A theoretical exploration of the second-order NLO properties of linked sandwich double-layered metallacarboranes: charge transfer mediated by linker groups.

Hetero-bimetallic organic compounds have great potential for the development of new nonlinear optical (NLO) materials, due to their large first hyperpolarizabilities (ßtot). Herein, due to their versatility and ease of functionalization, the second-order NLO properties of a series of linked sandwich metallacarboranes were studied by changing their linkages to different organic groups. The calculated ßtot values suggest that the NLO response was significantly enhanced when an alkenyl group of appropriate length was inserted into the B-B or C-C bonds connecting the metallacarborane units. Time-dependent density-functional theory was used to explain how the connection modes and the use of organic groups as linkers can give rise to different types of charge transfer. Moreover, the NLO responses of the redox states (+1 and -1) were calculated, with the aim of investigating the NLO switching effects of the -1/0/+1 states. Comparison of the ßtot values for the different states shows that the studied linked sandwich metallacarboranes could serve as three-state NLO molecular switches stimulated by redox processes.

Par6 regulates cell cycle progression through enhancement of Akt/PI3K/GSK-3ß signaling pathway activation in glioma.

As the key factor of the polarity protein complex, Par6 not only regulates polarization processes, but also plays important roles in tumor metastasis and progression in many epithelium malignancy tumors. Here, we showed that Par6 is an essential component in glioma tumorigenesis. Our results indicated the aberrant expression of Par6 in malignant glioma tissues and cell lines. We found that the regulation of Par6 expression induces cell proliferation and tumor growth in vivo and in vitro. Additionally, RNA-seq revealed the effects of Par6 were associated with cyclin D1-regulated cell cycle progression in glioma cells. Moreover, our results demonstrated that the regulation of Par6 can enhance the activation of Akt/PI3K signaling pathway, and subsequently upregulate the expression level of GSK-3ß protein, which then regulate cyclin D1-mediated cell cycle regulation. Furthermore, we found that TGF-ß-induced the upregulation of Par6 expression may be involved in this process. The pathological analysis confirmed the correlation between Par6 expression and the prognosis in human glioma tissues, suggesting the regulation of Par6 expression regulates glioma tumorigenesis and progression. Thus, our findings showed that Par6 might be a potential biomarker for the diagnosis and providing a therapeutic strategy for the treatment of malignant glioma.

Aerobic Oxidative Hydroxylation of Arylboronic Acids under Visible-Light Irradiation without Metal Catalysts or Additives.

Phenols are versatile synthetic intermediates and key structural motifs in many natural products and biologically active compounds. We herein report a visible-light-induced aerobic oxidative hydroxylation of arylboronic acids/pinacol esters using air as oxidant and without using any catalysts and base, etc., additives, providing a green entry to a variety of phenols in a highly efficient and concise fashion. This novel reaction is enabled by photoactivation of an electron donor-acceptor complex, in which THF serves as both the solvent and electron donor. DFT studies indicated that the oxidation process involves a concerted hydrogen abstraction transfer from THF and dehydroxylation of boronic acid undergoing spin crossover from triplet to singlet to produce an active peroxoboronic acid intermidiate. Salient merits of this chemistry include broad substrate scope and excellent functional group tolerance, gram-scale synthesis, and versatile late-stage functionalizations as well as the use of air, visible light, and catalyst- and additive-free conditions. This strategy introduces a novel photoreaction mode with the aid of a solvent, offering a succinct and environmentally sustainable route for synthesizing phenols. The strong practicability and highly efficient access to modifying complex biorelevant molecules bode well for the potential applications of this chemistry in pharmaceutical chemistry.

Expression of FMD virus-like particles in yeast Hansenula polymorpha and immunogenicity of combine with CpG and aluminum adjuvant.

BACKGROUND: Inactivated vaccines are limited in preventing foot-and-mouth disease (FMD) due to safety problems. Recombinant virus-like particles (VLPs) are an excellent candidate for a novel vaccine for preventing FMD, given that VLPs have similar immunogenicity as natural viruses and are replication- and infection-incompetent. OBJECTIVES: The 3C protease and P1 polyprotein of type O FMD virus (FDMV) was expressed in yeast Hansenula polymorpha to generate self-resembling VLPs, and the potential of recombinant VLPs as an FMD vaccine was evaluated. METHODS: BALB/c mice were immunized with recombinant purified VLPs using CpG oligodeoxynucleotide and aluminum hydroxide gel as an adjuvant. Cytokines and lymphocytes from serum and spleen were analyzed by enzyme-linked immunosorbent assay, enzyme-linked immunospot assay, and flow cytometry. RESULTS: The VLPs of FMD were purified successfully from yeast protein with a diameter of approximately 25 nm. The immunization of mice showed that animals produced high levels of FMDV antibodies and a higher level of antibodies for a longer time. In addition, higher levels of interferon-γ and CD4+ T cells were observed in mice immunized with VLPs. CONCLUSIONS: The expression of VLPs of FMD in H. polymorpha provides a novel strategy for the generation of the FMDV vaccine.

UPLC-ESI-QTOF-MS/MS Analysis of the Phytochemical Compositions From Chaenomeles speciosa (Sweet) Nakai Fruits.

Chaenomeles speciosa (Sweet) Nakai (C. speciosa Nakai) is a popular fruit widely used in China for its health-promoting properties. The presences of phytochemical compositions in the plants play an important role in the health benefits. Nevertheless, the detailed information of these ingredients is still unknown. Therefore, in this work, an untargeted analytical method based on ultra-high-performance liquid chromatography-quadrupole-time of flight coupled to mass spectrometry in two different ionization modes was used to qualitative the phytochemicals in C. speciosa Nakai, meanwhile, the anti-inflammatory activity of these phytochemicals was researched through detecting the inhibition of nitric oxide (NO) that was induced by lipopolysaccharide in RAW 264.7 murine macrophage cells. The results showed that there were totally 175 primary and secondary metabolites were identified in the fruit of C. speciosa Nakai, including phenols, terpenoids, flavonoids and other phyto-constituents. Actually, most compounds were described in C. speciosa Nakai fruits for the first time. Besides, the anti-inflammatory activity was measured by the result of NO inhibition rate, the consequence showed that the value of half-inhibitory concentration (IC50) was 365.208 µg/mL. These results indicate that C. speciosa Nakai is an efficient medicinal fruit, which owns various bioactivities and has the potential to treat various diseases.

The Analyses of Chemical Components From Oldenlandia hedyotidea (DC.) Hand.-Mazz and Anticancer Effects in vitro.

Oldenlandia hedyotidea (DC.) Hand.-Mazz (OH), also known as sweet tea, is a valuable functional food with medicinal properties and is used for the treatment of cold, cough, gastroenteritis, heatstroke, herpes zoster, and rheumatoid arthritis. The phytochemicals in plant-based foods are responsible for the occurrence of these diseases to some extent. However, there is a scarcity of information on the chemical components of OH. We, therefore, aimed to investigate the phytochemical components of OH using ultra high-performance liquid chromatography-mass spectrometry (UHPLC-MS) and UHPLC triple time-of-flight mass spectrometry (UHPLC-Triple-TOF-MS). The main component of the OH extract, asperulosidic acid, was additionally quantified using UHPLC with ultraviolet detection (UHPLC-UV). The anticancer activity of the OH extract was assessed by a cell proliferation assay and a scratch assay using an esophageal cancer cell line. Ten compounds were tentatively identified in the aqueous extract of OH, including five iridoids, two anthraquinones, and one phenolic acid. The content of asperulosidic acid in the aqueous extract of OH was approximately 42 µg ml-1, and the extract exerted definite in vitro anticancer effects. The results can be used for quality control and assessment of the OH extract, which can serve as a promising source of functional ingredients for potential use in the food and drug industries.

Anti-hypertensive and cardioprotective activities of traditional Chinese medicine-derived polysaccharides: A review.

Cardiovascular diseases (CVDs), a leading cause of death in modern society, have become a major public health issue globally. Although numerous approaches have been proposed to reduce morbidity and mortality, the pursuit of pharmaceuticals with more preventive and/or therapeutic value remains a focus of attention. Being a vast treasure trove of natural drug molecules, Traditional Chinese Medicine (TCM) has a long history of clinical use in the prophylaxis and remedy of CVDs. Increasing lines of preclinical evidence have demonstrated the effectiveness of TCM-derived polysaccharides on hindering the progression of CVDs, e.g. hypertension, myocardial infarction. However, to the best of our knowledge, there are few reviews on the application of TCM-derived polysaccharides in combating CVDs. Hence, we provide an overview of primary literature on the anti-hypertensive and cardioprotective activities of herbal polysaccharides. Additionally, we also discuss the current limitations and propose a new hypothesis about how polysaccharides exert cardiovascular effects based on the metabolism of polysaccharides.

[Expression of CD21 in peripheral blood B lymphocytes of neonates].

OBJECTIVE: To study the cause of low immunologic function and insufficiency of immunoglobulin synthesis in neonates by detecting CD21 expression in B lymphocytes in different age group children. METHODS: This study consisted of three age group children: 2-26 days (n=18), 6 months-2 years (n=12) and 3-12 years (n=17). CD21 expression in B lymphocytes was detected with flow cytometry. Serum levels of immunoglobulins were measured by immunoturbidimetry. RESULTS: The percentage and the number of B lymphocytes expressing CD21 in the neonate group were significantly lower than in the other two age groups. The neonate group also showed lower mean fluorescence intension (MFI) of CD21. The percentage and the number of B lymphocytes expressing CD21 as well as the MFI of CD21 increased significantly with the age. The serum levels of IgA and IgM in the neonate group were noticeably lower than those in the other two age groups. The serum levels of IgA and IgM also increased significantly with the age. CONCLUSIONS: Low CD21 expression in B lymphocytes may be related to low function of humoral immunity in neonates.