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1.
Ann Transl Med ; 10(6): 286, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35434044

RESUMO

Background: Atherosclerosis is the most common cause of cardiovascular disease, accompanied by high mortality and poor prognosis. Low-density lipoprotein (LDL) and its oxidized form oxidized low-density lipoprotein (oxLDL) play an important role in atherosclerosis. This article will explore the role of the lncRNA COLCA1 (colorectal cancer associated 1)/hsa-miR-371a-5p/SPP1 (secreted phosphoprotein 1) pathway in oxLDL in causing human coronary artery endothelial cells (HCAECs) inflammation and related biological function changes. Methods: OxLDL was used to stimulate HCAECs. The inflammatory response and biological function changes of HCAECs were analyzed, total RNA-seq was performed on HCAECs before and after stimulation, and RT-Qpcr (real-time quantitative PCR) was used to verify the differential genes. Interference of the expression of COLCA1 in HCAECs was performed by siRNA interference technology to verify the role of COLCA1 in the biological function changes of HCAECs after oxLDL stimulation, and further prove that COLCA1 affects SPP1 through hsa-miR-371a-5p. Results: OxLDL can affect the oxidative stress response of HCAECs, which in turn affects the apoptosis and wound healing ability of HCAECs. COLCA1 and SPP1 were highly expressed after oxLDL stimulation, while hsa-miR-371a-5p was the opposite. After COLCA1 interference, the oxidative stress level of HCAECs stimulated by oxLDL decreased, the apoptosis level also significantly decreased, and the wound healing ability was enhanced. After simultaneous COLCA1 interference and recovery of the expression of hsa-miR-371a-5p, these improved functions disappeared. The dual-luciferase assay confirmed that hsa-miR-371a-5p and COLCA1, hsa-miR-371a-5p and SPP1 has binding targets. Conclusions: OxLDL can up-regulate the expression of COLCA1 in HCAECs, which in turn affects the intracellular COLCA1/hsa-miR-371a-5p/SPP1 pathway to regulate the level of oxidative stress in cells. This in turn affects the level of apoptosis and wound healing ability, which causes cells to produce a continuous inflammatory response.

2.
Chem Sci ; 13(9): 2721-2728, 2022 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-35340863

RESUMO

Iron-catalyzed organic reactions have been attracting increasing research interest but still have serious limitations on activity, selectivity, functional group tolerance, and stability relative to those of precious metal catalysts. Progress in this area will require two key developments: new ligands that can impart new reactivity to iron catalysts and elucidation of the mechanisms of iron catalysis. Herein, we report the development of novel 2-imino-9-aryl-1,10-phenanthrolinyl iron complexes that catalyze both anti-Markovnikov hydrosilylation of terminal alkenes and 1,2-anti-Markovnikov hydrosilylation of various conjugated dienes. Specifically, we achieved the first examples of highly 1,2-anti-Markovnikov hydrosilylation reactions of aryl-substituted 1,3-dienes and 1,1-dialkyl 1,3-dienes with these newly developed iron catalysts. Mechanistic studies suggest that the reactions may involve an Fe(0)-Fe(ii) catalytic cycle and that the extremely crowded environment around the iron center hinders chelating coordination between the diene and the iron atom, thus driving migration of the hydride from the silane to the less-hindered, terminal end of the conjugated diene and ultimately leading to the observed 1,2-anti-Markovnikov selectivity. Our findings, which have expanded the types of iron catalysts available for hydrosilylation reactions and deepened our understanding of the mechanism of iron catalysis, may inspire the development of new iron catalysts and iron-catalyzed reactions.

3.
Org Biomol Chem ; 17(48): 10172-10177, 2019 12 28.
Artigo em Inglês | MEDLINE | ID: mdl-31755519

RESUMO

In this paper, regiospecific, double intraannular C-N bond cleavages of N-alkyl 4-oxopiperidinium salts are presented. The reaction sequence involves a charge-transfer complex, in situ formed between sulfonyl chloride and N-methylmorpholine, which induces S-Cl bond homolysis of sulfonyl chloride, yielding a reactive sulfonyl radical that further induces the double C-N bond cleavages of N-alkyl 4-oxopiperidinium salt. The secondary amine thus produced was trapped by sulfonyl chloride to yield the desired sulfonamide product. The key feature of this protocol is that two intraannular C-N bonds of the 4-oxopiperidine ring are cleaved in one step under metal- and oxidant-free conditions.

4.
ChemistryOpen ; 8(1): 127-131, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30723657

RESUMO

A novel charge-transfer complex triggered sulfonylation of 1,4-diazabicyclo[2.2.2]octane (DABCO) with mild reaction conditions has been developed. The formation of a charge-transfer complex between electron-withdrawing (hetero)aryl sulfonyl chloride and DABCO allows the synthesis of N-ethylated piperazine sulfonamide in good yields. The reaction has a high functional group tolerance. Spectroscopic studies confirmed the charge-transfer complex formation between sulfonyl chlorides and DABCO, which facilitates the C-N bond cleavage of DABCO.

5.
Sci Rep ; 5: 16405, 2015 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-26549418

RESUMO

A facile and environmentally friendly method was introduced to incorporate montmorillonite (MMT) as an inorganic phase into quaternized hemicelluloses (QH) for forming hemicellulose-based films. Two fillers, polyvinyl alcohol (PVA) and chitin nanowhiskers (NCH), were added into the hemicelluloses/MMT hybrid matrices to prepare hybrid films, respectively. The hybrid films were nanocomposites with nacre-like structure and multifunctional characteristics including higher strength and good oxygen barrier properties via the electrostatic and hydrogen bonding interactions. The addition of PVA and NCH could induce changes in surface topography, and effectively enhance mechanical strength, thermal stability, transparency, and oxygen barrier properties. The tensile strengths of the composite films FPVA(0.3), FPVA(0.5), and FNCH(0.8) were 53.7, 46.3, and 50.1 MPa, respectively, which were 171%, 134%, and 153% larger than the FQH-MMT film (19.8 MPa). The tensile strength, and oxygen transmission rate of QH-MMT-PVA film were better than those of quaternized hemicelluloses/MMT films. Thus, the proper filler is very important for the strength of the hybrid film. These results provide insights into the understanding of the structural relationships of hemicellulose-based composite films in coating and packaging application for the future.

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