RESUMEN
A new macrocyclic arene, dibenzofuran[3]arene, was synthesized, which could be conveniently transformed to an O-doped aromatic belt with a rigid ring-shaped structure and deep cavity. Moreover, the O-doped aromatic belt also showed a high HOMO energy and a narrow HOMO-LUMO gap experimentally and theoretically.
RESUMEN
A calix[3]carbazole-based cavitand was conveniently synthesized. It was found that the cavitand with adjustable conformation could show excellent complexation with fullerenes C60 and C70 in both solution and the solid state. Moreover, the crystal structures of the host-guest complexes show that the cavitand can stack into channel-like architectures, in which fullerenes are orderly arranged inside.
RESUMEN
Modular synthesis of novel biphen[n]arenes (n = 2-4) with customizable heterocycle blocks, functional skeletons, binding sites, and topological structures could be facilely achieved through the rational design and replacement of reaction modules (furan and thiophene), functional modules (substituted benzene, biphenyl, and naphthalene), and linking modules (methylene). These biphen[n]arenes were characterized by NMR, HRMS, and X-ray crystalline diffraction, complemented by DFT calculations. Their photophysical properties were thoroughly studied.
RESUMEN
A pair of inherently chiral belt-shaped conjugated macrocycles were conveniently synthesized starting from 2,7-fluoren[3]arene triflate, and they not only exhibited green fluorescence, but also showed circularly polarized luminescence with a |glum| of 2.0 × 10-3.
RESUMEN
Triple-stranded metallo-supramolecular helicates were readily constructed by achieving a coordination of the gallium(iii) cation by ligands based on 2,7- and 2,6-disubstituted triptycenes. The significance of these building blocks in the construction of helicates with the capability for guest encapsulation was also revealed.
RESUMEN
Chiral pseudo[1]rotaxanes and [1]rotaxanes constructed from macrocyclic arenes still remain a big challenge mainly owing to the lack of such chiral macrocycles. In this work, a new system of chiral pseudo[1]rotaxanes formed by self-inclusion of helic[6]arene containing amide linked with the terminal tertiary amines was first discovered. Based on an atom-economic stopping strategy, a pair of chiral [1]rotaxanes were conveniently obtained in almost quantitative yields by blocking the pseudo[1]rotaxanes with monobenzyl bromide of tetraphenylethene. The structures of pseudo[1]rotaxanes and [1]rotaxanes were characterized by 2D NMR spectra in solution, combined with DFT calculations. The photophysical properties further revealed the efficient chirality transfer of helic[6]arene to the tetraphenylethene moiety, compared to their unthreaded chiral isomers. The discovery of the chiral pseudo[1]rotaxanes allows for a wide and available synthesis of chiral [1]rotaxanes, and also opening a new avenue to the design of chiral supramolecular materials.
RESUMEN
The design and synthesis of nitrogen-doped aromatic belts with conjugated structures still remain a challenge. Here, we report the first nitrogen-doped aromatic belt with a [6]cycloparaphenylene skeleton, which is conveniently synthesized from the easily available calix[3]carbazole. The aromatic belt has a rigid conjugated structure and deep cavity, and it can encapsulate one dichloromethane both in solution and in the solid state. Interestingly, the aromatic belt shows strong green fluorescence with a quantum yield of 0.39 and exhibits a narrow HOMO-LUMO energy gap of 2.02â eV. The belt-shaped conjugated structure composed of three carbazole subunits has specific optoelectronic properties that will promote wide applications in supramolecular chemistry and materials science.
RESUMEN
An approach to the highly efficient synthesis of C(sp3)-bridged [6]cycloparaphenylenes (C[6]CPPs) from fluoren[3]arenes (F[3]As) was developed. Consequently, F[3]As as a new kind of macrocyclic arenes were synthesized. Followed by the demethylation, triflation and intramolecular aryl-aryl coupling reactions, C[6]CPPs were then conveniently obtained. Interestingly, C[6]CPPs could be selectively methylated to produce their fully outer-methyl-substituted derivatives. The crystal structures showed the hydroxyl-substituted F[3]As had bowl-shaped conformations, and the C[6]CPPs exhibited rigid belt-shaped structures with deep cavities. Moreover, C[6]CPPs exhibited high HOMO energies and narrow energy gaps. An unclosed belt was further obtained, and it not only showed a similar narrow energy gap to those of the aromatic belts, but also displayed strong fluorescence property, which can play a vital role in the design and synthesis of new aromatic belts.
RESUMEN
We report a new mono-armed pillar[5]arene with the amino-substituent self-included in the pillarene cavity, which can stabilize the hemiaminals and imines formed from the reaction of aliphatic amines and aldehydes as monitored by mass spectroscopy.
RESUMEN
Superinfection of Marek's disease virus (MDV) and avian leukosis virus subgroup J (ALV-J) causes lethal neoplasia and death in chickens. However, whether there is synergism between the two viruses in viral replication and pathogenicity has remained elusive. In this study, we found that the superinfection of MDV and ALV-J increased the viral replication of the two viruses in RNA and protein level, and synergistically promoted the expression of IL-10, IL-6, and TGF-ß in chicken embryo fibroblasts (CEF). Moreover, MDV and ALV-J protein expression in dual-infected cells detected by confocal laser scanning microscope appeared earlier in the cytoplasm and the nucleus, and caused more severe cytopathy than single infection, suggesting that synergistically increased MDV and ALV-J viral-protein biosynthesis is responsible for the severe cytopathy. In vivo, compared to the single virus infected chickens, the mortality and tumor formation rates increased significantly in MDV and ALV-J dual-infected chickens. Viral loads of MDV and ALV-J in tissues of dual-infected chickens were significantly higher than those of single-infected chickens. Histopathology observation showed that more severe inflammation and tumor cells metastases were present in dual-infected chickens. In the present study, we concluded that synergistic viral replication of MDV and ALV-J is responsible for the enhanced pathogenicity in superinfection of chickens.
Asunto(s)
Virus de la Leucosis Aviar/patogenicidad , Mardivirus/patogenicidad , Sobreinfección/virología , Animales , Leucosis Aviar/virología , Virus de la Leucosis Aviar/fisiología , Pollos/virología , Mediadores de Inflamación/metabolismo , Mardivirus/fisiología , Enfermedad de Marek/virología , Carga Viral , Virulencia , Replicación ViralRESUMEN
We report a quantitative synthetic strategy of a [1]rotaxane from a representative pseudo[1]rotaxane. The structure of the [1]rotaxane was characterized by 1H NMR, 13C NMR, 2D NMR, mass spectroscopy, and melting point, and its optimized geometry in CHCl3 by theoretical calculation at the B3LYP/6-31G(D) level using the PCM model matched well with 2D NOESY. This [1]rotaxane proves to be a good catalyst for the Knoevenagel reaction in CHCl3, which follows second order kinetics.
RESUMEN
Lung cancer is the leading cause of cancer death in the world. Safflower polysaccharide (SPS) has been used for the improvement of immunomodulatory activities and treatment of cancers. However, studies on the effect of SPS on the progression of lung cancer have rarely been reported. To study the antitumor effect of SPS on human lung cancer and its potential mechanism, non-small cell lung cancer cell lines (NSCLC), A549 and YTMLC-90 were treated with SPS at various concentrations ranging from 0.04 to 2.56 mg/ml and BALB/c nude tumor-bearing mice were injected intraperitoneally with SPS at concentrations ranging from 15 to 135 mg/kg. Results showed that SPS suppressed the proliferation of A549 and YTMLC-90 cells and induced apoptosis by increasing mRNA levels of bax and caspase-3, and inhibited tumor growth in vivo. SPS induced cell cycle arrest in the G2/M phase by decreasing the expression of cdc25B and cyclin B1. Moreover, SPS decreased the expression of Akt, p-Akt and PI3K. In mice, SPS injection enhanced immunomodulatory activities by increasing levels of TNF-α and IL-6 in tumor-bearing mice. Our findings suggest that SPS suppresses tumor growth by enhancing immunomodulatory activities and blocking the PI3K/Akt pathway. This study provides new insight into the anticancer mechanism of SPS.