Impact of oxidation-induced ordering on the electrical and mechanical properties of a polythiophene co-processed with bistriflimidic acid

The interplay between the nanostructure of a doped polythiophene with oligoether side chains and its electrical as well as mechanical properties is investigated. The degree of order of the polymer is found to strongly vary when co-processed with bistriflimidic acid (H-TFSI). The neat polythiophene as well as strongly oxidized material are largely disordered while intermediate concentrations of H-TFSI give rise to a high degree of π-stacking. The structural disorder of strongly oxidized material correlates with a decrease in the kinetic fragility with H-TFSI concentration, suggesting that positive interactions between TFSI anions and the polymer reduce the ability to crystallize. The electrical conductivity as well as the Young\u27s modulus first increase upon the addition of 4-10 mol% of H-TFSI, while the loss of π-stacking observed for strongly oxidized material more significantly affects the latter. As a result, material comprising 25 mol% H-TFSI displays an electrical conductivity of 58 S cm−1 but features a relatively low Young\u27s modulus of only 80 MPa. Decoupling of the electrical and mechanical properties of doped conjugated polymers may allow the design of soft conductors that are in high demand for wearable electronics and bioelectronics

Novel inhibitors of human glucose-6-phosphate dehydrogenase (HsG6PD) affect the activity and stability of the protein

Background: The pentose phosphate pathway (PPP) has received significant attention because of the role of NADPH and R-5-P in the maintenance of cancer cells, which are necessary for the synthesis of fatty acids and contribute to uncontrollable proliferation. The HsG6PD enzyme is the rate-limiting step in the oxidative branch of the PPP, leading to an increase in the expression levels in tumor cells; therefore, the protein has been proposed as a target for the development of new molecules for use in cancer. Methods: Through in vitro studies, we assayed the effects of 55 chemical compounds against recombinant HsG6PD. Here, we present the kinetic characterization of four new HsG6PD inhibitors as well as their functional and structural effects on the protein. Furthermore, molecular docking was performed to determine the interaction of the best hits with HsG6PD. Results: Four compounds, JMM-2, CCM-4, CNZ-3, and CNZ-7, were capable of reducing HsG6PD activity and showed noncompetitive and uncompetitive inhibition. Moreover, experiments using circular dichroism and fluorescence spectroscopy showed that the molecules affect the structure (secondary and tertiary) of the protein as well as its thermal stability. Computational docking analysis revealed that the interaction of the compounds with the protein does not occur at the active site. Conclusions: We identified two new compounds (CNZ-3 and JMM-2) capable of inhibiting HsG6PD that, compared to other previously known HsG6PD inhibitors, showed different mechanisms of inhibition. General significance: Screening of new inhibitors for HsG6PD with a future pharmacological approach for the study and treatment of cancer

Mortality and pulmonary complications in patients undergoing surgery with perioperative SARS-CoV-2 infection: an international cohort study

Background: The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods: This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings: This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (74·0%) had emergency surgery and 280 (24·8%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (26·1%) patients. 30-day mortality was 23·8% (268 of 1128). Pulmonary complications occurred in 577 (51·2%) of 1128 patients; 30-day mortality in these patients was 38·0% (219 of 577), accounting for 81·7% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 1·75 [95% CI 1·28–2·40], p\textless0·0001), age 70 years or older versus younger than 70 years (2·30 [1·65–3·22], p\textless0·0001), American Society of Anesthesiologists grades 3–5 versus grades 1–2 (2·35 [1·57–3·53], p\textless0·0001), malignant versus benign or obstetric diagnosis (1·55 [1·01–2·39], p=0·046), emergency versus elective surgery (1·67 [1·06–2·63], p=0·026), and major versus minor surgery (1·52 [1·01–2·31], p=0·047). Interpretation: Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding: National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Design and baseline characteristics of the finerenone in reducing cardiovascular mortality and morbidity in diabetic kidney disease trial

Background: Among people with diabetes, those with kidney disease have exceptionally high rates of cardiovascular (CV) morbidity and mortality and progression of their underlying kidney disease. Finerenone is a novel, nonsteroidal, selective mineralocorticoid receptor antagonist that has shown to reduce albuminuria in type 2 diabetes (T2D) patients with chronic kidney disease (CKD) while revealing only a low risk of hyperkalemia. However, the effect of finerenone on CV and renal outcomes has not yet been investigated in long-term trials. Patients and Methods: The Finerenone in Reducing CV Mortality and Morbidity in Diabetic Kidney Disease (FIGARO-DKD) trial aims to assess the efficacy and safety of finerenone compared to placebo at reducing clinically important CV and renal outcomes in T2D patients with CKD. FIGARO-DKD is a randomized, double-blind, placebo-controlled, parallel-group, event-driven trial running in 47 countries with an expected duration of approximately 6 years. FIGARO-DKD randomized 7,437 patients with an estimated glomerular filtration rate >= 25 mL/min/1.73 m(2) and albuminuria (urinary albumin-to-creatinine ratio >= 30 to <= 5,000 mg/g). The study has at least 90% power to detect a 20% reduction in the risk of the primary outcome (overall two-sided significance level alpha = 0.05), the composite of time to first occurrence of CV death, nonfatal myocardial infarction, nonfatal stroke, or hospitalization for heart failure. Conclusions: FIGARO-DKD will determine whether an optimally treated cohort of T2D patients with CKD at high risk of CV and renal events will experience cardiorenal benefits with the addition of finerenone to their treatment regimen. Trial Registration: EudraCT number: 2015-000950-39; ClinicalTrials.gov identifier: NCT02545049

Correlating Acceptor Structure and Blend Nanostructure with the Photostability of Nonfullerene Organic Solar Cells

The formation of photoinduced traps resulting in the loss of electron mobility deteriorates the performance of organic solar cells under continuous light soaking. The genesis of these loss mechanisms is elucidated by examining the structural stability of halogenated ITIC derivative films and the phase behavior of the respective binary systems by blending with the donor polymer PBDBT-2F. Under constant illumination, ITIC-4Cl is found to maintain its structural integrity, whereas fluorine on the peripheral moieties of ITIC-4F undergoes chemical substitution to form a mixture of ITIC and ITIC-4F. Thermal analysis of the light-soaked binary films reveals that ITIC-4Cl loses its crystalline phase while the crystallinity of ITIC-4F does not undergo changes. Further, it is shown that the addition of a small amount of ITIC-4F as a third component hinders the loss of ITIC-4Cl crystalline phase in bulk heterojunction blends through the formation of cocrystals. These results suggest that long-range ordering of NFAs does not necessarily improve the photostability of organic solar cells and that the addition of a third component, irrespective of the crystalline nature, can prevent changes in bulk heterojunction blend nanostructure

Uso de atrayentes y suplementos alimenticios para el incremento de depredadores de escama blanca del mango, Aulacaspis tubercularis Newstead (Hemiptera: Diaspididae)

Mango is an economically important crop in Mexico, important population increases of mango white scale Aulacaspis tubercularis have been observed. The application of attractive nutritionalsupplements to arrest and/or attract predators of A. tubercularis were evaluated during two seasons. Application of 0.25 mL of methyl salicilate per tree has an effect on the number of eggs of Ceraeochrysa spp. Adults of Pentilia spp were lured whit different doses of methy salicilate (MS). Whit 4 mL of MS per tree, 60% fewer groups of A. tubercularis nymphs occurred. In the first year, adults of the predator Chilochorus cacti were no observed, but in the second year, the use of sugar, yeast and powdered milk had an attractive effect. More eggs of Ceraeochrysa spp were observed when water plus yeast plus sugar treatments were applied. At two sites, nymphs of A. tubercularis decreased in the second year, inthe first site decrease reached 65.6% while in the second site it was 93% in comparison to the untreated controls. The observed abatement is attributed to a general increase in predator numbers and their action on pest population.El mango es un cultivo importante en México, en años recientes se ha observado un incremento poblacional de Aulacaspos tubercularis en este frutal. Se evaluaron atrayentes y suplementos alimenticios para retener y/o atraer depredadores de A. tubercularis en dos ciclos de producción (2009-2010). Se observó mayor efecto de tratamientos en la variable huevos de Ceraeochrysa con el uso de0.25 mL de salicilato de metilo (SM) por árbol. Adultos de Pentilia fueron ligeramente atraídos con las diferentes dosis de SM. Con el uso de 4 mL de SM por árbol, se observó 60% menos colonias de ninfas de A. tubercularis comparado con el testigo absoluto. En el primer año de evaluación no se observaron adultos de Chilochorus cacti, en cambio en el segundo año en los tratamientos con azúcar, levadura de cerveza y leche nido en polvo si se presentaron. Con la aplicación de suplementos alimenticios a base de agua + levadura de cerveza y azúcar, se observó una diferencia numérica importante de huevos de Ceraeochrysa sp. El número de colonias de A. tubercularis por hoja, claramente disminuyó en el segundo año de evaluación en ambos sitios, en el sitio uno la disminución de colonias en promedio fue de 65.6% y para el sitio dos fue de un 93%. Esta disminución podría ser el resultado de un incremento general de los depredadores y la acción conjunta de estos sobre las colonias de escamas

New host plant and distribution records in Mexico for Anastrepha spp., Toxotrypana curvicauda gerstacker, Rhagoletis zoqui bush, Rhagoletis sp., and Hexachaeta sp. (Diptera: Tephritidae)

Volume: 102Start Page: 802End Page: 81

Understanding crystallization features of P(VDF-TrFE) copolymers under confinement to optimize ferroelectricity in nanostructures

The successful development of ferroelectric polymer devices depends on the effective fabrication of polar ferroelectric crystalline nanostructures. We demonstrate, by scanning X-ray microdiffraction using synchrotron light, the heterogeneous character of high aspect ratio one-dimensional nanoarrays of poly(vinylidene fluoride-co-trifluoroethylene) copolymers supported by a residual polymer film. They were prepared by melt and solution template wetting, using porous anodic aluminum oxide as a template. The spatial evolution of different polymorphs from the mixture of paraelectric and ferroelectric crystal forms (residual film) to the pure ferroelectric form (nanoarray) is evidenced for the samples prepared by solution wetting. However, for samples prepared by melt wetting the ferroelectric phase is exclusively obtained in both the residual film and nanoarray. The crystal nuclei formed in the polymer film connected to the nanoarray play a key role in determining the formation of a crystallinity distribution gradient, where the crystallinity decreases along the first 5-10 microns in the nanorods reaching a steady value afterwards. The minimum decrease in crystallinity is revealed for samples prepared by melt wetting. The results reported in this work endeavour to enhance the understanding of crystallization under confinement for ferroelectric copolymers and reveal the parameters for improving the ferroelectric character of polymer nanostructures. \uc2\ua9 2013 The Royal Society of Chemistry

Diffusion-Limited Crystallization: A Rationale for the Thermal Stability of Non-Fullerene Solar Cells

\ua9 2019 American Chemical Society. Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature Tg of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high Tg of ∼180 \ub0C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above Tg, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high-Tg materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells

Dissecting the structure-stability relationship of Y-series electron acceptors for real-world solar cell applications

Despite striking progress toward improving the photovoltaic (PV) performance of organic solar cells (OSCs) with recent Y-series non-fullerene acceptors (Y-NFAs), knowledge about their outdoor performance under real-world conditions and photodegradation mechanisms remains elusive, which is urgently needed to close the lab-to-fab gap of OSCs. Herein, for the first time, we study the structure-outdoor-stability relationship of Y-NFAs. We show that Y-NFAs with long internal side-chains exhibit high energy barriers for photoisomerization, and fluorinated end-groups can enhance the structural confinement to inhibit the photodegradation pathway and thereby improve device stability. Furthermore, the performance loss of Y-NFA-based OSCs under illumination is mainly driven by increased trap-assisted recombination over time. The structure-stability correlation and demonstration of outdoor performance of these state-of-the-art Y-NFA cells provided in this study highlight molecular engineering of device stability control to minimize power output losses in real-world climates