Syndiotactic- and heterotactic-specific radical polymerization of N-n-propylmethacrylamide complexed with alkali metal ions

We investigated the radical polymerization of N-n-propylmethacrylamide (NNPMAAm) in the presence of alkali metal bis(trifluoromethanesulfonyl)imides (MNTf2), in particular LiNTf2. The addition of MNTf2 led to a significant improvement in the yield and molecular weight of the resulting poly(NNPMAAm)s. Furthermore, the solvent employed influenced stereospecificity in the presence of LiNTf2. The stoichiometry of the NNPMAAm–Li+ complex appeared to be critical to determining the stereospecificity in the NNPMAAm polymerization. The 1:1-complexed monomer in protic polar solvents provided syndiotactic-rich polymers, whereas the 2:1-complexed monomer in aprotic solvents gave heterotactic-rich polymers. Stereochemical analyses revealed that m-addition by an r-ended radical was the key step in the induction of heterotactic specificity in the aprotic solvents. Spectroscopic analyses suggested that the Li+ cation played a dual role in the polymerization process, with Li+ stabilizing the propagating radical species and also activating the incoming monomer. Kinetic studies with the aid of electron spin resonance spectroscopy revealed that the addition of LiNTf2 caused a significant increase in the kp value and a decrease in the kt value. The stereoregularity of poly(NNPMAAm)s was found to influence the phase transition behavior of their aqueous solutions. In a series of syndiotactic-rich polymers, the phase-transition temperature decreased gradually with increase in rr triad content. Furthermore, heterotactic-rich poly(NNPMAAm) exhibited high hysteresis, which increased in magnitude with increasing mr triad content

Thermally induced cationic polymerization of isobutyl vinyl ether in toluene in the presence of solvate ionic liquid

Radical polymerization of isobutyl vinyl ether (IBVE) was attempted with the aid of the interaction between the corresponding propagating radical and lithium cation (Li+). LiN(SO2CF3)2 (LiNTf2) and ester compounds, such as methyl methacrylate (MMA) and vinyl acetate (VAc), were added as a Li+ source and dissolving agent for LiNTf2, respectively. Homopolymers of cationically polymerizable IBVE were obtained despite the presence of radically polymerizable monomers such as MMA and VAc. Contrary to our expectation, the polymerization proceeded via not a radical mechanism but a cationic mechanism. However, this cationic polymerization was found to be unusual. In particular, the polymer yield increased with the polymerization temperature; successful polymerization was observed at 100 °C, whereas no polymerization occurred at lower temperatures such as at 0 °C. The behavior of the present system was therefore defined as “thermally induced cationic polymerization”. The mechanism of thermally induced cationic polymerization is still not clear, but it is assumed that the propagating cation is markedly stabilized through its interaction with the solvate ionic liquid formed between LiNTf2 and the Lewis base

Assessment of Olfactory Nerve by SPECT-MRI Image with Nasal Thallium-201 Administration in Patients with Olfactory Impairments in Comparison to Healthy Volunteers

Purpose: The aim of this study was to assess whether migration of thallium-201 (201Tl) to the olfactory bulb were reduced in patients with olfactory impairments in comparison to healthy volunteers after nasal administration of 201Tl. Procedures: 10 healthy volunteers and 21 patients enrolled in the study (19 males and 12 females; 26-71 years old). The causes of olfactory dysfunction in the patients were head trauma (n = 7), upper respiratory tract infection (n = 7), and chronic rhinosinusitis (n = 7). 201TlCl was administered unilaterally to the olfactory cleft, and SPECT-CT was conducted 24 h later. Separate MRI images were merged with the SPECT images. 201Tl olfactory migration was also correlated with the volume of the olfactory bulb determined from MRI images, as well as with odor recognition thresholds measured by using T&T olfactometry. Results: Nasal201Tl migration to the olfactory bulb was significantly lower in the olfactory-impaired patients than in healthy volunteers. The migration of 201Tl to the olfactory bulb was significantly correlated with odor recognition thresholds obtained with T&T olfactometry and correlated with the volume of the olfactory bulb determined from MRI images when all subjects were included. Conclusions: Assessment of the 201Tl migration to the olfactory bulb was the new method for the evaluation of the olfactory nerve connectivity in patients with impaired olfaction. © 2013 Shiga et al

COVID-19 vaccine effectiveness against severe COVID-19 requiring oxygen therapy, invasive mechanical ventilation, and death in Japan: A multicenter case-control study (MOTIVATE study).

INTRODUCTION: Since the SARS-CoV-2 Omicron variant became dominant, assessing COVID-19 vaccine effectiveness (VE) against severe disease using hospitalization as an outcome became more challenging due to incidental infections via admission screening and variable admission criteria, resulting in a wide range of estimates. To address this, the World Health Organization (WHO) guidance recommends the use of outcomes that are more specific to severe pneumonia such as oxygen use and mechanical ventilation. METHODS: A case-control study was conducted in 24 hospitals in Japan for the Delta-dominant period (August-November 2021; "Delta") and early Omicron (BA.1/BA.2)-dominant period (January-June 2022; "Omicron"). Detailed chart review/interviews were conducted in January-May 2023. VE was measured using various outcomes including disease requiring oxygen therapy, disease requiring invasive mechanical ventilation (IMV), death, outcome restricting to "true" severe COVID-19 (where oxygen requirement is due to COVID-19 rather than another condition(s)), and progression from oxygen use to IMV or death among COVID-19 patients. RESULTS: The analysis included 2125 individuals with respiratory failure (1608 cases [75.7%]; 99.2% of vaccinees received mRNA vaccines). During Delta, 2 doses provided high protection for up to 6 months (oxygen requirement: 95.2% [95% CI:88.7-98.0%] [restricted to "true" severe COVID-19: 95.5% {89.3-98.1%}]; IMV: 99.6% [97.3-99.9%]; fatal: 98.6% [92.3-99.7%]). During Omicron, 3 doses provided high protection for up to 6 months (oxygen requirement: 85.5% [68.8-93.3%] ["true" severe COVID-19: 88.1% {73.6-94.7%}]; IMV: 97.9% [85.9-99.7%]; fatal: 99.6% [95.2-99.97]). There was a trend towards higher VE for more severe and specific outcomes. CONCLUSION: Multiple outcomes pointed towards high protection of 2 doses during Delta and 3 doses during Omicron. These results demonstrate the importance of using severe and specific outcomes to accurately measure VE against severe COVID-19, as recommended in WHO guidance in settings of intense transmission as seen during Omicron