IR and NMR Properties of Ionic Liquids: Do They Tell Us the Same Thing?

We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids.     

The formal translation equation for iteration groups of type II

We investigate the translation equation $$F(s+t, x) = F(s, F(t, x)),\quad \quad s,t\in{\mathbb{C}},\qquad\qquad\qquad\qquad({\rm T})$$ in ${\mathbb{C}\left[\kern-0.15em\left[{x}\right]\kern-0.15em\right]}$ , the ring of formal power series over ${\mathbb{C}}$ . Here we restrict ourselves to iteration groups of type II, i.e. to solutions of (T) of the form ${F(s, x) \equiv x + c_k(s)x^k {\rm mod} x^{k + 1}}$ , where k ≥ 2 and c _k ≠ 0 is necessarily an additive function. It is easy to prove that the coefficient functions c _n (s) of $$F(s, x) = x + \sum_{n \ge q k}c_n(s)x^n$$ are polynomials in c _k (s). It is possible to replace this additive function c _k by an indeterminate. In this way we obtain a formal version of the translation equation in the ring ${(\mathbb{C}[y])\left[\kern-0.15em\left[{x}\right]\kern-0.15em\right]}$ . We solve this equation in a completely algebraic way, by deriving formal differential equations or an Aczél–Jabotinsky type equation. This way it is possible to get the structure of the coefficients in great detail which are now polynomials. We prove the universal character (depending on certain parameters, the coefficients of the infinitesimal generator H of an iteration group of type II) of these polynomials. Rewriting the solutions G(y, x) of the formal translation equation in the form ${\sum_{n\geq 0}\phi_n(x)y^n}$ as elements of ${(\mathbb{C}\left[\kern-0.15em\left[{x}\right]\kern-0.15em\right])\left[\kern-0.15em\left[{y}\right]\kern-0.15em\right]}$ , we obtain explicit formulas for ${\phi_n}$ in terms of the derivatives H ^(j)(x) of the generator ${H}$ and also a representation of ${G(y, x)}$ as a Lie–Gröbner series. Eventually, we deduce the canonical form (with respect to conjugation) of the infinitesimal generator ${H}$ as x ^k + hx ^2k-1 and find expansions of the solutions ${G(y, x) = \sum_{r\geq 0} G_r(y, x)h^r}$ of the above mentioned differential equations in powers of the parameter h.     

ON THE ACRIDINE AND THIAZINE DYE SENSITIZED PHOTODYNAMIC INACTIVATION OF LYSOZYME—SINGLET OXYGEN SELF-QUENCHING BY THE SENSITIZERS

Abstract— The quantum yield of the photodynamic inactivation of lysozyme increases in the sequence acridine orange, methylene blue, proflavine and acriflavine (1:5:6:12). At least up to protein concentrations of 0.1 m M , singlet oxygen is exclusively responsible for the inactivation of the enzyme. For methylene blue, acriflavine and proflavine the quantum yields decrease considerably with increasing dye concentrations. From measurements in H₂O and D₂O buffer solutions it was concluded that in the case of methylene blue the effect is mainly caused by the quenching of singlet oxygen [rate constant (3–4) × 10⁸ M ⁻¹ s⁻¹]. For the acridine sensitizers both singlet oxygen and dye triplet quenching processes have to be taken into consideration. It has been found that all sensitizers act as competitive inhibitors of the enzymatic reaction of lysozyme. However, the dye-protein interaction near the active center cannot be responsible for the observed dye self-quenching effect.     

Formation of polymeric toroidal-spiral particles

Compared to spherical matrices, particles with well-defined internal structure provide large surface to volume ratio and predictable release kinetics for the encapsulated payloads. We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (T-S) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form T-S channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the T-S shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. We anticipate applications of the T-S particle in drug delivery, wherein diffusion through these T-S channels and the polymer matrix would offer parallel release pathways for molecules of different sizes. Polyphosphate, as a model macromolecule, is entrained in T-S particles during their formation. The in vitro release kinetics of polyphosphate from the T-S particles with various channel length and width is reported. In addition, self-assembly of T-S particles occurs in a single step under benign conditions for delicate macromolecules, and appears conducive to scaleup.     

Hilberts satz Über Flächen Konstanter Negativer Krümmung

Ohne Zusammenfassung     

Colloidal stabilization of nanoparticles in concentrated suspensions

The stabilization of nanoparticles in concentrated aqueous suspensions is required in many manufacturing technologies and industrial products. Nanoparticles are commonly stabilized through the adsorption of a dispersant layer around the particle surface. The formation of a dispersant layer (adlayer) of appropriate thickness is crucial for the stabilization of suspensions containing high nanoparticle concentrations. Thick adlayers result in an excessive excluded volume around the particles, whereas thin adlayers lead to particle agglomeration. Both effects reduce the maximum concentration of nanoparticles in the suspension. However, conventional dispersants do not allow for a systematic control of the adlayer thickness on the particle surface. In this study, we synthesized dispersants with a molecular architecture that enables better control over the particle adlayer thickness. By tailoring the chemistry and length of these novel dispersants, we were able to prepare fluid suspensions (viscosity < 1 Pa.s at 100 s-1) with more than 40 vol % of 65-nm alumina particles in water, as opposed to the 30 vol % achieved with a state-of-the-art dispersing agent. This remarkably high concentration facilitates the fabrication of a wide range of products and intermediates in materials technology, cosmetics, pharmacy, and in all other areas where concentrated nanoparticle suspensions are required. On the basis of the proposed molecular architecture, one can also envisage other similar molecules that could be successfully applied for the functionalization of surfaces for biosensing, chromatography, medical imaging, drug delivery, and aqueous lubrication, among others.     

Bayesian‐type count data models with varying coefficients: estimation and testing in the presence of overdispersion

In this paper we study varying‐coefficient models for count data. A Bayesian approach is taken to model the variability of the regression parameters. Based on a Kalman filter procedure the varying coefficients are estimated as the mode of the posterior distribution. All hyperparameters, including an overdispersion parameter in the negative binomial varying‐coefficient model (NBVC), are estimated as ML‐estimators using an EM‐type algorithm. A bootstrapping test of the fixed‐coefficient hypothesis against a varying‐coefficient alternative is proposed, which is evaluated running a simulation study. The study shows that the choice of a suitable count data model is of special importance in the framework of varying‐coefficient models. The methodology is illustrated analysing the determinants of the number of individual doctor visits. Copyright © 2001 John Wiley & Sons, Ltd.