Well-defined nanoparticles formed by hydrophobic assembly of a short and polydisperse random terpolymer, amphipol A8-35

Amphipols are short amphilic polymers designed for applications in membrane biochemistry and biophysics and used, in particular, to stabilize membrane proteins in aqueous solutions. Amphipol A8-35 was obtained by modification of a short-chain parent polymer (poly(acrylic acid); PAA) with octyl- and isopropylamine, to yield an amphiphilic product with an average molar mass of 9-10 kg x mol(-1) (sodium salt form) and a polydispersity index of 2.0 to 3.1, depending on the source of PAA. The behavior of A8-35 in aqueous buffers was studied by size exclusion chromatography, static and dynamic light scattering, equilibrium and sedimentation velocity analytical ultracentrifugation, and small angle neutron scattering. Despite the variable length of the chains and the random distribution of hydrophobic groups along them, A8-35 self-organizes into well-defined assemblies. The data are best compatible with most of the polymer forming compact assemblies (particles) with a molar mass of approximately 40 kg x mol(-1), a radius of gyration of approximately 2.4 nm, and a Stokes radius of approximately 3.15 nm. Each particle contains, on average, four A8-35 macromolecules and 75-80 octyl chains. Neutron scattering reveals a sharp interface between the particles and water. A minor (approximately 0.1%) mass fraction of the material forms much larger aggregates, whose proportion may increase under certain conditions of preparation or handling, such as low pH. They can be removed by gel filtration.     

Enhancing the hydrophobic effect in confined water nanodrops

The distribution of hydrophobic solutes, such as methane, enclosed in a nanosized water droplet contained in a reverse micelle of diameter 2.82 nm is investigated using Monte Carlo simulations. The effect of the hydrophobic solute's atomic diameter on the solute-solute potential of mean force is also studied. The study reveals that confinement has a strong influence on the solute's tendency to associate. The potential of mean force exhibits only a single minimum, indicating that the contact pair is the only stable configuration between solutes. The solvent-separated pair that is universally observed for small solutes in bulk water is conspicuously absent. This enhanced hydrophobic effect is attributed to the lack of sufficient water to completely hydrate and stabilize the solvent-separated configurations. The study is expected to be important in understanding the role of hydrophobic forces during protein folding and nucleation under confinement.     

An example of lipophiloselectivity: the preferred oxidation, in water, of hydrophobic 2-alkanols catalyzed by a cross-linked polyethyleneimine-polyoxometalate catalyst assembly

A cross-linked polyethyleneimine polymer containing the [ZnWZn2(H2O)2(ZnW9O34)2]12- polyoxometalate was prepared from branched polyethyleneimine (Mw = 600), the polyoxometalate, and a n-octylamine-epichlorohydrin cross-linking reagent. This catalytic assembly was active for the selective oxidation of 2-alkanols to 2-alkanones with aqueous H2O2 with reactions presumably occurring at a hydrophobic domain. Most importantly, the catalyst showed distinctive lipophiloselectivity, that is selectivity as a function of the lipophilic nature of a reaction substrate. The lipophiloselectivity was proportional to the relative partition coefficient (1-octanol/water) of the substrates.     

Aerosol-OT-gamma-alumina admicelles for the concentration of hydrophobic organic compounds in water

A novel admicelle composing of a dialkylated anionic surfactant, di-2-ethylhexyl sodium sulfosuccinate (Aerosol-OT, AOT) and gamma-alumina was prepared by mixing them in acidic aqueous solution. The amount of the maximum sorption of AOT on 1 g of alumina at pH 2 was ca. 130 mg. By comparing the fluorescence spectra of N-phenyl-1-naphthylamine in different solvents, the solvent property of AOT-gamma-alumina admicelles was corresponding to that of toluene or diethyl ether. Thus, the AOT-gamma-alumina admicelles had greater hydrophobicity than SDS-gamma-alumina admicelles having similar hydrophobicity to 1-octanol or ethyl acetate. Hydrophobic organic compounds, chlorophenols having more than three chloro substituents, octylphenol, nonylphenol, dibutyl phthalate was almost quantitatively (98% or more) collected onto AOT admicelles composing of 1.5 g gamma-alumina and 150 mg AOT. The greater collection yields rather than those in SDS-admicellar system were ascribable to greater hydrophobicity and stability of AOT admicelles. After the 500-fold concentration, traces (nM) of organic contaminants in water samples were successfully detected with an HPLC having a photometric detector.     

Understanding organic reactions in water: from hydrophobic encounters to surfactant aggregates

A crucial factor in realising a green chemical process in solution involves the choice of a safe, non-toxic and cheap solvent. Water is the obvious choice. Despite solubility problems, considerable interest has developed recently in organic chemistry in water. This interest also results from the fact that association and chemical reactions often benefit noticeably from the special properties of water, resulting mainly from its small molecular size, its three-dimensional hydrogen-bond network and hydrophobic interactions which are so unique for liquid water. Here we discuss organic reactions and assembly processes in water, largely taken from experiments performed in the authors' laboratories. We show that non-covalent interactions in water can be utilised for fine tuning organic reactions in aqueous media.     

Multivalent supramolecular assembly with ultralong organic room temperature phosphorescence,high transfer efficiency and ultrahigh antenna effect in water

Multivalent supramolecular assemblies have recently attracted extensive attention in the applications of soft materials and cell imaging. Here, we report a novel multivalent supramolecular assembly constructed from 4-(4-bromophenyl)pyridine-1-ium bromide modified hyaluronic acid (HABr), cucurbit[8]uril (CB[8]) and laponite® clay (LP), which could emit purely organic room-temperature phosphorescence (RTP) with a phosphorescence lifetime of up to 4.79 ms in aqueous solution via multivalent supramolecular interactions. By doping the organic dyes rhodamine B (RhB) or sulfonated rhodamine 101 (SR101) into the HABr/CB[8]/LP assembly, phosphorescence energy transfer was realized with high transfer efficiency (energy transfer efficiency = 73–80%) and ultrahigh antenna effect (antenna effect value = 308–362) within the phosphorescent light harvesting system. Moreover, owing to the dynamic nature of the noncovalent interactions, a wide-range spectrum of phosphorescence energy transfer outputs could be obtained not only in water but also on filter paper and a glass plate by adjusting the donor–acceptor ratio and, importantly, white-light emission was obtained, which could be used in the application of information encryption.

An ultralong lifetime supramolecular assembly was constructed via multivalent supramolecular interactions and achieved phosphorescence light harvesting. Multicolor (including white) broad-spectrum outputs could be achieved in water and also on filter paper and a glass plate.     

Amphiphilic porphyrin assembly as a highly selective chemosensor for organic mercury in water

Homogeneously sized nanoparticles were successfully constructed based on amphiphilic porphyrin-cholesterol arrays, showing unique spectral and colourimetric response to organic mercury in water, even in the presence of Hg(2+).     

Transient behavior of the hydrophobic surface/water interface: from nanobubbles to organic layer

We report the formation and subsequent change of the water-depleted layer at a hydrophobic surface/water interface. With water as the solvent, surface plasmon resonance measurements indicate time dependent evolution of two separate states. The first state is the water-depleted layer, and it is characterized by a layer of nanobubbles on the surface and is short-lived in time (order of 10 min). The second state is a final equilibrium state, which occurs in approximately 30 h, where a layer is formed with organic characteristics. If, instead of water, an aqueous solution is exposed to the hydrophobic surface, the evolution from nanobubbles to an organic like layer shows dependency on the surface energy of the liquid media.     

The hydrophobic effect: molecular dynamics simulations of water confined between extended hydrophobic and hydrophilic surfaces

Structural and dynamic properties of water confined between two parallel, extended, either hydrophobic or hydrophilic crystalline surfaces of n-alkane C(36)H(74) or n-alcohol C(35)H(71)OH, are studied by molecular dynamics simulations. Electron density profiles, directly compared with corresponding experimental data from x-ray reflectivity measurements, reveal a uniform weak de-wetting characteristic for the extended hydrophobic surface, while the hydrophilic surface is weakly wetted. These microscopic data are consistent with macroscopic contact angle measurements. Specific water orientation is present at both surfaces. The ordering is characteristically different between the surfaces and of longer range at the hydrophilic surface. Furthermore, the dynamic properties of water are different at the two surfaces and different from the bulk behavior. In particular, at the hydrophobic surface, time-correlation functions reveal that water molecules have characteristic diffusive behavior and orientational ordering due to the lack of hydrogen bonding interactions with the surface. These observations suggest that the altered dynamical properties of water in contact with extended hydrophobic surfaces together with a partial drying of the surfaces are more indicative of the hydrophobic effect than structural ordering, which we suggest to be independent of surface topology.     

Water's hydrogen bonds in the hydrophobic effect: a simple model

We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy.     

Well-defined self-assembling supramolecular structures in water containing a small amount of C60

In this communication, we report for the first time on the spherical bilayer vesicle formation of a dendritic C(60)-amphiphile-surfactant hybrid in aqueous solutions.     

Rotational structure of water in a hydrophobic environment: carbon tetrachloride

Infrared spectroscopy has been used to probe the interaction between water and the hydrophobic solvent, carbon tetrachloride. At room temperature, water exists as monomers in carbon tetrachloride, presenting a system for studying the rotational properties of water free of strong hydrogen-bonding. The rotational structure suggests a very anisotropic motion consisting of essentially free rotation about the symmetry axis and highly hindered rotation about the two perpendicular axes of the asymmetric water molecule. The rotational lifetime is significantly shortened relative to gas-phase water. An upper limit of 0.93 ps is deduced from the spectrum. Interaction with carbon tetrachloride also slightly enhances the intensity of the symmetric stretch. The results are compared with results of interactions between water and the cations Li+, Na+, K+, and Cs+. It is concluded that the attractive interaction is between the oxygen of water and the electropositive carbon of carbon tetrachloride.     

Attaching organic semiconductors to gate oxides: in situ assembly of monolayer field effect transistors

This study unveils a new tetracene derivative that forms dense, upright monolayers on the surface of aluminum oxide. These monolayers spontaneously self-organize into the active layer in nanoscale field-effect transistor devices when aluminum oxide is used as the dielectric layer. This method gives high yields of working devices that have source-drain distances that are less than 60 nm, thereby providing a method to electrically probe the monolayer assemblies formed from approximately 10 zeptomoles of material (approximately 104 molecules). Moreover, this study delineates a new avenue for research in thin-film organic transistors where the active molecules are linked to the dielectric surface to form a monolayer transistor.     

The effect of dissolved water on the viscosities of hydrophobic room-temperature ionic liquids

Data for viscosity vs. water content for three hydrophobic room-temperature ionic liquids show that their viscosities are strongly dependent on the amount of dissolved water.     

Helical water chains in aquapores of organic hexahost: remarkable halogen-substitution effect on the handedness of water helix

Water helices surrounding the nano-channels of trichlorophloroglucinol and tribromophloroglucinol have different handedness, PMPMPM and PPPMMM (P = right-handed, M = left-handed), depending on halogenhalogen interactions between the host molecules.     

Role of spatial ionic distribution on the energetics of hydrophobic assembly and properties of the water/hydrophobe interface

We present results from all-atom molecular dynamics simulations of large-scale hydrophobic plates solvated in NaCl and NaI salt solutions. As observed in studies of ions at the air-water interface, the density of iodide near the water-plate interface is significantly enhanced relative to chloride and in the bulk. This allows for the partial hydration of iodide while chloride remains more fully hydrated. In 1 M solutions, iodide directly pushes the hydrophobes together (contributing -2.51 kcal mol(-1)) to the PMF. Chloride, however, strengthens the water-induced contribution to the PMF by ~-2.84 kcal mol(-1). These observations are enhanced in 3 M solutions, consistent with the increased ion density in the vicinity of the hydrophobes. The different salt solutions influence changes in the critical hydrophobe separation distance and characteristic wetting/dewetting transitions. These differences are largely influenced by the ion-specific expulsion of iodide from bulk water. Results of this study are of general interest to the study of ions at interfaces and may lend insight to the mechanisms underlying the Hofmeister series.