Solid-state NMR studies of methyl celluloses. Part 2: Determination of degree of substitution and O-6 vs. O-2/O-3 substituent distribution in commercial methyl cellulose samples

Solid state NMR spectroscopy was applied to determine the overall degree of substitution (DS) and the degrees of substitution at C-6 (DS_C-6) and C-2/3 (DS_C-2/3). Four commercial methyl cellulose samples were used, having a DS between 0.51 and 1.96 as determined by wet-chemical analysis. The strategy and optimization of the NMR data acquisition as well as the data evaluation procedures are explained in detail. Optimization of the approach mainly comprised (a) maximizing the signal by choice of NMR probe, MAS spinning frequency and B ₀ field, (b) minimizing the measurement time by a Torchia-type experiment and (c) suppressing probe background by rotor-synchronized echo detection. Data evaluation used simply the integration of three different spectral ranges in the ¹³C NMR spectrum. The results of the experiments were in good agreement with the wet-chemical data. The NMR approach takes about the same analysis time as the conventional hydrolysis/chromatography analysis. However, it is a generally applicable and simple alternative without need for an extended sample preparation which is most useful if wet-chemical/chromatographic analyses are undesired or unavailable. Further studies have to concentrate on the validation of the analytical method and application to a larger sample array.     

Terahertz applications of carbon nanotubes

We formulate and justify several proposals utilizing unique electronic properties of carbon nanotubes for a broad range of applications to THz optoelectronics, including THz generation by hot electrons in quasi-metallic nanotubes, frequency multiplication in chiral-nanotube-based superlattices controlled by a transverse electric field, and THz radiation detection and emission by armchair nanotubes in a strong magnetic field.     

Kinetics of phase separation in polymer blends for deep quenches

Electro microscopy was used to study the phase separation kinetics of a polystyrene/polyvinylmethylether system subjected to a critical deep quench. The size of the phase-separated domains was found to increase linearly with time, implying that hydrodynamic effects control the rate of growth of the domains in the time scale and temperature range under consideration. From these measurements the growth velocity and approximate diffusion constants can be determined for three different temperatures. Comparison of these results with those obtained by light scattering on other systems and with theoretical predictions is possible by replotting in dimensionless units.     

Plasma diffusion across a magnetic field

Using a simple model of a slowly diffusing plasma across a strong magnetic field, it is demonstrated that plasma mass and energy evolves from an initially given density and temperature distribution into isothermal state with a self-similar diffusion profile that depends only on its initial mass and energy.     

Cellulose solutions in N-methylmorpholine-N-oxide (NMMO) – degradation processes and stabilizers

Efficient stabilization of cellulose solutions in NMMO(1) against side reactions and their harmful effects meansprevention of both homolytic and heterolytic side reactions, which is mainlyaccomplished by trapping radicals, formaldehyde, andN-(methylene)iminium ions (5). Whileradical trapping is commonly reflected by the antioxidativeefficiency, the effectivity against heterolyticdegradationin the Lyocell dope can be expressed by the newly introduced termformaldehyde trapping capacity (FTC). Propyl gallate (PG,4), the most widely applied Lyocell stabilizer nowadays, actsas a phenolic antioxidant, and is finally oxidized to a deeply colored, highlyconjugated chromophore (11) via ellagicacid (10). It was demonstrated that 4 is alsoa quencher of formaldehyde and N-(methylene)iminium ions,both in organic solutions of NMMO and in Lyocell dope. The processes of radicaltrapping and scavenging of HCHO/5 are competitive in the caseof propyl gallate. A novel oxa-chromanol derivative, PBD (14),was designed as stabilizer for Lyocell solutions. In analogy to propyl gallate,PBD acts as a scavenger of all three dangerous species, namely HCHO,5 and radicals. Upon oxidation by radical species, PBDreleasesacetaldehyde which acts as a very efficient HCHO trap. Thus, in contrast topropyl gallate, radical trapping and HCHO trapping are not competitive. Boththeantioxidative efficiency and the capacity to trap HCHO and 5are higher for PBD as compared to propyl gallate. In preliminary stabilizertesting, mixtures of PBD and PG proved to be especially effective.     

On the invariants of the complex Ginzburg-Landau equation

Using Lie group theory, both the invariants and the similarity variables of the complex Ginzburg—Landau equation V_xx = a(V_t + bV) + cV|V|^2kwherea,b,c?Iandk?I are constructed.     

Chromophores from hexeneuronic acids: chemical behavior under peroxide bleaching conditions

Hexeneuronic acids (HexA) are a major cause of discoloration (yellowing/brightness reversion) in pulps from xylan-containing wood, being generated from the xylan’s 4-O-methylglucuronic acid residues. The HexA-derived chromophores, whose identification and structure confirmation have been described in the previous part of this series (Rosenau et al. in Cellulose, 2017), were subject to conditions of peroxide bleaching, i.e. treatment with hydrogen peroxide in alkaline medium. These chromophores, ladder-type oligomers of mixed aromatic-quinoid and mixed furanoid-benzoid character, are degraded relatively quickly to one major product, 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ), and a minor component, 2,5-dihydroxyacetophenone (DHA). These two compounds, which have already been identified as two of the three key chromophores (besides 5,8-dihydroxy-[1,4]-naphthoquinone, DHNQ) in aged cellulosics, are potent chromophores themselves and are subsequently more slowly degraded to non-colored degradation products, according to pathways already described in previous parts of this series. The occurrence of DHBQ and DHA in the bleaching treatment of the HexA-derived chromophores establishes the link between HexA chemistry and the key chromophore classes of residual chromophores found in aged cellulosic materials.     

Vitamin E chemistry. Studies into initial oxidation intermediates of alpha-tocopherol: disproving the involvement of 5a-C-centered "chromanol methide" radicals

Contrary to concepts handed down in the literature from the early days of vitamin E research, one-electron oxidation of vitamin E does not involve 5a-C-centered radicals. A combined approach of analytical techniques, in particular electron paramagnetic resonance spectroscopy (EPR), organic synthesis of special derivatives, isotopic labeling, kinetic studies, and computational chemistry was used to re-evaluate the one-electron and two-electron oxidation chemistry of alpha-tocopherol (alpha-toc). EPR in combination with 5a-13C-labeled compounds provided no indication of the involvement of 5a-C-centered radicals. Oxidation of special tocopherol derivatives were used to disprove the occurrence of 5a-C-centered one-electron intermediates. Additionally it was shown that those vitamin E reactions that were commonly evoked to plead for the involvement of C-centered tocopheryl radicals actually proceeded via heterolytic, i.e., non-radical, intermediates. The results will help to clear widely spread misunderstandings about the chemistry of vitamin E and will have mechanistic implications for the synthesis of tocopherol-based supramolecular structures and 5a-substituted alpha-tocopherol derivatives.     

Phase compactons in chains of dispersively coupled oscillators

We study the phase dynamics of a chain of autonomous oscillators with a dispersive coupling. In the quasicontinuum limit the basic discrete model reduces to a Korteveg-de Vries-like equation, but with a nonlinear dispersion. The system supports compactons: solitary waves with a compact support and kovatons which are compact formations of glued together kink-antikink pairs that may assume an arbitrary width. These robust objects seem to collide elastically and, together with wave trains, are the building blocks of the dynamics for typical initial conditions. Numerical studies of the complex Ginzburg-Landau and Van der Pol lattices show that the presence of a nondispersive coupling does not affect kovatons, but causes a damping and deceleration or growth and acceleration of compactons.