Radiolysis of liquid chloroform in an oxygen free atmosphere

Abadie, M. J. M.

doi:10.1016/0146-5724(82)90049-8

Cited by 11 publications

(8 citation statements)

References 27 publications

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“…In contrast to this, a marked difference between the irradiations in NaOH and CHCl 3 was the exclusive production of the short and long-wavelength isomers of biliverdin, respectively. This difference was attributed to the presence of different radiolytic products (such as Cl and OH free radicals) [18,19,20], in the different media. Irradiation of water generates free radicals and products associated with radiolytic hydrogen and oxygen.…”

Section: Similarities and Differencesmentioning

confidence: 99%

“…Irradiation of water generates free radicals and products associated with radiolytic hydrogen and oxygen. On the other hand, radiolysis of chloroform [18,19,20] generates no oxygen, but instead several chloro complexes, including carbon tetrachloride and dichloromethane. In aqueous solution the presence of oxygen enhances the oxidation of bilirubin [18].…”

Section: Similarities and Differencesmentioning

confidence: 99%

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A comparative study on gamma irradiation of unconjugated bilirubin in aqueous and non-aqueous solutions

Pillay

Salih

2003

Anal Bioanal Chem

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Dilute aqueous and non-aqueous solutions of bilirubin were exposed to gamma radiation to examine the effects of ionizing radiation on the concentrations of a specimen of this nature. The ionising radiation emanated from a (137)Cs source, and was applied to 5.2 x 10(-2) mmol L(-1) solutions of the unconjugated specimen in 0.05 mol L(-1) aqueous NaOH and chloroform. Depletion of bilirubin after exposure was common to both solvents. Complete degradation was accomplished with doses in excess of 100 Gy. In the case of NaOH, it was found that the presence of molecular oxygen contributed more efficiently to the degradation process, than irradiation in air. When the experimental conditions were changed to nitrogen, the degradation process was suppressed. The sole by-product of merit originating from the NaOH work was the short-wavelength isomer of biliverdin, at 330 nm. In the case of chloroform, the exclusive product of interest was characterised as the long-wavelength isomer of biliverdin that absorbs in the broad region commencing from about 620 nm. The non-aqueous study was conducted in the presence and absence of molecular oxygen, with no significant changes in the results. Optimum production of the isomers in question occurred at a gamma dose of about 80 Gy. The general species of interest were monitored spectrophotometrically, and the results were treated mathematically to facilitate evaluation of the data. Our work represents the development of a facile gamma-ray method for the exclusive production of specific isomers of biliverdin, which are useful components in biosynthetic research.

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Section: Similarities and Differencesmentioning

confidence: 99%

Section: Similarities and Differencesmentioning

confidence: 99%

A comparative study on gamma irradiation of unconjugated bilirubin in aqueous and non-aqueous solutions

Pillay

Salih

2003

Anal Bioanal Chem

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“…Consideration was given to potential production of solute radical anions, solute excited states, and the species that absorbs in neat chloroform, also seen in Figures and . Reduction of solutes is not expected due to dissociative attachment of the ionized electron to solvent molecules or rapid recombination that produces many radicals such as Cl • . , However, if an electron is ejected to a site in contact with a solute molecule, it may be possible that capture by pF or CPT is faster. To determine if solute radical anions are formed, pF solutions were saturated with oxygen (11.6 mM), which will quench radical anions in ∼10 ns but not radical cations.…”

Section: Resultsmentioning

confidence: 99%

“…As noted earlier, oxidation by Cl • occurs in competition with H atom abstraction from CDCl 3 or the pF solubilizing alkyl side chains, likely reducing its impact. Cl • is reported to be formed in high yield, with G = 5.7 × 10 –7 mol J –1 in chloroform; however, it is not clear how many exist in the first 20 ps following radiolysis. While many are likely formed promptly from dissociation of chloroform excited states produced rapidly, others are made from reactions of radicals and ions, as well as excited states made at times after 20 ps from recombination.…”

Section: Discussionmentioning

confidence: 99%

Rapid “Step Capture” of Holes in Chloroform during Pulse Radiolysis

et al. 2013

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The fundamental process of hole capture in solution was investigated following pulse radiolysis with polyfluorene and 4-cyano-4″-pentyl-p-terphenyl scavengers. Contrary to expectation, a large fraction of holes were captured in experimental time-resolution limited ∼20 ps steps, by a process much faster than diffusion of the initially formed solvent molecular cation. At the highest concentrations, 1.92 mM for a 52 unit long polyfluorene and 800 mM for 4-cyano-4″-pentyl-p-terphenyl, 66% and 99%, respectively, of the initially formed holes were captured by 20 ps, with radiation chemical yield G = 1.2 × 10(-7) and 1.7 × 10(-7) mol J(-1). The data can be explained by capture of presolvated holes, analogous to presolvated electrons, possibly possessing extended wave functions, high mobilities, or excess kinetic energy for the first few picoseconds after their creation. Such a process is not generally known in solution; however, the observed step capture as a function of solute concentration is shown to be well explained by this model. In addition to understanding the capture process in solution, the very large step yields formed in 20 ps will provide the ability to resolve subsequent hole transfer on the polymers with >2 orders of magnitude better time resolution than expected.

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“…It is established that γ-ray irradiation is an efficient means to extract halogen ions from inert halohydrocarbons, which has been well-studied over the past few decades. − Moreover, the tolerance of perovskite single crystals and solar cells to γ-rays has been shown to be remarkable, resulting in no significant changes in their structures and properties under a large dosage of irradiation. − …”

Section: Introductionmentioning

confidence: 99%

Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals via Radiation Chemistry of Halohydrocarbons

Zang

et al. 2022

J. Phys. Chem. C

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Cesium halide lead (CsPbX 3 ) perovskite nanocrystals (NCs) have been extensively studied in recent years for their unique capability of postsynthesis anion exchange, providing facile tunability of band gaps and optical properties. In this work, we demonstrate for the first time a simple approach to the tunable anion exchange of CsPbX 3 perovskite NCs via radiation chemistry of inert halohydrocarbons. The anion exchange extents are monitored by shifting of fluorescence emission peaks and ultraviolet−visible absorbance edges and are precisely controlled by tuning the absorbed doses and the adjustable addition of halohydrocarbons. At the same absorbed doses, the anion exchange extents by halohydrocarbons are dependent on the linear attenuation coefficients of halohydrocarbons. Radiation-induced anion exchange can passivate defects in CsPbX 3 NCs, resulting in the fluorescence enhancement. The morphology of perovskite NCs almost remains intact after radiation-induced anion exchange.

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Radiolysis of liquid chloroform in an oxygen free atmosphere

Cited by 11 publications

References 27 publications

A comparative study on gamma irradiation of unconjugated bilirubin in aqueous and non-aqueous solutions

A comparative study on gamma irradiation of unconjugated bilirubin in aqueous and non-aqueous solutions

Rapid “Step Capture” of Holes in Chloroform during Pulse Radiolysis

Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals via Radiation Chemistry of Halohydrocarbons

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