Tuning of MgO's base characteristics by blending it with amphoteric ZnO facilitating the selective glucose isomerization to fructose for bioenergy development.

Fructose serves as an important intermediate in the preparation of liquid fuel compounds. Herein, we report its selective production via a chemical catalysis method over ZnO/MgO nanocomposite. The blending of an amphoteric ZnO with MgO reduced the latter's unfavorable moderate/strong basic sites that can influence the side reactions in the sugar interconversion, reducing fructose productivity. Of all the ZnO/MgO combinations, a 1 : 1 ratio of ZnO and MgO showed a 20% reduction in moderate/strong basic sites in MgO with ∼2-2.5 times increase in weak basic sites (overall), which is favorable for the reaction. The analytical characterizations affirmed that MgO settles on the surface of ZnO by blocking the pores. The amphoteric ZnO undertakes the neutralization of the strong basic sites and improves the weak basic sites (cumulative) by the Zn-MgO alloy formation. Therefore, the composite afforded as high as 36% fructose yield and 90% selectivity at 90 °C; especially, the improved selectivity can be accounted for by the effect of both basic and acidic sites. The favorable action of acidic sites in controlling the unwanted side reactions was maximum when an aqueous medium contained 1/5th methanol. However, ZnO's presence regulated the glucose's degradation rate by up to 40% compared to the kinetics of pristine MgO. From the isotopic labelling experiments, the proton transfer pathway (or LdB-AvE mechanism by the formation of 1,2-enediolate) is dominant in the glucose-to-fructose transformation. The composite exhibited a long-lasting ability based on the good recycling efficiency of up to 5 cycles. The insights into the fine-tuning of the physicochemical characteristics of widely available metal oxides would help develop a robust catalyst for sustainable fructose production for biofuel production (via a cascade approach).

Bi2WO6/C-Dots/TiO2: A Novel Z-Scheme Photocatalyst for the Degradation of Fluoroquinolone Levofloxacin from Aqueous Medium.

Photocatalytic materials and semiconductors of appropriate structural and morphological architectures as well as energy band gaps are materials needed for mitigating current environmental problems, as these materials have the ability to exploit the full spectrum of solar light in several applications. Thus, constructing a Z-scheme heterojunction is an ideal approach to overcoming the limitations of a single component or traditional heterogeneous catalysts for the competent removal of organic chemicals present in wastewater, to mention just one of the areas of application. A Z-scheme catalyst possesses many attributes, including enhanced light-harvesting capacity, strong redox ability and different oxidation and reduction positions. In the present work, a novel ternary Z-scheme photocatalyst, i.e., Bi2WO6/C-dots/TiO2, has been prepared by a facile chemical wet technique. The prepared solar light-driven Z-scheme composite was characterized by many analytical and spectroscopic practices, including powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), N2 adsorption-desorption isotherm, Fourier-transform infrared spectroscopy (FT-IR), photoluminescence (PL) and UV-vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of the Bi2WO6/C-dots/TiO2 composite was evaluated by studying the degradation of fluoroquinolone drug, levofloxacin under solar light irradiation. Almost complete (99%) decomposition of the levofloxacin drug was observed in 90 min of sunlight irradiation. The effect of catalyst loading, initial substrate concentration and pH of the reaction was also optimized. The photocatalytic activity of the prepared catalyst was also compared with that of bare Bi2WO6, TiO2 and TiO2/C-dots under optimized conditions. Scavenger radical trap studies and terephthalic acid (TPA) fluorescence technique were done to understand the role of the photo-induced active radical ions that witnessed the decomposition of levofloxacin. Based on these studies, the plausible degradation trail of levofloxacin was proposed and was further supported by LC-MS analysis.

Efficient Conversion of Glucose into Fructose via Extraction-Assisted Isomerization Catalyzed by Endogenous Polyamine Spermine in the Aqueous Phase.

In the present study, natural polyamine spermine is demonstrated as a potential basic catalyst for glucose-to-fructose isomerization. For instance, spermine achieves a decent fructose yield (30% wt) and selectivity (74%) during the single-step aqueous phase isomerization under the modest operating conditions (100 °C for 15 min). In addition to the expected reaction byproduct monosugar mannose, spermine also assists in the synthesis of rare and important monosugar, that is, psicose up to 4% wt. Psicose is a zero calorie rare sugar, exhibits a low caloric value, and possesses anti-adipogenic property. A comparative study involving other polyamines concluded that the presence of 20 amines tends to exhibit the most significant impact in improving the target product yield by releasing a higher number of OH- ions, which are responsible for isomerization through the formation of an enediol anion. An attempt was made to further improve the fructose yield through the addition of neutral salts, but it promoted a meager achievement. In an alternate study, a selective extraction strategy was followed for the isolation of fructose from the reaction mixture. The employed aryl monoboronic acid remarkably improved the net fructose concentration, that is, fructose productivity up to 75% wt (cumulative) and 70% selectivity within three consecutive extractions and isomerization cycles, which is comparatively three times shorter than that reported in the literature. Notably, spermine itself provided the essential and necessary basic environment for selective fructose extraction and glucose isomerization, ruling out the use of any external reagents and thus establishing itself as a versatile material suitable for a typical isomerization reaction in an upscaled reactor.

Improved levulinic acid production from agri-residue biomass in biphasic solvent system through synergistic catalytic effect of acid and products.

In this study, levulinic acid (LA) was produced from rice straw biomass in co-solvent biphasic reactor system consisting of hydrochloric acid and dichloromethane organic solvent. The modified protocol achieved a 15% wt LA yield through the synergistic effect of acid and acidic products (auto-catalysis) and the designed system allowed facile recovery of LA to the organic phase. Further purification of the resulting extractant was achieved through traditional column chromatography, which yielded a high purity LA product while recovering ∼85% wt. Upon charcoal treatment of the resultant fraction generated an industrial grade target molecule of ∼99% purity with ∼95% wt recovery. The system allows the solvent to be easily recovered, in excess of 90%, which was shown to be able to be recycled up to 5 runs without significant loss of final product concentrations. Overall, this system points to a method to significantly reduce manufacturing cost during large-scale LA preparation.

Nano silver particle synthesis using Swertia paniculata herbal extract and its antimicrobial activity.

In the present study, green synthesis of silver nanoparticles (AgNPs) is demonstrated using medicinal herb Swertia paniculata extract. The plant extract acted both as reducing and capping agents during synthesis process, where silver nitrate was used as silver source. Subsequent analysis revealed that particles had size range between 31 and 44 nm and were spherical in shape. Among reaction parameters, temperature and time had significantly influenced the synthesis reaction. Also, synthesized nanoparticles were found stable up to 90 days. Further, antimicrobial activity against gram negative and gram positive bacterial strains was done and results showed that synthesized AgNPs had better antimicrobial activity against Pseudomonas aeruginosa, Klebsiella pneumoniae under standard incubation conditions. Study shows that these particles can be very promising in biomedical applications in future.

Expeditious isomerization of glucose to fructose in aqueous media over sodium titanate nanotubes.

Isomerization reaction of glucose to fructose over sodium titanate nanotubes (Na-TNTs) as a Lewis base catalyst was studied. Analytical instruments recorded the specific structural, textural and basic properties of the as-synthesized Na-TNTs. Furthermore, studying the catalytic isomerization performance of the Na-TNTs confirmed their high catalytic efficiency and suitability in aqueous media. The catalyst prompted rapid glucose isomerization within 2 min by achieving nearly half of the maximum yield, whereas with a prolonged reaction up to 15 min the maximum glucose conversion could be reached with 31.26% fructose yield and 65.26% selectivity under relatively lower operating conditions (100 °C and 10% wt catalyst dose). However, the recyclability performance of the catalyst was not impressive due to the accelerated leaching of cations and surface retention of carbonaceous content, resulting in ∼16% reduced yield after 4 runs. A simple regeneration technique using NaOH led to the initial catalytic activity being totally regained. Overall, a titania-based catalyst (preferably nanotube structured sodium titanate) was shown as a potential catalyst for large-scale demonstration of glucose isomerization to achieve high fructose productivity.

Thermo-chemical pretreatment of rice straw for further processing for levulinic acid production.

A variety of pretreatment protocols for rice straw fiber reconstruction were evaluated under mild conditions (upto 0.2%wt. and 121°C) with the object of improving polymer susceptibility to chemical attack while preserving carbohydrate sugars for levulinic acid (LA) production. Each of the protocols tested significantly enhanced pretreatment recoveries of carbohydrate sugars and lignin, and a NaOH protocol showed the most promise, with enhanced carbohydrate preservation (upto 20% relative to the other protocols) and more effective lignin dissolution (upto 60%). Consequently, post-pretreatment fibers were evaluated for LA preparation using an existing co-solvent system consisting of HCl and THF, in addition supplementation of DMSO was attempted, in order to improve final product recovery. In contrast to pretreatment response, H2SO4 protocol fibers yielded highest LA conc. (21%wt. with 36% carbohydrate conversion efficiency) under the modest reaction conditions. Apparent spectroscopic analysis witnessed for fiber destruction and delocalization of inherent constituents during pretreatment protocols.

Integrated two-stage chemically processing of rice straw cellulose to butyl levulinate.

A two-stage reaction system was developed to synthesize butyl levulinate (BL), a derivative chemical of levulinic acid, from agricultural residue (rice straw). A single reactor was employed during the first processing stage for the conversion of rice straw cellulose to levulinic acid (LA) in a novel co-solvent system consisting of dilute phosphoric acid and tetrahydrofuran. The highest yield of 10.8% wt. LA concentration (i.e., ∼42% of theoretical LA yield) with intermediate residuals concentration of 1.5% wt. glucose and 0.5% wt. 5-hydroxymethylfurfural (5-HMF) on dry weight basis of biomass was obtained at modest reaction conditions. During subsequent esterification reaction, approximately 7.8% wt. BL yield (at 89% conversion yield) was achieved from the solvent extracted precipitate containing majorly LA and residual 5-HMF in the presence of 0.5M sulfuric acid using n-butanol. Based on comparative esterification results obtained using commercial chemicals (LA and 5-HMF), apparently 5-HMF exhibited ∼8% wt. BL yield through direct synthesis in the presence of sulfuric acid using n-butanol under the same specified reaction conditions. Alongside, effectiveness of co-solvent treatment on rice straw for potential fermentable sugar release (glucose) was investigated by subjecting the respective post-reaction solid residues to enzymatic digestion using cellulase and yielded highest of 11% wt. per wt. solids (27% wt. glucose conversion efficiency), amongst solid residues underwent different processing conditions.

Epigallocatechin gallate incorporation into lignin enhances the alkaline delignification and enzymatic saccharification of cell walls.

BACKGROUND: Lignin is an integral component of the plant cell wall matrix but impedes the conversion of biomass into biofuels. The plasticity of lignin biosynthesis should permit the inclusion of new compatible phenolic monomers such as flavonoids into cell wall lignins that are consequently less recalcitrant to biomass processing. In the present study, epigallocatechin gallate (EGCG) was evaluated as a potential lignin bioengineering target for rendering biomass more amenable to processing for biofuel production. RESULTS: In vitro peroxidase-catalyzed polymerization experiments revealed that both gallate and pyrogallyl (B-ring) moieties in EGCG underwent radical cross-coupling with monolignols mainly by ß-O-4-type cross-coupling, producing benzodioxane units following rearomatization reactions. Biomimetic lignification of maize cell walls with a 3:1 molar ratio of monolignols and EGCG permitted extensive alkaline delignification of cell walls (72 to 92%) that far exceeded that for lignified controls (44 to 62%). Alkali-insoluble residues from EGCG-lignified walls yielded up to 34% more glucose and total sugars following enzymatic saccharification than lignified controls. CONCLUSIONS: It was found that EGCG readily copolymerized with monolignols to become integrally cross-coupled into cell wall lignins, where it greatly enhanced alkaline delignification and subsequent enzymatic saccharification. Improved delignification may be attributed to internal trapping of quinone-methide intermediates to prevent benzyl ether cross-linking of lignin to structural polysaccharides during lignification, and to the cleavage of ester intra-unit linkages within EGCG during pretreatment. Overall, our results suggest that apoplastic deposition of EGCG for incorporation into lignin would be a promising plant genetic engineering target for improving the delignification and saccharification of biomass crops.

Hydroxycinnamate conjugates as potential monolignol replacements: in vitro lignification and cell wall studies with rosmarinic acid.

The plasticity of lignin biosynthesis should permit the inclusion of new compatible phenolic monomers, such as rosmarinic acid (RA) and analogous catechol derivatives, into cell-wall lignins that are consequently less recalcitrant to biomass processing. In vitro lignin polymerization experiments revealed that RA readily underwent peroxidase-catalyzed copolymerization with monolignols and lignin oligomers to form polymers with new benzodioxane inter-unit linkages. Incorporation of RA permitted extensive depolymerization of synthetic lignins by mild alkaline hydrolysis, presumably by cleavage of ester intra-unit linkages within RA. Copolymerization of RA with monolignols into maize cell walls by in situ peroxidases significantly enhanced alkaline lignin extractability and promoted subsequent cell wall saccharification by fungal enzymes. Incorporating RA also improved cell wall saccharification by fungal enzymes and by rumen microflora even without alkaline pretreatments, possibly by modulating lignin hydrophobicity and/or limiting cell wall cross-linking. Consequently, we anticipate that bioengineering approaches for partial monolignol substitution with RA and analogous plant hydroxycinnamates would permit more efficient utilization of plant fiber for biofuels or livestock production.