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Mesoporous Acridinium-Based Covalent Organic Framework for Long-lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation
No full textReadily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor-acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of approximate to 4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor-acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of approximate to 4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.
Decreased hip flexion during spike jump-landings after fatigue is predictive of patellar tendinopathy in volleyball
No full textContext:Patellar tendinopathy (PT) is a highly prevalent overuse injury in volleyball. However, little is known if and how the risk for developing PT is increased through fatigue-induced alterations during repetitive jump-landing activities in volleyball.Objective:The purpose of this study was to explore fatigue-induced risk factors for PT during a spike jump-landing task in volleyball.Design:Prospective cohort study.Setting:3D biomechanical laboratory screening.Patients or Other Participants:Seventy-nine adult, male volleyball players.Main Outcome Measure(s):At baseline (pre-season), 3D full-body kinematics and kinetics were collected while performing a spike jump before and after a volleyball-specific fatigue protocol. Throughout the season, players were followed for the occurrence of PT and survival analysis with competing risks was performed to identify significant predictors for the development of PT (p < 0.05).Results:During follow-up, 10 of the 79 players developed PT (13%). Players with significantly less hip flexion during the horizontal landing/push-off phase of the spike jump after fatigue were at higher risk for developing PT (HR = 0.898; 95% CI 0.826 to 0.977; p = 0.023) as well as players with a significantly more elongated rectus femoris muscle-tendon unit (HR = 3.258; 95% CI 1.136 to 9.343; p = 0.032).Conclusions:Despite the low (injured) sample size of this study, preliminary research findings indicate less hip flexion and more elongated rectus femoris muscle-tendon units during landing after fatigue as potential risk factors for developing PT. Future prevention programs for PT may wish to focus on hip-specific exercises and technique modifications (e.g., more hip flexion during landing) under fatigued circumstances.Context:Patellar tendinopathy (PT) is a highly prevalent overuse injury in volleyball. However, little is known if and how the risk for developing PT is increased through fatigue-induced alterations during repetitive jump-landing activities in volleyball.Objective:The purpose of this study was to explore fatigue-induced risk factors for PT during a spike jump-landing task in volleyball.Design:Prospective cohort study.Setting:3D biomechanical laboratory screening.Patients or Other Participants:Seventy-nine adult, male volleyball players.Main Outcome Measure(s):At baseline (pre-season), 3D full-body kinematics and kinetics were collected while performing a spike jump before and after a volleyball-specific fatigue protocol. Throughout the season, players were followed for the occurrence of PT and survival analysis with competing risks was performed to identify significant predictors for the development of PT (p < 0.05).Results:During follow-up, 10 of the 79 players developed PT (13%). Players with significantly less hip flexion during the horizontal landing/push-off phase of the spike jump after fatigue were at higher risk for developing PT (HR = 0.898; 95% CI 0.826 to 0.977; p = 0.023) as well as players with a significantly more elongated rectus femoris muscle-tendon unit (HR = 3.258; 95% CI 1.136 to 9.343; p = 0.032).Conclusions:Despite the low (injured) sample size of this study, preliminary research findings indicate less hip flexion and more elongated rectus femoris muscle-tendon units during landing after fatigue as potential risk factors for developing PT. Future prevention programs for PT may wish to focus on hip-specific exercises and technique modifications (e.g., more hip flexion during landing) under fatigued circumstances.A
The role of education as a socialization mechanism in addressing the social gradient in depression treatment in Belgium (2004–2018)
No full textIntroduction: Previous studies have identified socioeconomic inequalities in the treatment of depression. However, these studies often take a narrow approach, focusing on a single treatment type and lacking a comprehensive theoretical framework. Moreover, income and education are frequently used interchangeably as indicators of disadvantage, without distinguishing their unique impacts. This study argues that relying solely on income to explain treatment inequalities is overly simplistic, suggesting instead that education influences treatment through two distinct pathways. The study’s objectives are twofold: first, to investigate the presence of a social gradient in depression treatment, and second, to examine how this gradient is manifested.Methods: This study utilizes data from the Belgian Health Interview Survey (BHIS), covering four successive waves: 2004, 2008, 2013, and 2018. The weighted data represent a sample of the adult Belgian population. Multinomial regression models are used to address the research aims, and models are plotted to detect trends over time using marginal means post-estimation.Results: Findings indicate that income is not significantly related to depression treatment, while persistent educational inequalities in treatment are observed over time. Individuals with longer educational attainment are more likely to use psychotherapy alone or a combination treatment, whereas individuals with shorter educational attainment are more likely to use pharmaceutical treatment alone.Discussion: This study demonstrates that education plays a critical role in fostering health-related knowledge and reasoning, making individuals with longer education more likely to engage in rational health behaviors and choose more effective treatments, even when these treatments require more effort and competencies. The findings underscore the importance of considering education as a key determinant of depression treatment inequalities.Introduction: Previous studies have identified socioeconomic inequalities in the treatment of depression. However, these studies often take a narrow approach, focusing on a single treatment type and lacking a comprehensive theoretical framework. Moreover, income and education are frequently used interchangeably as indicators of disadvantage, without distinguishing their unique impacts. This study argues that relying solely on income to explain treatment inequalities is overly simplistic, suggesting instead that education influences treatment through two distinct pathways. The study’s objectives are twofold: first, to investigate the presence of a social gradient in depression treatment, and second, to examine how this gradient is manifested.Methods: This study utilizes data from the Belgian Health Interview Survey (BHIS), covering four successive waves: 2004, 2008, 2013, and 2018. The weighted data represent a sample of the adult Belgian population. Multinomial regression models are used to address the research aims, and models are plotted to detect trends over time using marginal means post-estimation.Results: Findings indicate that income is not significantly related to depression treatment, while persistent educational inequalities in treatment are observed over time. Individuals with longer educational attainment are more likely to use psychotherapy alone or a combination treatment, whereas individuals with shorter educational attainment are more likely to use pharmaceutical treatment alone.Discussion: This study demonstrates that education plays a critical role in fostering health-related knowledge and reasoning, making individuals with longer education more likely to engage in rational health behaviors and choose more effective treatments, even when these treatments require more effort and competencies. The findings underscore the importance of considering education as a key determinant of depression treatment inequalities.A
Replication stress, microcephalic primordial dwarfism, and compromised immunity in ATRIP deficient patients
No full textAtaxia telangiectasia and Rad3-related (ATR) kinase and its interacting protein ATRIP orchestrate the replication stress response. Homozygous splice variants in the ATRIP gene, resulting in ATRIP deficiency, were identified in two patients of independent ancestry with microcephaly, primordial dwarfism, and recurrent infections. The c.829+5G>T patient exhibited lymphopenia, poor vaccine responses, autoimmune features with hemolytic anemia, and neutropenia. Immunophenotyping revealed reduced CD16(+)/CD56(dim) NK cells and absent na & iuml;ve T cells, MAIT cells, and iNKT cells. Lymphocytic defects were characterized by TCR oligoclonality, abnormal class switch recombination, and impaired T cell proliferation. ATRIP deficiency resulted in low-grade ATR activation but impaired CHK1 phosphorylation under genotoxic stress. ATRIP-deficient cells inadequately regulated DNA replication, leading to chromosomal instability, compromised cell cycle control, and impaired cell viability. CRISPR-Select(TIME) confirmed reduced cell fitness for both variants. This study establishes ATRIP deficiency as a monogenic cause of microcephalic primordial dwarfism, highlights ATRIP's critical role in protecting immune cells from replication stress, and offers new insights into its canonical functions.Ataxia telangiectasia and Rad3-related (ATR) kinase and its interacting protein ATRIP orchestrate the replication stress response. Homozygous splice variants in the ATRIP gene, resulting in ATRIP deficiency, were identified in two patients of independent ancestry with microcephaly, primordial dwarfism, and recurrent infections. The c.829+5G>T patient exhibited lymphopenia, poor vaccine responses, autoimmune features with hemolytic anemia, and neutropenia. Immunophenotyping revealed reduced CD16(+)/CD56(dim) NK cells and absent na & iuml;ve T cells, MAIT cells, and iNKT cells. Lymphocytic defects were characterized by TCR oligoclonality, abnormal class switch recombination, and impaired T cell proliferation. ATRIP deficiency resulted in low-grade ATR activation but impaired CHK1 phosphorylation under genotoxic stress. ATRIP-deficient cells inadequately regulated DNA replication, leading to chromosomal instability, compromised cell cycle control, and impaired cell viability. CRISPR-Select(TIME) confirmed reduced cell fitness for both variants. This study establishes ATRIP deficiency as a monogenic cause of microcephalic primordial dwarfism, highlights ATRIP's critical role in protecting immune cells from replication stress, and offers new insights into its canonical functions.A
The pan-PPAR agonist lanifibranor reduces portal pressure independent of fibrosis reduction through the splanchnic vasculature
No full textPortal hypertension (PH) can cause severe complications in patients with advanced chronic liver disease (aCLD). The pan-peroxisome proliferator-activated receptor (pan-PPAR) agonist lanifibranor reduces portal pressure in preclinical models of aCLD. Since the effect on PH might be secondary to fibrosis improvement, we investigated the effect of lanifibranor on PH, hepatic and splanchnic angiogenesis in mouse models of fibrotic and prehepatic non-fibrotic PH. Mice with fibrotic PH (common bile duct ligation; CBDL) and prehepatic PH (partial portal vein ligation; PPVL) received daily lanifibranor/vehicle for 14 or 7 days, respectively. Hemodynamics, serum, hepatic and mesenteric histology, and hepatic, mesenteric and liver sinusoidal endothelial cells (LSEC) gene expression levels were analyzed. Vascular corrosion casts of the venous mesenteric and hepatic vasculature were analyzed using scanning electron microscopy and µCT. Portal pressure was increased in CBDL mice. Lanifibranor treatment demonstrated a dose-dependent trend towards decreasing the elevated portal pressure, and reduced fibrosis. Hepatic mRNA levels of inflammatory, fibrotic and angiogenic markers were significantly downregulated in lanifibranor-treated CBDL mice. LSEC dysfunction was improved by lanifibranor. Compared to CBDL mice, portal pressure was more extensively elevated in PPVL mice, which was significantly reduced by lanifibranor. Superior mesenteric artery blood flow, which was increased in vehicle-treated PPVL mice, tended to decrease by lanifibranor. The expansion of the mesenteric vasculature and mesenteric protein level of angiogenetic markers in PPVL mice were reduced after lanifibranor. In conclusion, lanifibranor improves PH, independently from fibrosis reduction, potentially through reducing the venous mesenteric vasculature expansion and intrahepatic angiogenesis, and ameliorating LSEC function.Portal hypertension (PH) can cause severe complications in patients with advanced chronic liver disease (aCLD). The pan-peroxisome proliferator-activated receptor (pan-PPAR) agonist lanifibranor reduces portal pressure in preclinical models of aCLD. Since the effect on PH might be secondary to fibrosis improvement, we investigated the effect of lanifibranor on PH, hepatic and splanchnic angiogenesis in mouse models of fibrotic and prehepatic non-fibrotic PH. Mice with fibrotic PH (common bile duct ligation; CBDL) and prehepatic PH (partial portal vein ligation; PPVL) received daily lanifibranor/vehicle for 14 or 7 days, respectively. Hemodynamics, serum, hepatic and mesenteric histology, and hepatic, mesenteric and liver sinusoidal endothelial cells (LSEC) gene expression levels were analyzed. Vascular corrosion casts of the venous mesenteric and hepatic vasculature were analyzed using scanning electron microscopy and µCT. Portal pressure was increased in CBDL mice. Lanifibranor treatment demonstrated a dose-dependent trend towards decreasing the elevated portal pressure, and reduced fibrosis. Hepatic mRNA levels of inflammatory, fibrotic and angiogenic markers were significantly downregulated in lanifibranor-treated CBDL mice. LSEC dysfunction was improved by lanifibranor. Compared to CBDL mice, portal pressure was more extensively elevated in PPVL mice, which was significantly reduced by lanifibranor. Superior mesenteric artery blood flow, which was increased in vehicle-treated PPVL mice, tended to decrease by lanifibranor. The expansion of the mesenteric vasculature and mesenteric protein level of angiogenetic markers in PPVL mice were reduced after lanifibranor. In conclusion, lanifibranor improves PH, independently from fibrosis reduction, potentially through reducing the venous mesenteric vasculature expansion and intrahepatic angiogenesis, and ameliorating LSEC function.A
Counterfactual thinking is associated with impoverished attentional control in women prone to self-critical rumination
No full textBackground and objectives: Excessive engagement in counterfactual thinking (CFT), where individuals imagine alternative outcomes to past events, is associated with rumination, a process characterized by repetitive negative self-referential thoughts. Attentional control difficulties are closely linked with rumination, and negative thoughts can negatively impact attentional control among rumination-prone individuals. This study aimed to investigate the relationship between CFT and emotional and non-emotional attentional control among individuals with varying levels of self-critical rumination. Methods: A sample of 100 female participants, characterized by varying levels of self-critical rumination, completed a choice task resulting in goal failure, during which they reported their levels of CFT. Subsequently, participants performed an attentional control task involving eye-tracking measures to assess emotional attentional engagement, emotional attentional disengagement, and emotional and non-emotional attentional shifting. Results: Among women with high (but not low) self-critical rumination tendencies, increased levels of CFT were associated with slower attentional shifting from emotional stimuli of opposing valence, as well as between non- emotional stimuli. Limitations: The correlational design of the study prevents causal interpretations of the findings. Additionally, the exclusive inclusion of female participants may limit the generalizability of the results. Conclusions: This study underscores the association of CFT with subsequent attentional control among women prone to self-critical rumination, aligning with prior research suggesting a link between negative thoughts and attentional processes. Future research should explore these relationships in diverse populations and consider longitudinal designs to elucidate causal pathways.Background and objectives: Excessive engagement in counterfactual thinking (CFT), where individuals imagine alternative outcomes to past events, is associated with rumination, a process characterized by repetitive negative self-referential thoughts. Attentional control difficulties are closely linked with rumination, and negative thoughts can negatively impact attentional control among rumination-prone individuals. This study aimed to investigate the relationship between CFT and emotional and non-emotional attentional control among individuals with varying levels of self-critical rumination. Methods: A sample of 100 female participants, characterized by varying levels of self-critical rumination, completed a choice task resulting in goal failure, during which they reported their levels of CFT. Subsequently, participants performed an attentional control task involving eye-tracking measures to assess emotional attentional engagement, emotional attentional disengagement, and emotional and non-emotional attentional shifting. Results: Among women with high (but not low) self-critical rumination tendencies, increased levels of CFT were associated with slower attentional shifting from emotional stimuli of opposing valence, as well as between non- emotional stimuli. Limitations: The correlational design of the study prevents causal interpretations of the findings. Additionally, the exclusive inclusion of female participants may limit the generalizability of the results. Conclusions: This study underscores the association of CFT with subsequent attentional control among women prone to self-critical rumination, aligning with prior research suggesting a link between negative thoughts and attentional processes. Future research should explore these relationships in diverse populations and consider longitudinal designs to elucidate causal pathways.A
Activated phenyl ester vitrimers
No full textAromatic esters are amongst the oldest known chemical motifs that allow for thermal (re)processing of thermosetting polymers. Moreover, phenyl esters are generally known as activated esters that do not require a catalyst to undergo acyl transfer reactions. Even though dynamic aromatic esters find applications in commercialized thermoset formulations, all-aromatic esters have found limited use so far in the design of covalent adaptable networks (CAN) as a result of their high glass transition temperature (Tg) and specific curing process. Here, a strategy to include partly aromatic esters as dynamic cross-links inside low Tg (-40 degrees C) thermosetting formulations, using aliphatic esters derived from para-hydroxybenzoic acid, which serves as a highly activated phenol or as a reactive "phenylogous anhydride" is reported. A small molecule study shows that the activated phenyl ester bonds can readily exchange with free phenol moieties at 200 degrees C under catalyst-free conditions, while the addition of a catalyst allows for a faster exchange. Robust and hydrophobic polymer networks are conveniently prepared via rapid thiol-ene UV-curing of unsaturated phenol esters. The obtained networks show high thermal stability (350 degrees C), fast processability, good water resistance, and low creep up to 120 degrees C, thus showing good promise as a platform for CAN.Aromatic esters are amongst the oldest known chemical motifs that allow for thermal (re)processing of thermosetting polymers. Moreover, phenyl esters are generally known as activated esters that do not require a catalyst to undergo acyl transfer reactions. Even though dynamic aromatic esters find applications in commercialized thermoset formulations, all-aromatic esters have found limited use so far in the design of covalent adaptable networks (CAN) as a result of their high glass transition temperature (Tg) and specific curing process. Here, a strategy to include partly aromatic esters as dynamic cross-links inside low Tg (-40 degrees C) thermosetting formulations, using aliphatic esters derived from para-hydroxybenzoic acid, which serves as a highly activated phenol or as a reactive "phenylogous anhydride" is reported. A small molecule study shows that the activated phenyl ester bonds can readily exchange with free phenol moieties at 200 degrees C under catalyst-free conditions, while the addition of a catalyst allows for a faster exchange. Robust and hydrophobic polymer networks are conveniently prepared via rapid thiol-ene UV-curing of unsaturated phenol esters. The obtained networks show high thermal stability (350 degrees C), fast processability, good water resistance, and low creep up to 120 degrees C, thus showing good promise as a platform for CAN.A
