A cautionary note on thermal runaway reactions in mixtures of 1-alkyl-3-methylimidazolium ionic liquids and N-methylmorpholine-N-oxide

Nicht verfügbarN-Methylmorpholine-N-oxide (NMMO) cannot be completely separated by extraction from mixtures with common 1,3-dialkylimidazolium ionic liquids (ILs) due to strong ionic interactions between the two components. At elevated temperatures, above approx. 90 C, especially under dry conditions and in the presence of acid, alkylating or acylating agents, remaining NMMO in ILs tends to undergo autocatalytic degradation. This is a highly exothermic, unstoppable process that results in explosions, flames, and complete charring of the reaction mixtures. Thus, caution must be exercised when drying or heating ILs that were in previous contact with NMMO, and the absence of amine oxide must be confirmed to avoid potential danger.(VLID)192930

Upper Plate Response to a Sequential Elastic Rebound and Slab Acceleration During Laboratory‐Scale Subduction Megathrust Earthquakes

An earthquake‐induced stress drop on a megathrust instigates different responses on the upper plate and slab. We mimic homogenous and heterogeneous megathrust interfaces at the laboratory scale to monitor the strain relaxation on two elastically bi‐material plates by establishing analog velocity weakening and neutral materials. A sequential elastic rebound follows the coseismic shear‐stress drop in our elastoplastic‐frictional models: a fast rebound of the upper plate and the delayed and smaller rebound on the elastic belt (model slab). A combination of the rebound of the slab and the rapid relaxation (i.e., elastic restoration) of the upper plate after an elastic overshooting may accelerate the relocking of the megathrust. This acceleration triggers/antedates the failure of a nearby asperity and enhances the early slip reversal in the rupture area. Hence, the trench‐normal landward displacement in the upper plate may reach a significant amount of the entire interseismic slip reversal and speeds up the stress build‐up on the upper plate backthrust that emerges self‐consistently at the downdip end of the seismogenic zones. Moreover, the backthrust switches its kinematic mode from a normal to reverse mechanism during the coseismic and postseismic stages, reflecting the sense of shear on the interface

Chiroptical properties of an alternatingly functionalized cellotriose bearing two porphyrin groups.

Right-handedness derived from bisporphyrins attached to a cellotriose backbone at O-6 and O''-6 positions is revealed for the first time. This cellotriose is proposed as a model of alternatingly functionalized cellulosics, which have promising properties for applications in optoelectronics and molecular receptors owing to the chirality and rigid backbone effects

The 2013 cholesterol guideline controversy: Would better evidence prevent pharmaceuticalization?

AbstractCardiovascular disease (CVD) remains the leading cause of death globally. A class of medications, known as statins, lowers low-density lipoprotein cholesterol levels, which are associated with CVD. The newest 2013 U.S. cholesterol guideline contains an assessment of risk that greatly expands the number of individuals without CVD for whom statins are recommended. Other countries are also moving in this direction. This article examines the controversy surrounding these guidelines using the 2013 cholesterol guidelines as a case study of broader trends in clinical guidelines to use a narrow evidence base, expand the boundaries of disease and overemphasize pharmaceutical treatment.We find that the recommendation in the 2013 cholesterol guidelines to initiate statins in individuals with a lower risk of CVD is controversial and there is much disagreement on whether there is evidence for the guideline change. We note that, in general, clinical guidelines may use evidence that has a number of biases, are subject to conflicts of interest at multiple levels, and often do not include unpublished research. Further, guidelines may contribute to the “medicalization” or “pharmaceuticalization” of healthcare.Specific policy recommendations to improve clinical guidelines are indicated: these include improving the evidence base, establishing a public registry of all results, including unpublished ones, and freeing the research process from pharmaceutical sector control

Exploring Alkyl-O-Alkyl Ether Structures in Softwood Milled Wood Lignins

Recent studies have suggested that there are significant amounts of various alkyl ether (Alk-O-Alk; Alk = alkyl) moieties in a spruce native lignin preparation, milled wood lignin (SMWL). However, the comprehensive NMR assignment to these moieties has not been addressed yet. This study focused on investigating different types of Alk-O-Alk structures at the alpha-and gamma-positions of the lignin side chain in an heteronuclear single-quantum coherence (HSQC) spectrum of SMWL using experimental NMR data of lignin and synthesized model compounds. Ambiguous structural features were predicted by computer simulation of 1H and 13C NMR spectra to complement the experimental NMR data. As a result, specific regions in the HSQC spectrum were attributed to different Alk-O-Alk moieties of Alk-O-Alk/beta-O-4 and Alk-O-Alk/beta-beta ' structures. However, the differences between the specific regions were rather subtle; they were not well separated from each other and some major lignin moieties. Furthermore, SMWL contained a large variety of Alk-O-Alk moieties but in minute individual amounts, resulting in rather broad, superimposing resonances. Thus, evaluation did not allow assigning individual types of Alk-O-Alk moieties from the HSQC spectra; instead, they were quantified as total (alpha-and gamma-linked) Alk-O-Alk based on the balance of structural units in the 13C NMR spectra. At last, potential formation mechanisms of various Alk-O-Alk ether structures in lignin biosynthesis, lignin aging, and during ball milling of wood were and discussed.Peer reviewe

Cellulose / Drying of a cellulose II gel: effect of physical modification and redispersibility in water

nicht verf\ufcgbarThe agglomeration of cellulosic materials upon drying, often called hornification, causes a reduction of water retention, among other undesired effects. It is one of the main issues in industrial cellulose processing, especially with regard to nanocelluloses. As a consequence, high transportation and storage costs arise since nanocelluloses need to remain in aqueous suspensions unless trade-offs in reactivity, redispersibility and surface properties are accepted. In this study, different drying strategies for TENCEL\uae gel, a nanostructured gel derived from the Lyocell process consisting of spherical particles, are compared and evaluated. First, freeze-drying with consideration of the influence of freezing temperature and the use of tert-butanol as cryo-protectant, and second, simple oven-drying at 60 \ub0C. Surprisingly, oven-dried xerogels showed higher water retention values and also better colloidal stability than the cryogels. This is in stark contrast to cellulose nanofibrils for which freeze-drying has been shown to be significantly superior to oven drying in terms of redispersibility. For the TENCEL\uae gel, oven-drying was thus selected and the influence of additives on the redispersibility of the cellulose II gel was studied by means of the common water retention value, particle size, colloidal stability, appearance of the redispersed gel and viscosity. The addition of the polysaccharides carboxymethyl cellulose or xanthan showed the most promising results with regard to redispersibility. Also sucrose and ammonium bicarbonate provided higher colloidal stabilities than that of the untreated TENCEL\uae gel. The redispersibility of the cellulose II xerogels could thus be significantly improved by simple and cost-efficient mixing with additives prior to drying

BMC Pharmacology / Spin trapping experiments with ethyl-substituted EMPO derivatives (EEMPO)

Meeting Abstract from 13th Scientific Symposium of the Austrian Pharmacological Society (APHAR). Joint Meeting with the Austrian Society of Toxicology (ASTOX) and the Hungarian Society for Experimental and Clinical Pharmacology (MFT) Vienna, Austria. 22\u201324 November 200

Cellulose / Surface properties and porosity of highly porous, nanostructured cellulose II particles

Abstract in deutscher Sprache nicht verf\ufcgbarRecently, a new member of the nanocellulose family was introduced, a cellulose II gel consisting of nanostructured and spherical particles. In this study, we compared two different drying techniques to obtain highly porous powders from this gel with preserved meso- and macroporous nanostructure: first, freeze-drying after solvent exchange to tBuOH and second, supercritical drying of the respective EtOH alcogel. The approaches yielded aerogel powders with surface areas of 298 and 423 m2/g, respectively. Both powders are amphiphilic and possess energetically heterogeneous surfaces with dominating dispersive term of the surface energy in the range of 50\u201352 mJ/m2, as determined by a combination of physicochemical surface characterization techniques, such as iGC, BET and SEM. Despite the lower surface area, the cheaper and more widespread method, freeze-drying, yields a more polar and reactive cryogel

Cellulose / 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\u2019s 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

Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions. The efficiency of chemical reactions in biological systems is often connected to the properties of confined water, but the developments and applications of artificial mimicking systems are impeded by the complexity of the biological systems. Here, the authors show how surface bound water in nanoporous cellulosic fibers can increase the reaction rate of surface acetylation reactions and enable regioselectivity of the reactionPeer reviewe