NaOH Aqueous Solution Research Articles

Theoretical Mechanism of Rh-Containing Species Catalyzing the Hydrogenolysis of Lignin Model Compounds Using -CαO-H and -Cα-H Groups as Superior H-Sources.

The hydrogenolysis of lignin model compounds (MCs) into high-value chemicals has received increasing attention, but their catalytic reaction mechanisms are not yet very clear. Here, we report the reaction mechanisms of the hydrogenolysis of MC into 4-acetylanisole (AAL) and guaiacol (GAL) catalyzed by LRuCl3 (L = 4'-(4-methoxyphenyl)-2,2':6',2″-terpyridine) with MC, H2, and 1-phenylethan-1-ol (PEO) as the H-sources in aqueous solution with the Bro̷nsted base (NaOH), at the M06/def2-TZVP, 6-311++G (d,p) theoretical level, namely, RS-Self, RS-H2, and RS-PEO, respectively. After dissociation in NaOH aqueous solution, the LRuCl3 compound can form a stable complex LRh (OH)3 as the initial catalytically active species. Their rate-determining steps are related to the cleavage of the -CαO-H bond in both RS-Self-and RS-PEO, whereas it is associated with the heterolysis of the H-H bond in RS-H2. From NaOH aqueous solution, the OH- ligand of LRh(OH)3 promotes the cleavage of the -CαO-H bond with MC and PEO as H-sources, whereas it advances the heterolysis of the H-H bond with H2 as the H-source, owing to its strong Bro̷nsted basicity. Furthermore, the Rh center of LRh(OH)3 mediates the cleavage of the -Cα-H bond, because of its Lewis acidity. The reaction activity lowers as RS-Self > RS-PEO ≫ RS-H2, which is positively dependent on the protonation degree of the departing H atom. Compounds containing both -CαO-H and -Cα-H groups can act as effective donors for H-sources. In the meantime, the stronger the electron-withdrawing groups they contain, the more pronounced the protonation of the -CαO-H group and the higher the reaction activity in providing H-sources. The present results provide insights into utilizing lignin's own functional groups as a hydrogen source for high-value conversion.

In-situ X-ray analysis of cold alkali dissolution of cellulose pulps of various origin

AbstractThis article elucidates the dissolution of cellulose from different raw materials in NaOH aqueous solution via the combination of synchrotron-radiation-based SAXS/WAXS characterization. The X-ray measurements probed the mesostructure of the cellulose samples during the freeze-thawing cycle allowing tracking the initial swelling of the structure, the kinetics of disintegration of the cellulose crystallites as well as controlling the final state of the cellulose solution, i.e. presence or absence of cellulose aggregates. The individual SAXS and WAXS measurements were fitted and modelled to enable visualisation and tracking of the changes in the structure in relation to temperature during cooling and warming phases. To further increase the understanding of the parameters affecting dissolution different cellulose samples and solution compositions were considered. For this purpose the effect of increasing the concentration of NaOH and adding Zn2+ has been carefully investigated as well as the importance of the cellulose origin. We found consistent development that the dissolution occurs faster at higher concentrations of NaOH and with Zn2+ regardless the origin. Nevertheless, SAXS data show that materials with a larger amount of cellulose I show more apparent swelling in mesoscopic structure than bleached agricultural containing cellulose II. Despite few crystalline residues after the complete cooling-heating cycle shown by WAXS, some cellulose was not completely dissolved as some network structure remained in the samples under the test condition as suggested by SAXS.

A multi-approach study on CO2 absorption in packed beds: Theoretical, experimental, and CFD perspectives on gas phase pulsation

This work seeks to improve CO2 absorption efficiency in packed bed columns by substituting amine-based solvents with sodium hydroxide and implementing gas phase pulsation to enhance mass transfer coefficients. Experimental analysis and computational fluid dynamics modeling were employed to investigate the impact of pulsation on absorption efficiency under various conditions. Essential parameters comprised superficial liquid velocity (1.2–4.6 cm/s), pulsation frequency (0–10 Hz), amplitude (0–20 mm), and NaOH concentration (0.25 N to 2 N), while maintaining a constant superficial gas velocity of 120 cm/s and a solute gas concentration of 13 %. Three packing materials—glass spheres, ceramic Raschig rings, and ceramic Pall rings—were evaluated. The results demonstrated that ceramic Pall rings exhibited the greatest efficiency. Pulsation, namely at 9.06 Hz and 20 mm amplitude, enhanced the volumetric mass transfer coefficient by as much as 4.53 times for Pall rings. Increased column diameters (from 7.00 cm to 11.5 cm) enhanced performance. The findings show advancement of more efficient CO2 absorption (by switching from chemical absorption using amine based solvents to classical chemical absorption using aqueous NaOH solution) for industrial applications, aiding climate change mitigation initiatives.

A method of pretreating incineration ashes containing metallic aluminium using NaOH to mitigate volume expansion under highly alkaline conditions

Globally, millions of tonnes of incineration ashes are produced with a substantial portion remaining underutilized in low-value applications or disposed in landfills. Many types of fly ashes and bottom ashes contain metallic aluminium (Al0), which causes volume expansion when the ashes are used in alkali-activated materials and as a supplementary cementitious material due to the generation of hydrogen gas at high-pH conditions. This phenomenon significantly restricts the potential applications of these ashes. To address this issue, ashes can be pretreated with NaOH to oxidize the metallic aluminium (Al0) before their utilization. This study focuses on investigating the effect of the NaOH pre-treatment duration on fly ashes from the co-combustion of recovered solid fuel, peat, and wood. A pre-treatment process was conducted using 8 mol/L aqueous NaOH solution to treat the fly ash for up to 60 minutes. The formed slurry was subsequently used to prepare alkali-activated material by mixing it with bottom ash and employing either sodium silicate or sodium carbonate as an alkali activator. The NaOH pre-treatment demonstrated a 100 % metallic aluminium conversion into oxidized form resulting enhancement in mechanical performance, microstructure, and water absorption properties. The proposed method offers a highly efficient and rapid solution for eliminating the drawbacks caused by the presence of metallic aluminium and it can be conveniently implemented on construction sites. Concurrently, this study also explores the leaching behaviour of heavy metals during alkali-activation. Significant reductions in the leaching of Ba, Cr, Cu, Mo, and Pb were observed, highlighting the environmental remediation potential of alkali-activation methods.

Green syntheses of novel luminescent lanthanide compounds based on pentafluorobenzoate

Green syntheses employing aqueous solutions of lanthanide chloride, NaOH, and pentafluorobenzoic acid were successfully developed and produced pure dinuclear α-Ln compounds, [Ln(L)3(H2O)4]2·2H2O (L: pentafluorobenzoate) and new ones: η-Ln, Na[Ln(L)3(H2O)4]·L·2H2O, and θ-Ln, with Ln: Eu(III), Gd(III), and Tb(III). The synthesis becomes even greener when mechanochemistry is employed because it is quantitative, solvent-free, fast (30 min), and energy efficient. The θ-Ln compounds still have unknown composition and structure, so its description and properties are not explored. The η-Ln compounds are 1-D coordination polymer with only one bridging L, which leads to a large Ln···Ln distance (6.865 Å). Heteronuclear α-Ln0.50Ln0.50′ and η-LnxLn1−x′ compounds, with x = 0.05, 0.25, 0.50, and 0.75, Ln, Ln′: Eu, Tb, and Gd, have been synthesized by mixing the proper proportion of the lanthanide chlorides in the initial solution. The η-EuxTb1−x materials present Tb(III) → Eu(III) energy transfer, which confers interesting luminescent and photophysical properties with relevant potential applications. The color of the emission under UV irradiation can be tuned by the composition of the η-EuxTb1−x materials as well as by the excitation wavelength. In addition, it was observed a significant increase (ca. 35–260 %) of the D05 Eu(III) emission lifetime in the η-EuxTb1−x compounds by varying the excitation wavelength.

Simultaneously enhancing strength and toughness of coir fiber through NaOH and sodium alginate treatment

Coir fibers are commonly subjected to alkali treatment to eliminate impurities and tune their mechanical properties. However, this process can damage the fibers’ microstructures, posing a challenge in significantly enhancing both strength and toughness simultaneously. Herein, we successfully enhanced both strength and toughness of coir fibers through a combined treatment with NaOH and sodium alginate aqueous solution. Coir fibers treated with 5 wt% NaOH solution, followed by 0.5 wt% sodium alginate solution, exhibit a tensile modulus of 2475.0 MPa, a tensile strength of 126.4 MPa, and a toughness of 30.7 MJ/m³, representing improvements of 57.1 %, 72.7 %, and 116.2 %, respectively, compared to the raw fibers. Mechanistic studies revealed that NaOH treatment effectively removes pectin, hemicellulose and lignin from coir fibers but introduces numerous defects. Sodium alginate can repair these defects by forming hydrogen bonds with the rich oxygen-containing group of coir fibers. The combined treatment also increases the crystallinity of coir fibers from 30.3 % for the raw fibers to 44.1 % by removing a large number of amorphous substances. Additionally, the combined treatment reduces the microfibril angle from ∼63.6° to ∼46.6° by elongating the helix structure and filling the gaps between helical fibers. Our cost-effective strategy not only promotes the applications of coir fibers but also provides guidance for the modification of other natural plant fibers.

Sustainable construction materials from alkali-activated waste fiberglass and waste refractory

In this work, waste fiberglass was up-cycled, alone, or mixed with used alumina-zirconia-silica (AZS) refractory from dismantled glass melting furnaces. Alkali activation was performed by suspending fiberglass and fiberglass/AZS powders in NaOH aqueous solution of various concentrations (8M, 6M, and 3M). The activation of waste fiberglass with 8M NaOH yields a gel with calcium and sodium-containing aluminosilicate hydrates. The addition of AZS refractory enabled the release of aluminates into the solution, which had beneficial effects on the mechanical properties. Low molarity activation yielded weaker materials which could be used as precursors for firing at moderate temperatures (800 °C and 1000 °C) to create cellular glass-ceramics, with a total porosity of up to 92 %. The firing of 8M activated samples resulted in glass ceramics with a 66–75 % porosity range and compressive strength of 10–23Mpa. The compressive strength-to-density ratio before and after firing was comparable to that of established commercial construction materials.

Enhancement in the Stability of Porous Silicon Using Electrochemical Grafting of Polymer 2,6 Dihydroxy Naphthalene

While there have been many advancements related to porous silicon, the reactivity of silicon with the ambient (particularly in environments with oxygen and humidity) has limited its use and integration in a wide variety of applications. Therefore, it is important to passivate the surface of nanostructured/porous silicon. To this end, there have been many reports in literature where passivation of bare (or unpassivated) porous silicon (UPSi) surface has been performed using gas phase techniques (thermal carbonization) and solution-based methods. In this work, we have studied the influence of the electrochemical deposition of polymer 2,6 dihydroxynaphthalene (2,6 DHN), in enhancing the stability of porous silicon surfaces.Porous silicon was synthesized by the electrochemical etching of pre-cleaned p-type silicon substrates with resistivity of about 0.001 Ω-cm to 0.005 Ω-cm, in a PTFE cell that we have fabricated, with 48% HF and ethanol mixture (7:3) as the electrolyte solution, at a current density of about 1.08 A/cm². The polymer solution used for electrodeposition was prepared as a solution of 1 mM 2,6-dihydroxy naphthalene (2,6-DHN) in 100 mL of 1x phosphate buffer solution, which was vacuum infiltrated in the synthesized porous silicon and electrodeposited on the same with the standard three electrodes chronopotentiometry method, at a constant current density of about 2 mA/cm² for 120 seconds. Electrodeposited porous silicon was kept on the hot plate for 10 min at 220℃, followed by a thermal treatment at 600℃, for 180 min, in the presence of N2 flow (1 L/min).The surface morphology of the unpassivated porous silicon (UPSi) and passivated porous silicon (PPSi) are shown in the insets of Fig. 1(a) and (b), respectively. This suggests the presence of an incredibly thin coating of the polymer on the pore walls. The pores in, both, unpassivated and passivated porous silicon samples (UPSi and PPSi) remained open and unobstructed, offering a uniform distribution of pores with sizes ranging between 5 nm and 20 nm.To perform a corrosion test of the UPSi and PPSi, we look at these layers after they have been exposed to 1 M NaOH aqueous solution, for different time durations. We have seen the formation of a spontaneous bubble on the surface of the UPSi sample during the test. To this end, we have observed visible and morphological changes of both UPSi and PPSi samples after the corrosion stability test for 5 seconds and 120 minutes, respectively, as seen in Fig. 1(a) to (h). Due to the very high internal area and the hydrogen-terminated surface, in an aqueous solution, UPSi is oxidized by water at room temperature and degrades. In comparison, the PPSi sample is stable for more than 120 minutes.Electrochemical characterisation of UPSi and PPSi was performed in a 10 mM NaCl aqueous electrolyte with a three-electrode cyclic voltammetry (C-V) setup. C-V measurements of the UPSi sample show strong redox reaction in the potential window of 0 V to 1 V, whereas, the PPSi sample shows a nearly constant charging current response in the potential window of -1 V to 1 V, as shown in Fig. 1(i). These results emphasize that the passivation of porous silicon using 2,6 DHN polymer makes it more stable and less reactive in an aqueous medium. Figure 1

Eco-friendly solvent-based liquid-liquid extraction of phenolic acids from winery wastewater streams

This study proposes liquid-liquid extraction (LLE) for the recovery of phenolic acids from winery wastewater replacing common volatile organic compounds (VOCs) with environmentally friendly solvents. On one hand, terpenes (α-pinene and p-cymene) and terpenoids (eucalyptol and linalool) were selected as green solvents and compared to common VOCs (ethyl acetate or 1-butanol). On the other hand, gallic acid (GA), vanillic acid (VA), syringic acid (SA) and caffeic acid (CA) were selected as phenolic acids to be recovered. The extraction performance was evaluated under different operation conditions: solvent-to-feed ratio, initial concentration of phenolic acids and temperature.This work also evaluated the back-extraction whole process global recovery and solvent regeneration, by means of aqueous NaOH solution. Eucalyptol has shown the highest overall global extraction performance (21.07 % for GA, 93.21 % for VA, 78.79 % for SA, and 80.57 % for CA) and lower water solubility compared to the best performing VOC solvent (1-butanol). Therefore, eucalyptol can be a potential eco-friendly solvent to replace VOCs for sustainable phenolic acid recovery from winery wastewater. Finally, to ensure a clean water stream after the LLE, the traces of solvent were completely removed by electrooxidation with boron-doped diamond anode at a current density of 422.54 A/m2.

Bioadhesive-Inspired Ionomer for Membrane Electrode Assembly Interface Reinforcement in Fuel Cells.

Anion exchange membrane fuel cells promise a sustainable and ecofriendly energy conversion pathway yet suffer from insufficient performance and durability. Drawing inspiration from mussel foot adhesion proteins for the first time, we herein demonstrate catechol-modified ionomers that synergistically reinforce the membrane electrode assembly interface and triple-phase boundary inside catalyst layers. The resulting ionomers present exceptional alkaline stability with only slight ionic conductivity declines after treatment in 2 M NaOH aqueous solution at 80 °C for 2500 h. Adopting catechol-modified ionomer as both anion exchange membrane and binder achieves a single-cell performance increase of 34%, and more importantly, endows fuel cell operation at a current density of 0.4 A cm-2 for over 300 h with negligible performance degradation (with a cell voltage decay rate of 0.03 mV h-1). Combining theoretical and experimental investigations, we reveal the molecular adhesion mechanism between the catechol-modified ionomer and Pt catalyst and illuminate the effect on the catalyst layer microstructure. Of fundamental interest, this bioadhesive-inspired strategy is critical to enabling knowledge-driven ionomer design and is promising for diverse membrane electrode assembly configurational applications.

Simultaneous Determination of Glycerol and Carbohydrates in Sweat by Capillary Electrophoresis with Amperometric Detection

Background: Glycerol, sucrose, lactose, glucose, and fructose are important biomarkers in human sweat because their contents can reflect physiological status and health conditions. It is of high importance to determine them in sweat for health monitoring, disease diagnosis, physical training, etc. Aim: The aim of this work is to develop a method based on capillary electrophoresis and amperometric detection for the simultaneous determination of glycerol and carbohydrates in sweat. Objective: A capillary electrophoretic method based on pipette-tip-based detection electrodes and micro-injectors was developed for the simultaneous determination of glycerol, sucrose, lactose, glucose, and fructose in sweat samples Method: Sweat samples diluted in the background electrolyte of 75 mM NaOH aqueous solution were electrokinetically introduced into a piece of separation capillary via pipette tip-based microinjectors. Glycerol, sucrose, lactose, glucose, and fructose were determined by capillary electrophoresis in combination with a pipette-tip-based copper electrode. Results: At a DC voltage of 12 kV, the capillary electrophoretic separation of the five analytes could be achieved in less than 11 min in a piece of 40 cm long fused silica capillary containing 75 mM NaOH aqueous solution. Linearity was observed between the currents and concentrations, with the limits of detection ranging from 0.21 to 0.72 µM at a detection potential of 0.65 V. Glycerol, sucrose, lactose, glucose, and fructose in sweat samples were positively identified and accurately measured. Conclusion: The method was successfully applied in the simultaneous determination of glycerol and carbohydrates in sweat samples with satisfactory assay results. It will find a wide range of applications in clinical diagnosis, health monitoring, and drug and food analysis.

Influence of anodic treatment of a copper-nickel alloy in a eutectic mixture of choline chloride and urea on the surface morphology and electrocatalytic behavior in the hydrogen evolution reaction

For the first time, we investigated the process of potentiostatic anodic treatment of the surface of a copper (≈55%)-nickel alloy in a eutectic mixture of urea and choline chloride (reline), which is a typical representative of a new generation of ionic liquids, deep eutectic solvents. The anodic behavior of the alloy in the used solvent was characterized by cyclic voltammetry, and the nature of the electrochemical dissolution reactions of individual components of the alloy corresponding to several anodic current waves registered in voltammograms was determined. It was established that the anodic dissolution of the alloy occurs under conditions of salt surface passivation due to the formation of a layer of poorly soluble products of the electrode reaction. It was shown that under conditions of prolonged (150 min) potentiostatic polarization of the alloy in reline for various values of the electrode potential (in the range from 0.1 to 1.7 V relative to the Ag reference electrode), the chemical composition of the surface remained unchanged (i.e., there was no selective etching of individual components of the alloy), but an evolution of surface morphology patterns was observed, the specific type of which depended on the value of the applied potential. Anodic treatment of the Cu-Ni alloy in the reline solvent at any of the investigated anodic potentials led to an increase in the surface roughness coefficient, and electrochemical polishing did not occur. Analysis of kinetic data related to the hydrogen evolution reaction on the surfaces of reline-treated copper-nickel alloys in a 1 M NaOH aqueous solution showed a significant increase in exchange current density. This indicates enhancement of electrocatalytic activity compared to the untreated surface. The observed effect is likely associated with an increase in the true surface area of the alloy available for electrochemical reaction and an increase in the surface concentration of electrocatalytic sites resulting from the anodic dissolution of the alloy. The obtained results can be used in the development of highly efficient and relatively inexpensive electrocatalysts for hydrogen energy.

Effect of NaOH Concentration on Rapidly Quenched Cu–Al Alloy-Derived Cu Catalyst for CO2 Hydrogenation to CH3OH

By utilizing greenhouse gas CO2 and renewable energy-sourced H2 to produce methanol, the “methanol economy” can replace fossil fuels and H2 as the energy storage medium, which not only reduces CO2 emissions, but also mitigates the energy shortage issue. However, the traditional Cu-based catalysts for CO2-to-methanol conversion suffer from low activity at low temperature and high vulnerability to sintering and deactivation. In this contribution, rapidly quenched skeletal Cu catalysts (RQ Cu) are prepared by leaching the RQ Cu–Al alloy with NaOH aqueous solutions of different concentrations. It is found that high NaOH concentration of 10 wt% favors the preparation of the RQ Cu-10 catalyst with higher porosity, lower residual Al content, and larger active Cu surface area (SCu) than the RQ Cu-3 catalyst leached with 3 wt% of NaOH solution. However, in aqueous-phase CO2 hydrogenation at 473 K and 4.0 MPa, the CO2 conversion over the RQ Cu-3 catalyst is more than two times greater than that over the RQ Cu-10 catalyst, and the selectivity and productivity of methanol are 1.20 and 2.69 times of the corresponding values over the RQ Cu-10 catalyst. At 5.0 MPa, the selectivity and productivity of methanol are further boosted to 97.9% and 1.329 mmol gCu–1 h–1 on the RQ Cu-3 catalyst. It is identified that the SCu of the RQ Cu-3 catalyst is well preserved after reaction, while dramatic growth of the Cu crystallites occurs for the RQ Cu-10 catalyst. The better catalytic performance and stability of the RQ Cu-3 catalyst are tentatively attributed to the presence of more residual Al species by using NaOH solution with lower concentration for Al leaching, which acts as the dispersant for the Cu crystallites during the reaction.

Coupling geometric and electronic engineering over RuNi ultrafine alloys for fast boosting hydrolytic dehydrogenation of NH3BH3

Developing a suitable catalyst for ammonia borane (AB, NH3BH3) hydrolysis and clarifying the catalytic mechanism are essential and challenging at present. In this work, RuNi nanoalloys are supported on an N/O co-coped glucose-derived carbon (g-C) with the adsorption-NaBH4 reduction method. Attributed to the particular geometric and anchoring effects, as well as the improved hydrophilicity of the multi-level porous support, the RuNi alloys are highly and firmly confined in the framework of g-C. Specifically, the optimal Ru0.25Ni0.75@g-C with an average alloy particle size of 1.4 nm exhibits pleasurable specific hydrogen evolution rate (437,990 mL min−1 gRu−1) and turnover frequency (1612.37 min−1) in NaOH aqueous solution (1.5 M) at 303 K, superior to the corresponding monometallic counterparts (i.e., Ni@g-C and Ru@g-C) and many previous results. In addition, apart from satisfactory durability, the optimal alloy catalyst delivers an encouraging apparent activation energy (28.1 kJ mol−1). Our work not only explains the geometric and electronic effects on the catalytic performance but also offers a promising catalyst for hydrogen release from liquid-phase AB.

Cellulose aerogel beads and monoliths from CO2-based reversible ionic liquid solution

The CO2-based reversible ionic liquid solution of 1,1,3,3-tetramethylguanidine (TMG) and ethylene glycol (EG) in dimethyl sulfoxide (DMSO) after capturing CO2, (2[TMGH]+[O2COCH2CH2OCO2]2−/DMSO (χRILs = 0.1), provides a sustainable and effective platform for cellulose dissolution and homogeneous utilization. Highly porous cellulose aerogel beads and monoliths were successfully prepared via a sol-gel process by extruding cellulose solution into different coagulation baths (NaOH aqueous solution or alcohols) and exposing the cellulose solution in open environment, respectively, and followed by different drying techniques, including supercritical CO2-drying, freeze-drying and air-drying. The effect of the coagulation baths and drying protocols on the multi-scale structure of the as-prepared cellulose aerogel beads and monoliths were studied in detail, and the sol-gel transition mechanism was also studied by the solvatochromic parameters determination. High specific surface area of 252 and 207 m2/g for aerogel beads and monoliths were achieved, respectively. The potential of cellulose aerogels in dye adsorption was demonstrated.

Calcium-Based Metal-Organic Framework: Detection and Idiosyncratic Removal of Copper by Nano-Particle Deposition.

A novel calcium-based metal-organic framework (CaMOF@LSB) was designed and synthesized, exhibiting dual functionality for both selective detection and removal of Cu2+ ions from aqueous solutions. The framework's stability, including solvent and pH variations, was established with notable thermal resilience. Colorimetric Cu2+ detection (≥5 ppm) with a high capture capacity of 484.2 mg g-1 by CaMOF@LSB places this material among the few that ensure efficient colorimetric detection and high removal capabilities of Cu2+ ions. Batch adsorption experiments revealed pH-dependent behavior and competitive interactions. Langmuir and pseudo-second-order kinetics models aptly described adsorption isotherms and kinetics, respectively. Thermodynamic assessments confirmed spontaneous and endothermic adsorption. Mechanistically, nanoparticle deposition contributes to the Cu2+ uptake. CaMOF@LSB also exhibited one of the best removal behaviour of Cu2+ by means of oxide formation on the surface. Regeneration of CaMOF@LSB was achieved by simple sonication in 0.1 M aqueous NaOH solution. The recyclability was also tested up to 5 cycles, and it exhibited a small decrease in adsorption capacity observed across the cycles. This research presents a promising avenue for addressing heavy metal pollution using metal-organic frameworks, thereby offering potential applications in water purification and environmental pollution monitoring and remediation.

Aggregation behavior and hydrolysis rate of amphiphilic water-dispersed polyester with different contents of sulfonate groups in NaOH aqueous solution

Amphiphilic water-dispersed polyester (WPET) has broad application prospects in the textile field. However, due to the potential interactions between WPET molecules, the stability of WPET solution is susceptible to external factors. In NaOH solution, WPET was first aggregated and then hydrolyzed, and the molecular structure of WPET had a certain effect on the aggregation behavior and hydrolysis rate. In this paper, the aggregation patterns and hydrolysis rate of hydrophilic WPETs with different sulfonate contents in NaOH solution were studied. The results showed that the sulfonate content had a great effect on the aggregation behavior and hydrolytic process in NaOH solution in the PEG-free water-dispersed polyester. Compared with the water-dispersed polyester 9.5 % S-0 % PEG with low sulfonate content, the conformation of the water-dispersed polyester with high sulfonate content 14.1 % S-0 % PEG was looser (ρ = 1.65), and NaOH was more likely to penetrate into the molecule. Hence it is more sensitive to NaOH solution and has the characteristics of rapid aggregation and rapid hydrolysis. The increase of NaOH concentration can accelerate the aggregation and hydrolysis of WPET. Furthermore, the aggregation mechanism of WPET in NaOH solution was revealed. These findings are very useful for predicting the stability and phase transition of water-dispersed polyester in NaOH solution and are of great significance for promoting the application of water-dispersed polyester in the textile field.

Drug Crystal Precipitation in Biorelevant Bicarbonate Buffer: A Well-Controlled Comparative Study with Phosphate Buffer.

The purpose of the present study was to clarify whether the precipitation profile of a drug in bicarbonate buffer (BCB) may differ from that in phosphate buffer (PPB) by a well-controlled comparative study. The precipitation profiles of structurally diverse poorly soluble drugs in BCB and PPB were evaluated by a pH-shift precipitation test or a solvent-shift precipitation test (seven weak acid drugs (pKa: 4.2 to 7.5), six weak base drugs (pKa: 4.8 to 8.4), one unionizable drug, and one zwitterionic drug). To focus on crystal precipitation processes, each ionizable drug was first completely dissolved in an HCl (pH 3.0) or NaOH (pH 11.0) aqueous solution (450 mL, 50 rpm, 37 °C). A 10-fold concentrated buffer solution (50 mL) was then added to shift the pH value to 6.5 to initiate precipitation (final volume: 500 mL, buffer capacity (β): 4.4 mM/ΔpH (BCB: 10 mM or PPB: 8 mM), ionic strength (I): 0.14 M (adjusted by NaCl)). The pH, β, and I values were set to be relevant to the physiology of the small intestine. For an unionizable drug, a solvent-shift method was used (1/100 dilution). To maintain the pH value of BCB, a floating lid was used to avoid the loss of CO2. The floating lid was applied also to PPB to precisely align the experimental conditions between BCB and PPB. The solid form of the precipitants was identified by powder X-ray diffraction and differential scanning microscopy. The precipitation of weak acids (pKa ≤ 5.1) and weak bases (pKa ≥ 7.3) was found to be slower in BCB than in PPB. In contrast, the precipitation profiles in BCB and PPB were similar for less ionizable or nonionizable drugs at pH 6.5. The final pH values of the bulk phase were pH 6.5 ± 0.1 after the precipitation tests in all cases. All precipitates were in their respective free forms. The precipitation of ionizable weak acids and bases was slower in BCB than in PPB. The surface pH of precipitating particles may have differed between BCB and PPB due to the slow hydration process of CO2 specific to BCB. Since BCB is a physiological buffer in the small intestine, it should be considered as an option for precipitation studies of ionizable weak acids and bases.

Catalytic pyrolysis of high-density polyethylene (HDPE) over hierarchical ZSM-5 zeolites produced by microwave-assisted chelation-alkaline treatment

A new microwave (MW) assisted chelation-alkaline strategy was developed to produce hierarchical ZSM-5 zeolites (with external surface area of 203 m2/g) in minutes, leading to the formation of heterogeneous structure with a high-silica shell and aluminium-rich core (silicon-to-aluminium ratios of 49.2 and 37.6, respectively). The zeolites were assessed comparatively by catalytic pyrolysis of high-density polyethylene (HDPE). Compared to the mesoporous ZSM-5 zeolite prepared by the conventional alkaline treatment (via desilication by the NaOH aqueous solution), the hierarchical zeolite by the MW-assisted method showed comparable kinetics in catalytic pyrolysis of HDPE, but with the improved stability in the cyclic pyrolysis-regeneration tests. The improved stability could be due to the better-preserved structural integrity thanks to the relatively milder surface etching by the MW-assisted chelation dealumination method. In addition, compared to the parent ZSM-5, the product distribution of HDPE catalytic pyrolysis over the hierarchical ZSM-5 zeolite showed a higher portion of oil products (i.e., 12 wt% vs. 6.9 wt%) and an improved alkane-to-olefin ratio in the oil products (2.22 vs. 1.86, respectively) due to the reduced acidity and improved hydrogen transfer ability. The MW-assisted chelation-alkaline treatment could be a new strategy to regulate the trade-off between stability and activity of zeolites for catalytic applications.

Dynamic kinetic resolution of an azlactone catalyzed by octahedral chiral-at-metal cobalt(III) complexes under phase-transfer alcoholysis

A family of well-defined octahedral cationic chiral-at- cobalt(III) catalysts based on (R,R)-1,2-cyclohexanediamine and (R,R)-1,2-diphenylethylenediamine has been examined in the dynamic kinetic resolution of an azlactone derived from N-benzoyl-tert-leucine. The reactions catalyzed by 10 mol% of CoIII complexes in the presence of 1 M aqueous NaOH solution under phase-transfer alcoholysis afforded the corresponding benzyl ester of tert-leucine with up to 76% yield and up to 66% enantioselectivity (ee).