Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications.

Radicals based on arylamine cyclophanes can be used as functional materials and show application potential in fields such as synthetic chemistry, molecular electronic components, organic light-emitting diodes, and catalytic chemistry. Using a Buchwald-Hartwig palladium-catalyzed aryl halide amination method, we synthesized a series of neutral hexaazacyclophane compounds 1-3 with different substituents in the meta-meta-meta positions of the phenyl rings. Three characteristic high-spin hexaazacyclophane diradical dications were obtained by two-electron oxidation using AgSbF6: 12·+•2[SbF6]-, 22·+•2[SbF6]-, and 32·+•2[SbF6]-. The electronic structures and physical properties of these compounds were then investigated by 1H and 13C nuclear magnetic resonance spectroscopy, cyclic voltammetry, electron paramagnetic resonance spectroscopy, superconducting quantum interferometry, ultraviolet-visible spectroscopy, and density functional theory calculations. The findings provide new ideas for designing radical species with novel physical properties and electronic structures. Importantly, the obtained radical species are not sensitive to air, making them valuable functional materials for practical applications.

Evaluation of Antioxidant Activity and Drug Delivery Potential of Cell-Derived Extracellular Vesicles from Citrus reticulata Blanco cv. 'Dahongpao'.

Plant extracellular vesicles (PEVs) have attracted increasing attention due to their rich composition, good antioxidant and anti-inflammatory activity, and ability to transport drugs. As a common fruit, citrus is an ideal material for extracting PEVs because of the diversity and abundance of bioactive substances in it. In our study, citrus-derived extracellular vesicles (CEVs) were extracted from red mandarin (Citrus reticulata Blanco cv. 'Dahongpao') and it was found that they contain high levels of lipids, proteins, and carbohydrates. The high levels of total phenols and total flavonoids suggest that CEVs have good chemical antioxidant properties. We also demonstrated through cell experiments that CEVs have significant antioxidant and anti-inflammatory effects. Furthermore, we found that CEVs have an encapsulation rate of 71.5 ± 0.19% and a high drug-carrying capacity of 4.96 ± 0.22% and can enhance antioxidant and anti-inflammatory activity when loaded with tangeretin. Our results show that CEVs contain abundant bioactive components, have low toxicity, exhibit good antioxidant and anti-inflammatory properties, and can serve as drug delivery agents. This study has important implications for utilizing citrus materials and developing natural anti-oxidative and anti-inflammatory biomaterials.

Comparative Analysis of the Impact of Three Drying Methods on the Properties of Citrus reticulata Blanco cv. Dahongpao Powder and Solid Drinks.

Citrus reticulata Blanco cv. Dahongpao is a traditional Chinese citrus variety. Due to the high investment in storage and transport of Citrus reticulata Blanco cv. Dahongpao and the lack of market demand, the fresh fruit is wasted. The processing of fresh fruit into fruit drinks can solve the problem of storage and transport difficulties and open up new markets. Investigating the effects of different drying processes (hot air, freeze, and spray drying) on fruit powders is a crucial step in identifying a suitable production process. The experiment measured the effects of different drying methods (hot air drying, freeze drying, and spray drying) on the nutrient, bioactive substance, and physical characteristics of fruit powder. This study measured the influence of three different drying methods (hot air, freeze, and spray drying) on the nutritional, bioactive substance, and physical characteristics of fruit powder. The results showed that compared to vacuum freeze-drying at low temperature (-60 °C) and spray-drying at high temperatures (150 °C), hot air drying at 50 °C produced fruit powder with superior nutritional quality, higher levels of active substances, and better physical properties. Hot air drying produced fruit powder that had the highest content of amino acids (11.48 ± 0.08 mg/g DW), vitamin C (112.09 ± 2.86 µg/g DW), total phenols (14.78 ± 0.30 mg/g GAE DW), total flavonoids (6.45 ± 0.11 mg/g RE DW), organic acids, and antioxidant activity capacity. Additionally, this method yielded the highest amounts of zinc (8.88 ± 0.03 mg/Kg DW) and soluble sugars, low water content, high solubility, and brown coloration of the fruit powder and juice. Therefore, hot air drying is one of the best production methods for producing high-quality fruit powder in factory production.

The OsSGS3-tasiRNA-OsARF3 module orchestrates abiotic-biotic stress response trade-off in rice.

Recurrent heat stress and pathogen invasion seriously threaten crop production, and abiotic stress often antagonizes biotic stress response against pathogens. However, the molecular mechanisms of trade-offs between thermotolerance and defense remain obscure. Here, we identify a rice thermo-sensitive mutant that displays a defect in floret development under high temperature with a mutation in SUPPRESSOR OF GENE SILENCING 3a (OsSGS3a). OsSGS3a interacts with its homolog OsSGS3b and modulates the biogenesis of trans-acting small interfering RNA (tasiRNA) targeting AUXIN RESPONSE FACTORS (ARFs). We find that OsSGS3a/b positively, while OsARF3a/b and OsARF3la/lb negatively modulate thermotolerance. Moreover, OsSGS3a negatively, while OsARF3a/b and OsARF3la/lb positively regulate disease resistance to the bacterial pathogen Xanthomonas oryzae pv. oryzae (Xoo) and the fungal pathogen Magnaporthe oryzae (M. oryzae). Taken together, our study uncovers a previously unknown trade-off mechanism that regulates distinct immunity and thermotolerance through the OsSGS3-tasiRNA-OsARF3 module, highlighting the regulation of abiotic-biotic stress response trade-off in plants.

S = 1/2 tetracene monoradical cation/anion: ion-based one-dimensional antiferromagnetic chains.

The monoradical cation 1˙+ and anion 1˙- based on tetracene were generated by one-electron oxidation and one-electron reduction of the bulky tetracene (1), respectively, which contain the largest π-fused skeletons reported to date. For monoradical species, 1˙+ and 1˙-, EPR spectra and DFT calculation results indicate the spin density delocalized over the whole molecules. Notably, in the solid state, 1˙+ and 1˙-, respectively, pack into (1˙+)n and (1˙--K-crown)n, characterized by single-crystal X-ray diffraction studies. The intermolecular interactions of 1˙+ and 1˙- are, respectively, through van der Waals forces and exchange couplings supported by metal ions. The monoradical cation polymer (1˙+)n was the first example based on PAHs. The EPR spectra at 90 K of 1˙+ and 1˙- all show forbidden transitions (Δms = ±2), indicating the existence of electronic coupling between the neighboring radicals, with respective 2J = -6.54 K and 2J = -0.22 K characterized by SQUID measurements.

A novel method for noninvasive diagnosis of monogenic diseases from circulating fetal cells.

OBJECTIVE: To establish a method for noninvasive fetal cell isolation from maternal blood and prenatal testing of monogenic diseases by a combination of direct sequencing and targeted NGS-based SNP haplotyping from single fetal cells. METHOD: Peripheral blood of pregnant women in two families (congenital deafness and ichthyosis) was collected. After density-based separation and immunostaining with multiple biomarkers, candidate fetal cells were identified by high-throughput imagine analysis and picked up by automation. Individual fetal cells were subjected to STR-genotyping to identify their origin. Pathogenic mutations were identified by direct Sanger sequencing, and a combination of targeted NGS and SNP haplotyping using a custom panel. All the results were compared with amniotic fluid DNA. RESULTS: Fetal trophoblasts were successfully harvested from maternal blood. STR-genotyping confirmed the fetal origin. Direct sequencing of pathogenic genetic mutations in fetal cells showed consistent results with amniotic fluid samples. For congenital deafness family, NGS-based SNP haplotyping also correctly identified the fetal haplotype. This single cell haplotyping method can be used to diagnose various genetic diseases. CONCLUSION: We have established a method for noninvasive prenatal testing of monogenic diseases from circulating trophoblast cells. This cell-based NIPT can be further applied to the prenatal diagnosis of various monogenic diseases.