Thermally-Activated, Delayed Fluorescence in O,B,O- and N,B,O-Strapped Boron Dipyrromethene Derivatives.

A small series of boron dipyrromethene (BODIPY) dyes has been synthesized whereby the boron atom is constrained in a five-membered ring formed from either o-dihydroxypyridine or o-aminophenol. In the latter case, the amino group has been converted into the corresponding amide derivative so as to curtail the possibility for light-induced charge transfer from strap to BODIPY. These compounds are weakly emissive in fluid solution but cleavage of the strap, by treatment with a photoacid generator, restores strong fluorescence. Surprisingly, the same compounds remain weakly fluorescent in a rigid glass at 80 K where light-induced charge transfer is most unlikely. In fluid solution, the fluorescence quantum yield increases with increasing temperature due to a thermally activated step but does not correlate with the thermodynamics for intramolecular charge transfer. It is proposed that the strap causes rupture of the potential energy surface for the excited state, creating traps that provide new routes by which the wave packet can return to the ground state. Access to the trap from the excited state is reversible, leading to the delayed emission. Analysis of the temperature dependent emission intensities allows estimation of the kinetic parameters associated with entering and leaving the trap.

Design, synthesis, docking, ADMET and anticancer evaluations of N-alkyl substituted iodoquinazoline derivatives as dual VEGFR-2 and EGFR inhibitors.

Fifteen new 1-alkyl-6-iodoquinazoline derivatives 5a-d to 9a-e were designed and synthesized and their anticancer activities were evaluated against HepG2, MCF-7, HCT116 and A549 cancer cell lines via dual targeting of EGFR and VEGFR-2. The newly synthesized compounds were designed based on the structure requirements of the target receptors and were confirmed using spectral data. Compound 9c showed the highest anticancer activities with EC50 = 5.00, 6.00, 5.17 and 5.25 µM against HepG2, MCF-7, HCT116 and A549 cell lines correspondingly. Moreover, compounds 5d, 8b, 9a, 9b, 9d, and 9e exhibited very good anticancer effects against the tested cancer cell lines. The highly effective seven derivatives 5d, 8b, 9a-e were examined against VERO normal cell lines to estimate their cytotoxic capabilities. Compounds 9c, 9b, 9d, 9a, 9e and 5d excellently inhibited VEGFR-2 activity with IC50 = 0.85, 0.90, 0.90, 1.00, 1.20 and 1.25 µM respectively. Moreover, compounds 9c, 9d, 9e, 5d, 8b and 9b excellently inhibited EGFRT790M activity with IC50 = 0.22, 0.26, 0.30, 0.40, 0.45 and 0.50 µM respectively. Also, compounds 9c, 9d and 9e excellently inhibited EGFRWT activity with IC50 = 0.15, 0.20 and 0.25 µM respectively. As planned, compound 9c showed excellent dual EGFR/VEGFR-2 inhibitory activities. Consonantly, ADMET study was calculated in silico for the supreme three worthwhile compounds 9b, 9c and 9e in contrast to sorafenib and erlotinib as reference drugs. The obtained results concluded that, our compounds might be useful as prototype for design, optimization, adaptation and investigation to have more powerful and selective dual VEGFR-2/EGFRT790M inhibitors with higher antitumor activity.

Journey of anthraquinones as anticancer agents - a systematic review of recent literature.

Anthraquinones are privileged chemical scaffolds that have been used for centuries in various therapeutic applications. The anthraquinone moiety forms the core of various anticancer agents. However, the emergence of drug-resistant cancers warrants the development of new anticancer agents. The research endeavours towards new anthraquinone-based compounds are increasing rapidly in recent years. They are used as a core chemical template to achieve structural modifications, resulting in the development of new anthraquinone-based compounds as promising anticancer agents. Mechanistically, most of the anthraquinone-based compounds inhibit cancer progression by targeting essential cellular proteins. Herein, we review new anthraquinone analogues that have been developed in recent years as anticancer agents. This includes a systematic review of the recent literature (2005-2021) on anthraquinone-based compounds in cell-based models and key target proteins such as kinases, topoisomerases, telomerases, matrix metalloproteinases and G-quadruplexes involved in the viability of cancer cells. In addition to this, the developments in PEG-based delivery of anthraquinones and the toxicity aspects of anthraquinone derivatives are also discussed. The review dispenses a compact background knowledge to understanding anthraquinones for future research on the expansion of anticancer therapeutics.

The Impact of Addition Oats (Avena sativa) and Cinnamon on Cookies and their Biological Effects on Rats Treated with Cirrhosis by CCL4.

Oats are represented an important source for nutrition, and it have attracted a lot of attention in recent years. In this study we produced oatmeal cookies and oats was added to formula wheat by 50% and 75%. Also, we added cinnamon to treatments 3 and 4 by 5% to increase nutrition value of oatmeal cookies, improvement sensory evaluation and increase antioxidant properties. All the cookies treatments were storage at room temperature. The purposes of this study were to study antioxidant activity for oats and cinnamon. Also determined the chemical composition include (moisture content, protein, ash, total lipids, crude fibers, carbohydrates and total calories) for oats, white flour and oatmeal cookies treatments. In addition evaluated all of sensory evaluation contain (appearance, color, texture, taste and odor) and microbiological evaluation such as (total bacterial count, spore forming bacteria and mold and yeasts count) for oatmeal cookies treatments. Also, biological assays were preformed to measure level of GPT, GOT, urea, creatinine, total cholesterol, triglycerides, HDL, LDL, and glucose. Furthermore, histopathological examination of both liver and kidneys was analyzed. The obtained results were clarified that the antioxidant activity for oats and cinnamon were 52.91% and 87.91%. Moreover, addition of oats and cinnamon to the cookies improve sensory evaluation as made it more acceptable, decreasing microbial load principally treatments 4 (prepared by 75% oats + 5% cinnamon). Biochemical assays were improved in rats with cirrhosis of carbon tetrachloride and their histopathological examination of liver and kidneys. It was clear that the additions ground whole grain oats and cinnamon to wheat flour based cookies improve its nutritional, chemical, and biological functions properties.

DDQ as a versatile and easily recyclable oxidant: a systematic review.

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is the most widely used quinone with a high reduction potential, and it commonly mediates hydride transfer reactions and shows three accessible oxidation states: quinone (oxidized), semiquinone (one-electron-reduced), and hydroquinone (two-electron-reduced). DDQ has found broad utility as a stoichiometric oxidant in the functionalization of activated C-H bonds and the dehydrogenation of saturated C-C, C-O, and C-N bonds. The cost and toxicity of DDQ triggered recent efforts to develop methods that employ catalytic quantities of DDQ in combination with alternative stoichiometric oxidants. The aerobic catalytic approach was established for the selective oxidation of non-sterically hindered electron-rich benzyl methyl ethers and benzylic alcohols, and effectively extended to the oxidative deprotection of p-methoxybenzyl ethers to generate the alcohols in high selectivity. A combination of DDQ and protic acid is known to oxidize several aromatic donors to the corresponding cation radicals. The excited-state DDQ converts benzyls, heteroarenes, fluoroarenes, benzene, and olefins into their radical cation forms as well as chloride and other anions into their respective radicals. These reactive intermediates have been employed for the generation of C-C and C-X (N, O, or Cl) bonds in the synthesis of valuable natural products and organic compounds. To the best of our knowledge, however, there is still no review article exclusively describing the applications of DDQ in organic synthesis. Therefore, in the present review, we provide an overview of DDQ-induced organic transformations with their scope, limitations and the proposed reaction mechanisms.

Optical spectroscopic properties recorded for simple BOPHY dyes in condensed media: The mirror-symmetry factor.

The BOPHY structural scaffold provides opportunities for the synthesis of innumerable derivatives with linear geometries and well-controlled π-conjugation pathways. The simpler BOPHY chromophores are highly fluorescent but exhibit poor mirror symmetry between absorption and fluorescence spectra at ambient temperature. In particular, the absorption (and excitation) spectra are broad and appear as two overlapping bands of comparable intensity. In constrained media, such as low-temperature rigid glasses or stretched poly(ethylene) films, mirror symmetry is restored. Analysis of the temperature dependence recorded for simple BOPHY derivatives indicates that the vibronic envelope accompanying the electronic transitions can be well described in terms of low- and medium-frequency modes. Whereas the fluorescence spectral profile is only weakly dependent on temperature, the excitation spectrum is far more affected. The magnitude of the low-frequency mode, and the associated electron-phonon coupling, increase substantially with increasing temperature and is responsible for temperature broadening and distortion of the excitation spectrum in solution. This critical low-frequency vibronic mode is associated with out-of-plane torsional bending of the BOPHY unit. Variable temperature NMR studies failed to provide unequivocal evidence for conformational changes of one of the derivatives over the temperature range 193-353 K.