Self-assembly of a hydrophobic groove

Heptakis(2,6-di-O-methyl)-β-cyclodextrin interacts with 5,15-diphenylporphine to produce a 2:1 complex in dimethyl sulfoxide. This complex possesses a hydrophobic groove that circumscribes the metal binding site of the porphyrin moiety.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Preparation and characterization of dealuminated metakaolin and its use in the transformation of waste plastics to aromatic hydrocarbons

Acid activated metakaolins (AAMKs) have been prepared by calcination of the natural clay at 600 degrees C to provide a metakolin which was then leached at 80 degrees C for 3 h using 1M, 2M, 3M, and 6M HCl. These materials were characterized and their ability to transform the off gases from HDPE decomposition into useful aromatic species was evaluated. The amount of adsorbed water and the number of acid sites increased with the severity of acid treatment. Variable temperature DRIFTS spectroscopy of pyridine treated samples revealed that both Br?nsted and Lewis acid centers were present until 425 degrees C. Pyridine bonded to the Lewis acid centers was more thermally stable. The AAMKs were all selective to the production of toluene with respectable, but lesser, amounts of xylenes and trimethylbenzenes. This selectivity contrasts with that of acid leached and pillared smectites which are selective toward trimethylbenzene.     

OVERVIEW ON SURFACE MICROSTRUCTURING BY PHOTODESORPTION ETCHING OF CHLORINATED SILICON

Developing a mechanistic interpretation of complex dynamical chemical systems such as halogen photoetching requires correlated microscopic data on the kinetics, dynamics, surface composition and microstructure of prototypical and real surfaces. This overview is concerned especially with two important variables which significantly influence the microetching mechanisms and structures; (I) the role of electronic point defects induced by substitutional doping in producing site-specific reactions and, (II) the quantum mechanical enhancement of chemical reaction induced by uv-radiation at low fluences and temperatures.

From uv-photoetching and photodesorption studies of heavily doped Si(100) and Si(111) with chlorine beams at low laser fluences, the mechanisms of photostimulated desorption is analyzed based primarily on the kinetics of chemisorption and surface layer microanalysis obtained from core-level photoemission. These results are coupled with time-of-flight dynamical measurements on the energetics of the photodesorption process to provide a more unified understanding of anisotropic photon-stimulated microetching.

Substantial alterations of the etching mechanisms occur when selective surface molecular processes are driven quantum mechanically by low level photon radiation rather than thermally. This is clearly reflected in the dynamical mechanisms for photodesorption which become strongly site- and atomic process-selective illustrated by the energetics of the processes. Creation and transport of charged carriers, especially at high doping levels by photoionization coupled with field-induced charge transport, introduces new reaction channels into the surface chemistry leading to resultant changes in the microstructure on an atomic scale. The results from the kinetics, velocity dynamics and film composition measurements are combined in terms of the dependency of chlorine adsorption on doping at high carrier levels and low laser fluences, to provide an improved interpretation of the anisotropic microetching in terms of field-promoted electron-hole activation.     

Miscibility in systems containing aqueous solutions of various alkylbenzenesulfonates, toluene and, n-butanol

Miscibility relationships in four-component systems containing sodium alkylbenzenesulfonates, toluene, n-butanol, and water were studied at 25°C in the hope of clarifying the complex systems used in the “micellar flood” enhanced oil recovery process. Phase boundary curves for the pseudo three-component systems (constant sulfonate/water ratios, 2.5 moles sulfonate per kg water) were determined. The sulfonates included those of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, mesitylene, cymene, methyl-t-butylbenzene, and diisopropylbenzene, in all of which the alkyl substituents are smaller than in the usual surfactants. The phase boundary curves have similar and fairly symmetrical shapes. The amount of n-butanol (cosolvent) required to produce miscibility decreases with increasing number of alkyl carbons on the benzene ring of the sulfonates and seems relatively independent of the isomeric structure. The sodium salt of diisopropylbenzenesulfonate gives the lowest phase boundary curve (least n-butanol required for miscibility) among the nine sulfonates studied.     

Copolymerization reactivities and conductivities of some living polymers of p-substituted styrenes

A kinetic study in tetrahydrofuran of the addition of 1,1-diphenylethylene on para-substituted styrylcarbanions (with Cs⁺ as counterion) has given the reactivities of free ions and ion-pairs. For both species, the addition rate constant increased in the following sequence for the substituent of the phenyl ring: pH < p-CH₃ <p-CH₃O. It was also shown that in the same solvent, the dissociation constants of the polystyryl ion-pairs decreased with the electron-donating power of the substituent.