DNA Antenna Tile‐Associated Deoxyribozyme Sensor with Improved Sensitivity

Some natural enzymes increase the rate of diffusion‐limited reactions by facilitating substrate flow to their active sites. Inspired by this natural phenomenon, we developed a strategy for efficient substrate delivery to a deoxyribozyme (DZ) catalytic sensor. This resulted in a three‐ to fourfold increase in sensitivity and up to a ninefold improvement in the detection limit. The reported strategy can be used to enhance catalytic efficiency of diffusion‐limited enzymes and to improve sensitivity of enzyme‐based biosensors.     

Enhanced transport properties of Sn-substituted proton-conducting BaZr0.8Sc0.2O3–δ ceramic materials

High-temperature proton conductors based on acceptor-doped barium zirconate exhibit excellent chemical stability in atmospheres containing CO₂ or H₂O. However, due to their refractory nature, these conductors have a low grain growth rate, which negatively affects the overall electrical conductivity. A possible strategy for increasing the ionic conductivity of zirconates lies in the partial substitution of Zr-ions with other isovalent dopants. In this work, we carried out systematic studies of the crystal structure, microstructure, hydration capacity, transport, and thermal properties of BaZr_0.8–xSn_xSc_0.2O_3–δ (x = 0, 0.1, and 0.2). According to X-ray powder diffraction and scanning electron microscopy data, all studied ceramic samples have a cubic perovskite structure, whose average grain size decreases with tin doping. It is found that the composition with x = 0.1 exhibits the highest values in terms of total, ionic, grain, and grain-boundary conductivities. The complex analysis of the obtained data shows that a low-level substitution of Zr⁴⁺- with Sn⁴⁺-ions is a competent approach for designing new proton-conducting electrolytes attractive for high-temperature applications.     

Peculiar electric properties of polarized layer in alkaline silicate glasses

Broadband dielectric spectroscopy (BDS) was applied to study polarization phenomena in alkaline silicate glasses, in particular, properties and structure of subsurface (anodic) polarized layers forming in poling with deposited film electrodes of different structures. A model of poled glasses which does not contradict experimental data is proposed. In accordance with the model, a poled glass is presented as two resistor-capacitor circuits in a series connection, one of which is the polarized layer and another is the rest of the sample. It is found that the electric properties of the layers essentially depend on the structure of the anodic electrode used in glass poling. It is also shown that the dielectric response of poled glass samples is mainly determined by the electric properties of the submicron polarized layers and this gives an opportunity to reveal specific properties of the layers rather than ones of the glass sample bulk. Revealed temperature dependence of DC conductivity of the polarized layers obeys Arrhenius's law, and determining activation energy does not depend on the electrode. Finally, it is noted that today above-mentioned information about polarized layers can be obtained only by BDS.     

Furfural Oxidation with Hydrogen Peroxide Over ZSM-5 Based Micro-Mesoporous Aluminosilicates

Micro-mesoporous aluminosilicates based on ZSM-5 zeolite, obtained by a dual template method, as well as in the presence of a dual-functional template (i.e. a Gemini-type surfactant), were tested in the oxidation of furfural with hydrogen peroxide. Even substantial changes in acidity and porosity of the catalysts result in minor variations of selectivity towards the desired products. Application of the synthesized zeolite-based materials in the oxidation of furfural with hydrogen peroxide leads to formation of 2(5H)-furanone (yield up to 28.5%) and succinic acid (up to 19.5%) as the main C4 reaction products. The kinetic model developed previously to treat the results for oxidation of furfural over sulfated zirconia was able to describe the data also for micro-mesoporous aluminosilicates.

Graphical Abstract

     

Operating limits and features of direct air capture on K2CO3/ZrO2 composite sorbent

Potassium carbonate-based sorbents are prospective materials for direct air capture (DAC). In the present study, we examined and revealed the influence of the temperature swing adsorption (TSA) cycle conditions on the CO₂ sorption properties of a novel aerogel-based K₂CO₃/ZrO₂ sorbent in a DAC process. It was shown that the humidity and temperature drastically affect the sorption dynamic and sorption capacity of the sorbent. When a temperature at the sorption stage was 29 ℃ and a water vapor pressure in the feed air was 5.2 mbar (1 bar = 10⁵ Pa), the composite material demonstrated a stable CO₂ sorption capacity of 3.4% (mass). An increase in sorption temperature leads to a continuous decrease in the CO₂ absorption capacity reaching a value of 0.7% (mass) at T = 80 ℃. The material showed the retention of a stable CO₂ sorption capacity for many cycles at each temperature in the range. Increasing P_H2O in the inlet air from 5.2 to 6.8 mbar leads to instability of CO₂ sorption capacity which decreases in the course of 3 consecutive TSA cycles from 1.7% to 0.8% (mass) at T = 29 ℃. A further increase in air humidity only facilitates the deterioration of the CO₂ sorption capacity of the material. A possible explanation for this phenomenon could be the filling of the porous system of the sorbent with solid reaction products and an aqueous solution of potassium salts, which leads to a significant slowdown in the CO₂ diffusion in the composite sorbent grain. To investigate the regeneration step of the TSA cycle in situ, the macro ATR-FTIR (attenuated total reflection Fourier-transform infrared) spectroscopic imaging was applied for the first time. It was shown that the migration of carbonate-containing species over the surface of sorbent occurs during the thermal regeneration stage of the TSA cycle. The movement of the active component in the porous matrix of the sorbent can affect the sorption characteristics of the composite material. The revealed features make it possible to formulate the requirements and limitations that need to be taken into account for the practical implementation of the DAC process using the K₂CO₃/ZrO₂ composite sorbent.     

Modeling of particle deposition in a vertical turbulent pipe flow at a reduced probability of particle sticking to the wall

Particle deposition on the wall in a dilute turbulent vertical pipe flow is modeled. The different mechanisms of particle transport to the wall are considered, i.e., Brownian motion, turbulent diffusion and turbophoresis. The Saffman lift force, the electrostatic force, the virtual mass effect and wall surface roughness are taken into account in the model developed. A boundary condition that accounts for the probability of particle sticking to the wall is suggested. An analytical solution for deposition of small Brownian particles is obtained. A particle relaxation time range, where the model developed is reliably applicable, is evaluated. Computational results obtained at different particle-wall sticking probabilities in the wide particle relaxation time range are presented and discussed.     

Selective Hydrolysis of Arabinogalactan into Arabinose and Galactose Over Heterogeneous Catalysts

Abstract  

The application of solid acid catalysts for the production of monomers from hemicelluloses can be one of the key steps in developing the concept of an integrated forest biorefinery. Arabinogalactans (AG) are hemicelluloses which can be extracted on an industrial scale from larch wood species and has a great potential as a sustainable feedstock for bio-based products. Hydrolysis of AG to monomers over acidic heterogeneous catalysts (Smopex-101 and Amberlyst 15) was successfully demonstrated for the first time to selectively produce arabinose as the primary product, followed by the release of galactose without further degradation of the monomers.     

The final bleaching of eucalypt kraft pulps with hydrogen peroxide: relationship with industrial ECF bleaching history and cellulose degradation

BACKGROUND: The process of chemical pulp bleaching is based for the most part in chlorine dioxide within elemental chlorine free (ECF) technologies. The use of greener alternatives such as bleaching with hydrogen peroxide (P stage) is not widely used owing to selectivity concerns related to transition metal‐catalyzed decomposition reactions. Even at the final stage where peroxide is recognized to boost brightness and improve the brightness stability of the bleached pulp, cellulose degradation often overcomes these advantages. This paper presents the results of studies intended to optimize final peroxide bleaching performance considering two standard ECF industrial bleaching sequences: the conventional DED and the ECF‐light OQ(PO)D (stages name: D—chlorine dioxide; E—alkaline extraction; O—oxygen; Q—chelation, (PO)—hydrogen peroxide pressurized with oxygen). RESULTS: The addition of sodium diethylenetriaminepentaacetate (DTPA) was the most effective option in terms of DED pulp bleachability and selectivity with hydrogen peroxide, as well as in terms of brightness reversion. As regards the OQ(PO)D pulp, a blend of DTPA and magnesium was the most beneficial in those properties. CONCLUSIONS: The choice of the best hydrogen peroxide stabilizer, among the different tested combinations of magnesium and chelants (EDTA and DTPA) studied, in terms of pulp bleachability, bleaching selectivity and brightness reversion is dependent on the impact of the previous bleaching stages on metallic nature and content. The pulp Mg/(Fe + Cu) ratio was highlighted as a process parameter controlling cellulose degradation in peroxide bleaching. Copyright © 2010 Society of Chemical Industry     

Kinetics of catalytic reactions with two types of sites: nonuniform surfaces

Several aspects of heterogeneous catalytic kinetics over induced nonuniform surfaces are considered. The reaction mechanism is thought to occur through a surface collision of species, adsorbed on two distinct surface sites, which display nonuniform behavior. The expressions for rates of elementary reactions have been deduced within the framework of the surface electronic gas model, which accounts for the case of inhomogeneous surface. Equations for catalyst activity in the range of medium coverage have been derived and compared with the power-law model.