Hydrogen bond, ring tension and pi-conjugation effects: methyl and vinyl substitutions dramatically change the photodynamics of Criegee intermediates
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Authors: Li, Yazhen; Gong, Qianqian; Yang, Jiawei; Feng, Qianqian; Song, Tingting; Wang, Wenliang; Liu, Fengyi
Abstract
The substitution effect in chemistry is a concept that is probably too common to mention, while for a molecule with an elusive electronic structure, substitution can introduce an unusual effect that dramatically tunes the chemical process. To reveal the substitution effects on the photodynamics of Criegee Intermediates (CIs), we carried out the multireference CASSCF trajectory surface-hopping (TSH) molecular dynamics and CASPT2 electronic-structure calculations for a methyl-substituted CI (MCI) and a vinyl-substituted CI (VCI). The results show that for different substituents, the hydrogen bond, ring tension and pi-conjugation not only alter the relative stabilities of the conformers/configurations, but also dramatically change the photo-induced channel of CIs. For ananti-MCI, the dominant channel starting from the S(1)state is the ring-closure process leading to dioxirane, while in thesynconfiguration, the intramolecular CHMIDLINE HORIZONTAL ELLIPSISO hydrogen bond hinders the rotation around the C-O bond and thus leads to a high yield of in-plane O-O dissociation towards acetaldehyde (X(1)A ') and the O(D-1) atom. In a VCI with an unsaturated substituent, the pi-conjugation greatly strengthens the O-O bond and therefore no O-O dissociation is observed in all configurations. In addition, the CHMIDLINE HORIZONTAL ELLIPSISO hydrogen bond in thesyn((CO))-VCI further stabilizes the S-1-state intermediates and makes them less reactive; in contrast, isomerization to dioxirane becomes the globally dominant channel in theanti((CO))-VCI. The dramatic substitution effects by saturated and unsaturated substituents on CIs found here will deepen the understanding of Criegee-intermediate chemistry.
Do Patients with Differentiated Thyroid Cancer Face the Risk of Hyponatremia at the Expense of Preparation for Radioactive Iodine Treatment?
EUROPEAN JOURNAL OF THERAPEUTICS
Authors: Ozdemir, Elif; Polat, Sefika Burcak; Talay, Nahide Belgit
Abstract
Objective: Differentiated thyroid cancer (DTC) is the most common endocrine cancer. The main therapeutic strategies are surgery and radioactive iodine (RAI) treatment in selected intermediate- and high-risk patients. Hyponatremia is the most frequent form of electrolyte imbalance and few studies have assessed the frequency and clinical impact of hyponatremia in patients with thyroid cancer. In this study, we aimed to determine the prevalence and severity of hyponotsignnatremia among hypothyroid patients in the peri-ablation period. The secondary objective was to assess the correlation between Sodium (Na) level and hypothyroidism severity, age, and RAI dosage. Methods: A total of 51 patients with DTC who were referred to our Nuclear Medicine Department for RAI ablation/treatment were enrolled. Serum Na, thyroid-stimulating hormone ( TSH), and free triiodothyronine and thyroxine levels were measured three times during the study (under LT4 suppression, when the patient was hypothyroid before and after receiving RAI). Baseline, pre-, and post-RAI mean serum Na and other hormonal parameters were compared. The number of patients with hyponatremia and possible related symptoms were noted. Correlation of serum Na levels with age, RAI dosage, and hypothyroidism severity was determined. Results: The number of patients with hyponatremia did not differ significantly in the baseline, pre-, and post-RAI periods. None of the patients experienced moderate-to-severe hyponatremia. There was no significant correlation between serum Na levels and age, serum TSH, or the hormone levels. Conclusion: In conclusion, preparation for RAI treatment with LT4 withdrawal and or a low-iodine diet is not a common etiological factor for the development of hyponatremia in patients with DTC.