Multi-responsive organo- and hydrogelation based on the supramolecular assembly of fluorocarbon- and hydrocarbon-containing hybrid surfactants.

HYPOTHESIS: Novel photoresponsive hybrid surfactants, in which a combination of perfluoroalkyl and alkyl chains and cationic head groups are connected via azobenzene moieties, are excellent candidates for assembling low-molecular-weight organogels (LMOGs) with reversibly switchable viscoelasticities triggered by external stimuli. EXPERIMENTS: The structure-composition-property relationships of gels assembled with the hybrid surfactants were investigated by UV-vis and NMR spectroscopy, SEM, XRD, and rheology. FINDINGS: Hybrid surfactants containing perfluorohexyl chains with more than six carbons gelled in a variety of organic solvents at concentrations of less than a few percent. In particular, compositions with the perfluorooctyl and somewhat shorter hydrocarbon chains (C1-C4) gelled in both organic solvents and water. The gellable solvent species can be well grouped according to their solubility parameters, suggesting that gelation properties can be predicted from the chemical structure of the surfactant. Mechanical and structural investigations revealed that gel viscoelasticity can be reversibly altered by applying photo, shear, and heat stimuli, which is achieved through the formation and deformation of lamella-like molecular aggregates. The multi-responsive gelation and facile molecular design of the present hybrid surfactants will expand the fields in which fluorinated LMOGs can be applied.

Synthesis and surface activity of photoresponsive hybrid surfactants containing both fluorocarbon and hydrocarbon chains.

HYPOTHESIS: Hybrid surfactants containing both alkyl and fluoroalkyl chains within the same molecule where modification of the azobenzene group will enable us to switch the superhydrophobic nature with an external light source, and the optical behavior will vary depending on the structure of the hydrophobic chains. EXPERIMENTS: Surface activity and its optically-induced variation of the azobenzene-modified hybrid surfactants were characterized using the surface tensiometry, UV-vis and NMR spectroscopy and theoretical calculation. FINDINGS: The hybrid surfactants are superhydrophobic in nature reducing the surface tension of water to near 20 mN/m. Photo-isomerization of the azobenzene group induces a drastic surface tension variation (Δγ), and particularly the compositions containing the octyl-fluorocarbon chain exhibit remarkable Δγ as much as 30 mN/m which is even higher than that of the conventional surfactants (Δγ ≈ 14-20 mN/m). Theoretical calculation suggests significantly higher hydrophilicity of the cis isomer, causing the drastic switch in the surface activity. These results indicate the promise of the hybrid surfactants as efficient surface/interface manipulators.

Screening and isolation of the liamocin-producing yeast Aureobasidium melanogenum using xylose as the sole carbon source.

Xylose, the main component of xylan, is the second most abundant sugar in nature after glucose. Consequently, xylose represents an attractive feedstock for the production of value-added compounds such as biosurfactants (BSs), which are produced by various bacteria and yeasts. In this study, we screened and isolated yeast strains that synthesize BSs using xylose as the sole carbon source. We applied matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to screen for BS-producing yeasts and isolated eight strains as the liamocin producers. Two of the eight strains, AS37 and SK25, were identified as Aureobasidium melanogenum, which is known as black yeasts, by based on 26S ribosomal RNA gene sequences. Both strains produced a wide variety of liamocin structures from not only xylose but also glucose and sucrose. According to the MALDI-TOF MS analysis, signals corresponding to sodium ion adducts of di-, tri-, tetra-, penta- and hexa-acylated C6-liamocins and di-, tri- and tetra-acylated C5-liamocins were detected. In addition, their mono-acetylated form was also detected. The dominant sugar component of liamocins produced by strains AS37 and SK25 is mannitol as estimated by HPLC analysis. This is the first report to describe the screening of liamocins-producing yeasts using xylose as the sole carbon source.

Reversible Destabilization of UV-Responsive Polymer Particles (Latex) using a Photoresponsive Surfactant.

Production of aqueous dispersions of polymeric nanoparticles via heterogeneous radical polymerization in emulsion-type systems is of enormous commercial importance. The ability to reversibly destabilize such a latex is highly desirable, for example, to save transportation costs. Herein, a method for synthesis of photo-responsive polymer latexes that can be destabilized (leading to sedimentation) by only using UV irradiation (no addition of chemicals or change in the experimental conditions) and subsequently redispersed by stirring under visible light irradiation is described. The destabilization/redispersion mechanism relies on photoinduced trans-cis isomerization of the cationic diazene surfactant 2-(4-(4-butylphenyl)diazenylphenoxy)ethyltrimethylammonium bromide (C4AzoTAB) used in conjunction with the anionic surfactant sodium dodecyl sulfate. It is demonstrated that reversible destabilization can be achieved very rapidly (90 s residence time) employing continuous flow technology.

Synthesis and Characterization of a Novel Glycolipid with Glucosylglycerate as a Hydrophile Showing Protective Effects on Heat-induced Protein Denaturation.

A novel glycolipid featuring a glucosylglycerate moiety as a polar head group was synthesized in two steps from sucrose, glycerate, and N-dodecylamine. Glucosylglyceric acid was formed from sucrose and glyceric acid using sucrose synthase as a catalyst, followed by condensation with N-dodecylamine using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) as a condensing agent. A white solid compound was recovered with a yield of 21% after purification by hydrophobic column chromatography. The structure and purity of the isolated compound, identified as N-dodecyl glucosylglyceric acid amide (aGGA), were confirmed by 1H and 13C nuclear magnetic resonance and liquid chromatography-electrospray ionization-mass spectrometry. aGGA was soluble in several polar solvents, including acetone, dimethyl formamide, and short chain alcohols. The dissolution of aGGA in water reduced the surface tension to 27.8 mN m-1 at a critical micellar concentration of 1.57 × 10-4 M. In addition, the presence of aGGA at concentrations as low at 0.68 mM protected egg white from heat-induced denaturation. These results suggest that aGGA could be useful as a protein-protecting surfactant.

Boosting Effect of Amphiphilic Random Copolymers for Bicontinuous Phases.

Amphiphilic random copolymers, poly(oxyethylene)/poly(oxypropylene) butyl ethers (C4EmPn), have been used as raw materials for cosmetics. This paper reports on the influence of amphiphilic random copolymers on mixtures of n-decane, water, and a nonionic surfactant, hexa(oxyethylene) dodecyl ether (C12E6). Bicontinuous phases are formed from decane/water/C12E6 mixtures at high C12E6 weight fractions (> 70 wt%). Adding C4EmPn to decane/water/C12E6 mixtures brings about the formation of bicontinuous phases and a decrease in the amount of the surfactant required for their formation, indicating efficiency boosting. The bicontinuous phase formation region in the phase diagram of the decane/water/C12E6+C4E5P5 system is largest at a specific C4E5P5 weight fraction in the C12E6/C4E5P5 mixture. When a hydrophobic polymer, in which the poly(ethylene oxide) group in C4EmPn is absent, is added to decane/water/C12E6 mixtures, no efficiency boosting is observed. These results suggest that the adjustment of the hydrophilicity-hydrophobicity balance of C12E6/C4EmPn mixture causes the efficiency boosting.

Preparation of Hollow Polystyrene Particles and Microcapsules by Radical Polymerization of Janus Droplets Consisting of Hydrocarbon and Fluorocarbon Oils.

In this article, we have demonstrated a method for producing hollow particles and microcapsules using oil droplets consisting of hydrocarbon oil (styrene) and fluorocarbon oil (perfluoro-n-octane, PFO) in aqueous surfactant (sodium dodecylsulfate, SDS) solutions. Since fluorocarbon oils are immiscible with hydrocarbon oils, the two oils are separated. Emulsions are prepared by stirring styrene/PFO/aqueous SDS solution mixtures at 80 °C. The type of emulsions and the morphology of droplets in the emulsions are observed by light microscope and scanning confocal fluorescence microscope. It is found that oil droplets with Janus-type morphologies consisting of mutually immiscible styrene and PFO are formed in aqueous SDS solutions. Polystyrene particles are fabricated by radical polymerization of the ternary mixtures of styrene/PFO/aqueous SDS solution at 80 °C. The morphologies of the polystyrene are confirmed by scanning electron microscopy and scanning transmission electron microscopy observations. These observations show the preparation of hollow polystyrene particles with a single hole on the surface. To our knowledge, this method is a novel strategy using the immiscibility of hydrocarbon and fluorocarbon oils. The hollow particles can also be applied to the preparation of microcapsules.

Demulsification of Redox-Active Emulsions by Chemical Oxidation.

This article reports the influence of redox reactions on emulsions of n-octane and an aqueous solution of a ferrocene-containing surfactant (FTMA; (11-ferrocenylundecyl)trimethylammonium bromide). Above a certain surfactant concentration, stable O/W emulsions were formed from an aqueous solution of reduced FTMA; in contrast, mixtures of n-octane and an aqueous solution of oxidized FTMA did not form emulsions at any surfactant concentration. Furthermore, adding an oxidant to the stable O/W emulsions of reduced FTMA led to coalescence of the oil (octane) droplets in the emulsions, and subsequently, the oil and water (aqueous FTMA solution) phases fully separated from the emulsions, i.e., demulsification occurred. Equilibrated interfacial tension measurements indicate that oxidation of the ferrocenyl group in FTMA brings about an increase in the interfacial tension between the octane and aqueous surfactant solution phases. From these results, we concluded that the oxidation of reduced FTMA to oxidized FTMA led to the desorption of surfactant molecules adsorbed at the interface of the octane/aqueous surfactant solution, leading to demulsification.

Photoinduced formation of threadlike micelles from mixtures of a cationic surfactant and a stilbene amphiphile.

This study examined the influence of ultraviolet (UV) irradiation on aqueous surfactant solutions containing an anionic stilbene derivative (sodium [4-[(E)-2-(4-butylphenyl)ethenyl]phenoxy]acetate; C4StilNa) as a photoresponsive skeleton. Prior to UV irradiation, an aqueous solution of cetyltrimethylammonium bromide (CTAB) and C4StilNa was a low-viscosity fluid forming spheroidal micelles. Exposure of the low-viscosity fluid to UV light resulted in the formation of threadlike micelles and an increase in the viscosity of the aqueous CTAB/C4StilNa solution. (1)H nuclear magnetic resonance spectroscopy indicated that the photochemically induced isomerization and dimerization reactions of C4StilNa molecules had occurred in the aggregates due to UV irradiation. Overall, the structural transformation of the stilbene groups in the C4StilNa molecules with the photochemical reactions leads to an increase in the critical packing parameter and consequently a photoinduced transition of spheroidal micelles to threadlike micelles.

Synthesis and Characterization of Dioctanoyl Glycerate as Water-soluble Trypsin Inhibitor.

Glyceric acids (GAs) esterified with long acyl chains (> C16) exhibit antitrypsin activity (Folia Microbiol. 46, 21-23 (2001)). However, their hydrophobic nature, derived from the long acyl chains, has limited the number of studies on their physical and biological properties. To improve the water solubility of diacyl GAs, GA was esterified with octanoyl groups (C8), and its physical properties were investigated. Synthesized dioctanoyl GA was not water-soluble, whereas its sodium salt was. Surface tension measurements of dioctanoyl GA sodium salt (diC8GA-Na) in water revealed that the critical micelle concentration (CMC) was 0.82 mM, and surface tension at the CMC was 25.5 mN/m. Additionally, diC8GA-Na inhibited casein digestion by trypsin to a greater extent than dioleoyl GA. These data suggest that water-soluble diacyl GAs may have utility as surfactants and bioactive compounds.

Active Demulsification of Photoresponsive Emulsions Using Cationic-Anionic Surfactant Mixtures.

The influence of ultraviolet (UV) light irradiation on the emulsification properties of mixtures of an anionic surfactant, sodium dodecyl sulfate (SDS), and a photoresponsive cationic surfactant, 2-(4-(4-butylphenyl)diazenylphenoxy)ethyltrimethylammonium bromide (C4AzoTAB), containing an azobenzene group has been investigated. When mixtures of n-octane and aqueous SDS/trans-C4AzoTAB solution are homogenized, stable emulsions are obtained in regions of specific surfactant concentrations and molar ratios of the mixed surfactants. The stable emulsions are stable for over a week and found to be of the oil-in-water (O/W) type. UV light irradiation of the stable O/W emulsions leads to the coalescence of smaller oil droplets into larger ones in the emulsions, i.e., demulsification. As a result, the oil and aqueous surfactant solution phases are fully separated by UV light irradiation for 90 min, even shorter than our previous result (6 h; Langmuir 2014 , 30 , 41 - 47 ). The use of a microreactor shortens the time required for the photoinduced demulsification into 3.5 min. When mixtures of octane and aqueous SDS/cis-C4AzoTAB solution are homogenized, no emulsions are obtained. The interfacial tension (IFT) between octane and aqueous SDS/cis-C4AzoTAB solution is higher than that between octane and aqueous SDS/trans-C4AzoTAB solution, indicating that the IFT of SDS/trans-C4AzoTAB mixtures increases with the cis photoisomerization of the trans isomer. These results suggest that cis isomerization of the SDS/trans-C4AzoTAB mixtures due to UV light irradiation causes Ostwald ripening of the octane droplets in the emulsions, thereby reducing the interfacial area between the octane and water phases as the IFT between octane and the aqueous surfactant solution increases. Subsequently, the octane and aqueous solution phases separate.

Influence of the Phase State of Self-Assembling Redox Mediators on their Electrochemical Activity.

Self-assembling redox mediators have the potential to be broadly useful in a range of interfacial electrochemical contexts because the oxidation state and state of assembly of the mediator are closely coupled. In this paper, we report an investigation of the self-assembly of single- and double-tailed ferrocenyl amphiphiles (FTMA and BFDMA, respectively) at the surfaces of Pt electrodes and the impact of the dynamic assembled state of the amphiphiles on their rate of oxidation. We conclude that frozen aggregates of BFDMA adsorb to the surfaces of the Pt electrodes, and that slow dynamics of reorganization BFDMA within these aggregates limits the rate of electrooxidation of BFDMA. In contrast, FTMA, while forming assemblies on the surfaces of Pt electrodes, is characterized by fast reorganization dynamics and a corresponding rate of oxidation that is an order of magnitude greater than BFDMA.

Gold-colored organic crystals of an azobenzene derivative.

A new azobenzene derivative, bis[4-(3-methylbutoxy)phenyl]diazene (DC-azo), was synthesized as yellow powder through a three-step reaction. DC-azo was crystallized from a mixture of acetone/water in the form of highly insulating gold-colored crystals with a specular reflectance of 21% over the wavelength range of 520-800 nm. The CIELAB color space of the crystals indicated that the crystals were slightly more reddish and less yellowish than metallic Au. The crystals retained their gold coloration under dry conditions and were stable up to 383 K. The X-ray diffraction (XRD) measurements estimated the long-range periodical thickness in the crystal to be 1.12 nm, thereby indicating that the DC-azo molecules were oriented such that the azobenzene moieties showed a tilt angle of 32.2° against the crystal surface. The gold-colored crystals of DC-azo could be a potential substitute for the conventional metallic paints.

Control of dual stimuli-responsive vesicle formation in aqueous solutions of single-tailed ferrocenyl surfactant by varying pH and redox conditions.

This paper reports a method to control the formation and disruption of vesicles from a novel single-tailed surfactant (11-ferrocenylundecylammonium bromide, 11-FAB), which contains two stimuli-responsive groups corresponding to pH variation and redox reaction conditions, by external stimuli. Although 11-FAB is a single-tailed surfactant, pure 11-FAB spontaneously forms vesicles in water. Microscopic observations of 2.5 mM aqueous solutions of pure 11-FAB (pH = 5.2) show that a number of 11-FAB vesicles are giant, with diameters of 10-30 µm. The disruption of vesicles is observed in aqueous 11-FAB solutions under basic conditions. The vesicles are then reformed under acidic conditions. Reduced 11-FAB also forms large vesicles in electrolyte solutions. These vesicles are disrupted by electrochemical oxidation and reformed by subsequent chemical reduction. This reversible disruption and reformation of vesicles is attributed to the drastic change in the molecular structure of 11-FAB. To our knowledge, this is the first report of control over the formation and disruption of vesicles using two stimuli responses.

Photoinduced demulsification of emulsions using a photoresponsive gemini surfactant.

This Article reports on the influence of light irradiation on the stability of emulsions prepared using a photoresponsive gemini surfactant (C7-azo-C7) having an azobenzene skeleton as a spacer. When mixtures of trans C7-azo-C7 aqueous solution and n-octane are homogenized, stable emulsions are obtained in a specific region of weight fraction and surfactant concentration. Fluorescence microscopy observations using a small amount of fluorescent probes show that the stable emulsions are oil-in-water (O/W)-type. UV irradiation of stable O/W emulsions promotes the cis isomerization of trans C7-azo-C7 and leads to the coalescence of the oil (octane) droplets in the emulsions, that is, demulsification. While the equilibrated interfacial tension (IFT) between aqueous trans C7-azo-C7 solution and octane is almost the same as that between aqueous cis C7-azo-C7 and octane, the occupied area per molecule for C7-azo-C7 at octane/water interface decreases with the cis photoisomerization of trans isomer. Dynamic IFT measurement shows that UV irradiation to the interface between aqueous trans C7-azo-C7 solution and octane brings about an increase in the interfacial tension, indicating that the Gibbs free energy at the interface increases. From these results, the cis isomerization of trans C7-azo-C7 molecules at the O/W interface due to UV irradiation leads to direct contact between the water and octane phases, because of the reduction of molecular area at the interface, and subsequently makes the emulsions demulsified.

Spatial control of cell transfection using soluble or solid-phase redox agents and a redox-active ferrocenyl lipid.

We report principles for active, user-defined control over the locations and timing with which DNA is expressed in cells. Our approach exploits unique properties of a ferrocenyl cationic lipid that is inactive when oxidized, but active when chemically reduced. We show that methods that exert spatial control over the administration of reducing agents can lead to local activation of lipoplexes and spatial control over gene expression. The versatility of this approach is demonstrated using both soluble and solid-phase reducing agents. These methods provide control over cell transfection, including methods for remote activation and the patterning of expression using solid-phase redox agents, that are difficult to achieve using conventional lipoplexes.

Unusual viscoelasticity behaviour in aqueous solutions containing a photoresponsive amphiphile.

Here, we report unusual behaviour of the viscoelasticity of surfactant aqueous solutions consisting of cationic cetyltrimethylammonium bromide (CTAB) and an anionic photoresponsive amphiphile, sodium [4-(4-butylphenylazo)phenoxy]acetate (C4AzoNa). When C4AzoNa molecules are trans-isomers, spheroidal micelles are formed in the surfactant solution, the viscosity of which is low. Irradiation of this solution by ultraviolet (UV) light yields an aqueous solution of CTAB/cis-C4AzoNa (cis-isomers of C4AzoNa), which is a highly viscous gel consisting of wormlike micelles. The drastic change in the surfactant solution viscosity is attributed to the formation and disruption of wormlike micelles. The geometrical structural transformation of the azobenzene groups in the C4AzoNa molecules of the CTAB/C4AzoNa mixture would lead to a change in the critical packing parameter of the mixture, thereby inducing the morphological transformation of the aggregates (spheroidal micelles to wormlike micelles). To our knowledge, this is the first report of a drastic increase in surfactant solution viscosity by UV light irradiation.

Redox-based control of the transformation and activation of siRNA complexes in extracellular environments using ferrocenyl lipids.

We report physical characterization and biological evaluation of complexes of small interfering RNA (siRNA) formed using a cationic lipid [bis(11-ferrocenylundecyl)dimethylammonium bromide (BFDMA)] containing redox-active ferrocenyl groups at the end of each hydrophobic tail. We demonstrate that control over the redox state of BFDMA can be used to influence key physical properties and control the activities of lipoplexes formed using siRNA-based constructs. Specifically, lipoplexes of siRNA and reduced BFDMA lead to high levels of sequence-specific gene silencing in cells, but lipoplexes formed using oxidized BFDMA do not. Lipoplexes of oxidized BFDMA can be activated in situ to induce high levels of silencing by addition of a chemical reducing agent, demonstrating a basis for external control over the activation/delivery of siRNA in cellular environments. Differences in activity arise from the inability of oxidized BFDMA to promote efficient internalization of siRNA; these differences also correlated to significant differences in the nanostructures of these lipoplexes (determined by cryo-TEM) and their ζ potentials as a function of oxidation state. These results are considered in view of recent studies characterizing the nanostructures, properties, and behaviors of lipoplexes formed using BFDMA and macromolecular plasmid DNA. We find that several key structural features and aspects of redox control observed for lipoplexes of plasmid DNA are maintained in complexes formed using smaller and more rigid siRNA. The ability to transform BFDMA in complex media presents opportunities to exert control over the nanostructures and behaviors of siRNA lipoplexes in ways not possible using conventional lipids. The approaches reported here could thus prove useful in both fundamental and applied contexts.

Chemical oxidation of a redox-active, ferrocene-containing cationic lipid: influence on interactions with DNA and characterization in the context of cell transfection.

We report an approach to the chemical oxidation of a ferrocene-containing cationic lipid [bis(11-ferrocenylundecyl)dimethylammonium bromide, BFDMA] that provides redox-based control over the delivery of DNA to cells. We demonstrate that BFDMA can be oxidized rapidly and quantitatively by treatment with Fe(III)sulfate. This chemical approach, while offering practical advantages compared to electrochemical methods used in past studies, was found to yield BFDMA/DNA lipoplexes that behave differently in the context of cell transfection from lipoplexes formed using electrochemically oxidized BFDMA. Specifically, while lipoplexes of the latter do not transfect cells efficiently, lipoplexes of chemically oxidized BFDMA promoted high levels of transgene expression (similar to levels promoted by reduced BFDMA). Characterization by SANS and cryo-TEM revealed lipoplexes of chemically and electrochemically oxidized BFDMA to both have amorphous nanostructures, but these lipoplexes differed significantly in size and zeta potential. Our results suggest that differences in zeta potential arise from the presence of residual Fe(2+) and Fe(3+) ions in samples of chemically oxidized BFDMA. Addition of the iron chelating agent EDTA to solutions of chemically oxidized BFDMA produced samples functionally similar to electrochemically oxidized BFDMA. These EDTA-treated samples could also be chemically reduced by treatment with ascorbic acid to produce samples of reduced BFDMA that do promote transfection. Our results demonstrate that entirely chemical approaches to oxidation and reduction can be used to achieve redox-based 'on/off' control of cell transfection similar to that achieved using electrochemical methods.

Incorporation of DOPE into Lipoplexes formed from a Ferrocenyl Lipid leads to Inverse Hexagonal Nanostructures that allow Redox-Based Control of Transfection in High Serum.

We report small angle X-ray and neutron scattering measurements that reveal that mixtures of the redox-active lipid bis(11-ferrocenylundecyl)dimethylammonium bromide (BFDMA) and dioleoylphosphatidylethanolamine (DOPE) spontaneously form lipoplexes with DNA that exhibit inverse hexagonal nanostructure (H(II) (c)). In contrast to lipoplexes of DNA and BFDMA only, which exhibit a multilamellar nanostructure (L(α) (c)) and limited ability to transfect cells in the presence of serum proteins, we measured lipoplexes of BFDMA and DOPE with the H(II) (c) nanostructure to survive incubation in serum and to expand significantly the range of media compositions (e.g., up to 80% serum) over which BFDMA can be used to transfect cells with high efficiency. Importantly, we also measured the oxidation state of the ferrocene within the BFDMA/DNA lipoplexes to have a substantial influence on the transfection efficiency of the lipoplexes in media containing serum. Specifically, whereas lipoplexes of reduced BFDMA and DOPE transfect cells with high efficiency, lipoplexes of oxidized BFDMA and DNA lead to low levels of transfection. Complementary measurements using SAXS reveal that the low transfection efficiency of the lipoplexes of oxidized BFDMA and DOPE correlates with the presence of weak Bragg peaks and thus low levels of H(II) (c) nanostructure in solution. Overall, these results provide support for our hypothesis that DOPE-induced formation of the H(II) (c) nanostructure of the BFDMA-containing lipoplexes underlies the high cell transfection efficiency measured in the presence of serum, and that the oxidation state of BFDMA within lipoplexes with DOPE substantially regulates the formation of the H(II) (c) nanostructure and thus the ability of the lipoplexes to transfect cells with DNA. More generally, the results presented in this paper suggest that lipoplexes formed from BFDMA and DOPE may offer the basis of approaches that permit active and external control of transfection of cells in the presence of high (physiologically relevant) levels of serum.