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Bacterial small molecule metabolites such as adenosine-diphosphate-d-glycero-ß-d-manno-heptose (ADP-heptose) and their derivatives act as effective innate immune agonists in mammals. We show that functional nucleotide-diphosphate-heptose biosynthetic enzymes (HBEs) are distributed widely in bacteria, archaea, eukaryotes, and viruses. We identified a conserved STTR5 motif as a hallmark of heptose nucleotidyltransferases that can synthesize not only ADP-heptose but also cytidine-diphosphate (CDP)- and uridine-diphosphate (UDP)-heptose. Both CDP- and UDP-heptoses are agonists that trigger stronger alpha-protein kinase 1 (ALPK1)-dependent immune responses than ADP-heptose in human and mouse cells and mice. We also produced ADP-heptose in archaea and verified its innate immune agonist functions. Hence, the ß-d-manno-heptoses are cross-kingdom, small-molecule, pathogen-associated molecular patterns that activate the ALPK1-dependent innate immune signaling cascade.
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Heptosas , Nucleotidiltransferasas , Moléculas de Patrón Molecular Asociado a Patógenos , Animales , Humanos , Ratones , Secuencias de Aminoácidos , Archaea/enzimología , Bacterias/enzimología , Bacterias/metabolismo , Heptosas/biosíntesis , Heptosas/inmunología , Inmunidad Innata , Nucleotidiltransferasas/química , Nucleotidiltransferasas/clasificación , Nucleotidiltransferasas/genética , Moléculas de Patrón Molecular Asociado a Patógenos/inmunología , Moléculas de Patrón Molecular Asociado a Patógenos/metabolismo , Proteínas Quinasas/metabolismo , Virus/enzimologíaRESUMEN
This study employed potassium carbonate (K2CO3) activation using ball milling in conjunction with pyrolysis to produce biochar from one traditional Chinese herbal medicine Atropa belladonna L. (ABL) residue. The resulting biochar KBC800 was found to possess a high specific surface area (S BET = 1638 m2/g) and pore volume (1.07 cm3/g), making it effective for removing norfloxacin (NOR) from wastewater. Batch adsorption tests confirmed its effectiveness in eliminating NOR, along with its excellent resistance to interference from impurity ions or antibiotics. Notably, the maximum experimental NOR adsorption capacity on KBC800 was 666.2 mg/g at 328 K, surpassing those of other biochar materials reported. The spontaneous and endothermic adsorption of NOR on KBC800 could be better suited to the Sips model. Additionally, KBC800 adsorbs NOR mainly by pore filling, with electrostatic attraction, π-π EDA interactions, and hydrogen bonds also contributing significantly. The machine learning model revealed that NOR adsorption on the biochar was significantly affected by the initial concentration, followed by S BET and average pore size. Based on the random forest model, it is demonstrated that biochar is able to adsorb NOR effectively. It is noteworthy that the use of low-cost pharmaceutical wastes to produce adsorbents for emerging contaminants such as antibiotics could have greater potential for future practical applications under the ongoing dual carbon policy.
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Modular polyketide synthases (PKSs) are capable of synthesizing diverse natural products with fascinating bioactivities. Canonical enoyl-CoA hydratases (ECHs) are components of the ß-branching cassette that modifies the polyketide chain by adding a ß-methyl branch. Herein, it is demonstrated that the deletion of an atypical ECHQ domain (featuring a Q280 residue) of Art21, a didomain protein contains an ECHQ domain and a thioesterase (TE) domain, reprograms the polyketide assembly line from synthesizing tetracyclic aurantinins (ARTs) to bicyclic auritriacids (ATAs) with much lower antibacterial activities. Genes encoding the ECHQ-TE didomain proteins distribute in many PKS gene clusters from different bacteria. Significantly, the ART PKS machinery can be directed to make ARTs, ATAs, or both of them by employing appropriate ECHQ-TE proteins, implying a great potential for using this reprogramming strategy in polyketide structure diversification.
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A diverse set of neutral half-sandwich iminoamido iridium and ruthenium organometallic complexes is synthesized through the utilization of Schiff base pro-ligands with NËN donors. Notably, these metal complexes with varying leaving groups (Cl- or OAc-) are formed by employing different quantities of the deprotonating agent NaOAc, and exhibit promising cytotoxicity against various cancer cell lines such as A549 and cisplatin-resistant A549/DDP lung cancer cells, as well as HeLa cells, with IC50 values spanning from 9.26 to 15.98 µM. Cytotoxicity and anticancer selectivity (SI: 1.9-2.4) of these metal complexes remain unaffected by variations in the metal center, leaving group, and ligand substitution. Further investigations reveal that these metal complexes specifically target mitochondria, leading to the depolarization of the mitochondrial membrane and instigating the production of intracellular reactive oxygen species. Furthermore, the metal complexes are found to induce late apoptosis and disrupt the cell cycle, leading to G2/M cell cycle arrest specifically in A549 cancer cells. In light of these findings, it is evident that the primary mechanism contributing to the anticancer effectiveness of these metal complexes is the redox pathway.
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Antineoplásicos , Apoptosis , Cisplatino , Complejos de Coordinación , Resistencia a Antineoplásicos , Iridio , Mitocondrias , Rutenio , Humanos , Iridio/química , Iridio/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Rutenio/química , Rutenio/farmacología , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Mitocondrias/efectos de los fármacos , Mitocondrias/metabolismo , Cisplatino/farmacología , Resistencia a Antineoplásicos/efectos de los fármacos , Células A549 , Células HeLa , Apoptosis/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Potencial de la Membrana Mitocondrial/efectos de los fármacosRESUMEN
Electrochemical impedance spectroscopy (EIS), a conventional and alternating-current-(AC)-based technique for impedance measurement, is commonly used in battery diagnosis. However, it requires expensive equipment and demanding operating conditions and is complex and model-dependent in data analysis. Recently, novel direct current (DC) analytics have emerged as an alternative to EIS. They are simple yet powerful, being capable of revealing impedance information that traditionally could only be obtained through EIS and determining Li-ion diffusion coefficient. Besides, a complete EIS spectrum can be predicted based on constant current charging curves in the support of machine learning methods. This work highlights the similarities and discrepancies between DC techniques and EIS in the electrochemical analysis of Liion batteries. Looking ahead, DC techniques may be a promising substitute for EIS in future battery diagnosis, requiring simplified equipment while offering a deep understanding of battery impedance and its underlying electrochemical processes.
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Formamidinium-lead triiodide (FAPbI3) perovskite holds promise as a prime candidate in the realm of perovskite photovoltaics. However, the photo-active α-FAPbI3 phase, existing as a metastable state, is observable solely at elevated temperatures and is susceptible to degradation into the δ-phase in ambient air. Therefore, the attainment of phase-stable α-FAPbI3 in ambient conditions has become a crucial objective in perovskite research. Here, we proposed an efficient conversion process of PbI2 into the α-FAPbI3 perovskites in ambient air. This conversion was facilitated by the introduction of chelating molecules, which interacted with PbI2 to form an intermediate phase. Due to the reduced formation barrier resulting from the altered reaction pathway, this stable intermediate phase transitioned directly into α-FAPbI3 upon the deposition of the organic cation solution, effectively bypassing the formation of δ-FAPbI3. Consequently, the ambient-fabricated FAPbI3 perovskite solar cells (PSCs) exhibited an outstanding power conversion efficiency of 25.08 %, along with a high open-circuit voltage of 1.19â V. Furthermore, the unencapsulated devices demonstrated remarkable environmental stability. Notably, this innovative approach promises broad applicability across various chelating molecules, opening new avenues for further progress in the ambient air fabrication of FAPbI3 PSCs.
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Fruit ripening is associated with the degreening process (loss of chlorophyll) that occurs in most fruit species. Kiwifruit is one of the special species whose fruits may maintain green flesh by accumulating a large amount of chlorophyll even after ripening. However, little is known about the genetic variations related to the fruit degreening process. Here, a graph-based kiwifruit pangenome by analyzing 14 chromosome-scale haplotype-resolved genome assemblies from seven representative cultivars or lines in Actinidia chinensis is built. A total of 49,770 non-redundant gene families are identified, with core genes constituting 46.6%, and dispensable genes constituting 53.4%. A total of 84,591 non-redundant structural variations (SVs) are identified. The pangenome graph integrating both reference genome sequences and variant information facilitates the identification of SVs related to fruit color. The SV in the promoter of the AcBCM gene determines its high expression in the late developmental stage of fruits, which causes chlorophyll accumulation in the green-flesh fruits by post-translationally regulating AcSGR2, a key enzyme of chlorophyll catabolism. Taken together, a high-quality pangenome is constructed, unraveled numerous genetic variations, and identified a novel SV mediating fruit coloration and fruit quality, providing valuable information for further investigating genome evolution and domestication, QTL genes function, and genomics-assisted breeding.
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Actinidia , Frutas , Genoma de Planta , Actinidia/genética , Actinidia/metabolismo , Frutas/genética , Frutas/metabolismo , Genoma de Planta/genética , Clorofila/metabolismo , Clorofila/genética , Variación Genética/genéticaRESUMEN
One-step carbonization was explored to prepare biochar using the residue of a traditional Chinese herbal medicine, Atropa belladonna L. (ABL), as the raw material. The resulting biochar, known as ABLB4, was evaluated for its potential as a sustainable material for norfloxacin (NOR) adsorption in water. Subsequently, a comprehensive analysis of adsorption isotherms, kinetics, and thermodynamics was conducted through batch adsorption experiments. The maximum calculated NOR adsorption capacity was 252.0 mg/g at 298 K, and the spontaneous and exothermic adsorption of NOR on ABLB4 could be better suited to a pseudo-first-order kinetic model and Langmuir model. The adsorption process observed is influenced by pore diffusion, π-π interaction, electrostatic interaction, and hydrogen bonding between ABLB4 and NOR molecules. Moreover, the utilization of response surface modeling (RSM) facilitated the optimization of the removal efficiency of NOR, yielding a maximum removal rate of 97.4% at a temperature of 304.8 K, an initial concentration of 67.1 mg/L, and a pH of 7.4. Furthermore, the biochar demonstrated favorable economic advantages, with a payback of 852.5 USD/t. More importantly, even after undergoing five cycles, ABLB4 exhibited a consistently high NOR removal rate, indicating its significant potential for application in NOR adsorption.
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Carbón Orgánico , Medicamentos Herbarios Chinos , Norfloxacino , Contaminantes Químicos del Agua , Norfloxacino/química , Carbón Orgánico/química , Adsorción , Medicamentos Herbarios Chinos/química , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/aislamiento & purificación , Cinética , Termodinámica , Purificación del Agua/métodos , Concentración de Iones de HidrógenoRESUMEN
To develop reversible pH-responsive emulsifiers of natural origin, alkali lignin (AL) was used to develop oil-in-water Pickering emulsions. AL was first modified to synthesize quaternized alkali lignin (QAL), which displayed pH-responsive properties and demonstrated solubility in both acidic and alkaline solutions. In contrast, QAL exhibited insolubility and formed particles in neutral solutions, thereby making it a suitable candidate for utilization as an emulsifier in doubly pH-responsive Pickering emulsions. At pH 5-9, the emulsions were stable. Above or below this pH range, the system demulsifies, resulting in a reversible Pickering emulsifier with two pH-controlled transitions. On the basis of this pH-dependent behavior, lignin-based Pickering emulsions (LPE) could be subjected to several cycles of emulsification-demulsification by alternating the pH of the aqueous phase between basic and acidic, while the droplet size and storage stability were maintained. Curcumin was used as a drug model to study the loading/release behavior of LPE, finding that 50.08% of curcumin could be encapsulated in LPE. The in vitro release of curcumin was pH-dependent. In addition, LPE exhibited an outstanding protective effect against the ultraviolet-induced degradation of curcumin.
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Perovskite/organic tandem solar cells (PO-TSCs) demonstrate exceptional suitability for emerging applications such as building-integrated photovoltaics, wearable devices, and greenhouse farming. By leveraging the distinctive attributes of perovskite and organic materials, which encompass expanded solar spectrum utilization, chemically benign solubility, and soft nature, PO-TSCs position themselves as ideal candidates for high-performance semi-transparent photovoltaics (ST-PVs). Despite these advantages, their development significantly lags behind other perovskite-based counterparts, such as perovskite/perovskite, perovskite/silicon, and perovskite/Cu(In, Ga)Se2. To address existing challenges and unlock the full potential of PO-TSCs, an exploration of the fundamental mechanisms governing tandem photovoltaic devices is embarked. Delving into critical aspects such as charge generation/separation, energy level alignment, and material choices becomes pivotal for optimizing PO-TSC performance. The investigation of monolithic two-terminal PO-TSCs offers insights into achievements and barriers, recognizing the competitive landscape with other TSC counterparts. Further scrutiny of perovskite absorbers and organic absorbers in TSCs reveals strategies aimed at enhancing stability and efficiency. The discussion extends to interconnection layers, elucidating their role in optimizing light transmission and balancing carrier recombination. In conclusion, a compelling outlook on the dynamic landscape of PO-TSCs is presented, highlighting the remarkable efficiency progression and signaling their potential to revolutionize solar energy harvesting technologies.
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Needle-type sensor, characterized by its slender, elongated shape, is a promising sensing method due to its rapid response, high sensitivity, and portability. Recently, the needle-type sensor technology has garnered increasing attention, leading to its accelerated development and extensive use in medical and healthcare, environmental monitoring, and geosciences. However, there remains a need for a comprehensive review of existing research. Here, we utilize scientometric analysis, which is booming recently, to conduct a comprehensive investigation of the needle-type sensor field. This analysis covers various aspects, including annual trends, journals, institutions, countries, disciplines, authors, references, and keywords of 136,667 publications from the Web of Science Core Collection (WoSCC) database spanning from January 1, 2004, to January 1, 2024. Additionally, we identify current hotspots, frontiers, and predict future trends. Eventually, three research hotspots are refined: multidisciplinary materials science, sensor miniaturization and integration, and biomedical engineering, indicating that further investigations may focus on creating biocompatible materials to enhance sensing properties, optimizing sensor structure through miniaturization and integration methods, and improving clinical applications in biomedical engineering. This work may facilitate the development of needle-type sensors.
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This study employed hydrothermal carbonization (HTC) in conjunction with ZnCl2 activation and pyrolysis to produce biochar from one traditional Chinese medicine astragali radix (AR) residue. The resultant biochar was evaluated as a sustainable adsorbent for tetracycline (TC) elimination from water. The adsorption performance of TC on two micropore-rich AR biochars, AR@ZnCl2 (1370 m2 g-1) and HAR@ZnCl2 (1896 m2 g-1), was comprehensively evaluated using adsorption isotherms, kinetics, and thermodynamics. By virtue of pore diffusion, π-π interaction, electrostatic attraction, and hydrogen bonding, the prepared AR biochar showed exceptional adsorption properties for TC. Notably, the maximum adsorption capacity (930.3 mg g-1) of TC on HAR@ZnCl2 can be achieved when the adsorbent dosage is 0.5 g L-1 and C0 is 500 mg L-1 at 323 K. The TC adsorption on HAR@ZnCl2 took place spontaneously. Furthermore, the impact of competitive ions behavior is insignificant when coexisting ion concentrations fall within the 10-100 mg L-1 range. Additionally, the produced biochar illustrated good economic benefits, with a payback of 701 $ t-1. More importantly, even after ten cycles, HAR@ZnCl2 still presented great TC removal efficiency (above 77%), suggesting a good application prosperity. In summary, the effectiveness and sustainability of AR biochar, a biowaste-derived product, were demonstrated in its ability to remove antibiotics from water, showing great potential in wastewater treatment application.
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Carbón Orgánico , Medicamentos Herbarios Chinos , Tetraciclina , Contaminantes Químicos del Agua , Adsorción , Carbón Orgánico/química , Tetraciclina/química , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Medicamentos Herbarios Chinos/química , Antibacterianos/química , Purificación del Agua/métodos , Cinética , Cloruros , Compuestos de ZincRESUMEN
Lithium-ion batteries (LIBs) have become the most popular portable secondary energy storage facilities. However, the limited lithium resource results in possible unsustainable development. Potassium-ion batteries (PIBs) are considered promising alternatives to LIBs because of their high resource availability, low cost, and environmentally friendly features. In this field, high energy density layered cathodes and carbon-based anodes are also the main research objectives. However, compared to the most appealing alternative sodium-ion batteries (SIBs), despite having various theoretical advantages, PIBs exhibit poorer electrochemical performance in practice. Their poor capacity retention and narrow working voltage range seriously limit their applications. The performance of the electrodes is usually considered an important factor for battery performance, life, and safety. To solve these problems, many significant research studies have been carried out in the last decade, achieving numerous breakthroughs. Nevertheless, there are still many drawbacks and unclear mechanisms. In this comprehensive review, we examine the current state of high-performance layered oxide cathodes, electrolytes, and carbon-based anodes, to identify potential candidates for PIBs. Our focus lies on their structural characteristics, interface properties, underlying mechanisms, and modification techniques. The viewpoints of these advanced strategies are integrated, and concise development suggestions and strategies are subsequently proposed.
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The transformation and gene editing of the woody species kiwifruit are difficult and time-consuming. The fast and marker-free genetic modification system for kiwifruit has not been developed yet. Here, we establish a rapid and efficient marker-free transformation and gene editing system mediated by Agrobacterium rhizogenes for kiwifruit. Moreover, a removing-root-tip method was developed to significantly increase the regeneration efficiency of transgenic hairy roots. Through A. rhizogenes-mediated CRISPR/Cas9 gene editing, the editing efficiencies of CEN4 and AeCBL3 achieved 55 and 50%, respectively. And several homozygous knockout lines for both genes were obtained. Our method has been successfully applied in the transformation of two different species of kiwifruit (Actinidia chinensis 'Hongyang' and A.eriantha 'White'). Next, we used the method to study the formation of calcium oxalate (CaOx) crystals in kiwifruit. To date, little is known about how CaOx crystal is formed in plants. Our results indicated that AeCBL3 overexpression enhanced CaOx crystal formation, but its knockout via CRISPR/Cas9 significantly impaired crystal formation in kiwifruit. Together, we developed a fast maker-free transformation and highly efficient CRISPR-Cas9 gene editing system for kiwifruit. Moreover, our work revealed a novel gene mediating CaOx crystal formation and provided a clue to elaborate the underlying mechanisms.
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Most platinum group-based cyclometalated neutral and cationic anticancer complexes with the general formula [(C^N)2Ir(XY)]0/+ (neutral complex: XY = bidentate anionic ligand; cationic complex: XY = bidentate neutral ligand) are notable owing to their intrinsic luminescence properties, good cell permeability, interaction with some biomolecular targets and unique mechanisms of action (MoAs). We herein synthesized a series of neutral and cationic amine-imine cyclometalated iridium(III) complexes using Schiff base ligands with sp2-N/sp3-N N^NH2 chelating donors. The cyclometalated iridium(III) complexes were identified by various techniques. They were stable in aqueous media, displayed moderate fluorescence and exhibited affinity toward bovine serum albumin (BSA). The complexes demonstrated promising cytotoxicity against lung cancer A549 cells, cisplatin-resistant lung cancer A549/DDP cells, cervical carcinoma HeLa cells and human liver carcinoma HepG2 cells, with IC50 values ranging from 9.98 to 19.63 µM. Unfortunately, these complexes had a low selectivity (selectivity index: 1.62-1.98) towards A549 cells and BEAS-2B normal cells. The charge pattern of the metal center (neutral or cationic) and ligand substituents showed little influence on the cytotoxicity and selectivity of these complexes. The study revealed that these complexes could target mitochondria, cause depolarization of the mitochondrial membrane, and trigger the production of intracellular ROS. Additionally, the complexes were observed to induce late apoptosis and perturb the cell cycle in the G2/M or S phase in A549 cells. Based on these results, it appears that the anticancer efficacy of these complexes was predominantly attributed to the redox mechanism.
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Antineoplásicos , Carcinoma , Complejos de Coordinación , Neoplasias Pulmonares , Humanos , Antineoplásicos/farmacología , Antineoplásicos/metabolismo , Células HeLa , Iridio/farmacología , Complejos de Coordinación/farmacología , Complejos de Coordinación/metabolismo , Ligandos , Quelantes/farmacología , Mitocondrias/metabolismo , Neoplasias Pulmonares/metabolismo , Carcinoma/metabolismo , Apoptosis , Línea Celular TumoralRESUMEN
The synthesis and biological evaluation of stable 16-electron half-sandwich complexes have remained scarce. We herein present the different coordination modes (16-electron or 18-electron) between half-sandwich iridium(III) complexes and ruthenium(II) complexes derived from the same amine-imine ligands chelating hybrid sp3-N/sp2-N donors. The 16-electron iridium(III) and 18-electron ruthenium(II) complexes with different counteranions were obtained and identified by various techniques. The promising cytotoxicity of these complexes against A549 lung cancer cells, cisplatin-resistant A549/DPP cells, cervical carcinoma HeLa cells, and human hepatocellular liver carcinoma HepG2 cells was observed with IC50 values ranging from 5.4 to 16.3 µM. Moreover, these complexes showed a certain selectivity (selectivity index: 2.1-3.7) toward A549 cells and BEAS-2B normal cells. The variation of metal center, counteranion, 16/18-electron coordination mode, and ligand substituents showed little influence on the cytotoxicity and selectivity of these complexes. The mechanism of action study showed that these complexes could target mitochondria, induce the depolarization of the mitochondrial membrane, and promote the generation of intracellular reactive oxygen species (ROS). Further, the induction of cell apoptosis and the perturbation of the cell cycle in the G0/G1 phase were also observed for these complexes. Overall, it seems that the redox mechanism dominated the anticancer efficacy of these complexes.
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Antineoplásicos , Carcinoma , Complejos de Coordinación , Rutenio , Humanos , Antineoplásicos/farmacología , Células HeLa , Iminas , Iridio/farmacología , Rutenio/farmacología , Complejos de Coordinación/farmacología , Aminas/farmacología , Ligandos , Electrones , Apoptosis , Línea Celular Tumoral , Especies Reactivas de Oxígeno/metabolismoRESUMEN
Glycosylation is one of the most common post-translational modifications of proteins across all kingdoms of life. Diverse monosaccharides and polysaccharides can be attached to a range of amino acid residues generating N-glycosylation, O-glycosylation, C-glycosylation, S-glycosylation, as well as P-glycosylation. The functions of the eukaryotic glycosylation system during protein folding in the endoplasmic reticulum (ER) and Golgi are well-studied. Increasing evidence in the recent decade has demonstrated the presence of oligosaccharyltransferases (OSTs) in bacteria and archaea. In particular, the oligosaccharyltransferase (PglB) of Campylobacter jejuni and oligosaccharyltransferase (PglL) enzyme of Neisseria meningitidis are the most characterized OSTs that catalyze bacterial N-linked glycosylation and O-linked glycosylation, respectively. Glycoprotein administered as glycoconjugate vaccines have been shown to be effective prophylactic to protect against numerous pathogenic bacteria. The chemical synthesis of glycoproteins is complex and expensive, which limits its application to the development of glycoconjugate vaccines. However, studies have demonstrated that the biosynthesis of glycoproteins is realizable by transferring PglB, a plasmid encoding a substrate protein, or PglL, a plasmid encoding genes for glycan synthesis to Escherichia coli. This strategy can be applied to the development of glycoconjugate vaccines using engineered host E. coli. This review summarizes the structure and mechanism of action of the bacterial OSTs, PglB and PglL, and discusses their potential application to glycoconjugate vaccine design.
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Escherichia coli , Vacunas , Escherichia coli/genética , Proteínas Bacterianas/metabolismo , Glicoconjugados/metabolismo , Glicoproteínas/metabolismo , Bacterias/metabolismoRESUMEN
Clathrin-mediated vesicular formation and trafficking are responsible for molecular cargo transport and signal transduction among organelles. Our previous study shows that CHLOROPLAST VESICULATION (CV)-containing vesicles (CVVs) are generated from chloroplasts for chloroplast degradation under abiotic stress. Here, we show that CV interacts with the clathrin heavy chain (CHC) and induces vesicle budding toward the cytosol from the chloroplast inner envelope membrane. In the defective mutants of CHC2 and the dynamin-encoding DRP1A, CVV budding and releasing from chloroplast are impeded. The mutations of CHC2 inhibit CV-induced chloroplast degradation and hypersensitivity to water stress. Moreover, CV-CHC2 interaction is impaired by the oxidized GLYCERALDEHYDE-3-PHOSPHATE DEHYDROGENASE (GAPC). GAPC1 overexpression suppresses CV-mediated chloroplast degradation and hypersensitivity to water stress, while CV silencing alleviates the hypersensitivity of the gapc1gapc2 plant to water stress. Together, our work identifies a pathway of clathrin-assisted CVV budding outward from chloroplast, which is involved in chloroplast degradation and stress response.
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Proteínas de Arabidopsis , Arabidopsis , Humanos , Proteínas de Arabidopsis/genética , Proteínas de Arabidopsis/metabolismo , Arabidopsis/metabolismo , Deshidratación/metabolismo , Cloroplastos/metabolismo , Clatrina/metabolismo , Endocitosis/fisiologíaRESUMEN
The biological efficacy of half-sandwich platinum group organometallic complexes of the formula [(η5-Cpx)/(η6-arene)M(XY)Cl]0/+ (XY = bidentate ligands; Cpx = functionalized cyclopentadienyl; M = Ir, Rh, Ru, Os) has received considerable attention due to the significance of the metal center, chelating ligand, and Cpx/arene moieties in defining their anticancer potency and selectivity. With a facile access to the BIAN-derived imine-amine ligands using alkylaluminum as the reductant, we herein described the preparation and characterization of 16 half-sandwich Ir(III), Rh(III), and Ru(II) complexes chelating the hybrid sp2-N/sp3-N donor ligand. A nonplanar five-member metallacycle was confirmed by X-ray single-crystal structures of Ir1-Ir3, Ir7, Rh1, Ru1, and Ru4. The attempt to prepare imine-amido complexes using a base as the deprotonating agent led to the mixture of imine-amine complexes, within which the leaving group Cl- was displaced, and 16-electron imine-amido complexes without Cl-. The half-sandwich imine-amine complexes in this system underwent rapid hydrolysis in aqueous solution, exhibited weak photoluminescence, and showed the ability of binding to CT-DNA and BSA. The cytotoxicity of all imine-amine complexes against A549 lung cancer cell lines, HeLa cervical cancer cell lines, and 4T1 mouse breast cancer cells was determined by an MTT assay. The IC50 values of these complexes were in a range of 5.71-67.28 µM. Notably, most of these complexes displayed improved selectivity toward A549 cancer cells versus noncancerous BEAS-2B cells in comparison with the corresponding α-diimine complexes chelating the sp2-N/sp2-N donor ligand, which have been shown no selectivity in our previous report. The anticancer selectivity of these complexes appeared to be related to the redox-based mechanism including the catalytic oxidation of NADH to NAD+, reactive oxygen species (ROS) generation, and depolarization of the mitochondrial membrane. Further, inducing apoptosis of these complexes in A549 cancer cells and BEAS-2B normal cells also correlated with their anticancer selectivity, indicating the apoptosis mode of cell death in this system. In addition, these complexes could enter A549 cells via energy-dependent pathway and were able to impede the in vitro migration of A549 cells.
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Rodio , Rutenio , Animales , Ratones , Humanos , Rodio/farmacología , Rutenio/farmacología , Iridio/farmacología , Ligandos , Aminas , Células HeLaRESUMEN
Despite the remarkable progress made in perovskite solar cells, great concerns regarding potential Pb contamination risk and environmental vulnerability risks associated with perovskite solar cells pose a significant obstacle to their real-world commercialization. In this study, we took inspiration from the ensnaring prey behavior of spiders and chemical components in spider web to strategically implant a multifunctional mesoporous amino-grafted-carbon net into perovskite solar cells, creating a biomimetic cage traps that could effectively mitigate Pb leakage and shield the external invasion under extreme weather conditions. The synergistic Pb capturing mechanism in terms of chemical chelation and physical adsorption is in-depth explored. Additionally, the Pb contamination assessment of end-of-life perovskite solar cells in the real-world ecosystem, including Yellow River water and soil, is proposed. The sustainable closed-loop Pb management process is also successfully established involving four critical steps: Pb precipitation, Pb adsorption, Pb desorption, and Pb recycling. Our findings provide inspiring insights for promoting green and sustainable industrialization of perovskite solar cells.