Mapping research on LGBT+ persons' health: a bibliometric analysis.

AIMS: Lesbian, gay, bisexual, transgender and other people (LGBT+) individuals may have a greater risk of experiencing mental and physical health issues. In the past years, the predominant theme of research was HIV/AIDS and sexually transmitted infections (STIs). This study aimed to explore the most recent patterns in medical research concerning LGBT+ persons. METHODS: A bibliometric analysis using Biblioshiny was conducted. Based on previous studies, years of observation ranged between 2008 and 2021. Web of Science Core Collection was used. RESULTS: A total of 31,039 articles were selected. Top journals centered around HIV/AIDS and STIs (n = 6), followed by sexual behaviors/sexuality (n = 2) and LGBT+ health (n = 2). The US led in research output (n = 16,249). Papers were categorized into three main clusters (which showed different evolution across time): one addressing HIV/AIDS, STIs, and sexual behaviors, another focusing on mental health, discrimination, and stigma, and a third, smaller cluster examining transgender, intersex, and gender-diverse health. CONCLUSIONS: This article highlighted a growth in LGBT+ health research, uncovering research disparities among countries. While HIV/AIDS and STIs still dominated, a crucial theme concerning mental health, discrimination, and stigma has been rising. Declining interest in gender-diverse health, and disparities in research attention to different LGBT+ subgroups, underscored the need for more comprehensive and inclusive research to address complex health disparities.

Magnetic Exchange Coupling in Zeolite Copper Dimers and Its Contribution to Methane Activation.

The highly reactive binuclear [Cu2O]2+ active site in copper zeolites activates the inert C-H bond of methane at low temperatures, offering a potential solution to reduce methane flaring and mitigate atmospheric methane levels. While substantial progress has been made in understanding the activation of methane by this core, one critical aspect, the active site's spin, has remained undetermined. In this study, we use variable-temperature, variable-field magnetic circular dichroism spectroscopy to define the ground state spin of the [Cu2O]2+ active sites in Cu-CHA and Cu-MFI. This novel approach allows for site-selective determination of the magnetic exchange coupling between the two copper centers of specific [Cu2O]2+ cores in a heterogeneous mixture, circumventing the drawbacks of bulk magnetic techniques. These experimental findings are coupled to density functional theory calculations to elucidate magnetostructural correlations in copper zeolites that are different from those of homogeneous binuclear Cu(II) complexes. The different spin states for the [Cu2O]2+ cores have different reactivities governed by how methane approaches the active site. This introduces a new understanding of zeolite topological control on active site reactivity.

In Situ UV-Vis-NIR Absorption Spectroscopy and Catalysis.

This review highlights in situ UV-vis-NIR range absorption spectroscopy in catalysis. A variety of experimental techniques identifying reaction mechanisms, kinetics, and structural properties are discussed. Stopped flow techniques, use of laser pulses, and use of experimental perturbations are demonstrated for in situ studies of enzymatic, homogeneous, heterogeneous, and photocatalysis. They access different time scales and are applicable to different reaction systems and catalyst types. In photocatalysis, femto- and nanosecond resolved measurements through transient absorption are discussed for tracking excited states. UV-vis-NIR absorption spectroscopies for structural characterization are demonstrated especially for Cu and Fe exchanged zeolites and metalloenzymes. This requires combining different spectroscopies. Combining magnetic circular dichroism and resonance Raman spectroscopy is especially powerful. A multitude of phenomena can be tracked on transition metal catalysts on various supports, including changes in oxidation state, adsorptions, reactions, support interactions, surface plasmon resonances, and band gaps. Measurements of oxidation states, oxygen vacancies, and band gaps are shown on heterogeneous catalysts, especially for electrocatalysis. UV-vis-NIR absorption is burdened by broad absorption bands. Advanced analysis techniques enable the tracking of coking reactions on acid zeolites despite convoluted spectra. The value of UV-vis-NIR absorption spectroscopy to catalyst characterization and mechanistic investigation is clear but could be expanded.

Advancements and Perspectives toward Lignin Valorization via O-Demethylation.

Lignin represents the largest aromatic carbon resource in plants, holding significant promise as a renewable feedstock for bioaromatics and other cyclic hydrocarbons in the context of the circular bioeconomy. However, the methoxy groups of aryl methyl ethers, abundantly found in technical lignins and lignin-derived chemicals, limit their pertinent chemical reactivity and broader applicability. Unlocking the phenolic hydroxyl functionality through O-demethylation (ODM) has emerged as a valuable approach to mitigate this need and enables further applications. In this review, we provide a comprehensive summary of the progress in the valorization of technical lignin and lignin-derived chemicals via ODM, both catalytic and non-catalytic reactions. Furthermore, a detailed analysis of the properties and potential applications of the O-demethylated products is presented, accompanied by a systematic overview of available ODM reactions. This review primarily focuses on enhancing the phenolic hydroxyl content in lignin-derived species through ODM, showcasing its potential in the catalytic funneling of lignin and value-added applications. A comprehensive synopsis and future outlook are included in the concluding section of this review.

Plasma-Enabled Selective Synthesis of Biobased Phenolics from Lignin-Derived Feedstock.

Converting abundant biomass-derived feedstocks into value-added platform chemicals has attracted increasing interest in biorefinery; however, the rigorous operating conditions that are required limit the commercialization of these processes. Nonthermal plasma-based electrification using intermittent renewable energy is an emerging alternative for sustainable next-generation chemical synthesis under mild conditions. Here, we report a hydrogen-free tunable plasma process for the selective conversion of lignin-derived anisole into phenolics with a high selectivity of 86.9% and an anisole conversion of 45.6% at 150 °C. The selectivity to alkylated chemicals can be tuned through control of the plasma alkylation process by changing specific energy input. The combined experimental and computational results reveal that the plasma generated H and CH3 radicals exhibit a "catalytic effect" that reduces the activation energy of the transalkylation reactions, enabling the selective anisole conversion at low temperatures. This work opens the way for the sustainable and selective production of phenolic chemicals from biomass-derived feedstocks under mild conditions.

Analysis of a direct access testing system for the detection of SARS-CoV-2 in the paediatric population attending school.

Background: During the COVID-19 pandemic, the paediatric population plays a minor role in the spread of the SARS-CoV-2 virus. However, in order to keep schools open and reduce SARS-CoV spreading, it is necessary to identify and isolate early SARS-CoV-2 positive paediatric patients even if they are asymptomatic. The aim of this study was to describe a setting for SARS-CoV 2 testing based on the spontaneous presentation of paediatric patients attending school without a medical prescription and explore its appropriateness. Study design: Cross-sectional study. Methods: The study performed between September 2020 and March 2021 among a sample of 13,283 paediatric patients who underwent a swab in four different hospital settings (school hot spot, emergency department, day hospital setting and hospital wards). For each patients we collected: date of swab execution, type of swab, execution setting of the swab, result of the swab, information about community spread of the virus in the 14 days prior to the swab execution, sex and age. Results: In our sample, females accounted for 45.8%. The median age was 6.8 years (IQR 3.0-11.2) and the most frequent age category was between 6 and 11 years (27.9%). At multivariable models with a swab tested positive as outcome. The swabs executed in all the hospital settings had a lower likelihood of resulting positive compared with the school hot spot setting. Compared with adolescents aged between 14 and 19 years old, new-borns below 3 months (adjOR 1.83, 95% C.I. 1.14-3) and patients aged between 11 and 14 years old (adjOR 1.32, 95% C.I. 1.07-1.63) reported a higher probability of a swab tested positive. Instead, children aged between 3 months and 3 years (adjOR 0.77, 95% C.I. 0.61-0.96) and children aged between 3 years and 6 years (adjOR 0.66, 95% C.I. 0.53-0.83) were less likely to result positive. The higher was the mean of pooled Rt in the 14 days preceding the swab, the higher was the likelihood of resulting positive (adjOR 1.75, 95% C.I. 1.53-1.99). Conclusion: In conclusion, we found a high incidence of paediatric patients positive to the test for the detection of SARS-CoV-2 at the school hot spot compared with other settings during the period of observation. The free access modality to the nasopharyngeal swab was effective in identifying patients with COVID-19. Public health authorities should implement these testing modality in order to help reduce the spread of SARS-CoV-2 in school settings.

Coupled sorptive and oxidative antimony(III) removal by iron-modified biochar: Mechanisms of electron-donating capacity and reactive Fe species.

Sorption and oxidation are two potential pathways for the decontamination of trivalent antimony (Sb(III))-bearing water, using iron (Fe)-modified biochar (FeBC). Here we investigated the sorption and oxidation behavior of FeBC for Sb(III) in aqueous solutions. Results revealed that Sb(III) removal by FeBC was significantly improved showing the maximum Sb(III) sorption (64.0 mg g-1). Density functional theory (DFT) calculations indicated that magnetite (Fe3O4) in FeBC offered a sorption energy of -0.22 eV, which is 5 times that of non-modified biochar. With the addition of peroxymonosulfate (PMS), the sorption of Sb(III) on FeBC was 7 times higher than that on BC, indicating the sorption capacity of FeBC for Sb(III) could be substantially increased by adding oxidizing agents. Electrochemical analysis showed that Fe modification imparted FeBC higher electron-donating capacity than that of BC (0.045 v. s. 0.023 mmol e- (g biochar)-1), which might be the reason for the strong Sb(III) oxidation (63.6%) on the surface of FeBC. This study provides new information that is key for the development of effective biochar-based composite materials for the removal of Sb(III) from drinking water and wastewater. The findings from this study have important implications for protecting human health and agriculture.

Prevention of the Werther effect: compliance of the Italian newspapers to the 'reporting on suicide' recommendations.

OBJECTIVES: Suicide media coverage could lead to imitation, the so-called 'Werther effect'. The World Health Organization (WHO) published specific recommendations for reporting suicide news. This study aimed to quantify the compliance of Italian newspapers with the WHO suicide reporting guidelines. STUDY DESIGN: This was a quantitative content analysis study. METHODS: All articles published by the three main Italian newspapers from June 2019 to May 2020 describing suicides or attempted suicides were included. The articles were analyzed using a checklist based on the WHO recommendations, which included 18 'negative' items (e.g. 'presence of the word 'suicide' in the title') and nine 'positive' items (e.g. 'the article reports the contacts of a suicide prevention hotline'). Each negative item was scored -1, and each positive item was scored +1. Multivariate linear regressions were performed to identify factors associated with lower adherence to WHO recommendations and higher social media engagement with the articles. RESULTS: A total of 3483 articles were screened, and 110 articles were included in the final analysis. The suicidal was male in 73.6% of cases. The median checklist score was -6 (interquartile range 3). Five percent of the articles had at least one positive item. The word 'suicide' was found in 90% of the titles. Female suicides were associated with a higher checklist score (coefficient 0.81, P = 0.039). No correlation was found between the checklist score and the social media engagement of the articles. CONCLUSIONS: Italian newspapers do not adhere completely to the WHO recommendations on reporting suicide, leading to a potential imitation effect. Public health professionals should make decision-makers and journalists aware of the importance of these recommendations.

Tuning Copper Active Site Composition in Cu-MOR through Co-Cation Modification for Methane Activation.

The industrial implementation of a direct methane to methanol process would lead to environmental and economic benefits. Copper zeolites successfully execute this reaction at relatively low temperatures, and mordenite zeolites in particular enable high methanol production. When loaded to a Cu/Al ratio of 0.45, mordenite (Si/Al 5 to 9) has been shown to host three active sites: two [CuOCu]2+ sites labeled MOR1 and MOR2, and a mononuclear [CuOH]+ site. Also at low copper loadings (Cu/Al < 0.20), mordenite has been demonstrated to activate methane, but its active site has never been reported. Here, we investigate Na+ mordenite with varying copper loadings to better understand copper speciation in mordenite. At low copper loadings, we uncover an unidentified active site ('MOR3') with a strong overlap with the [CuOH]+ site's spectroscopic signal. By changing the co-cation, we selectively speciate more MOR3 relative to [CuOH]+, allowing its identification as a [CuOCu]2+ site. Active site identification in heterogeneous catalysts is a frequent problem due to signal overlap. By changing cation composition, we introduce an innovative method for simplifying a material to allow better analysis. This has implications for the study of Cu zeolites for methane to methanol and NOx catalysis, but also for studying and tuning heterogeneous catalysts in general.

Chitin and crawfish shell biochar composite decreased heavy metal bioavailability and shifted rhizosphere bacterial community in an arsenic/lead co-contaminated soil.

Sustainable management of ever-increasing organic biowaste and arable soil contamination by potentially toxic elements are of concern from both environmental and agricultural perspectives. To tackle the waste issue of crawfish shells and simultaneously minimize the threat of arsenic (As) and lead (Pb) to human health, a pot trial was conducted using chitin (CT), crawfish shell biochar (CSB), crawfish shell powder (CSP), and CT-CSB composite to compare their remediation efficiencies in As/Pb co-contaminated soil. Results demonstrated that addition of all amendments decreased Pb bioavailability, with the greatest effect observed for the CT-CSB treatment. Application of CSP and CSB increased the soil available As concentration, while significant decreases were observed in the CT and CT-CSB treatments. Meanwhile, CT addition was the most effective in enhancing the soil enzyme activities including acid phosphatase, α-glucosidase, N-acetyl-ß-glucosaminidase, and cellobiohydrolase, whereas CSB-containing treatments suppressed the activities of most enzymes. The amendments altered the bacterial abundance and composition in soil. For instance, compared to the control, all treatments increased Chitinophagaceae abundance by 2.6-4.7%. The relative abundance of Comamonadaceae decreased by 1.6% in the CSB treatment, while 2.1% increase of Comamonadaceae was noted in the CT-CSB treatment. Redundancy and correlation analyses (at the family level) indicated that the changes in bacterial community structure were linked to bulk density, water content, and As/Pb availability of soils. Partial least squares path modeling further indicated that soil chemical property (i.e., pH, dissolved organic carbon, and cation exchange capacity) was the strongest predictor of As/Pb availability in soils following amendment application. Overall, CT-CSB could be a potentially effective amendment for simultaneously immobilizing As and Pb and restoring soil ecological functions in contaminated arable soils.

Decreasing the Crystallinity and Degree of Polymerization of Cellulose Increases Its Susceptibility to Enzymatic Hydrolysis and Fermentation by Colon Microbiota.

Cellulose can be isolated from various raw materials and agricultural side streams and might help to reduce the dietary fiber gap in our diets. However, the physiological benefits of cellulose upon ingestion are limited beyond providing fecal bulk. It is barely fermented by the microbiota in the human colon due to its crystalline character and high degree of polymerization. These properties make cellulose inaccessible to microbial cellulolytic enzymes in the colon. In this study, amorphized and depolymerized cellulose samples with an average degree of polymerization of less than 100 anhydroglucose units and a crystallinity index below 30% were made from microcrystalline cellulose using mechanical treatment and acid hydrolysis. This amorphized and depolymerized cellulose showed enhanced digestibility by a cellulase enzyme blend. Furthermore, the samples were fermented more extensively in batch fermentations using pooled human fecal microbiota, with minimal fermentation degrees up to 45% and a more than eight-fold increase in short-chain fatty acid production. While this enhanced fermentation turned out to be highly dependent on the microbial composition of the fecal pool, the potential of engineering cellulose properties to increased physiological benefit was demonstrated.

Toward a Hydrogen-Free Reductive Catalytic Fractionation of Wheat Straw Biomass.

The reductive catalytic fractionation (RCF) of lignocellulosic biomass is an attractive method for the conversion of lignin toward valuable low-molecular weight aromatics. A limitation to the upscaling of such technology is represented by the use ofpressurized hydrogen gas. Here, the role of hydrogen gas within the RCF of wheat straw biomass is investigated. The use of H2 is shown to enhance lignin depolymerization, by virtue of an improved hydrogenolysis and hydrogenation of lignin fragments, with a yield of phenolic monomers that increased from ca. 12 wt % of acid-insoluble lignin in the initial biomass under inert atmosphere to up to ca. 25 wt % under H2 (in methanol, at 250 °C, with Ru/C). The adoption of methanol, ethanol or isopropanol as hydrogen-donor solvents was also investigated in the absence of H2 . Ethanol was found to give the highest yield of monophenolic compounds (up to ≈20 wt %) owing to a better balance between solvolysis, hydrogenolysis, and hydrogenation of lignin. Nevertheless, a substantial loss of the carbohydrate fraction was observed. The use of a lower temperature (200 °C) in combination with H3 PO4 resulted in an improved recovery of cellulose in the pulp and in the solubilization of hemicellulose and lignin, with the formation of monosaccharides (≈14 wt % of polysaccharides in the initial biomass) and phenolic monomers (up to 18 wt %, in the absence of H2 ). Overall, a tradeoff exists between the removal of H2 from the process and the production of low-molecular weight phenolics during RCF.

Rational Positioning of Metal Ions to Stabilize Open Tin Sites in Beta Zeolite for Catalytic Conversion of Sugars.

Via hydrothermal synthesis of Sn-Al gels, mild dealumination and ion exchange, a bimetallic Sn-Ni-Beta catalyst was prepared which can convert glucose to methyl lactate (MLA) and methyl vinyl glycolate (MVG) in methanol at yields of 71.2 % and 10.2 %, respectively. Results from solid-state magic-angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, transmission electron microscopy, spectroscopic analysis, probe-temperature-programmed desorption, and density functional theory calculations conclusively reveal that the openness of the Sn sites, such as by the formation of [(SiO)3 -Sn-OH] entities, is governed by an adjacent metal cation such as Ni2+ , Co2+ , and Mn2+ . This relies on the low structure-defective pore channel, provided by the current synthesis scheme, and the specific silica hydroxyl anchor point is associated with the incorporation of Sn for additional and precise metal ion localization. The presence of metal cations significantly improved the catalytic performance of Sn-Ni-Beta for glucose isomerization and conversion to MLA of sugar compared with Sn-Beta.

Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity.

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures and pressures at a previously defined O2-activated [Cu2O]2+ site. However, after autoreduction of the copper-containing zeolite mordenite and removal of the [Cu2O]2+ active site, the zeolite is still methane reactive. In this study, we use diffuse reflectance UV-vis spectroscopy, magnetic circular dichroism, resonance Raman spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy to unambiguously define a mononuclear [CuOH]+ as the CH4 reactive active site of the autoreduced zeolite. The rigorous identification of a mononuclear active site allows a reactivity comparison to the previously defined [Cu2O]2+ active site. We perform kinetic experiments to compare the reactivity of the [CuOH]+ and [Cu2O]2+ sites and find that the binuclear site is significantly more reactive. From the analysis of density functional theory calculations, we elucidate that this increased reactivity is a direct result of stabilization of the [Cu2OH]2+ H-atom abstraction product by electron delocalization over the two Cu cations via the bridging ligand. This significant increase in reactivity from electron delocalization over a binuclear active site provides new insights for the design of highly reactive oxidative catalysts.

Outbreaks of COVID-19 in indoor places of worship: a systematic review.

AIMS: This review aimed to describe what has been published on COVID-19 outbreaks originating from indoor places of worship. METHODS: A systematic review was conducted following the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) checklist by searching PubMed, Scopus and Embase from 1 January 2020 to 29 March 2021. Citation chasing was also performed. Studies with information about COVID-19 outbreaks originating in indoor places of worship of any religion were included. RESULTS: A total of 9729 records were identified and 36 were selected. The articles reported 119 descriptions of outbreaks linked to churches, mosques, synagogues, and temples, referring to approximately 52-74 unique outbreaks. The outbreaks were mostly located in three major areas: East and Southeast Asia (46%), the USA (27%), Europe (22%). All the outbreaks began in 2020. Mainly, there were no restrictive measures, or such measures were not followed at the time of the outbreak. Choir practices presented the highest attack rate (up to 0.867). CONCLUSIONS: The lack of preventive measures and the role of singing practices were highlighted. Reports were often lacking contact tracing and sometimes did not report the date of outbreak extinction. Moreover, reports came from few geographical areas. Thus, the impact of transmission in places of worship may be largely underestimated.

Decreasing the degree of polymerization of microcrystalline cellulose by mechanical impact and acid hydrolysis.

Depolymerization of cellulose is often used as a (pre)treatment protocol within the catalytic valorization strategies of cellulose. Typical depolymerization protocols yield polymerization degrees above 70 anhydroglucose units (AGU). However, shorter cellulose fibers are of interest in the search for accessible dietary fiber additives or renewable materials with distinct mechanical properties (bio-composites). In this work, short-polymer microcrystalline celluloses (SMCC) with an average polymerization degree between 29 and 70 AGU were produced with material yields of 95 % and above by combining a planetary ball mill pretreatment with mild acid hydrolysis. By first decreasing the levelling-off degree of polymerization (LODP) with an intensive ball mill treatment, a mild acid hydrolysis protocol was sufficient to ensure high yields of SMCC. Furthermore, the desired polymerization degree could be obtained by tuning the process parameters.

Hydrogen Borrowing: towards Aliphatic Tertiary Amines from Lignin Model Compounds Using a Supported Copper Catalyst.

Upcoming biorefineries, such as lignin-first provide renewable aromatics containing unique aliphatic alcohols. In this context, a Cu-ZrO2 catalyzed hydrogen borrowing approach was established to yield tertiary amine from the lignin model monomer 3-(3,4-dimethoxyphenyl)-1-propanol and the actual lignin-derived monomers, (3-(4-hydroxyphenyl)-1-propanol and dihydroconiferyl alcohol), with dimethylamine. Various industrial metal catalysts were evaluated, resulting in nearly quantitative mass balances for most catalysts. Identified intermediates, side and reaction products were placed into a corresponding reaction network, supported by kinetic evolution experiments. Cu-ZrO2 was selected as most suitable catalyst combining high alcohol conversion with respectable aliphatic tertiary amine selectivity. Low pressure H2 was key for high catalyst activity and tertiary amine selectivity, mainly by hindering undesired reactant dimethylamine disproportionation and alcohol amidation. Besides dimethylamine model, diverse secondary amine reactants were tested with moderate to high tertiary amine yields. As most active catalytic site, highly dispersed Cu species in strong contact with ZrO2 is suggested. ToF-SIMS, N2 O chemisorption, TGA and XPS of spent Cu-ZrO2 revealed that imperfect amine product desorption and declining surface Cu lowered the catalytic activity upon catalyst reuse, while thermal reduction readily restored the initial activity and selectivity demonstrating catalyst reuse.

Catalytic Hydroconversion of 5-HMF to Value-Added Chemicals: Insights into the Role of Catalyst Properties and Feedstock Purity.

5-hydroxymethylfurfural (HMF) is an important bio-derived platform molecule that is generally obtained from hexoses via acid-catalyzed dehydration. It can be effectively transformed into a variety of value-added derivatives, thus being an ideal candidate for fossil replacement. Both HMF oxidation and hydrogenation processes enable the synthesis of numerous chemicals, monomers for polymerization, and biofuel precursors. This Review summarizes the most recent advances in heterogeneous catalytic hydroconversion of HMF into valuable chemicals with strong focus on 2,5-bishydroxymethyl furan (BHMF), 2,5-bishydroxymethyltetrahydrofuran (BHMTHF), and 2,5-dimethyltetrahydrofuran (DMTHF). In addition, multifunctional catalytic systems that enable a tunable production of various HMF derived intermediates are discussed. Within this chemistry, the surprising impact of HMF purity on the catalytic performance, such as selectivity and activity, during its upgrading is highlighted. Lastly, the remaining challenges in the field of HMF hydroconversion to the mentioned chemicals are summarized and discussed, taking into account the knowledge gain of catalyst properties and feedstock purity.

Second-Sphere Lattice Effects in Copper and Iron Zeolite Catalysis.

Transition-metal-exchanged zeolites perform remarkable chemical reactions from low-temperature methane to methanol oxidation to selective reduction of NOx pollutants. As with metalloenzymes, metallozeolites have impressive reactivities that are controlled in part by interactions outside the immediate coordination sphere. These second-sphere effects include activating a metal site through enforcing an "entatic" state, controlling binding and access to the metal site with pockets and channels, and directing radical rebound vs cage escape. This review explores these effects with emphasis placed on but not limited to the selective oxidation of methane to methanol with a focus on copper and iron active sites, although other transition-metal-ion zeolite reactions are also explored. While the actual active-site geometric and electronic structures are different in the copper and iron metallozeolites compared to the metalloenzymes, their second-sphere interactions with the lattice or the protein environments are found to have strong parallels that contribute to their high activity and selectivity.

Lignin-First Monomers to Catechol: Rational Cleavage of C-O and C-C Bonds over Zeolites.

A catalytic route is developed to synthesize bio-renewable catechol from softwood-derived lignin-first monomers. This process concept consists of two steps: 1) O-demethylation of 4-n-propylguaiacol (4-PG) over acidic beta zeolites in hot pressurized liquid water delivering 4-n-propylcatechol (4-PC); 2) gas-phase C-dealkylation of 4-PC providing catechol and propylene over acidic ZSM-5 zeolites in the presence of water. With large pore sized beta-19 zeolite as catalyst, 4-PC is formed with more than 93 % selectivity at nearly full conversion of 4-PG. The acid-catalyzed C-dealkylation over ZSM-5 zeolite with medium pore size gives a catechol yield of 75 %. Overall, around 70 % catechol yield is obtained from pure 4-PG, or 56 % when starting from crude 4-PG monomers obtained from softwood by lignin-first RCF biorefinery. The selective cleavage of functional groups from biobased platform molecules through a green and sustainable process highlights the potential to shift feedstock from fossil oil to biomass, providing drop ins for the chemicals industry.