Pumping Between Phases With a Pulsed-Fuel Molecular Ratchet

The sorption of species from solution into and onto solids, surfaces, crystals, gels and other matrices, underpins the sequestering of waste and pollutants, the recovery of precious metals, heterogeneous catalysis, many forms of chemical and biological analysis and separation science, and numerous other technologies. In such cases the transfer of the substrate between phases tends to proceed spontaneously, in the direction of equilibrium. Molecular ratchet mechanisms, where kinetic gating selectively inhibits or accelerates particular steps in a process, makes it possible to drive dynamic systems out of equilibrium. Here we report on a small-molecule pump immobilised on and near the surface of polymer beads, that uses an energy ratchet mechanism to actively transport substrates from solution onto the beads away from equilibrium. One complete cycle of the pump occurs with each pulse of a chemical fuel, synchronizing the ratchet dynamics so that the immobilised molecular machines all act in unison. Upon addition of the trichloroacetic acid fuel, micrometre-diameter polystyrene beads functionalised with an average of ~8×10exp10 molecular pumps per bead, sequester from solution crown ethers appended with a fluorescent tag. Following consumption of the fuel, the rings are mechanically trapped in a higher energy, out-of-equilibrium, state on the beads and cannot be removed by dilution nor by switching the binding interactions off. This differs from dissipative assembled materials that require a continuous supply of energy to persist. Addition of a second pulse of fuel causes the uptake of more macrocycles, which can be labelled with a different fluorescent tag. This drives the system progressively further away from equilibrium and also confers sequence information on the deposited structure. The polymer-bound substrates (and the stored energy) can subsequently be released back to the bulk on demand, either emptying one compartment at a time or all at once. Non-equilibrium sorption by using immobilised artificial molecular machines to pump substrates from solution onto and into materials, offers potential for the transduction of energy from chemical fuels for the storage and release of energy and information.

Water Absorption Kinetics in Composites Degraded by the Radiation Technique

Rubber-based wastes represent challenges facing the global community. Human health protection and preservation of environmental quality are strong reasons to find more efficient methods to induce degradation of latex/rubber products in order to replace devulcanization, incineration, or simply storage, and electron beam irradiation is a promising method that can be can be taken into account. Polymeric composites based on natural rubber and plasticized starch in amounts of 10 to 50 phr, obtained by benzoyl peroxide cross-linking, were subjected to 5.5 MeV electron beam irradiation in order to induce degradation, in the dose range of 150 to 450 kGy. A qualitative study was conducted on the kinetics of water absorption in these composites in order to appreciate their degradation degree. The percentages of equilibrium sorption and mass loss after equilibrium sorption were found to be dependent on irradiation dose and amount of plasticized starch. The mechanism of water transport in composites was studied not only through the specific absorption and diffusion parameters but also by the evaluation of the diffusion, intrinsic diffusion, permeation, and absorption coefficients.

Influence of non-equilibrium sorption on the vertical migration of 137Cs in forest mineral soils of Fukushima prefecture

<p>Vertical migration of radiocesium is a key issue in soils impacted by Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. Among radioactive substances deposited on terrestrial ecosystems, <sup>134</sup>Cs (with half-life 2.07 years) and <sup>137</sup>Cs (with half-life 30.2 years) were dominant and have by far the most radiological significance.</p><p>This work investigates the importance of non-equilibrium sorption on the vertical migration of <sup>137</sup>Cs in field conditions. The equilibrium-kinetic (EK) sorption model was selected as a non-equilibrium parameterization embedding the K<sub>d</sub> approach. It supposes the existence of two types of sorption sites. The first sites are at equilibrium with solution; whereas for the second sites, kinetics of the sorption and desorption are taken into consideration.</p><p>We focused our study on four <sup>137</sup>Cs soil contamination plots measured in a young cedar stand situated around 35 km northwest of the FDNPP. Profiles were sampled at four different dates (2013, 2014, 2016, and 2018) by measuring <sup>137</sup>Cs activity in both organic (humus + litter layer) and mineral soil layers reaching a maximum depth of 20cm.</p><p>To successfully simulate the <sup>137</sup>Cs transfer throughout these soil profiles, the input flux at the top of the mineral soil surface was reconstructed from global monitoring data from the forest stand and a first-order compartment model for the organic layer.</p><p>Our results showed that the inclusion of non-equilibrium sorption slightly improves the realism of simulated <sup>137</sup>Cs profiles compared to the equilibrium hypothesis. While both models were able to reproduce the overall vertical distribution throughout the profiles, the persistent contamination at the surface was closer to the measured value with the EK approach. As a consequence, the K<sub>d</sub> model overestimated the contamination into deeper layers and therefore overestimated the migration velocity of <sup>137</sup>Cs. Fitted sorption parameters suggested a fast sorption kinetic (1 - 7 hours) and a pseudo-irreversible desorption rate (3.2 - 3.4 x 10<sup>6</sup> years), whereas equilibrium sorption (4.0 x 10<sup>-3</sup> L kg<sup>-1</sup> on average) only affected a negligible portion of <sup>137</sup>Cs inventory.</p><p>To further distinguish the models behaviors, short and long term simulations were conducted. By June 2011, EK parameters fitted on our plots realistically reproduced different profiles measured in the same forest study site. Predictive modeling of <sup>137</sup>Cs profiles in soil suggested a strong persistence of the surface <sup>137</sup>Cs contamination by 2030, with exponential profiles consistent with those reported after the Chernobyl accident.</p><p>These results prove that the choice of the sorption model is critical in post-accidental situations. An equilibrium approach can result in an underestimation of <sup>137</sup>Cs residence time in the surface. Whereas a kinetic approach, by distinguishing different sorption and desorption rates, is able to reproduce the slow evolution of <sup>137</sup>Cs soil profiles with time that is already observed in the case of Chernobyl contaminated areas 30 years after the accident. Non equilibrium sorption parameters can be partially inferred from in situ measurements. However, further experiments in controlled conditions are required to better estimate the sorption parameters and to identify the processes behind non-equilibrium sorption.</p>

Adsorption Studies of Volatile Organic Compound (Naphthalene) from Aqueous Effluents: Chemical Activation Process Using Weak Lewis Acid, Equilibrium Kinetics and Isotherm Modelling

This study deals with the preparation of activated carbon (CDSP) from date seed powder (DSP) by chemical activation to eliminate polyaromatic hydrocarbon—PAHs (naphthalene—C10H8) from synthetic wastewater. The chemical activation process was carried out using a weak Lewis acid of zinc acetate dihydrate salt (Zn(CH3CO2)2·2H2O). The equilibrium isotherm and kinetics analysis was carried out using DSP and CDSP samples, and their performances were compared for the removal of a volatile organic compound—naphthalene (C10H8)—from synthetic aqueous effluents or wastewater. The equilibrium isotherm data was analyzed using the linear regression model of the Langmuir, Freundlich and Temkin equations. The R2 values for the Langmuir isotherm were 0.93 and 0.99 for naphthalene (C10H8) adsorption using DSP and CDSP, respectively. CDSP showed a higher equilibrium sorption capacity (qe) of 379.64 µg/g. DSP had an equilibrium sorption capacity of 369.06 µg/g for C10H8. The rate of reaction was estimated for C10H8 adsorption using a pseudo-first order, pseudo-second order and Elovich kinetic equation. The reaction mechanism for both the sorbents (CDSP and DSP) was studied using the intraparticle diffusion model. The equilibrium data was well-fitted with the pseudo-second order kinetics model showing the chemisorption nature of the equilibrium system. CDSP showed a higher sorption performance than DSP due to its higher BET surface area and carbon content. Physiochemical characterizations of the DSP and CDSP samples were carried out using the BET surface area analysis, Fourier-scanning microscopic analysis (FSEM), energy-dispersive X-ray (EDX) analysis and Fourier-transform spectroscopic analysis (FTIR). A thermogravimetric and ultimate analysis was also carried out to determine the carbon content in both the sorbents (DSP and CDSP) here. This study confirms the potential of DSP and CDSP to remove C10H8 from lab-scale synthetic wastewater.

Derivation of pesticide aged sorption parameters from laboratory incubation data

The results of the incubation laboratory experiment showed that the decomposition of cyantraniliprole is bi-phasic and the rapid decomposition in the period after the application of the pesticide is accompanied by a subsequent slowdown of this process. The use of the biexponential equation increased the accuracy of the description of the dynamics of decomposition of cyantraniliprole, as evidenced by the static indices. The bi-exponential equation coefficients were used to calculate the parameters of non-equilibrium sorption. The obtained parameters served as input data for the PEARL model. Modelling the migration of cyantraniliprole with considering aged sorption, showed a significant decrease in the predicted concentrations of the pesticide in percolate.

Adsorption kinetic characteristics of molybdenum in yellow-brown soil in response to pH and phosphate

Molybdenum (Mo) adsorption by acidic yellow-brown soil was investigated as a function of a pH (1–13) and the equilibrium of P solution (0, 3.1, and 31 mg L−1) concentration. Mo adsorption by acidic yellow-brown soil increased within the pH range from 1 to 4. Above pH 4, Mo adsorption decreases with an increase in pH. The maximum adsorption was found between pH 2 and 4. Competitive adsorption experiments showed that the equilibrium sorption data fitted into Langmuir and Freundlich isotherms. The sorption data of Mo on the acidic yellow-brown soil fitted well with the Langmuir isotherm model due to the higher R2 value. A reduction in Mo adsorption by the acidic yellow-brown soil was noticed at higher addition levels of P (3.1 and 31 mg L−1). Therefore, P increasing the bioavailability of Mo and enhancing Mo uptake by plants might be related to the inhibition of Mo absorption by the acidic yellow-brown soil.