Carbonyl Research Articles

Synthesis of Long‐Chain Polyamides via Main‐Chain Modification of Polyethyleneketones

AbstractLong‐chain polyamides (polyethyleneamides) were prepared from polyethylenes bearing in‐chain carbonyl groups (polyethyleneketones) by the oxime formation and successive Beckmann rearrangement. (Diethylamino)sulfur trifluoride (DAST) was utilized as a promoter, which allowed mild conversion of the oxime group in spite of low solubility of the polymers. The polyethyleneamide exhibited different tensile property compared to a commercial HDPE.

The Effect of Ultrasound Treatment on the Structural and Functional Properties of Tenebrio molitor Myofibrillar Protein.

The objective of this study was to explore the impacts of various ultrasonic powers (0, 300, 500, 700, and 900 W) on the structure and functional attributes of the myofibrillar protein (MP) of Tenebrio molitor. As the ultrasonic intensity escalated, the extraction efficiency and yield of the MP rose, while the particle size and turbidity decreased correspondingly. The reduction in sulfhydryl group content and the increase in carbonyl group content both suggested that ultrasonic treatment promoted the oxidation of the MP to a certain extent, which was conducive to the formation of a denser and more stable gel network structure. This was also affirmed by SEM images. Additionally, the findings of intrinsic fluorescence and FTIR indicated that high-intensity ultrasound significantly altered the secondary structure of the protein. The unfolding of the MP exposed more amino acid residues, the α-helix decreased, and the β-helix improved, thereby resulting in a looser and more flexible conformation. Along with the structural alteration, the surface hydrophobicity and emulsification properties were also significantly enhanced. Besides that, SDS-PAGE demonstrated that the MP of T. molitor was primarily composed of myosin heavy chain (MHC), actin, myosin light chain (MLC), paramyosin, and tropomyosin. The aforementioned results confirmed that ultrasonic treatment could, to a certain extent, enhance the structure and function of mealworm MP, thereby providing a theoretical reference for the utilization of edible insect proteins in the future, deep-processing proteins produced by T. molitor, and the development of new technologies.

Features of spectral characteristics of phenyl-containing vanadium (III) β-diketonates

Tris-dibenzoylmethanate ([V(dbm)3 ]) and tris-benzoylacetonate vanadium ([V(bac)3 ]) were obtained by electrochemical synthesis. The composition of chelates was determined using elemental analysis and IR spectral data. It was shown that the formation of a quasi-aromatic metallocycle, the main structural element of chelate, occurred as a result of electrolysis. At the same time, the batachromic shift of absorption bands of carbonyl groups was more than 100 cm–1. The overwhelming majority of absorption bands in the IR spectra of both compounds had mixed nature. For ([V(dbm)3 ] the characteristic of absorption bands did not exceed 13.5 %, and for [V(bac)3 ] – 10.3 %. The peripheral groups of ligands (phenyl and methyl) did not undergo transformation when influenced by electric current.

Enhancing the Electrocatalytic Hydrogenation of Furfural via Anion-Induced Molecular Activation and Adsorption.

The electrocatalytic hydrogenation (ECH) of furfural (FF) to furfuryl alcohol, which does not require additional hydrogen or high pressure, is a green and promising production route. In this study, we explore the effects of anions on FF ECH in two buffer electrolytes (KHCO3 and phosphate-buffered saline [PBS]). Anions influence the yield of furfuryl alcohol through molecular activation and adsorption. Molecular dynamics simulations show that bicarbonate is present in the first shell layer of the FF molecule and induces strong hydrogen bonding interactions. In contrast, hydrogen phosphate is present only in the second shell layer, resulting in weak hydrogen bonding interactions. Owing to the interfacial anions and hydrogen bonding, FF molecules exhibit strong flat adsorption on the electrode surface in the KHCO3 solution, while weak adsorption is observed in the PBS solution, as confirmed by operando synchrotron-radiation Fourier-transform infrared spectroscopy and in situ Raman spectroscopy. Density-functional theory calculations reveal that the overall anionic hydrogen bonding network promotes the activation of the carbonyl group in the FF molecule in KHCO3, whereas electrophilic activity is inhibited in PBS. Consequently, FF ECH demonstrates much faster kinetics in KHCO3, while it exhibits sluggish ECH kinetics and a severe hydrogen evolution reaction in PBS. This work introduces a new strategy to optimize the catalytic process through the modulation of the microenvironment.

2D coordination polymers of cadmium(II) and zinc(II) derived from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size.

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[diaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O''']cadmium(II)], [Cd(C14H6N2O8)(H2O)2]n (1), and poly[[tetraaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O'''][μ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']dizinc(II)] dihydrate], {[Zn(C14H6N2O8(H2O)2]·H2O}n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH3COO)2·2H2O and Zn(CH3COO)2·2H2O, respectively, with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetic acid, H2L}. In the crystal structure of 1, the CdII ion is six-coordinated by four carboxylate O atoms from four symmetry-related L2- dianions and two coordinated water molecules, furnishing an octahedral coordination geometry. The bridging L2- dianion links four symmetry-related CdII cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the ZnII ion is five-coordinated by three carboxylate O atoms from three different L2- dianions and two coordination water molecules, furnishing a trigonal bipyramidal coordination geometry. Two crystallographically independent ligands serve as μ4- and μ2-bridges, respectively, to connect the ZnII ions, thereby forming a 2D layer with a 3,3-connected hcb topology. Crystal structure analysis reveals the presence of n→π* interactions between two carbonyl groups of the pyromellitic diimide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission compared with free H2L. The framework of 2 decomposes from 720 K, indicating its high thermal stability. A comparative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.

Ligand‐Hybridization Activates Lattice‐Hydroxyl‐Groups of NiCo(OH)x Nanowires for Efficient Electrosynthesis

AbstractElectrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high‐valence metal active sites toward 5‐hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value‐added chemical of 2,5‐furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand‐hybridized NiCo(OH)x nanowires (BZ‐NiCo(OH)x) with ample electron‐deficient Ni/Co sites for HMFOR. The robust electron‐withdrawing capability of benzoic acid ligands in BZ‐NiCo(OH)x speeds up the electrochemical activation and dehydrogenation of lattice‐hydroxyl‐groups (M2+−O−H⇌M3+−O), boosting the formation of abundant electron‐deficient and high‐valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ‐NiCo(OH)x delivers a remarkable current density of 111.20 mA cm−2 at 1.4 V for HMFOR, exceeding that of NiCo(OH)x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand‐hybridized strategy in this work introduces a novel perspective for designing high‐performance transition metal‐based electrocatalysts for biomass conversion.

Ligand-Hybridization Activates Lattice-Hydroxyl-Groups of NiCo(OH)x Nanowires for Efficient Electrosynthesis.

Electrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high-valence metal active sites toward 5-hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value-added chemical of 2,5-furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand-hybridized NiCo(OH)x nanowires (BZ-NiCo(OH)x) with ample electron-deficient Ni/Co sites for HMFOR. The robust electron-withdrawing capability of benzoic acid ligands in BZ-NiCo(OH)x speeds up the electrochemical activation and dehydrogenation of lattice-hydroxyl-groups (M2+-O-H⇌M3+-O), boosting the formation of abundant electron-deficient and high-valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ-NiCo(OH)x delivers a remarkable current density of 111.20 mA cm-2 at 1.4 V for HMFOR, exceeding that of NiCo(OH)x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand-hybridized strategy in this work introduces a novel perspective for designing high-performance transition metal-based electrocatalysts for biomass conversion.

Thiocarbohydrazide-cross-linked pectin: A promising support material for palladium nanoparticles in the water-mediated Suzuki-Miyaura cross-coupling reaction and the catalytic reduction of 4-nitrophenol

Suzuki-Miyaura reaction is a classic palladium-catalyzed reaction for forming Csp2-Csp2 bonds. However, the leaching of Pd species and using organic solvents are two important problems that adversely affect their performance, reusability, and greenness. Considering the abundant resources, cheapness, and availability of pectin (Pec), a Pec-based catalyst for the Suzuki reaction in pure water as a non-toxic reaction medium was developed for the first time. In this regard, Pec was chosen as a benign support and cross-linked by thiocarbohydrazide (TCH) to prepare Pec-TCH. The Pec-TCH acted as an efficient reducing and stabilizing agent for in-situ fabrication of Pd(0) nanoparticles. The heterogeneous and air-stable Pec-TCH-Pd(0) nanoparticles were thoroughly characterized. The results exhibited a significant catalytic activity (up to 99%) and reusability (at least 7 times) for in-water Suzuki-Miyaura cross-coupling reaction. The use of TBAB as a phase-transfer catalyst improved the yield of Suzuki reaction since it prevented the problems related to the immiscibility of water and aryl halides as well as the gelation of catalyst. The catalyst was also utilized for water-mediated 4-nitrophenol reduction to 4-aminophenol with NaBH4 which showed excellent activity (k = 9.2 × 10−3 s−1). A very good compatibility with iodobenzene, bromobenzene, and chlorobenzene was observed for the Suzuki reaction. Because of various binding sites such as amino, hydroxyl, carbonyl and thiocarbonyl groups, negligible leach of Pd nanoparticles was observed, as shown by ICP-MS after runing 7th of reusability studies. Moreover, the leaching, mercury poisoning, and large-scale tests showed its potential for industrial applications.

Rational Tailored Polyfluorosubstituted Amide Molecule for Stabilizing PbI6 Framework and Inhibiting Ion Migration Toward Highly Efficient and Stable Perovskite Solar Cells

AbstractPerovskite solar cells (PSCs), while highly efficient, face stability challenges that hinder their commercial application. These instability issues mainly arise from the fragile nature of Pb─I bonds in perovskites, which easily break under environmental stresses such as heat and light, leading to the breakdown of the [PbI6] framework and irreversible degradation. To address these issues, a multifunctional molecule, N1,N4‐bis(2,3,5,6‐tetrafluoro‐4‐iodophenyl)terephthalamide (FIPh‐A), is designed and synthesized to enhance the stability of perovskite films and devices. FIPh‐A molecule possesses carbonyl, amino, and iodotetrafluorophenyl groups that bind and stabilize Pb2+ ions and [PbI6]4− octahedra structure, preventing ion migration in perovskite films. The activation energy of ion migration increases obviously from 0.28 eV to 0.39 eV by adding FIPh‐A verified by experiment results. The residual strain is also released efficiently by introducing FIPh‐A molecule into perovskite films characterized by grazing incidence X‐ray diffraction. The champion PSC with FIPh‐A achieves a power conversion efficiency of 24.60%. After 500 h of continuous illumination (ISOS‐L‐1) and 300 h of thermal aging at 80 °C (ISOS‐D‐2I), these PSCs with FIPh‐A maintained 93% and 77% of their initial efficiency, respectively. These results emphasize the potential of multifunctional additives in overcoming the stability challenges of PSCs, thereby facilitating their commercial advancement.

Control for selective sorption of heavy metals cations with anion exchanger AB-17-8 by modifying the surface with citrate groups

The citric acid modification produces an intermediate layer on the AB-17-8:C6H8O7 surface; the layer, on one hand, is firmly secured to the surface owing to the electrostatic coupling between the citrate anion and the positively charged trimethylammonium centers of the anion exchanger surface; on the other hand, it has carbonyl groups with a local negative electron density. The sorption of heavy metals cations occurs through coordination interactions via electrostatic mechanism with local centers of negative electron density, in particular, with the carbonylic oxygen atom.

Facile Ring Opening of Novel Bisoxazolone with Substituted Aromatic Amines: Synthesis, Antimicrobial, Antioxidant Potential, In Silico ADME Profile and Molecular Docking Study

AbstractThis article describes the controlled synthesis and characterization of an olefin‐linked oxazolone scaffold compound containing multifunctional groups, including the carbonyl group, imine, and carbon‐carbon double bond. The reaction of the bisoxazolone with aromatic amines led to the ring‐opening of the bisoxazolone into the corresponding bisdiamide derivatives in a short time (average 10 min), resulting in a high yield (>90 %). The compounds were characterized by FT‐IR, 1H‐NMR, 13C‐NMR, and MS. Besides, screened against Escherichia coli, Staphylococcus aureus, and Candida albicans using ciprofloxacin as a standard. All compounds exhibited significant inhibition potency against E. coli, with a lower potency against S. aureus. Compounds 3 a, 3 b, and 3 d showed more reactivity against E. coli, while compound 3 i has the highest activity against S. aureus (MIC=128 μg/mL). Additionally, the antioxidant activity was performed utilizing DPPH radical scavenging activity. The findings indicated that some compounds possessed moderate antioxidant activity in comparison to ascorbic acid as a control. A molecular docking study demonstrated a positive interaction between synthesized compounds and the bacterial DNA gyrase target (PDB ID: 1KZN) in S. aureus. Subsequently, in silico ADME simulations were conducted for all the synthesized compounds, indicating favorable properties in comparison to the established antibiotic ciprofloxacin.

Zein spray-dried microparticles loaded with chemically modified curcumin for active wound healing

Wound healing is a delicate process comprising various phases, of which inflammation constitutes the most critical one, as some wounds fail to evolve from this state due to pre-existing pathologies or medical conditions, becoming chronic and causing pain and serious consequences for the patients. Given this context, innovative strategies able to support the body in the transition through the inflammatory and the proliferative phases are needed. Here, we propose to deliver to the wound zein microparticles (ZμP) loaded with chemically modified curcumin (mCUR), a novel bioactive molecule with strong antioxidant properties. Derived from the classic curcumin, mCUR chemical structure has been modified with an amino phenyl carbonyl group on C4 to overcome the poor bioavailability in the human body and to reach stronger inhibition of inflammatory markers thanks to a higher in vitro efficacy (lower IC50). ZμP were fabricated via spray drying starting from various zein/mCUR ratios. An exhaustive characterization of the physico-chemical properties of ZμP, either empty or loaded, has been carried out, alongside with bioactivity assessments via human keratinocytes and Escherichia coli cultures. All the formulations presented average diameters of 1 μm, resulted biocompatible, and led to an encapsulation efficiency in the range of 78.1–83.0 %. Finally, antioxidant properties of loaded microparticles were assessed via DCFH-DA assay, where a fluorescence decrease proportional to mCUR concentration was clearly visible (down to 41.7 %). These promising results highlight our formulations’ ability to reduce oxidative stress inside the cells, representing a promising strategy to address the problem of chronic wounds, supporting the body in overcoming the inflammatory stage.

Recovering Valuable Chemicals from Polypropylene Waste via a Mild Catalyst-Free Hydrothermal Process.

Waste polypropylene (PP) presents a significant environmental challenge, owing to its refractory nature and inert C-C backbone. In this study, we introduce a practical chemical recovery strategy from PP waste using a mild catalyst-free hydrothermal treatment (HT). The treatment converts 64.1% of the processed PP into dissolved organic products within 2 h in an air atmosphere at 160 °C. Higher temperatures increase the PP conversion efficiency. Distinct electron absorption and emission characteristics of the products are identified by spectral analysis. Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) reveals the oxidative cracking of PP into shorter-chain homologues (10-50 carbon atoms) containing carboxylic and carbonyl groups. Density functional theory (DFT) calculations support a reaction pathway involving thermal C-H oxidation at the tertiary carbon sites in the polymer chain. The addition of 1% H2O2 further enhances the oxidation reaction to produce valuable short-chain acetic acids, enabling gram-scale recycling of both pure PP and disposable surgical masks from the real world. Techno-economic analysis (TEA) and environmental life cycle costing (E-LCC) analysis suggest that this hydrothermal oxidation recovery technology is financially viable, which shows significant potential in tackling the ongoing plastic pollution crisis and advancing plastic treatment methodologies toward a circular economy paradigm.

Interaction mechanism of soy protein isolate with aldehyde flavor compounds: Differences in carbon chain length and unsaturation

Soy protein isolate (SPI) can interact with volatile compounds, which affect flavor perception and limit its application in liquid foods. This study aimed to elucidate the interaction mechanism between SPI and six main flavors of bean (aldehyde flavor compounds with different carbon chain length and unsaturation). The results showed that carbon chain length and unsaturation of compounds influenced the combining ability with SPI. (E, E)-2,4-decadienal and (E, E)-2,4-nonadienal with longer carbon chain length and higher unsaturation showed higher affinity with SPI. Multi-spectroscopy showed that aldehyde flavor compounds could induce the unfolding of SPI structure and expose hydrophobic groups. The presence of CC enhanced the hydrogen bonding between the carbonyl group and SPI. Thermodynamic analysis revealed that complexes mainly relied on hydrophobic interaction and hydrogen bonding-driven interactions. Molecular simulations further confirmed that aldehyde flavor compounds maintained binding stability with SPI the high-flexibility key amino acid residues (Leu79, Pro82, Lys113, Glu358, etc.). This study improves the understanding of interactions between SPI and volatile compounds at the molecular level and provides a theoretical basis for SPI flavor improvement.

Surface Microstructure Study on Corona Discharge-Treated Polyethylene Using Positron Annihilation Spectroscopy.

The microstructure and chemical properties of the corona discharge process could provide an effective method for predicting the performance of high-voltage cable insulation materials. In this work, the depth profile of the microstructure and chemical characteristics of corona discharge-treated PE were extensively investigated using Doppler broadening of position annihilation spectroscopy accompanied with positron annihilation lifetime spectroscopy, attenuated total reflectance Fourier transform infrared spectra, Raman spectra and contact angle measurement. By increasing corona discharge duration, the oxygen-containing polar groups, including hydroxyl, carbonyl and ester groups, strongly contribute to the deterioration of hydrophobicity and the enhancement of hydrophilicity. And the mean free volume size, with a broadening distribution, decreases slightly. The line shape S parameter decreases because of the decrease in free volume elements and the appearance of oxygen-containing groups. Also, the thickness of the degradation layer, determined from the S parameter with positron injection depth, increases and diffuses into the PE matrix. A linear S-W plot within the degradation layer of different corona treatment duration samples indicates the defect type does not change. The S parameter decreases and the W parameter increases with an increasing corona duration. Using a slow positron beam, the nondestructive probe can be used to profile the microstructure and chemical environment across the corona discharge damage depth, which is beneficial for investigating the surface and interfacial insulation materials.

An anthraquinone derivative for modulating the energy levels of polysulfide molecular orbitals to enhance the kinetics of redox reactions

The shuttle effect of lithium polysulfides (LiPSs) and the slow kinetics of sulfur redox reactions severely hinder the commercialization of lithium-sulfur (Li–S) batteries. In this study, 2,6-dihydroxyanthraquinone (DHAQ) is absorbed onto the surface of carbon materials through π-π interactions to facilitate the adsorption and catalytic conversion of LiPSs. Electrostatic potential (ESP) results indicate that introducing hydroxyl groups into the molecule enhances the carbonyl group's ability to adsorb LiPSs and thereby facilitates the formation of covalent Li-O bonds for their immobilization. The interaction between DHAQ and LiPSs results in a complex with a higher energy level for the highest occupied molecular orbital (HOMO) and a lower energy level for the lowest unoccupied molecular orbital (LUMO). This leads to enhanced redox activity, which accelerates the kinetics of LiPSs conversion reactions. Consequently, the S@DHAQ/C composite demonstrates a capacity decay rate of just 0.040 % per cycle after 600 cycles at 1 C. At a sulfur loading of 5 mg cm−2, it retains an initial discharge specific capacity of 643 mAh g−1 at 0.2 C. This work introduces a novel approach to improving polysulfide adsorption capacity through organic molecules while also accelerating the kinetics of redox reactions.

THE EFFECTS OF NaClO2 AND H2O2 AS BLEACHING AGENTS IN THE SYNTHESIS OF CELLULOSE ACETATE FROM OIL PALM EMPTY FRUIT BUNCH

Indonesia is one of the largest palm oil-producing countries in the world. The results of palm oil processing produce a lot of waste, such as oil palm empty fruit bunches (OPEFB). The utilization of OPEFB in Indonesia is minimal, so it needs further development. OPEFB has a very high α-cellulose content, so that it can be used as raw material for manufacturing cellulose acetate. Making cellulose acetate from OPEFB consists of three main steps: delignification, bleaching, and acetylation. This study aims to compare the effects of the concentration of NaClO2 or H2O2 in the bleaching process on the physical properties of cellulose acetate from OPEFB. In the delignification process, 100 mesh-sized OPEFB powder is reacted with 5% sodium hydroxide (NaOH) at 100oC for 2 hours. The residue from deliglinfication was washed using distilled water until pH 7, filtered using filter paper, and dried using an oven at 50oC. The next step is the bleaching process using NaClO2 or H2O2 with concentration variations (1%, 2%, 3%, 4% and 5%). The bleaching process was carried out at 90oC for 1.5 hours. After filtration, the bleached residue was washed using distilled water until pH 7, filtered using filter paper, and dried using an oven at 50oC. After the bleaching process, α-cellulose powder was produced. The next step is acetylation, containing three main steps. The first step is the reaction between α-cellulose powder with acetic acid (CH3COOH) and sulfuric acid (H2SO4) at 40oC for 1.5 hours to perform activation. The second step is the addition of anhydrous cellulose in a ratio of 1:10 and mixed at 40oC for 1.5 hours. The third step is the addition of distilled water, acetic acid, and sodium acetate (CH3COONa) at 40oC for 5 minutes. Then, followed by filtration, the residue was washed using distilled water and methanol until pH 7 and dried at 50oC. The best result is using NaClO2 as a bleaching agent with a concentration of 2%, resulting in cellulose acetate yielding 98.85%, density of 1.954 g/mL, and L value of 91.897 for colorimetric test results. The density and L-value were close to commercial cellulose acetate (Sigma Aldrich). From the results of FTIR analysis, it can be concluded that the acetylation of α-cellulose into cellulose acetate has been successful, as evidenced by the formation of carbonyl groups (C=O).

Near-infrared TADF-type organic afterglow materials

Because of the energy gap law, as well as the spin-forbidden nature of triplet formation and transformation, it remains formidable task to achieve efficient and long-lived organic afterglow materials with long emission wavelengths, especially in the near-infrared region, under ambient conditions. Here we incorporate TADF-type afterglow mechanism in dopant-matrix systems which features a moderate kRISC of 101-102 s−1 to harvest triplet energies, boost afterglow efficiency and maintain afterglow lifetime. Specifically, we design a series of boron difluoride curcuminoid (CurBF2) compounds to serve as luminescent dopants. Organic matrices of crystalline nature and with carbonyl groups are selected to suppress triplet quenching by their rigid microenvironment and populate triplet states via dipole effect developed in our group. The resultant dopant-matrix systems display near-infrared TADF-type organic afterglow with emission wavelength >700 nm, quantum yield around 10 % and afterglow lifetime >10 ms, which can function as deep-penetrating and background-independent bioimaging probes.

Machine learning models for predicting the rejection of organic pollutants by forward osmosis and reverse osmosis membranes and unveiling the rejection mechanisms

While forward osmosis (FO) and reverse osmosis (RO) processes have been proven effective in rejecting organic pollutants, the rejection rate is highly dependent on compound and membrane characteristics, as well as operating conditions. This study aims to establish machine learning (ML) models for predicting the rejection of organic pollutants by FO and RO and providing insights into the underlying rejection mechanisms. Among the 14 ML models established, the random forest model (R2 = 0.85) and extreme gradient boosting model (R2 = 0.92) emerged as the best-performing models for FO and RO, respectively. Shapley additive explanations (SHAP) analysis identified the length of the compound, water flux, and hydrophobicity as the top three variables contributing to the FO model. For RO, in addition to the length of the compound and operating pressure, advanced variables including four molecular descriptors (e.g., ATSC2m and Balaban J) and three fingerprints (e.g., C=C double bond and carbonyl group) significantly contributed to the prediction. Besides, the associations between these highly ranked variables and their SHAP values shed light on the rejection mechanisms, such as size exclusion, adsorption, hydrophobic interaction, and electrostatic interaction, and illustrate the role of the operating parameters, such as the FO permeate water flux and RO operating pressure, in the rejection process. These findings provide interpretable predictive models for the removal of organic pollutants and advance the mechanistic understanding of the rejection mechanisms in the FO and RO processes.

Enhancing long-segmental tracheal restoration: A self-repairing hydrogel loaded with chondrocytokines for sutureless anastomosis and cartilage regeneration

Artificial tracheal substitutes encounter significant challenges during long-segmental tracheal defects (LSTD) reconstruction, notably early postoperative anastomotic stenosis and tracheal chondromalacia. Mitigating early anastomotic stenosis by creating a compliant sutureless substitute is pivotal. Enhancing its chondrogenic capacity is equally critical for sustained healthy tracheal cartilage regeneration. This study proposes a self-healing hydrogel for sutureless tracheal anastomosis to mitigate anastomotic stenosis, enriched with kartogenin (KGN) and transforming growth factor-β1 (TGFβ1) to bolster chondrogenic properties. Initially, two precursor solutions were prepared: 1) aldehyde-modified hyaluronic acid with sulfonation and β-cyclodextrin-CHO loaded with KGN; 2) hydrazide-grafted gelatin loaded with TGFβ1. Coextrusion of these solutions resulted in a gelated G + TGFβ1/sH-CD + KGN hydrogel, characterized by a robust covalent bonding network of acylhydrazones between hydrazide and aldehyde groups, imparting excellent self-healing properties. The G + TGFβ1/sH-CD + KGN hydrogels, showcasing favorable cytocompatibility, excellent injectability, and rapid gelation, were loaded with bone marrow stem cells. These were customized into O-shaped rings and assembled into a malleable tracheal substitute using our established ring-to-tube method. This resultant compliant substitute facilitated sutureless anastomosis of LSTD in a rabbit model, attributed to the Schiff base reaction between the hydrogel's carbonyl group and the tissue's amino group. Notably, the tracheal substitute reduced early postoperative anastomotic stenosis, maintained tracheal patency, alleviated sputum blockage, promoted reepithelization, and increased the survival rate of the experimental rabbits. The sustained release of chondrocytokines resulted in excellent tracheal cartilage regeneration. Employing chondrocytokines-loaded hydrogels with self-healing properties represents a significant advancement in sutureless tracheal anastomosis and tracheal cartilage regeneration, holding promising potential in inhibiting early postoperative anastomotic stenosis and tracheal chondromalacia when treating LSTD.