From Equilibrium Liquid Crystal Formation and Kinetic Arrest to Photonic Bandgap Films Using Suspensions of Cellulose Nanocrystals

in Crystals (2020), 10(3), 199

The lyotropic cholesteric liquid crystal phase developed by suspensions of cellulose nanocrystals (CNCs) has come increasingly into focus from numerous directions over the last few years. In part, this is ... [more ▼]

The lyotropic cholesteric liquid crystal phase developed by suspensions of cellulose nanocrystals (CNCs) has come increasingly into focus from numerous directions over the last few years. In part, this is because CNC suspensions are sustainably produced aqueous suspensions of a fully bio-derived nanomaterial with attractive properties. Equally important is the interesting and useful behavior exhibited by solid CNC films, created by drying a cholesteric-forming suspension. However, the pathway along which these films are realized, starting from a CNC suspension that may have low enough concentration to be fully isotropic, is more complex than often appreciated, leading to reproducibility problems and confusion. Addressing a broad audience of physicists, chemists, materials scientists and engineers, this Review focuses primarily on the physics and physical chemistry of CNC suspensions and the process of drying them. The ambition is to explain rather than to repeat, hence we spend more time than usual on the meanings and relevance of the key colloid and liquid crystal science concepts that must be mastered in order to understand the behavior of CNC suspensions, and we present some interesting analyses, arguments and data for the first time. We go through the development of cholesteric nuclei (tactoids) from the isotropic phase and their potential impact on the final dry films; the spontaneous CNC fractionation that takes place in the phase coexistence window; the kinetic arrest that sets in when the CNC mass fraction reaches ~10 wt.\%, preserving the cholesteric helical order until the film has dried; the 'coffee-ring effect' active prior to kinetic arrest, often ruining the uniformity in the produced films; and the compression of the helix during the final water evaporation, giving rise to visible structural color in the films. [less ▲]

Water Chemistry and Hydrometeorology in a Glacierized Catchment in the Polar Urals, Russia

in Journal of Mountain Science (2014), 11(5), 1097-1111

This study aims to determine the relationships between local meteorological conditions, proglacial river discharge and biogeochemical processes operating in a periglacial basin located in the Polar Ural ... [more ▼]

This study aims to determine the relationships between local meteorological conditions, proglacial river discharge and biogeochemical processes operating in a periglacial basin located in the Polar Ural mountain range, Russia. Fieldwork was conducted in the catchment of Obruchev Glacier (13 km2) during the summer peak flow period in 2008. River discharge was dominated by snowmelt and changed from 3300 l s-1 to less than 1000 l s-1. The mean daily air temperatures of stations situated in the mountain tundra and near Obruchev Glacier from July 11th to August 1st 2008 were 14.4°C and 10.3°C, respectively. The glacial river had low total dissolved solids varying from 4.5 to 9 mg l-1 and coefficients of correlation between Na+ and Cl-, K+ and Cl-, as well as NH4+ and Cl- were 0.94, 0.90 and 0.84, respectively. Rainfall events affected the snowmelt initiation and provided an essential part of the discharge during the intense snowmelt period, which occurred from July 11th to July 18th 2008. Data showed that Na+ and K+ in the surface water derived from snowmelt rather than chemical weathering of silicates. Also, it was obtained that NO3- derived from the melting snowpack, whereas ammonification occurring under the snowpacks was the primary source for NH4+. [less ▲]

Increase of apatite dissolution rate by Scots pine roots associated or not with Burkholderia glathei PML1(12)Rp in open-system flow microcosms

in Geochimica et Cosmochimica Acta (2013), 106

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems ... [more ▼]

The release of nutritive elements through apatite dissolution represents the main source of phosphorus, calcium, and several micronutrients (e.g., Zn, Cu) for organisms in non-fertilized forest ecosystems. The aim of this study was to quantify, for the first time, the dissolution rate of apatite grains by tree roots that were or were not associated with a mineral weathering bacterial strain, and by various acids known to be produced by tree roots and soil bacterial strains in open-system flow microcosms. In addition, we explored whether the mobilization of trace elements (including rare earth elements) upon apatite dissolution was affected by the presence of trees and associated microorganisms. The dissolution rate of apatite by Scots pine plants that were or were not inoculated with the strain Burkholderia glathei PML1(12)Rp, and by inorganic (nitric) and organic (citric, oxalic and gluconic) acids at pH 5.5, 4.8, 3.8, 3.5, 3.0, and 2.0 was monitored in two controlled experiments: “plant–bacteria interaction” and “inorganic and organic acids”. Analyses of the outlet solutions in the “plant–bacteria interaction” experiment showed that Scots pine roots and B. glathei PML1(12)Rp produced protons and organic acids such as gluconate, oxalate, acetate, and lactate. The weathering budget alculation revealed that Scots pines (with or without PML1(12)Rp) significantly increased (factor > 10) the release of Ca, P, As, Sr, Zn, U, Y, and rare earth elements such as Ce, La, Nd from apatite, compared to control abiotic treatment. Scanning electron microscopy observation confirmed traces of apatite dissolution in contact of roots. Most dissolved elements were taken up by Scots pine roots, i.e., approximately 50% of Ca, 70% of P, 30% of As, 70% of Sr, 90% of Zn, and 100% of U, Y, and rare earth elements. Interestingly, no significant additional effect due to the bacterial strain PML1(12)Rp on apatite dissolution and Scots pine nutrition and growth was observed. The “inorganic and organic acids” experiment demonstrated that the apatite dissolution efficacy of organic acids was higher than for the inorganic acid and varied in function of the acids: oxalic acid > citric acid > gluconic acid > nitric acid for pH 63.5. In addition, apatite dissolution increased with increasing acidity for each acid. Only oxalic acid generated non-stoichiometric release of calcium and phosphorus from apatite in the solution at pH 63.5, due to the precipitation of Ca-oxalate crystals at apatite surfaces. Comparison of the experiments revealed that the apatite dissolution rate by Scots pines supplied with nutritive solution at pH 5.5 reached 2.0 10 13 mol cm 2 s 1 and Altogether our results highlight that, through the production of weathering agents, notably protons and organic acids, tree roots and root-associated microorganisms are able to significantly increase the release of macro- and micro-nutrients from apatite, thus maintaining high-nutrient conditions to support their growth. [less ▲]