Importance of micellar kinetics in relation to technological processes

The association of many classes of surface-active molecules into micellar aggregates is a well-known phenomenon. Micelles are in dynamic equilibrium, constantly disintegrating and reforming. This relaxation process is characterized by the slow micellar relaxation time constant, tau(2), which is directly related to the micellar stability. Theories of the kinetics of micelle formation and disintegration have been discussed to identify the gaps in our complete understanding of this kinetic process. The micellar stability of sodium dodecyl sulfate micelles has been shown to significantly influence technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification, solubilization, and detergency. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the breakup of micelles. Especially when the free monomer concentration is low, which is the case for many nonionic surfactant solutions, the micellar breakup time is a rate-limiting step in the supply of monomers. The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped flow and pressure jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results showed that the ionic surfactants such as SDS exhibit slow relaxation times in the range from milliseconds to seconds, whereas nonionic surfactants exhibit slow relaxation times in the range from seconds (for Triton X-100) to minutes (for polyoxyethylene alkyl ethers). The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation times showed a direct correlation with dynamic surface tension and foaming experiments. In conclusion, relaxation time data of surfactant solutions correlate with the dynamic properties of the micellar solutions. Moreover, the results suggest that appropriate micelles with specific stability or tau(2) can be designed by controlling the surfactant structure, concentration, and physicochemical conditions (e.g., salt concentration, temperature, and pressure). One can also tailor micelles by mixing anionic/cationic or ionic/nonionic surfactants for a desired stability to control various technological processes.     

Structure, bonding, and reactivity of Ti and Zr amidate complexes: DFT and X-ray crystallographic studies

Easily prepared and highly modular organic amide proligands have been used to synthesize a series of new bis(amidate)-bis(amido) Ti and Zr complexes via protonolysis. These complexes have been structurally characterized by NMR spectroscopy and X-ray crystallography. The solid-state molecular structures of these complexes indicate that the amidate ligands bind to the metal centers in an exclusively bidentate fashion, resulting in discrete monomeric species. Geometric isomerism in these species is highly dependent upon the steric characteristics of the proligands utilized in the synthesis. In solution, these complexes are observed to isomerize on the NMR time scale, with one isomer being predominant. Bonding in the bis(amidate)-bis(amido) complexes was investigated by DFT calculations. The geometric isomers predicted by theory matched the experimentally observed results, within experimental error. The orbitals associated with amidate-metal bonding are energetically well below the frontier orbitals. The HOMO in these complexes is a pi orbital associated with amido ligand-to-metal bonding character, while the LUMO in all cases is a vacant d orbital on the metal center.     

Relaxation dynamics in glycerol-water mixtures: I. Glycerol-rich mixtures

We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed.     

Neurosteroid analogues: synthesis of 6-aza-allopregnanolone

An efficient synthesis of 6-azapregnane derivatives and their biological activity is described. The nitrogen was introduced into the B ring using Beckmann rearrangement of the (E)-oxime of 6-oxo-B-nor-5α-pregnane derivatives. The required 3α-hydroxyl was produced either by solvolysis of the corresponding 3β-mesyloxy group or by the Meerwein-Ponndorf-Verley reduction of the 3-oxo group; this reduction could be carried out selectively with an unprotected 3,20-dioxo derivative. The binding of the 6-aza-steroids to the γ-aminobutyric acid receptor (GABA_A) was measured using [³⁵S]-tert-butyl-bicyclo[2.2.2]phosphorothionate (TBPS) and [³H]flunitrazepam. The only analogue to be slightly active was that lacking any oxygen function in position 3.     

Path integral Monte Carlo simulation of the absorption spectra of an Al atom embedded in helium

We use a multilevel path integral Monte-Carlo (PIMC) method to simulate the arrangement of He atoms around a single Al atom doped in a He cluster. High-level ab initio Al-He pair potentials and a Balling and Wright pairwise Hamiltonian model are used to describe the full potential and the electronic asymmetry arising from the open-shell character of the Al atom in its ground and excited electronic states. Our calculations show that the doping of the Al 3p electron strongly influences the He packing. The results of the PIMC simulation are used to predict the electronic excitation spectrum of an Al atom embedded in He clusters. With inclusion of tail corrections for the ground and excited states potentials, the calculated 3d<--3p spectrum agrees reasonably well with the experimental spectrum. The blueshift of the calculated spectrum associated with the 4s<--3p transition of solvated Al is about 25 nm (2000 cm-1) larger than seen in experiments on Al embedded in bulk liquid He. We predict that the spectrum associated with the 4p<--3p transition will be blueshifted by approximately 7000 cm-1 (nearly 1 eV).     

Electrochemical and spectral studies on the reductive nitrosylation of water-soluble iron porphyrin

The reaction of iron(III) (meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(III)TMPyP) with nitric oxide (NO) was studied by electronic absorption spectroscopy, ESR, and electrochemical and spectroelectrochemical techniques in aqueous solutions with pH from 2.2 to 12.0. Fe(III)TMPyP has been found to undergo a reductive nitrosylation in all pHs, and the product of nitric oxide binding to the porphyrin has been determined as iron(II) porphyrin nitrosyl complex ([Fe(II)(NO)TMPyP]). The rate of the reductive nitrosylation exhibits a tendency to get faster with increase in pH. An intermediate species was observed around neutral pH by spectroelectrochemical technique and was proposed to be the iron(II) nitrosyl complex of the mu-oxo dimeric form of FeTMPyP, which is known to be a predominant in neutral solutions.     

Mechanistic study into the direct epoxidation of propene over gold/titania catalysts

The epoxidation of propene over gold/titania based catalysts was investigated using different techniques. Infrared spectroscopic information showed that one key step in the reaction mechanism is a reaction catalyzed by gold between titania surface groups and propene. In this reaction step, a bidentate propoxy species is formed on titania. This species adsorbs strongly on the catalyst, and it is the same species which is formed when propene oxide adsorbs on titania. Gravimetrical adsorption experiments and catalytic tests show that product adsorption and desorption are important factors determining the catalytic activity and the catalyst stability. By combining the information from different techniques, a kinetic mechanism is proposed.     

Layer-by-Layer electrostatic self-assembly of polyelectrolyte nanoshells on individual carbon nanotube templates

Carbon nanotubes have been featured prominently in the nanotechnology research for some time, yet robust strategies for noncovalent chemical modification of the nanotube surface are still missing. Such strategies are essential for the creation of functional device architectures. Here, we present a new general procedure for carbon nanotube modification based on polyelectrolyte layer-by-layer assembly. We have built multilayer structures around individual carbon nanotube bridges by first modifying the nanotube surface with a pyrene derivative followed by layer-by-layer deposition of polyelectrolyte macroions on the nanotube. Transmission electron microscopy and scanning confocal fluorescence microscopy images confirm the formation of nanometer-thick amorphous polymer nanoshells around the nanotubes. These multilayer polyelectrolyte shells on individual carbon nanotubes introduce nearly unlimited opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent structures.     

Catalytic Sandmeyer cyanation as a synthetic pathway to aryl nitriles

Aryl nitriles ArCN were obtained by the Cu(I)/Cu(II) catalysed reaction of aryl diazonium salts with KCN in good yields.     

Inelastic collisions between 4He and H2: Study of dynamical approximations

We report a detailed study of the convergence and accuracy of HeH₂ rotationally and ro-vibrationally inelastic cross sections, determined within both the coupled states (CS) and effective potential (EP) formalisms. Two different potential surfaces were used. CS total cross sections appear insensitive to the specific choice of centrifugal barrier. Although the CS results are more accurate, the EP method reproduces the important qualitative features of the various inelastic processes. In addition, with the counting-of-states correction, the EP cross sections for ro-vibrationally inelastic transitions out of low-lying rotational levels agree with the CS values to within a factor of two, with only few exceptions.