Colorimetric fluoride detection in dimethyl sulfoxide using a heteroleptic ruthenium(ii) complex with amino and amide groups: X-ray crystallographic and spectroscopic analyses.

A bis-heteroleptic ruthenium(ii) complex, [Ru(Hdpa)2(H2pia)]X2 (1·X2; X = Cl, OTf, or F; Hdpa = di-2-pyridylamine; H2pia = 2-pycolinamide; OTf- = CF3SO3 -), was synthesized and spectroscopically and crystallographically characterized. The crystal structures of 1·Cl2·2.5H2O and 1·F2·2EtOH revealed essentially identical geometries for the 12+ dication; however, the dihedral angle between the two pyridyl groups in the Hdpa ligands, which represented the degree of bending of the bent conformation, was affected by hydrogen-bonding interactions between the NH group and counterions. In 1·F2·2EtOH, one of the Hdpa ligands had an unusually smaller dihedral angle (15.8°) than the others (29.9°-35.0°). The two NH groups of each Hdpa ligand and the NH2 group of the H2pia ligand in 12+ acted as receptors for F- anion recognition via hydrogen-bonding interactions in a dimethyl sulfoxide (DMSO) solution, and the reaction showed an unambiguous color change in the visible region. Upon the addition of tetra-n-butylammonium fluoride to the red DMSO solution of 1·(OTf)2·H2O, the solution turned dark brown. 1H NMR analysis and absorption spectroscopy of the reaction between 12+ and the added F- anions revealed that the F- anions did not distinguish between the two amino groups of Hdpa and the amide group of H2pia, although they were in different environments in the DMSO solution. A tris-F-adduct with 12+, 1·F3 -, was formed when sufficient F- anions were present in the solution, despite the presence of four NH protons in 12+. Time-dependent DFT calculations of 12+ and 1·F3 - were consistent with their absorption spectra.

Factors Associated with Potassium-Competitive Acid Blocker Non-Response in Patients with Proton Pump Inhibitor-Refractory Gastroesophageal Reflux Disease.

BACKGROUND/AIMS: Approximately 20-40% of patients with gastroesophageal reflux disease (GERD) are refractory to proton pump inhibitor (PPI) treatment. The acid-inhibitory effect of vonoprazan, a novel potassium-competitive acid blocker (P-CAB), is significantly greater when compared to the effect of PPIs. We investigated the efficacy of vonoprazan treatment for PPI-refractory GERD and factors associated with P-CAB non-response. METHODS: We enrolled 277 GERD patients receiving continuous PPI therapy. Subjects completed a self-report questionnaire including the frequency scale for the symptoms of GERD (FSSG). Patients with PPI-refractory GERD received 20 mg of vonoprazan once daily for 8 weeks. After that, subjects completed the same questionnaire, and the results were used to identify P-CAB responders and non-responders. RESULTS: Twenty-eight patients were identified as P-CAB responders and 26 were non-responders. Vonoprazan treatment significantly decreased scores of FSSG, nighttime symptom, and Athens Insomnia Scale. Multivariate analysis demonstrated co-existing functional dyspepsia (FD; OR 4.94) and the presence of sleep disturbances (OR 4.34) was associated with P-CAB non-response, whereas alcohol consumption was inversely associated. CONCLUSIONS: Vonoprazan treatment might be appropriate as a promising new strategy for PPI-refractory GERD. Co-existing FD, sleep disturbances, and alcohol abstinence were significantly associated with P-CAB non-response. Other therapeutic options should be considered in patients with these factors.

Associations among gastroesophageal reflux disease, psychological stress, and sleep disturbances in Japanese adults.

BACKGROUND AND AIM: Gastroesophageal reflux disease (GERD) and psychological stress are associated with sleep disturbances. The aim of the present study was to examine the prevalence of sleep disturbances, anxiety, and depression by GERD subtypes and to identify factors associated with sleep disturbances in general population. METHODS: A total of 2002 Japanese subjects, who underwent annual health checkups, were enrolled and asked to fill out a questionnaire, including the frequency scale for the symptoms of GERD (FSSG), Athens Insomnia Scale (AIS), Rome III questionnaire, and Hospital Anxiety and Depression Scale (HADS). GERD was divided into asymptomatic erosive reflux disease (a-ERD), symptomatic ERD (s-ERD), and non-erosive reflux disease (NERD), according to the presence or absence of esophageal mucosal injury on endoscopy, and the FSSG scores. Sleep disturbances were diagnosed in subjects with AIS score ≥6. RESULTS: Prevalence of sleep disturbances was significantly higher in GERD subjects than in controls (35.9 and 14.7%, respectively), especially, in the NERD group (45.1%). Sleep duration was significantly shorter in the s-ERD group compared with other groups. Subjects in the NERD and s-ERD groups showed higher HADS scores, resulting in higher incidences of anxiety and depression than those in the control and a-ERD groups. Reflux symptoms, anxiety, depression, and coexisting functional dyspepsia, but not the presence of esophageal mucosal injury, were associated with an increased odds ratio for sleep disturbances. CONCLUSION: There were significant positive associations among reflux symptoms, psychological stress, and sleep disturbance in Japanese adults. Further studies investigating the efficacy of therapy are needed.