Unveiling the Multielectron Acceptor Properties of π-Expanded Pyracylene: Reversible Boat to Chair Conversion.

In this work, the chemical reduction of a hybrid pyracylene-hexa--hexabenzocoronene () nanographene was investigated with different alkali metals (Na, K, Rb) to reveal its remarkable multielectron acceptor abilities. The UV-vis and H NMR spectroscopy monitoring of the stepwise reduction reactions supports the existence of all intermediate reduction states up to the hexaanion for . Tuning the experimental conditions enabled the synthesis of the anions with gradually increasing reduction states (up to -5) isolated with different alkali metal ions as crystalline materials.

The anti-aromatic dianion and aromatic tetraanion of [18]annulene.

π-Conjugated macrocycles behave differently from analogous linear chains because their electronic wavefunctions resemble a quantum particle on a ring, leading to aromaticity or anti-aromaticity. [18]Annulene, (CH), is the archetypal non-benzenoid aromatic hydrocarbon. Molecules with circuits of 4n + 2 π electrons, such as [18]annulene (n = 4), are aromatic, with enhanced stability and diatropic ring currents (magnetic shielding inside the ring), whereas those with 4n π electrons, such as the dianion of [18]annulene, are expected to be anti-aromatic and exhibit the opposite behaviour.

Homoleptic Rare-Earth-Metal Sandwiches with Dibenzo[,]cyclooctatetraene Dianions.

A family of rare-earth complexes [RE(III) = Y, La, Gd, Tb, Dy, and Er] with doubly reduced dibenzo[,]cyclooctatetraene (DBCOT) has been synthesized and structurally characterized. X-ray diffraction analysis confirms that all products of the [RE(DBCOT)(THF)][RE(DBCOT)] composition consist of the anionic sandwich [RE(DBCOT)] and the cationic counterpart [RE(DBCOT)(THF)]. Within the sandwich, two elongated π decks are slightly bent toward the metal center (avg.

Crystallographic evidence for global aromaticity in the di-anion and tetra-anion of a cyclophane hydrocarbon.

[2]Paracyclophanetetraene is a classic example of a macrocyclic hydrocarbon that becomes globally aromatic on reduction to the di-anion, and switches to globally anti-aromatic in the tetra-anion. This redox activity makes it promising as an electrode material for batteries. Here, we report the solid-state structures of the di- and tetra-anions of this cyclophane, in several coordination environments.

Stepwise deprotonation of truxene: structures, metal complexation, and charge-dependent optical properties.

As a planar subunit of C-fullerene, truxene (CH) represents a highly symmetrical rigid hydrocarbon with strong blue emission. Herein, we used truxene as a model to investigate the chemical reactivity of a fullerene fragment with alkali metals. Monoanion, dianion, and trianion products with different alkali metal counterions were crystallized and fully characterized, revealing the core curvature dependence on charge and alkali metal coordination.

Twisted Diindeno-Fused Dibenzo[a,h]anthracene Derivatives and their Dianions.

We report a facile synthesis of diindeno-fused dibenzo[a,h]anthracene derivatives (DIDBA-2Cl, DIDBA-2Ph, and DIDBA-2H) with different degrees of non-planarity using three substituents (chloro, phenyl, and hydrogen) of various sizes. The planarization of their cores, as evidenced by the decreased end-to-end torsional angles, was confirmed by X-ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, which showed a transition from singlet open-shell to closed-shell configuration.

Association Between Circulating Levels of C1q/TNF-Related Protein-9 and Type 2 Diabetes Mellitus: A Systematic Review and Meta-analysis.

Context: According to growing research, C1q/TNF-Related Protein-9 (CTRP9) appears to be linked to type 2 diabetes mellitus (T2DM). But the literature on circulating levels of CTRP9 in patients with T2DM has been contradictory.

Objective: This is a systematic review and meta-analysis to reassess the circulating level of CTRP9 in patients with T2DM, with and without complications.

A phase III randomized, double-blind, placebo-controlled trial of the denosumab biosimilar QL1206 in postmenopausal Chinese women with osteoporosis and high fracture risk.

The current study evaluated the efficacy and safety of a denosumab biosimilar, QL1206 (60 mg), compared to placebo in postmenopausal Chinese women with osteoporosis and high fracture risk. At 31 study centers in China, a total of 455 postmenopausal women with osteoporosis and high fracture risk were randomly assigned to receive QL1206 (60 mg subcutaneously every 6 months) or placebo. From baseline to the 12-month follow-up, the participants who received QL1206 showed significantly increased bone mineral density (BMD) values (mean difference and 95% CI) in the lumbar spine: 4.

Long noncoding RNA PVT1 regulates the proliferation and apoptosis of ARPE-19 cells via the miR-1301-3p/KLF7 axis.

Diabetic retinopathy (DR) as a frequent diabetic microvascular complication shows signs in one-third of diabetic patients. Long non-coding RNAs (lncRNAs) have drawn increasing attention because of their regulatory roles in DR. LncRNA plasmacytoma variant translocation 1 (PVT1) is documented to be upregulated in diabetes-related diseases, while its effects in DR remains unexplored.

Stepwise reduction of a corannulene-based helical molecular nanographene with Na metal.

The chemical reduction of a corannulene-based molecular nanographene, CH (1), with Na metal in the presence of 18-crown-6 afforded the doubly-reduced state of 1. This reduction provokes a distortion of the helicene core and has a significant impact on the aromaticity of the system.

Reversible structural rearrangement of π-expanded cyclooctatetraene upon two-fold reduction with alkali metals.

The chemical reduction of a π-expanded COT derivative, octaphenyltetrabenzocyclooctatetraene (1), with lithium or sodium metals in the presence of secondary ligands affords a new doubly-reduced product (1). The X-ray diffraction study revealed a reductive core rearrangement accompanied by the formation of a single C-C bond and severe twist of the central tetraphenylene core. The reversibility of two-electron reduction and core transformation is further confirmed by NMR spectroscopy and DFT calculations.

Site-Specific Reduction-Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb Complexation.

The chemical reduction of π-conjugated bilayer nanographene 1 (C H ) with K and Rb in the presence of 18-crown-6 affords [K (18-crown-6)(THF) ][{K (18-crown-6)} (THF) ][C H ] (2) and [Rb (18-crown-6) ][{Rb (18-crown-6)} (C H )] (3). Whereas K cations are fully solvent-separated from the trianionic core thus affording a "naked" 1 anion, Rb cations are coordinated to the negatively charged layers of 1 . According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site-specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone.

NORAD lentivirus shRNA mitigates fibrosis and inflammatory responses in diabetic cardiomyopathy via the ceRNA network of NORAD/miR-125a-3p/Fyn.

Objective: Diabetic cardiomyopathy (DCM) is a serious complication of diabetes, but its pathogenesis is still unclear. This study investigated the mechanism of long noncoding RNA (lncRNA) NORAD in DCM.

Methods: Male leptin receptor-deficient (db/db) mice and leptin control mice (db/ +) were procured.

Circular Ribonucleic Acid circFTO Promotes Angiogenesis and Impairs Blood-Retinal Barrier Targeting the miR-128-3p/Thioredoxin Interacting Protein Axis in Diabetic Retinopathy.

Increasing attention has been attracted by the role of circular RNAs (circRNAs) in ocular diseases. Previous study has revealed that circ_0005941 (also known as circFTO, an alpha-ketoglutarate-dependent dioxygenase) was upregulated in the vitreous humor of diabetic retinopathy (DR), while its underlying mechanism in DR remains unknown. Retinal vascular endothelial cells (RVECs) treated with high glucose (HG) were used to establish the DR cell model.

Subclinical hypothyroidism contributes to poor glycemic control in patients with type 2 diabetes mellitus, and ellagic acid attenuates methimazole-induced abnormal glucose metabolism in mice model.

Subclinical hypothyroidism (SCH) as mild thyroid disorder or comorbidity in patients with endocrine disorders is closely related with insulin resistance (IR) and poor glycemic control. The present study attempted to investigate the effect of SCH on IR and glycemic control in patients with type 2 diabetes mellitus (T2DM). In addition, the effects of ellagic acid (EA) on SCH C57BL/6J and db/db mice were also investigated to explore potential therapeutic drug against SCH-induced abnormal glucose metabolism.

Charging a Negatively Curved Nanographene and Its Covalent Network.

This study explores a bottom-up approach toward negatively curved carbon allotropes from octabenzo[8]circulene, a negatively curved nanographene. Stepwise chemical reduction reactions of octabenzo[8]circulene with alkali metals lead to a unique highly reduced hydrocarbon pentaanion, which is revealed by X-ray crystallography suggesting a local view for the reduction and alkali metal intercalation processes of negatively curved carbon allotropes. Polymerization of the tetrabromo derivative of octabenzo[8]circulene by the nickel-mediated Yamamoto coupling reaction results in a new type of porous carbon-rich material, which consists of a covalent network of negatively curved nanographenes.

Reduction of π-Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra-Anion through Internal Li Coordination.

The chemical reduction of a π-expanded polycyclic framework comprising a cyclooctatetraene moiety, octaphenyltetrabenzocyclooctatetraene, with lithium metal readily affords the corresponding tetra-anion instead of the expected aromatic dianion. As revealed by X-ray crystallography, the highly contorted tetra-anion is stabilized by coordination of two internally bound Li , while two external cations remain solvent separated. The variable-temperature Li NMR spectra in THF confirm the presence of three types of Li ions and clearly differentiate internal binding, consistent with the crystal structure.

Citrus flavone tangeretin is a potential insulin sensitizer targeting hepatocytes through suppressing MEK-ERK1/2 pathway.

Background: Tangeretin, a flavonoid derived from citrus peel, showed anti-diabetic effects. However, the role of tangeretin on liver, the organ that act as target of insulin and play the central role in maintaining the blood glucose level control, is still largely unknown. The current study was designed to assess the effect of tangeretin on liver insulin sensitivity in vitro and in vivo.

Niclosamide and its derivative DK-520 inhibit RANKL-induced osteoclastogenesis.

Niclosamide is a potent inhibitor of osteoclastogenesis and bone remodeling. DK-520 is an acyl derivative of Niclosamide and significantly increased both the plasma concentration and the duration of exposure of Niclosamide when dosed orally. However, at present the effect of DK-520 on osteoclastogenesis has not been reported.

Sex differences in the association between marital status and the risk of cardiovascular, cancer, and all-cause mortality: a systematic review and meta-analysis of 7,881,040 individuals.

Purpose: To ascertain whether sex differences exist in the relationship between marital status and cardiovascular diseases (CVD), coronary heart disease (CHD), cancer and all-cause mortality in the general population and to explore the potential effect of age, location, the duration of follow-up and publication years on these outcomes.

Methods: A systematic search was performed in PubMed and EMBASE from inception through to April 2018 and review of references to obtain sex-specific relative risks and their 95% confidence intervals. These were used to derive the women-to-men ratio of RRs (RRR) and 95% CI for each study.

Sex differences in the association between diabetes and risk of cardiovascular disease, cancer, and all-cause and cause-specific mortality: a systematic review and meta-analysis of 5,162,654 participants.

Background: Studies have suggested sex differences in the mortality rate associated with diabetes. We conducted a meta-analysis to estimate the relative effect of diabetes on the risk of all-cause, cancer, cardiovascular disease (CVD), infectious disease, and respiratory disease mortality in women compared with men.

Methods: Studies published from their inception to April 1, 2018, identified through a systematic search of PubMed and EMBASE and review of references.

5-HTT, BMPR2, EDN1, ENG, KCNA5 gene polymorphisms and susceptibility to pulmonary arterial hypertension: A meta-analysis.

Background: The influence of 5-HTT, BMPR2, EDN1, ENG, KCNA5 genes polymorphisms on susceptibility of pulmonary arterial hypertension remains uncertain. This meta-analysis is conducted for further study.

Methods: We conducted a literature search on PubMed and ISI web of science databases for searching relevant articles until November 2017.