scholarly journals Pyrithione Metal (Cu, Ni, Ru) Complexes as Photo-Catalysts for Styrene Oxide Production

Author(s):  
Venkata D. B. C. Dasireddy ◽  
Jerneja Kladnik ◽  
Romana Cerc Korošec ◽  
Blaž Likozar ◽  
Iztok Turel

Abstract Selective photochemical oxidation of styrene was performed in an active acetonitrile medium, using H2O2 with or without ultraviolet (UV) light radiation. Pyrithione metal complexes (M–Pth: M = Cu(II), Ni(II), Ru(II); Pth = 2-mercaptopyridine-N-oxide) were used as catalysts. Catalytic testing measurements were done by varying the time, chemical reaction temperature and H2O2 concentration with or without UV energy. Epoxide styrene oxide (SO), benzaldehyde and acetophenone were the major synthesized products. A high batch rate, conversion and selectivity towards SO was shown in the presence of UV. A minor constant formation of CO2 was observed in the stream. Coordinated Ru-based compounds demonstrated the highest process productivity of SO at 60 °C. The effect of the functional alkyl substituent on the ligand Pth, attached to the specific ruthenium(II) centre, decreased the activity of the substance. Ni-Pth selectively yielded benzaldehyde. The stability of the catalysts was examined by applying nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric analysis coupled with mass spectrometry. Tested metal complexes with pyrithione (M–Pth) exhibited excellent reuse recyclability up to 3 cycles.

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Venkata D. B. C. Dasireddy ◽  
Jerneja Kladnik ◽  
Romana Cerc Korošec ◽  
Blaž Likozar ◽  
Iztok Turel

AbstractSelective photochemical oxidation of styrene was performed in an active acetonitrile medium, using H2O2 with or without ultraviolet (UV) light radiation. Pyrithione metal complexes (M–Pth: M = Cu(II), Ni(II), Ru(II); Pth = 2-mercaptopyridine-N-oxide) were used as catalysts. Catalytic testing measurements were done by varying the time, chemical reaction temperature and H2O2 concentration with or without UV energy. Epoxide styrene oxide (SO), benzaldehyde and acetophenone were the major synthesized products. A high batch rate, conversion and selectivity towards SO was shown in the presence of UV. A minor constant formation of CO2 was observed in the stream. Coordinated Ru-based compounds demonstrated the highest process productivity of SO at 60 °C. The effect of the functional alkyl substituent on the ligand Pth, attached to the specific ruthenium(II) centre, decreased the activity of the substance. Ni-Pth selectively yielded benzaldehyde. The stability of the catalysts was examined by applying nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric analysis coupled with mass spectrometry. Tested metal complexes with pyrithione (M–Pth) exhibited excellent reuse recyclability up to 3 cycles.


2020 ◽  
Vol 90 (5-6) ◽  
pp. 439-447 ◽  
Author(s):  
Andrew Hadinata Lie ◽  
Maria V Chandra-Hioe ◽  
Jayashree Arcot

Abstract. The stability of B12 vitamers is affected by interaction with other water-soluble vitamins, UV light, heat, and pH. This study compared the degradation losses in cyanocobalamin, hydroxocobalamin and methylcobalamin due to the physicochemical exposure before and after the addition of sorbitol. The degradation losses of cyanocobalamin in the presence of increasing concentrations of thiamin and niacin ranged between 6%-13% and added sorbitol significantly prevented the loss of cyanocobalamin (p<0.05). Hydroxocobalamin and methylcobalamin exhibited degradation losses ranging from 24%–26% and 48%–76%, respectively; added sorbitol significantly minimised the loss to 10% and 20%, respectively (p < 0.05). Methylcobalamin was the most susceptible to degradation when co-existing with ascorbic acid, followed by hydroxocobalamin and cyanocobalamin. The presence of ascorbic acid caused the greatest degradation loss in methylcobalamin (70%-76%), which was minimised to 16% with added sorbitol (p < 0.05). Heat exposure (100 °C, 60 minutes) caused a greater loss of cyanocobalamin (38%) than UV exposure (4%). However, degradation losses in hydroxocobalamin and methylcobalamin due to UV and heat exposures were comparable (>30%). At pH 3, methylcobalamin was the most unstable showing 79% degradation loss, which was down to 12% after sorbitol was added (p < 0.05). The losses of cyanocobalamin at pH 3 and pH 9 (~15%) were prevented by adding sorbitol. Addition of sorbitol to hydroxocobalamin at pH 3 and pH 9 reduced the loss by only 6%. The results showed that cyanocobalamin was the most stable, followed by hydroxocobalamin and methylcobalamin. Added sorbitol was sufficient to significantly enhance the stability of cobalamins against degradative agents and conditions.


2020 ◽  
Author(s):  
MAK Williams ◽  
V Cornuault ◽  
AH Irani ◽  
VV Symonds ◽  
J Malmström ◽  
...  

© 2020 American Chemical Society. Evidence is presented that the polysaccharide rhamnogalacturonan I (RGI) can be biosynthesized in remarkably organized branched configurations and surprisingly long versions and can self-assemble into a plethora of structures. AFM imaging has been applied to study the outer mucilage obtained from wild-type (WT) and mutant (bxl1-3 and cesa5-1) Arabidopsis thaliana seeds. For WT mucilage, ordered, multichain structures of the polysaccharide RGI were observed, with a helical twist visible in favorable circumstances. Molecular dynamics (MD) simulations demonstrated the stability of several possible multichain complexes and the possibility of twisted fibril formation. For bxl1-3 seeds, the imaged polymers clearly showed the presence of side chains. These were surprisingly regular and well organized with an average length of ∼100 nm and a spacing of ∼50 nm. The heights of the side chains imaged were suggestive of single polysaccharide chains, while the backbone was on average 4 times this height and showed regular height variations along its length consistent with models of multichain fibrils examined in MD. Finally, in mucilage extracts from cesa5-1 seeds, a minor population of chains in excess of 30 μm long was observed.


1985 ◽  
Vol 50 (3) ◽  
pp. 581-599 ◽  
Author(s):  
Petr Vaňura ◽  
Emanuel Makrlík

Extraction of microamounts of Sr2+ and Ba2+ (henceforth M2+) from the aqueous solutions of perchloric acid (0.0125-1.02 mol/l) by means of the nitrobenzene solutions of dicarbolide (0.004-0.05 mol/l of H+{Co(C2B9H11)2}-) was studied in the presence of monoglyme (only Ba2+), diglyme, triglyme, and tetraglyme (CH3O-(CH2-CH2O)nCH3, where n = 1, 2, 3, 4). The distribution of glyme betweeen the aqueous and organic phases, the extraction of the protonized glyme molecule HL+ together with the extraction of M2+ ion and of the glyme complex with the M2+ ion, i.e., ML2+ (where L is the molecule of glyme), were found to be the dominating reactions in the systems under study. In the systems with tri- and tetraglymes the extraction of H+ and M2+ ions solvated with two glyme molecules, i.e., the formation of HL2+ and ML22+ species, can probably play a minor role. The values of the respective equilibrium constants, of the stability constants of complexes formed in the organic phase, and the theoretical separation factors αBa/Sr were determined. The effect of the ligand structure on the values of extraction and stability constants in the organic phase is discussed.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Sean Swetledge ◽  
Renee Carter ◽  
Rhett Stout ◽  
Carlos E. Astete ◽  
Jangwook P. Jung ◽  
...  

AbstractPolymeric nanoparticles have been investigated as potential delivery systems for therapeutic compounds to address many ailments including eye disease. The stability and spatiotemporal distribution of polymeric nanoparticles in the eye are important regarding the practical applicability and efficacy of the delivery system in treating eye disease. We selected poly(lactic-co-glycolic acid) (PLGA) nanoparticles loaded with lutein, a carotenoid antioxidant associated with eye health, as our model ophthalmic nanodelivery system and evaluated its stability when suspended in various conditions involving temperature and light exposure. We also assessed the ocular biodistribution of the fluorescently labeled nanoparticle vehicle when administered topically. Lutein-loaded nanoparticles were stable in suspension when stored at 4 °C with only 26% lutein release and no significant lutein decay or changes in nanoparticle morphology. When stored at 25 °C and 37 °C, these NPs showed signs of bulk degradation, had significant lutein decay compared to 4 °C, and released over 40% lutein after 5 weeks in suspension. Lutein-loaded nanoparticles were also more resistant to photodegradation compared to free lutein when exposed to ultraviolet (UV) light, decaying approximately 5 times slower. When applied topically in vivo, Cy5-labled nanoparticles showed high uptake in exterior eye tissues including the cornea, episcleral tissue, and sclera. The choroid was the only inner eye tissue that was significantly higher than the control group. Decreased fluorescence in all exterior eye tissues and the choroid at 1 h compared to 30 min indicated rapid elimination of nanoparticles from the eye.


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