Viscoelastic and shear viscosity studies of colloidal silica particles dispersed in monoethylene glycol (MEG), diethylene glycol (DEG), and dodecane stabilized by dodecyl hexaethylene glycol monoether (C12E6)

Silica dispersions stabilized by a nonionic surfactant, dodecyl hexaethylene glycol monoether (C 12E 6), were studied using rheological measurements. The viscosity-shear rate flow behavior of silica in monoethylene glycol (MEG) is shear thinning at low shear rates, leading to a Newtonian plateau at high shear rates for all dispersions studied. All rheological properties showed an increase above a critical surfactant concentration. The dispersions were stable at low levels of C 12E 6 concentrations because of electrostatic repulsions as deduced from the zeta potentials of silica that were on the order of about -30 to -65 mV in monoethylene glycol (MEG). Instability on further addition of C 12E 6 to the silica particles, a phenomenon normally obtained with high-molecular-weight polymers, was observed in MEG. Viscoelatic measurements of silica in monoethylene glycol at various surfactant concentrations showed a predominantly viscous response at low frequency and a predominantly elastic response at high frequencies, indicative of weak flocculation. Instability is explained in terms of hydrophobic and bridging interactions. Restabilization observed at high surfactant concentration was due to the steric repulsion of ethoxy groups of micellar aggregates adsorbed on silica particles. The study also revealed that the presence of trace water introduced charge repulsion that moderated rheological measurements in glycol media and introduced the charge reversal of silica particles in dodecane.     

Unusual spin transition behavior in 2,6-bis((pyrazol-3-yl)-pyridine) iron(II)-bis-oxalato-platinate(II)

[Fe(bpp)2][Pt(ox)2].H2O (with bpp=2,6-bis(pyrazol-3-yl)-pyridine and ox=oxalate) was prepared, and its spin crossover behavior was characterized. The two-step spin transition behavior changes over several cycles. The original behavior is restored when the sample is allowed to relax for a week. Furthermore, the ST exhibits a strong dependence on the heating and cooling rate. Heating the compound at 1 K/min leads to a spin transition with a third step and a second plateau at gammaHS approximately 0.8. Quenching the sample to 77 K also affects the spin transition behavior. The kinetic relaxation is followed after quenching and after light-induced excited spin state trapping experiments.     

Complexation and redox chemistry of neptunium,plutonium and americium with a hydroxylaminato ligand

There is significant interest in ligands that can stabilize actinide ions in oxidation states that can be exploited to chemically differentiate 5f and 4f elements. Applications range from developing large-scale actinide separation strategies for nuclear industry processing to carrying out analytical studies that support environmental monitoring and remediation efforts. Here, we report syntheses and characterization of Np(iv), Pu(iv) and Am(iii) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(^tBuNO)py]⁻(interchangeable hereafter with [(^tBuNO)py]⁻), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(^tBuNO)py]₄ (An = Pu, 1; Np, 2) have been synthesized, characterized by X-ray diffraction, X-ray absorption, ¹H NMR and UV-vis-NIR spectroscopies, and cyclic voltammetry, along with computational modeling and analysis. In the case of Pu, oxidation of Pu(iii) to Pu(iv) was observed upon complexation with the [(^tBuNO)py]⁻ ligand. The Pu complex 1 and Np complex 2 were also isolated directly from Pu(iv) and Np(iv) precursors. Electrochemical measurements indicate that a Pu(iii) species can be accessed upon one-electron reduction of 1 with a large negative reduction potential (E_1/2 = −2.26 V vs. Fc^+/0). Applying oxidation potentials to 1 and 2 resulted in ligand-centered electron transfer reactions, which is different from the previously reported redox chemistry of U^IV[(^tBuNO)py]₄ that revealed a stable U(v) product. Treatment of an anhydrous Am(iii) precursor with the [(^tBuNO)py]⁻ ligand did not result in oxidation to Am(iv). Instead, the dimeric complex [Am^III(μ₂-(^tBuNO)py)((^tBuNO)py)₂]₂ (3) was isolated. Complex 3 is a rare example of a structurally characterized non-aqueous Am-containing molecular complex prepared using inert atmosphere techniques. Predicted redox potentials from density functional theory calculations show a trivalent accessibility trend of U(iii) < Np(iii) < Pu(iii) and that the higher oxidation states of actinides (i.e., +5 for Np and Pu and +4 for Am) are not stabilized by [2-(^tBuNO)py]⁻, in good agreement with experimental observations.

The coordination modes and electronic properties of a strongly coordinating hydroxylaminato ligand with Np, Pu and Am were investigated.Complexes were characterized by a range of experimental and computational techniques.     

… zur Forschung in der Didaktik: 7 Thesen …

Goals and contents of chemical education research are presented as a list of seven statements in order to be discussed.     

Dielectric and dynamic mechanical relaxation studies on poly(aryl ether ketone)s

The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851–859, 1998     

Phenylated poly(P-phenylene vinylenes) prepared via the chlorine precursor route (CPR)

The synthesis of several highly phenylated PPV derivatives by a chlorine precursor route (CPR) was investigated in order to understand its scope. Three 1,4-bis(chloromethyl)benzene monomers were prepared via a robust and versatile synthetic procedure involving the Diels-Alder reaction. The monomers were then polymerized to the corresponding precursor polymers with about 1.0 equivalent of potassium t-butoxide in THF. Only one monomer gave a soluble precursor polymer while the other two gave insoluble precursor polymers. The soluble precursor polymer was deposited as thin films and then converted to the corresponding PPV derivative, which showed green photoluminesence and electroluminesence.     

In situ SIMS analysis and reactions of surfaces prepared by soft landing of mass-selected cations and anions using an ion trap mass spectrometer

Mass-selected polyatomic cations and anions, produced by electrosonic spray ionization (ESSI), were deposited onto polycrystalline Au or fluorinated self-assembled monolayer (FSAM) surfaces by soft landing (SL), using a rectilinear ion trap (RIT) mass spectrometer. Protonated and deprotonated molecules, as well as intact cations and anions generated from such molecules as peptides, inorganic catalysts, and fluorescent dyes, were soft-landed onto the surfaces. Analysis of the modified surfaces was performed in situ by Cs⁺ secondary ion mass spectrometry (SIMS) using the same RIT mass analyzer to characterize the sputtered ions as that used to mass select the primary ions for SL. Soft-landing times as short as 30 s provided surfaces that yielded good quality SIMS spectra. Chemical reactions of the surfaces modified by SL were generated in an attached reaction chamber into which the surface was transferred under vacuum. For example, a surface on which protonated triethanolamine had been soft landed was silylated using vapor-phase chlorotrimethylsilane before being returned still under vacuum to the preparation chamber where SIMS analysis revealed the silyloxy functionalization. SL and vapor-phase reactions are complementary methods of surface modification and in situ surface analysis by SIMS is a simple way to characterize the products produced by either technique.     

Orbits of parabolic subgroups on metabelian ideals

Let k be an algebraically closed field, t∈Z?1, and let B be the Borel subgroup of GLt(k) consisting of upper-triangular matrices. Let Q be a parabolic subgroup of GLt(k) that contains B and such that the Lie algebra qu of the unipotent radical of Q is metabelian, i.e. the derived subalgebra of qu is abelian. For a dimension vector with , we obtain a parabolic subgroup P(d) of GLn(k) from B by taking upper-triangular block matrices with (i,j) block of size di×dj. In a similar manner we obtain a parabolic subgroup Q(d) of GLn(k) from Q. We determine all instances when P(d) acts on qu(d) with a finite number of orbits for all dimension vectors d. Our methods use a translation of the problem into the representation theory of certain quasi-hereditary algebras. In the finite cases, we use Auslander-Reiten theory to explicitly determine the P(d)-orbits; this also allows us to determine the degenerations of P(d)-orbits.     

Molecular dynamics in a miscible polyester blend

The dynamic mechanical and dielectric spectra of a miscible polyester and polycarbonate blend are investigated with emphasis on the latter technique. It was found that relaxation spectra for the blends from both techniques are broader than those of the constituent homopolymers. This is ascribed to greater intermolecular coupling and concentration fluctuations within the blends. The composition at which the greatest coupling occurs is dependent on the relaxation technique used and is skewed towards the component which shows the highest degree of intermolecular coupling. A number of parameters, such as relaxation time of the polymer molecules in the blend and relaxation strength, are compared as a function of reduced temperature (experimental temperature scaled by the glass transition temperature). Whereas blend behavior is generally intermediate between that of the homopolymers, it appears as though mobility of compositions with low polyester content have a greater relaxation time and possess a higher activation energy when compared to a simple, weighted average of the corresponding homopolymer values. © 1996 John Wiley & Sons, Inc.