABSTRACT FROM AUTHOR]

The influence of temperature conditions on the level of damage of rabbit erythrocytes under posthypertonic shock and the level of their protection by amphiphilic compounds was investigated. We observed the maximum cell damage at 0°C. When the temperature increased to 20°C, the level of hemolysis decreased by 1.8 times. Further increase in temperature up to 37°C did not lead to a decrease in damage. The investigated amphiphilic compounds at 0°C and 10°C effectively protected rabbit erythrocytes from posthypertonic shock. Reduction of hemolytic damage was 2–3 times. At 20°C amphiphilic compounds did not affect the level of cell damage, and at 30°C and 37°C they increased it. The existence of temperature dependence of posthypertonic damage showed the involvement of the phospholipid component of the erythrocyte membrane in the process. Lower temperature is characterized by greater orderliness of lipids, its increase is accompanied by disorder and increased fluidity, and hence elasticity of the membrane. As a result, erythrocyte damage in posthypertonic shock is less at the temperature of 20–37°C. The addition of amphiphilic compounds at 0 and 10°C acts similarly to increasing the temperature, disorganizes the bilayer, increases the elasticity of the membrane and reduces damage during the transfer from hypertonic to isotonic solution. Above 20°C, the introduction of amphiphilic compounds leads not only to disorder, but also to the formation of mixed micelles consisting of phospholipids and amphiphilic molecules. This disrupts the bilayer, gives it instability and leads to increased damage of erythrocytes.

The effect of ATP depletion on the protection of rabbit erythrocytes by amphiphilic substances in posthypertonic shock conditions was studied. For this, the level of hemolysis in posthypertonic shock of native and ATP-depleted erythrocytes in the presence of amphiphilic substances was determined. It was shown that ATP depletion reduces posthypertonic cell damage by 15-17% both at 0°С and at 37°С. It was found that amphiphilic compounds are able to protect rabbit erythrocytes in conditions of posthypertonic shock, but only at a temperature of 0°С. In conditions of ATP-depletion of cells, only anionic sodium decyl sulfate and nonionic decyl-β, D-glucopyranoside retain their protective effect in posthypertonic shock conditions, whereas cationic chlorpromazine and trifluoroperazine lose this ability. This can be explained based on the features of the incorporation of amphiphiles into the erythrocyte membrane. All studied amphiphilic compounds increase the level of damage in both control and ATP-depleted cells under conditions of posthypertonic shock at a temperature of 37°C. Probably, easier intercalation and increased fluidity of the membrane at this temperature destabilize the bilayer and reduce the protective effect of amphiphilic compounds. [ABSTRACT FROM AUTHOR]

This review is devoted to self-organizing systems based on amphiphilic compounds of different types, i.e., open-chain and macrocyclic ones. Conventional colloidal surfactants have been considered both in the individual form and in the presence of modifiers, including electrolytes and cosurfactants. Special attention has been focused on the role of structural factors, in particular, an analysis has been performed for the cases of the most pronounced influence of surfactant structure (the nature of head groups and counterions, the passage to dicationic surfactants, and the occurrence of calix[4]arene cores) on the aggregation characteristics, morphological behavior, and functional activity of the systems. Macrocyclic amphiphiles are typical objects of supramolecular chemistry. The final part of the review presents the comparison between two types of the systems: (1) amphiphilic calixarenes (covalent functionalization of macrocycles with alkyl fragments) and (2) calixarene–surfactant binary composites (noncovalent modification of the macrocyclic platform). [ABSTRACT FROM AUTHOR]

Ru-based chemotherapy is emerging as an effective alternative to the well-established Pt-based one, typically associated with high toxicity. In this context, our recent efforts were devoted to the preparation of nucleolipid-based Ru(III) complexes able to form, under physiological conditions, supramolecular aggregates which can efficiently prevent metal deactivation and convey Ru(III) inside the cells where it exerts its activity. Within an interdisciplinary program for the development of multifunctional nanoparticles for theranostic applications, we here report the design, synthesis, and characterization of a novel functionalized Ru(III) salt, carrying a lipoic acid moiety in the nucleolipid-based scaffold to allow its incorporation onto metal-based nanoparticles.

Carboxylato-type transition metal complexes with agaric acid, a bioactive natural compound derived from citric acid, were prepared, and tested in vitro for their antimicrobial activity and cytotoxicity. The products as well as agaric acid itself are amphiphilic compounds containing a hydrophilic head (citric acid moiety) and a hydrophobic tail (non-polar alkyl chain). The putative composition of the carboxylates was assigned on grounds of elemental analysis, infrared (IR) and high-resolution mass spectra (HR-MS), as well as in analogy with known complexes containing the citrate moiety. The metal carboxylates showed interesting activity in several microbial strains, especially against S. aureus (vanadium complex; MIC = 0.05 mg/ml). They were also tested for their cytotoxic activity in hepatocytes, the highest activity having been found in the copper(II) and manganese(II) complexes. Further research based on these preliminary results is needed in order to evaluate the influence of parameters like stability of the metal complexes in solution on the bioactivity of the complexes.

The effects of trifluoroperazine and sodium decyl sulfate on posthypertonic shock of human and rabbit erythrocytes were studied. For this purpose, the level of hemolysis in posthypertonic shock and the percentage of potassium ions released from erythrocytes in dehydration and rehydration solutions in the presence of trifluoroperazine and sodium decyl sulfate were determined. It is shown that the protective effect of amphiphilic compounds is manifested at 0°C, but not at 37°C. There is a decrease in the level of hemolysis in a certain concentration range of each of the studied substances. It was found that human erythrocytes are more sensitive to the protective action of the studied amphiphilic compounds and are characterized by a wider range of protective concentrations. This could be explained by the different lipid composition of the erythrocyte membranes of the studied mammals. Measurement of the leak of potassium ions in dehydration and rehydration media in the presence of amphiphilic compounds suggested that the latter do not affect the permeability of the membrane of mammalian erythrocytes for potassium in posthypertonic shock. Based on the obtained results and literature data, it is assumed that the protective effects of trifluoroperazine and sodium decyl sulfate occur independenly of the formation of temporary defects in permeability for potassium ions, but involve an increase in the cell surface area due to the incorporation of amphiphilic molecules. This results to an increase in the critical hemolytic volume of erythrocytes and reduction in the level of damage during change from hypertonic conditions to isotonic ones. [ABSTRACT FROM AUTHOR]

This study investigated the effect of solubility of amphiphilic compounds of acidic crude oil in water on the surface and interfacial tension (IFT) with NaCl, MgCl2, CaCl2, and Na2SO4 salts. Accordingly, distilled water, along with the salts mentioned in zero ionic strength up to 2 mol were put in contact with crude oil to become saturated with amphiphilic compounds. The effects of these compounds were investigated on the properties of contact water by pH, total organic carbon (TOC), FTIR (Fourier transform infrared spectroscopy), water‐air surface tension (ST), and water‐n‐decane IFT tests. The results showed that some of the organic components of crude oil, especially acidic and basic compounds, are present or soluble in water, which have a significant effect on reducing the surface and IFT. The IFT reduction of water‐n‐decane was greater than the water‐air ST system. Also, the observations showed that for both NaCl and Na2SO4 salt water, with increasing ionic strength of water, there was an optimum salinity within the range of 0.1‐0.25 mol/L for both salts with the amount of surface and IFT minimized at this point. In the other two salts, this point was delayed upon elevation of ionic strength and was observed at high salinity. In this case, divalent cations reduce tension rate compared to monovalent cations. Due to solubility of acidic and basic groups in water, pH of salt water illustrates an acidic trend. Results of the FTIR test confirmed solubility of these compounds as well. [ABSTRACT FROM AUTHOR]

Background: The present study describes the production of biosurfactant (BS) and emulsifier (BE) by the filamentous fungus Mucor hiemalis UCP 0039, as well as the characterization and stability of the both biomolecules for environmental or industrial applications. Results: Biosurfactants and bioemulsifiers are amphiphilic compounds and are produced as extracellular molecules. The results showed that bioproduct obtained by shaker condition reduced the water surface tension of 72 to 32 mN/m and reached an emulsification index of 96%, while the static cultivation resulted in a biomolecule with a surface tension of 40 mN/m and an emulsification index of 96%, suggesting the production of a biosurfactant and bioemulsifier, respectively. The compounds showed glycolipid nature but the biosurfactant presented cationic charge, while the bioemulsifier, anionic charge. Thus, the results confirmed that M. hiemalis produced two distinct biomolecules under different parameters and in the same culture medium. Conclusions: It is the first time that biosurfactant and emulsifier production has been described in the same medium and under different physical conditions by Mucor hiemalis. Both biomolecules showed thermal stability, as well as have significant effect on the viscosity of hydrophobic compounds, indicating the excellent potential for environmental safety or industrial applications to improve the efficiency of sustainable and economic technologies. How to cite: Ferreira INS, Rodríguez DM, Campos-Takaki, GM, et al. Biosurfactant and bioemulsifier as promissing molecules produced by Mucor hiemalis isolated from Caatinga soil. Electron J Biotechnol 2020; 47. https://doi.org/10.1016/j.ejbt.2020.06.006.

We present a series of cationic membrane-targeted azobenzene molecules, with the aim to understand how variations in molecular architecture influence the relative optical and biological properties. 1,4-Amino-substituted azobenzene was chosen as the switching unit while the number of linked alkyl chains and their cationic end-group were systematically varied. Their photophysics, membrane partitioning, and electrophysiological efficacy were studied. We found that the polar end group is a key-factor determining the interaction with the phospholipid heads in the plasma membrane bilayer and consequently the ability to dimerize. The monosubstituted photoswitch with a pyridinium-terminated alkyl chain was found to be the best candidate for photostimulation. This study provides a structure-property investigation that can guide the chemical engineering of a new generation of molecular photo-actuators.

Effects of moisture and amphiphilic compounds, including oleic acid, lecithin, and monoacylglycerols (MAGs), on the oxidative stability are evaluated in microwave‐treated corn oil. Moreover, the physical properties including critical micelle concentration (CMC) and moisture content are determined in oils treated by microwave irradiation. The CMC of lecithin and moisture content of oils decreases remarkably, whereas the temperature of the oil increases rapidly with microwave irradiation. The addition of lecithin results in increased moisture content significantly in the edible oils, whereas oleic acid and MAGs do not exhibit these effects. Primary oxidation products in all the oil samples increase, despite the type of amphiphilic compounds used. Corn oil containing oleic acid and samples with lecithin exhibits lower and higher p‐anisidine values (p‐AV), respectively. Remarkably high moisture content in corn oils containing lecithin may contribute to the formation of volatile compounds and high p‐AV. Collectively, moisture and amphiphilic compounds affect the degree of lipid oxidation in microwave‐irradiated bulk oils. Practical application: A microwave oven is an irreplaceable home appliance and is widely used in households nowadays. Effects of amphiphilic compounds and moisture on the oxidative stability are evaluated and it is found that the amphiphilic compounds in lipids affect heat transfer and oxidative stability of oils. The results of this study can provide fundamental insights into lipid oxidation in edible oils, and can provide a direction to the food industry with respect to the development of more efficient and safe methods for the preparation of microwavable foods. [ABSTRACT FROM AUTHOR]

Carboxylato-type transition metal complexes with agaric acid, a bioactive natural compound derived from citric acid, were prepared, and tested in vitro for their antimicrobial activity and cytotoxicity. The products as well as agaric acid itself are amphiphilic compounds containing a hydrophilic head (citric acid moiety) and a hydrophobic tail (non-polar alkyl chain). The putative composition of the carboxylates was assigned on grounds of elemental analysis, infrared (IR) and high-resolution mass spectra (HR-MS), as well as in analogy with known complexes containing the citrate moiety. The metal carboxylates showed interesting activity in several microbial strains, especially against S. aureus (vanadium complex; MIC = 0.05 mg/ml). They were also tested for their cytotoxic activity in hepatocytes, the highest activity having been found in the copper(II) and manganese(II) complexes. Further research based on these preliminary results is needed in order to evaluate the influence of parameters like stability of the metal complexes in solution on the bioactivity of the complexes. [ABSTRACT FROM AUTHOR]

Background: The present study describes the production of biosurfactant (BS) and emulsifier (BE) by the filamentous fungus Mucor hiemalis UCP 0039, as well as the characterization and stability of the both biomolecules for environmental or industrial applications. Results: Biosurfactants and bioemulsifiers are amphiphilic compounds and are produced as extracellular molecules. The results showed that bioproduct obtained by shaker condition reduced the water surface tension of 72 to 32 mN/m and reached an emulsification index of 96%, while the static cultivation resulted in a biomolecule with a surface tension of 40 mN/m and an emulsification index of 96%, suggesting the production of a biosurfactant and bioemulsifier, respectively. The compounds showed glycolipid nature but the biosurfactant presented cationic charge, while the bioemulsifier, anionic charge. Thus, the results confirmed thatM. hiemalis produced two distinct biomolecules under different parameters and in the same culturemedium. Conclusions: It is the first time that biosurfactant and emulsifier production has been described in the same medium and under different physical conditions by Mucor hiemalis. Both biomolecules showed thermal stability, as well as have significant effect on the viscosity of hydrophobic compounds, indicating the excellent potential for environmental safety or industrial applications to improve the efficiency of sustainable and economic technologies. [ABSTRACT FROM AUTHOR]

Amphiphilic compounds have the ability to alter the plant morphology which may improve the conventional process for isolating essential oil. In the present study, various hydrotropes, surfactants, ionic liquids, and sodium salt have been assessed in extracting essential oil from Cymbopogon winterianus grass using hydrodistillation. The highest yield (4.18%) of oil was attained using 5% NaCl solution without affecting the quality of oil. This approach has reduced the extraction time, which further reduced the utility consumption, power consumption, and carbon footprints. Moreover, incorporation of sonication has provided 4.08% yield in 15 min, thereby further improving the process. [ABSTRACT FROM AUTHOR]

The work presents the results of a study of the negative photochromism and luminescent properties of 1',3'-dihydro-3',3'-dimethyl-6-nitro-1'-octadecyl-[1-benzopyran-2,2'-indole]-8-methyl pyridinium chloride (SP2) in solutions, Langmuir monolayers, and cast films. It has been demonstrated that the introduction of the pyridine substituent into the chromene part of the amphiphilic spiropyran leads to stabilization of the open form of the compound under dark conditions, both in the dissolved and in the ordered planar state. The kinetic characteristics of photoreactions occurring in organic solvents upon irradiation by visible light and during relaxation in darkness are determined. Negative solvatochromism of SP2, which consists in the hypsochromic shift of the maximum absorption of the merocyanine form of the compound upon increase of the solvent polarity, is revealed. The luminescent properties of solutions of negative spiropyran and its cast films are investigated. For the first time, SP2 monolayers are formed at the air/water interface and their properties are studied. It is established that SP2 retains its photochromic properties upon transition from solutions to a two-dimensional condensed state. The results obtained open up broad prospects for the development of switchable optoelectronic and information systems based on negative spiropyrans. [ABSTRACT FROM AUTHOR]

Functional siloxane dimmers and polymers carrying two types of hydrophilic groups (tris-(hydroxymethyl)aminomethane and 4-aminopyridyne) were previously prepared and characterized. Their surface properties were investigated by tensiometry, DLS and TEM in water or organic media. The un-modified methylsiloxane units induce hydrophobic character while the balance between the two moieties with antagonist behavior is responsible for self-assembling and surface activity, which can be tuned by adjusting the proportion of hydrophilic groups and the molecular architecture. Water soluble self-assembling functionalized siloxanes have been tested for biocompatibility by MTT method. They are efficient for stabilization of polymer nanoparticles of interest for drug delivery systems, encapsulation of hydrophobic drugs by micellar solubilization, and water dispersion of magnetic nanoparticles of interest for biomedical applications. The same compounds exhibit the ability to act as ligands for complexation of 3d and 4f –block metals, with implications in environment remediation and preparation of metallosurfactants or catalysts. In addition, pyridyl-modified siloxanes act as phase transfer agents for water soluble organic molecules. The previously reported properties and applications are summarized, compared and completed with new experiments, in order to show a broad picture of the applicative potential of these amphiphilic compounds. [ABSTRACT FROM AUTHOR]

E-selectin, which is highly expressed in vascular endothelial cells near tumor and get involved in the all tumor growth steps: occurrence, proliferation and metastasis, is considered as a promise targeted protein for antitumor drug discovery. Herein, we would like to report the design, preparation and the anticancer evaluation of the peptide-PEG-podophyllotoxin conjugate(PEG-Pep-PODO), in which the short peptide (CIELLQAR) was used as the E-selectin ligand for the targeting purpose and the PEG portion the molecule got the conjugate self-assembled to form a water soluble nanoparticle. In vitro release study showed that the conjugated and entrapped PODO could be released simultaneously in the presence of GSH (highly expressed in tumor environmental conditions) and the GSH would catalyze the break of the disufur bond which linked of the PODO and the peptide-PEG portion of the conjugate. Cell adhesion test of the PEG-Pep-PODO indicated that E-selectin ligand peptide CIELLQAR could get specifically and efficiently binding to the E-selectin expressing human umbilical vein endothelial cells (HUVEC). In vitro cytotoxicity assay further revealed that PEG-Pep-PODO significantly improved the selectivity of PEG-Pep-PODO for killing the tumor cells and normal cells compared with PODO solution formulation. More importantly, the in vivo experiment demonstrated that the conjugate would accumulate of the PODO payload in tumor through targeting endothelial cells in the tumor microenvironment, which resulted in the much improved in vivo inhibition of tumor growth, intratumoral microvessel density, and decreased systemic toxicity of this nanoparticle over the free PODO. Furthermore, this water soluble conjugate greatly improved the pharmacokinetic properties of the mother molecule. [Display omitted] • Novel tumor targeting nanoparticle PEG-PEP-PODO and fluorescence probe conjugate PEG-Pep-ICG were designed and synthesized. • The water soluble PEG-PEP-PODO could maintain the PODO's potency and significantly reduce the side effect. • PEG-PEP-PODO exhibited much better tumor inhibitory potency, improved pharmacokinetic property and safety in vivo. • Distribution analysis with PEG-Pep-ICG demonstrated that CIELLQAR could orient tumor where E-selectin is overexpressed. [ABSTRACT FROM AUTHOR]

The Lacinutrix genus was discovered in 2005 and includes 12 Gram-negative bacterial species. To the best of our knowledge, the secondary metabolite production potential of this genus has not been explored before, and examination of Lacinutrix species may reveal novel chemistry. As part of a screening project of Arctic marine bacteria, the Lacinutrix sp. strain M09B143 was cultivated, extracted, fractionated and tested for antibacterial and cytotoxic activities. One fraction had antibacterial activity and was subjected to mass spectrometry analysis, which revealed two compounds with elemental composition that did not match any known compounds in databases. This resulted in the identification and isolation of two novel isobranched lyso-ornithine lipids, whose structures were elucidated by mass spectrometry and NMR spectroscopy. Lyso-ornithine lipids consist of a 3-hydroxy fatty acid linked to the alpha amino group of an ornithine amino acid through an amide bond. The fatty acid chains were determined to be iso-C15:0 (1) and iso-C16:0 (2). Compound 1 was active against the Gram-positive S. agalactiae, while 2 showed cytotoxic activity against A2058 human melanoma cells.

Amphiphilic calixarene derivatives with different lipophilicities and containing four 4,5-dicarboxytriazolyl fragments on the upper rim in a cone stereoisomeric form are obtained via azide-alkyne addition reaction. We showed that the amphiphilic macrocycles substituted with four octyl and tetradecyl groups on the lower rim form the monodisperse nanoaggregates in aqueous solutions. We found that the macrocycles possess fluorescence in the blue region. When concentration increases, there is a bathofloric shift of the emission maximum, which is due to aggregates. The resulting macrocycles were successfully used as a micellar medium for the Suzuki coupling reaction to show quantitative yields of iodine and bromoarenes in aqueous medium at room temperature. [ABSTRACT FROM AUTHOR]

Abstract A new analytical method exploiting supramolecular solvent-based microextraction (SUPRAS) combined with ultrasound-assisted extraction to preconcentrate cadmium from medicinal plant, with further determination by thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS), is proposed. The proposed method is based on the cadmium ultrasound-assisted extraction from Ginkgo biloba L. leaf samples with diluted acid (0.10 mol L−1 HNO 3), followed by the metal complexation with diethyl dithiophosphate and preconcentration using a supramolecular solvent composed of inverted hexagonal aggregates of dodecanoic acid arranged in tetrahydrofuran/water medium. The limits of detection (LOD) and quantification (LOQ) were found to be 0.11 μg L−1 and 0.36 μg L−1, respectively. Intraday and interday precision assessed in terms of relative standard deviations (RSD, %) were lower than 8.50% to 0.70, 1.75 and 5.00 μg L−1 cadmium solutions. The efficiency of ultrasound-assisted extraction was comparable to microwave-assisted digestion and the method accuracy was checked by analysis of certified reference material (Tomato Leaves, SRM 1573a). Samples of Ginkgo biloba L. were analyzed and cadmium contents between 0.21 and 0.33 μg g−1 were found, thereby showing clearly the importance of investigating toxic metals in medicinal plants. The proposed method is simple, highly sensitive, environmentally friendly and has great potential to be applied in the quality control of medicinal plants aiming trace cadmium determination. Highlights • Easy and low cost combination of ultrasound-assisted extraction and SUPRAS for Cd2+ determination in herbal medicine • Similar results of ultrasound-assisted extraction and microwave digestion • The limit of detection of method was found to be 0.11 μg L−1. [ABSTRACT FROM AUTHOR]

The results of a study of the photochromic properties of 1´-hexadecyl-3´,3´-dimethyl-6-nitro-1´,3´-dihydrospiro[chromene-2,2´-indole] (SP) are presented. The kinetic characteristics of photophysical processes occurring in acetonitrile solution of SP upon irradiation with UV light and during dark relaxation are determined. It is shown that spiropyran modified at the nitrogen atom by a long-chain hydrocarbon radical exhibits photochromic properties in the dissolved state, with the rate of the direct photocoloration exceeding the rate of dark relaxation by an order of magnitude. Comparative studies of SP photoreaction in dissolved and 2D states are carried out. The obtained results open up broad prospects for application of such photochromes in thin-film devices obtained using the Langmuir monolayer technique. [ABSTRACT FROM AUTHOR]

Organoselenium compounds are well-known glutathione peroxidase (GPx) mimetics that possess antioxidants/prooxidant properties and are able to modulate the concentration of reactive oxygen species (ROS), preventing oxidative stress in normal cells or inducing ROS formation in cancer cells leading to apoptosis. The purpose of this study was the synthesis of potent GPx mimics with antioxidant and anticancer activity along with improved bioavailability, as a result of good solubility in protic solvents. As a result of our research, glutathione peroxidase (GPx) mimetics in the form of water-soluble benzeneseleninic acid salts were obtained. The procedure was based on the synthesis of 2-(N-alkylcarboxyamido)benzeneselenenic acids, through the oxidation of benzisoselenazol-3(2H)-ones or analogous arenediselenides with an amido group, which were further converted to corresponding potassium salts by the treatment with potassium tert-butanolate. All derivatives were tested as potential antioxidants and anticancer agents. The areneseleninic acid salts were significantly better peroxide scavengers than analogous acids and the well-known organoselenium antioxidant ebselen. The highest activity was observed for the 2-(N-ethylcarboxyamido)benzeneselenenic acid potassium salt. The strongest cytotoxic effect against breast cancer (MCF-7) and human promyelocytic leukemia (HL-60) cell lines was found for 2-(N-cyclohexylcarboxyamido)benzeneselenenic acid potassium salt and the 2-(N-ethylcarboxyamido)benzeneselenenic acid, respectively. The structure−activity correlations, including the differences in reactivity of benzeneseleninic acids and corresponding salts were evaluated.

Abstract: Many biologically important compounds are amphiphilic in character. Glycolipids, for example, represent a biologically important class of amphiphiles. Receptors and sensors for such compounds must also be amphiphilic making them a challenge to prepare. Here, a cucurbit[8]uril (CB[8])‐based sensor system has been prepared and tested for detection of amphiphilic compounds. This multi‐component system consists: a CB[8], which acts as a hydrophobic lipid receptor, a hydrophilic pyridinium‐based carbohydrate receptor, and a fluorescent indicator. The system self‐assembles in aqueous solution. The pyridinium quenches the fluorescence of the indicator giving a strong turn‐on response when it is displaced by the analyte. The sensor system was characterized by NMR, X‐ray crystallography, and fluorescence titrations. [ABSTRACT FROM AUTHOR]

[Display omitted] • Esters of palmitic acid with L(+) arabinose have been synthesized. • The synthesis is catalysed by a lipase, therefore environmentally friendly. • Only the primary hydroxyl group is esterified. • Both reagents are from renewable source. The direct esterification of palmitic acid with l -(+)-arabinose has been carried out. The use of Candida antartica lipase B as the catalyst and the choice of suitable solvent and experimental conditions allowed carrying out the reaction successfully. In particular 10% dimethyl-sulfoxide in tert -butanol was found to be the optimal solvent. The product has been fully characterized by means of FTIR, ESI-MS, DSC, mono and bidimensional 1H and 13C NMR. These techniques confirm that only the primary alcoholic group was involved in the esterification reaction. [ABSTRACT FROM AUTHOR]

[Display omitted] For cystic fibrosis gene therapy, the aerosolization of genetic materials is the most relevant delivery strategy to reach the airway epithelium. However, aerosolized formulations have to resist shear forces while maintaining the integrity of plasmid DNA (pDNA) during its journey from the nebulization to the epithelial cells. Herein, we compared the efficiency of gene delivery by aerosolization of two types of formulations: (i) BSV163, a branched cationic amphiphilic compound, co-formulated with different DOPE ratios (mol/mol) and DMPE-PEG5000 and (ii) 25 KDa branched polyethylenimine (b-PEI)-based formulation used as control. This study also aims to determine whether BSV163-based formulations possess the ability to resist the nebulization mechanisms and protect the nucleic acids (pDNA) cargo. Therefore, two CpG free plasmids (pGM144 or pGM169) encoding either the luciferase reporter gene or hCFTR respectively were used. Air-Liquid Interface (ALI) cell-culture was selected as an in-vitro model for aerosol experiments due to its closer analogy with in vivo morphology. Results highlighted that DOPE ratio influences the capacity of the BSV163 based-formulations to mediate high transfection efficacies. Furthermore, we proved that addition of DMPE-PEG5000 upon the formation of the BSV163/DOPE (1/1) lipid film instead of post-insertion led to a higher transgene expression. The aerosolization of this formulation on ALI cell-culture was more efficient than the use of b-PEI-based formulation. [ABSTRACT FROM AUTHOR]

A part of the importance of fats and oils derives from the functional properties that they confer to the foods. This is a consequence of their chemical nature and structural features. Lipids are relatively insoluble in water because their large non-polar region. However, they also contain groups with some degree of polarity. The combination of these polar and non-polar groups and their variations is what gives the range of functional properties observed and what made them so valuable. This issue of Grasas y Aceites reviews some of the functional properties of fats and oils. The Editors hope that the studies included will provide an state of the art reference volume of present knowledge and applications in these areas.

The microenvironment formed by surface active compounds is being recognized as the active site of lipid oxidation. Trace amounts of water occupy the core of micro micelles and several amphiphilic minor components (e.g., phospholipids, monoacylglycerols, free fatty acids, etc.) act as surfactants and affect lipid oxidation in a complex fashion dependent on the structure and stability of the microemulsions in a continuous lipid phase such as bulk oil. The structures of the triacylglycerols and other lipid-soluble molecules affect their organization and play important roles during the course of the oxidation reactions. Antioxidant head groups, variably located near the water-oil colloidal interfaces, trap and scavenge radicals according to their location and concentration. According to this scenario, antioxidants inhibit lipid oxidation not only by scavenging radicals via hydrogen donation but also by physically stabilizing the micelles at the microenvironments of the reaction sites. There is a cut-off effect (optimum value) governing the inhibitory effects of antioxidants depending inter alias on their hydrophilic/lipophilic balance and their concentrations. These complex effects, previously considered as paradoxes in antioxidants research, are now better explained by the supramolecular chemistry of lipid oxidation and antioxidants, which is discussed in this review. The evolution of micellar size and number during and after the induction period of lipid oxidation. Amphiphilic compounds, including lipid hydroperoxides, contribute to micelle formation and act as prooxidants. Antioxidants and retarders stabilize micelles and prevent their breakdown. [ABSTRACT FROM AUTHOR]

Amphiphilic pillar[5]arene-containing [2]rotaxanes have been prepared and fully characterized. In the particular case of the [2]rotaxane incorporating a 1,4-diethoxypillar[5]arene subunit, the structure of the compound was confirmed by X-ray crystal structure analysis. Owing to a good hydrophilic/hydrophobic balance, stable Langmuir films have been obtained for these rotaxanes and the size of the peripheral alkyl chains on the pillar[5]arene subunit has a dramatic influence on the reversibility during compression-decompression cycles. Indeed, when these are small enough, molecular reorganization of the rotaxane by gliding motions are capable of preventing strong π-π interactions between neighboring macrocycles in the thin film. [ABSTRACT FROM AUTHOR]

We report herein the synthesis of a novel family of cationic lipids, characterized by a trimethylammonium headgroup linked through a phosphate function to either two identical or two different lipid chains. The novelty of this study arises from the use of a trialkyl phosphate group to associate the hydrophobic domain to the cationic polar head. The structure of these new cationic lipids, which differs from that of previously reported lipophosphoramidates, is closer to the phospholipids encountered in the plasma membrane, and possesses a phosphocholine polar head. Evaluation of the transfection activity allowed us to compare the efficacy of cationic lipophosphates with that of lipophosphoramidates. These results demonstrate that cationic lipophosphates and lipophosphoramidates having otherwise identical chemical structures exhibit similar transfection efficacies. The second conclusion is that the structure of the lipid domain is a much more important parameter in governing transfection efficacy than the composition of the linker moiety. The best results were obtained with cationic lipophosphates or lipophosphoramidates possessing two different lipid chains, for example one oleyl chain with one phytanyl chain. These nonsymmetric cationic lipids exhibited transfection efficacies that were 10- to 200-fold better than those obtained with Lipofectamine used as a commercial standard. [ABSTRACT FROM AUTHOR]

Abstract: A simple method for estimation of the 2D spontaneous clusterization temperature of substituted alkanes at the air/water interface versus alkyl chain length is proposed using the quantum chemical semiempirical PM3 method. The method is approved by long-chain amines, alcohols, thioalcohols, saturated and unsaturated carboxylic acids, α-amino acids and amides of carboxylic acids. The method is based on the experimental fact that short chain amphiphilic molecules cannot form condensed 2D monolayers whereas above a specific alkyl chain length condensed monolayer phases can be observed under the same conditions. That is, elongation of the alkyl chain of amphiphilic molecules causes the increase of intermolecular interaction energy between them what stimulates their close packing and structuring. This leads to linear or stepwise dependencies of enthalpy and entropy of cluster formation on the alkyl chain length. It is possible to obtain an equation for the estimation of the temperature of the spontaneous clusterization threshold of the considered substituted alkane types by setting Gibbs’ energy equal to zero and by knowing the regression expressions for determination of enthalpy and entropy of cluster formation calculated under the condition of 298K using coefficients which determine the contribution of the hydrophilic head group interactions of molecules and CH⋯HC-interactions between the alkyl chains. It is shown that the temperature dependence of the spontaneous clusterization threshold on the alkyl chain length of the amphiphile is fractionally linear with a relative error of 3–8%. The effect of the alkyl chain elongation of substituted alkanes by two methylene units corresponds to subphase temperature reduction (ΔТ) by 10–20K in good agreement with the available experimental data. The difference between ΔТ values for considered types of amphiphilic compounds becomes less significant with the lengthening of the alkyl chain. This indicates the basic contribution of intermolecular CH⋯HC-interactions between the alkyl chains to the process of the 2D clusterization. [Copyright &y& Elsevier]

Abstract: New amphiphilic cyclodextrins are synthesized by selective modification. Two synthetic strategies are investigated. Per-(6-thio-2,3-trimethylsilyl)cyclodextrins can only be obtain by synthesizing first the per-6-thio-cyclodextrin and then silylating the remaining hydroxy functions. Characterizations of the products were achieved by ESI-MS and intramolecular coupling between thiol functions was evidenced. These new compounds are shown to be amphiphilic, and form stable Langmuir–Blodgett films that can be transferred on the upstroke and the downstroke of a substrate with a transfer ratio close to unity. [Copyright &y& Elsevier]

Abstract: This work reports on the synthesis and characterization of the ligand 3-hexadecylpentane-2,4-dione (Hhdacac) and its Eu3+ complexes Eu(hdacac)6·2H2O, Eu(hdacac)6·phen and Eu(hdacac)6·tta, where phen and tta denote 1,10-phenanthroline and thenoyltrifluoroacetone, respectively. These new compounds present long carbon chains and their expected miscibility into non-polar ambients is confirmed by the emission spectra of Eu(hdacac)6·tta in hexane. Moreover, the amphiphilic properties of Eu(hdacac)6 complexes allow the obtainment of thin luminescent films by the Langmuir–Blodgett technique. In both cases (solids and films), the typical antenna effect of β-diketonates is observed. The alluring characteristics of these compounds raise great interest in many fields of Materials Science, like photo- and electro-luminescent materials (mainly thin “organic” films), metal catalysts or probes in non-polar solutions, and Langmuir–Blodgett films of several compositions. For the characterization of these products, nuclear magnetic resonance spectroscopy (1H NMR), thermogravimetric analysis, elementary analyses (C, H), scanning electron microscopy (energy dispersive X-ray spectroscopy), absorption (UV–vis/FT–IR) and photoluminescence spectroscopies were used. [Copyright &y& Elsevier]

Abstract: Changes in the cell surface hydrophobicity (CSH) of bacteria Zymomonas mobilis 113S were examined in response to varied environmental conditions (temperature and phase of growth, concentration or type of carbon source, the presence of amphiphilic compounds). The values of CSH were elevated with a decreased growth rate over the time of cultivation up to 20–22% at the stationary phase. CSH values increased proportionally with the growth of cultivation temperature and concentration of carbon source (glucose or sucrose) or amphiphilic compound (aliphatic alcohols, Tween80) in the medium. Replacement of sucrose by glucose and the presence of Tween20 in the growth medium resulted in reduced values of CSH. An inverse relationship was detected between the number of attached cells to the hydrophilic glass surfaces and the CSH values of Z. mobilis whereas direct linear relationship was observed for hydrophobic surfaces. Permeation rates of the fluorescent probe (NPN) into the cells were directly proportional to the concentration of extracellular protein in the medium and to the values of CSH indicating the impaired barrier function for more hydrophobic cells. The multiple correlation between the CSH values and absorption indices of FT-IR spectra at the fingerprint region (866–1088cm−1) suggests the possible contribution of carbohydrates and/or lipopolysaccharides in observed changes of Z. mobilis hydrophobicity. [Copyright &y& Elsevier]

The amphiphilic calix[4]resorcinolarenes, aminomethylated calix[4]resorcinolarenes, o-aminomethylphenols, and their quaternary derivatives in water—dimethylformamide media (10—75 vol.% DMF) form aggregates, which catalyze the hydrolysis of phosphonous esters. The ability to self-association and the catalytic activity of the aggregates depend on the hydrophobicity of the amphiphilic compound, the pH of solution, and the content of DMF. [ABSTRACT FROM AUTHOR]

The Lacinutrix genus was discovered in 2005 and includes 12 Gram-negative bacterial species. To the best of our knowledge, the secondary metabolite production potential of this genus has not been explored before, and examination of Lacinutrix species may reveal novel chemistry. As part of a screening project of Arctic marine bacteria, the Lacinutrix sp. strain M09B143 was cultivated, extracted, fractionated and tested for antibacterial and cytotoxic activities. One fraction had antibacterial activity and was subjected to mass spectrometry analysis, which revealed two compounds with elemental composition that did not match any known compounds in databases. This resulted in the identification and isolation of two novel isobranched lyso-ornithine lipids, whose structures were elucidated by mass spectrometry and NMR spectroscopy. Lyso-ornithine lipids consist of a 3-hydroxy fatty acid linked to the alpha amino group of an ornithine amino acid through an amide bond. The fatty acid chains were determined to be iso-C15:0 (1) and iso-C16:0 (2). Compound 1 was active against the Gram-positive S. agalactiae, while 2 showed cytotoxic activity against A2058 human melanoma cells. [ABSTRACT FROM AUTHOR]

Since the discovery of aggregation induced emission (AIE) phenomenon, various stimuli-responsive materials have been rapidly developed. However, the development of self-assembled amphiphilic light-responsive materials in aqueous solution needs to be solved urgently. In this work, three new amphiphilic tetraphenylethylene (TPE) derivatives (TPE-1 , TPE-2 and TPE-3) with AIE properties and photochromism were synthesized and investigated. Owing to the different electron-donating abilities of the three groups attached to TPE units, the TPE-1 , TPE-2 and TPE-3 displayed blue-green, yellow-green, and orange fluorescence emission in the aggregation state respectively. Furthermore, ordered nanoparticles formed via self-assembly in aqueous solution showed interesting photocyclization behaviors, which lead to fluorescence quenching under ultraviolet light irradiation (λ = 365 nm). Therefore, the compounds can be used as anti-counterfeiting ink in the information encryption due to their amphiphilicity and photo-responsiveness. This work contributes new members to the amphiphilic light-responsive materials family and demonstrates the potential for applications in the fields of optical information storage, information security protection, and erase/rewrite systems. [Display omitted] • Three tetraphenylethylene derivatives with AIE properties and photochromism were synthesized and investigated. • The designed compounds displayed different fluorescence emission in the aggregation state. • The ordered nanoparticles formed via self-assembly in aqueous solution showed interesting photocyclization behaviors. • The compounds were successfully used as anti-counterfeiting ink in the information encryption. [ABSTRACT FROM AUTHOR]

New monodisperse nonionic surfactant molecules, based on lysine with two fatty acid chains in the hydrophobic part and one or two polyoxyethylene methoxycapped chains (EO−Me) in the hydrophilic headgroup, are synthesized as mimics of natural lecithins. Their surface-activity properties indicate that these compounds have surfactant behavior whose global hydrophobic contribution is comparable to that of one fatty chain. [ABSTRACT FROM AUTHOR]

Four new amphiphilic long chain amidoamine derivatives displaying different structure variations are synthesized and tested in 27 liquids and compared to the study of two similar molecules already reported in the literature. In many cases, these compounds can act as low molecular weight gelators to form a three-dimensional network in organic liquids or water, which can be confirmed by FE-SEM observations and rheology measurements. For each sample, XRD diffraction of the corresponding xerogel and FT-IR analysis of native supramolecular gels reveal that they can self-assemble into lamellar-like aggregates or in pseudo-cubic structures, depending on the alkyl chain length and the steric hindrance of the polar head. The number of amide bonds and their positions inside gelator structures are determinant for the nature of the packing. For each gelator, we perform a series of gelation tests in each of the solvents and show that Hansen parameters, which are known characteristics of each liquid, can be used to successfully predict their gelation properties via machine learning in the vast majority of liquids at a concentration of 4 wt%. Unlabelled Image • Six different amphiphilic amidoamines were tested in 28 liquids for their gelation abilities. • These compounds could assemble into pseudo-cubic or lamellar-like structures. • The phenomena were dependent on both their alkyl chain length and polar head nature. • A machine learning study was also efficient to predict gelation of various liquids. [ABSTRACT FROM AUTHOR]

Small Conductance Calcium (Ca2+)-activated potassium (K+) channels (SKCa) are now proved to be involved in many cancer cell behaviors such as proliferation or migration. The SK3 channel isoform was particularly described in breast cancer where it can be associated with the Orai1 Ca2+ channel to form a complex that regulates the Ca2+ homeostasis during tumor development and acts as a potent mediator of bone metastases development in vivo. Until now, very few specific blockers of Orai1 and/or SK3 have been developed as potential anti-metastatic compounds. In this study, we illustrated the synthesis of new families of lipophilic pyridine and tetrahydropyridine derivatives designed as potential modulators of SK3 channel. The toxicity of the newly synthesized compounds and their migration effects were evaluated on the breast cancer cell line MDA-MB-435s. Two molecules (7a and 10c) demonstrated a significant decrease in the SK3 channel-dependent migration as well as the SK3/Orai1-related Ca2+ entry. Current measurements showed that these compounds are more likely SK3-selective. Taken all together these results suggest that such molecules could be considered as promising anti-metastatic drugs in breast cancer. Image 1 [ABSTRACT FROM AUTHOR]