Comparison of the coadsorption of benzyl alcohol and phenyl ethanol with the cationic surfactant, hexadecyl trimethyl ammonium bromide, at the air-water interface

A comparison of the coadsorption of benzyl alcohol and phenyl ethanol with the cationic surfactant, hexadecyl trimethyl ammonium bromide, C16TAB, at the air-water interface is made using the specular reflection of neutrons. The phenyl ethanol is more surface active than the benzyl alcohol, and competes more effectively with the C16TAB for the interface. The structure of the C16TAB component in the mixed monolayer is compared with the structure of the pure C16TAB monolayer at an equivalent area per molecule. The addition of the aromatic alcohol subtly alters the conformation of the C16TAB and draws it closer to the aqueous subphase. The center of the alcohol distribution is located in the interface adjacent to the C6 group of the C16TAB alkyl chain closest to the headgroup. Compared to the benzyl alcohol, the more hydrophobic phenyl ethanol is slightly farther away from the headgroup, and has a greater impact on the conformation of the alkyl chain of the C16TAB.     

Syntheses and crystal structures of mono- and bi-metallic zinc compounds of symmetrically- and asymmetrically-substituted bis(amino)cyclodiphosph(V)azanes

The dioxocyclodiphosph(V)azane cis-[(^tBuHN)OP(μ-N^tBu)₂PO(NH^tBu)] reacted with two equivalents of diethylzinc to form the centrosymmetric dimer {[(OPN^tBu)₂(N^tBu)₂ZnEt](ZnEt · THF)}₂ (1) while under identical conditions, the sulfur and selenium analogues afforded only the monoethylzinc compounds {[(^tBuHN)EP(μ-N^tBu)₂PE(N^tBu)](ZnEt · THF)}ES(2), Se (3). To further probe the apparent ligand effects on coordination number and coordination site, cis-[(PhHN)SP(μ-N^tBu)₂PS(NH^tBu)] (5) was synthesized from cis-[ClP(μ-N^tBu)₂P(NH^tBu)] (4) and both were characterized by single-crystal X-ray diffraction. Two equivalents of 5 reacted with diethylzinc to produce the homoleptic, trispirocyclic complex {[(^tBuHN)SP(μ-N^tBu)₂PS(NPh)]₂Zn} (6). A second asymmetrically-substituted cyclodiphosph(V)azane, namely [(^tBuNH)SP(μ-N^tBu)₂PNp-tol(NH^tBu)] (7), was also synthesized and structurally characterized. In contrast to 5, only one equivalent of this ligand reacted with excess diethylzinc, via its N,N^′, rather than its N,S side, to afford {[(^tBuHN)SP(μ-N^tBu)₂PNp-tolyl(N^tBu)](ZnEt)} (8).     

Syntheses and structures of dinuclear gold(I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types

The dinuclear gold(I) dithiophosphonate complex, [Au(2)(dtp)(2)] (1), where dtp = [S(2)P(R)(OR')](-) with R = p-C(6)H(4)OCH(3); R'= c-C(5)H(9), has been synthesized and its reaction studied with the phosphine ligands PPh(3) and Ph(2)P(CH(2))(n)PPh(2) (n = 1-4). Compound 1 contains two gold atoms homobridged by the anionic dithiophosphonate ligand, forming an eight-membered ring complex in a chair form. After the reaction of 1 with diphosphine ligands, the dinuclear open-ring complexes Au(2)(dppm)(dtp)(2) (2), Au(2)(dppe)(dtp)(2) (3), Au(2)(dppp)(dtp)(2) (4), Au(2)(dppb)(dtp)(2) (5) were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when 1 reacts with 2 equiv of dppm, the ionic complex [Au(2)(dppm)(2)(dtp)]dtp forms. This dtp counterion was exchanged with tetrafluoroborate to yield [Au(2)(dppm)(2)(dtp)]BF(4), the crystallization of which afforded two interconvertible isomers, 6-yellow and 7-white. Reaction of 1 with PPh(3) affords the tetracoordinate mononuclear complex [Au(dtp)(PPh(3))(2)] (8). The molecular structures of 1-8 were confirmed by X-ray crystallography and show multiple coordination modes and geometries. The crystal structures of 1 and its reaction products with dppm (2, 6, 7) show short intramolecular Au.Au aurophilic bonding interactions of 2.95-3.10 A while no intermolecular interactions were discernible. However, reaction products of 1 with longer-chain Ph(2)P(CH(2))(n)PPh(2) ligands, n = 2-4, exhibit structures that lack both intra- and intermolecular Au.Au interactions.     

Manipulation of the adsorption of ionic surfactants onto hydrophilic silica using polyelectrolytes

This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.     

Syntheses and structures of P-anilino-P-chalcogeno- and P-anilino-P-iminodiazasilaphosphetidines and their group 12 and 13 metal compounds

The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me(2)Si(mu-N(t)Bu)(2)P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me(2)Si(N(t)Bu)(2)P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce ([Me(2)Si(mu-N(t)Bu)(2)P=S(NPh)-kappaN-kappaS]Tl)(7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe(3) gave the monoligand dimethylaluminum complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE]AlMe(2)) (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4-6 reacted with diethylzinc to produce the homoleptic diligand complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE](2)Zn)(E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.     

Ethyl 5‐methyl‐4‐(2,5,5‐tri­methyl‐1,3‐dioxan‐2‐yl)­isoxazole‐3‐carboxyl­ate

The title compound, C₁₄H₂₁NO₅, possesses an isoxazolyl group in the axial position of the 1,3‐dioxanyl ring. The two rings are rotated about the bond joining them such that the two C(methyl)—C(dioxanyl)—C—C torsion angles are 92.1 (2) and ?84.1 (2)°. In this conformation, neither the methyl nor ethoxy­carbonyl substituents on the isoxazole are presented towards the dioxanyl chair.     

Adaptive resolution refinement for pseudospectral simulations of isotropic homogeneous turbulence

Pseudospectral simulations of homogeneous turbulence provide an important class of benchmark flow problems used for fundamental studies of turbulence and for numerical validation purposes. Depending on the numerical resolution, fully resolved computations of homogeneous turbulence can consume large amounts of central processing unit (CPU) time. Here, we present an approach analogous to adaptive mesh refinement for computations performed in physical space to adaptively refine the spectral resolution for pseudospectral computations of isotropic homogeneous turbulent flows. The method is applied to simulations of two-dimensional and three-dimensional isotropic homogeneous turbulence, and the results are compared with direct numerical simulations (DNS) performed using a fixed fine mesh. Significant savings in computational time are found in each case, with little to no compromise in the accuracy of the solutions.