Porous Azatruxene Covalent Organic Frameworks for Anion Insertion in Battery Cells.

Covalent organic frameworks (COFs) containing well-defined redox-active groups have become competitive materials for next-generation batteries. Although high potentials and rate performance can be expected, only a few examples of p-type COFs have been reported for charge storage to date with even fewer examples on the use of COFs in multivalent ion batteries. Herein, we report the synthesis of a p-type highly porous and crystalline azatruxene-based COF and its application as a positive electrode material in Li- and Mg-based batteries. When this material is used in Li-based half cells as a COF/carbon nanotube (CNT) electrode, a discharge potential of 3.9 V is obtained with discharge capacities of up to 70 mAh g-1 at a 2 C rate. In Mg batteries using a tetrakis(hexafluoroisopropyloxy)borate electrolyte, cycling proceeds with an average discharge voltage of 2.9 V. Even at a fast current rate of 5 C, the capacity retention amounts to 84% over 1000 cycles.

Pulmonary function and atherosclerosis in the general population: causal associations and clinical implications.

Reduced lung function is associated with cardiovascular mortality, but the relationships with atherosclerosis are unclear. The population-based Swedish CArdioPulmonary BioImage study measured lung function, emphysema, coronary CT angiography, coronary calcium, carotid plaques and ankle-brachial index in 29,593 men and women aged 50-64 years. The results were confirmed using 2-sample Mendelian randomization. Lower lung function and emphysema were associated with more atherosclerosis, but these relationships were attenuated after adjustment for cardiovascular risk factors. Lung function was not associated with coronary atherosclerosis in 14,524 never-smokers. No potentially causal effect of lung function on atherosclerosis, or vice versa, was found in the 2-sample Mendelian randomization analysis. Here we show that reduced lung function and atherosclerosis are correlated in the population, but probably not causally related. Assessing lung function in addition to conventional cardiovascular risk factors to gauge risk of subclinical atherosclerosis is probably not meaningful, but low lung function found by chance should alert for atherosclerosis.

Anion-Rocking Chair Batteries with Tuneable Voltage using Viologen- and Phenothiazine Polymer-based Electrodes.

Organic battery electrode materials offer the unique opportunity for full cells to operate in an anion-rocking chair mode. For this configuration a pair of p-type redox-active electrode materials is required with a substantial potential gap between their redox processes. We herein investigate viologen-functionalized polystyrenes as negative electrode paired with a phenothiazine polymer as positive electrode in all-organic full cells. The 10 % crosslinked viologen polymer X10 -PVBV gave better performance than the linear PVBV and was employed in a full cell as negative electrode with cross-linked poly(3-vinyl-N-methylphenothiazine) (X-PVMPT) as positive electrode. Three cell configurations regarding the voltage range were investigated, of which one with an operating potential of 0.9 V gave the highest performance. The full cell delivered a specific discharge capacity of 64 mA h g-1 (of X-PVMPT) in the first cycle and a capacity retention of 79 % after 100 cycles. This is one of only few reported anion rocking chair all-organic cells and the first employing a phenothiazine-based positive electrode material.

One-year follow-up of children hospitalized with COVID-19: a prospective cohort study.

OBJECTIVE: Currently, little is known about the long-term outcomes of COVID-19 in the pediatric population. The aim of this study was to investigate the long-term clinical outcomes of pediatric patients hospitalized with COVID-19. METHODS: This was a prospective cohort study involving unvaccinated children and adolescents admitted to a tertiary hospital in southern Brazil with a COVID-19 diagnosis. Data were collected from electronic medical records for one year after the diagnosis. RESULTS: A total of 66 children were included: the median age was 2.9 years; 63.6% were male; and 48.5% were under 2 years of age. Over 70% had at least one comorbidity prior to the COVID-19 diagnosis. During the one-year follow-up period, 59.1% of the children revisited the emergency department, 50% required readmission, and 15.2% died. Younger children with longer hospital stays were found to be at greater risk of readmission. Having cancer and impaired functionality were found to increase the risk of death within one year. CONCLUSIONS: Our findings indicate that most children hospitalized with COVID-19 have comorbidities. Younger age at admission and a longer hospital stay seem to be risk factors for readmission. In addition, the presence of cancer and impaired functionality are apparently associated with the poor outcome of death within the first year after the diagnosis of COVID-19.

Association of Intima-Media Thickness Measured at the Common Carotid Artery With Incident Carotid Plaque: Individual Participant Data Meta-Analysis of 20 Prospective Studies.

Background The association between common carotid artery intima-media thickness (CCA-IMT) and incident carotid plaque has not been characterized fully. We therefore aimed to precisely quantify the relationship between CCA-IMT and carotid plaque development. Methods and Results We undertook an individual participant data meta-analysis of 20 prospective studies from the Proof-ATHERO (Prospective Studies of Atherosclerosis) consortium that recorded baseline CCA-IMT and incident carotid plaque involving 21 494 individuals without a history of cardiovascular disease and without preexisting carotid plaque at baseline. Mean baseline age was 56 years (SD, 9 years), 55% were women, and mean baseline CCA-IMT was 0.71 mm (SD, 0.17 mm). Over a median follow-up of 5.9 years (5th-95th percentile, 1.9-19.0 years), 8278 individuals developed first-ever carotid plaque. We combined study-specific odds ratios (ORs) for incident carotid plaque using random-effects meta-analysis. Baseline CCA-IMT was approximately log-linearly associated with the odds of developing carotid plaque. The age-, sex-, and trial arm-adjusted OR for carotid plaque per SD higher baseline CCA-IMT was 1.40 (95% CI, 1.31-1.50; I2=63.9%). The corresponding OR that was further adjusted for ethnicity, smoking, diabetes, body mass index, systolic blood pressure, low- and high-density lipoprotein cholesterol, and lipid-lowering and antihypertensive medication was 1.34 (95% CI, 1.24-1.45; I2=59.4%; 14 studies; 16 297 participants; 6381 incident plaques). We observed no significant effect modification across clinically relevant subgroups. Sensitivity analysis restricted to studies defining plaque as focal thickening yielded a comparable OR (1.38 [95% CI, 1.29-1.47]; I2=57.1%; 14 studies; 17 352 participants; 6991 incident plaques). Conclusions Our large-scale individual participant data meta-analysis demonstrated that CCA-IMT is associated with the long-term risk of developing first-ever carotid plaque, independent of traditional cardiovascular risk factors.

Body weight at age 20 and in midlife is more important than weight gain for coronary atherosclerosis: Results from SCAPIS.

BACKGROUND AND AIMS: Elevated body weight in adolescence is associated with early cardiovascular disease, but whether this association is traceable to weight in early adulthood, weight in midlife or to weight gain is not known. The aim of this study is to assess the risk of midlife coronary atherosclerosis being associated with body weight at age 20, body weight in midlife and body weight change. METHODS: We used data from 25,181 participants with no previous myocardial infarction or cardiac procedure in the Swedish CArdioPulmonary bioImage Study (SCAPIS, mean age 57 years, 51% women). Data on coronary atherosclerosis, self-reported body weight at age 20 and measured midlife weight were recorded together with potential confounders and mediators. Coronary atherosclerosis was assessed using coronary computed tomography angiography (CCTA) and expressed as segment involvement score (SIS). RESULTS: The probability of having coronary atherosclerosis was markedly higher with increasing weight at age 20 and with mid-life weight (p < 0.001 for both sexes). However, weight increase from age 20 until mid-life was only modestly associated with coronary atherosclerosis. The association between weight gain and coronary atherosclerosis was mainly seen in men. However, no significant sex difference could be detected when adjusting for the 10-year delay in disease development in women. CONCLUSIONS: Similar in men and women, weight at age 20 and weight in midlife are strongly related to coronary atherosclerosis while weight increase from age 20 until midlife is only modestly related to coronary atherosclerosis.

Functional status of hospitalized pediatric patients with COVID-19 in southern Brazil: a prospective cohort study.

OBJECTIVE: The present study aimed to assess the functional status of children diagnosed with COVID-19 at the time of hospitalization and the associations with clinical features. METHODS: This prospective cohort study was carried out with children diagnosed with COVID-19 admitted to a tertiary hospital. The patients' functioning was assessed using the pediatric Functional Status Scale (FSS). RESULTS: A total of 62 children with a median age of 3 years old were included in the study, and 70% had some comorbidity prior to the diagnosis of COVID-19. The median length of stay was nine days, during which period five patients died. The FSS assessment of the sample showed that approximately 55% had some functional alteration. The group of patients with the highest FSS scores presented a lengthier hospital stay (p = 0.016), required more oxygen therapy (p < 0.001), mechanical ventilation (p = 0.001), and intensive care unit admissions (p = 0.019), and had more cardiac (p = 0.007), neurological (p = 0.003), and respiratory (p = 0.013) comorbidities. In the multivariate analysis, there was an association between the dependent variable length of stay and the total FSS score (b = 0.349, p = 0.004) and the presence of comorbidities (b = 0.357, p = 0.004). CONCLUSIONS: We observed that more than half of the children hospitalized due to COVID-19 had some level of functional change. Greater alterations in functional status were associated with the presence of previous comorbidities, a greater need for ventilatory support, and longer hospital stays.

One-year follow-up of children hospitalized with COVID-19: a prospective cohort study / Acompanhamento de um ano de crianças hospitalizadas com COVID-19: estudo prospectivo de coorte

ABSTRACT Objective: Currently, little is known about the long-term outcomes of COVID-19 in the pediatric population. The aim of this study was to investigate the long-term clinical outcomes of pediatric patients hospitalized with COVID-19. Methods: This was a prospective cohort study involving unvaccinated children and adolescents admitted to a tertiary hospital in southern Brazil with a COVID-19 diagnosis. Data were collected from electronic medical records for one year after the diagnosis. Results: A total of 66 children were included: the median age was 2.9 years; 63.6% were male; and 48.5% were under 2 years of age. Over 70% had at least one comorbidity prior to the COVID-19 diagnosis. During the one-year follow-up period, 59.1% of the children revisited the emergency department, 50% required readmission, and 15.2% died. Younger children with longer hospital stays were found to be at greater risk of readmission. Having cancer and impaired functionality were found to increase the risk of death within one year. Conclusions: Our findings indicate that most children hospitalized with COVID-19 have comorbidities. Younger age at admission and a longer hospital stay seem to be risk factors for readmission. In addition, the presence of cancer and impaired functionality are apparently associated with the poor outcome of death within the first year after the diagnosis of COVID-19.

RESUMO Objetivo: Atualmente, pouco se sabe sobre os desfechos em longo prazo da COVID-19 na população pediátrica. O objetivo deste estudo foi investigar os desfechos clínicos em longo prazo de pacientes pediátricos hospitalizados com COVID-19. Métodos: Trata-se de um estudo prospectivo de coorte com crianças e adolescentes não vacinados internados em um hospital terciário do Sul do Brasil com diagnóstico de COVID-19. Os dados referentes ao período de um ano após o diagnóstico foram extraídos dos prontuários médicos eletrônicos. Resultados: Foram incluídas 66 crianças: a mediana da idade foi de 2,9 anos; 63,6% eram do sexo masculino; 48,5% tinham menos de 2 anos de idade. Mais de 70% tinham pelo menos uma comorbidade antes do diagnóstico de COVID-19. Durante o período de um ano de acompanhamento, 59,1% das crianças retornaram ao pronto-socorro, 50% necessitaram de readmissão e 15,2% morreram. O risco de readmissão foi maior em crianças mais novas que permaneceram internadas durante mais tempo. Câncer e funcionalidade prejudicada aumentaram o risco de morte até um ano depois. Conclusões: Nossos achados indicam que a maioria das crianças hospitalizadas com COVID-19 apresenta comorbidades. Ser mais jovem no momento da internação hospitalar e permanecer internado durante mais tempo parecem ser fatores de risco de readmissão. Além disso, câncer e funcionalidade prejudicada são fatores aparentemente relacionados com o mau desfecho de óbito no primeiro ano após o diagnóstico de COVID-19.

Prevalence and Predictors of Burnout Among Occupational Therapy Practitioners in the United States.

IMPORTANCE: Identifying the extent and predictors of burnout among occupational therapy practitioners is important so strategies can be developed to reduce burnout and mitigate associated consequences within the profession. OBJECTIVE: To investigate the prevalence and determinants of burnout reported by U.S. occupational therapy practitioners. DESIGN: Cross-sectional survey. PARTICIPANTS: Occupational therapy practitioners working in a wide range of clinical settings who spent at least 50% of their time in direct patient care and who had been employed continuously for more than 6 mo. OUTCOMES AND MEASURES: The outcome of interest was burnout, which was measured using the Emotional Exhaustion, Depersonalization, and Personal Accomplishment subscales of the Maslach Burnout Inventory-Human Services Survey (MBI-HSS). Predictor variables included sociodemographic and workplace characteristics. The relationship between MBI-HSS subscale scores and predictor variables was jointly estimated using a multivariate multivariable linear regression analysis. RESULTS: One hundred seventy-eight occupational therapy practitioners completed the survey. Higher perceived level of supervisor support, satisfaction with income, and educational attainment were associated with lower MBI-HSS subscale scores (ps = .001, .002, and .005, respectively). CONCLUSIONS AND RELEVANCE: Burnout among occupational therapy practitioners can be conceptualized as an issue of workplace health and safety. Various stakeholder groups can consider potential systematic interventions involving measures to promote positive supervisor support in the workplace and salary negotiation skills for early-stage clinicians. Future research should explore broad interventions to reduce burnout among clinicians. What This Article Adds: We estimated the extent and predictors of burnout among U.S. occupational therapy practitioners. Future research, advocacy, and policy should address structural-level interventions to promote workplace cultures and conditions that can protect the occupational therapy workforce from burnout.

Growth of microaerophilic Fe(II)-oxidizing bacteria using Fe(II) produced by Fe(III) photoreduction.

Iron(II) (Fe(II)) can be formed by abiotic Fe(III) photoreduction, particularly when Fe(III) is organically complexed. Light-influenced environments often overlap or even coincide with oxic or microoxic geochemical conditions, for example, in sediments. So far, it is unknown whether microaerophilic Fe(II)-oxidizing bacteria are able to use the Fe(II) produced by Fe(III) photoreduction as electron donor. Here, we present an adaption of the established agar-stabilized gradient tube approach in comparison with liquid cultures for the cultivation of microaerophilic Fe(II)-oxidizing microorganisms by using a ferrihydrite-citrate mixture undergoing Fe(III) photoreduction as Fe(II) source. We quantified oxygen and Fe(II) gradients with amperometric and voltammetric microelectrodes and evaluated microbial growth by qPCR of 16S rRNA genes. We showed that gradients of dissolved Fe(II) (maximum Fe(II) concentration of 1.25 mM) formed in the gradient tubes when incubated in blue or UV light (400-530 nm or 350-400 nm). Various microaerophilic Fe(II)-oxidizing bacteria (Curvibacter sp. and Gallionella sp.) grew by oxidizing Fe(II) that was produced in situ by Fe(III) photoreduction. Best growth for these species, based on highest gene copy numbers, was observed in incubations using UV light in both liquid culture and gradient tubes containing 8 mM ferrihydrite-citrate mixtures (1:1), due to continuous light-induced Fe(II) formation. Microaerophilic Fe(II)-oxidizing bacteria contributed up to 40% to the overall Fe(II) oxidation within 24 h of incubation in UV light. Our results highlight the potential importance of Fe(III) photoreduction as a source of Fe(II) for Fe(II)-oxidizing bacteria by providing Fe(II) in illuminated environments, even under microoxic conditions.

Danger signal extracellular calcium initiates differentiation of monocytes into SPP1/osteopontin-producing macrophages.

The danger signal extracellular calcium is pathophysiologically increased in the synovial fluid of patients with rheumatoid arthritis (RA). Calcium activates the NLRP3-inflammasome via the calcium-sensing receptor in monocytes/macrophages primed by lipopolysaccharide, and this effect is mediated by the uptake of calciprotein particles (CPPs) formed out of calcium, phosphate, and fetuin-A. Aim of the study was to unravel the influence of calcium on monocytes when the priming signal is not present. Monocytes were isolated from the blood of healthy controls and RA patients. Macrophages were characterized using scRNA-seq, DNA microarray, and proteomics. Imaging flow cytometry was utilized to study intracellular events. Here we show that extracellular calcium and CPPs lead to the differentiation of monocytes into calcium-macrophages when the priming signal is absent. Additional growth factors are not needed, and differentiation is triggered by calcium-dependent CPP-uptake, lysosomal alkalization due to CPP overload, and TFEB- and STAT3-dependent increased transcription of the lysosomal gene network. Calcium-macrophages have a needle-like shape, are characterized by excessive, constitutive SPP1/osteopontin production and a strong pro-inflammatory cytokine response. Calcium-macrophages differentiated out of RA monocytes show a stronger manifestation of this phenotype, suggesting the differentiation process might lead to the pro-inflammatory macrophage response seen in the RA synovial membrane.

Influence of Fe(III) source, light quality, photon flux and presence of oxygen on photoreduction of Fe(III)-organic complexes - Implications for light-influenced coastal freshwater and marine sediments.

Iron(III) photoreduction is an important source of Fe(II) in illuminated aquatic and sedimentary environments. Under oxic conditions, the Fe(II) can be re-oxidized by oxygen (O2) forming reactive O-species such as hydrogen peroxide (H2O2) which further react with Fe(II) thus enhancing Fe(II) oxidation rates. However, it is unknown by aquatic sediments how the parameters wavelength of radiation, photon flux, origin of Fe(III) source and presence or absence of O2 influence the extent of Fe(II) and H2O2 turnover. We studied this using batch experiments with different Fe(III)-organic complexes mimicking sedimentary conditions. We found that wavelengths <500 nm are necessary to initiate Fe(III) photoreduction and that the photon flux, wavelength and identity of Fe(III)-complexing organic acids control the kinetics of Fe(III) photoreduction. The formation of photo-susceptible Fe(III)-organic complexes did not depend on whether the Fe(III) source was biogenically produced, poorly-crystalline Fe(III) oxyhydroxides or chemically synthesized ferrihydrite. Oxic conditions caused chemical re-oxidation of Fe(II) and accumulation of H2O2. The photon flux, wavelength and availability of Fe(III)-complexing organic molecules are critical for the balance between concurrent Fe(III) photoreduction and abiotic Fe(II) oxidation and may even lead to a steady-state concentration of Fe(II) in the micromolar range. These results help understand and predict Fe(III) photoreduction dynamics and in-situ formation of Fe(II) in oxic or anoxic, illuminated and organic-rich environments.

Accelerometer derived physical activity patterns in 27.890 middle-aged adults: The SCAPIS cohort study.

The present study aims to describe accelerometer-assessed physical activity (PA) patterns and fulfillment of PA recommendations in a large sample of middle-aged men and women, and to study differences between subgroups of socio-demographic, socio-economic, and lifestyle-related variables. A total of 27 890 (92.5% of total participants, 52% women, aged 50-64 years) middle-aged men and women with at least four days of valid hip-worn accelerometer data (Actigraph GT3X+, wGT3X+ and wGT3X-BT) from the Swedish CArdioPulmonary bioImage Study, SCAPIS, were included. In total, 54.5% of daily wear time was spent sedentary, 39.1% in low, 5.4% in moderate, and only 0.1% in vigorous PA. Male sex, higher education, low financial strain, born in Sweden, and sedentary/light working situation were related to higher sedentary time, but also higher levels of vigorous PA. High BMI and having multiple chronic diseases associated strongly with higher sedentary time and less time in all three PA intensities. All-year physically active commuters had an overall more active PA pattern. The proportion fulfilling current PA recommendations varied substantially (1.4% to 92.2%) depending on data handling procedures and definition used. Twenty-eight percent was defined as having an "at-risk" behavior, which included both high sedentary time and low vigorous PA. In this large population-based sample, a majority of time was spent sedentary and only a fraction in vigorous PA, with clinically important variations between subgroups. This study provides important reference material and emphasizes the importance of a comprehensive assessment of all aspects of the individual PA pattern in future research and clinical practice.

Randomised controlled trial of interventions for bothersome tinnitus: DesyncraTM versus cognitive behavioural therapy.

OBJECTIVE: Compare the relative efficacy of DesyncraTM and Cognitive Behavioural Therapy (CBT). DESIGN AND STUDY SAMPLE: Sixty-one participants were randomly assigned to receive either DesyncraTM (n = 29) or CBT (n = 32). Randomisation included stratification regarding current hearing aid (HA) use. Depending on group assignment, participants attended approximately 7-12 visits. Tinnitus distress was measured using the Tinnitus Questionnaire (TQ). RESULTS: Mean TQ scores decreased post-baseline from 5-15 points across treatment arms and strata. Model-based findings for the no-HA stratum showed a difference of -2.0 TQ points favouring Desyncra at 24-weeks, with a 90% posterior interval varying from -5.4 points favouring Desyncra to 0.8 TQ points favouring CBT. For the HA stratum, results show a difference of -1.0 TQ points favouring Desyncra, with a 90% posterior interval ranging from -4.7 points favouring Desyncra to 2.9 points favouring CBT. CONCLUSIONS: The difference between Desyncra and CBT on average showed greater improvement with Desyncra in the no-HA stratum by about 2 TQ points. To the extent that the study sample represents a clinical population and recognising the assumptions in the design and analysis, these results suggest Desyncra is just as effective or more so than CBT in reducing tinnitus distress.

Functional status of hospitalized pediatric patients with COVID-19 in southern Brazil: a prospective cohort study / Estado funcional de pacientes pediátricos hospitalizados com COVID-19 no sul do Brasil: um estudo de coorte prospectivo

ABSTRACT Objective: The present study aimed to assess the functional status of children diagnosed with COVID-19 at the time of hospitalization and the associations with clinical features. Methods: This prospective cohort study was carried out with children diagnosed with COVID-19 admitted to a tertiary hospital. The patients' functioning was assessed using the pediatric Functional Status Scale (FSS). Results: A total of 62 children with a median age of 3 years old were included in the study, and 70% had some comorbidity prior to the diagnosis of COVID-19. The median length of stay was nine days, during which period five patients died. The FSS assessment of the sample showed that approximately 55% had some functional alteration. The group of patients with the highest FSS scores presented a lengthier hospital stay (p = 0.016), required more oxygen therapy (p < 0.001), mechanical ventilation (p = 0.001), and intensive care unit admissions (p = 0.019), and had more cardiac (p = 0.007), neurological (p = 0.003), and respiratory (p = 0.013) comorbidities. In the multivariate analysis, there was an association between the dependent variable length of stay and the total FSS score (b = 0.349, p = 0.004) and the presence of comorbidities (b = 0.357, p = 0.004). Conclusions: We observed that more than half of the children hospitalized due to COVID-19 had some level of functional change. Greater alterations in functional status were associated with the presence of previous comorbidities, a greater need for ventilatory support, and longer hospital stays.

RESUMO Objetivo: O objetivo do presente estudo foi de avaliar o estado funcional de crianças diagnosticadas com COVID-19 no momento da internação e as associações com suas características clínicas. Métodos: Este estudo de coorte prospectivo foi realizado com crianças diagnosticadas com COVID-19 internadas em um hospital terciário. A funcionalidade dos pacientes foi avaliada por meio da Escala de Estado Funcional (FSS) pediátrica. Resultados: Foram incluídas no estudo 62 crianças com idade mediana de 3 anos, das quais 70% apresentavam alguma comorbidade antes do diagnóstico de COVID-19. O tempo mediano de internação foi de nove dias, período no qual cinco pacientes vieram a óbito. A avaliação da FSS da amostra mostrou que aproximadamente 55% apresentavam alguma alteração funcional. O grupo de pacientes com os maiores escores na FSS teve um maior tempo de internação (p = 0,016), necessitou de mais oxigenoterapia (p < 0,001), ventilação mecânica (p = 0,001) e internações em unidade de terapia intensiva (p = 0,019) e tinha mais comorbidades cardíacas (p = 0,007), neurológicas (p = 0,003) e respiratórias (p = 0,013). Na análise multivariada, observou-se uma associação entre a variável dependente tempo de internação e o escore total da FSS (b = 0,349, p = 0,004) e a presença de comorbidades (b = 0,357, p = 0,004). Conclusões: Verificou-se que mais da metade das crianças internadas devido à COVID-19 apresentaram algum nível de alteração funcional. Maiores alterações no estado funcional foram associadas à presença de comorbidades prévias, maior necessidade de suporte ventilatório e maior tempo de internação.

The influence of the cation structure on the basicity-related polarity of ionic liquids.

UV/Vis absorption data of (E)-4-(2-[5-{4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl}thiene-2-yl]vinyl)-2-(dicyano-methylene)-3-cyano-5,5-dimethyl-2,5-dihydrofuran (ThTCF) as a solvatochromic probe is applied to examine the anion coordination strength (e.g. of N(CN)2, BF4, PF6, N(Tf)2, CF3COO) as a function of the cation structure of ionic liquids. Several 1-n-alky-3-methylimidazolium- and tetraalkylammonium CH3-NR3+-based ILs with different n-alkyl chain lengths (R = -C4H9, -C6H11, -C8H17, -C10H21) are considered. UV/Vis absorption data of ThTCF show subtle correlations with hydrogen bond accepting (HBA) ability-related measurands such as Kamlet-Taft ß, Freire's EHB, and Laurence ß1 parameter as a function of anion and cation structure. The different influence of the n-alkyl chain length of imidazolium- and tetraalkylammonium-based ILs on the dipolarity and HBA strength is confirmed by comparison with the 14N isotropic hyperfine coupling constants (Aiso) of a positively (CATI) and negatively charged spin probe (TSKCr) of TEMPO-type [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] and quantum chemically derived dipoles of the cations. The Aiso values correlate with the absorption energy of ThTCF and EHB, but in different ways depending on the anion or charge of the spin probe. In a final discussion of the ß, EHB, and ß1 scales in relation to ThTCF, the importance of the molar concentration N of ionic liquids for the physical significance of the respective parameters is discussed.

PI3Kγ Mediates Microglial Proliferation and Cell Viability via ROS.

(1) Background: Rapid microglial proliferation contributes to the complex responses of the innate immune system in the brain to various neuroinflammatory stimuli. Here, we investigated the regulatory function of phosphoinositide 3-kinase γ (PI3Kγ) and reactive oxygen species (ROS) for rapid proliferation of murine microglia induced by LPS and ATP. (2) Methods: PI3Kγ knockout mice (PI3Kγ KO), mice expressing catalytically inactive PI3Kγ (PI3Kγ KD) and wild-type mice were assessed for microglial proliferation using an in vivo wound healing assay. Additionally, primary microglia derived from newborn wild-type, PI3Kγ KO and PI3Kγ KD mice were used to analyze PI3Kγ effects on proliferation and cell viability, senescence and cellular and mitochondrial ROS production; the consequences of ROS production for proliferation and cell viability after LPS or ATP stimulation were studied using genetic and pharmacologic approaches. (3) Results: Mice with a loss of lipid kinase activity showed impaired proliferation of microglia. The prerequisite of induced microglial proliferation and cell viability appeared to be PI3Kγ-mediated induction of ROS production. (4) Conclusions: The lipid kinase activity of PI3Kγ plays a crucial role for microglial proliferation and cell viability after acute inflammatory activation.

The physical significance of the Kamlet-Taft π* parameter of ionic liquids.

The Kamlet-Taft dipolarity/polarizability parameters π* for various ionic liquids were determined using 4-tert-butyl-2-((dicyanomethylene)-5-[4-N,N-diethylamino)-benzylidene]-Δ3-thiazoline and 5-(N,N-dimethylamino)-5'-nitro-2,2'-bithiophene as solvatochromic probes. In contrast to the established π*-probe N,N-diethylnitroaniline, the chromophores presented here show excellent agreement with polarity measurement using the chemical shift of 129Xe. They do not suffer from additional bathochromic UV/vis shifts caused by hydrogen-bonding resulting in too high π*-values for some ionic liquids. In combination with large sets of various ionic liquids, these new chromophores thereby allow for detailed analysis of the physical significance of π* and the comparison to quantum-mechanical methods. We find that π* correlates strongly with the ratio of molar refractivity to molar volume, and thus with the refractive index.