Near-infrared absorption of fused core-modified expanded porphyrins for dye-sensitized solar cells.

Photophysical, photovoltaic, and charge transport properties of fused core-modified expanded porphyrins containing two pyrroles, one dithienothiophene (DTT) unit, and 1-4 thiophenes (1-4) were inspected by using density functional theory (DFT) and time-dependent DFT. Compounds 1-3 have been investigated experimentally before, but 4 is a theoretical proposal whose photophysical features match those extrapolated from 1 to 3. They exhibit absorption in the range of 700-970 nm for their Q bands and 500-645 nm for their Soret bands. The rise of thiophene rings placed in front of the DTT unit in the expanded porphyrin ring causes a bathochromic shift of the longest absorption wavelength, leading to near-infrared absorptions, which represent 49% of the solar energy. All the systems show a thermodynamically favorable process for the electron injection from the dye to TiO2 and adsorption on a finite TiO2 model. The electron regeneration of the dye is only thermodynamically feasible for the smallest expanded porphyrins 1 and 2 when I-/I3- electrolyte is used. The charge transport study shows that for voltages lower than 0.4 V, junctions featuring pentaphyrin 1 and octaphyrin 4 are more conductive than those containing hexaphyrin 2 or heptaphyrin 3. The results showed that the four fused core-modified expanded porphyrins investigated are potential dyes for applications in dye-sensitized solar cells, mainly pentaphyrin 1 and hexaphyrin 2. Moreover, increasing the number of thiophene rings in the macrocycle proved fruitful in favoring absorption in the near-infrared region, which is highly desired for dye-sensitized solar cells.

Awareness, Prevention, Detection, and Therapy Applications for Depression and Anxiety in Serious Games for Children and Adolescents: Systematic Review.

BACKGROUND: Depression and anxiety in children and adolescents are major health problems worldwide. In recent years, serious games research has advanced in the development of tools to address these mental health conditions. However, there has not been an extensive analysis of these games, their tendencies, and capacities. OBJECTIVE: This review aims to gather the most current serious games, published from 2015 to 2020, with a new approach focusing on their applications: awareness, prevention, detection, and therapy. The purpose is also to analyze the implementation, development, and evaluation of these tools to obtain trends, strengths, and weaknesses for future research lines. METHODS: The identification of the serious games through a literature search was conducted on the databases PubMed, Scopus, Wiley, Taylor and Francis, Springer, PsycINFO, PsycArticles, Web of Science, and Science Direct. The identified records were screened to include only the manuscripts meeting these criteria: a serious game for PC, smartphone, or virtual reality; developed by research teams; targeting only depression or anxiety or both; aiming specifically at children or adolescents. RESULTS: A total of 34 studies have been found that developed serious games for PC, smartphone, and virtual reality devices and tested them in children and adolescents. Most of the games address both conditions and are applied in prevention and therapy. Nevertheless, there is a trend that anxiety is targeted more in childhood and depression targeted more in adolescence. Regarding design, the game genres arcade minigames, adventure worlds, and social simulations are used, in this order. For implementation, these serious games usually require sessions of 1 hour and are most often played using a PC. Moreover, the common evaluation tools are normalized questionnaires that measure acquisition of skills or reduction of symptoms. Most studies collect and compare these data before and after the participants play. CONCLUSIONS: The results show that more awareness and detection games are needed, as well as games that mix the awareness, prevention, detection, and therapy applications. In addition, games for depression and anxiety should equally target all age ranges. For future research, the development and evaluation of serious games should be standardized, so the implementation of serious games as tools would advance. The games should always offer support while playing, in addition to collecting data on participant behavior during the game to better analyze their learning. Furthermore, there is an open line regarding the use of virtual reality for these games due to the capabilities offered by this technology.

Iron Complexes Anchored onto Magnetically Separable Graphene Oxide Sheets: An Excellent Catalyst for the Synthesis of Dihydroquinazoline-Based Compounds.

In this work, a green, sustainable, and efficient protocol for the syntheses of dihydroquinazoline derivatives is proposed. Initially, three Schiff base complexes of iron containing the ligand (2,2-dimethylpropane-1,3-diyl)bis(azanylylidene)bis(methanylylidene)bis(2,4-Xphenol), where X = Cl (complex 1)/Br (complex 2)/I (complex 3), were synthesized, fully characterized, and used in the desired syntheses. Complex 1 excelled as a catalyst, closely followed by complexes 2 and 3. DFT calculations helped in rationalizing the role of the halide substituent in the ligand backbone as a relevant factor in the catalytic superiority of complex 1 over complexes 2 and 3 for the synthesis of the dihydroquinazoline derivatives. Finally, to facilitate catalyst recoverability and reusability, complex 1 was immobilized on GO@Fe3O4@APTES (GO, graphene oxide; APTES, 3-aminopropyltriethoxysilane) to generate GO@Fe3O4@APTES@FeL1 (GOTESFe). GOTESFe was thoroughly characterized through scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy and efficiently used for the synthesis of dihydroquinazoline derivatives. GOTESFe could be magnetically recovered and reused up to five cycles without compromising its catalytic efficiency. Therefore, immobilization of the chosen iron complex onto magnetic GO sheets offers an extremely competent route in providing a blueprint of a readily recoverable, reusable, robust, and potent catalyst for the synthesis of dihydroquinazoline-based compounds.

Surfactant-Mediated Solubilization of Magnetically Separable Nanocatalysts for the Oxidation of Alcohols.

Cetrimonium bromide (CTAB)-coated water disperse magnetically separable nanocatalysts CTAB/Fe3O4@dopa@ML (M = Fe or Mn, L = cyclohexane-1,2-diylbis(azanylylidene)bis(methanylylidene)bis(2,4-diXphenol; X = Cl, Br, and I) have been synthesized using a simple synthetic strategy. This approach provides a new fruitful strategy to reduce the leaching of the active metal complex from the catalyst surface to the aqueous media. The synthesized catalysts have been found to be excellent for oxidation of alcohols in aqueous medium at room temperature. A probable catalytic pathway involving the generation of hydroperoxo intermediates has been assumed, and these intermediates have been characterized using density functional theory and several spectroscopic techniques. It is worthy of mention that the synthesized CTAB-coated magnetically separable nanocatalysts can be magnetically recovered from the aqueous reaction mixture after more than five cycles, which renders this approach as a sustainable and accessible one.

Torquoselective Mechanochemical Activation of the Staudinger Reaction To Form ß-Lactams.

The Staudinger reaction yielding ß-lactam rings via [2 + 2] cycloaddition is a torquoselective reaction where the stereochemistry of the product can be steered by suitable substituents. Although the mechanochemical ring-opening of ß-lactams has been investigated recently, the force-assisted synthesis of this important functional four-ring motif remains unexplored. As it will be computationally demonstrated, mechanochemical activation greatly reduces the barrier of the rate-limiting ring-closure step while, at the same time, preserves its torquoselectivity. This finding strongly suggests that strained four-membered rings can be readily incorporated in chain molecules using sonication techniques that greatly enhance reactivity while conserving selectivity.

Prescripción potencialmente inapropiada en mayores de 65 años en un centro de salud de atención primaria / Potentially inappropriate prescribing in patients over 65 years-old in a primary care health centre

OBJETIVO: Identificar las prescripciones potencialmente inapropiadas (PPI) y omisiones de prescripción (OP) mediante los criterios STOPP/START y factores asociados en pacientes ≥ 65 años en un centro de salud de atención primaria. DISEÑO: Estudio descriptivo-transversal. Emplazamiento: Centro de Salud Monóvar, atención primaria. Período de estudio: 6 meses. Participantes: Doscientos cuarenta y siete sujetos identificados mediante aleatorización simple. CRITERIOS DE INCLUSIÓN: individuos de ≥ 65 años que acudieron a la consulta médica ≥ 2 veces en el período de estudio. Exclusión: situación terminal y pertenecientes a residencias. MÉTODOS: Recogida de datos a través de historias clínicas electrónicas. Se evaluaron: criterios STOPP/START, edad, sexo, comorbilidad y número de fármacos crónicos. Variables principales: PPI y OP identificadas por los criterios STOPP y START, respectivamente. RESULTADOS: Se identificaron 81 pacientes (32,8%) con PPI; la más frecuente correspondió a benzodiacepinas de vida media larga en 17 (6,9%). Se encontraron 73 (29,6%) con OP; la más frecuente fue la ausencia de estatinas en pacientes con diabetes mellitus, y uno o más factores mayores de riesgo cardiovascular en 21 (8,5%). Asociación de PPI con polimedicación ajustado por edad y sexo (OR: 2,02; IC 95%: 1,15-3,53; p = 0,014) y asociación de OP con polimedicación ajustado por edad y sexo (OR: 2,37; IC 95%: 1,32-4,24; p = 0,004). CONCLUSIONES: La prescripción inapropiada en mayores es frecuente y está relacionada con el uso de benzodiacepinas de vida media larga. Existen diabéticos con factores de riesgo cardiovascular en los que se omiten las estatinas. La polimedicación juega un papel importante en las PPI y OP

OBJECTIVE: To identify potentially inappropriate prescriptions (PPI) and prescribing omissions(OP) by means of the STOPP/START criteria, as well as associated factors in≥65 year old patients in a Primary Care setting in Spain. Study DESIGN: A cross-sectional, descriptive study. Setting: Centro de Salud Monóvar, Primary Health Care. Study period: 6 months. Patients Random sample: 247 patients. Eligibility criteria:≥65 years patients who attended an urban Primary Care clinic 2 or more times were studied. Terminally ill and nursing home residents were excluded. METHODS: Data were collected from electronic clinical records. STOPP and START criteria were evaluated in each clinical record, including age, sex, co-morbidity, number of chronic prescriptions. Main outcomes: PPI and OP identified by STOPP and START criteria, respectively. RESULTS: A total of 81 patients (32.8%) had PPI, with the most common being the long-term use of long-acting benzodiazepines in 17 (6.9%). OP was found in 73 (29.6%) patients, with the most common being the omission of statins in patients diagnosed with diabetes mellitus and/or one or more major cardiovascular risk factors in 21 (8.5%). After adjustment by gender and age, correlations were found between PPI and multiple medication (OR: 2.02; 95% CI: 1.15-3.53;P = .014), and OP and polypharmacy (OR: 2.37; 95% CI: 1.32-4.24; P = 0.004). CONCLUSIONS: Inappropriate prescribing in older people is frequent, and is mainly associated with long-acting benzodiazepines. There are diabetic patients who do not have statins prescribed. Multiple medication is associated with PPI and OP

[Potentially inappropriate prescribing in patients over 65 years-old in a primary care health centre]. / Prescripción potencialmente inapropiada en mayores de 65 años en un centro de salud de atención primaria.

OBJECTIVE: To identify potentially inappropriate prescriptions (PPI) and prescribing omissions (OP) by means of the STOPP/START criteria, as well as associated factors in ≥65year old patients in a Primary Care setting in Spain. STUDY DESIGN: A cross-sectional, descriptive study. SETTING: Centro de Salud Monóvar, Primary Health Care. STUDY PERIOD: 6months. PATIENTS RANDOM SAMPLE: 247patients. ELIGIBILITY CRITERIA: ≥65years patients who attended an urban Primary Care clinic 2 or more times were studied. Terminally ill and nursing home residents were excluded. METHODS: Data were collected from electronic clinical records. STOPP and START criteria were evaluated in each clinical record, including age, sex, co-morbidity, number of chronic prescriptions. MAIN OUTCOMES: PPI and OP identified by STOPP and START criteria, respectively. RESULTS: A total of 81 patients (32.8%) had PPI, with the most common being the long-term use of long-acting benzodiazepines in 17 (6.9%). OP was found in 73 (29.6%) patients, with the most common being the omission of statins in patients diagnosed with diabetes mellitus and/or one or more major cardiovascular risk factors in 21 (8.5%). After adjustment by gender and age, correlations were found between PPI and multiple medication (OR: 2.02; 95%CI: 1.15-3.53; P=.014), and OP and polypharmacy (OR: 2.37; 95%CI: 1.32-4.24; P=0.004). CONCLUSIONS: Inappropriate prescribing in older people is frequent, and is mainly associated with long-acting benzodiazepines. There are diabetic patients who do not have statins prescribed. Multiple medication is associated with PPI and OP.

Theoretical study of the oxidation of histidine by singlet oxygen.

Herein we present a theoretical study of the reaction of singlet oxygen with histidine performed both in the gas phase and in aqueous solution. The potential energy surface of the reactive system was explored at the B3LYP/cc-pVTZ level of theory and the electronic energies were refined by means of single-point CCSD(T)/cc-pVTZ(-f) calculations. Solvent effects were taken into account by using a solvent continuum model (COSMO) and by adding explicit water molecules. The results show that the first step in the reaction mechanism corresponds to a nearly symmetric Diels-Alder addition of the singlet oxygen molecule to the imidazole ring to yield an endoperoxide, in agreement with experimental evidence. The intermediate formed can evolve along two different reaction paths leading to two isomeric hydroperoxides and, eventually, to open-chain or internally cyclised oxidised products. Water plays a significant role in stabilising the reaction structures by solvation and by acting as a bifunctional catalyst in the elimination/addition reaction steps. Our results explain why substituents at the N1-imidazole ring can hamper the evolution of the initial endoperoxide and result in Gibbs energy barriers in solution similar to those experimentally measured and suggest a likely route to the formation of peptide aggregates during the oxidation of histidine by singlet molecular oxygen.

Molecular magnetic properties of heteroporphyrins: a theoretical analysis.

B3LYP/6-31G(d) optimization of porphyrin, tetraphenylporphyrin and their 21,23-diheteroatom substituted derivatives with O, S, and Se heteroatoms was performed. A planar macrocycle was found in all cases except 21,23-dioxatetraphenylporphyrin which presents only slight deviations from planarity. A Bader analysis uncovers the presence of S-S and Se-Se interactions in the four corresponding heteroporphyrins, which appreciably distort the original unsubstituted macrocycles. In the minimum energy structures of heterotetraphenylporphyrins the four meso phenyl groups slant alternatively to right or left so that the two pairs of opposite phenyls present a staggered conformation. The pi current induced by a perpendicular magnetic field in porphyrin bifurcates across both types of pyrrole subunits but the presence of O, S and Se heteroatoms in 21,23-diheteroporphyrins causes a diminution of the current density through the inner section of the two heterorings and, consequently, the current path goes then through the outer section of these rings. The NICS values at the ring critical points of the heterorings are much larger (in absolute value) than those at the pyrrole ring critical points but appreciably smaller than that at the ring critical point of a pyrrole molecule. In agreement with experimental data the (1)H NMR present appreciable downfield shifts for the beta H atoms of the heterorings in the 21,23-heterosubstituted molecules.

Formation of trichlorinated dibenzo-p-dioxins from 2,4-dichlorophenol and 2,4,5-trichlorophenolate: a theoretical study.

The reaction of the 2,4,5-trichlorophenolate anion with 2,4-dichlorophenol to afford trichlorinated dibenzo-p-dioxins (T3CDDs) is investigated at the B3LYP/6-31+G(d) and B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d)+ZPVE(B3LYP/6-31+G(d)) levels of theory. The first stage of the process corresponds to the formation of a predioxin, which can evolve through four different routes. Two of them lead directly to the products 2,3,7-T3CDD and 1,3,8-T3CDD, and the other two afford different predioxin-type intermediates, which in turn can evolve through all or some of the four routes to give new predioxins or T3CDD. Consequently, the theoretical results obtained show plainly the complex chemistry implied in the formation of dioxins from chlorophenols via anionic mechanisms by disclosing all the critical structures through which the system evolves, thus allowing assessment of the viability of the different mechanistic routes and the accessible products. The statistical thermodynamics treatment at 1 atm and 298.15, 600, 900, and 1200 K indicates that at higher temperatures, the Gibbs energy barrier for the formation of the initial predioxin is clearly the rate-determining step for the whole process, but at lower temperatures the Gibbs energy barrier for this step is similar to those for its evolution into 2,3,7-T3CDD. This result is in contrast with previous proposals that the closure of the central ring is the rate-limiting step. Finally, according to our results the rate constant for the formation of polychlorinated dibenzo-p-dioxins increases with the temperature, in agreement with the experimental observation that the conversion of trichlorophenols increases when going from 600 to 900 K in the gas phase in the absence of catalysts, and with DFT molecular dynamics results.