Development of an Innovative Lightweight Composite Material with Thermal Insulation Properties Based on Cardoon and Polyurethane.

The search for innovative and sustainable solutions to improve the energy efficiency of the construction industry has been a hot topic for researchers due to the tremendous impact of insulator materials in the thermal comfort of buildings. In the present work, an innovative lightweight composite material with thermal insulation properties was developed, for the first time, by using cardoon particles and polyurethane. The formulation of the composite material was optimized in terms of cardoon fraction and the polyol/isocyanate ratio, to achieve the best compromise between internal bond (IB) strength and thickness swelling (TS). The best performing composite was PU75-CP45, with 45 wt% of cardoon particles and 75% of isocyanate, achieving an IB of 0.41 MPa and a TS of 5.3%. Regarding insulation properties, the PU75-CP45 composite material exhibits a promising performance when compared to conventional construction industry materials by tuning its thickness. Additionally, the composite material presented very low emissions of volatile organic compounds and formaldehyde (bellow to legislation levels) and high resistance to biological degradation.

Synthesis of Vitamin B3 through a Heterogeneous Photocatalytic Approach Using Metal-Free Carbon Nitride-Based Catalysts.

Vitamin B3 (nicotinic acid, VB3) was synthesized through the photocatalytic oxidation of 3-pyridinemethanol (3PM) under visible-light-emitting diode (LED) irradiation using metal-free graphitic carbon nitride (GCN) - based materials. A bulk (GCN) material was prepared by a simple thermal treatment using dicyandiamide as the precursor. A post-thermal treatment under static air and nitrogen flow was employed to obtain the GCN-T and GCN-T-N materials, respectively. The conditions adopted during the post-treatment revealed differences in the resulting materials' morphological, electronic, and optical properties. The post-treated photocatalysts revealed an enhanced efficiency in the oxidation of 3PM into VB3, with the GCN-T-N photocatalyst being the best-performing material. The defective surface, reduced crystallinity, and superior photoabsorption of GCN-T-N account for this material's improved performance in the production of VB3. Nevertheless, the presence of nitrogen vacancies in the carbon nitride structure and, consequently, the creation of mid-gap states also accounts to its highly oxidative ability. The immobilization of GCN-T-N in sodium alginate hydrogel was revealed as a promising strategy to produce VB3, avoiding the need for the photocatalyst separation step. Concerning the mechanism of synthesis of VB3 through the photocatalytic oxidation of 3PM, it was possible to identify the presence of 3-pyridinecarboxaldehyde (3PC) as the intermediary product.

Aqueous solution photocatalytic synthesis of p-anisaldehyde by using graphite-like carbon nitride photocatalysts obtained via the hard-templating route.

Graphite-like carbon nitride (GCN)-based materials were developed via the hard-templating route, using dicyandiamide as the GCN precursor and silica templates. That resulted in urchin-like GCN (GCN-UL), 3D ordered macroporous GCN (GCN-OM) and mesoporous GCN (GCN-MP). The introduction of silica templates during GCN synthesis produced physical defects on its surface, as confirmed by SEM analysis, increasing their specific surface area. A high amount of nitrogen vacancies is present in modified catalysts (revealed by XPS measurements), which can be related to an increase in the reactive sites available to catalyse redox reactions. The textural and morphological modifications induced in GCN an enhanced light absorption capacity and reduced electron/hole recombination rate, contributing to its improved photocatalytic performance. In the photocatalytic conversion of p-anisyl alcohol to p-anisaldehyde in deoxygenated aqueous solutions under UV-LED irradiation, the GCN-UL was the best photocatalyst reaching 60% yield at 64% conversion for p-anisaldehyde production after 240 min of reaction. Under oxygenated conditions (air), the process efficiency was increased to 79% yield at 92% conversion only after 90 min reaction. The GCN-based photocatalyst kept its performance when using visible-LED radiation under air atmosphere. Trapping of photogenerated holes and radicals by selective scavengers showed that under deoxygenated conditions, holes played the primary role in the p-anisaldehyde synthesis. Under oxygenated conditions, the process is governed by the effect of reactive oxygen species, namely superoxide radicals, with a significant contribution from holes.

Efficient removal of parabens from real water matrices by a metal-free carbon nitride photocatalyst.

Metal-free graphite-like carbon nitride (GCN-500) was obtained by thermal post-treatment of bulk polymeric carbon nitride at 500 °C. The catalyst was thoroughly characterized by morphological, optical and textural analysis techniques. The efficiency of GCN-500 was evaluated under visible (λexc = 417 nm) LED excitation for the photocatalytic degradation of methyl-, ethyl- and propyl-paraben in different water matrices either isolated or in a mixture of the three compounds. The GCN-500 proved to be more efficient than the benchmark TiO2 P25, with complete conversion of the individual parabens within 20 min of irradiation, contrasting with 120 min needed for total degradation using TiO2. Experiments in the presence of selected scavengers confirmed the high importance of superoxide radicals in the photocatalytic oxidation of parabens using GCN-500. The effect of the nature of the aqueous matrix in the kinetics of the photocatalytic process was assessed using ultrapure, tap and river waters spiked with a mixture of the three parabens. Although still very efficient, the complexity of the real water samples turned the degradation process slower due to the presence of other components such as ions and dissolved organic matter. GCN-500 proved to be stable in a continuous-flow system using GCN-500 coated glass rings (GCN-500-GR) to remove MP, EP and PP from real water matrices.

Trial of Electrical Direct-Current Therapy versus Escitalopram for Depression.

BACKGROUND: We compared transcranial direct-current stimulation (tDCS) with a selective serotonin-reuptake inhibitor for the treatment of depression. METHODS: In a single-center, double-blind, noninferiority trial involving adults with unipolar depression, we randomly assigned patients to receive tDCS plus oral placebo, sham tDCS plus escitalopram, or sham tDCS plus oral placebo. The tDCS was administered in 30-minute, 2-mA prefrontal stimulation sessions for 15 consecutive weekdays, followed by 7 weekly treatments. Escitalopram was given at a dose of 10 mg per day for 3 weeks and 20 mg per day thereafter. The primary outcome measure was the change in the 17-item Hamilton Depression Rating Scale (HDRS-17) score (range, 0 to 52, with higher scores indicating more depression). Noninferiority of tDCS versus escitalopram was defined by a lower boundary of the confidence interval for the difference in the decreased score that was at least 50% of the difference in the scores with placebo versus escitalopram. RESULTS: A total of 245 patients underwent randomization, with 91 being assigned to escitalopram, 94 to tDCS, and 60 to placebo. In the intention-to-treat analysis, the mean (±SD) decrease in the score from baseline was 11.3±6.5 points in the escitalopram group, 9.0±7.1 points in the tDCS group, and 5.8±7.9 points in the placebo group. The lower boundary of the confidence interval for the difference in the decrease for tDCS versus escitalopram (difference, -2.3 points; 95% confidence interval [CI], -4.3 to -0.4; P=0.69) was lower than the noninferiority margin of -2.75 (50% of placebo minus escitalopram), so noninferiority could not be claimed. Escitalopram and tDCS were both superior to placebo (difference vs. placebo, 5.5 points [95% CI, 3.1 to 7.8; P<0.001] and 3.2 points [95% CI, 0.7 to 5.5; P=0.01], respectively). Patients receiving tDCS had higher rates of skin redness, tinnitus, and nervousness than did those in the other two groups, and new-onset mania developed in 2 patients in the tDCS group. Patients receiving escitalopram had more frequent sleepiness and obstipation than did those in the other two groups. CONCLUSIONS: In a single-center trial, tDCS for the treatment of depression did not show noninferiority to escitalopram over a 10-week period and was associated with more adverse events. (Funded by Fundação de Amparo à Pesquisa do Estado de São Paulo and others; ELECT-TDCS ClinicalTrials.gov number, NCT01894815 .).

Nonverbal behaviors are associated with increased vagal activity in major depressive disorder: Implications for the polyvagal theory.

BACKGROUND: Major depressive disorder (MDD) is associated with impairments in nonverbal behaviors (NVBs) and vagal activity. The polyvagal theory proposes that vagal activity regulates heart rate and NVBs by modulating a common anatomically and neurophysiologically discrete social engagement system. However, the association between these putative endophenotypes has not yet been explored. We hypothesize that in MDD, NVBs indicating positive affects and social interest and those indicating negative feelings and social disinterest could be associated with different patterns of vagal activity. METHODS: For this cross-sectional study we recruited 50 antidepressant-free participants with moderate-to-severe MDD. Vagal activity was indexed by heart rate variability (HRV) measures, and positive and negative nonverbal behaviors (NVBs) by a validated ethogram. Associations between NVBs and HRV were explored by bivariate analyses and multivariable models were adjusted by age, gender, depression severity, and self-reported positive and negative affects. RESULTS: HRV measures indicative of higher vagal activity were positively correlated with positive NVBs exhibited during the clinical interview. Conversely, NVBs related to negative affects, low energy and social disinterest were not associated with HRV. LIMITATIONS: Absence of a control group. CONCLUSIONS: The findings highlight that the examined depression endophenotypes (nonverbal behaviors and vagal activity) are related, shedding light on MDD pathophysiology in the context of the polyvagal theory.