Although Ru(II)-based agents are expected to be promising candidates for substituting Pt-drug, their in vivo biomedical applications are still limited by the short excitation/emission wavelengths and ...unsatisfactory therapeutic efficiency. Herein, we rationally design a Ru(II) metallacycle with excitation at 808 nm and emission over 1000 nm, namely Ru1085, which holds deep optical penetration (up to 6 mm) and enhanced chemo-phototherapy activity. In vitro studies indicate that Ru1085 exhibits prominent cell uptake and desirable anticancer capability against various cancer cell lines, especially for cisplatin-resistant A549 cells. Further studies reveal Ru1085 induces mitochondria-mediated apoptosis along with S and G2/M phase cell cycle arrest. Finally, Ru1085 shows precise NIR-II fluorescence imaging guided and long-term monitored chemo-phototherapy against A549 tumor with minimal side effects. We envision that the design of long-wavelength emissive metallacycle will offer emerging opportunities of metal-based agents for in vivo biomedical applications.
Terpyridine (tpy)‐based 3D discrete metallosupramolecular architectures, which are often inspired by polyhedral geometry and the biological structures found in nature, have drawn significant ...attention from the community of metallosupramolecular chemistry. Because of the linear tpy–M(II)–tpy connectivity, the creation of sophisticated 3D metallosupramolecules based on tpy remains a formidable synthetic challenge. Nevertheless, with recent advancement in ligand design and self‐assembly, diverse 3D metallosupramolecular polyhedrons, such as Platonic solids, Archimedean solids, prims as well as Johnson solids, have been constructed and their potential applications have been explored. This review summarizes the progress on tpy‐based discrete 3D metallosupramolecules, aiming to shed more light on the design and construction of novel discrete architectures with molecular‐level precision through coordination‐driven self‐assembly.
This review summarizes the recent progress on terpyridine‐based discrete 3D metallosupramolecules, aiming to shed more light on the design and construction of novel discrete architectures with molecular‐level precision through coordination‐driven self‐assembly. Three major strategies including direct self‐assembly, stepwise self‐assembly, and multicomponent self‐assembly are highlighted with the focus on the control over the size and shape of 3D metallosupramolecules.
This study aims to compare the clinical manifestations, imaging findings, routine tests, biochemistry indicators and cerebrospinal fluid cytology between neurobrucellosis and tuberculous meningitis. ...The objective is to evaluate the similarities and differences of these two diseases and improve early diagnosis.
A comprehensive evaluation was conducted by comparing clinical data, imaging results, routine tests findings, biochemistry indicators and cerebrospinal fluid cytology of patients admitted to the Department of Neurology, the Second Hospital of Hebei Medical University from 2019 to 2021. Statistical analysis was applied to identify significant differences and similarities between the two diseases.
Preliminary analysis demonstrated both diseases commonly present with symptoms such as fever, headache. However, there were no statistical differences between neurobrucellosis and tuberculous meningitis in early clinical data, imaging results, routine tests findings, biochemistry indicators. Further analysis indicates there is a statistically significantly difference in the lymphocyte ratio and neutrophil ratio in the cerebrospinal fluid between the two groups.
Neurobrucellosis and tuberculous meningitis share similarities in early clinical manifestations, imaging findings and initial cerebrospinal fluid parametes, making early-stage differentiation challenging. The ratio of lymphocytes and neutrophil in the cerebrospinal fluid and a detailed medical history investigation can provide clues for early clinical diagnosis. So the examination of CSF cytology might be a potential to distinguish these two diseases and become a powerful tool in the future.
Integrating the advantages of terpyridine (tpy) ligands with excellent chromophoric sensitization ability and lanthanides (Lns) with characteristic luminescent and magnetic properties, discrete ...terpyridine-lanthanide (tpy-Ln) molecular and supramolecular complexes are of great value in many fields and have drawn significant attention from the community of supramolecular chemistry, coordination chemistry and materials science. Compared to the well-documented coordination behavior between transition metals and tpy, the construction of tpy-Ln molecular and supramolecular complexes remains a longstanding challenge due to the high coordination diversity and the lack of stereochemical preference of Lns. Nevertheless, with the advancement of self-assembly strategies, i.e., employing diverse anions as capping components and utilizing secondary auxiliary ligands as well as engineering of tpy ligands, diverse tpy-Ln molecular and supramolecular complexes have been constructed and their potential applications have been explored. This review comprehensively summarizes the progress of discrete tpy-Ln molecular and supramolecular complexes in the past decades, covering the structures of mononuclear, binuclear and multinuclear architectures. Beyond structures, the potential applications of these tpy-Ln complexes are also introduced. This review aims to shed more light on the design and construction of novel discrete tpy-Ln supramolecular complexes and materials with molecular level precision and multiple functions through coordination-driven self-assembly.
Abstract In patients with amyotrophic lateral sclerosis (ALS), various mutations were identified in TAR DNA-binding protein-43 (TDP-43). In the present study, we found that mutant TDP-43 inhibited ...the neurite outgrowth. Subsequently, we tested the effect of MG132 on the mutant TDP-43 cell lines. Non-toxic doses of MG132 promoted neurite extension and decreased the level of thiobarbituric acid-reactive substances (TBARS). Heme oxygenase-1 (HO-1) known as antioxidase was restored by MG132. Conversely, Zinc protoporphyrin IX (ZnPP IX), which is an inhibitor of heme oxygenase, inhibited neurite outgrowth induced by MG132. It was well known that HO-1 was regulated by nuclear factor E2-related factor 2 (Nrf2). However, MG132 increased the expression of HO-1 independent of the Nrf2 pathway.
The aims of this study were to comprehensively evaluate the cephalometric features of patients with obstructive sleep apnea syndrome (OSAS), and to elucidate the relationship between cephalometric ...variables and severity of the apnea-hypopnea index (AHI).
The study population consisted of 62 male patients with OSAS, classified into 33 obese patients (body mass index BMI ≥ 27) and 29 nonobese patients (BMI < 27), and 13 male simple snorers (AHI < 5 events per hour).
Diagnostic polysomnography and measurements of 22 cephalometric variables were carried out for all patients and simple snorers.
Patients with OSAS in both subgroups showed several significant cephalometric features compared with simple snorers: (1) inferiorly positioned hyoid bone, (2) enlarged soft palate, and (3) reduced upper airway width at soft palate. More extensive and severe soft-tissue enlargements including anteriorly positioned hyoid bone and a longer tongue were found in the obese patients. In the nonobese patients, the anteroposterior distances of the bony nasopharynx and oropharynx were significantly smaller than those of simple snorers and obese patients. Stepwise regression analysis showed that anterior displacement of the hyoid bone and retroposition of the mandible were the dominant overall determinants for AHI in patients with OSAS, and that narrowing of the bony oropharynx and inferior displacement of the hyoid bone were dominant determinants for AHI in nonobese patients. A significant regression model for AHI using cephalometric variables could not be obtained for the obese patients, but the BMI proved to be the most significant determinant.
Characteristics of the craniofacial bony structure such as narrowing of the nasopharynx and oropharynx and enlargement of the soft tissue in the upper airway may be important risk factors for the development of OSAS in nonobese patients. In obese patients, the deposition of adipose tissue in the upper airway may aggravate the severity of OSAS.
We report a new strategy for the synthesis of robust hierarchical micro- and mesoporous MOFs from water stable MOFs
a selective acid etching process. The process is controlled by the size-selective ...diffusion of acid molecules through the MOF windows. This method enables the fine-tuning of the porosity of hierarchical MOFs, allowing for the generation of well-defined mesopores with high mesopore volume. Because of the size-selective diffusion of acid molecules, the inherent crystallinity and external morphology of the resulting MOFs are well-maintained after acid treatment. This novel strategy may provide an alternative route towards the synthesis of diverse hierarchical MOFs.
Obstructive sleep apnea is common in obese people. Leptin is an adipocyte-derived signaling factor that has an important role in metabolic control. There is growing evidence that leptin regulation is ...altered in obstructive sleep apnea syndrome (OSAS). The aim of this study was to investigate the relation between polymorphisms of the leptin and leptin receptor (LEPR) genes and OSAS.
The study population consisted of 130 patients with OSAS and 50 healthy control subjects. All the subjects were Japanese. Diagnostic polysomnography was performed in all patients and control subjects. A highly polymorphic tetranucleotide repeat polymorphism in the 3′-flanking region of the leptin gene and three single nucleotide polymorphisms (SNPs) Lys109Arg (A/G) in exon 4, Gln223Arg (A/G) in exon 6, and Lys656Asn (G/C) in exon 14 in the LEPR gene were examined.
There were no significant differences in allelic frequencies and genotype distributions of the examined polymorphisms of the leptin and LEPR genes between OSAS patients and control subjects. For the LEPR gene, the wild-type alleles of the Gln223Arg and Lys656Asn SNPs had a marginally significant effect on mild OSAS, which was defined as an apnea-hypopnea index from 10 and 20 events/h in the dominant model.
The tetranucleotide repeat polymorphism of the leptin gene and the Lys109Arg, Gln223Arg, and Lys656Asn SNPs in the LEPR gene were not associated with OSAS in the Japanese population. Further studies are required to confirm the association of the wild types of Gln223Arg and Lys656Asn SNPs with the severity of OSAS.
The development of more effective tumor therapy remains challenging and has received widespread attention. In the past decade, there has been growing interest in synergistic tumor therapy based on ...supramolecular coordination complexes. Herein, we describe two triangular metallacycles (1 and 2) constructed by the formation of pyridyl boron dipyrromethene (BODIPY)-platinum coordination. Metallacycle 2 had considerable tumor penetration, as evidenced by the phenylthiol-BODIPY ligand imparting red fluorescent emission at ∼660 nm, enabling bioimaging, and transport visualization within the tumor. Based on the therapeutic efficacy of the platinum(II) acceptor and high singlet oxygen (
O
) generation ability of BODIPY, 2 was successfully incorporated into nanoparticles and applied in chemo-photodynamic tumor therapy against malignant human glioma U87 cells, showing excellent synergistic therapeutic efficacy. A half-maximal inhibitory concentration of 0.35 μM was measured for 2 against U87 cancer cells in vitro. In vivo experiments indicated that 2 displayed precise tumor targeting ability and good biocompatibility, along with strong antitumor effects. This work provides a promising approach for treating solid tumors by synergistic chemo-photodynamic therapy of supramolecular coordination complexes.
Luminescent metallo-supramolecules have received tremendous attention in recent years owing to their diverse yet well-defined structures, tunable luminescent properties, and broad applications. In ...this context, the development of terpyridine (tpy)-based luminescent metallo-supramolecular systems has seen rapid growth. This review aims to summarize the recent progress of luminescent metallo-supramolecular assemblies from tpy ligands with metal ions, with a focus on discrete metallo-supramolecular architectures and metallo-supramolecular polymers. The design strategies and common approaches for tuning the luminescence properties are detailed along with representative applications. Finally, the pitfalls and unmet challenges regarding the structural characterization and practical applications of tpy-based metallo-supramolecules are discussed followed by our perspectives on the future directions of this field.
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