Carboxylic Research Articles

A deep eutectic solvent with a lignin stabilization and functionalization for lignocellulosic biomass pretreatment

This study synthesized a functional deep eutectic solvent (DES) using betaine and glyoxylic acid (GA) for lignocellulosic biomass pretreatment. The Betaine/GA DES pretreatment resulted a high delignification efficiency of 81.89% and xylan removal of 83.25% while preserving most of cellulose. During pretreatment, lignin was stabilized by GA, preventing its condensation and introducing carboxyl groups onto its molecular backbone. The GA stabilized lignin (GASL), with a high β-O-4 linkage content of 62.92%, was depolymerized for phenolic monomer production with a bio-oil yield of 55.40%. Additionally, the functional lignin was used as a surfactant for GASL-based O/W emulsion (GA-O/W emulsion) preparation. With 0.5% of lignin addition and an optimal O/W ratio of 6:4, the resulting GA-O/W emulsion exhibited a high cream index value of 100% and excellent storage stability without any phase transition or emulsion aggregation. When using the lignin to prepare curcumin-encapsulated microcapsules, a cumulative curcumin remaining of 74.19% under UV radiation and an extraordinary encapsulation efficiency of 62.86% were achieved. Furthermore, this DES pretreatment promoted enzymatic saccharification of the pretreated cellulose substrate, resulting in a glucose yield of 91.49%. After adding 15 wt% of the fibers in soft wood pulp for papermaking, the tear index, ring crush strength index, and tensile index of the produced paper-sheets reached 112.04%, 98.58%, and 83.55% of those of the pure softwood pulp papers, respectively.

Regenerated carboxymethyl cellulose beads for selective removal of low-density lipoprotein from whole blood

Low-density lipoprotein (LDL) plays a crucial role in the development of cardiovascular disease. Lowering the level of LDL is an effective therapeutic strategy for treating cardiovascular disease. Here, we developed a facile and robust method to prepare carboxymethyl cellulose beads (CMCBs) for selectively adsorbing LDL. CMCBs had plentiful carboxyl groups and large numbers of nanopores on their surface. The in vitro assay reveals that CMCBs had a high LDL adsorbing capability of 7.67 ± 0.16 mg/g, owing to the carboxyl group-induced electrostatic adsorption and the nanopore-mediated trapping effect. CMCBs also possessed the excellent mechanical strength to resist the impact of rushing blood. Moreover, CMCBs were highly blood-compatible and had anticoagulant activity. The in vivo experiment reveals that LDL were significantly reduced from 15.02 ± 1.62 to 9.35 ± 1.71 mmol/L after blood perfusion using CMCBs, while minimal side effects were detected for the blood routine parameters. The study provides an easy-to-fabricate adsorbent for selective and efficient clearance of LDL in hemoperfusion.

Tissue derivatization for visualizing lactate and pyruvate in mouse testis tissues using matrix-assisted laser desorption/ionization-mass spectrometry imaging.

Pyruvate and lactate are the final metabolites of the glycolytic system that are formed under oxygen-rich and anaerobic conditions, respectively. They play an important role in energy metabolism. Obtaining a tissue distribution image of pyruvate and lactate holds great significance in molecular biology because the glycolytic system plays an essential role in diseases, such as tumors and diabetes; microbial activities, such as alcohol production and lactic acid fermentation; and maintaining homeostasis in the gut environment. However, it is difficult to obtain images of the distribution of in vivo metabolites because of the low detection sensitivities of current methods. In this study, a novel derivatization method for pyruvate and lactate was developed using matrix-assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) to detect pyruvate and lactate in vivo and obtain biodistribution images. We investigated derivatization methods using readily available 3-nitrophenylhydrazine (3NPH), the addition of which improves the sensitivity of pyruvate detection, and the distribution of pyruvate in mouse testes was successfully visualized. Furthermore, the distribution of lactate in the mouse testes could be visualized, and improved detection sensitivity for the main metabolites of the tricarboxylic acid cycle was demonstrated. This derivatization method can be used to detect carboxyl-containing metabolites, including pyruvate, via MALDI-MSI. Furthermore, 3NPH forms amide bonds with carbonyl, phosphate, and carboxyl groups, suggesting the possibility of visualizing its distribution in many metabolites.

Characterization of bio-crude produced by graphene carbon tetranitrate catalyzed hydrothermal liquefaction and ultrasonication of Ulva prolifera mixed Chicken waste

<p style="text-align:justify;"><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">The utilization of macroalgae, specifically </span><em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">Ulva prolifera</span></em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">, for the manufacture of bio-crude demonstrates great potential as a viable alternative to conventional fossil fuels. This is mostly owing to its abundant availability and renewable characteristics, making it an optimal choice for bio-oil production. This study examined the synthesis of bio-crude through the Hydrothermal Liquefaction (HTL) method. The combination of Ultra-sonicated </span><em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">Ulva prolifera</span></em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">, Chicken Waste, and water facilitated the transformation of the moist biomass into Bio-crude. The study also examined the influence of process parameters, including the optimal operational temperature, retention time, and feedstock mixing ratio (275 <sup>o</sup>C, 30 minutes, and 1:4 ratio) for the graphene-C<sub>3</sub>N<sub>4 </sub>catalyst, KOH. The study's findings verified that a significant amount of bio-oil, specifically 23.5wt.% based on dry weight measurements, was successfully produced. The bio-oil mostly consists of alcohols, esters, phenols, ketones, and acidic chemicals. Furthermore, the bio-oil exhibited a significant heating value of 38.15 MJ/kg, which can be attributed to the presence of carboxylic acid groups and aliphatic hydrocarbons. Furthermore, the carbon content in the bio-oil was found to be double that of the macroalgae used as feedstock. Additionally, the heating value of the bio-oil was shown to be 2.5 times greater than that of the macroalgae. Hydrothermal liquefaction may be used to efficiently create bio-oil from </span><em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">Ulva prolifera</span></em><span style="font-family:"Times New Roman",serif;font-size:12pt;line-height:200%;">, a third-generation fuel that has great potential as an environmentally benign and sustainable energy source.</span></p>

Meso-Hydroxylmethyl-1,3,5,7-tetramethylBODIPY: A Visible-Light Photoremovable Protective Group for Carboxyl Groups

AbstractA meso-BODIPY-type photoremovable protecting group for carboxyl group is developed. BODIPYs are well-known for brilliant color, favorable to reaction monitoring and purification. meso-BODIPY esters are achieved via esterification in 44–89% yields, while deprotection is fulfilled under irradiation of blue LED bulb in the presence of photocatalyst and organic hydrogen donor in 43–95% yields. This method is applicable to a variety of acids, such as aromatic, heteroaromatic, alkyl, α,β-unsaturated carboxylic acids, etc. Our BODIPY-deprotective condition is almost neutral that both methyl and tert-butyl esters are compatible.

Crosslinkable Ligands for High-Density Photo-Patterning of Perovskite Nanocrystals.

Perovskite nanocrystals (PNCs) are promising luminescent materials for electronic color displays due to their high luminescence efficiency, widely-tunable emission wavelengths, and narrow emission linewidth. Their application in emerging display technologiesnecessitates precise micron-scale patterningwhile maintaining good optical performance. Although photolithography is a well-established micro-patterning technique in the industry, conventional processes are incompatible with PNCs as the use of polar solvents can damage the ionic PNCs, causingsevere luminescence quenching. Here,we report the rational design and synthesis of a new bidentate photo-crosslinkable ligand for the direct photo-patterning of PNCs. Each ligand contains two photosensitive acrylate groups and two carboxylate groups, and is introduced to the PNCs via an entropy-driven ligand exchange process. In a close-packed thin film, the acrylate ligands photo-polymerize and crosslink under ultraviolet light, rendering the PNCs insoluble in developing solvents. A high-density crosslinked PNC film with an optical density of 1.1 is attained at 1.4µm thickness, surpassing industry requirements on the absorption coefficient. Micron-scale patterning is further demonstrated using direct laser writing, producing well-defined 20µm features. This study thus offers an effective and versatile approach for micro-patterning PNCs, and may also be broadly applicable to other nanomaterial systems.

Preparation and characterization of carboxymethyl microcrystalline cellulose from pineapple leaf fibre

Highly functional and robust biobased materials are still in research to produce valuable composites for various applications. The literature shows the gap of new raw biobased materials in market which can functionally tuned and structurally modified for development of 2d/3d architectures. Thus, in the present study, very cheap, easily available agricultural waste, pineapple leaf fiber (PL-raw) was used for the isolation of microcrystalline cellulose (PL-MCC) and further functionalized using upscaled chemical approach to carboxymethyl microcrystalline cellulose (PL-CMMCC). Very advanced techniques like Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction analysis (XRD), and differential scanning calorimetry (DSC) served to characterize the raw material, high crystalline PL-MCC, and modified carboxy methyl MCC. FTIR determined presence of different absorbed peak at approximately 1620.2 cm−1, and at 1423.8 cm−1, carboxyl groups were assigned to PL-CMMCC. On the other hand, the XRD findings verified that PL-CMMCC’s crystalline structure has decreased. Analysis by SEM revealed a damaged surface morphology for PL-CMMCC. Following chemical treatments, the EDX analysis revealed that each fiber sample contained a highly pure cellulose elemental composition. Thus, results explain the utilization of agricultural waste, pineapple leaf fiber to high valuable products like highly crystalline PL-MCC, in addition further modification of PL-MCC could leads to formation of highly functional material that could be used for other applications too in future.

Bio-adsorption of Fe (II) by dry biomass of metal-tolerant haloarchaeon Haloferax alexandrinus GUSF-1.

Mining-associated activities result in iron pollution exceeding the acceptable limit of 0.3 mg L- 1 and are rampant in estuarine soil and water bodies that harbor halophilic microorganisms. Biotechnologies are underway to unveil the concentrations and recover the metals that skip existing physico-chemical methods. Concerning this, the present study describes for the first time the development of a bio-adsorption batch system using dried cells of Haloferax alexandrinus GUSF-1 for Fe (II) from saline water under microaerophilic conditions. A maximum of 99.5% Fe (II) was adsorbed at pH 6.0, 30 ºC in 3h with 92% efficiency over three adsorption-desorption cycles with saturation and pseudo-second-order kinetics and heterogeneity of Freundlich model having KF of 1.38 mg g- 1 with the n value of 0.96. Adsorbed Fe (II) by the cells was detected by scanning electron microscopy. The involvement of the carboxyl, amino, hydroxyl, and phosphate groups of the cells in interaction with the metal ions was detected by infrared spectroscopy. Conclusively, the study is the first report of whole dried cells mediated metal adsorption by the haloarcheon Haloferax alexandrinus GUSF-1 which acts as promising candidate for metal clean-up strategy and bioremediation in hypersaline ecosystems.

Chemical characteristics of Salix psammophila sand barriers are accelerated degradation by ultraviolet irradiation and water.

The implementation of Salix psammophila sand barriers measures constitutes a crucial element in desertification control, providing a solid theoretical foundation for the future application and pretreatment of sand barriers in production practices. To address the specific damage types predominant in desert environments, we executed simulations of ultraviolet irradiation and rainfall phenomena on mechanical sand barriers in sandy areas and also inspected the variations in chemical properties during accelerated aging processes. The findings unequivocally demonstrate that: (1) The synergistic impact of ultraviolet irradiation and water accelerated the deformation and fracturing of the S.psammophila sand barriers, thereby causing a partial degradation of its chemical properties and conspicuous lignin oxidation; (2) The fissure of the sand barrier deepened, resulting in structural alterations. The existence of water expedites the degradation process of S.psammophila sand barriers under ultraviolet irradiation. (3)With respect to the binding form of C atoms, the carbon atoms at S.psammophila sand barriers were highly oxidized after 576 hours of accelerated aging. The components of C2 (C-O) and C3 (C=O) rising to 40.16% and 12.24% respectively, while the components of C1 (C-C) declined to 47.60%. The amount of hydroxyl (O-C-O), carbonyl (C=O), and carboxyl (O-C=O) groups increases in line with the expansion of the contact area between the sand barrier structure and ultraviolet irradiation as well as water. More free radical substances are generated, thereby causing the chemical binding properties to tend to be more stable. In summary, Ultraviolet irradiation and water change are the primary factors influencing the degradation of S.psammophila sand barriers material structure and properties. In future desertification control, it is imperative to focus on enhancing the longevity of sand barriers by ensuring their waterproofing capabilities and resistance to ultraviolet irradiation.

Synthesis and properties of graphene-like porous carbon from modified cellulose

The work is devoted to the synthesis of graphene-like magnetic nanocomposites by direct pyrolysis of hemp microcrystalline cellulose modified with citric acid containing nickel or cobalt salts. Their chemical structure and morphology were characterized by X-ray diffraction (XRD), electron microscopy (SEM), Raman spectroscopy, low-temperature N2 adsorption-desorption, and Fourier transform infrared spectroscopy (FT-IR). Thermogravimetry has established a possible mechanism of pyrolysis of a modified cellulose matrix containing Ni and Co metals. X-ray diffraction analysis and Raman spectroscopy have shown that an increase in the number of carboxyl groups accelerates the process of graphitization of the cellulose matrix with transition metals (Ni and Co), as well as increases the degree of structural order and the level of graphitization. The conducted studies have shown that nanoparticles of metals of the zero-valence state are enclosed in graphene-like shells having a mainly mesoporous structure.

In Situ Formation of Acidic Comonomer during Thermal Treatment of Copolymers of Acrylonitrile and Its Influence on the Cyclization Reaction.

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1-10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100-130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150-190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode.

All-in-One Polymer Gel Electrolyte towards High-Efficiency and Stable Fiber Zinc-Air Battery.

Fiber zinc-air batteries are explored as promising power systems for wearable and portable electronic devices due to their intrinsic safety and the use of ambient oxygen as cathode material. However, challenges such as limited zinc anode reversibility and sluggish cathode reaction kinetics result in poor cycling stability and low energy efficiency. To address these challenges, we design a polydopamine-based all-in-one gel electrolyte (PAGE) that simultaneously regulates the reversibility of zinc anodes and the kinetics of air cathodes through polydopamine interfacial and redox chemistry, respectively. The intrinsic catechol and carboxylate groups in PAGE regulate the transport and solvation structure of Zn2+, facilitating dendrite-free zinc deposition with a lamellar stacking morphology. Additionally, the oxidation of redox-active catechol groups in PAGE replaces the sluggish oxygen evolution reaction on the air cathode and reduces the energy barrier for charging, enabling fiber zinc-air batteries to achieve a significantly improved energy efficiency of 95% and a longer lifespan of 40 hours. Further integration into self-powered electronic textiles underscores its potential for next-generation wearable systems.

All‐in‐One Polymer Gel Electrolyte towards High‐Efficiency and Stable Fiber Zinc‐Air Battery

Fiber zinc‐air batteries are explored as promising power systems for wearable and portable electronic devices due to their intrinsic safety and the use of ambient oxygen as cathode material. However, challenges such as limited zinc anode reversibility and sluggish cathode reaction kinetics result in poor cycling stability and low energy efficiency. To address these challenges, we design a polydopamine‐based all‐in‐one gel electrolyte (PAGE) that simultaneously regulates the reversibility of zinc anodes and the kinetics of air cathodes through polydopamine interfacial and redox chemistry, respectively. The intrinsic catechol and carboxylate groups in PAGE regulate the transport and solvation structure of Zn2+, facilitating dendrite‐free zinc deposition with a lamellar stacking morphology. Additionally, the oxidation of redox‐active catechol groups in PAGE replaces the sluggish oxygen evolution reaction on the air cathode and reduces the energy barrier for charging, enabling fiber zinc‐air batteries to achieve a significantly improved energy efficiency of 95% and a longer lifespan of 40 hours. Further integration into self‐powered electronic textiles underscores its potential for next‐generation wearable systems.

Design and characterization of novel A2B2 porphyrins: Solar cell applications, antimicrobial properties, and molecular docking insights

We synthesized novel A2B2 porphyrin derivatives (5a-e, 7a,b) with yields of 60–73 %. Porphyrin 2 was prepared by reacting dipyrromethane 1 with p-bromobenzaldehyde. Porphyrin 2 was then treated with n-BuLi in DMF at -15 °C to produce porphyrin 3. The final compounds, 5a-e and 7a,b, were synthesized by reacting porphyrin 3 with activated nitriles (4a-e) and thiazolone derivatives (6a,b). The structures of the novel compounds were confirmed using infrared (IR) spectroscopy, proton nuclear magnetic resonance (1H NMR), carbon-13 nuclear magnetic resonance (13C NMR), mass spectrometry (MS), and elemental analysis. DFT calculations were used to explore the electronic structures and energy levels of the synthesized compounds. Compounds 7a and 7b showed improved electron transfer efficiency compared to 5a-e, with HOMO and LUMO levels aligned for optimal DSSC performance. The HOMO levels are below the electrolyte's redox potential (-5.2 eV), and the LUMO levels are above TiO2's conduction band (-4.2 eV), facilitating efficient electron injection and dye regeneration. Key parameters such as open-circuit voltage (VOC), free energy of injection (ΔGinj), and regeneration (ΔGreg) were calculated, highlighting these compounds' potential for DSSC applications. The newly synthesized compounds were tested for antibacterial activity against C. albicans, B. subtilis, and E. coli. Compounds 5e (MIC50 3.125 µg/mL, with inhibition zone 45 mm against B. subtilis) and (MIC50 12.5 µg/mL, with inhibition zone 31 mm against E. coli) and 7a (MIC50 3.125 µg/mL, with inhibition zone 44 mm against B. subtilis) and (MIC50 12.5 µg/mL, with inhibition zone 30 mm against E. coli) showed the highest antimicrobial activity. Compound 5e's carboxylic acid group likely enhances activity through strong hydrogen bonding and improved solubility, aiding interaction with microbial enzymes or cell walls. Compound 7a's dimalononitrile groups, being highly electron-withdrawing, increase reactivity, while phenylthiazolidine rings offer additional binding sites through hydrogen bonding and pi-stacking interactions. Docking studies of the most potent antibacterial porphyrin analogues, 5e and 7a, against the target protein PDB: 1ECl showed promising results. Compound 5e achieved a docking score of ‐7.9559 kcal/mol with an RMSD of 1.9743 Å, while compound 7a had an even better score of ‐8.9174 kcal/mol. Compound 7a formed interactions with two H-acceptors from its cyano groups, binding to Arg136 and Lys488, and a Pi-H interaction between the thiazolone ring and Asn158, with distances of 3.19, 3.63, and 3.71 Å, respectively.

Facile and scalable method to synthesize MOFs/PET composite fibers for indoor VOCs adsorption

Volatile organic compounds (VOCs) that are emitted into indoor environments pose significant risks to human health, necessitating air purification to protect individuals from VOC-induced harm. Metal–organic frameworks (MOFs) are characterized by their extensive porosity and accessible metal sites and have attracted significant interest owing to their efficacy in VOC adsorption. However, the inherent difficulty in collecting powdered MOFs hinders their practical application. Thus, integrating MOFs with textiles presents an innovative solution for overcoming these challenges. In this study, MOFs/PET composite textiles (MOFs@STP-PET) were synthesized via an in-situ growth process on polyethylene terephthalate (PET) fiber substrates using thermal crosslinking coating and pre-soaked seed hot-solvent methodologies. The capacities of the composites to adsorb and mitigate VOCs, including benzene and formaldehyde, were evaluated. The presence of carboxyl groups (–COOH) on the polyacrylic acid coating facilitated the chelation of metal ions via electrostatic interactions, providing a foundation for MOF growth. Moreover, the obtained textiles exhibited good adsorption performance. Notably, the 10 % breakthrough time of ethylbenzene on the U6N@STP-PET textile increased to 267.9 min, resulting in a maximum adsorption capacity of 4.3 mg/g. Uniformly anchored MOFs on the fiber surface ensured a high specific surface area of 292.3 m2/g, further enhancing adsorption capabilities. In addition, the textile exhibited excellent mechanical properties, with a tensile strength of approximately 20 MPa. This straightforward, effective, and scalable approach paves the way for the development of novel VOC adsorption materials and holds promise for improving indoor air quality.

Cellulose fiber drainage improvement via citric acid crosslinking

Wheat straw, as a non-wood fiber waste, is available worldwide and can be used in cellulosic matric production, promoting the application of sustainable materials. However, poor fiber properties and water drainage are the primary obstacles to its utilization. In this study, wheat straw pulp fibers were chemically crosslinked by citric acid (CA) in an environmentally friendly process. X-ray photoelectron spectroscopy and Fourier transform infrared spectra confirmed that the chemical treatment introduced carboxylic groups to cellulose fibers. Meanwhile, X-ray diffraction patterns showed that the crystallinity of cellulose was reduced. The average fiber length and water retention value of the pulp decreased with increasing CA dosage under the conditions of 3 mL/g CA4 (4 wt% CA), and the drainage performance of the cellulose pulp improved by 21 %. Also, the crosslinking of fibers contributed to the mechanical properties of the cellulosic matrix, increasing the dry and wet strength by 21 % and 282 %, respectively. These results demonstrated that citric acid could be a sustainable method for improving the properties of wheat straw fibers, thereby promoting its application in fabricating sustainable materials.

Carbon-13 Hyperpolarization of α-Ketocarboxylates with Parahydrogen in Reversible Exchange.

Signal Amplification by Reversible Exchange (SABRE) is a relatively simple and fast hyperpolarization technique that has been used to hyperpolarize the α-ketocarboxylate pyruvate, a central metabolite and the leading hyperpolarized MRI contrast agent. In this work, we show that SABRE can readily be extended to hyperpolarize 13C nuclei at natural abundance on many other α-ketocarboxylates. Hyperpolarization is observed and optimized on pyruvate (P13C=17%) and 2-oxobutyrate (P13C=25%) with alkyl chains in the R-group, oxaloacetate (P13C=11%) and alpha-ketoglutarate (P13C=13%) with carboxylate moieties in the R group, and phenylpyruvate (P13C=2%) and phenylglyoxylate (P13C=2%) with phenyl rings in the R-group. New catalytically active SABRE binding motifs of the substrates to the hyperpolarization transfer catalyst-particularly for oxaloacetate-are observed. We experimentally explore the connection between temperature and exchange rates for all of these SABRE systems and develop a theoretical kinetic model, which is used to fit the hyperpolarization build-up and decay during SABRE activity.

Construction of 2D zinc(II) MOFs with tricarboxylate and N-donor mixed ligands for multiresponsive luminescence sensors and CO2 adsorption.

The solvothermal reactions of ZnCl2·6H2O, benzene-1,3,5-tribenzoic acid (H3btb), and N-heterocyclic ancillary imidazole (Im) or aminopyrimidine (a mp) ligands led to the creation of two-dimensional (2D) zinc(II) based metal-organic frameworks (MOFs), (Me2NH2)2[Zn2(btb)2(Im)2]·2DMF·3MeOH (1) and (Me2NH2)2[Zn2(btb)2(amp)]·H2O·2DMF·MeOH (2). The btb3- ligands in 1 and 2 form an anionic 2D layered structure with a (63) honeycomb (hcb) topology by linking to Zn(II) centres through their carboxylate groups. The incorporation of N-heterocyclic auxiliary ligands Im and amp into the hcb nets resulted in the formation of a 2D hydrogen-bonded and covalently pillared bilayer structure featuring two-fold interpenetrating networks. Each of these networks consists of small channels that are occupied by Me2NH2 cations and solvent molecules. Both 1 and 2 emit blue luminescence emissions in the solid state at room temperature and exhibit a great selectivity and sensitivity for the detection of acetone and multiple heavy metal ions including Hg2+, Cu2+, Fe2+, Pb2+, Cr3+, and Fe3+ ions. At 1 bar, activated 1 and 2 demonstrate moderate capacities for adsorbing CO2 at room temperature, with a preference for CO2 over N2. Notably, at higher pressures (up to 20 bar), their activated samples 1 and 2 show a temperature-dependent enhancement of CO2 uptake while retaining good stability.

Modifications of Prenyl Side Chains in Natural Product Biosynthesis.

In recent years, there has been a growing interest in understanding the enzymatic machinery responsible for the modifications of prenyl side chains and elucidating their roles in natural product biosynthesis. This interest stems from the pivotal role such modifications play in shaping the structural and functional diversity of natural products, as well as from their potential applications to synthetic biology and drug discovery. In addition to contributing to the diversity and complexity of natural products, unique modifications of prenyl side chains are represented by several novel biosynthetic mechanisms. Representative unique examples of epoxidation, dehydrogenation, oxidation of methyl groups to carboxyl groups, unusual C-C bond cleavage and oxidative cyclization are summarized and discussed. By revealing the intriguing chemistry and enzymology behind these transformations, this comprehensive and comparative review will guide future efforts in the discovery, characterization and application of modifications of prenyl side chains in natural product biosynthesis.

Liquid carboxylated nitrile butadiene rubber via metathetic degradation with acrylic acid as chain transfer agent

Liquid carboxylated nitrile butadiene rubber (LXNBR) shows promising application in various fields. Facing the challenges in its preparation via radical emulsion copolymerization, such as gelation, molecular weight and carboxyl group content, novel approach has been developed for the controlled preparation of LXNBR via the metathetic degradation of nitrile butadiene rubber (NBR) with acrylic acid (AA) as chain transfer agent (CTA). Based on the molecular weight and carboxyl group content of the resultant products, the reaction pathway was proposed. Such understanding is expected to prepare LXNBR with designed Mn and carboxyl group content for various applications, by facile adjusting the reaction condition, mainly the feeding mode of AA, NBR concentration and reaction time.