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International Journal of Molecular... Apr 2022The effect of sodium thiosulfate (ST) on the photodegradation of azathioprine (AZA) was analyzed by UV-VIS spectroscopy, photoluminescence (PL), FTIR spectroscopy, Raman...
The effect of sodium thiosulfate (ST) on the photodegradation of azathioprine (AZA) was analyzed by UV-VIS spectroscopy, photoluminescence (PL), FTIR spectroscopy, Raman scattering, X-ray photoelectron (XPS) spectroscopy, thermogravimetry (TG) and mass spectrometry (MS). The PL studies highlighted that as the ST concentration increased from 25 wt.% to 75 wt.% in the AZA:ST mixture, the emission band of AZA gradual downshifted to 553, 542 and 530 nm. The photodegradation process of AZA:ST induced: (i) the emergence of a new band in the 320-400 nm range in the UV-VIS spectra of AZA and (ii) a change in the intensity ratio of the photoluminescence excitation (PLE) bands in the 280-335 and 335-430 nm spectral ranges. These changes suggest the emergence of new compounds during the photo-oxidation reaction of AZA with ST. The invoked photodegradation compounds were confirmed by studies of the Raman scattering, the FTIR spectroscopy and XPS spectroscopy through: (i) the downshift of the IR band of AZA from 1336 cm to 1331 cm, attributed to N-C-N deformation in the purine ring; (ii) the change in the intensity ratio of the Raman lines peaking at 1305 cm and 1330 cm from 3.45 to 4.57, as the weight of ST in the AZA:ST mixture mass increased; and (iii) the emergence of a new band in the XPS O1s spectrum peaking at 531 eV, which was associated with the C=O bond. Through correlated studies of TG-MS, the main key fragments of ST-reacted AZA are reported.
Topics: Azathioprine; Photolysis; Spectroscopy, Fourier Transform Infrared; Spectrum Analysis, Raman; Thiosulfates
PubMed: 35409337
DOI: 10.3390/ijms23073975 -
Chemosphere May 2021Enrofloxacin (ENR) belongs to the fluoroquinolone (FQ) antibiotics family, which are contaminants of emerging concern frequently found in effluents. Although many works...
Enrofloxacin (ENR) belongs to the fluoroquinolone (FQ) antibiotics family, which are contaminants of emerging concern frequently found in effluents. Although many works studying photo-Fenton process for FQ degradation have been reported, there are no reports analysing in deep the effect of iron complexation, as well as other metals, towards FQs' photolysis, which, evidently, also contributes in the overall degradation of the pollutant. Therefore, in this work, we report a comparative study between the photochemical fate of ENR and its complex with Fe(III) under simulated sunlight irradiation. In addition, the effect of dissolved oxygen, self-sensitization process, and HO addition on the studied photochemical systems are also investigated. Results indicate that, for free and iron-complexed ENR, singlet oxygen (O) is generated from the interaction of its triplet state with ground state oxygen. Half-life time (t) of ENR under sun simulated conditions is estimated to be around 22 min, while complexation with iron enhances its photostability, leading to a t of 2.1 h. Such finding indicates that at least the presence of iron, might notably increase the residence time of these pollutants in the environment. Eventually, only with the addition of HO, the FQ-iron complex is efficiently degraded due to photo-Fenton process even at circumneutral pH values due to the high stability of the formed complex. Finally, after LC/FT-ICR MS analysis, 39 photoproducts are detected, of which the 14 most abundant ones are identified. Results indicate that photoproducts formation is pH and iron dependent.
Topics: Enrofloxacin; Hydrogen Peroxide; Iron; Photolysis; Water Pollutants, Chemical
PubMed: 33556815
DOI: 10.1016/j.chemosphere.2021.129791 -
The Journal of Organic Chemistry Mar 2010Photolysis of triazolo[1,5-b]pyridazine 8 isolated in Ar matrix generates diazomethylpyridazines 9Z and 9E and diazopentenynes 11Z and 11E as detected by IR...
Photolysis of triazolo[1,5-b]pyridazine 8 isolated in Ar matrix generates diazomethylpyridazines 9Z and 9E and diazopentenynes 11Z and 11E as detected by IR spectroscopy. ESR spectroscopy detected the 3-pydidazylcarbene 10 as well as pent-2-en-3-yn-1-ylidene 12 formed by loss of one and two molecules of N(2), respectively. Further photolysis caused rearrangement of the carbenes to 1,2-pentadien-4-yne 13 and 3-ethynylcyclopropene 14. Flash vacuum thermolysis (FVT) of 8 at 400-500 degrees C with Ar matrix isolation of the products yielded 13, 14, and 1,4-pentadiyne 15. At higher temperatures, glutacononitriles 27Z and 27E were formed as well together with minor amounts of 2- and 3-cyanopyrroles 28 and 29. Tetrazolo[1,5-a]pyridine/2-azidopyridine 22T/22A yields 2-pyridylnitrene 19 as well as the novel open-chain cyanodienylnitrene 23 and the ring-expanded 1,3-diazacyclohepta-1,2,4,6-tetraene 21 on short wavelength photolysis. Nitrenes 19 and 23 were detected by ESR spectroscopy, and cumulene 21 by IR and UV spectroscopy. FVT of 22T/22A also affords 2-pyridylnitrene 19 and diazacycloheptatetraene 21, as well as glutacononitriles 27Z,E and 2- and 3-cyanopyrroles 28 and 29. Photolysis of 21 above 300 nm yields the novel spiroazirene 25, identified by its matrix IR spectrum. The reaction pathways connecting the four carbenes (10Z,E and 12Z,E) and three nitrenes (19, 23EZ, and 23ZZ) in their open-shell singlet and triplet states are elucidated with the aid of theoretical calculations at DFT, CASSCF, and CASPT2 levels. Three possible mechanisms of ring-contraction in arylnitrenes are identified: (i) via ring-opening to dienylnitrenes, (ii) concerted ring-contraction, and (iii) via spiroazirenes 25, whereby (i) is the energetically most favorable.
Topics: Cyclization; Imines; Magnetic Resonance Spectroscopy; Methane; Molecular Structure; Nitriles; Photolysis; Pyridazines; Spiro Compounds
PubMed: 20131858
DOI: 10.1021/jo902570d -
The Journal of Organic Chemistry Apr 2022Cobalamin has shown promise as a light-sensitive drug delivery platform owing to its ease of modification and the high quantum yields for drug photorelease. However,...
Cobalamin has shown promise as a light-sensitive drug delivery platform owing to its ease of modification and the high quantum yields for drug photorelease. However, studies to date on the general photochemistry of alkyl cobalamins have primarily focused on methyl and adenosyl-substituted derivatives, the natural cofactors present in various enzymatic species. We describe the synthesis and photolytic behavior of cobalamin conjugates comprised of different combinations of fluorophores and β-axial ligands. In general, cobalamin conjugates containing β-axial alkyl substituents undergo efficient photolysis under aqueous conditions, with quantum yields up to >40%. However, substituents that are large and hydrophobic, or unable to readily support the presumed radical intermediate, suffer less efficient photolysis (<15%) than smaller, water-soluble, analogs. By contrast, quantum yields improve by 2-fold in DMF for cobalamins containing large hydrophobic β-axial substituents. This suggests that drug release from carriers comprised of membranous compartments, such as liposomes, may be significantly more efficient than the corresponding photorelease in an aqueous environment. Finally, we explored the impact of fluorophores on the photolysis of alkyl cobalamins under tissue-mimetic conditions. Cobalamins substituted with efficient photon-capturing fluorophores display up to 4-fold enhancements in photolysis relative to unsubstituted derivatives. In summary, we have shown that the photosensitivity of alkyl cobalamin conjugates can be tuned by altering the Co-appended alkyl moiety, modulating the polarity of the environment (solvent), and installing photon-capturing fluorophores onto the cobalamin framework.
Topics: Fluorescent Dyes; Ligands; Photolysis; Vitamin B 12; Water
PubMed: 35353509
DOI: 10.1021/acs.joc.1c02931 -
Mitochondria-Targeted COUPY Photocages: Synthesis and Visible-Light Photoactivation in Living Cells.The Journal of Organic Chemistry Jun 2023Releasing bioactive molecules in specific subcellular locations from the corresponding caged precursors offers great potential in photopharmacology, especially when...
Releasing bioactive molecules in specific subcellular locations from the corresponding caged precursors offers great potential in photopharmacology, especially when using biologically compatible visible light. By taking advantage of the intrinsic preference of COUPY coumarins for mitochondria and their long wavelength absorption in the visible region, we have synthesized and fully characterized a series of COUPY-caged model compounds to investigate how the structure of the coumarin caging group affects the rate and efficiency of the photolysis process. Uncaging studies using yellow (560 nm) and red light (620 nm) in phosphate-buffered saline medium have demonstrated that the incorporation of a methyl group in a position adjacent to the photocleavable bond is particularly important to fine-tune the photochemical properties of the caging group. Additionally, the use of a COUPY-caged version of the protonophore 2,4-dinitrophenol allowed us to confirm by confocal microscopy that photoactivation can occur within mitochondria of living HeLa cells upon irradiation with low doses of yellow light. The new photolabile protecting groups presented here complement the photochemical toolbox in therapeutic applications since they will facilitate the delivery of photocages of biologically active compounds into mitochondria.
Topics: Humans; HeLa Cells; Light; Mitochondria; Coumarins; Photolysis
PubMed: 37209100
DOI: 10.1021/acs.joc.3c00387 -
Scientific Reports Aug 2022Photocatalysis process is a promising technology for environmental remediation. In the continuous search of new heterogeneous photocatalysts, metal-organic frameworks...
Photocatalysis process is a promising technology for environmental remediation. In the continuous search of new heterogeneous photocatalysts, metal-organic frameworks (MOFs) have recently emerged as a new type of photoactive materials for water remediation. Particularly, titanium-based MOFs (Ti-MOFs) are considered one of the most appealing subclass of MOFs due to their promising optoelectronic and photocatalytic properties, high chemical stability, and unique structural features. However, considering the limited information of the reported studies, it is a hard task to determine if real-world water treatment is attainable using Ti-MOF photocatalysts. In this paper, via a screening with several Ti-MOFs, we originally selected and described the potential of a Ti-MOF in the photodegradation of a mixture of relevant Emerging Organic Contaminants (EOCs) in real water. Initially, two challenging drugs (i.e., the β-blocker atenolol (At) and the veterinary antibiotic sulfamethazine (SMT)) and four water stable and photoactive Ti-MOF structures have been rationally selected. From this initial screening, the mesoporous Ti-trimesate MIL-100(Ti) was chosen as the most promising photocatalyst, with higher At or SMT individual photodegradation (100% of At and SMT photodegradation in 2 and 4 h, respectively). Importantly, the safety of the formed by-products from the At and SMT photodegradation was confirmed. Finally, the At and SMT photodegradation capacity of MIL-100(Ti) was confirmed under realistic conditions, by using a mixture of contaminants in tap drinking water (100% of At and SMT photodegradation in 4 h), proven in addition its potential recyclability, which reinforces the potential of MIL-100(Ti) in water remediation.
Topics: Metal-Organic Frameworks; Photolysis; Sulfamethazine; Titanium; Water Purification
PubMed: 36008470
DOI: 10.1038/s41598-022-18590-1 -
Molecules (Basel, Switzerland) Nov 2022The mechanism of photolytic degradation of 2-4-6-trinitrotoluene (TNT) by UVA−visible light (>320 nm) in ethanolic, aqueous-ethanolic, and aqueous solutions was...
Photolysis by UVA-Visible Light of TNT in Ethanolic, Aqueous-Ethanolic, and Aqueous Solutions According to Electrospray and Aerodynamic Thermal Breakup Droplet Ionization Mass Spectrometry.
The mechanism of photolytic degradation of 2-4-6-trinitrotoluene (TNT) by UVA−visible light (>320 nm) in ethanolic, aqueous-ethanolic, and aqueous solutions was investigated by electrospray and aerodynamic thermal breakup droplet ionization mass-spectrometric analyses. For the photolysis, a DRK-120 mercury-quartz lamp was used. Products of the photolysis reaction were compared with known products of TNT transformation in the environment. Because the photochemistry of some compounds in alcohols (in contrast to aqueous solutions) features a transfer of electrons from the solvent to the light-excited compound, we believe that the efficiency of photolysis (polymerization) of TNT in ethanol and aqueous-ethanolic solutions is based on this mechanism.
Topics: Photolysis; Trinitrotoluene; Light; Mass Spectrometry; Water; Ethanol
PubMed: 36432093
DOI: 10.3390/molecules27227992 -
Scientific Reports Jun 2022In this work, new optical evidences concerning the changes induced of the UV light on pantoprazole sodium (PS), in solid state and as aqueous solution, are reported by...
In this work, new optical evidences concerning the changes induced of the UV light on pantoprazole sodium (PS), in solid state and as aqueous solution, are reported by UV-VIS spectroscopy, photoluminescence (PL), Raman scattering and FTIR spectroscopy. New evidences concerning the products of the PS photodegradation pathways are reported by the correlated studies of thermogravimetry and mass spectrometry. The influence of the excipients and alkaline medium on the PS photodegradation is also studied. New aspects regarding the chemical mechanism of the PS photodegradation in the presence of the water vapor and oxygen form air and the alkaline medium are shown. Our results confirm that the PS photodegradation induced of the water vapors and oxygen from air leads to the generation of 5-difluoromethoxy-3H-benzimidazole-2-thione sodium, 5-difluoromethoxy-3H-benzimidazole sodium, 2-thiol methyl-3, 4-dimethoxypyridine and 2-hydroxymethyl-3, 4-dimethoxypyridine, while in the alkaline medium, compounds of the type of the 2-oxymethyl-3,4-dimethoxypyridine sodium salts are resulted.
Topics: Benzimidazoles; Mass Spectrometry; Oxygen; Pantoprazole; Photolysis; Sodium; Spectroscopy, Fourier Transform Infrared
PubMed: 35680962
DOI: 10.1038/s41598-022-13648-6 -
Molecules (Basel, Switzerland) Jun 2023The unavailability of non-poisonous and hygienic food substances is the most challenging issue of the modern era. The uncontrolled usage of toxic colorant moieties in... (Review)
Review
The unavailability of non-poisonous and hygienic food substances is the most challenging issue of the modern era. The uncontrolled usage of toxic colorant moieties in cosmetics and food manufacturing units leads to major threats to human life. The selection of environmentally benign approaches for the removal of these toxic dyes has gained the utmost attention from researchers in recent decades. This review article's main aim is the focus on the application of green-synthesized nanoparticles (NPs) for the photocatalytic degradation of toxic food dyes. The use of synthetic dyes in the food industry is a growing concern due to their harmful effects on human health and the environment. In recent years, photocatalytic degradation has emerged as an effective and eco-friendly method for the removal of these dyes from wastewater. This review discusses the various types of green-synthesized NPs that have been used for photocatalytic degradation (without the production of any secondary pollutant), including metal and metal oxide NPs. It also highlights the synthesis methods, characterization techniques, and photocatalytic efficiency of these NPs. Furthermore, the review explores the mechanisms involved in the photocatalytic degradation of toxic food dyes using green-synthesized NPs. Different factors that responsible for the photodegradation, are also highlighted. Advantages and disadvantages, as well as economic cost, are also discussed briefly. This review will be advantageous for the readers because it covers all aspects of dyes photodegradation. The future feature and limitations are also part of this review article. Overall, this review provides valuable insights into the potential of green-synthesized NPs as a promising alternative for the removal of toxic food dyes from wastewater.
Topics: Humans; Wastewater; Coloring Agents; Photolysis; Metal Nanoparticles; Nanostructures; Oxides
PubMed: 37375155
DOI: 10.3390/molecules28124600 -
Proceedings of the National Academy of... Feb 2020Rhodopsins are the most abundant light-harvesting proteins. A new family of rhodopsins, heliorhodopsins (HeRs), has recently been discovered. Unlike in the known...
Rhodopsins are the most abundant light-harvesting proteins. A new family of rhodopsins, heliorhodopsins (HeRs), has recently been discovered. Unlike in the known rhodopsins, in HeRs the N termini face the cytoplasm. The function of HeRs remains unknown. We present the structures of the bacterial HeR-48C12 in two states at the resolution of 1.5 Å, which highlight its remarkable difference from all known rhodopsins. The interior of HeR's extracellular part is completely hydrophobic, while the cytoplasmic part comprises a cavity (Schiff base cavity [SBC]) surrounded by charged amino acids and containing a cluster of water molecules, presumably being a primary proton acceptor from the Schiff base. At acidic pH, a planar triangular molecule (acetate) is present in the SBC. Structure-based bioinformatic analysis identified 10 subfamilies of HeRs, suggesting their diverse biological functions. The structures and available data suggest an enzymatic activity of HeR-48C12 subfamily and their possible involvement in fundamental redox biological processes.
Topics: Computational Biology; Hydrogen-Ion Concentration; Models, Molecular; Photolysis; Protein Conformation; Rhodopsins, Microbial
PubMed: 32034096
DOI: 10.1073/pnas.1915888117