Enantiomer Recognition Based on Chirality Transfer from Chiral Amines to Ternary Dynamic Covalent Systems.

Enantiomer recognition is usually required in organic synthesis and materials and life sciences. This paper describes an enantiomer recognition method based on ternary dynamic covalent systems constructed via the complexation of chiral amines with a chiral boronate derived from 1,4-phenylenediboric acid and an L-DOPA-modified naphthalenediimide. The ternary systems aggregate into chiral assemblies driven by π-π interactions, and the chirality is transferred from the chiral amines to assemblies with high stereospecificity. Consequently, the enantiomer composition of chiral amines and the absolute configuration of the major enantiomer can be determined according to the sign of the Cotton effect of the ternary system by using circular dichroism (CD) spectroscopy. This method offers the advantage of using the long wavelength CD signals of the boronate at around 520 nm, thereby avoiding interference with those of the carbon skeleton. This ternary system provides a novel approach to the design of enantiomer recognition systems.

Chiral Naphthalenediimides with High-Efficiency Fluorescence and Circularly Polarized Luminescence in the Solid State for the Application in Organic Optoelectronics.

Naphthalenediimides (NDIs) have been extensively studied due to their tunable luminescent properties. However, generally, the monomers or aggregates of non-core substituted NDIs exhibit low fluorescence quantum yields (ΦFL <10 %) in the solid state, which limit their applications as light-emitting materials and render their chiral species unsuitable for circularly polarized luminescence (CPL). Herein, a series of non-core substituted chiral NDIs that exhibit high luminous efficiencies (ΦFL up to 56.8 % for racemate and 36.5 % for enantiomer) and a strong CPL behavior in the solid state is reported. These significant improvements are attributed to the unique molecular conformation of the chiral NDIs and the formation of distinctive discrete dimers. The structures of the NDIs were significantly simpler and more accessible than those of other NDIs. The findings evidence that non-core substituted NDIs can exhibit strong fluorescence in the solid state and provide a new pathway to improve photophysical properties of NDIs.

Preliminary study of hemodynamics of iliac venous compression syndrome using magnetic resonance imaging.

OBJECTIVE: In clinical practice, the degree of iliac vein stenosis has often been inconsistent with the symptoms of chronic venous disease (CVD). To the best of our knowledge, no clinical studies have evaluated the hemodynamic changes associated with iliac vein stenosis. Magnetic resonance imaging (MRI) can noninvasively provide hemodynamic information. In the present study, we assessed the degree of stenosis associated with iliac venous compression syndrome and the relationships between iliac venous compression syndrome-induced, MRI-determined hemodynamic changes and lower limb symptoms. METHODS: Stenosis severity, the presence of collateral vessels, and flow rate (FR) differences between the common and external iliac veins secondary to iliac vein stenosis were measured using MRI in 69 patients with CVD. Villalta scores were used as a measure of symptom severity for all patients, and the percentage of change in the Villalta score was used as a measure of symptom improvement for the patients who had received iliac vein stents. Symptom severity for all patients, a subgroup of patients with iliac vein compression (affected limbs), and a group of patients with unilateral iliac vein compression treated with stents was correlated with stenosis, differences in the external and common iliac vein FRs (<0-mL/s group, indicating stenosis-induced decreased common iliac vein flow, and ≥0-mL/s group), and stenosis-induced collateral vessel formation. RESULTS: Iliac vein stenosis severity and FR differences in all affected limbs were correlated with the Villalta scores of the affected limbs (stenosis: r = 0.38, P < .001, n = 95; FR difference: r = -0.44, P < .001). In the unilateral compression subgroup, stenosis severity, FR differences, and the presence of collateral vessels were not associated with significant changes in contralateral symptoms. In the endovascular treatment subgroup, both lower limbs exhibited significant improvement after stent implantation (affected limb symptom remission, 64.6% ± 18.2%, n = 15; contralateral limb symptom remission, 49.1% ± 29.1%, n = 11). The rate of symptom remission was greater for patients with decreased iliac vein flow in the affected limbs (<0-mL/s group: 74.6% ± 16.4%, n = 7; ≥0-mL/s group: 52.2% ± 16.6%, n = 6; P = .032). CONCLUSIONS: Iliac vein stenosis, the presence of collateral vessels, and decreased FRs due to stenosis correlated significantly with lower limb symptom severity. Endovascular treatment yielded good outcomes in patients with stenosis >50%. A decreased iliac venous FR could indicate a better response to stent implantation and could be used in the diagnosis and guiding decisions to treat iliac venous compression.

Antibody Mimics as Bio-orthogonal Catalysts for Highly Selective Bacterial Recognition and Antimicrobial Therapy.

Bacterial infectious diseases seriously threaten public health and life. The specific interaction between an antibody and its multivalent antigen is an attractive way to defeat infectious disease. However, due to the high expense and strict storage and applied conditions for antibodies, it is highly desirable but remains an urgent challenge for disease diagnosis and treatment to construct artificial antibodies with strong stability and binding ability and excellent selectivity. Herein, we designed and synthesized antibody-like bio-orthogonal catalysts with the ability to recognize specific bacteria and accomplish in situ drug synthesis in captured bacteria by using improved bacterial imprinting technology. On one hand, the artificial antibody possesses a matching morphology for binding pathogens, and on the other hand, it acts as a bio-orthogonal catalyst for in situ synthesis of antibacterial drugs in live bacteria. Both in vitro and in vivo experiments have demonstrated that our designed antibody can distinguish and selectively bind to specific pathogens and eliminate them on site with the activated drugs. Therefore, our work provides a strategy for designing artificial antibodies with bio-orthogonal catalytic activity and may broaden the application of bio-orthogonal chemistry.

A naphthyridine-indole ligand for selective stabilization of G-quadruplexes and conformational conversion of hybrid topology.

The development of ligands to stabilize G-quadruplexes (G4s) or induce G4s to transition from metastable topology to stable topology is a potential strategy for inhibiting cancer cell proliferation. In this study, a novel G-quadruplex (G4) ligand based on a naphthyridine scaffold with two indole pendants, L5-DA, is reported to convert hybrid to the parallel topology. Circular dichroism (CD) and fluorescence spectroscopies were used to investigate the interactions between L5-DA and G4s. The CD spectra revealed that the L5-DA induced the conformational conversion from hybrid topologies to parallel topologies with a melting temperature increase of more than 30 °C. According to Förster resonance energy transfer assays, the presence of excess duplex competitor had no effect on the ligand-induced stabilization of the hybrid topology, confirming the L5-DA's selectivity for G4s over ds26. With IC50 values of 4.3 µM, the ligand showed significant cytotoxicity against HeLa cells and effectively induced growth inhibition and apoptosis in HeLa cells. Immunofluorescence microscopy revealed an increase in BG4 foci in the presence of the L5-DA, confirming ligand-induced G4s stabilization in HeLa cells. According to these results, the combination of naphthyridine and indole scaffold was an effective design strategy for G4s stabilization and conformational conversion of metastable G4 topology for inhibiting cancer cell growth.

Hydrogen-bond-driven dimers of naphthyridine derivatives for selective identification of DNA G-quadruplexes.

G-quadruplex (GQ) ligands as potential anti-cancer drugs have received extensive attention. Large aromatic systems are usually considered in the design of the ligands to improve the binding with GQs, which are typically constructed by the combination of small modules with covalent bonds. In this study, we presented a non-covalent bond approach to construct GQ ligands with an extended planar structure. The ligands were stable dimers assembled through quadruplex intermolecular hydrogen bonds between two molecules of naphthyridine derivatives. Spectroscopic analyses showed that dimeric ligands could stabilize GQs with an increase of the melting temperature up to 12 °C and induced conformational conversion of hybrid GQs. Confocal fluorescence microscopy confirmed the enrichment of naphthyridine ligands in the nucleus. The ligands showed moderate cytotoxicity against HeLa cells with an IC50 value of 7.5 µg mL-1 and effectively induced growth inhibition and apoptosis in HeLa cells. These results confirmed the feasibility of the quick building of GQ ligands through intermolecular interactions of simple molecules that are easily obtained during synthesis, which is helpful for GQ ligand design and quick establishment of a ligand library through the self-assembly of easily available molecular components.