Search

The quest to explore chemical space is vital for identifying novel disease targets, impacting both the effectiveness and safety profile of therapeutic agents. The tangible chemical space, currently estimated at a conservative 10 8 synthesized compounds, pales in comparison to the theoretically conceivable diversity of 10 60 molecules. To bridge this vast gap, organic chemists are spearheading innovative methodologies that promise to broaden this limited chemical diversity. A beacon of this progressive wave is Asymmetric Carbene Transfer (ACT), a burgeoning strategy that significantly boosts molecular diversity with efficient bond-formation and precise chiral control. This review focuses on the capabilities of ACT in creating pharmaceutically significant molecules, encompassing an array of natural products and bioactive compounds. Through the lens of ACT, we discern its substantial influence on drug discovery, paving the way for novel therapeutic avenues by expanding the boundaries of molecular diversity. This review will shed light on prospective methodological developments of ACT and articulate their conceivable contributions to the medicinal chemistry arena., (© 2024 Wiley-VCH GmbH.)

While photo-cross-linking (PXL) with alkyl diazirines can provide stringent distance restraints and offer insights into protein structures, unambiguous identification of cross-linked residues hinders data interpretation to the same level that has been achieved with chemical cross-linking (CXL). We address this challenge by developing an in-line system with systematic modulation of light intensity and irradiation time, which allows for a quantitative evaluation of diazirine photolysis and photo-reaction mechanism. Our results reveal a two-step pathway with mainly sequential generation of diazo and carbene intermediates. Diazo intermediate preferentially targets buried polar residues, many of which are inaccessible with known CXL probes for their limited reactivity. Moreover, we demonstrate that tuning light intensity and duration enhances selectivity towards polar residues by biasing diazo-mediated cross-linking reactions over carbene ones. This mechanistic dissection unlocks the full potential of PXL, paving the way for accurate distance mapping against protein structures and ultimately, unveiling protein dynamic behaviors., (© 2024. The Author(s).)

Methyl-coenzyme M reductase (MCR) is a central player in methane biogeochemistry, governing methanogenesis and the anaerobic oxidation of methane (AOM) in methanogens and anaerobic methanotrophs (ANME), respectively. The prosthetic group of MCR is coenzyme F 430 , a nickel-containing tetrahydrocorphin. Several modified versions of F 430 have been discovered, including the 17 2 -methylthio-F 430 (mtF 430 ) used by ANME-1 MCR. Here, we employ molecular dynamics (MD) simulations to investigate the active site dynamics of MCR from Methanosarcina acetivorans and ANME-1 when bound to the canonical F 430 compared to 17 2 -thioether coenzyme F 430 variants and substrates (methyl-coenzyme M and coenzyme B) for methane formation. Our simulations highlight the importance of the Gln to Val substitution in accommodating the 17 2 methylthio modification in ANME-1 MCR. Modifications at the 17 2 position disrupt the canonical substrate positioning in M. acetivorans MCR. However, in some replicates, active site reorganization to maintain substrate positioning suggests that the modified F 430 variants could be accommodated in a methanogenic MCR. We additionally report the first quantitative estimate of MCR intrinsic electric fields that are pivotal in driving methane formation. Our results suggest that the electric field aligned along the CH 3 -S-CoM thioether bond facilitates homolytic bond cleavage, coinciding with the proposed catalytic mechanism. Structural perturbations, however, weaken and misalign these electric fields, emphasizing the importance of the active site structure in maintaining their integrity. In conclusion, our results deepen the understanding of MCR active site dynamics, the enzyme's organizational role in intrinsic electric fields for catalysis, and the interplay between active site structure and electrostatics.

Cyclopropane fatty acid synthases (CFAS) are a class of S-adenosylmethionine (SAM) dependent methyltransferase enzymes able to catalyse the cyclopropanation of unsaturated phospholipids. Since CFAS enzymes employ SAM as a methylene source to cyclopropanate alkene substrates, they have the potential to be mild and more sustainable biocatalysts for cyclopropanation transformations than current carbene-based approaches. This work describes the characterisation of E. coli CFAS (ecCFAS) and its exploitation in the stereoselective biocatalytic synthesis of cyclopropyl lipids. ecCFAS was found to convert phosphatidylglycerol (PG) to methyl dihydrosterculate 1 with up to 58 % conversion and 73 % ee and the absolute configuration (9S,10R) was established. Substrate tolerance of ecCFAS was found to be correlated with the electronic properties of phospholipid headgroups and for the first time ecCFAS was found to catalyse cyclopropanation of both phospholipid chains to form dicyclopropanated products. In addition, mutagenesis and in silico experiments were carried out to identify the enzyme residues with key roles in catalysis and to provide structural insights into the lipid substrate preference of ecCFAS. Finally, the biocatalytic synthesis of methyl dihydrosterculate 1 and its deuterated analogue was also accomplished combining recombinant ecCFAS with the SAM regenerating AtHMT enzyme in the presence of CH 3 I and CD 3 I respectively., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A backbone-substituted N-heterocyclic carbene (NHC) zinc complex, in combination with alcohol initiators, has been shown to be an effective catalyst for the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) to poly(trimethylene carbonate) (PTMC) devoid of oxetane linkages. The ROP of TMC proceeded in solution to give PTMC, possessing controlled molecular mass (2500 < M n < 10000) and low dispersity ( Đ ∼ 1.2). Changing the alcohol initiators, PTMCs with different end-groups were obtained, included a telechelic polymer. The results of MALDI-ToF and NMR analysis confirmed the controlled/living nature of the present ROP catalytic system, where side reactions, such as inter- and intramolecular transesterifications, were minimized during the polymerization. Solution studies in different solvents demonstrated the polymerization reaction to proceed via a mechanism first order in monomer and in catalyst. The zinc complex was also able to convert substituted cyclic carbonates, which were purposely synthesized from renewable feedstocks such as CO 2 and 1,3-diols. For the asymmetric 2-Me TMC monomer, good regioselectivity was observed ( X reg up to 0.92). The excellent control of the polymerization process was finally brought to light through the preparation of polycarbonate/polyether triblock copolymers by using polyethylene glycol (PEG) as a macroinitiator and of well-defined di- and triblock polycarbonate/polylactide copolymers by sequential ROP of TMC and L-LA.

Due to the low permeability characteristics of the deep gas-containing coal seam, the conventional prevention and control measures that cannot solve the problems of gas outbursts are unsatisfactory for the prevention and control of the coal and gas outbursts disaster. Therefore, in this study, a strain of methane-oxidizing bacteria M 07 with high-pressure resistance, strong resistance, and high methane degradation rate was selected from coal mines. The growth and degradation abilities of M 07 in chelating wetting agent solutions to assess its adaptability and find the optimal agent-to-M07 ratio. It provides a new method for integrating the reduction of impact tendency and gas pressure in deep coal mines. The experimental results show that M 07 is a Gram-positive bacterium of the genus Bacillus, which has strong resistance and adaptability to high-pressure water injection. By degrading 70 mol of methane, M 07 produces 1 mol of carbon dioxide, which can reduce gas pressure and reduce the risk of gas outbursts in coal mines. As the experiment proves, the best effect was achieved when the M 07 concentration of the chelating wetting agent was 0.05%. The methane-oxidizing bacteria based on the chelating wetting agent as carriers prove a new prevention and control method for the integrated prevention and control of coal and gas outbursts in coal mines and also provide a new idea for microbial application in coal mine disaster control., (© 2024. The Author(s).)

In articular cartilage defect, particularly in arthroscopy, regenerative hydrogels are urgently needed. It should be able to firmly adhere to the cartilage tissue and maintain sufficient mechanical strength to withstand approximately 10 kPa of arthroscopic hydraulic flushing. In this study, we report a carbene-mediated ultra adhesive hybrid hydrogel paints for arthroscopic cartilage repair, which combined the photo initiation of double crosslinking system with the addition of diatomite, as a further reinforcing agent and biological inorganic substances. The double network consisting of ultraviolet initiated polymerization of hyaluronic acid methacrylate (HAMA) and carbene insertion chemistry of diazirine-grafted gelatin (GelDA) formed an ultra-strong adhesive hydrogel paint (H2G5DE). Diatomite helped the H2G5DE hydrogel paint firmly adhere to the cartilage defect, withstanding nearly 100 kPa of hydraulic pressure, almost 10 times that in clinical arthroscopy. Furthermore, the H2G5DE hydrogel supported cell growth, proliferation, and migration, thus successfully repairing cartilage defects. Overall, this study demonstrates a proof-of-concept of ultra-adhesive polysaccharide hydrogel paints, which can firmly adhere to the articular cartilage defects, can resist continuous hydraulic pressure, can promote effective cartilage regeneration, and is very suitable for minimally invasive arthroscopy., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this paper, we propose a multi-RREH (Remote Renewable Energy Hub) based optimization framework. This framework allows a valorization of CO 2 using carbon capture technologies. This valorization is grounded on the idea that CO 2 gathered from the atmosphere or post combustion can be combined with hydrogen to produce synthetic methane. The hydrogen is obtained from water electrolysis using renewable energy. Such renewable energy is generated in RREH, which are locations where RE is cheap and abundant (e.g., solar PV in the Sahara Desert, or wind in Greenland). We instantiate our framework on a case study focusing on Belgium and 2 RREH, and we conduct a techno-economic analysis under uncertainty. This analysis highlights, among others, the interest in capturing CO 2 via Post Combustion Carbon Capture (PCCC) rather than only through Direct Air Capture (DAC) for methane synthesis in RREH. By doing so, a notable reduction of 10% is observed in the total cost of the system under our reference scenario. In addition, we use our framework to derive a carbon price threshold above which carbon capture technologies may start playing a pivotal role in the decarbonation process of our industries., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The ability to tame high-energy intermediates is important for synthetic chemistry, enabling the construction of complex molecules and propelling advances in the field of synthesis. Along these lines, carbenes and carbenoid intermediates are particularly attractive, but often unknown, high-energy intermediates 1,2 . Classical methods to access metal carbene intermediates exploit two-electron chemistry to form the carbon-metal bond. However, these methods are usually prohibitive because of reagent safety concerns, limiting their broad implementation in synthesis 3-6 . Mechanistically, an alternative approach to carbene intermediates that could circumvent these pitfalls would involve two single-electron steps: radical addition to metal to forge the initial carbon-metal bond followed by redox-promoted α-elimination to yield the desired metal carbene intermediate. Here we realize this strategy through a metallaphotoredox platform that exploits iron carbene reactivity using readily available chemical feedstocks as radical sources and α-elimination from six classes of previously underexploited leaving groups. These discoveries permit cyclopropanation and σ-bond insertion into N-H, S-H and P-H bonds from abundant and bench-stable carboxylic acids, amino acids and alcohols, thereby providing a general solution to the challenge of carbene-mediated chemical diversification., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

Particulate MMO (pMMO) catalyzes the oxidation of methane to methanol and also ammonia to hydroxylamine. Experimental characterization of the active site has been very difficult partly because the enzyme is membrane-bound. However, recently, there has been major progress mainly through the use of cryogenic electron microscopy (cryoEM). Electron paramagnetic resonance (EPR) and X-ray spectroscopy have also been employed. Surprisingly, the active site has only one copper. There are two histidine ligands and one asparagine ligand, and the active site is surrounded by phenyl alanines but no charged amino acids in the close surrounding. The present study is the first quantum chemical study using a model of that active site (Cu D ). Low barrier mechanisms have been found, where an important part is that there are two initial proton-coupled electron transfer steps to a bound O 2 ligand before the substrate enters. Surprisingly, this leads to large radical character for the oxygens even though they are protonated. That result is very important for the ability to accept a proton from the substrates. Methods have been used which have been thoroughly tested for redox enzyme mechanisms.

Many cancer-driving protein targets remain undruggable due to a lack of binding molecular scaffolds. In this regard, octahedral metal complexes with unique and versatile three-dimensional structures have rarely been explored as inhibitors of undruggable protein targets. Here, we describe antitumor iridium(III) pyridinium-N-heterocyclic carbene complex 1a , which profoundly reduces the viability of lung and breast cancer cells as well as cancer patient-derived organoids at low micromolar concentrations. Compound 1a effectively inhibits the growth of non-small-cell lung cancer and triple-negative breast cancer xenograft tumors, impedes the metastatic spread of breast cancer cells, and can be modified into an antibody-drug conjugate payload to achieve precise tumor delivery in mice. Identified by thermal proteome profiling, an important molecular target of 1a in cellulo is Girdin, a multifunctional adaptor protein that is overexpressed in cancer cells and unequivocally serves as a signaling hub for multiple pivotal oncogenic pathways. However, specific small-molecule inhibitors of Girdin have not yet been developed. Notably, 1a exhibits high binding affinity to Girdin with a K d of 1.3 μM and targets the Girdin-linked EGFR/AKT/mTOR/STAT3 cancer-driving pathway, inhibiting cancer cell proliferation and metastatic activity. Our study reveals a potent Girdin-targeting anticancer compound and demonstrates that octahedral metal complexes constitute an untapped library of small-molecule inhibitors that can fit into the ligand-binding pockets of key oncoproteins., Competing Interests: Competing interests statement:The authors declare no competing interest.

A family of bifunctional dihetarylmethanes and dibenzoxanthenes is assembled via a reaction of acetals containing a 2-chloroacetamide moiety with phenols and related oxygen-containing heterocycles. These compounds demonstrated selective antitumor activity associated with the induction of cell apoptosis and inhibition of the process of glycolysis. In particular, bis(heteroaryl)methane containing two 4-hydroxy-6-methyl-2 H -pyran-2-one moieties combine excellent in vitro antitumor efficacy with an IC 50 of 1.7 µM in HuTu-80 human duodenal adenocarcinoma models with a high selectivity index of 73. Overall, this work highlights the therapeutic potential of dimeric compounds assembled from functionalized acetals and builds a starting point for the development of a new family of anticancer agents.

To explore the impact of different functional groups on Hg(II) adsorption, a range of poly(pyrrole methane)s functionalized by -Cl, -CN, -NH 2 , -OH and -COOH were synthesized and applied to reveal the interaction between different functional groups and mercury ions in water, and the adsorption mechanism was revealed through combined FT-IR, XPS, and DFT calculations. The adsorption performance can be improved to varying degrees by the incorporation of functional groups. Among them, the oxygen-containing functional groups (-OH and -COOH) exhibit stronger affinity for Hg(II) and can increase the adsorption capacity from 180 mg g -1 to more than 1400 mg g -1 at 318 K, with distribution coefficient (K d ) exceeding 10 5  mL g -1 . The variations in the capture and immobilization capabilities of functionalized poly(pyrrole methane)s predominantly stem from the unique interactions between their functional groups and mercury ions. In particular, oxygen-containing -OH and -COOH effectively capture Hg(OH) 2 through hydrogen bonding, and further deprotonate to form the -O-Hg-OH and -COO-Hg-OH complexes which are more stable than those obtained from other functionalized groups. Finally, the ecological safety has been fully demonstrated through bactericidal and bacteriostatic experiments to prove the functionalized poly(pyrrole methane)s can be as an environmentally friendly adsorbent for purifying contaminated water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdO x nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdO x nanoparticles, creating an Ir 4f -O-Pd cus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdO x and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir 4f -O-Pd cus , reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr 0.1 /S-1 showed outstanding low-temperature activity for methane combustion ( T 50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr 0.1 /S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al 2 O 3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

Silver compounds are mainly studied as antimicrobial agents, but they also have anticancer properties, with the latter, in some cases, being better than their gold counterparts. Herein, we analyse the first example of a new Ag(I)-biscarbene that can bind non-canonical structures of DNA, more precisely G-quadruplexes (G4), with different binding signatures depending on the type of G4. Moreover, we show that this Ag-based carbene binds the i-motif DNA structure. Alternatively, its Au(I) counterpart, which was investigated for comparison, stabilises mitochondrial G4. Theoretical in silico studies elucidated the details of different binding modes depending on the geometry of G4. The two complexes showed increased cytotoxic activity compared to cisplatin, overcoming its resistance in ovarian cancer. The binding of these new drug candidates with other relevant biosubstrates was studied to afford a more complete picture of their possible targets. In particular, the Ag(I) complex preferentially binds DNA structures over RNA structures, with higher binding constants for the non-canonical nucleic acids with respect to natural calf thymus DNA. Regarding possible protein targets, its interaction with the albumin model protein BSA was also tested.

Detection of amyloid β (Aβ) oligomers, regarded as the most toxic aggregated forms of Aβ, can contribute to the diagnosis and treatment of Alzheimer's disease (AD). Thus, the development of imaging probes for in vivo visualization of Aβ oligomers is crucial. However, the structural uncertainty regarding Aβ oligomers makes it difficult to design imaging probes with high sensitivity to Aβ oligomers against highly aggregated Aβ fibrils. In this study, we developed Aβ oligomer-selective fluorescent probes based on triphenylmethane dyes through screening of commercially available compounds followed by structure-activity relationship (SAR) studies on cyclic or acyclic 4-dialkylamino groups. We synthesized 11 triarylmethane-based Aβ oligomer probe (TAMAOP) derivatives. In vitro evaluation of fluorescence properties, TAMAOP-9, which had bulky 4-diisobutylamino groups introduced into three benzenes of a twisted triphenylmethane backbone, showed marked fluorescence enhancement in the presence of Aβ oligomers and demonstrated high selectivity for Aβ oligomers against Aβ fibrils. In docking studies using the Aβ trimer model, TAMAOP-9 bound to the hydrophobic surface and interacted with the side chain of Phe 20 . In vitro section staining revealed that TAMAOP-9 could visualize Aβ oligomers in the brains of AD model mice. An in vivo fluorescence imaging study using TAMAOP-9 showed significantly higher fluorescence signals from the brains of AD model mice than those of age-matched wild-type mice, confirmed by ex vivo section observation. These results suggest that TAMAOP-9 is a promising Aβ oligomer-targeting fluorescent probe applicable to in vivo imaging.

The growing demand for sustainable and efficient gas separation technologies has prompted the exploration of advanced materials to enhance the gas permeability and selectivity. Polyethersulfone (PES) membranes are widely used in gas separation, gas upgrading, and clean energy production owing to their environmental friendliness and low cost. However, their gas permeability and selectivity can be further improved for commercial application. This study explored the incorporation of 10 wt % of MIL-68(ln)-NH2 into PES membranes using a phase-inversion approach to enhance gas permeability and selectivity. The morphological, structural, and thermal properties of the resulting MOF/PES membrane were characterized using SEM, AFM, BET, XRD, FTIR, and TGA-DTG. Gas permeation experiments were conducted using different gases (CO2, N2, CH4, and H2) under different heating conditions (20-60 °C) to evaluate the gas permeability and selectivity of the MOF/PES membrane. The results showed that the incorporation of MOF into the mixed matrix membrane (MMMs) led to a 9% increase in porosity, 87% reduction in roughness, and 32% decrease in pore size compared to neat PES membranes. Significant changes in the morphology, crystallinity, and thermal stability were observed, with notable improvements of up to 22%. Moreover, the MOF/PES membrane exhibited high gas permeability (CO2 = 124656, N2 = 83650, CH4 = 159298, and H2 = 427075 Barrer) and selectivity (H2/N2 = 5.7, H2/CO2 = 4, CH4/N2 = 2, and CH4/CO2 = 1.7) for flammable gases. The optimal gas separation performance was observed at 20 °C and 60 °C for H2/N2 and H2/CO2 separation, respectively. These findings demonstrate the potential of MOF-based PES membranes for gas separation applications, particularly in H2 purification., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Herein, four silver(I) complexes bearing acetylated d-galactopyranoside-based N-heterocyclic carbene ligands were synthesized and fully characterized by elemental analysis, NMR, and X-ray photoelectron spectroscopy. All complexes were obtained with an anomeric β-configuration and as monocarbene species. In this study, we investigated the biological effects of the silver(I) complexes 2a-d on the human rhabdomyosarcoma cell line, RD. Our results show concentration-dependent effects on cell density, growth inhibition, and activation of key signaling pathways such as Akt 1/2, ERK 1/2, and p38-MAPK, indicating their potential as anticancer agents. Notably, at 35.5 µM, the complexes induced mitochondrial network disruption, as observed with 2b and 2c, whereas with 2a, this disruption was accompanied by nuclear content release. These results provide insight into the utility of carbohydrate incorporated NHC complexes of silver(I) as new agents in cancer therapy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The separation of CO 2 from the biogas mixtures (CH 4 /CO 2 ) is essential for biogas upgradation. However, polymer membranes used for CO 2 separation exhibit low permeability. Mixed Matrix Membranes (MMMs) incorporating inorganic filler in the polymer enhance CO 2 separation. In this work, bio-degradable cellulose acetate (CA) based MMMs with varying filler weight percentages (2-20 wt.%) of ZIF-8 were studied for the separation of CO 2 from a model biogas (CH 4 /CO 2 ) mixture. The MMMs were characterized by analysis of TGA and DSC for thermal stability and FTIR for alteration or formation of any new functional group. FESEM was done to evaluate the dispersion and interaction of ZIF-8 in the CA polymer matrix. Considering the economic aspect, the fabricated MMMs were tested for gas separation performance at reasonably lower feed pressure (1.5, 2 bar). MMM with 5 and 10 wt.% of ZIF-8/ CA MMMs showed the best performance with CO 2 permeability of 9.65 Barrer and 9.5 Barrer, approximately two folds as compared to pure CA, and CO 2 /CH 4 selectivity was 10.37 and 15.3. The experimental results were compared with the predicted gas permeation results determined using MMM transport predictive models, and found that the permeabilities were higher than the model predictions.

This works proposes a dynamic thermoeconomic analysis of a liquefied biomethane production plant to meet the fuel demand of a fleet of heavy duty trucks in the south of Italy. The biomethane is obtained from the upgrading of the biogas produced by means of anaerobic digestion through a plug flow reactor fed by organic fraction of municipal solid waste. The upgrading of the biogas is realized using a three-stage membrane compression process, producing a 96 % pure biomethane. The biomethane liquefaction is realized using a single-mixed refrigerant process and compared to a Linde cycle process. The whole system is assisted by solar energy to reduce the fossil energy consumption of the process and feed-in tariffs are considered as funding policy. The models for the anaerobic digestion, the biogas upgrading, and the biomethane liquefaction are in detail developed in MatLab. The anaerobic digestion model is based on the ADM1 biological model, integrated with a suitable heat transfer model. The biogas upgrading model is based on a simplified Fick model. The liquefaction model is based on an equivalent two heat-exchangers model, taking into account the transient heat transfer. All the components are then integrated in TRNSYS to perform the dynamic simulation for one operating year of the whole system. Results from the thermoeconomic analysis are outstanding in terms of profitability, showing a payback period of less than 2 years and a Net Present Value of the system of 402 M€. The great environmental impact is also confirmed by a Primary Energy Saving of 91 % and a dramatic reduction of 86 % of the CO 2 equivalent emissions., Competing Interests: Declaration of competing interest The corresponding author confirms that all the other authors have read and approved the manuscript and no ethical issues and conflict of interest are involved. In particular the authors confirm that have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Carbene-based bioadhesives have favourable attributes for tissue adhesion, including non-specific bonding to wet and dry tissues, but suffer from relatively weak fracture strength after photocuring. Light irradiation of carbene-precursor (diazirine) also creates inert side products that are absent under thermal activation. Herein, a dual activation method combines light irradiation at elevated temperatures for the evaluation of diazirine depletion and effects on cohesive properties. A customized photo/thermal-rheometer evaluates viscoelastic properties, correlated to the kinetics of carbene:diazoalkane ratios via 19 F NMR). The latter exploits the sensitive -CF 3 functional group to determine joule-based light/temperature kinetics on trifluoroaryl diazirine consumption. The combination of heat and photoactivation produced bioadhesives that are 3× tougher compared to control. Dual thermal/light irradiation may be a strategy to improve viscoelastic dissipation and toughness of photo-activated adhesive resins., (© 2024 The Authors. Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

Lingering inconsistencies in the global methane (CH 4 ) budget and ambiguity in CH 4 sources and sinks triggered efforts to identify new CH 4 formation pathways in natural ecosystems. Herein, we reported a novel mechanism of light-induced generation of hydroxyl radicals (•OH) that drove the production of CH 4 from aquatic dissolved organic matters (DOMs) under ambient conditions. A total of five DOM samples with different origins were applied to examine their potential in photo-methanification production under aerobic conditions, presenting a wide range of CH 4 production rates from 3.57 × 10 -3 to 5.90 × 10 -2 nmol CH 4 mg-C -1 h -1 . Experiments of •OH generator and scavenger indicated that the contribution of •OH to photo-methanificaiton among different DOM samples reached about 4∼42 %. In addition, Fourier transform infrared spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry showed that the carbohydrate- and lipid-like substances containing nitrogen-bonded methyl groups, methyl ester, acetyl groups, and ketones, were the potential precursors for light-induced CH 4 production. Based on the experimental results and simulated calculations, the contribution of photo-methanification of aquatic DOMs to the diffusive CH 4 flux across the water-air interface in a typical eutrophic shallow lake (e.g., Lake Chaohu) ranged from 0.1 % to 18.3 %. This study provides a new perspective on the pathways of CH 4 formation in aquatic ecosystems and a deeper understanding on the sources and sinks of global CH 4 ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The increasing anthropogenic emissions of greenhouse gases (GHG) is encouraging extensive research in CO 2 utilisation. Dry reforming of methane (DRM) depicts a viable strategy to convert both CO 2 and CH 4 into syngas, a worthwhile chemical intermediate. Among the different active phases for DRM, the use of nickel as catalyst is economically favourable, but typically deactivates due to sintering and carbon deposition. The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts. XRD and TPR-H 2 analyses confirmed the existence of different phases according to the Ni loading in these materials. Besides, superficial Ni is observed as well as the existence of a CeNiO 3 perovskite structure. The catalytic activity was tested, proving that 10 wt.% Ni loading is the optimum which maximises conversion. This catalyst was also tested in long-term stability experiments at 600 and 800°C in order to study the potential deactivation issues at two different temperatures. At 600°C, carbon formation is the main cause of catalytic deactivation, whereas a robust stability is shown at 800°C, observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO 2 and biogas mixtures upgrading catalysts., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this article., (Copyright © 2023. Published by Elsevier B.V.)

Leach bed reactors (LBRs) are dry anaerobic systems that can handle feedstocks with high solid content, like chicken manure, with minimal water addition. In this study, the chicken manure was mixed with zeolite, a novel addition, and packed in the LBR to improve biogas production. The resulting leachate was then processed in a continuous stirred tank reactor (CSTR), where most of the methane was produced. The supernatant of the CSTR was returned to the LBR. The batch mode operation of the LBR led to a varying methane production rate (MPR) with a peak in the beginning of each batch cycle when the leachate was rich in organic matter. Comparing the MPR in both systems, the peaks in the zeolite system were higher and more acute than in the control system, which was under stress, as indicated by the acetate accumulation at 2328 mg L -1 . Moreover, the presence of zeolite in the LBR played a crucial role, increasing the overall methane yield from 0.142 (control experiment) to 0.171 NL CH 4 per g of volatile solids of chicken manure entering the system at a solid retention time of 14 d. Zeolite also improved the stability of the system. The ammonia concentration increased gradually due to the little water entering the system and reached 3220 mg L -1 (control system) and 2730 mg L -1 (zeolite system) at the end of the experiment. It seems that zeolite favored the accumulation of the ammonia at a lower rate (14.0 mg L -1 d -1 ) compared to the control experiment (17.3 mg L -1 d -1 ). The microbial analysis of the CSTR fed on the leachate from the LBR amended with zeolite showed a higher relative abundance of Methanosaeta (83.6%) compared to the control experiment (69.1%). Both CSTRs established significantly different bacterial profiles from the inoculum after 120 days of operation ( p < 0.05). Regarding the archaeal communities, there were no significant statistical differences between the CSTRs and the inoculum ( p > 0.05).

Mattresses are a difficult waste to manage in landfills due to their large volume and low density. Pyrolysis treatment could reduce its volume while producing fuel or products valuable for the chemical industry. Pressurized pyrolysis at 400, 450, and 500 °C is carried out in a lab-scale autoclave at initial pressures 4.2, 8.4, and 16.8 bar. Product gas yield increases slightly along with elevated pressure as well as temperature. However, beyond 8.4 bar the initial pressure makes no discernible differences. CO and CO 2 are the major gas species followed by CH 4 . CO contributes the most to the product gas energy content followed by C 3 species, C 2 H 6 , and H 2 . Calculated energy content (heating value) is between 2 and 15 MJ·Nm -3 . In terms of product gas energy content, low pressure pyrolysis is favorable over high pressure pyrolysis. According to integration areas of chromatographic measurements the liquid phase contains up to 25 % of N-compounds, with benzonitrile being the most abundant, followed by toluene, o-xylene, and ethylbenzene. The solid char maintains constant properties across operating conditions, with carbon and energy contents of approximately 75 wt% and 30 MJ·kg -1 , respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This study introduces a novel approach for synthesizing Benzoxazine-centered Polychiral Polyheterocycles (BPCPHCs) via an innovative asymmetric carbene-alkyne metathesis-triggered cascade. Overcoming challenges associated with intricate stereochemistry and multiple chiral centers, the catalytic asymmetric Carbene Alkyne Metathesis-mediated Cascade (CAMC) is employed using dirhodium catalyst/Brønsted acid co-catalysis, ensuring precise stereo control as validated by X-ray crystallography. Systematic substrate scope evaluation establishes exceptional diastereo- and enantioselectivities, creating a unique library of BPCPHCs. Pharmacological exploration identifies twelve BPCPHCs as potent Nav ion channel blockers, notably compound 8 g. In vivo studies demonstrate that intrathecal injection of 8 g effectively reverses mechanical hyperalgesia associated with chemotherapy-induced peripheral neuropathy (CIPN), suggesting a promising therapeutic avenue. Electrophysiological investigations unveil the inhibitory effects of 8 g on Nav1.7 currents. Molecular docking, dynamics simulations and surface plasmon resonance (SPR) assay provide insights into the stable complex formation and favorable binding free energy of 8 g with C5aR1. This research represents a significant advancement in asymmetric CAMC for BPCPHCs and unveils BPCPHC 8 g as a promising, uniquely acting pain blocker, establishing a C5aR1-Nav1.7 connection in the context of CIPN., (© 2024 Wiley-VCH GmbH.)

This paper describes the process of producing chemiresistors based on hybrid nanostructures obtained from graphene and conducting polymers. The technology of graphene presumed the following: dispersion and support stabilization based on the chemical vapor deposition technique; transfer of the graphene to the substrate by spin-coating of polymethyl methacrylate; and thermal treatment and electrochemical delamination. For the process at T = 950 °C, a better settlement of the grains was noticed, with the formation of layers predominantly characterized by peaks and not by depressions. The technology for obtaining hybrid nanostructures from graphene and conducting polymers was drop-casting, with solutions of Poly(3-hexylthiophene (P3HT) and Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2). In the case of F8T2, compared to P3HT, a 10 times larger dimension of grain size and about 7 times larger distances between the peak clusters were noticed. To generate chemiresistors from graphene-polymer structures, an ink-jet printer was used, and the metallization was made with commercial copper ink for printed electronics, leading to a structure of a resistor with an active surface of about 1 cm 2 . Experimental calibration curves were plotted for both sensing structures, for a domain of CH 4 of up to 1000 ppm concentration in air. A linearity of the curve for the low concentration of CH 4 was noticed for the graphene structure with F8T2, presenting a sensitivity of about 6 times higher compared with the graphene structure with P3HT, which makes the sensing structure of graphene with F8T2 more feasible and reliable for the medical application of irritable bowel syndrome evaluation.

Invited for the cover of this issue are Tatiyana Serebryanskaya, Mikhail Kinzhalov and co-workers at St. Petersburg State University, the Research Institute for Physical Chemical Problems, Belarusian State University, Togliatti State University and Blokhin National Medical Research Center of Oncology. The image depicts the shield of Pallas Athena with the structure of a palladium carbene complex that protects against triple-negative breast cancer. Read the full text of the article at 10.1002/chem.202400101., (© 2024 Wiley-VCH GmbH.)

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H 2 , CO, CO 2 , and CH 4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H 2 yield with a test R 2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH 4 , CO, and CO 2 , with test R 2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H 2 , CH 4 , CO, and CO 2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Genetically encoding proximal-reactive unnatural amino acids (PrUaas), such as fluorosulfate-l-tyrosine (FSY), into natural proteins of interest (POI) confer the POI with the ability to covalently bind to its interacting proteins (IPs). The PrUaa-incorporated POIs hold promise for blocking undesirable POI-IP interactions. Selecting appropriate PrUaa anchor sites is crucial, but it remains challenging with the current methodology, which heavily relies on crystallography to identify the proximal residues between the POIs and the IPs for the PrUaa anchorage. To address the challenge, here, we propose a footprinting-directed genetically encoded covalent binder (footprinting-GECB) approach. This approach employs carbene footprinting, a structural mass spectrometry (MS) technique that quantifies the extent of labeling of the POI following the addition of its IP, and thus identifies the responsive residues. By genetically encoding PrUaa into these responsive sites, POI variants with covalent bonding ability to its IP can be produced without the need for crystallography. Using the POI-IP model, KRAS/RAF1, we showed that engineering FSY at the footprint-assigned KRAS residue resulted in a KRAS variant that can bind irreversibly to RAF1. Additionally, we inserted FSY at the responsive residue in RAF1 upon footprinting the oncogenic KRAS G12D /RAF1, which lacks crystal structure, and generated a covalent binder to KRAS G12D . Together, we demonstrated that by adopting carbene footprinting to direct PrUaa anchorage, we can greatly expand the opportunities for designing covalent protein binders for PPIs without relying on crystallography. This holds promise for creating effective PPI inhibitors and supports both fundamental research and biotherapeutics development.

Human herpesvirus type 6A (HHV-6A) can cause a series of immune and neurological diseases, and the establishment of a sensitive biosensor for the rapid detection of HHV-6A is of great significance for public health and safety. Herein, a bis-tridentate iridium complex (BisL T -Ir-NHC) comprising the N-heterocyclic carbene (NHC) ligand as a novel kind of efficient ECL luminophore has been unprecedently reported. Based on its excellent ECL properties, a new sensitive ECL-based sandwich immunosensor to detect the HHV-6A virus was successfully constructed by encapsulating BisL T -Ir-NHC into silica nanoparticles and embellishing ECL sensing interface with MXene@Au-CS. Notably, the immunosensor illustrated in this work not only had a wide linear range of 10 2 to 10 7 cps/μL but also showed outstanding recoveries (98.33-105.11%) in real human serum with an RSD of 0.85-3.56%. Undoubtedly, these results demonstrated the significant potential of the bis-tridentate iridium(III) complex containing an NHC ligand in developing ECL-based sensitive analytical methods for virus detection and exploring novel kinds of efficient iridium-based ECL luminophores in the future.

Total solids (TS) content may provide a regulatory strategy for optimizing anaerobic digestion enhanced by high-temperature thermal hydrolysis, but the role of TS content is not yet clear. In this study, the effect of TS content on the high-temperature thermal hydrolysis and anaerobic digestion of sludge and its mechanism were investigated. The results showed that increasing the TS content from 2% to 8% increased the sludge solubility and methane production potential, reaching peak values of 26.6% and 336 ± 6 mL/g volatile solids (VS), respectively. With a further increase in TS content to 12%, the strong Maillard reaction increased the aromaticity and structural stability of extracellular polymer substances, decreasing sludge solubility to 18.6%. Furthermore, the decrease in sludge biodegradability and the formation of inhibitory by-products resulted in a reduction in methane production to 272 ± 4 mL/g VS. This article provides a new perspective to understand the role of TS content in the thermal hydrolysis of sludge and a novel approach to regulate the Maillard reaction., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900-1,400 °C and at pressures of 5-6 GPa (refs.  1,2 ). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon 3 . Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs.  4-6 ). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature 7 . Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

Porous solids with highly microporous structures for effective carbon dioxide uptake and separation from mixed gases are highly desirable. Here we present the use of polyethylene glycol (20,000 g/mol) as a soft template for the simple and rapid synthesis of a highly microporous Cu-BTC (denoted as HKUST-1). The polyethylene glycol-templated HKUST-1 obtained at room temperature in 10 min exhibited a very high Brunauer-Emmett-Teller (BET) surface area of 1904 m 2 /g, pore volume of 0.87 cm 3 /g, and average micropore size of 0.84 nm. However, conventional HKUST-1 exhibits a BET surface area of 700-1700 m 2 /g confirming the advantages of using this method. X-ray powder diffraction and electron microscopy analysis confirm the formation of highly crystalline and uniform octahedral particles with sizes ranging from 100 nm to 120 µm. Adsorption isotherms recorded at temperatures between 273 and 353 K and pressures up to 40 bar revealed a more favorable adsorption capacity of HKUST-1 for CO 2 vs. CH 4 and N 2 (708 mg (CO 2 )/g, 214 mg (CH 4 )/g and 177 mg (N 2 )/g at 298 K and 40 bar). The Langmuir, isotherm model, and isosteric heats of adsorption were evaluated. The CO 2 interaction at PEG-templated HKUST-1 is physical, exothermic, and spontaneous with DH° =  - 6.52 kJ/mol, DS° =  - 13.72 J/mol, and DG° =  - 2.43 kJ/mol at 298 K at 40 bar. The selectivities in equimolar mixtures were determined as 53 and 24, respectively, for CO 2 over N 2 and CH 4 . CO 2 adsorption-desorption tests reveal high adsorbent reusability. The cost-effective and quickly prepared PEG-templated HKUST-1 demonstrates high efficacy as a gas adsorbent, particularly in selectively capturing CO 2 ., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The increasing concentration of CO 2 and CH 4 in the environment is a global concern. Tri-reforming of methane (TRM) is a promising route for the conversion of these two greenhouse gases to more valuable synthesis gas with an H 2 /CO ratio of 1.5-2. In this study, a series of Zr-MOF synthesized via the solvothermal method and impregnation technique was used to synthesize the nickel impregnated on MOF-derived ZrO 2 catalyst. The catalyst was characterized by various methods, including N 2 -porosimetry, X-ray diffraction (XRD), temperature programmed reduction (TPR), CO 2 -temperature programmed desorption (CO 2 -TPD), thermo-gravimetric analysis (TGA), chemisorption, field-emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM). Characterization results confirmed the formation of the Zr-MOF and nickel metal dispersed on MOF-derived ZrO 2 . Further, the tri-reforming activity of the catalyst developed was evaluated in a downflow-packed bed reactor. The various catalysts were screened for TRM activity at different temperatures (600-850 °C). Results demonstrated that TRM was highly favorable over the NZ-1000 catalyst due to its desirable physicochemical properties, including nickel metal surface area (2.3 m 2 /g cat -1 ), metal dispersion (7.1%), and nickel metal reducibility (45%), respectively. Over the NZ-1000 catalyst, an optimum H 2 /CO ratio of ~ 1.6-2 was achieved at 750 °C, and it was stable for a longer period of time., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The valorization of CO 2 as a biofuel, transforming it through methanation as part of the power-to-gas (P2G) process, will allow the reduction of the net emissions of this gas to the atmosphere. Catalysts with 13 wt.% of nickel (Ni) loading incorporated into alumina and graphene derivatives were used, and the effect of the support on the activity was examined at temperatures between 498 and 773 K and 10 bar of pressure. Among the graphene-based catalysts (13Ni/AGO, 13Ni/BGO, 13Ni/rGO, 13Ni-Ol/GO, 13Ni/Ol-GO, and 13Ni/Ol-GO Met), the highest methane yield was found for 13Ni/rGO (78% at 810 K), being the only system comparable to the catalyst supported on alumina 13Ni/Al 2 O 3 (89.5% at 745 K). The incorporation of 14 wt.% of lanthanum (La) into the most promising supports, rGO and alumina, led to nickel-support interactions that enhanced the catalytic activity of 13Ni/Al 2 O 3 (89.5% at lower temperature, 727 K) but was not effective for 13Ni/rGO. The resistance against deactivation by H2S poisoning was also studied for these catalysts, and a fast deactivation was observed. In addition, activity recovery was impossible despite the regeneration treatment carried out over catalysts. The resistance against deactivation by H2S poisoning was also studied for these catalysts, observing that both suffered a rapid/immediate deactivation and which in addition/unfortunately was impossible to solve despite the regeneration treatment carried out over catalysts., (© 2023. The Author(s).)

Bio-electrochemical conversion of anthropogenic CO 2 into value-added products using cost-effective metal-free catalysts represents a promising strategy for sustainable fuel production. Herein, N-doped carbon nanosheets synthesized via pyrolysis of the zeolitic-imidazolate framework (ZIF) are developed for constructing efficient biohybrids to facilitate CO 2 -to-CH 4 conversion. The microbial enrichment and bio-interfacial charge transfer are significantly affected by the proportion of the co-existed graphitic-N, pyridinic-N, and pyrrolic-N in the defective carbon nanosheets. It is unfolded that pyridinic-N and pyrrolic-N with the doped N atoms near the edge can significantly enhance the adsorption of their adjacent C atoms toward O, leading to improved microbe enrichment. Especially, pyridinic-N which can provide one p electron to the aromatic π system, greatly enhances the electron-donating capability of the carbon nanosheets to the microorganisms. Correspondingly, due to its largest amount of pyridinic-N doping, the N-doped carbon nanosheets derived from ZIF pyrolysis at 900 °C (denoted 900-NC) achieve the highest methane production of ≈215.7 mmol m -2  day -1 with a high selectivity (Faradaic efficiency = ≈94.2%) at -0.9 V versus Ag/AgCl. This work demonstrates the effectiveness of N-doped carbon catalysts for bio-electrochemical CO 2 fixation and contributes to the understanding of N functionalities toward microbiome response and biotic-abiotic charge transfer in various bio-electrochemical systems., (© 2023 Wiley‐VCH GmbH.)

Anaerobic digestion (AD) of sewage sludge reduces organic solids and produces methane, but the complex nature of sludge, especially the difficulty in solubilization, limits AD efficiency. Pretreatments, by destroying sludge structure and promoting disintegration and hydrolysis, are valuable strategies to enhance AD performance. There is a plethora of reviews on sludge pretreatments, however, quantitative comparisons from multiple perspectives across different pretreatments remain scarce. This review categorized various pretreatments into three groups: Physical (ultrasonic, microwave, thermal hydrolysis, electric decomposition, and high pressure homogenization), chemical (acid, alkali, Fenton, calcium peroxide, and ozone), and biological (microaeration, exogenous bacteria, and exogenous hydrolase) pretreatments. The optimal conditions of various pretreatments and their impacts on enhancing AD efficiency were summarized; the effects of different pretreatments on microbial community in the AD system were comprehensively compared. The quantitative comparison based on dissolution degree of COD (DD COD ) indicted that the sludge solubilization performance is in the order of physical, chemical, and biological pretreatments, although with each below 40 % DD COD . Biological pretreatment, particularly microaeration and exogenous bacteria, excel in AD enhancement. Pretreatments alter microbial ecology, favoring Firmicutes and Methanosaeta (acetotrophic methanogens) over Proteobacteria and Methanobacterium (hydrogenotrophic methanogens). Most pretreatments have unfavorable energy and economic outcomes, with electric decomposition and microaeration being exceptions. On the basis of the overview of the above pretreatments, a full energy and economy assessment for sewage sludge treatment was suggested. Finally, challenges associated with sludge pretreatments and AD were analyzed, and future research directions were proposed. This review may broaden comprehension of sludge pretreatments and AD, and provide an objective basis for the selection of sludge pretreatment technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

As human society has advanced, nuclear energy has provided energy security while also offering low carbon emissions and reduced dependence on fossil fuels, whereas nuclear power plants have produced large amounts of radioactive wastewater, which threatens human health and the sustainability of water resources. Here, we demonstrate a hydrate-based desalination (HBD) technology that uses methane as a hydrate former for freshwater recovery and for the removal of radioactive chemicals from wastewater, specifically from Cs- and Sr-containing wastewater. The complete exclusion of radioactive ions from solid methane hydrates was confirmed by a close examination using phase equilibria, spectroscopic investigations, thermal analyses, and theoretical calculations, enabling simultaneous freshwater recovery and the removal of radioactive chemicals from wastewater by the methane hydrate formation process described in this study. More importantly, the proposed HBD technology is applicable to radioactive wastewater containing Cs + and Sr 2+ across a broad concentration range of low percentages to hundreds of parts per million (ppm) and even subppm levels, with high removal efficiency of radioactive chemicals. This study highlights the potential of environmentally sustainable technologies to address the challenges posed by radioactive wastewater generated by nuclear technology, providing new insights for future research and development efforts.

Inland alkaline wetlands play a crucial role in maintaining ecological functions. However, these wetlands are becoming more vulnerable to the effects of water level fluctuations caused by global climate change, especially concerning carbon (C) and nitrogen (N) cycling. Here, metagenomics sequencing was used to investigate microorganism diversity, C and N cycling gene abundance at three water level types (D (dry), MF (middle flooded), HF (high flooded)) along an inland alkaline wetland. Our findings reveal that water level was the most important factor in regulating the microbial communities. Distinct shifts in community composition were found along the water level increases, without fundamentally altering their composition. With the increase of water level, the relative abundance of pmoA decreased from 2.5 × 10 -5 to 5.1 × 10 -6 . The C cycling processes shift from predominantly CO 2 -generated processes under low water levels to CO 2 and CH 4 co-generated processes under high water levels. The relative abundance of nosZ reached 4.9 × 10 -5 in HF, while in D and MF, it is recorded at 4.5 × 10 -5 and 3.4 × 10 -5 , respectively. Water levels accelerate N cycling and generating N 2 O intermediates. Furthermore, our study highlights the dynamic competition and cooperation between C and N cycling processes. This research provides a comprehensive biological understanding of the influence of varying water levels on soil C and N cycling processes in wetland., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Aerobic treatment, mesophilic anaerobic digestion, thermophilic anaerobic digestion, and dark fermentation were evaluated for on-site biological treatment of municipal sludge derived HTL aqueous. For all four described batch test scenarios, municipal sludge-derived HTL aqueous samples obtained under 290-360 °C and 0-30 min retention time were used. In the aerobic respirometric tests, HTL aqueous samples resulted in a five-day biochemical oxygen demand range of 40.75 g/L (350 °C-25.6 min) to 54 g/L (325 °C-0 min). The calculated aerobic biodegradability index showed that approximately 50 % of the organics in HTL aqueous were easily biodegradable. Mesophilic and thermophilic biochemical methane potential tests resulted in specific yields of 151-179 mL CH 4 /g chemical oxygen demand (COD) and 103-122 mL CH 4 /g COD, respectively. HTL aqueous obtained under 360 °C-15 min condition caused total inhibition in both mesophilic and thermophilic anaerobic digestion. Possible causes for this inhibition were pyridine, pyrrolidinone, piperidinone, pyridinol, and phenolic compounds, which were higher in abundance in the 360 °C-15 min sample. HTL aqueous was found unfit for hydrogen production in dark fermentation due to inhibitory composition. In summary, on-site biological treatment of HTL aqueous was found to be most suitable under aerobic and mesophilic anaerobic conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

(1) Background: Particulate methane monooxygenase (pMMO) has a strong dependence on the natural electron transfer path and is prone to denaturation, which results in its redox activity centers being unable to transfer electrons with bare electrodes directly and making it challenging to observe an electrochemical response; (2) Methods: Using methanobactin (Mb) as the electron transporter between gold electrodes and pMMO, a bionic interface with high biocompatibility and stability was created. The Mb-AuNPs-modified functionalized gold net electrode as a working electrode, the kinetic behaviors of pMMO bioelectrocatalysis, and the effect of Mb on pMMO were analyzed. The CV tests were performed at different scanning rates to obtain electrochemical kinetics parameters. (3) Results: The values of the electron transfer coefficient (α) and electron transfer rate constant ( k s ) are relatively large in test environments containing only CH 4 or O 2 . In contrast, in the test environment containing both CH 4 and O 2 , the bioelectrocatalysis of pMMO is a two-electron transfer process with a relatively small α and k s ; (4) Conclusions: It was inferred that Mb formed the complex with pMMO. More importantly, Mb not only played a role in electron transfer but also in stabilizing the enzyme structure of pMMO and maintaining a specific redox state. Furthermore, the continuous catalytic oxidation of natural substrate methane was realized.

Biochar amendment for landfill soil cover has the potential to enhance methane removal efficiency while minimizing the soil depth. However, there is a lack of information on the response of biochar-mediated soil cover to the changes in configuration and operational parameters during the methane transport and transformation processes. This study constructed three biochar-amended landfill soil covers, with reduced soil depths from 75 cm (C2) to 55 cm (C3) and 45 cm (C4), and the control group (C1) with 75 cm and no biochar. Two operation phases were conducted under two soil moisture contents and three inlet methane fluxes in each phase. The methane removal efficiency increased for all columns along with the increase in methane flux. However, increasing moisture content from 10% to 20% negatively influenced the methane removal efficiency due to mass transfer limitation when at a low inlet methane flux, especially for C1; while this adverse effect could be alleviated by a high flux. Except for the condition with low moisture content and flux combination, C3 showed comparable methane removal efficiency to C2, both dominating over C1. As for C4 with only 45 cm, a high moisture content combined with a high methane flux enabled its methane removal efficiency to be competitive with other soil depths. In addition to the geotechnical reasons for gas transport processes, the evolution in methanotroph community structure (mainly type I methanotrophs) induced by biochar amendment and variations in soil properties supplemented the biological reasons for the varying methane removal efficiencies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Manipulating the methanotroph (MOB) composition and microbial diversity is a promising strategy to optimize the methane (CH 4 ) biofiltration efficiency of an engineered landfill cover soil (LCS) system. Inoculating soil with exogenous MOB-rich bacteria and amending soil with biochar show strong manipulating potential, but how the two stimuli interactively shape the microbial community structure and diversity has not been clarified. Therefore, three types of soils with active CH 4 activities, including paddy soil, river wetland soil, and LCS were selected for enriching MOB-dominated communities (abbreviated as B&#95;PS, B&#95;RWS, and B&#95;LCS, respectively). They were then inoculated to LCS which was amended with two distinct biochar. Besides the aerobic CH 4 oxidation efficiencies, the evolution of the three microbial communities during the MOB enrichment processes and their colonization in two-biochar amended LCS were obtained. During the MOB enriching, a lag phase in CH 4 consumption was observed merely for B&#95;LCS. Type II MOB Methylocystis was the primary MOB for both B&#95;PS and B&#95;LCS; while type I MOB dominated for B&#95;RWS and the major species were altered by gas concentrations. Compared to biochar, a more critical role was demonstrated for the bacteria inoculation in determining the community diversity and function of LCS. Instead, biochar modified the community structures by mainly stimulating the dominant MOB but could induce stochastic processes in community assembly, possibly related to its inorganic nutrients. Particularly, combined with biochar advantages, the paddy soil-derived bacteria consortiums with diverse MOB species demonstrated the potent adaption to LCS niches, not only retaining the high CH 4 -oxidizing capacities but also shaping a community structure with more diverse soil function. The results provided new insights into the optimization of an engineered CH 4 -mitigation soil system by manipulating the soil microbiomes with the cooperation of exogenous bacteria and biochar., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Dandan Huang reports financial support was provided by Basic and Applied Basic Research Foundation of Guangdong Province., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

From a synthetic perspective, bis(indolyl)methanes have undergone extensive investigation over the past two to three decades owing to their remarkable pharmacological activities, encompassing anticancer, antimicrobial, antioxidant, and antiinflammatory properties. These highly desirable attributes have spurred significant interest within the scientific community, leading to the development of various synthetic strategies that are not only more efficient but also ecofriendly. This synthesis-based literature review delves into the advancements made in the past 5 years, focusing on the synthesis of symmetrical as well as unsymmetrical bis(indolyl)methanes. The review encompasses a wide array of methods, ranging from well-established techniques to more unconventional and innovative approaches. Furthermore, it highlights the exploration of various substrates, encompassing readily available chemicals such as indole, aldehydes/ketones, indolyl methanols, etc. as well as the use of some specific compounds as starting materials to achieve the synthesis of this invaluable molecule. By encapsulating the latest developments in this field, this review provides insights into the expanding horizons of bis(indolyl)methane synthesis., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

N -heterocyclic carbene (NHC) silver(I) and gold(I) complexes have found different applications in various research fields, as in medicinal chemistry for their antiproliferative, anticancer, and antibacterial activity, and in chemistry as innovative and effective catalysts. The possibility of modulating the physicochemical properties, by acting on their ligands and substituents, makes them versatile tools for the development of novel metal-based compounds, mostly as anticancer compounds. As it is known, chemotherapy is commonly adopted for the clinical treatment of different cancers, even though its efficacy is hampered by several factors. Thus, the development of more effective and less toxic drugs is still an urgent need. Herein, we reported the synthesis and characterization of new silver(I) and gold(I) complexes stabilized by caffeine-derived NHC ligands, together with their biological and catalytic activities. Our data highlight the interesting properties of this series as effective catalysts in A 3 -coupling and hydroamination reactions and as promising anticancer, anti-inflammatory, and antioxidant agents. The ability of these complexes in regulating different pathological aspects, and often co-promoting causes, of cancer makes them ideal leads to be further structurally functionalized and investigated.

The information of biochemical methane potential (BMP) of wasted sludge is essential to ensure the stable operation of sludge management processes. However, conventional anaerobic digestion (AD) approach for BMP test is time-consuming and labour-intensive. Currently, the technique of Near Infrared Spectroscopy (NIRS) is gaining prominence in the biogas production within AD process. Previous studies mostly focused on predicting BMP values for fibrous plant biomass and solid waste, with only a limited number of studies attempting to apply NIRS to obtain BMP values across a wide array of wasted sludge types. To obtain BMP values for this diverse range of wasted sludge efficiently and accurately, it is imperative to develop precise models for assessing BMP values using NIRS. In this study, the possibility of using NIRS to predict the BMP values of wasted sludge was evaluated. A total of 70 sludge samples from different sources were investigated to develop a BMP-prediction model by correlating the measured BMP values with the obtained NIR spectra. As a result, a reliable and successful BMP-prediction model was established with the determination coefficient of 0.90, residual prediction deviation of 3.50 and low root mean square error of prediction of 36.8 mL CH 4 /g VS. This BMP-prediction model is satisfactory for predicting BMP values of various types of sludge. It could provide support for plant operators to make decisions rapidly, thereby improving the process efficiency and optimizing sludge management procedures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The fragmentation of bioplastics (BPs) before pretreatment and anaerobic digestion is conducted for higher efficiency; however, based on the literature, the size reduction varies widely. In this study, initially, various combinations of thermal-alkaline pretreatments were applied at different strengths to the polylactic acid (PLA) in three groups (<0.5, 0.5 < size < 1.0, and 1.0 < size < 2.0 mm). After pretreatment, the solubilization of PLA was increased to 11.5-40.0 % using alkaline dosage and temperature ranging from 50 to 200 g OH - /kg BP, 60-100 °C, respectively, in a 1-10 h timeframe. The results were statistically proved using a 3D response surface graph, where the pretreatment was more effective for smaller particle sizes. The reduction in particle size also increased the CH 4 production, which was more pronounced at the strong pretreatment (24 % increment vs. 10-15 %). Computed results indicated 44-86 % conversion of pretreated PLA particles to CH 4 , supported by Fourier transform infrared spectroscopy analysis, especially focusing on the intensity of -OH bands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study investigated the use of H 2 -driven CO 2 biomethanation for integrated CO 2 capture and conversion (iCCC). Anaerobic chambers containing Na 2 CO 3 -amended microbial growth medium provided with H 2 were inoculated with anaerobic granular sludge. Microorganisms were enriched that could regenerate carbonate by using the bicarbonate formed from CO 2 absorption to generate methane. Multiple absorption-regeneration cycles were performed and effective restoration of CO 2 absorption capacity and stable carbonate recycling via CO 2 biomethanation were observed for CO 2 absorbents adjusted to three different pH values (9.0, 9.5, and 10.0). The pH = 10.0 group had the highest CO 2 absorption capacity; 65.3 mmol/L in the 5th cycle. A slight alkaline inhibition of acetoclastic methanogenesis occurred near the end of regeneration, but had limited impact on the cyclic performance of the iCCC process. Microbial communities were dominated by H 2 -utilizing and alkali-tolerant species that could participate in CO 2 biomethanation and survive under alternating neutral and alkaline conditions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

State-of-the-art methods in photoproximity labeling center on the targeted generation and capture of short-lived reactive intermediates to provide a snapshot of local protein environments. Diazirines are the current gold standard for high-resolution proximity labeling, generating short-lived aryl(trifluoromethyl) carbenes. Here, we present a method to access aryl(trifluoromethyl) carbenes from a stable diazo source via tissue-penetrable, deep red to near-infrared light (600-800 nm). The operative mechanism of this activation involves Dexter energy transfer from photoexcited osmium(II) photocatalysts to the diazo, thus revealing an aryl(trifluoromethyl) carbene. The labeling preferences of the diazo probe with amino acids are studied, showing high reactivity toward heteroatom-H bonds. Upon the synthesis of a biotinylated diazo probe, labeling studies are conducted on native proteins as well as proteins conjugated to the Os photocatalyst. Finally, we demonstrate that the conjugation of a protein inhibitor to the photocatalyst also enables selective protein labeling in the presence of spectator proteins and achieves specific labeling of a membrane protein on the surface of mammalian cells via a two-antibody photocatalytic system.