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Chemical Communications (Cambridge,... Jun 2024The azo linkage (NN) is one of the very few functional groups in organic chemistry that exhibits sensitivity towards thermal, chemical, photochemical, and biological... (Review)
Review
The azo linkage (NN) is one of the very few functional groups in organic chemistry that exhibits sensitivity towards thermal, chemical, photochemical, and biological stimuli. Consequently, this property has given rise to a distinct class of responsive materials. For example, thermal sensitivity has led to generation of free radical initiators useful in curing and polymerization applications. Chemically-induced cleavage has aided the development of self-immolative polymers and reactive scaffolds for proteomics applications. Photo-isomerization capability has given rise to photo-responsive systems. Azobenzene cleavage in biologically reducing environments, such as that of the colon, and under tumor hypoxia conditions has led to diagnostic, therapeutic, and delivery materials. Such conditions have also allowed for control over formation (assembly) and disruption (disassembly) of micellar nanoparticles. The aim of this review article is to look beyond the prevalent photosensitivity aspect of the aromatic azo compounds and draw attention to the azo scission reaction as a trigger of the change in the structure and properties of organic materials. Thus, the main discussion begins with the mechanism of the reductive cleavage. Then, its application in the design of molecules that can be activated as drugs and fluorescent sensors, (nano)materials with potential to release active substances, and polymers with side-chain and main-chain self-immolative capacity is discussed. Finally, the status and future challenges in this field are discussed.
PubMed: 38872512
DOI: 10.1039/d4cc02311k -
Angewandte Chemie (International Ed. in... Jun 2024Azobenzenes (ABs) are versatile compounds featured in numerous applications for energy storage systems, such as solar thermal storages or phase change materials....
Azobenzenes (ABs) are versatile compounds featured in numerous applications for energy storage systems, such as solar thermal storages or phase change materials. Additionally, the reversible one-electron reduction of these diazenes to the nitrogen-based anion radical has been used in battery applications. Although the oxidation of ABs is normally irreversible, 4,4'-diamino substitution allows a reversible 2e- oxidation, which is attributed to the formation of a stable bis-quinoidal structure. Herein, we present a system that shows a bipolar redox behaviour. In this way, ABs can serve not only as anolytes, but also as catholytes. The resulting redox potentials can be tailored by suitable amine- and ring-substitution. For the first time, the solid-state structure of the oxidized form could be characterized by X-ray diffraction.
PubMed: 38869230
DOI: 10.1002/anie.202405618 -
Angewandte Chemie (International Ed. in... Jun 2024Perovskite precursor inks suffer various forms of degradation, such as iodide anion oxidation and organic cation breakdown, hindering reliable perovskite solar cell...
Perovskite precursor inks suffer various forms of degradation, such as iodide anion oxidation and organic cation breakdown, hindering reliable perovskite solar cell manufacturing. Here we report that benzylhydrazine hydrochloride (BHC) not only retards the buildup of iodine as previously reported but also prevents the breakdown of organic cations. Through investigating BHC and iodine chemical reactions, we elucidate protonation and dehydration mechanisms, converting BHC to harmless volatile compounds, thus preserving perovskite film crystallization and solar cell performance. This inhibition effect lasts nearly a month with minimal BHC, contrasting control inks without BHC where organic cations fully react in less than a week. This enhanced understanding, from additive stabilization to end products, promises improved perovskite solar cell production reliability.
PubMed: 38858169
DOI: 10.1002/anie.202405422 -
Chemical Communications (Cambridge,... Jun 2024Functionalized lipid probes are a critical new tool to interrogate the function of individual lipid species, but the structural parameters that constrain their utility...
Functionalized lipid probes are a critical new tool to interrogate the function of individual lipid species, but the structural parameters that constrain their utility have not been thoroughly described. Here, we synthesize three palmitic acid derivatives with a diazirine at different positions on the acyl chain and examine their metabolism, subcellular localization, and protein interactions. We demonstrate that while they produce very similar metabolites and subcellular distributions, probes with the diazirine at either end pulldown distinct subsets of proteins after photo-crosslinking. This highlights the importance of thoughtful diazirine placement when developing probes based on biological molecules.
Topics: Diazomethane; Humans; Fatty Acids; Molecular Structure; Palmitic Acid
PubMed: 38856656
DOI: 10.1039/d4cc00974f -
Chemosphere Aug 2024Increasing multidrug-resistant pathogenic microbial around the world become a global problem, making it imperative to develop effective methods for bacterial...
Increasing multidrug-resistant pathogenic microbial around the world become a global problem, making it imperative to develop effective methods for bacterial inactivation in wastewater. In this study, we propose a multifunctional photoelectrochemical (PEC) system to successfully disinfect microbial cells and degrade orange (II) dyes. CoO NP were synthesized by spin-coating onto hydrothermally synthesized TiO nanorod arrays followed by electrodeposited NiFe-LDH to develop the NiFe-LDH/CoO NP-TiO NRs. Interestingly, spin-coated CoO NP-TiO NRs exhibited a 1.5-fold enhancement in photocurrent (1.384 mA/cm) than pristine TiO NRs (0.92 mA/cm). A NiFe-layered double hydroxide (LDH) cocatalysts layer further exhibits the maximum photocurrent density of 1.64 mA/cm with IPCE of 84.5% at 1.0 V at 380 nm. Furthermore, NiFe-LDH/CoO-TiO NR photoanodes were effectually employed for photoelectrochemical bacteria disinfection and organic pollutant removals. With NiFe-LDH/CoO-TiO NR, 99% (120 min) bacterial inactivation and 99% (60 min) orange II dye decomposition efficiency was achieved. Superoxide radicals (O), hydroxyl radicals (HO•), and holes (h) played a critical role in the PEC degradation systems. Due to the synergy between NiFe-LDH cocatalyst and CoO interlayer, surface water oxidation reactions were accelerated over NiFe-LDH/CoO NP-TiO NRs. The charge transport process in NiFe-LDH/CoO NP-TiO NRs photoanode-based PEC system was proposed in detail.
Topics: Titanium; Wastewater; Catalysis; Electrodes; Electrochemical Techniques; Water Pollutants, Chemical; Hydroxides; Waste Disposal, Fluid; Photochemical Processes; Nanotubes; Coloring Agents; Azo Compounds; Water Purification; Disinfection
PubMed: 38851502
DOI: 10.1016/j.chemosphere.2024.142554 -
Journal of Environmental Management Jul 2024Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface...
Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO microsheets (AgIO-O) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (•O). The AgIO-O possesses an outstanding degradation rate constant of 0.035 min, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm, which is 7 and 3.5 times that of the pristine AgIO and C-AgIO (AgIO is calcined in air without generating Ov). In addition, the AgIO-O also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO-O. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO-O exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO-O under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO-O are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO-O catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO-O catalyst to treat organic contaminants in real water under natural sunlight illumination.
Topics: Sunlight; Photolysis; Oxygen; Water Pollutants, Chemical; Azo Compounds; Catalysis; Rhodamines
PubMed: 38850920
DOI: 10.1016/j.jenvman.2024.121393 -
Environmental Geochemistry and Health Jun 2024This study reported the synthesis and assessment of zinc oxide/iron oxide (ZnO/FeO) nanocomposite as photocatalysts for the degradation of a mixture of methylene red and...
This study reported the synthesis and assessment of zinc oxide/iron oxide (ZnO/FeO) nanocomposite as photocatalysts for the degradation of a mixture of methylene red and methylene blue dyes. X-ray diffraction analysis confirms that the crystallite of zinc oxide (ZnO) has a hexagonal wurtzite phase and iron oxide (FeO) has a rhombohedral phase. Fourier Transform Infra-Red spectrum confirms the presence of Zn-O vibration stretching at 428, 480 and 543 cm stretching confirming Fe-O bond formation. Scanning Electron Microscope images exhibited a diverse size and shape of the nanocomposites. The ZnO-90%/FeO-10% and ZnO-10%/FeO-90% nanocomposites reveal good photocatalytic activity with reaction rate constants of 1.5 × 10 and 0.66 × 10; and 1.3 × 10 and 0.60 × 10 for methylene blue and methyl red dye respectively. The results revealed that the synthesized ZnO/FeO nanocomposite is the best catalyst for dye degradation and can be used for industrial applications in future.
Topics: Zinc Oxide; Nanocomposites; Methylene Blue; Ferric Compounds; Catalysis; Coloring Agents; X-Ray Diffraction; Microscopy, Electron, Scanning; Azo Compounds; Water Pollutants, Chemical; Photolysis; Spectroscopy, Fourier Transform Infrared
PubMed: 38849635
DOI: 10.1007/s10653-024-02000-8 -
Environmental Geochemistry and Health Jun 2024Dyes, considered as toxic and persistent pollutants, must be removed from organic wastes prior to their composting and application in sustainable agriculture. Azo dyes,...
Dyes, considered as toxic and persistent pollutants, must be removed from organic wastes prior to their composting and application in sustainable agriculture. Azo dyes, capable of altering the physicochemical properties of soil, are difficult to expel by conventional wastewater treatments. C.I. Acid Black 1 (AB 1), a sulfonated azo dye, inhibits nitrification and ammonification in the soil, lessens the nitrogen use efficacy in crop production and passes substantially unaltered through an activated sludge process. The retention of C.I. Acid Black 1 by raw and expanded perlite was investigated in order to examine the potential effectiveness of this aluminosilicate material toward organic waste cleanup. Dye adsorption proved spontaneous and endothermic in nature, increasing with temperature for both perlites. Expanded perlite having a more open structure exhibited a better performance compared to the raw material. Several of the most widely recognized two-parameter theoretical models, i.e., Langmuir, Freundlich, Temkin, Brunauer-Emmett-Teller (BET), Harkins-Jura, Halsey, Henderson, and Smith, were applied to reveal physicochemical features characterizing the adsorption. The Langmuir, Freundlich, Temkin, BET, Henderson, and Smith equations best fitted experimental data indicating that the adsorption of anionic dye on perlites is controlled by their surface, i.e., non-uniformity in structure and charge. This heterogeneity of surface is considered responsible for promoting specific dye adsorption areas creating dye "islands" with local dye supersaturations.
Topics: Aluminum Oxide; Adsorption; Silicon Dioxide; Coloring Agents; Naphthalenesulfonates; Waste Management; Azo Compounds; Anthraquinones
PubMed: 38849572
DOI: 10.1007/s10653-024-02013-3 -
Acta Biomaterialia Jun 2024Alzheimer's disease (AD) is the most common form of senile dementia, presenting a significant challenge for the development of effective treatments. AD is characterized...
Alzheimer's disease (AD) is the most common form of senile dementia, presenting a significant challenge for the development of effective treatments. AD is characterized by extracellular amyloid plaques and intraneuronal neurofibrillary tangles. Therefore, targeting both hallmarks through inhibition of amyloid beta (Aβ) and tau aggregation presents a promising approach for drug development. Carbon dots (CD), with their high biocompatibility, minimal cytotoxicity, and blood-brain barrier (BBB) permeability, have emerged as promising drug nanocarriers. Congo red, an azo dye, has gathered significant attention for inhibiting amyloid-beta and tau aggregation. However, Congo red's inability to cross the BBB limits its potential to be used as a drug candidate for central nervous system (CNS) diseases. Furthermore, current studies only focus on using Congo red to target single disease hallmarks, without investigating dual inhibition capabilities. In this study, we synthesized Congo red-derived CD (CRCD) by using Congo red and citric acid as precursors, resulting in three variants, CRCD1, CRCD2 and CRCD3, based on different mass ratios of precursors. CRCD2 and CRCD3 exhibited sustained low cytotoxicity, and CRCD3 demonstrated the ability to traverse the BBB in a zebrafish model. Moreover, thioflavin T (ThT) aggregation assays and AFM imaging revealed CRCD as potent inhibitors against both tau and Aβ aggregation. Notably, CRCD1 emerged as the most robust inhibitor, displaying IC values of 0.2 ± 0.1 and 2.1 ± 0.5 µg/mL against tau and Aβ aggregation, respectively. Our findings underscore the dual inhibitory role of CRCD against tau and Aβ aggregation, showcasing effective BBB penetration and positioning CRCD as potential nanodrugs and nanocarriers for the CNS. Hence, CRCD-based compounds represent a promising candidate in the realm of multi-functional AD therapeutics, offering an innovative formulation component for future developments in this area. STATEMENT OF SIGNIFICANCE: This article reports Congo red-derived carbon dots (CRCD) as dual inhibitors of tau and amyloid-beta (Aβ) aggregation for the treatment of Alzheimer's disease (AD). The CRCD are biocompatible and show strong fluorescence, high stability, the ability to cross the blood-brain barrier, and the function of addressing two major pathological features of AD.
PubMed: 38849023
DOI: 10.1016/j.actbio.2024.06.001 -
Chemical Communications (Cambridge,... Jun 2024We developed a centromere-associated protein E (CENP-E) inhibitor employing to photoisomerization with 405 nm visible light illumination and fast thermal relaxation....
We developed a centromere-associated protein E (CENP-E) inhibitor employing to photoisomerization with 405 nm visible light illumination and fast thermal relaxation. This photoswitching characteristic of the inhibitor enabled selective blockage or release of the motion of particular chromosomes within a single mitotic cell. Using this technique, we successfully demonstrated targeted chromosome gain and loss in daughter cells by introducing asymmetric chromosome segregation.
Topics: Chromosomal Proteins, Non-Histone; Humans; Light; Photochemical Processes; HeLa Cells; Azo Compounds; Molecular Structure; Chromosome Segregation
PubMed: 38845591
DOI: 10.1039/d4cc01922a