Search

A practical and efficient method to access polysubstituted aryl sulfides has been discovered via a Lewis acid-catalyzed reaction between alkynyl sulfide and 2-pyrone, involving a Diels-Alder/retro-Diels-Alder pathway. Alkynyl sulfide as an electron-rich dienophile and 2-pyrones as electron-poor dienes are conjunctively transformed into a series of polysubstituted aryl sulfides with broad functional group compatibility in good to excellent yields (40 examples, 43-88% yield). The robustness and practicality of the protocol has been demonstrated through gram-scale synthesis and the ease of transformation of the resulting products.

To address the challenges associated with formaldehyde emissions in engineered wood adhesives and simultaneously enhance adhesive properties related to water resistance, fire resistance, and mold resistance, a novel environmentally sustainable biomass-based adhesive was formulated. In this work, kraft lignin was carboxymethylated and then blended with the soy protein isolate (SPI)-based adhesive, the dry and wet shear strength of the plywood bonded by the resultant adhesive was enhanced from 1.10 and 0.63 MPa to 1.73 and 1.23 MPa, respectively, resulting in improvements of 157% and 195%. Carboxymethylated lignin (CML) significantly improved the mold resistance and flame-resistance residual rate of the adhesive and decreased the water absorption rate from 190% to 108%. Furthermore, the adhesive exhibits outstanding flame-retardancy, with self-extinguishing capability rendering it suitable for industrial production. In addition, we also evaluated the performances of resulting adhesives cured with different diepoxides and triepoxides, and the comparisons of the adhesive in this work to commercial urea glue and soy protein-based adhesives were conducted. To our delight, the SPI-10CML adhesive presented comparable or even improved performances, showing its promising practical applications such as for fire doors., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The efficient synthesis of γ-thiapyrones by a base-mediated Diels-Alder/retro-Diels-Alder reaction of α-pyrones with 5- H -1,2,3-thiadiazoles is reported herein. Thioketenes in situ generated from thiadiazoles as electron-poor dienophile and electron-rich 4-hydroxy-2-pyrones as dienes are conjunctively transformed into a series of γ-thiapyrones with broad functional group compatibility in good to excellent yields (35 examples, 67% average yield).

We report the ionothermal carbonization (ITC) of lignocellulosic biomass in imidazolium tetrachloroferrate ionic liquids (ILs) as an advantageous approach for the preparation of nanostructured carbonaceous materials, namely, ionochars. In a previous study, we investigated the role of the imidazolium cation and demonstrated the possibility of controlling both the textural and morphological properties of ionochars by cation engineering. Although essential for providing intermediate Lewis acidity and relatively high thermal stability, the role of the chloroferrate anion is still open to debate. Herein, we investigated the ITC of sugarcane bagasse and its main component, cellulose, in 1-alkyl-3-methylimidazolium ILs with different chloroferrate anions. We identified anionic speciation and its impact on the properties of the IL by Raman spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The obtained ionochars were characterized by gas physisorption, electron microscopy, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and 13 C solid-state CP-MAS NMR spectroscopy. We show that the anionic species have a predominant impact on the textural and morphological properties of the ionochars.

Valorization of the lignocellulosic side and waste streams is key to making industrial processes more efficient from both an economic and ecological perspective. Currently, the production of sugars from beets results in pulps in large quantities. However, there is a lack of promising opportunities for upcycling these materials despite their promising properties. Here, we investigate beet pulps from two different stages of the sugar manufacturing process as raw materials for supercapacitor electrodes. We demonstrate that these materials can be efficiently converted to activated, highly porous carbons. The carbons exhibit pore dimensions approaching the size of the desolvated K + and SO 4 2- ions with surface areas up to 2600 m 2 g -1 . These carbons were subsequently manufactured into electrodes, assembled in supercapacitors, and tested with environmentally friendly aqueous electrolytes (6 M KOH and 1 M H 2 SO 4 ). Further analysis demonstrated the presence of capacitance-enhancing functionalities, and up to 193 and 177 F g -1 in H 2 SO 4 and KOH, respectively, were achieved, which outperformed supercapacitors prepared from commercial YP80 F. Overall, our study suggests that side streams from sugar manufacturing offer a hidden potential for use in high-performance energy storage devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The utilization of waste generated by natural resources is a crucial problem nowadays. The current study describes the utilization of pineapple ( Ananas comosus ) crown residue husk (PCRh) as a strength additive for low-density polyethylene (LDPE) and ethylene propylene rubber (EPR) composites. The blend composites with 30% husk, 10 wt % EPR, and 60% LDPE content showed much better mechanical properties, such as tensile strength and flexural properties, than pristine LDPE and its binary composite with 10 wt % EPR. The high tensile strength (∼19.28 MPa) and tensile modulus (522.97 MPa) were obtained for the composite consisting of 30 wt % PCRh in the basic polymer matrix. Similarly, the highest flexural strength (∼18.09 MPa) and modulus (∼790.29 MPa) were recorded for the same composition. The incorporation of PCRh with LDPE and EPR was further characterized by attenuated total reflection-Fourier transform infrared, differential scanning calorimetry, field emission scanning electron microscopy, dynamic mechanical analysis, and a universal testing machine to evaluate its impact on various properties., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Polyketone compounds are powerful building blocks to synthesize various organic functional materials. Despite that a great many number of planar and non-planar polyketone building blocks have been developed, one issue is that generally there are only ketone functional groups on the molecular skeleton, which will constrain their transformation and further limit the development of functional materials. In this work, we report the design and synthesis of a building block 9,10-diethyl-9,10-ethenoanthracene-2,3,6,7(9 H ,10 H )-tetraone with additional vinyl functional groups. In addition, its azaacene derivatives were also synthesized, and their preliminary physicochemical properties were studied., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

This study aims to investigate the impact of coating with ground calcium carbonate (GCC) on the optical properties and filler content of white top testliner (WTT) papers. The paper properties investigated include brightness, whiteness, opacity, color coordinates, and yellowness. The results showed that the amount of filler mineral used in the coating process significantly affected the optical properties of the paper. The use of 15% total solids of GCC in the coating suspension resulted in the highest level of whiteness and improved the brightness value by 6.8%. The use of 7% total solids of starch and 15% total solids of GCC reduced the yellowness index by 85%. However, the use of only 7 and 10% total solids of starch had an adverse effect on the yellowness values. The surface treatment led to a significant increase in the filler content of the papers, with a maximum of 23.8% achieved using a coating suspension with 10% total solids of starch solution, 15% total solids of GCC suspension, and 1% dispersant. The starch and GCC in the coating suspension were found to have a direct impact on the filler content of the WTT papers. The addition of a dispersant improved the uniform distribution of the filler minerals and increased the filler content of the WTT. The water resistance of WTT papers increases due to the use of GCC, while their surface strength remains at an acceptable level. The study demonstrates the potential benefits of the surface treatment in terms of cost savings and provides valuable information on the impact of the treatment on the properties of WTT papers., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Cellulose nanocrystals (CNCs) with varied unique properties have been widely used in emulsions, nanocomposites, and membranes. However, conventional CNCs for industrial use were usually prepared through acid hydrolysis or heat-controlled methods with sulfuric acid. This most commonly used acid method generally suffers from low yields, poor thermal stability, and potential environmental pollution. Herein, we developed a high-efficiency and large-scale preparation strategy to produce carboxylated cellulose nanocrystals (Car-CNCs) via carboxymethylation-enhanced ammonium persulfate (APS) oxidation. After carboxymethylation, the wood fibers could form unique "balloon-like" structures with abundant exposed hydroxy groups, which facilitated exfoliating fibril bundles into individual nanocrystals during the APS oxidation process. The production process under controlled temperature, time period, and APS concentrations was optimized and the resultant Car-CNCs exhibited a typical structure with narrow diameter distributions. In particular, the final Car-CNCs exhibited excellent thermal stability (≈346.6 °C) and reached a maximum yield of 60.6%, superior to that of sulfated cellulose nanocrystals (Sul-CNCs) prepared by conventional acid hydrolysis. More importantly, compared to the common APS oxidation, our two-step collaborative process shortened the oxidation time from more than 16 h to only 30 min. Therefore, our high-efficiency method may pave the way for the up-scaled production of carboxylated nanocrystals. More importantly, Car-CNCs show potential for stabilizing Pickering emulsions that can withstand changeable environments, including heating, storage, and centrifugation, which is better than the conventional Sul-CNC-based emulsions., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Here, we investigate the electrochemical properties and stability of 1,1'-ferrocene-bisphosphonates in aqueous solutions. 31 P NMR spectroscopy enables to track decomposition at extreme pH conditions revealing partial disintegration of the ferrocene core in air and under an argon atmosphere. ESI-MS indicates the decomposition pathways to be different in aqueous H 3 PO 4 , phosphate buffer, or NaOH solutions. Cyclovoltammetry exhibits completely reversible redox chemistry of the evaluated bisphosphonates, sodium 1,1'-ferrocene-bis(phosphonate) ( 3 ) and sodium 1,1'-ferrocene-bis(methylphosphonate) ( 8 ), from pH 1.2 to pH 13. Both the compounds feature freely diffusing species as determined using the Randles-Sevcik analysis. The activation barriers determined by rotating disk electrode measurements revealed asymmetry for oxidation and reduction. The compounds are tested in a hybrid flow battery using anthraquinone-2-sulfonate as the counterside, yielding only moderate performance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The regulation of coordination configurations of single-atom sites is highly desirable to boost the catalytic performances of SA catalysts. Here, we demonstrate a versatile complexation-deposition strategy for the synthesis of 13 kinds of dual-metal SA site pairs with uniform and exclusive coordination configurations. The preparation is specifically exemplified by the fabrication of Cu and Co single-atom pairs with the co-existence of N and P heteroatoms through etching and pyrolysis of a pre-synthesized metal-organic framework template. Systematic characterizations reveal the uniform and exclusive coordinative configuration of Cu and Co SA sites in CuN 4 /CoN 3 P 1 and CuN 4 /CoN 2 P 2 , over which the electrons are unsymmetrically distributed. Impressively, the CuN 4 /CoN 2 P 2 site pairs exhibit significantly enhanced catalytic activity and selectivity in the synthesis of a variety of natural flavonoids in comparison with the CuN 4 /CoN 3 P 1 and CuN 4 /CoN 4 counterparts. Theoretical calculation results suggest that the unsymmetrical electron distribution over the CuN 4 /CoN 2 P 2 sites could facilitate the adsorption and disassociation of oxygen molecules via reducing the energy barriers of the generation of the key intermediates and thus kinetically accelerate the oxidative-coupling reaction process., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The valorization of lignin into value-added products by oxidative conversion is a widely studied strategy. However, in many cases, this approach has limited scope for integration into industrial processes. The objective of our work is to maximize overall lignin utilization to produce diverse value-added products with a focus on integration in the existing industrial pulp and paper processes. The utilization of the sequential oxidation strategy using oxygen and ozone resulted in kraft lignin with a marked improvement in carboxyl content and also allowed the formation of vanillin and vanillic acid in the oxygen stage. The sequentially oxidized lignin (OxL-COOH) was then cured with poly(ethylene glycol) diglycidyl ether (PEG-epoxy) to form high-lignin-content (>48 wt %) vitrimers with high thermal stability, fast relaxation, swelling, and self-healing due to the presence of bond-exchangeable cross-linked networks. Overall, this study provides a novel approach for the multidimensional valorization of lignin and demonstrates an integrated approach for kraft lignin valorization in the pulp and paper industry., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Lignin is exceptionally abundant in nature and is regarded as a renewable, cheap, and environmentally friendly resource for the manufacture of aromatic chemicals. A novel Ni 12 P 5 /P-N-C catalyst for catalytic hydrogenolysis of lignin was synthesized. The catalysts were prepared by simple impregnation and carbonization using the nonprecious metal Ni taken up by the cell wall of Chlorella in Ni(NO 3 ) 2 solution. There were only two steps in this process, making the whole process very simple, efficient, and economical. Ni 12 P 5 was uniformly distributed in the catalyst. During the hydrogenolysis of lignin, after 4 h reaction at 270 °C, the yield of bio-oil reached 65.26%, the yield of monomer reached 9.60%, and the selectivity to alkylphenol reached 76.15%. The mixed solvent of ethanol/isopropanol (1:1, v/v) is used as the solvent for the hydrogenolysis of lignin, which not only had excellent hydrogen transferability but also improved the yield of bio-oil, inhibiting the generation of char. No external hydrogen was used, thus avoiding safety issues in hydrogen transport and storage., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The photocatalytic performance of common photocatalysts is limited by their low surface area, insufficient absorption of light energy, and fast photogenerated electron-hole recombination rate. The introduction of Z-scheme photocatalysts decorated with hexagonal boron nitride (h-BN) has already been confirmed to be an effective way to extend the surface area and increase the charge separation, thereby enhancing the photocatalytic performance. In this study, a hexagonal boron nitride (h-BN)-decorated WO 3 /g-C 3 N 4 heterojunction photocatalyst was successfully synthesized via an in situ method using tungstic acid, melamine, and hexagonal boron nitride as the precursors. The physical and chemical properties of the resulting samples were thoroughly characterized. The surface, morphological, and optical properties of the resulting materials were thoroughly characterized by XRD, XPS, SEM, TEM, UV-vis DRS, BET surface areas, PL, and ESR analysis. The WO 3 /g-C 3 N 4 /BN composite exhibited a much higher photocatalytic activity for tetracycline degradation under visible light irradiation than pure g-C 3 N 4 , WO 3 , and BN. The favorable photocatalytic activity of WO 3 /g-C 3 N 4 /BN composites can be ascribed to the increased surface area and enhanced separation efficiency of photogenerated electron-hole pairs by adding h-BN nanosheets and forming the WO 3 /g-C 3 N 4 heterojunction. This work indicates that the WO 3 /g-C 3 N 4 /BN photocatalyst is a promising material in wastewater treatment., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

This study describes the optimization of a eucalyptus elemental chlorine-free (ECF) bleach plant to reduce adsorbable organic halogen (AOX). The correlations between operating conditions of each stage and pulp quality indices as well as the AOX content in wastewater are analyzed, taking an ECF bleaching technology (D 0 EpPD 1 ) as an example. The calculation models of pulp quality indices and AOX content in wastewater are established. Then, an optimization model aiming at minimizing AOX emission is structured. The model shows a good simulation effect because the errors between the calculated and experimental values are within 6.3%. By analyzing the impact of various operating conditions on AOX emissions, it was found that chlorine dioxide reduced in the D 0 stage has the greatest impact on AOX. The optimization results show that AOX can be reduced from 90.84 to 79.58 kg/h, a decrease of 12.5%. The verification experiment results based on the optimized operating conditions showed that the experimental results are in good agreement with the calculated results of the optimization model, and the effect of reducing AOX based on the optimization model is obvious., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Nature sets a great example of how to precisely control self-assembly to obtain distinct structures upon external stimuli and perform specific functions to sustain important biological tasks. In the present study, we report the design and control of self-assembly of an amphiphilic conjugated alkene in water. The morphologies of the self-assembled structures are highly dependent on the anions. The hydrophilic tosylate group can trigger the formation of nanotubes, while the less-hydrophilic inorganic bromide generates vesicles. The interchange of the two different structures can be controlled by employing different anions combined with a couple of reactions that act as signals. The result shown here provides an important tool for manipulating self-assembled behaviors in water and paves the way toward more complex systems., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

In the present study, the immobilization of free pectinase onto polystyrene resin beads via crosslinking with glutaraldehyde was investigated. The immobilized pectinase was characterized by Fourier transform infrared spectroscopy and confocal laser scanning microscopy. After optimizing the immobilization conditions, the optimum pH of immobilized pectinase shifted from 8.0 to 8.5 and the optimum temperature shifted from 45 to 60 °C, showing its improved stability to temperature and pH compared with the free pectinase. The Michaelis-Menten constant K m value of free and immobilized pectinase was determined to be 1.95 and 5.36 mM, respectively. The storage stability of immobilized pectinase was demonstrated with 36.8% of the initial activity preserved after 30 days at 25 °C. The reusability of the immobilized pectinase activity was 54.6% of its initial activity after being recycled six times. Therefore, based on the findings mentioned above, it can be inferred that this simple immobilization technique for pectinase appears to be promising for industrial applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

We present how harmful different wood extractives carried over to paper mill with unbleached softwood Kraft pulp are for the strength of packaging papers and boards. The investigations were done by simulating industrial papermaking conditions in laboratory-scale trials for handsheet production. It was found that fatty acids are the most relevant compounds in the carryover pitch extractives (CPEs), as they readily interfere in fiber-fiber bonding strength, control the properties of CPE micelles, and are furthermore the most abundant compounds. Addition of cationic starch improved strength and evened out the strength differences of handsheets with different CPE compounds. Oleic acid (unsaturated fatty acid) was an exception, as it was above average harmful for paper strength without cationic starch and also heavily impaired the functioning of cationic starch. As a whole, these findings demonstrate that fatty acids, especially unsaturated ones, are the most relevant CPE compounds contributing to the reduced efficiency of cationic starch and decreased strength of unbleached softwood Kraft paper. This makes the cleaning of process waters by precipitating CPEs on the pulp fibers harmful for paper strength., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In recent years, nanocellulose has become an attractive and high-value-added product. The cotton stalk is a waste product with a high cellulose content. Therefore, nanocellulose can be isolated from the cotton stalk. Properties of nanocellulose are affected by its nanoscale. In this study, the characteristics of cellulose in nanoscale were investigated. A series of cotton stalk nanocelluloses were prepared by sulfuric acid hydrolysis to study their physicochemical properties and the differences of nanocelluloses on different nanoscales. The obtained nanocelluloses were analyzed by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TA), and X-ray diffractometry (XRD). From the morphology analysis, the mean length and width of nanocelluloses were decreased to 90.5 and 7.0 nm, respectively. From the FTIR analysis, with the particle size decreasing, hydrogen bonds were broken and recombined. Acid hydrolysis mainly acted on intramolecular hydrogen bonds of cellulose macromolecules, especially on O(3)H···O(5) bonds. The crystal arrangement model of nanocellulose was investigated. From the TA analysis, the thermal property was decreased with a reduction of nanocellulose particle size. The CrI of the cotton stalk nanocellulose was the highest at up to 87.10%. The differences of cotton stalk nanocelluloses give significant changes to physicochemical behaviors at the nanoscale. The research would provide a theoretical basis for the future application of nanocelluloses., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In this investigation, the relationship between fiber properties and papermaking properties of 22 non-wood materials at the unrefined and refined states was assessed. The fiber length had positive and the cell wall thickness had negative correlation on the strength properties for the refined pulp. The relationship between papermaking properties with pulp quality, such as fines, curl index, kink index, external fibrillation, and coarseness, was also determined. The correlations of multiple regression equations of fiber quality parameters were 70.4% for the tensile index and 84.9% for the tear index for the refined pulp. The correlations of multiple regression equations of chemical characteristics of the samples were 81.9% for the pulp yield and 42.7% for the kappa number. Holocellulose and α-cellulose had a positive and lignin had a negative effect on the pulp yield., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported thus far have shortcomings, such as expensive starting materials, complicated synthesis or purification operations, and a low LA yield under harsh reaction conditions. Herein, we develop a novel dual-functional catalyst, HScCl 4 , by combining Brønsted acid (HCl) and Lewis acid (ScCl 3 ) sites. The as-prepared HScCl 4 catalyst shows high efficiency and high selectivity for converting 5-hydroxymethylfurfural (HMF) to LA in a biphasic system consisting of methyl isobutyl ketone (MIBK) and water. The density functional theory (DFT) results show that the synergistic catalytic effect, originating from the Brønsted and Lewis acidic sites of HScCl 4 , significantly decreases the energy barriers of reactants and intermediates, thus facilitating the conversion of HMF to LA. Moreover, the efficient separation of LA in the water-MIBK biphasic system by extracting LA to the MIBK phase minimizes the side reactions of LA and thus the formation of humins while significantly improving the LA yield. The conversion of HMF and the selectivity for LA are 100 and 95.6% at 120 °C for 35 min, respectively. The free energy (Δ G ) and activation energy ( E a ) of the reaction are -30 kcal mol -1 and 13.7 kJ mol -1 , respectively. The developed process provides a green, sustainable, and efficient pathway to produce LA from biomass-derived HMF under mild conditions., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Sugarcane bagasse (SB) and sugarcane trash (SCT) containing 30% hemicellulose content are the waste from the sugarcane industry. Hemicellulose being heterogeneous, more complex, and less abundant than cellulose remains less explored. The optimized conditions for the pretreatment of SB and SCT for maximizing the delignification are soaking in aqueous ammonia (SAA), 18.5 wt %, followed by heating at 70 °C for 14 h. The optimization of hydrolysis of SAA pretreated (ptd) SB and SCT by the Box-Behnken design in the first step of saccharification by xylanase ( Ct Xyn11A) and α-l-arabinofuranosidase ( Ps GH43_12) resulted in the total reducing sugar (TRS) yield of xylooligosaccharides (TRS (XOS) ) of 93.2 mg/g ptd SB and 85.1 mg/g ptd SCT, respectively. The second step of saccharification by xylosidase ( Bo GH43) gave the TRS yield of 164.7 mg/g ptd SB and 147.2 mg/g ptd SCT. The high-performance liquid chromatography analysis of hydrolysate obtained after the second step of saccharification showed 69.6% xylan-to-xylose conversion for SB and 64.1% for SCT. This study demonstrated the optimization of the pretreatment method and of the enzymatic saccharification by recombinant xylanolytic enzymes, resulting in the efficient saccharification of ptd hemicellulose to TRS by giving 73.5% conversion for SB and 71.1% for SCT. These optimized conditions for the pretreatment and saccharification of sugarcane waste can also be used at a large scale., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Microbial endoglucanases belonging to the β-1-4 glycosyl hydrolase family are useful enzymes due to their vast industrial applications in pulp and paper industries and biorefinery. They convert lignocellulosic substrates to soluble sugars and help in the biodegradation process. Various biocomputational tools can be utilized to understand the catalytic activity, reaction kinetics, complexity of active sites, and chemical behavior of enzyme complexes in reactions. This might be helpful in increasing productivity and cost reduction in industries. The present review gives an overview of some interesting aspects of enzyme design, including computational techniques such as molecular dynamics simulation, homology modeling, mutational analysis, etc., toward enhancing the quality of these enzymes. Moreover, the review also covers the aspects of synthetic biology, which could be helpful in faster and reliable development of useful enzymes with desired characteristics and applications. Finally, the review also deciphers the utilization of endoglucanases in biodegradation and emphasizes the use of diversified protein engineering tools and the modification of metabolic pathways for enzyme engineering., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Cleaner production of sugars and pulp from renewable feedstocks has captured significant scientific attention in the recent past because they can be used for various end applications. In the papermaking industry, a major fraction of hemicellulosic sugars is lost during the pulping. The present study aims at retrieving these hemicellulosic sugars through alkali-, hot-water-, and acid-mediated extraction prior to pulping, which otherwise would have been lost during pulping and washing of pulp. These retrieved sugars can be used as feedstocks for renewable energy and value-added products. Different pretreatments were applied, aided with varying temperature, chemical concentrations, and time. Substantial amounts of total reducing sugars (TRSs) up to 21.98, 13.2, and 15.01% were extracted prior to pulping by acid, alkali, and hot-water pretreatments. Compositions of mono sugars present in the treated liquor were also characterized and confirmed by high-performance liquid chromatography analysis. The morphological changes in the wheat straw after pre-extraction were studied using the field emission gun scanning electron microscopy technique. Pulping of untreated and pretreated wheat straw was carried out at different alkali charges (12, 14, and 16% NaOH). Among all, acid-pretreated straw showed an increase in pulp yield by 10.9% at a 16% alkali charge. Physical strength properties of different pulps were further examined. Alkali- and hot-water-pretreated straw pulp retained 94.26 and 83.16% tensile indices and 92.43 and 87.02% burst indices, respectively. An increase in tear index up to 4.32, 2.01, and 2.30% for alkali-, hot-water-, and acid-pretreated straw pulp was achieved, respectively. Hot-water- and alkali-pretreated wheat straw was observed to be conducive for paper production. The integrated use of wheat straw for extraction of underutilized sugars and pulp production in this way may serve as a key stepping stone for future biorefinery designs in pulp and paper mills., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Herein, colloidal dispersions of alkaline nanoparticles (NPs: CaCO 3 and Mg(OH) 2 ) are stabilized by trimethylsilyl cellulose (TMSC) in hexamethyldisiloxane and employed to treat historical wood pulp paper by an effortless dip-coating technique. Both alkaline NPs exhibit high stability and no size and shape changes upon stabilization with the polymer, as shown by UV-vis spectroscopy and transmission electron microscopy. The long-term effect of NP/TMSC coatings is investigated in detail using accelerated aging. The results from the pH-test and back-titration of coated papers show a complete acid neutralization (pH ∼ 7.4) and introduction of adequate alkaline reserve even after prolonged accelerated aging. Scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and infrared and water contact angle measurements showed the introduction of a thin and smooth hydrophobic NP/TMSC coating on the paper fibers. Acid-catalyzed desilylation of TMSC was observed by declining C-Si infrared absorbance peaks upon aging. The CaCO 3 coatings are superior to Mg(OH) 2 with respect to a reduced yellowing and lower cellulose degradation upon aging as shown by colorimetric measurements and degree of polymerization analysis. The tensile strength and folding endurance of coated and aged papers are improved to 200-300 and 50-70% as illustrated by tensile strength and double folding endurance measurements., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

In this work, Kraft lignin (KL) was polymerized with 2-acrylamido-2-methylpropane sulfonic acid (AMPS) to generate an anionic water-soluble KL- g -AMPS polymer. The effects of reaction conditions on the charge density of polymers were evaluated to induce lignin-based polymers with the highest anionic charge density. The optimal process conditions were 2.5 mol/mol AMPS/lignin, 0.6 g/g solid/water ratio, 2.0 initiator/lignin weight ratio, 80 °C, 120 min, and pH 1.5, which yielded KL- g -AMPS with the anionic charge density of 4.28 mequiv/g and the grafting ratio of 285%. The chemical structure and compositions of the polymers were confirmed by 1 H NMR and elemental analysis. The flocculation performance of the polymer was evaluated in an aluminum oxide suspension, and its performance was compared with that of a homopolymer of AMPS produced under the same conditions. In addition, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory was applied to study the flocculation mechanism of the polymers and alumina particles. The results revealed that electrostatic interaction was found to be the dominant force in this flocculation process., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Defect spots degrade paper quality and often cause sheet breaks and other problems in the subsequent coating process. We encountered sporadic surges of defect spots on paper from a paper machine producing printing and writing grades of paper. We found that white or light-colored filler spots and waxy, translucent, elliptical spots accounted for 27.3 and 34.4% of these defects, respectively, and that both types of defect contained unhydrolyzed AKD as a major component. Paper machine's wet-end deposits, however, did not contain unhydrolyzed AKD as a deposit component. We hypothesized that the colloidal stability of AKD was the main factor causing the increase in spot defects, and we verified this by deposit testing experiments. Among the papermaking additives tested, bentonite caused the most significant increase in AKD deposition during testing, which was attributed to its causing the electrostatic coagulation of cationically charged AKD emulsion particles. In contrast, anionically charged AKD emulsions showed improved stability and less deposit formation in the presence of bentonite., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

A sudden surge in the number of translucent and oval-shaped waxy spots caused a serious production loss of the papermaking process. The investigation of the spots revealed that the alkyl ketene dimer (AKD) sizing agent caused the waxy spot problem. A ultraviolet/visible (UV/vis) spectrometry method for the quantitative analysis of AKD was developed and used to reduce the waxy spot problem in paper products. The results showed that the method could be used to quantify AKD in both papermaking stock and white water. The major factors in the papermaking wet end that were associated with the waxy spot problem were evaluated, and practical approaches to solving the AKD retention problem and the waxy spot problem were proposed and implemented. The dosage of a retention aid was found to be the principal factor controlling AKD retention. However, varying the retention aid dosage resulted in the deterioration of the paper formation; therefore, this was not a suitable solution to the waxy spot problem. The type of fixing agent and AKD used was found to be the secondary factor affecting the AKD retention and papermaking system cleanliness. Mill trials were conducted on a paper machine to examine the effects of different fixing agents and AKD types on AKD retention and the waxy spot count at the reel. This approach identified a combination of fixing agent and AKD type that substantially improved AKD retention and reduced the formation of translucent waxy spots in the resulting paper products., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

The properties of carbon, boron nitride, silicon, germanium, and molybdenum disulfide nanotubes in reline (cholinium chloride + urea) deep eutectic solvents were studied by using classical molecular dynamics simulations. These nanotubes + reline nanofluids provide a suitable platform for the development of sustainable thermal engineering applications. The reported results lead to the characterization of nanotube solvation and reline layering around the nanotube surfaces as well as the behavior of reline upon confinement inside the considered nanotube cavities. Changes in reline hydrogen bonding in the presence of the nanotubes are also analyzed and related with the development of stable nanotube dispersions, thus showing reline as a suitable vehicle for nanotubes.

Because of poor water solubility and low thermostability, the application of collagen is limited seriously in fields such as injectable biomaterials and cosmetics. In order to overcome the two drawbacks simultaneously, a novel bifunctional modifier based on the esterification of polyacrylic acid (PAA) with N -hydroxysuccinimide (NHS) was prepared. The esterification degree of PAA-NHS esters was increased upon increasing the NHS dose, which was confirmed by Fourier-transform infrared (FTIR) and nuclear magnetic resonance spectrascopy. FTIR results indicated that the triple helix of the modified collagens remained integrated, whereas the molecular weight became larger, as reflected by the sodium dodecyl sulfate-polyacrylamide gel electrophoresis pattern. The modified collagens displayed excellent water solubility under neutral condition, owing to lower isoelectric point (3.1-4.3) than that of native collagen (7.1). Meanwhile, denaturation temperatures of the modified collagens were increased by 4.8-5.9 °C after modification. The modified collagen displayed hierarchical microstructures, as reflected by field-emission scanning electron microscopy, while atomic force microscopy further revealed a "fishing net-like" network in the nanoscale, reflecting a unique aggregation behavior of collagen macromolecules after modification. As a whole, the PAA-NHS ester as a bifunctional modifier endowed collagen with desired water solubility and thermostability in a conflict-free manner, which was beneficial to the process and application of the water-soluble collagen., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Electrowetting has drawn significant interest because of the potential applications of displays, lab-on-a-chip microfluidic devices, electro-optical switches, and so forth. However, electrowetting display (EWD) is monostable, which needs extra continuous voltage supply to keep contracting the oil. This paper is concerned with the simulation of two-phase liquid flow in three-dimensional EWD pixels with two electrodes (E1 and E2) demonstrating bistability, where power is only needed to move the oil droplet between two stable states. The effects of E1 geometry, E2 geometry, and E2 pulse characteristics on the dynamics of the oil droplet motion have been analyzed. Also, predictions of the transient states in four stages of the reversible bistable operation process have been carried out by employing the finite element method, in qualitative agreement with our experimental results of the monostable EWD and the existing literature. We seek to shed more light on the fundamental two-phase liquid flow in three-dimensional pixels exhibiting bistability for low power EWD and guide optimizing the electrodes to the perfect patterns with the aid of rigorous modeling., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

MOSCED (modified separation of cohesive energy density) is a solubility parameter method that offers an improved treatment of association interactions. Solubility parameter methods are well known for their ability to both make quantitative predictions and offer a qualitative description of the underlying molecular-level driving forces, lending themselves to intuitive solvent selection and design. Currently, MOSCED parameters are available for 130 organic solvents, water, and 33 imidazolium-based room temperature ionic liquids (ILs). In this work, we expand MOSCED to cover 66 additional ILs containing the pyridinium, quinolinium, pyrrolidinium, piperidinium, bicyclic, morpholinium, ammonium, phosphonium, and sulfonium cations using 10,052 experimental limiting activity coefficients. The resulting parameters may readily be used to predict the phase behavior in mixtures involving ILs., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Contributing to recent lignin valorization efforts, this study uses an integrative approach to explore the effects of fractionation parameters on lignin characteristics. The following reaction parameters are explored: water content of the water-organic solvent mixture, reaction temperature, and sulfuric acid content. Ethylene glycol (EG) was selected as the fractionation solvent because of its promising lignin solubility and extractability. This study takes a novel approach in conducting EG-assisted biomass fractionation; instead of removing lignin from the biomass, lignin was extracted and characterized. Lignin characteristics involving recovery and linkages were analyzed. A maximum of 27 wt % lignin recovery was achieved at a low water content (25%) and high reaction temperature (180 °C) in the presence of sulfuric acid (1 wt %). From NMR analysis, aryl-ether linkages, which are important to preserve for lignin valorization, were decomposed as a result of relatively high temperature and the presence of sulfuric acid. Statistical analysis showed that all individual parameters and their interactions had significant effects on lignin recovery. Computational analysis revealed that hydrogen bonding between the EG and lignin macromolecules greatly decreased with an increasing amount of water., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Titanium dioxide nanoparticles were fixed on a glass fiber cloth using zeolite synthesis. This led to the formation of a photocatalytic zeolite cloth (PZC). Cloth samples were characterized by various diffraction and scanning electron microscopic techniques. The evoked results showed that zeolite X was synthesized on the PZC, while titanium dioxide was included within the PZC. Additional PZC analyses indicated that the fiber cross-section had three-layered structures. The outer layer (third layer) contained zeolite X. It was found that most of the titanium dioxide nanoparticles were present between the second (amorphous) and third layers (zeolite) but only a few existed in the zeolite layer. The photocatalytic activity of PZC was evaluated based on the degradation of methylene blue in the presence of ultraviolet irradiation. Findings showed that PZC exhibited increased adsorption and degradation activities compared to the glass fiber cloth on which only titanium dioxide nanoparticles were coated., Competing Interests: The author declares no competing financial interest.

Collagen-based bio-hydrogels are undoubtedly a hot spot in the development of biological dressings for wound healing promotion. Herein, glutamine transaminase (TGase), a biological nontoxic cross-linker with high specific activity and reaction rate under mild conditions, was utilized for the self-catalytic cross-linking of the regenerated collagen (COL) fibril hydrogel fabricated through a molecular self-assembly method. The results showed that the natural triple helical conformation of COL remained completely integrated after self-catalytic cross-linking TGase, which was definitively the fundamental for maintaining its superior bioactivity. It was worth noting that TGase could promote the self-assembly process of COL building blocks into a higher order D-period cross-striated structure. Also, the reconstructed TGase cross-linked COL fibrils exhibited a higher degree of interfiber entanglements with more straight and longer fibrils. Meanwhile, the thermal stability of COL was significantly improved after introducing TGase. Besides, the cytocompatibility analysis suggested that the regenerated COL fibril hydrogel showed excellent cell growth activity and proliferation ability when the dosage of TGase is less than 40 U/g. Further, animal experiments indicated that the targeted COL fibril hydrogel could significantly promote skin wound healing, exhibiting better capacity of skin tissue for regeneration than the COL hydrogel untreated as expected. Therefore, the reconstructed TGase cross-linked COL fibril hydrogel could serve as a novel soft material for wound healing promotion., Competing Interests: The authors declare no competing financial interest.

Annealing strategies for the citrate complexation-combustion method have been explored as a simple approach for improving the catalytic activity of mixed Cr-Mn oxides for the NH 3 -selective catalytic reduction of NO x . Materials prepared at 300 and 400 °C possess largely amorphous structures, consistent with highly dispersed Cr/Mn components. Annealing at 300 °C for 10 h facilitates the formation of catalysts possessing the largest surface area, reducibility, acidity, and activity window (92-239 °C), while areal activity is measured at 3.8 nmol s -1 m -2 and is comparable to values obtained for materials prepared at 400 °C. Conversely, shorter annealing times of 1 and 5 h at 300 °C produce materials that transform NO x about 2-3 times faster at equivalent surface area. Characterization demonstrates that simple annealing strategies have significant impact on the physiochemical and textural properties of these materials. Moreover, reducibility, O α species, and acidity were correlated against areal activity, but only the latter exhibited a near-linear correlation, indicating its dominance in controlling surface reaction rates., Competing Interests: The authors declare no competing financial interest.

Natural cellulose-based materials (CBMs) have considerable potential as strong and lightweight materials for advanced structural applications. Herein, we demonstrate a mechanically strong yet lightweight CBM with highly aligned wood fibers by the coupling pulping of wood blocks with mechanical pressing, which exhibits a tensile strength of 719.0 ± 30.2 MPa, an elastic modulus of 19.0 ± 1.4 GPa, and a density of 1.32 g/cm 3 . The extraordinary mechanical properties of the CBM are mainly ascribed to the good orientation of wood fibers in the longitudinal direction as well as the dramatically increased hydrogen bonds among adjacent fiber cells due to the lignin removal and mechanical pressing. More significantly, the resulting sheet-like anisotropic CBMs can be used to fabricate anisotropic and isotropic bulk CBMs with maximum tensile strengths of 561 and 330 MPa, respectively, through a facile and scalable layer-by-layer stacking method. This work exploits the mechanical potential of cellulose and the large-scale production of anisotropic and isotropic bulk CBMs with extraordinary mechanical performance and may open up a range of novel applications to CBMs., Competing Interests: The authors declare no competing financial interest.

Cellulose/graphene oxide (GO)/iron oxide (Fe 3 O 4 ) composites were prepared by coprecipitating iron salts onto cellulose/GO hydrogels in a basic solution. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and X-ray diffraction characterization showed that Fe 3 O 4 was successfully coated on GO sheets and cellulose. Cellulose/GO/Fe 3 O 4 composites showed excellent catalytic activity by maintaining almost 98% of the removal of acid orange 7 (AO7) and showed stability over 20 consecutive cycles. This performance is attributable to the synergistic effect of Fe 3 O 4 and GO during the heterogeneous Fenton-like reaction. Especially, the cellulose/GO/Fe 3 O 4 composites preserve their activity by keeping the ratio of Fe 3+ /Fe 2+ at 2 even after 20 catalysis cycles, which is supported by XPS analysis., Competing Interests: The authors declare no competing financial interest.

In the context of valorization of lignin produced from the pulp and paper industries, biodegradable UV-protection films were prepared using lignin and cellulose nanocrystals (CNCs). Initially, CNC films were optimized for improving their transparency by studying the effect of various sodium hydroxide (NaOH) concentrations. Maximum (%) transmittance of CNC film was obtained for NaOH addition between 3 and 4 wt %. The optimized CNC suspensions were used for incorporating alkaline lignin (AL) and softwood kraft lignin (SKL) in various concentrations (1-10 wt %). Morphological characterization showed homogeneity of the lignin distribution in CNC/lignin films. Complete UV blocking was achieved at 10 wt % lignin (AL or SKL) in CNC films. Cross-polarized optical microscopy and scanning electron microscopic images of films showed some degrees of global alignment of CNC rods upon addition of NaOH, which remained unaffected by lignin addition. Lignin modification through acetylation reduced the lignin color and improved visible light transmission of films without significantly affecting the UV-absorption properties. Presence of lignin also enhanced the thermal and contact angle stability of the films. This work shows for the first time that CNC aqueous suspensions with and without containing lignin could be tuned through the addition of NaOH to produce transparent and homogenous films, providing a simple and green approach in engineering CNC/lignin UV-protection films., Competing Interests: The authors declare no competing financial interest.

Percolation of contaminated water through paper sheets containing silver nanoparticles is a promising way to provide emergency drinking water. The silver nanoparticles are deposited by the in situ reduction of silver nitrate on the cellulose fibers of an absorbent blotting paper sheet. Sodium borohydride has been used as the reductant but is toxic and expensive. Glucose is a benign alternative but is much less reactive. In this note, we demonstrate an improved way to produce silver nanoparticles in paper sheets by adding sodium hydroxide to the glucose reductant. The silver content of the sheets, measured by diffuse reflectance spectroscopy, was around 2-3 mg of silver per gram of dry paper. This was sufficient to reduce the concentration of a model Escherichia coli suspension after percolation through the sheet., Competing Interests: The authors declare no competing financial interest.

In order to solve the uneven distribution of copper sulfide nanocrystals (CuS-NCs) on cellulose nanofibers (CNFs), this work reports a feasible method to in situ precipitate CuS-NCs on CNF by utilizing biopolymers (lignin, xylan, or starch) as stabilizer and adhesive for fabricating the multifunctional composite papers. In the presence of biopolymers, CuS-NCs deposited in situ on CNF could be capped and stabilized by the biopolymers molecular chains for uniform distribution. Subsequently, biopolymers could anchor CuS-NCs on CNF by the hydrogen bonding. Compared to the composite paper with lignin or xylan as stabilizer and adhesive, CuS-NCs/starch/CNF paper showed the highest content and most uniform and continuous distribution of CuS-NCs, which not only enhanced the conductivity of composite paper to 10.12 S/cm but also increased the reaction rate constant on photocatalytic degradation of rhodamine B to 0.317 min -1 . The reaction rate constant is higher than most of the other reported CuS photocatalysts to date. It indicates that our method has a potential to be a novel strategy to precipitate nanocrystals uniformly on cellulose fibers for fabricating the multifunctional composite paper., Competing Interests: The authors declare no competing financial interest.

Polymers or small molecules with functional groups were always employed to synthesize two-dimensional (2D) silver nanostructures, but the polysaccharides and derivatives have rarely been used for their preparation, let alone of uniform quadrilateral shapes. Herein, amylopectin derivatives containing concentrated carboxyl groups were first used for the synthesis of uniform 2D quadrilateral silver nanoplates (QAgNPs) with lamellar structure. As a native hyperbranched polysaccharide, amylopectin was esterified with 10-undecenoyl chloride and then modified via thiol-ene click chemistry to introduce high amount and high density of carboxyl groups. Then, QAgNPs were synthesized via UV photoreduction in the presence of the resultant amylopectin 11-((3-carboxyl)ethylthio)undecanoate (APUE 3 -MPA) in water-tetrahydrofuran binary system. QAgNPs showed novel uniform quadrilateral shapes with lamellar structure, as verified by their wide-angle X-ray scattering patterns. The average interlayer distance was around 1.3 nm, whereas the average edge lengths of QAgNPs varied between 0.29 ± 0.07 and 1.09 ± 0.25 μm. The concentration of APUE 3 -MPA and the amount of water in the reaction system strongly affected the shapes of QAgNPs. Thus, the reaction system and the arrangement of numerous carboxyl groups were the key factors for the formation of lamellar-structured QAgNPs., Competing Interests: The authors declare no competing financial interest.

The objective of the current research was to fabricate and explore the ability of a renewable resource-based paper strength agent to enhance fiber-fiber bonding and introduce antibacterial properties to recycled fiber paper sheets. The agent corn starch, was modified with diethylenetriamine pentaacetic acid (DTPA), complexed with chitosan, and added to recycled furnishes to provide a plethora of hydrogen bonding sites predicated by acid groups, hydroxyls, and amines. The goal was two-fold: (1) to not only increase interfiber bonding, but (2) afford antibacterial character. The modified corn starch was characterized in previous work by thermal gravimetric analysis, differential scanning calorimeter, and Fourier transform infrared spectroscopy. The recycled pulp slurry was mixed with a ∼1.5% modified starch/chitosan agent before manufacturing a two-dimensional paper substrate that was subjected to mechanical testing. The burst, STFI compressive strength, tensile, and interfiber bonding strength increased 48.8, 49.5, 49.9, and 176%, respectively, while significantly increased gloss was obtained despite slightly diminished tear and roughness. The antibacterial character of these substrates was confirmed by the substrates displaying a 97% bacteria kill rate., Competing Interests: The authors declare no competing financial interest.

In recent years, researchers have made significant progress in the development of inorganic nanofibers (including nanowires). Typically, inorganic nanofibers are synthesized via crystal growth in solution; however, a limited number of studies have focused on their preparation directly from solid raw materials (with no examples of synthesis conducted at room temperature and atmospheric pressure). In this work, we successfully synthesized nanofibers of calcium sulfate hemihydrate (bassanite, CaSO 4 ·0.5H 2 O) at 20 °C and 1 atm by mixing calcite and dilute sulfuric acid in methanol. The bassanite nanofibers are concluded to be synthesized by the formation of calcium sulfate on the calcite surface and its simultaneous reaction with the generated H 2 O. Because bassanite exhibits useful physical properties that include high mechanical strength, high thermal stability, and excellent chemical stability, its nanofibers can be widely applied to rubber, plastics, antifriction materials, and paper as a strengthening agent, for heat-resistance, or as a flame retardant, or for creep resistance., Competing Interests: The authors declare no competing financial interest.

Heavy-metal pollution poses severe threat to ecological systems and presents a great challenge for global sustainability. Portable point-of-care sensing platform for detection/monitoring of heavy-metal pollution in the environment is urgently demanded. Herein, a highly sensitive, robust, and low-cost microfluidic electrochemical carbon-based sensor (μCS) for detection of trace heavy metals is presented. The miniaturized μCS devices are based on a microfluidic paper channel combined with a novel three-dimensional layout with working and counter electrodes facing each other and analyte flowing along the microfluidic channel between these two electrodes. Pristine graphite foil free of any surface modifier is not only used as the electronically conductive pad but also directly employed as the working electrode for fabricating the μCS. The resulting simple and portable device was applied in Cd 2+ and Pb 2+ detection using square-wave anodic stripping voltammetry. Detection limits down to 1.2 μg/L for Cd 2+ and 1.8 μg/L for Pb 2+ can be achieved over the μCS. The μCS devices are also found to be highly robust, and 10 repetitive measurements with a single μCS device resulted to be highly reproducible.

This study describes a new strategy to fabricate a special magnetic catalyst via facile coating Au-Pd nanoalloy catalysts onto a commercial magnetic stirring bar, without the incorporation of iron element. First, the abundant natural "waste" lignin was utilized as the reducing and stabilizing agent to prepare Au-Pd nanoalloys in a green manner. The Au-Pd nanoalloys were assumed to have a core-shell structure with an Au-rich core and a Pd-rich shell. The Au-Pd nanoalloys could be well dispersed in aqueous medium due to the stabilizing effect of lignin and be conveniently coated onto the surface of a commercial stirring bar. The Au 1.0 Pd 1.0 nanoalloy catalyst exhibited excellent catalytic activities in the reduction of 4-nitrophenol to 4-amnophenol by NaBH 4 , with a rate constant ( k ) of 0.239 min -1 , which was higher than that of Au 0.5 Pd 1.0 and Au 2.0 Pd 1.0 nanoalloys and 4 times higher than that of a single-component Au or Pd nanoparticles. Besides, the catalytic ability of Au-Pd nanoalloy catalyst could be maintained even after seven cycles of catalysis. The catalytic rate constant was found to be positively correlated to the stirring speed of the bar. The scanning electron microscopy analysis revealed ravines and pores on the surface of lignin-nanoalloys composites, implying the possible mechanism of the catalytic activities. This study not only proved the feasibility of lignin for green synthesis of Au-Pd nanoalloys but also proposed a facile and innovated strategy for the future production of solid/liquid catalytic platforms where the developed method could be used to coat any surface interfacing the reagents., Competing Interests: The authors declare no competing financial interest.

In the current study, a mediator-free solid-state BiVO 4 /pyridine-doped g-C 3 N 4 nano-Z-scheme photocatalytic system (BDCN) with superior visible-light absorption and optimized photocatalytic activity was constructed via an in situ hydrothermal method for the first time. The pyridine-doped g-C 3 N 4 (DCN) nanosheets show strong absorbance in the visible-light region by pyridine doping, and the BiVO 4 (∼10 nm) nanoparticles are successfully in situ grown on the surface of DCN nanosheets by the controlled hydrothermal method. Under the irradiation of visible light (λ > 420 nm), the BiVO 4 /DCN nanocomposite photocatalysts efficiently degrade phenol and methyl orange (MO) and display much higher photocatalytic activity than the individual DCN, bulk BiVO 4 , or the simple physical mixture of DCN and BiVO 4 . The greatly improved photocatalytic ability is attributed to the construction of the direct Z-scheme system in the BiVO 4 /DCN nanocomposite free from any mediator, which leads to enhanced separation of photogenerated electron-hole pairs, as confirmed by the photocurrent analysis. The possible Z-scheme mechanism of the BiVO 4 /DCN nanocomposite photocatalyst was investigated by transient time-resolved luminescence decay spectrum, active species trapping experiments, electron paramagnetic resonance (EPR) technology, and hydrogen evolution test., Competing Interests: The authors declare no competing financial interest.

Molecular dynamics simulations were employed to both estimate the solubility of nonelectrolyte solids, such as acetanilide, acetaminophen, phenacetin, methylparaben, and lidocaine, in supercritical carbon dioxide and understand the underlying molecular-level driving forces. The solubility calculations involve the estimation of the solute's limiting activity coefficient, which may be computed using conventional staged free-energy calculations. For the case of lidocaine, wherein the infinite dilution approximation is not appropriate, we demonstrate how the activity coefficient at finite concentrations may be estimated without additional effort using the dilute solution approximation and how this may be used to further understand the solvation process. Combining with experimental pure-solid properties, namely, the normal melting point and enthalpy of fusion, solubilities were estimated. The results are in good quantitative agreement with available experimental data, suggesting that molecular simulations may be a powerful tool for understanding supercritical processes and the design of carbon dioxide-philic molecular systems. Structural analyses were performed to shed light on the microscopic details of the solvation of different functional groups by carbon dioxide and the observed solubility trends.

Aqueous suspensions of cellulose nanocrystals (CNCs), prepared from natural cellulose by sulfuric acid hydrolysis, form stable chiral nematic suspensions above a critical CNC concentration. The chiral nematic organization may be preserved in films prepared from the suspensions by evaporation. However, shrinkage, gelation, and shear during film formation impair the optical properties of the dry film. In this article, we report an unusual behavior for a sample in which gelation occurred before the sample reached iridescent pitch values. In attempting to decouple changes in texture due to evaporation from those due to shear relaxation effects for this sample, we observed a transitory nematic-like texture that was induced by shear during the preparation of the sample for polarized light microscopy. We propose that the transition between chiral nematic and nematic structures involves a twist-bend-like intermediate and not an untwisting of the chiral nematic phase., Competing Interests: The authors declare no competing financial interest.