Borylated Subphthalocyanines: Versatile Precursors for the Preparation of Functional Bowl-Shaped Aromatics

The peripheral borylation of porphyrinoids has become a key step to prepare advanced functional materials. This study reports the synthesis, electronic properties, and reactivity of borylated subphthalocyanines. These compounds, which are prepared by Suzuki–Miyaura borylation in excellent yields, are easily purified, display a great stability, and serve as powerful starting materials for the post-functionalization of SubPcs via cross-coupling reactions. Remarkably, this novel approach is more efficient than the methodologies already described and enables the preparation of exotic systems, such as SubPc dimeric species linked by C−C bonds, which are not accessible so far and present promising properties for optoelectronic devicesWe gratefully acknowledge financial support from MICINN (PID2020-116490GB-I00 and TED2021-131255B-C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“MATERIALES DISRUPTIVOS BIDIMENSIONALES (2D)” (MAD2D-CM)-MRR MATERIALES AVANZADOS], and the European Union through the Next Generation EU funds). IMDEA Nanociencia acknowledges support from the Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. Fellowshi

Modulating the electron transporting properties of Subphthalocyanines for inverted perovskite solar cells

The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of p-i-n PSCs. Specifically, ETMs based on three SubPcs (with either six or twelve peripheral fluorine and chlorine atoms) have been incorporated into PSCs with the perovskite layer deposited by solution processing (CsFAMAPbIBr). The device performance and morphology of these devices are deeply analyzed using several techniques, and the interfacial effects induced by the SubPcs are studied using photoluminescence and TR-PL. It is observed that the device stability is significantly improved upon insertion the SubPc layer. Moreover, the impact of the SubPc layer-thickness is assessed. Thus, a maximum power conversion efficiency of 13.6% was achieved with the champion devic

Anthracene-Fused Oligo-BODIPYs: a new class of π-extended NIR-absorbing materials

Large π-conjugated systems are key in the area of molecular materials. Herein, we prepare via AuI - catalyzed cyclization a series of fully π-conjugated anthracene-fused oligo-BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by means of Density Functional Theory (DFT) calculations. Depending on the size and shape of the π-conjugated skeleton, unique features—such as face-to-face supramolecular organization, NIR absorption and fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features render them valuable for technological applicationsments We gratefully acknowledge financial support from the Spanish MICINN through Projects PID2020-116490GB-I00 (Porphyrinoids) and TED2021-131255B-C43 (PERSOLAR). We also thank financial support to the Comunidad de Madrid (MAD2D-CM) and MICINN through project “Materiales disruptivos bidimensionales (2D)” within the Plan de recuperación, transformación y resiliencia (Materiales avanzados). IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. fellowship. European Commission under the Marie Sklodowska-Curie Action Cofund 2015 (EU project 713366-InterTalentum) is acknowledged for the support for G.D.S. Generous allocation of computational time from the Centro de Computación Científica UAM is gratefully acknowledged. Work in Erlangen was supported by the Deutsche Forschungsgemeinschaft (DFG) through SFB 953 project B10 and the Bavarian Collaborative Research Project “Solar Technologies go Hybrid” (SolTech

Supramolecular subphthalocyanine cage as catalytic container for the functionalization of fullerenes in water

Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo–organic Pd(II)-subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C60, we have prepared a water-soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C60, namely, Diels–Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes coencapsulation of insoluble C60 and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions. The lower stability of the host: guest complex with the resulting C60 cycloadduct facilitates its displacement by pristine C60, which grants catalytic turnover. Moreover, bis-addition compounds are regioselectively formed inside the cage when using excess anthracenements Financial support from the Spanish MCIN/AEI/10.13039/ 501100011033 (PID2020-116490GB-I00, PID2020- 115801RB-C21, TED2021-131255B-C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados], and the European Union through the Next Generation EU funds is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). S.K. acknowledges MSCA grant (101028059), and J.L. acknowledges MECD, Spain, for a F.P.U. fellowshi

Controlling Electronic Events Through Rational Structural Design in Subphthalocyanine–Corrole Dyads: Synthesis, Characterization, and Photophysical Properties

Porphyrinoids are considered perfect candidates for their incorporation into electron donor–acceptor (D–A) arrays due to their remarkable optoelectronic properties and low reorganization energies. For the first time, a series of subphthalocyanine (SubPc) and corrole (Cor) were covalently connected through a short-range linkage. SubPc axial substitution strategies were employed, which allowed the synthesis of the target molecules in decent yields. In this context, a qualitative synthetic approach was performed to reverse the expected direction of the different electronic events. Consequently, in-depth absorption, fluorescence, and electrochemical assays enabled the study of electronic and photophysical properties. Charge separation was observed in cases of electron-donating Cors, whereas a quantitative energy transfer from the Cor to the SubPc was detected in the case of electron accepting CorsThis work was supported by the Spanish MINECO, PID2020- 116490GB I00 (Porphyrinoids, T.T) and by the Italian PRIN MIUR “SUNSET“ 2017EKCS35_002. IMDEA-Nanociencia also acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686

A novel electron Donor-Acceptor Carbazole-Zn(II)Phthalocyanine – Perfluorinated Subphthalocyanine Conjugate: synthesis, characterization, and photoinduced electron-transfer

Porphyrinoids are considered perfect candidates for the preparation of model electron donor-acceptor (D-A) systems as they enable fast and efficient photoinduced electron transfer. Herein, we report on the synthesis and photophysical characterization of a ZnPc SubPc conjugate covalently connected through a short-range alkyne spacer. We designed and prepared the conjugate, which comprise, on the one hand, a perfluorinated SubPc with strong electron acceptor character and, on the other, a Pc peripherally functionalized with carbazoles with strong electron donor character. Photoinduced electron transfer events are in-depth analyzed by several techniques, including steady-state absorption, time-resolved emission and transient absorption measurements on different time scales. Our studies confirm a full charge separation occurring from a photoexcited charge transfer state68. Acknowledgements Financial support from Spanish MINECO (PID2020-116490GB I00, Porphyrinoids) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. fellowship. Kuwait Foundation for the Advancement of Science (KFAS) and the RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS 03/01, GS 01/03, GS 01/05) is acknowledged. Work in Erlangen was supported by the Deutsche Forschungsgemeinschaft (DFG) through SFB 953 project B10 and the Bavarian Collaborative Research Project “Solar Technologies go Hybrid" (SolTech

Non-Invasive Assessment of Pulmonary Vasculopathy

Right heart catheterization remains necessary for the diagnosis of pulmonary hypertension and, therefore, for the prognostic evaluation of patients with chronic heart failure. The non-invaSive Assessment of Pulmonary vasculoPathy in Heart failure (SAPPHIRE) study was designed to assess the feasibility and prognostic relevance of a non-invasive evaluation of the pulmonary artery vasculature in patients with heart failure and pulmonary hypertension. Patients will undergo a right heart catheterization, cardiac resonance imaging, and a pulmonary function test in order to identify structural and functional parameters allowing the identification of combined pre- and postcapillary pulmonary hypertension, and correlate these findings with the hemodynamic dataThis research was funded by European Regional Development Fund and the Carlos III Research Institute through a grant of the Health Strategy Action (PI17/01569).S

Composición corporal de universitarias que consumen desayunos hipercalóricos con relación a la cena

  Summary: Introduction: The suprachiasmatic nucleus (SCN) and the peripheral clocks regulate the circadian rhythmicity of the enzymatic activity and hormones involved in the energy balance and its alteration affects the increase in caloric reserve. Objective: To associate the hypercaloric intake of dinner with respect to the high-calorie breakfast with the body mass of university students. Material and methods: Cross-sectional and analytical study, final sample of 75 Clinical Nutrition university students, mean age 18±0.63 years. The following was obtained from each individual: weight, body mass index (BMI), percentage of body fat (%BF) and total muscle mass (%MMT), as well as dietary indicators- Statistics: Mean and standard deviation were calculated, in addition obtained the Student's T-test and simple ANOVA, with significance of p < 0.05. Results: The average caloric intake of the day: 1647 ± 385, with a high tendency of refined sugars and saturated fat. The average breakfast time was: 6:30-11:00, lunch: 12:00-15:00 and dinner. 7:00 p.m. to 10:00 p.m. 85% of university students with %BF > 28 and MMT < 34%, consumed 50±25% of total caloric intake at night compared to breakfast (15±30%), with a significant difference (p<0.05) regardless of the BMI. Conclusions: High-calorie dinners (based on refined sugars and saturated fat) were associated with excess GL and MMT depletion regardless of total caloric intake and BMI.Introducción: El núcleo supraquiasmático (NSQ) y los relojes periféricos regulan la ritmicidad circadiana de la actividad enzimática y hormonas involucradas en el balance energético y su alteración repercute en el aumento de la reserva calórica. Objetivo: Asociar la ingesta hipercalórica de la cena respecto al desayuno alto en calorías con la masa corporal de universitarias. Material y métodos: Estudio transversal y analítico, muestra final 75 universitarias de Nutrición Clínica, edad promedio 18±0.63 años. De cada individuo se obtuvo: peso, índice de masa corporal (IMC), porcentaje de grasa corporal (%GC) y de masa muscular total (%MMT), así como indicadores dietéticos- Estadística: Se calculó media y desviación estándar, además se obtuvo la Prueba T de Student y ANOVA simple, con significancia de p < 0.05. Resultados: La Ingesta calórica promedio del día: 1647± 385, con tendencia alta de azucares refinados y grasa saturada. El horario promedio del desayuno fue:  6:30‐11:00, comidas: 12:00‐15:00 y cenas. 19:00‐22: 00 horas. El 85% de las universitarias con %GC > 28 y MMT < 34%, consumían el 50±25% de la ingesta calórica total por la noche respecto al desayuno (15±30%) habiendo diferencia significativa (p<0.05) independientemente del IMC. Conclusiones: Las cenas altas en calóricas (a base de azúcares refinados y grasa saturada) se asociaron a exceso de GC y depleción de MMT independientemente de la ingesta calórica total y del IMC. &nbsp

Composición corporal de universitarias que consumen desayunos hipercalóricos con relación a la cena

Introducción: El núcleo supraquiasmático (NSQ) y los relojes periféricos regulan la ritmicidad circadiana de la actividad enzimática y hormonas involucradas en el balance energético y su alteración repercute en el aumento de la reserva calórica. Objetivo: Asociar la ingesta hipercalórica de la cena respecto al desayuno alto en calorías con la masa corporal de universitarias. Material y métodos: Estudio transversal y analítico, muestra final 75 universitarias de Nutrición Clínica, edad promedio 18±0.63 años. De cada individuo se obtuvo: peso, índice de masa corporal (IMC), porcentaje de grasa corporal (%GC) y de masa muscular total (%MMT), así como indicadores dietéticos- Estadística: Se calculó media y desviación estándar, además se obtuvo la Prueba T de Student y ANOVA simple, con significancia de p 28 y MMT < 34%, consumían el 50±25% de la ingesta calórica total por la noche respecto al desayuno (15±30%) habiendo diferencia significativa (p<0.05) independientemente del IMC. Conclusiones: Las cenas altas en calóricas (a base de azúcares refinados y grasa saturada) se asociaron a exceso de GC y depleción de MMT independientemente de la ingesta calórica total y del IMC.

Pulmonary vascular remodeling and prognosis in patients evaluated for heart transplantation: insights from the OCTOPUS-CHF study

[Abstract] Objective: In patients with advanced heart failure, the intravascular optical coherence tomography (OCT) of subsegmental pulmonary artery measurements is correlated with right heart catheterization parameters. Our aim was to study the prognostic value of pulmonary OCT, right heart catheterization data, and the echocardiographic estimation of pulmonary pressure in patients studied for elective heart transplants. Methods: This research is an observational, prospective, multicenter study involving 90 adults with a one-year follow-up. Results: A total of 10 patients (11.1%) died due to worsening heart failure before heart transplantation, 50 underwent a heart transplant (55.6%), and 9 died in the first year after the transplant. The patients with and without events (mortality or heart failure-induced hospitalization) had similar data regarding echocardiography, right heart catheterization, and pulmonary OCT (with a median estimated pulmonary artery systolic pressure of 42.0 mmHg, interquartile range (IQR) of 30.3-50.0 vs. 47.0 mmHg, IQR 34.6-59.5 and p = 0.79, median pulmonary vascular resistance of 2.2 Wood units, IQR 1.3-3.7 vs. 2.0 Wood units, IQR 1.4-3.2 and p = 0.99, and a median pulmonary artery wall thickness of 0.2 ± 0.5 mm vs. 0.2 ± 0.6 mm and p = 0.87). Conclusion: Pulmonary vascular remodeling (evaluated with echocardiography, right heart catheterization, and pulmonary OCT) was not associated with prognosis in a selected sample of adults evaluated for elective heart transplants. Pulmonary OCT is safe and feasible for the evaluation of these patients.Instituto de Salud Carlos III; PI18/00254European Regional Development Fund; CB16/11/0050