Molecular Complexes Involving Iodine<sup>1</sup>

Hastings, Sue; Franklin, J. L.; Schiller, Juergen; Matsen, F. A.

doi:10.1021/ja01108a033

Cited by 113 publications

(21 citation statements)

References 6 publications

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“…The frequency shifts in the other solvents are partly due to van der Waals interaction and partly due to charge-transfer interaction, and figure 2 indicates that the chargetransfer interaction between Is and solvent molecules increases in the following Downloaded by [ order: chloroform, cyclohexane, nitrobenzene, chlorobenzene, bromobenzene, benzene, toluene, m-xylene, and mesitylene. This result on the relative strengths of the charge-transfer interaction between I~ and different donors is consistent with the ultra-vioelt measurements [5,27]. concentration in the mixture, the line gradually shifts to lower frequencies (see figure 3) with little change in the line profile, and finally reaches a mean frequency of 204.6 cm -1 in pure benzene.…”

Section: Rarnan Spectra Of I2 In Various Solventssupporting

confidence: 89%

“…Our measurements on this mean frequency could be as accurate as + 0.1 cm -1. In figure 2, the mean frequency shifts, defined as (Awv~ COv0=213.3 cm -1 is the vibrational frequency of I2 in the vapour phase [25] are plotted against (n s-1) [2@ From ultra-violet absorption measurements, we know that 12 has essentially no charge-transfer interaction with n-hexane, n-heptane, and CC14 [27]. Figure 2 shows that the frequency shifts for I2 in these three solvents are small, and the three respective points indeed fall on a straight line.…”

Section: Rarnan Spectra Of I2 In Various Solventsmentioning

confidence: 99%

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Raman study of iodine complexes in solutions

1971

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Section: Rarnan Spectra Of I2 In Various Solventssupporting

confidence: 89%

Section: Rarnan Spectra Of I2 In Various Solventsmentioning

confidence: 99%

Raman study of iodine complexes in solutions

1971

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“…The ionization potential Ip of 2T2T can be evaluated (Ip = 8.75 ± 0.01 e.v.) using the relationships between the ionization potential and maxima frequency of the charge transfer band as described by McConnel and Hastings (7,8). …”

Section: Chemical Experimentsmentioning

confidence: 99%

Sites of Action of 2-Thiazoline-2-Thiol on Biogenesis of Thyroid Hormones.

et al. 1992

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ABSTRACT-2-Thiazoline-2-thiol is an antithyroid agent that strongly reduces thyroid hormone levels. Synthesis of these hormones is catalyzed in vivo by thyroid peroxidase. The interaction of this drug with molecular iodine and its effect on peroxidase activity were investigated. Iodine and 2-thiazoline-2-thiol form a complex of the charge transfer type of 1:1 stoichiometry characterized by a formation constant of 2,5271-mole-1 at 20°C. This drug was found to inhibit both horseradish peroxidase and lactoperoxidase (used as a model of thyroid peroxidase) in a competitive manner, giving inhibition con stants of 5.7 mM and 0.13 mM, respectively. T3 and T4 levels were reduced significantly after a three-week administration of this drug to a group of 10 rats. Histological ex amination of the thyroid gland showed the presence of a cylindrical epithelium, which is indicative of hyperactivity of the gland. The results indicated that 2-thiazoline-2-thiol acts on both molecular iodine and thyroid peroxidase.Synthetic antithyroid agents are thought to exert their action on thyroid peroxidase, the enzyme responsible for the oxidation of iodides and the coupling of iodotyrosines to iodothyronines (1, 2). We showed that they may also interact with molecular iodine (3). Iodine is complexed by the drug, and thus be comes unavailable for synthesis of thyroid hor mones. A drug which has activity towards TPO and which can complex molecular iodine will thus have particularly strong antithyroid activity. In the present study, we investigated the action of the antithyroid drug 2T2T (4), which has a partially hydrogenated thiazole nucleus. This drug also contains a thiol group, which is also found in MMI, a powerful anti thyroid agent. We also tested action of 2T2T in vivo in the rat to find out whether the com bined actions on peroxidase and iodine did in fact confer strong antithyroid activity.

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“…Spectrum due to I 2 + C6H 12...I2. (6) Spectrum of 10~5m C6H 12...I2 in cyclohexane (Hastings, Franklin, Schiller & Matsen 1953)…”

mentioning

confidence: 99%

Charge-transfer complexes in the scavenging by iodine of radicals formed on pulse radiolysis of cyclo hexane

Ebert

Keene

Land

et al. 1965

Proc. R. Soc. Lond. A

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Pulse radiolysis of solutions of iodine in cyclo hexane resulted in the formation of a transient absorption with wavelength maximum at 3300 Å. This transient spectrum was assigned to the C 6 H 12 ... I' charge-transfer complex. The spectrum and extinction coefficients of the complex over the wavelength range 2500 to 6500 Å were obtained, the coefficient at 3300 Å being 2025 1. mole -1 cm -1 . Hydrogen iodide in cyclo hexane gave rise to the same transient absorption. Pulse radiolysis of cyclo hexane and cyclo hexyl iodide alone gave rise to different transient spectra attributed to the cyclo hexyl radical, absorbing in the ultraviolet, extinction coefficient 3401. mole -1 cm -1 at 2550 Å and the C 6 H 11 .. .I* charge-transfer complex, absorption maximum 3900 A, extinction coefficient ~ 10 3 to 10 4 1. mole -1 cm -1 , respectively. During the course of the investigations rate constants were obtained for the following reactions: C 6 H 11 + I 2 C 6 H 11 I + I', k II = 7 x 10 9 1. mole -1 s -1 , 2C 6 H 12 ...I' -> 2C 6 H 12 + I 2 , k II = 1.06 x 10 10 1. mole -1 s -1 , or 21' -> I 2 , a C 6 H 10 + C 6 H 12 2C 6 H 11 k 11a + k 11b =2.5 x 10 9 1. mole -1 s -1 bC 12 H 22 Dilute solutions of iodine (10 -4 M) in cyclo hexane yielded experimental evidence for neutral radical intermediates only. There were, however, indications that ionic radical intermediates occur in more concentrated solutions ( > 10 -3 M). :

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Molecular Complexes Involving Iodine¹

Cited by 113 publications

References 6 publications

Raman study of iodine complexes in solutions

Raman study of iodine complexes in solutions

Sites of Action of 2-Thiazoline-2-Thiol on Biogenesis of Thyroid Hormones.

Charge-transfer complexes in the scavenging by iodine of radicals formed on pulse radiolysis of cyclo hexane

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Molecular Complexes Involving Iodine1

Cited by 113 publications

References 6 publications

Raman study of iodine complexes in solutions

Raman study of iodine complexes in solutions

Sites of Action of 2-Thiazoline-2-Thiol on Biogenesis of Thyroid Hormones.

Charge-transfer complexes in the scavenging by iodine of radicals formed on pulse radiolysis of cyclo hexane

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Molecular Complexes Involving Iodine¹