The split network analysis for exploring composition-structure correlations in multi-component glasses: II. Multinuclear NMR studies of alumino-borosilicates and glass-wool fibers

The preceding part [M. Edén, J. Non.-Cryst. Solids, 357, (2011) 1595-1602] introduced the “split network” strategy for estimating the network polymerization degree (r_A) and mean number of bridging oxygen (BO) atoms for a network former A, given that these parameters are known for all other network builders in the multi-component oxide glass. However, as the detailed ordering of BO and non-bridging oxygen (NBO) species is often difficult to assess experimentally, we summarize some “rules of thumb” for predicting the coordination number and tendency to accept NBO ions for Al³⁺, B³⁺, Si⁴⁺ and P⁵⁺ cations: they are helpful in scenarios devoid of experimental data. Using the parameters r and , we present expressions for the BO/NBO distributions among tetrahedrally coordinated cations, as predicted from the binary and random models. Multinuclear ¹¹B, ²⁷Al and ²⁹Si solid-state NMR is exploited to derive the split network representations of a set of Na-Ca-(Al)-(B)-Si-O glasses. These results are subsequently used to gain structural insight into two commercial glass-wool fibers that constitute alumino-borosilicate networks modified by Na⁺, K⁺, Ca²⁺ and Mg²⁺ ions.     

Beyond the speed of light on Finsler spacetimes

As a prototypical massive field theory we study the scalar field on the recently introduced Finsler spacetimes. We show that particle excitations exist that propagate faster than the speed of light recognized as the boundary velocity of observers. This effect appears already in Finsler spacetime geometries with very small departures from Lorentzian metric geometry. It switches on for a sufficiently large ratio of the particle four-momentum and mass, and is the consequence of a modified version of the Coleman–Glashow velocity dispersion relation. The momentum dispersion relation on Finsler spacetimes is shown to be the same as on metric spacetimes, which differs from many quantum gravity models. If similar relations resulted for fermions on Finsler spacetimes, these generalized geometries could explain the potential observation of superluminal neutrinos claimed by the Opera Collaboration.     

Polaron effects and electric field dependence of the charge carrier mobility in conjugated polymers

Charge transport in conjugated polymers has been investigated using Monte Carlo simulations implemented on top of the Marcus theory for donor-acceptor transition rates. In particular, polaron effects and the dependency of the mobility on the temperature and the applied electric field have been studied. The conclusions are that while the qualitative temperature dependence is similar to that predicted by Miller-Abrahams theory in the Gaussian disorder model (GDM), the electric field dependence is characterized by a crossover into the Marcus inverted region, not present in the GDM. Furthermore, available analytical approximations to describe the electric field dependence of the mobility in Marcus theory fail to fit the simulation data and hence cannot be used to directly draw conclusions about the importance of polaron effects for charge transport in conjugated polymers.     

Detection thresholds for gaps, overlaps, and no-gap-no-overlaps

Detection thresholds for gaps and overlaps, that is acoustic and perceived silences and stretches of overlapping speech in speaker changes, were determined. Subliminal gaps and overlaps were categorized as no-gap-no-overlaps. The established gap and overlap detection thresholds both corresponded to the duration of a long vowel, or about 120 ms. These detection thresholds are valuable for mapping the perceptual speaker change categories gaps, overlaps, and no-gap-no-overlaps into the acoustic domain. Furthermore, the detection thresholds allow generation and understanding of gaps, overlaps, and no-gap-no-overlaps in human-like spoken dialogue systems.     

Liquid Chromatographic Analysis of Various Formulations Containing Emtricitabine

A gradient liquid chromatographic (LC) method for control of emtricitabine (FTC) was validated for the analysis of FTC formulations (capsules and oral solution) and fixed-dose-combination tablets containing FTC [FTC combined with tenofovir disoproxil fumarate (TDF) and FTC combined with TDF and efavirenz (EFV)]. The method is based on the purity test recently prescribed in the International Pharmacopoeia and uses a Hypersil BDS C18 column (25 cm × 4.6 mm i.d.), 5 μm kept at a temperature of 35 °C. Other reversed-phase columns were also investigated. The mobile phases for gradient elution consist of acetonitrile, phosphate buffer and water. The flow rate is 1.0 mL min^?1 and UV detection is performed at 280 nm. The method is capable of separating the main components from one another, from the inactive ingredients and from the main degradation products. The method was validated with respect to accuracy, precision, sensitivity and linearity for each component and the solution media were optimized. Finally, commercial FTC capsules, FTC oral solution, FTC/TDF tablets and FTC/TDF/EFV tablets were examined.     

Enantioselective transesterification of a tertiary alcohol by lipase A from Candida antarctica

Chiral tertiary alcohols and their esters represent important flavor compounds and are useful building blocks. Unfortunately, they are accepted by only a few lipases/esterases as substrates and enantioselectivity is usually very low. We report here a highly enantioselective transesterification of the tertiary alcohol 2-phenylbut-3-yn-2-ol using lipase A from Candida antarctica (CAL-A). Under optimized conditions, the corresponding acetate was obtained with 94%ee at 35% conversion equivalent to an enantioselectivity factor of E=65. In contrast, enantioselective hydrolysis of the racemic acetate was not feasible as this is very prone to autohydrolysis.     

Silicate-Phenolic Networks: Coordination-Mediated Deposition of Bioinspired Tannic Acid Coatings

Surface modification with polyphenolic molecules has been pursued in biomedical materials owing to their antioxidant, anti-inflammatory, and antimicrobial characteristics. Recently, the use of silicic acid (Si_aq) as a mediator for efficient surface deposition of tannic acid (TA) was reported, but the postulated Si-TA polymeric networks were not characterized. Herein, we present unambiguous evidence for silicate-TA networks that involve Si−O−C motifs by using solid-state NMR spectroscopy, further supported by XPS and ToF-SIMS. By using QCM-D we demonstrate the advantages of Si_aq, compared to using transition-metal ions, to improve the coating efficiency under mildly acidic conditions. The presented homogenous coating buildup and validated applicability in inorganic buffers broadens the use of TA for surface modifications in technological and biomedical applications.     

A Soluble Donor–Acceptor Double-Cable Polymer: Polythiophene with Pendant Fullerenes

Summary.  We report the synthesis and the spectroscopic properties of a novel soluble thiophene-based copolymer carrying pendant fullerene moieties (donor–acceptor double-cable polymer). Photoinduced absorption (PIA) experiments on spin cast films reveal a photoinduced electron transfer from the polythiophene chain onto the fullerene moieties. The performance of photovoltaic devices produced with this copolymer is also discussed. Corresponding author. E-mail: antonio.cravino@jku.at Received August 16, 2002; accepted (revised) August 26, 2002     

Temperature dependence of electronic coupling through oligo-p-phenyleneethynylene bridges

A series of donor-bridge-acceptor (D-B-A) systems with varying donor-acceptor distances has been studied with respect to the temperature dependence of the triplet excitation energy transfer (TEET) rates. The donor and acceptor, zinc(II) and free-base porphyrin, respectively, were separated by oligo-p-phenyleneethynylene (OPE) bridges, where the number of phenyleneethynylene groups was varied between two and five, giving rise to edge-to-edge separations ranging between 12.7 and 33.4 A. The study was performed in 2-MTHF between room temperature and 80 K. It was found that the distance dependence was exponential, in line with the McConnell model, and the attenuation factor, beta, was temperature dependent. The experimentally determined temperature dependence of beta was evaluated by using a previously derived model for the conformational dependence of the electronic coupling based on results from extensive quantum chemical, DFT and time-dependent DFT (TD-DFT), calculations. Two regimes in the temperature interval could be identified: one high-temperature, low-viscosity regime, and one low-temperature, high-viscosity regime. In the first regime, the temperature dependence of beta was, according to the model, well described by a Boltzmann conformational distribution. In the latter, the molecular motions that govern the electronic coupling are slowed down to the same order of magnitude as the TEET rates. This, in effect, leads to a distortion of the conformational distribution. In the high-temperature regime the model could reproduce the temperature dependence of beta, and the extracted rotational barrier between two neighboring phenyl units of the bridge structure, E(i)=1.1 kJ mol(-1), was in line with previous experimental and theoretical studies. After inclusion of parameters that take the viscosity of the medium into account, successful modeling of the experimentally observed temperature dependence of the distance dependence was achieved over the whole temperature interval.