Innovative Insights into Water-Oxidation Mechanism: Investigating Birnessite's Reaction with Cerium(IV) Ammonium Nitrate.

Developing Mn-based water-oxidation reaction (WOR) catalysts is key for renewable energy storage, utilizing Mn's abundance, cost-effectiveness, and natural role. Cerium(IV) ammonium nitrate (CAN) has been widely utilized as a sacrificial oxidant in the exploration of WOR catalysts. In this study, advanced techniques, such as X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and in situ electron paramagnetic resonance (EPR), to delve into the WOR facilitated by CAN and birnessite were employed. XANES analysis has demonstrated that the average oxidation states (AOSs) of Mn in birnessite, a birnessite/CAN mixture, and in the birnessite/CAN mixture postwater addition are 3.7, 3.8, and 3.9, respectively. In situ Raman spectroscopy performed in the presence of birnessite and CAN revealed a distinct peak at 784 cm-1, which is attributed to Mn(IV)═O. A shift of this peak to 769 cm-1 in H218O confirms its association with Mn(IV)═O. No change in this peak was observed in D2O, further supporting the notion that it is linked to Mn(IV)═O rather than Mn-OH (D). Furthermore, EPR spectroscopy shows the presence of Mn(IV). It is suggested that the WOR mechanism initiates with the oxidation of birnessite by CAN, which enhances the concentration of Mn(IV) sites in the birnessite structure. Under acidic conditions, birnessite, enriched in Mn(IV), facilitates oxygen evolution and subsequently transitions into a form with reduced Mn(IV) levels. This process highlights the critical function of the Mn (hydr)oxide structure, similar to its role in the water-oxidizing complex of Photosystem II, where it serves as charge storage for oxidizing equivalents from CAN, paving the way for a four-electron reaction that drives the WOR.

Exploring an Electrochemical Route for Water-Enhanced Oxygenation Reactions Utilizing Nickel Molecular Structures: A Case Study.

Recently, Ni molecular catalysis has been extensively applied in oxygenation reactions. This work is underpinned by the characterization techniques and the discovered instability of the Ni-bipyridine/phenanthroline system, which results in Ni (hydr)oxide production under oxidative conditions. The practical applications of this mechanism by employing a prepared Ni (hydr)oxide-based electrode specifically in the oxygenation of sulfides, achieving noteworthy yields in contrast to noncatalyst control experiments, are explored. Thus, a Ni (hydr)oxide-based material is proposed as a candidate for the true catalyst for sulfide oxidation in the presence of the Ni-bipyridine/phenanthroline system. The findings of this study are expected to stimulate discussion and encourage new viewpoints within the chemical community regarding the potential applications and mechanisms of molecular catalysts in oxidation reactions.

Revolutionizing medicine: Molecularly imprinted polymers as precision tools in cancer diagnosis and antibiotic detection.

Molecularly imprinted polymers (MIPs) are pivotal in medicine, mimicking biological receptors with enhanced specificity and affinity. Comprising templates, functional monomers, and cross-linkers, MIPs form stable three-dimensional polymer networks. Synthetic templates like glycan and aptamers improve efficiency, guiding the molecular imprinting process. Cross-linking determines MIPs' morphology and mechanical stability, with printable hydrogels offering biocompatibility and customizable properties, mimicking native extracellular matrix (ECM) microenvironments. Their versatility finds applications in tissue engineering, soft robotics, regenerative medicine, and wastewater treatment. In cancer research, MIPs excel in both detection and therapy. MIP-based detection systems exhibit superior sensitivity and selectivity for cancer biomarkers. They target nucleic acids, proteins, and exosomes, providing stability, sensitivity, and adaptability. In therapy, MIPs offer solutions to challenges like multidrug resistance, excelling in drug delivery, photodynamic therapy, photothermal therapy, and biological activity regulation. In microbiology, MIPs serve as adsorbents in solid-phase extraction (SPE), efficiently separating and enriching antibiotics during sample preparation. They contribute to bacterial identification, selectively capturing specific strains or species. MIPs aid in detecting antibiotic residues using fluorescent nanostructures and developing sensors for sulfadiazine detection in food samples. In summary, MIPs play a pivotal role in advancing medical technologies with enhanced sensitivity, selectivity, and versatility. Applications range from biomarker detection to innovative cancer therapies, making MIPs indispensable for the accurate determination and monitoring of diverse biological and environmental samples.

Lifetime prevalence, comorbidities, and Sociodemographic predictors of post-traumatic stress disorder (PTSD): the National Epidemiology of Iranian Children and adolescents Psychiatric disorders (IRCAP).

OBJECTIVE: The aims of this study were to (a) evaluate the lifetime prevalence of post-traumatic stress disorder (PTSD) according to sociodemographic characteristics, (b) determine sociodemographic factors associated with PTSD, (c) estimate the lifetime prevalence rates of comorbidities by age and gender, and (d) assess the proportion of traumatic events in the non-PTSD sample and the PTSD sample, according to gender. METHODS: The data used for the present study were obtained from the IRCAP study which was a cross-sectional, community-based study on 29,250 children and adolescents aged 6-18 years from all provinces of Iran, which was done using multistage cluster sampling. Trained psychologists conducted diagnostic interviews with parents, children, and adolescents using the Persian version of the Kiddie Schedule for Affective Disorders and Schizophrenia for School-Age Children-Present and Lifetime Version (K-SADS-PL). RESULTS: In this study, the prevalence of PTSD across the sample population was 0.6% (95% CI, 0.5-0.7%). Higher rates of PTSD were observed among girls (0.7%, CI 0.5-0.8%), adolescents aged 15-18 years (0.8%, CI 0.6-1.0%), and participants who had unemployed (1.5%, CI 0.8-2.8%), or farmer fathers (1.1%, CI 0.5-2.5%). Of the participants with PTSD, 65.1% met the criteria for at least one other psychiatric disorder. PTSD had a high rate of comorbidity with oppositional defiant disorder (22.9%, CI 17.5-29.4%), generalized anxiety disorder (20.8%, CI 15.7-27.1%), separation anxiety disorder (20.3%, CI 15.2-26.6%), and major depressive disorder (19.8%, CI 14.8-26.0%). We found 9.5% of non-PTSD sample experienced at least one traumatic event. Witness to domestic violence was the most common traumatic event experienced by 32.8% of PTSD sample. CONCLUSION: Our results in the prevalence, comorbidities, and sociodemographic factors associated with PTSD supported findings of previous studies that used a structured diagnostic interview. It is recommended to use purposive sampling and to investigate comorbidities of PTSD and type of traumatic events in a large clinical population.

Trends and progress in application of cobalt-based materials in catalytic, electrocatalytic, photocatalytic, and photoelectrocatalytic water splitting.

There has been a growing interest in water oxidation in recent two decades. Along with that, remarkable discovery of formation of a mysterious catalyst layer upon application of an anodic potential of 1.13 V vs. standard hydrogen electrode (SHE) to an inert indium tin oxide electrode immersed in phosphate buffer containing Co(II) ions by Nocera et.al, has greatly attracted researchers interest. These researches have oriented in two directions; one focuses on obtaining better understanding of the reported mysterious catalyst layer, further modification, and improved performance, and the second approach is about designing coordination complexes of cobalt and investigating their properties toward the application in water splitting. Although there have been critical debates on true catalysts that are responsible for water oxidation in homogeneous systems of coordination complexes of cobalt, and the case is not totally closed, in this short review, our focus will be mainly on recent major progress and developments in the design and the application of cobalt oxide-based materials in catalytic, electrocatalytic, photocatalytic, and photoelectrocatalytic water oxidation reaction, which have been reported since pioneering report of Nocera in 2008 (Kanan Matthew and Nocera Daniel in Science 321:1072-1075, 2008).

Social Capital of Parents of Children and Adolescents and Its Relation to Psychiatric Disorders; A Population-Based Study.

Social capital is a complex concept that is considered an effective factor in the development of societies. Considering the importance of burdens of psychiatric disorders in Iran, we studied the relationship between various dimensions of social capital of parents of children and adolescents and psychiatric disorders among them. In this cross-sectional study, 18,940 parents of children and adolescents aged 6 to 18 years old were randomly selected from all provinces of Iran and were evaluated by the Millon clinical multiaxial inventory-III (MCMI-III) and a modified version of Nahapiet and Ghoshal questionnaire. MCMI-III was designed as a self-report tool for investigating psychiatric clinical disorders and personality traits in the general population. Modified Nahapiet and ghoshal questionnaire has 20 items and measures four components of social capital included trust, values, communication, and collaboration. Validity and reliability of both questionnaires have been approved in Iran. In the regression model, the relationship between social capital components and clinical and sever clinical syndromes, in the form of regression weight and standard weight for trust was - 0.558 and - 0.062 with p value less than 0.0001, and for values was - 0.466 and - 0.057, respectively, with p value less than 0.0001. There was a reverse correlation between social capital components of parents of children and adolescents and psychiatric disorders in Iran. In regression statistical models, the two components of values and trust were negative predictors of psychiatric disorders. Considering the high prevalence of psychiatric disorders in Iran, it seems that the strengthening of cognitive and structural aspects of social capital of parents of children and adolescents is one of the effective factors in reducing the prevalence of these disorders among them.

The Relationship of Parental Personality Disorders with Offspring Eating Disorders at Childhood and Adolescence Age.

This study aimed to investigate parents' PDs that could be associated with children and adolescents' EDs. We studied association of parental PDs with offspring EDs in age group 6-18 years in a nationally representative sample of Iranians with 27,111 children and adolescents and their parents. We used a multistage random cluster sampling method. We used Millon Clinical Multiaxial Inventory-Third Edition and Persian present and lifetime version of Kiddie Schedule for Affective Disorders and Schizophrenia to measure parental PDs and children and adolescents' EDs, respectively. We used descriptive statistics and binary logistic regression analysis methods to analyze the data. Maternal but not paternal PDs were significantly associated with EDs in offspring. Maternal antisocial, borderline, schizoid, histrionic, and compulsive PDs were significantly associated with EDs in offspring by 32.06, 4.66, 4.32, 3.15, and 1.71 odd ratios, respectively. Of EDs in offspring, anorexia nervosa and binge ED were significantly associated with maternal PDs.

Lifetime Prevalence, Predictors and Comorbidities of Tic Disorders: A Population-Based Survey of Children and Adolescents in Iran.

In this population-based survey, we have evaluated the lifetime prevalence of tic disorders and related sociodemographic factors and comorbidities of them. The data obtained from face-to-face interviews with 29,885 children and adolescents aged 6-18 years. We used the multistage cluster sampling method and a cross-sectional design. Tic disorders and other psychiatric disorders were assessed using the Persian version of the Kiddie Schedule for Affective Disorders and Schizophrenia-Present and Lifetime Version (K-SADS-PL). The lifetime prevalence of tic disorders was 1.5% (95% CI (1.3-1.7%)). The highest prevalence was in the age range of 15-18 years old with 1.9% (95% CI (1.6-2.3%)).57.7% (95% CI 51.8-63.3%) of patients with tic disorders had comorbidity with other psychiatric disorders. Increasing the prevalence of tic disorder with increasing age among Iranian children and adolescents, emphasizes the need to pay more attention to use of pharmacological and non-pharmacological treatments and increase education to families in this regard.

Operando tracking of oxidation-state changes by coupling electrochemistry with time-resolved X-ray absorption spectroscopy demonstrated for water oxidation by a cobalt-based catalyst film.

Transition metal oxides are promising electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), which is critical in electrochemical production of non-fossil fuels. The involvement of oxidation state changes of the metal in OER electrocatalysis is increasingly recognized in the literature. Tracing these oxidation states under operation conditions could provide relevant information for performance optimization and development of durable catalysts, but further methodical developments are needed. Here, we propose a strategy to use single-energy X-ray absorption spectroscopy for monitoring metal oxidation-state changes during OER operation with millisecond time resolution. The procedure to obtain time-resolved oxidation state values, using two calibration curves, is explained in detail. We demonstrate the significance of this approach as well as possible sources of data misinterpretation. We conclude that the combination of X-ray absorption spectroscopy with electrochemical techniques allows us to investigate the kinetics of redox transitions and to distinguish the catalytic current from the redox current. Tracking of the oxidation state changes of Co ions in electrodeposited oxide films during cyclic voltammetry in neutral pH electrolyte serves as a proof of principle.

Resveratrol adjunct to methylphenidate improves symptoms of attention-deficit/hyperactivity disorder: a randomized, double-blinded, placebo-controlled clinical trial.

Current pharmacological approaches have failed to provide complete remission for patients with Attention-Deficit/Hyperactivity Disorder (ADHD). This study aimed to evaluate the efficacy and tolerability of resveratrol (that have been shown to have antioxidative, anti-inflammatory, and anti-apoptotic effects) as an adjunct to methylphenidate in pharmacologic treatment of ADHD. This 8-week, double-blinded, placebo-controlled trial randomized 66 participants to receive either 500 mg/day resveratrol or matched placebo in addition to methylphenidate. ADHD symptoms were evaluated in the patients using the Parent and Teacher versions of ADHD-Rating Scale (ADHD-RS) at three measurement points with time intervals of 4 weeks. Furthermore, the tolerability of the treatment strategies was systematically compared. Repeated measures analysis demonstrated a significant effect for time-treatment interaction on all three subscales of the Parent ADHD-RS during the trial period (total: p = 0.015; inattention: p = 0.032; hyperactivity/impulsivity: p = 0.036). Nevertheless, the effect for time-treatment interaction was not significant for the Teacher version of ADHD-RS (total: F = 0.81, df = 1.33, p = 0.401; inattention: F = 0.57, df = 1.37, p = 0.507; hyperactivity/impulsivity: F = 0.65, df = 1.34, p = 0.466). The frequencies of complications in the treatment groups were similar. Resveratrol administration for a duration of 8 weeks improved characteristic symptoms in patients with ADHD according to their parents. Further investigations containing larger sample sizes, longer supplementation periods, and dose-response evaluations are required to replicate these findings in ADHD children more confidently.