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The first examples of tetrasubstituted conjugated bis‐guanidinate (CBG) supported monomeric and thermally stable gallium dihalides [LGaX2], (X=Cl (Ga−Cl), I (Ga−I)) and dihydride (Ga−H) [LGaH2] (where L={(ArHN)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et2−C6H3) compounds are reported. The reaction of in situ generated LLi with 1.0 equiv. GaX3 (X=Cl, I) afforded compounds Ga−Cl and Ga−I. The reaction between Ga−Cl and Li[HBEt3] in benzene yielded the dihydride compound Ga−H. All reported compounds (Ga−Cl, Ga−I, and Ga−H) were characterized by NMR, HRMS, and single‐crystal X‐ray diffraction studies. Ga−H was probed for the hydroboration of carbodiimides (CDI), isocyanates, and isothiocyanates with HBpin. Compound Ga−H was also found effective for the catalytic hydroboration of imines, nitriles, alkynes, esters, and formates, affording the corresponding products in quantitative yields. Stoichiometric reactions with a CDI were performed to establish the catalytic cycle. [ABSTRACT FROM AUTHOR]

Cyclohepta[b]indoles, prevalent in natural products and pharmaceuticals, are conventionally accessed via metal or Lewis acid‐mediated cycloadditions with prefunctionalized substrates. Our study introduces an innovative sequential catalytic assembly for synthesizing cyclohepta[b]indoles from readily available isatin derivatives. The process involves three catalytic sequences: ring‐closing metathesis, catalytic hydrogenation, and acid‐catalyzed ring expansion. The RCM of 2,2‐dialkene‐3‐oxindoles, formed by butenyl Grignard addition to 3‐allyl‐3‐hydroxy‐2‐oxindoles, yields versatile spirocyclohexene‐3‐oxindole derivatives. These derivatives undergo further transformations, including dibromination, dihydroxylation, epoxidation, Wacker oxidation at the double bond. Hydrogenation of spirocyclohexene‐3‐oxindole yields spirocyclohexane‐3‐oxindoles. Their subsequent acid‐catalyzed ring expansion/aromatization, dependent on the acid catalyst, results in either cyclohepta[b]indoles or cyclohepta[b]indole‐indoline conjugates, adding a unique synthetic dimension. The utility of this methodology is exemplified through the synthesis of an A‐FABP inhibitor, showcasing its potential in pharmaceutical applications. [ABSTRACT FROM AUTHOR]

Background: Influenza may contribute to coronary/cerebrovascular events and exacerbate underlying conditions. Methods: We used self‐controlled case series (SCCS) design to analyze data from US Veterans ≥18 years with coronary/cerebrovascular or exacerbation event +/−1 year of lab‐confirmed influenza (LCI) during 2010–2018. We estimated the incidence ratio (IR) (95% CI) of the event for risk interval (Days 1–7 post‐LCI) versus control interval (all other times +/−1 year of LCI) with fixed‐effects conditional Poisson regression. We included biomarker data for mediation analysis. Results: We identified 3439 episodes with coronary/cerebrovascular‐related hospitalizations. IRs (95% CI) for LCI risk versus control interval were STEMI 0.6 (0.1, 4.4), NSTEMI 7.3 (5.8, 9.2), ischemic stroke 4.0 (3.0, 5.4), hemorrhagic stroke 6.2 (3.4, 11.5), and coronary spasm 1.3 (0.5, 3.0). IR significantly increased for NSTEMI and ischemic stroke among those ≥ 65 years. IR for NSTEMI and ischemic stroke dropped 26% and 10%, respectively, when white blood cell (WBC) and platelet count were considered. LCI was significantly associated with exacerbation of preexisting asthma, chronic obstructive pulmonary disease, and congestive heart failure. Conclusions: We found significant association between LCI and hospitalization for NSTEMI, ischemic stroke, and hemorrhagic stroke, the latter possibly due to unaccounted time‐varying confounding in SCCS design. [ABSTRACT FROM AUTHOR]

In the middle of an ever‐changing landscape of diabetes care, precision medicine, and lifestyle therapies are becoming increasingly important. Dietary polyphenols are like hidden allies found in our everyday meals. These biomolecules, found commonly in fruits, vegetables, and various plant‐based sources, hold revolutionary potential within their molecular structure in the way we approach diabetes and its intimidating consequences. There are currently numerous types of diabetes medications, but they are not appropriate for all patients due to limitations in dosages, side effects, drug resistance, a lack of efficacy, and ethnicity. Currently, there has been increased interest in practicing herbal remedies to manage diabetes and its related complications. This article aims to summarize the potential of dietary polyphenols as a foundation in the treatment of diabetes and its associated consequences. We found that most polyphenols inhibit enzymes linked to diabetes. This review outlines the potential benefits of selected molecules, including kaempferol, catechins, rosmarinic acid, apigenin, chlorogenic acid, and caffeic acid, in managing diabetes mellitus as these compounds have exhibited promising results in in vitro, in vivo, in silico, and some preclinical trials study. This encompassing exploration reveals the multifaceted impact of polyphenols not only in mitigating diabetes but also in addressing associated conditions like inflammation, obesity, and even cancer. Their mechanisms involve antioxidant functions, immune modulation, and proinflammatory enzyme regulation. Furthermore, these molecules exhibit anti‐tumor activities, influence cellular pathways, and activate AMPK pathways, offering a less toxic, cost‐effective, and sustainable approach to addressing diabetes and its complications. [ABSTRACT FROM AUTHOR]

Lung transplantation remains an important therapeutic option for idiopathic pulmonary arterial hypertension (IPAH), yet short‐term survival is the poorest among the major diagnostic categories. We sought to develop a prediction model for 90‐day mortality using the United Network for Organ Sharing database for adults with IPAH transplanted between 2005 and 2021. Variables with a p value ≤ 0.1 on univariate testing were included in multivariable analysis to derive the best subset model. The cohort comprised 693 subjects, of whom 71 died (10.2%) within 90 days of transplant. Significant independent predictors of early mortality were: extracorporeal circulatory support and/or mechanical ventilation at transplant (OR: 3; CI: 1.4–5), pulmonary artery diastolic pressure (OR: 1.3 per 10 mmHg; CI: 1.07–1.56), forced expiratory volume in the first second percent predicted (OR: 0.8 per 10%; CI: 0.7–0.94), recipient total bilirubin >2 mg/dL (OR: 3; CI: 1.4–7.2) and ischemic time >6 h (OR: 1.7, CI: 1.01–2.86). The predictive model was able to distinguish 25% of the cohort with a mortality of ≥20% from 49% with a mortality of ≤5%. We conclude that recipient variables associated with increasing severity of pulmonary vascular disease, including pretransplant advanced life support, and prolonged ischemic time are important risk factors for 90‐day mortality after lung transplant for IPAH. [ABSTRACT FROM AUTHOR]

White‐rumped vultures (Gyps bengalensis) are critically endangered species, and protecting their habitats, particularly the nesting trees, may have a positive impact on their reproductive success. For a better understanding of vultures' habitat needs, the characteristics of nesting trees should be accounted. In this paper, we compare the characteristics of the trees that have vultures' nests and that do not by randomly select a control tree within a 10 m radius of the nesting tree. We extensively searched and monitored the white‐rumped vultures' nests, nesting trees, and nesting tree species in Nepal between 2002 and 2022, and measured the characteristics of sampled trees such as their height, girth, canopy spread, branching orders, and whorls. We recorded 1161 nests of white‐rumped vulture in total on 194 trees belonging to 19 species over the past two decades. White‐rumped vultures preferred the kapok trees (Bombax ceiba) for nest construction than other tree species (χ2 = 115.38, df = 1, p <.001) as 66.49% of nests were built on them. In the logistic regression model, the number of whorls on a tree, canopy spread, and the height of the first branch determined whether a nest was present or absent on a tree. These results help to prioritize the tree attributes in a habitat conservation plan for vultures. [ABSTRACT FROM AUTHOR]

Key Clinical Message: Thyroid storm represents a critical and life‐threatening complication from hyperthyroidism, with a notable mortality risk. Limited literature reports have explored the correlation between thyroid storm and peri‐myocarditis, although the precise pathophysiological underpinnings remain unclear. The pathophysiology of how thyroid storm and peri‐myocarditis are associated is not clearly understood; however, unfavorable prognostic factors include atrial fibrillation and recurrent thyrotoxicosis. Here, we present a case concerning recurrent peri‐myocarditis concomitant with a thyroid storm. [ABSTRACT FROM AUTHOR]

Aim: This cross‐sectional survey aimed to determine the prevalence of Interventional Nephrology (IN) practice amongst nephrologists in the Asia‐Pacific Region (APR), specifically related to dialysis access (DA). Methods: The Association of VA and intervenTionAl Renal physicians (AVATAR) Foundation from India conducted a multinational online survey amongst nephrologists from the Asia‐Pacific to determine the practice of IN in the planning, creation, and management of dialysis access. The treatment modalities, manpower and equipment availability, monthly cost of treatment, specifics of dialysis access interventions, and challenges in the training and practice of IN by nephrologists were included in the survey. Results: Twenty‐one countries from the APR participated in the survey. Nephrologists from 18 (85.7%) countries reported performing at least one of the basic dialysis access‐related IN procedures, primarily the placement of non‐tunnelled central catheters (n‐TCC; 71.5%). Only 10 countries (47.6%) reported having an average of <4% of nephrologists performing any of the advanced IN access procedures, the most common being the placement of a peritoneal dialysis (PD) catheter (20%). Lack of formal training (57.14%), time (42.8%), incentive (38%), institutional support (38%), medico‐legal protection (28.6%), and prohibitive cost (23.8%) were the main challenges to practice IN. The primary obstacles to implementing the IN training were a lack of funding and skilled personnel. Conclusion: The practice of dialysis access‐related IN in APR is inadequate, mostly due to a lack of training, backup support, and economic constraints, whereas training in access‐related IN is constrained by a lack of a skilled workforce and finances. [ABSTRACT FROM AUTHOR]

We analyze the effect that the presence of a standard‐setting organization (SSO) has on firms' choices of product quality and costly research and development (R&D) investment when consumers face uncertainty regarding product standardization. We construct a theoretical model with competing firms and compare frameworks where: (i) an SSO is exogenously absent and (ii) an SSO is present. Our first finding is a negative relationship between firms' product‐quality choices and R&D investment. The presence of the SSO standardizes quality which can be profitable for firms. Finally, we find conditions where the presence of an SSO could lead to welfare enhancement. [ABSTRACT FROM AUTHOR]

Estimating the accuracy of quaternary structural models of protein complexes and assemblies (EMA) is important for predicting quaternary structures and applying them to studying protein function and interaction. The pairwise similarity between structural models is proven useful for estimating the quality of protein tertiary structural models, but it has been rarely applied to predicting the quality of quaternary structural models. Moreover, the pairwise similarity approach often fails when many structural models are of low quality and similar to each other. To address the gap, we developed a hybrid method (MULTICOM_qa) combining a pairwise similarity score (PSS) and an interface contact probability score (ICPS) based on the deep learning inter-chain contact prediction for estimating protein complex model accuracy. It blindly participated in the 15th Critical Assessment of Techniques for Protein Structure Prediction (CASP15) in 2022 and performed very well in estimating the global structure accuracy of assembly models. The average per-target correlation coefficient between the model quality scores predicted by MULTICOM_qa and the true quality scores of the models of CASP15 assembly targets is 0.66. The average per-target ranking loss in using the predicted quality scores to rank the models is 0.14. It was able to select good models for most targets. Moreover, several key factors (i.e., target difficulty, model sampling difficulty, skewness of model quality, and similarity between good/bad models) for EMA are identified and analyzed. The results demonstrate that combining the multi-model method (PSS) with the complementary single-model method (ICPS) is a promising approach to EMA. [ABSTRACT FROM AUTHOR]

We present the results for CAPRI Round 54, the 5th joint CASP-CAPRI protein assembly prediction challenge. The Round offered 37 targets, including 14 homodimers, 3 homo-trimers, 13 heterodimers including 3 antibody–antigen complexes, and 7 large assemblies. On average ~70 CASP and CAPRI predictor groups, including more than 20 automatics servers, submitted models for each target. A total of 21 941 models submitted by these groups and by 15 CAPRI scorer groups were evaluated using the CAPRI model quality measures and the DockQ score consolidating these measures. The prediction performance was quantified by a weighted score based on the number of models of acceptable quality or higher submitted by each group among their five best models. Results show substantial progress achieved across a significant fraction of the 60+ participating groups. High-quality models were produced for about 40% of the targets compared to 8% two years earlier. This remarkable improvement is due to the wide use of the AlphaFold2 and AlphaFold2-Multimer software and the confidence metrics they provide. Notably, expanded sampling of candidate solutions by manipulating these deep learning inference engines, enriching multiple sequence alignments, or integration of advanced modeling tools, enabled top performing groups to exceed the performance of a standard AlphaFold2-Multimer version used as a yard stick. This notwithstanding, performance remained poor for complexes with antibodies and nanobodies, where evolutionary relationships between the binding partners are lacking, and for complexes featuring conformational flexibility, clearly indicating that the prediction of protein complexes remains a challenging problem. [ABSTRACT FROM AUTHOR]

We examine the relationship between research and development (R&D) expenditures and the expected impact of diseases in a simple theoretical framework that allows for intellectual property rights (IPR) protection to be strong or weak. In our theoretical model, an agent forms an expectation of the impact of a disease using a publicly available statistic on the (population level) disease burden, such as disability‐adjusted life year. We show that a profit‐maximising firm will exert relatively more R&D effort on diseases with intermediate expected impacts. We also discuss how a weak IPR regime alters the pattern of R&D investment. [ABSTRACT FROM AUTHOR]

Perovskite solar cells (PSCs) have made great strides in recent years, operating inside the theoretical Scholkely–Quisser efficiency limit with a certified power conversion efficiency (PCE) of 26.1%. However, lead toxicity from Pb‐based PSCs can harm the environment. As a result, the search for nontoxic and environmentally friendly substances to replace Pb in perovskites is the need of the hour. Tin has emerged as the most viable choice to replace Pb, due to its favorable electronic properties and smaller bandgaps of Sn‐based perovskites between 1.1 and 1.4 eV, strong charge carrier mobility, and high theoretical efficiency of 32%. Sn vacancies and point defects, on the other hand, are easily produced in Sn perovskites, leading to nonradiative recombination. Furthermore, interfacial flaws and traps impede further performance improvement. In this research, to produce high‐quality Pb‐free perovskites for high‐performance PSCs, a Lewis‐base thioacetamide (TAA) is added to the simple FASnI3 perovskite solution. FASnI3 and TAA additive‐based films effectively control perovskite film crystallinity and grain size via Lewis acid–base reaction. The champion FASnI3 + TAA‐based PSC achieves a maximum PCE of 10.67% while paving a facile way for other compositional perovskite analogues to be integrated into highly efficient and operationally stable PSCs. [ABSTRACT FROM AUTHOR]

Human‐wildlife conflict is a global issue that poses a major threat to biodiversity conservation and sustainable development. Wildlife adapted to human‐modified landscapes in developing countries can threaten the safety and livelihood of local communities. In such landscapes, where people and wildlife compete for resources, community involvement is promoted to achieve workable coexistence. We used a choice experiment methodology approach to identify community‐preferred policy alternatives in Chitwan National Park in south‐central Nepal. The results indicated that conflicts between the local community and wildlife are on the rise, crop damage being the highest form of damage and most perceived compensation and fencing as conflict‐mitigation tools. The choice experiment showed that residents have a positive preference for enhancing livelihood diversification skills, cultivating buffer crops, promoting alternative livelihoods, and strengthening rapid response teams. We identified concerned mitigators who are younger age group, encountered and concurred that HWC is increasing, and agreed that fencing and compensation are conflict‐mitigation tools. We designed scenario planning using community‐preferred policy alternatives to assist the park management. This is the first‐choice experiment study to design an evaluation framework under community resilience perspectives to achieve workable coexistence. Our study has potential implications for promoting coexistence in a human‐dominated landscape. [ABSTRACT FROM AUTHOR]

Passivated emitter and rear contact (PERC) on p‐type mono silicon has a roadmap for achieving >24% efficiency. The decrease of the full‐area rear metal contact to partial rear contact (<10%) accounts for the majority of the increase in efficiency of PERC solar cells over Al‐BSF solar cellswhich reached its maximum efficiency around 19.5%. P‐type tunnel oxide passivated contacts (TOPCon) solar cells have achieved further improvement in efficiency ≥25% by completely removing the partial rear metal contact and introducing a thin tunneling oxide layer at the rear. Thus passivating the partial rear and front metal contacts using SiOx/poly‐Si tunnelling layer stacks and an AlOx/SiNx stack on the entire back surface to passivate the remaining areas might lead to further advancements in PERC solar cells. Therefore, by integrating TOPCon and PERC architectures, as originally proposed by Fraunhofer lab, a modified design known as TOPerc solar cell has been studied in depth in this paper. Using 3D Sentaurus TCAD simulation software, a thorough numerical simulation of a p‐TOPerc solar cell has been performed. It is shown that efficiency of 25.2% and 26.0% is obtained for a p‐type wafer of bulk lifetime of 400 μs and 5.0 ms, respectively. [ABSTRACT FROM AUTHOR]

An efficient, one‐step method has been used to access a variety of substituted indenones in a regiospecific manner by Grignard addition to indene‐1,3‐dione. This method provides straightforward access to natural products such as neo‐lignans and isoampelopsin D analogues. Moreover, diallyl indenones have been synthesized and employed as ring‐closing metathesis (RCM) precursors for the facile synthesis of substituted fluorenone derivatives through an RCM‐aromatization sequence. [ABSTRACT FROM AUTHOR]

In this work, the molecular aluminium dihydride complex bearing an N, N'‐chelated conjugated bis‐guanidinate (CBG) ligand is used as a catalyst for reducing a wide range of aryl and alkyl esters with good tolerance of alkene (C=C), alkyne (C≡C), halides (Cl, Br, I and F), nitrile (C≡N), and nitro (NO2) functionalities. Further, we investigated the catalytic application of aluminium dihydride in the C−O bond cleavage of alkyl and aryl epoxides into corresponding branched Markovnikov ring‐opening products. In addition, the chemoselective intermolecular reduction of esters over other reducible functional groups, such as amides and alkenes, has been established. Intermediates are isolated and characterized by NMR and HRMS studies, which confirm the probable catalytic cycles for the hydroboration of esters and epoxides. [ABSTRACT FROM AUTHOR]

Key Clinical Message: It is of utmost importance to be aware of acute calcific periarthritis, as it may confuse the clinicians leading to misdiagnosis. Furthermore, patients may be subjected to various diagnostic and invasive procedures due to a lack of familiarity with this condition. Deposition of hydroxyapatite crystals in the para‐articular soft tissues is a well‐known condition, often involving the shoulder joint. However, the deposition of calcium salts in the para‐articular soft tissue of acromioclavicular joint has rarely been described. We report a case of a 55‐year‐old otherwise healthy man, presented with acute onset of pain and restriction of movement of left shoulder, who was diagnosed based on radiographic findings with calcific periarthritis of the acromioclavicular joint. As suggested by the literatures, he was managed conservatively, and no reoccurrence was reported after the episode. [ABSTRACT FROM AUTHOR]

The study aimed to determine the level of self‐reported adherence to antihypertensive drug(s) and its associated factors among patient with hypertension at a tertiary care center. The authors performed hospital based observational cross‐sectional study using semi‐structured questionnaires, WHO STEP tool and Hill and Bone high blood pressure compliance scale from December 1, 2021 to February 28, 2022. Descriptive statistics, Chi‐square/Fisher's exact test and non‐parametric tests were used for statistical analysis. Among 150 cases included in the study, majority (94, 62.67%) had good adherence based on Hill and Bone high blood pressure compliance scale with adherence level labelled as "good adherence" (score 3) and "not good adherence" (score < 3). The adherence to drug therapy was significantly better in females compared to males (50 [71.43%] vs. 44 [55.00%], p =.038). Among the factors related to hypertension and anti‐hypertensive therapy, people with higher body mass index (ρ = ‐.324, n = 56, p =.015) and taking three or more pills (6, 1.71%, p =.017) had lower adherence to therapy. Likewise, forgetfulness (30, 53.57%), ineffective counseling (7, 12.50%), and missed follow‐up (13, 23.21%) were the factors associated with lower adherence to anti‐hypertensive therapy. This study finds good adherence among the patients taking anti‐hypertensive medications. However, with the improved education, lesser number of pills and physical fitness help to adhere with the anti‐hypertensive therapy. [ABSTRACT FROM AUTHOR]

An unprecedented conjugated bis‐guanidinate (CBG) stabilized aluminium dihydride, [LAlH2; (L={(ArNH)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et2‐C6H3)] (I) catalyzed chemoselective hydroboration of heteroallenes such as carbodiimide (CDI)s, isocyanates, isothiocyanates, and isoselenocyanates is reported. A wide range of heteroallenes, including electron‐donating and withdrawing groups, experience hydroboration to obtain selectively N‐boryl amide, N‐borylaminal, and N‐boryl methyl amine products. More importantly, a single sustainable molecular aluminium‐based catalyst effectively catalyzes CDIs, isocyanates, isothiocyanates, and isoselenocyanates into formamidines, formamides, thioformamides, and selenoformamides, respectively. Further, heteroallene substrates undergo hydrodeoxygenation (HDO), hydrodesulfurization (HDS), and hydrodeselenization (HDSe) reactions leading to N‐boryl methyl amines. In addition, a series of control and kinetic experiments indicate that the aluminium hydride species are essential for all partial and complete reduction steps and breaking the C=X (X=O, S, and Se) bonds in heteroallenes. [ABSTRACT FROM AUTHOR]

Herein, we report the guanylation of carbodiimides with primary and secondary alkyl/aryl amines and the reduction of CDIs via hydroboration using molecular conjugated bis‐guanidinate (CBG) aluminum alkyl catalysts. The first example of structurally characterized unsymmetrical tetra‐aryl substituted CBG (LH) is reported. The reaction of LH; (L={(Ar1NH)(ArN)−C=N−C=(NAr)(NHAr1)}; Ar1=2,6‐iPr2−C6H3, Ar=2,6‐Me2−C6H3) with AlMe3 solution afforded a LAlMe2 (1) complex. The ligand (LH) and compound 1 were thoroughly characterized, including single‐crystal X‐ray diffraction studies. More importantly, compounds 1 and L'AlMe2 (2); (L'={(ArNH)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et2−C6H3) are utilized as catalysts for N−H and B−H addition to symmetrical aryl or alkyl carbodiimides to obtain the corresponding guanidines and N‐boryl formamidines in excellent yields. The developed catalytic methods are effectively used for the large‐scale synthesis of guanidine and formamidine derivatives under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Two new examples of β‐diketiminate or NacNac analogues, i. e. conjugated bis‐guanidinate (CBG) stabilized low valent germanium chloride (1) and germanium hydride (2) complexes, are reported. Deprotonation of LH upon treatment with n‐BuLi and an in situ generated LLi further treated with GeCl2⋅dioxane afforded LGeCl in 79 % yield. Compound 1 reacted with hydride source NaHBEt3 in toluene, afforded Ge (II) hydride (2) in 76 % yield. Both compounds 1 and 2 were characterized by NMR and mass spectroscopic methods. Further, germanium hydride catalyzed hydroboration and cyanosilylation of a wide range of ketones have been investigated. Control reactions suggest hydroboration reactions occurred via insertion and Ge−O/B−H bond metathesis pathways. It is worthy of mentioning that, in the case of hydroboration of ketones, reducible groups such as alkene, alkyne, halide, ester, nitro, and heterocycles were untouched. Furthermore, compound 2 was employed for the reduction of carbonate, formate, and anhydride substrates via the hydroboration technique. [ABSTRACT FROM AUTHOR]

Nucleophilic aromatic substitution (SNAr) reactions are exploited to prepare poly(arylene sulfide)s (PAS's) via the reaction of bis‐thiolates and dibrominated pyromellitic diimide (PMDI) derivatives. Small‐molecule model studies reveal the reaction is well‐defined and proceeds in quantitative yield in practical times at room temperature. Variation in comonomer feed ratios allowed some control over target polymer molecular weights in the step polymerization, but control was likely limited by the relatively poor polymer solubility in the dipolar aprotic solvents typically employed to promote SNAr reactions. One substitution pattern produces a steric "pocket" around the PMDI units, inducing a peculiar solubility trend in halogenated solvents; that is, greatly reduced solubility in CHCl3 relative to CH2Cl2 and C2H2Cl4. One example small‐molecule readily dissolves in CHCl3 at room temperature, then rapidly grows poorly soluble crystals revealed by single‐crystal XRD to contain CHCl3 molecules in the steric pockets. Finally, the recently demonstrated depolymerization of phthalonitrile‐based PAS's via ipso substitution with monothiolates as chain scission agents yields quantitative molecular weight reduction to monomeric species from the polymers reported here. [ABSTRACT FROM AUTHOR]

Because of their inferior film quality, Pb–Sn‐mixed low‐bandgap (LBG) perovskites suffer from poor charge transportation, compromising photovoltaic parameters of final solar cells. Herein, an approach to improve the quality of the charge interface layer is proposed, in which a thin layer of hydrophobic [bis (4‐phenyl) (2, 4, 6‐trimethylphenyl) amine] (PTAA) is inserted between the hole‐selective layer of hydrophilic poly (3, 4‐ethylenedioxythiophene) ‐polystyrenesulfonicacid (PEDOT:PSS) and LBG perovskite layer. The introduction of a tiny layer of the hydrophobic PTAA acts as a shield layer to protect the underlying acidic PEDOT:PSS layer from moisture‐related degradation and works as an intermediary layer to facilitate the growth of significantly larger perovskite grains; these enlarged grains are indicative of enhanced crystallinity and fewer grain boundaries in the perovskite layer. The fewer grain boundaries lead to suppression of interfacial defects and result in enhanced charge collection at the hole transport layer/perovskite interface, thus improving the open‐circuit voltage up to 0.85 V and fill factor up to ≈78%, eventually boosting the power conversion efficiency of the champion cell up to 19.08%. Herein, a simple interface engineering route to fabricate efficient and stable Pb–Sn‐mixed LBG perovskite solar cells is offered. [ABSTRACT FROM AUTHOR]

The N,N'‐chelated β‐diketiminate analogue i. e. conjugated bis‐guanidine (CBG) ligand L(3H) [L= {(ArHN)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et2‐C6H3], has been used to synthesize mono‐ and dinuclear Al(III) dimethyl complexes, [L(2H) AlMe2] (1) and [L(H)(AlMe2)2] (2). Compounds 1 and 2 are synthesized by deprotonation method using free ligand and appropriate stoichiometric amounts of AlMe3 and are structurally characterized by a single‐crystal X‐ray diffraction technique. Moreover, the reaction of compound 1 with B(C6F5)3 afforded a three‐coordinate aluminum methyl cation [L(2H)AlMe]+ [MeB(C6F5)3]−3 in good yield. Compound 3 was thermally stable and characterized by multinuclear NMR spectroscopy. Furthermore, we demonstrated that compound 3 catalyzed hydrosilylation of carbonyls, alkenes, and alkyne with triethylsilane (HSiEt3) under solvent‐free conditions. We found that catalyst 3 is also effective for large‐scale hydrosilylation reactions. Additionally, we have shown that compound 3 catalyzed benzaldehyde's intermolecular chemoselective hydrosilylation over other reducible functional groups. [ABSTRACT FROM AUTHOR]

Diffusion magnetic resonance imaging (dMRI) datasets are susceptible to several confounding factors related to data quality, which is especially true in studies involving young children. With the recent trend of large‐scale multicenter studies, it is more critical to be aware of the varied impacts of data quality on measures of interest. Here, we investigated data quality and its effect on different diffusion measures using a multicenter dataset. dMRI data were obtained from 691 participants (5–17 years of age) from six different centers. Six data quality metrics—contrast to noise ratio, outlier slices, and motion (absolute, relative, translation, and rotational)—and four diffusion measures—fractional anisotropy, mean diffusivity, tract density, and length—were computed for each of 36 major fiber tracts for all participants. The results indicated that four out of six data quality metrics (all except absolute and translation motion) differed significantly between centers. Associations between these data quality metrics and the diffusion measures differed significantly across the tracts and centers. Moreover, these effects remained significant after applying recently proposed harmonization algorithms that purport to remove unwanted between‐site variation in diffusion data. These results demonstrate the widespread impact of dMRI data quality on diffusion measures. These tracts and measures have been routinely associated with individual differences as well as group‐wide differences between neurotypical populations and individuals with neurological or developmental disorders. Accordingly, for analyses of individual differences or group effects (particularly in multisite dataset), we encourage the inclusion of data quality metrics in dMRI analysis. [ABSTRACT FROM AUTHOR]

Purpose: Mild to moderate vision loss affects many children and can negatively impact a child's early literacy and academic achievement. Nevertheless, there is no consensus on which factors present in early childhood indicate the need for long‐term ophthalmic follow up, particularly in children with a history of perinatal adversity. This study identified the relationship between visual, cognitive, motor and demographic factors at 2 years of age and visual acuity (VA) and stereoacuity at 4.5 years of age. Methods: Five hundred sixteen children identified as being at risk of neonatal hypoglycaemia were recruited soon after birth. At 2 years of age, binocular VA, stereoacuity and non‐cycloplegic refraction were measured and a clinical neuro‐developmental assessment with the Bayley Scales of Infant Development III (BSID‐III) was conducted by a trained examiner. Monocular VA and stereoacuity were measured at 4.5 years of age. Results: Three hundred twenty‐eight children completed both the 2 and 4.5 year vision and neurodevelopmental assessments. Multiple linear regression showed oblique astigmatism and motor function at 2 years were significantly associated with VA at 4.5 years of age, while spherical equivalent refraction, motor scores and stereoacuity at 2 years were significantly associated with stereoacuity at 4.5 years of age. BSID‐III motor scores had the best sensitivity (81.8%) and specificity (51.5%) for identifying impaired stereoacuity at 4.5 years. However, all measures at 2 years were poorly associated with VA at 4.5 years old. Conclusion: Vision and neurodevelopmental measures at 2 years were poorly associated with visual function at 4.5 years of age. However, lower scores on tests of motor function at 2 years may be associated with vision abnormalities, particularly reduced stereopsis, at 4.5 years of age and referral for comprehensive vision assessment for these children may be warranted. [ABSTRACT FROM AUTHOR]

Nutrients' mineralization‐immobilization in soil is crucial for their management in crop production. An incubation experiment was conducted to study the effects of phosphorus levels on mineralization of phosphorus (P) and potassium (K) under three soil types in laboratory conditions at the National Soil Science Research Center in Nepal with 3 × 4 factorial completely randomized design. Two factors were three soil types (silty clay loam, loam, and sandy loam) and four P levels: 0, 25, 50, and 75 kg P2O5 ha–1. Five incubation periods (1, 30, 60, 90, and 120 d after incubation) were replicated three times with total of 180 experimental units. The P and K mineralization patterns varied with soil types and P levels, with higher fluctuation of P content in silty clay loam soil as compared with loam and sandy loam soil. Phosphorus concentration with application of 25 kg, 50 kg, and 75 kg P2O5 ha–1 after 120 d of incubation were 95.6, 112.2, and 116.6 mg kg–1, respectively, which was 19.65% (25 kg P2O5 ha–1) to 45.93% (75 kg P2O5 ha–1) higher than control. There were four stages of mineralization‐immobilization turnover of Olsen‐P and available K: rapid declining trend up to 30 d, slow rise up to 60 d, rapid mineralization up to 90 d, and then slows down up to 120 d. On average, rapid reduction in soil pH from 6.60 to 5.42 was observed within 120 d of incubation. The study of mineralization of PK and change in pH during incubation could be helpful for predicting nutrient availability and requirement time for crops. Core Ideas: Phosphorus and potassium mineralization patterns varied with soil types and P levels.Four phases of phosphorus mineralization‐immobilization occurred during 120 d incubation.Soil with high levels of phosphorus obtained greater amount of available P compared with control.High mineralization due to temperature and moisture resulted higher reduction in soil pH. Mineralization study is helpful for predicting nutrient availability/requirement for crops. [ABSTRACT FROM AUTHOR]

Purpose: To evaluate the effect of the new heart transplant (HT) allocation system in left ventricular assist device (LVAD) supported patients listed as bridge to transplantation (BTT). Methods: Adult patients who were listed for HT between October 18, 2016 and October 17, 2019, and were supported with an LVAD, enrolled in the UNOS database were included in this study. Patients were classified in the old or new system if they were listed or transplanted before or after October 18, 2018, respectively. Results: A total of 3261 LVAD patients were listed for transplant. Of these, 2257 were classified in the old and 1004 in the new system. The cumulative incidence of death or removal from the transplant list due to worsening clinical status at 360‐days after listing was lower in the new system (4% vs. 7%, P =.011). LVAD Patients listed in the new system had a lower frequency of transplantation within 360‐days of listing (52% vs. 61%, P <.001). A total of 1843 LVAD patients were transplanted, 1004 patients in the old system and 839 patients in the new system. The post‐transplant survival at 360 days was similar between old and new systems (92.3% vs. 90%, P =.08). However, LVAD patients transplanted in the new system had lower frequency of the combined endpoint, freedom of death or re‐transplantation at 360 days (92.2% vs. 89.6%, P =.046). Conclusion: The new HT allocation system has affected the LVAD‐BTT population significantly. On the waitlist, LVAD patients have a decreased cumulative frequency of transplantation and a concomitant decrease in death or delisting due to worsening status. In the new system, LVAD patients have a decreased survival free of re‐transplantation at 360 days post‐transplant. [ABSTRACT FROM AUTHOR]

The effect of cations on the corrosion of galvanized steel (GS) is scarcely reported. In this study, a wet–dry cyclic test was conducted to study NH4+, Na+, and Mg2+ cation effect on the corrosion behavior of GS available in Nepal. Fourteen wet–dry cycles (18 h wet and 6 h dry) were performed by exposing samples at 298 K with a relative humidity of 90% in a wet cycle and 50% in a dry cycle for 14 days. The cations strongly affect the corrosion rate of the GS sample estimated by weight loss and potentiodynamic polarization. The potentiodynamic polarization curves showed the inhibition of cathodic and anodic reactions by Mg2+ ion, while the NH4+ ion only changed the cathodic reaction. Mg2+ ion was found to shift the corrosion potential to noble values compared with NH4+ and Na+ ions. A compact and thin corrosion products layer was developed in Mg2+ salt solution in contrast to a thick and porous corrosion products layer in NH4+ and Na+ salt solutions. Red rust due to corrosion of underlying steel appeared in the presence of NH4+ and Na+ salt solutions. Finally, the weight loss data revealed that the corrosivity of cations for GS decreased in the order Na+ > NH4+ > Mg2+. [ABSTRACT FROM AUTHOR]

Herein, we report a range of conjugated bis-guanidines (CBGs) L [L={(ArHN)(ArHN)C=N􀀀 C=(NAr)(NHAr)}; Ar=2, 6-Me2 - C6H3, (1), 2, 4, 6-Me3􀀀 C6H2, (2), 2, 6-Et2􀀀 C6H3, (3), 2, 6-iPr2􀀀 C6H3, (4)]. These compounds can be easily accessed by the reaction between N,N'-diaryl carbodiimide, and aq. ammonia in acetonitrile. Deprotonation of 1 with n-BuLi in a 1:1 ratio in THF resulted in the formation of four coordinate lithium complex, [1Li · (THF)2] (5), while at the same reaction conditions, ligands 3 and 4 gave three coordinate lithium complexes, [3Li·THF] (6) and [4Li·THF] (7), respectively. However, both compounds 1 and 4 upon deprotonation with n-BuLi in diethyl ether allowed [1Li·Et2O] (8) and [4Li·Et2O] (9), respectively, while compounds 1 and 3 in toluene afforded un-solvated lithium complexes [1Li] (10) and [3Li] (11), respectively. Significantly, a reaction between compound 4 and n-BuLi in a 1:1 ratio in toluene yielded sandwich lithium complex [4Li] (12). All new CBGs 1-4 and lithium salts of CBG, 5, 8, and 12 were characterized by single-crystal X-ray structural analysis. The compounds 5-12 were characterized by multinuclear magnetic resonance spectroscopy. Moreover, we have investigated the catalytic application of lithium salts of CBGs for the addition of B􀀀 H and TMSCN to carbonyls. [ABSTRACT FROM AUTHOR]

Herein, a remarkable conjugated bis‐guanidinate (CBG) supported zinc hydride, [{LZnH}2; L={(ArHN)(ArN)−C=N−C=(NAr)(NHAr); Ar=2,6‐Et2‐C6H3}] (I) catalyzed partial reduction of heteroallenes via hydroboration is reported. A large number of aryl and alkyl isocyanates, including electron‐donating and withdrawing groups, undergo reduction to obtain selectively N‐boryl formamide, bis(boryl) hemiaminal and N‐boryl methyl amine products. The compound I effectively catalyzes the chemoselective reduction of various isocyanates, in which the construction of the amide bond occurs. Isocyanates undergo a deoxygenation hydroboration reaction, in which the C=O bond cleaves, leading to N‐boryl methyl amines. Several functionalities such as nitro, cyano, halide, and alkene groups are well‐tolerated. Furthermore, a series of kinetic, control experiments and structurally characterized intermediates suggest that the zinc hydride species are responsible for all reduction steps and breaking the C=O bond. [ABSTRACT FROM AUTHOR]

Development of high‐performance wide‐bandgap perovskites is a key component to enable tandem solar cells with either a silicon or low‐bandgap perovskites. However, the presence of defects in the Br‐rich wide‐bandgap perovskites, especially in the grain boundaries (GBs) has been particularly challenging and limits its performance. Herein, to accomplish the passivation of these defects, a combination of cation management with rubidium (Rb) introduction into the triple cation combination of cesium/formamidinium/methylammonium (CsFAMA) is exercised. Passivation is further enhanced by secondary growth (SG) using guanidinium iodide. In‐depth assessments of GB defect passivation are performed using Kelvin probe force microscopy (KPFM) and nanoscale charge‐carrier dynamics mappings provide insightful details on the presence of GBs defects and their suppression by the cation management and SG techniques. Reduction of unreacted PbX2 to realize a highly crystalline perovskite surface is achieved after incorporating Rb and SG treatment. As a result, a champion cell for 1.78 eV (FA0.79MA0.16Cs0.05)0.95Rb0.05Pb(I0.6Br0.4)3 wide‐bandgap perovskite with an efficiency of 17.71% along with enhancement in all photovoltaic parameters is achieved. This study introduces a new way to analyze GB defects and reveals the consequence of defect passivation on charge‐carrier dynamics for realizing efficient perovskites. [ABSTRACT FROM AUTHOR]

Historically, adult congenital patients have longer waitlist time and worse outcomes on the heart transplant waitlist as well as poorer early post‐transplant survival. A new heart transplantation allocation system was implemented in the United States on October 18, 2018. The effect of the new allocation system on adult congenital patients is unknown. Adult congenital patients listed for transplantation between November 1, 2015 and September 30, 2019 registered in the United Network for Organ Sharing were included in the study. October 18, 2018 was used as the limit to distribute listed and transplanted patients into old and new groups. A total of 399 patients were listed for heart transplant only, 284 in the old system and 115 in the new system. Clinical characteristics were similar between both groups. The cumulative incidence of poor outcome on the transplant list was similar in both groups (P =.23), but the cumulative incidence of transplant was higher in the new system group (P <.009) and was associated with a shorter waitlist time. The one‐year post‐transplant outcome was similar between old and new groups (P =.37). The new allocation system has benefited adult congenital patients with increased cumulative frequency of transplantation without worsening short‐term survival after transplantation. [ABSTRACT FROM AUTHOR]

Objective: To evaluate the effect of a preexisting posttraumatic stress disorder (PTSD) diagnosis on suicide and non-suicide mortalities among men with newly diagnosed prostate cancer, and examine potential mediating factors for the relationship between PTSD and suicide.Methods: We used patient-level data from Veterans Health Administration electronic medical records to identify men (age ≥40 years) diagnosed with prostate cancer between 2004 and 2014. We used Fine and Gray regression model to estimate the risk for competing mortality outcomes (suicide, non-suicide, and alive). We used structural equation models to evaluate the mediating factors.Results: Our cohort comprised 214,649 men with prostate cancer, of whom 12,208 (5.7%) had a preexisting PTSD diagnosis. Patients with PTSD compared to those without utilized more healthcare services and had lower risk cancer at diagnosis. Additionally, they experienced more suicide deaths (N = 26, 0.21% vs. N = 269, 0.13%) and fewer non-suicide deaths (N = 1399, 11.5% vs. N = 45,625, 22.5%). On multivariable analysis, PTSD was an independent suicide risk factor (HR = 2.35; 95% CI: 1.16, 4.78). Depression, substance use disorder, and any definitive prostate cancer treatment were partial mediators. However, PTSD was associated with lower non-suicide mortality risk (HR = 0.86; 95% CI: 0.77, 0.96).Conclusion: Patients with PTSD experienced greater suicide risk even after adjusting for important mediators. They may have experienced lower non-suicide mortality risk due to favorable physical health resulting from greater healthcare service use and early diagnosis of lower risk cancer. Our findings highlight the importance of considering psychiatric illnesses when treating patients with prostate cancer and the need for interventions to ameliorate suicide risk. [ABSTRACT FROM AUTHOR]

Among the global coordinated patterns in soil temperature and methane emission from wetlands, a declining trend of optimal soil temperature for methane emissions from low to high latitudes has been witnessed, while the corresponding trend along the altitudinal gradient has not yet been investigated. We therefore selected two natural wetlands located at contrasting climatic zones from foothill and mountainside of Nepal Himalayas, to test: (1) whether the optimal temperature for methane emissions decreases from low to high altitude, and (2) whether there is a difference in temperature sensitivity of methane emissions from those wetlands. We found significant spatial and temporal variation of methane emissions between the two wetlands and seasons. Soil temperature was the dominant driver for seasonal variation in methane emissions from both wetlands, though its effect was perplexed by the level of standing water, aquatic plants, and dissolved organic carbon, particularly in the deep water area. When integrative comparison was conducted by adding the existing data from wetlands of diverse altitudes, and the latitude‐for‐altitude effect was taken into account, we found the baseline soil temperatures decrease whilst the altitude rises with respect to a rapid increase in methane emission from all wetlands, however, remarkably higher sensitivity of methane emissions to soil temperature (apparent Q10) was found in mid‐altitude wetland. We provide the first evidence of an apparent decline in optimal temperature for methane emissions with increasing elevation. These findings suggest a convergent pattern of methane emissions with respect to seasonal temperature shifts from wetlands along altitudinal gradient, while a divergent pattern in temperature sensitivities exhibits a single peak in mid‐altitude. [ABSTRACT FROM AUTHOR]

Due to the attraction of fabricating highly efficient tandem solar cells, wide‐bandgap perovskite solar cells (PSCs) have attracted substantial interest in recent years. However, polycrystalline perovskite thin‐films show the existence of trap states at grain boundaries which diminish the optoelectronic properties of the perovskite and thus remains a challenge. Here, a one‐step solution‐processing of [MA0.9Cs0.1Pb(I0.6Br0.4)3] wide‐bandgap perovskite using phenylhydrazine iodide with amino groups is demonstrated to successfully passivate the trap density within grain boundaries and increase the perovskite grain size. The reinforced morphology and grain boundaries treatment considerably enhanced the power conversion efficiency (PCE) from 12.16% for pristine to 14.63% for the treated devices. This strategy can be easily adopted to other perovskites and help realize highly efficient perovskite solar cells. [ABSTRACT FROM AUTHOR]

We herein disclose domino relay metathesis sequences using triallyl 3‐oxindole and indole precursors to access C2‐quaternary cyclic pseudooxindole and carbazole ring systems. Triallyl 3‐oxindoles undergo domino ring closing metathesis (RCM) and cross metathesis (CM) to provide C2‐spirocyclic 3‐oxindoles. Intriguingly, a catalyst specific relay metathesis sequence involving ring closing‐ring opening‐ring closing and cross metathesis (RC‐RO‐RC‐CM) of these trienes is established to provide fused bicyclic indoxyl dimers in high yields. Further, the CM of indoxyl dimer with methyl acrylate affords a new class of fused monomeric 3‐oxindole derivative. Moreover, a domino RCM‐CM process of triallyl indoles is demonstrated, enabling a quick access to dihydro‐carbazoles and carbazoles. [ABSTRACT FROM AUTHOR]

Background: Infective endocarditis (IE) is a rare complication following solid organ transplant (SOT); data on the clinical features and outcomes of IE in SOT recipients in the modern era are limited. Methods: We conducted a single‐center retrospective cohort study of IE diagnosed from 1/2008‐12/2014 in SOT recipients, who were matched by age and microorganism to cases of IE in non‐SOT, to describe the clinical features and outcomes. Results: There were 14 cases of IE identified in SOT recipients matched to 56 non‐SOT controls. Median time from transplant to IE was 1017 days (IQR 379‐1830). Compared to non‐SOT patients, SOT patients were more likely to be undergoing current hemodialysis (16% vs 36%) and to possess indwelling central venous catheters within the 30 days prior to diagnosis of IE (27% vs 50%). No SOT patients had documented drug use as a risk factor for IE whereas 6 (11%) non‐SOT did. Enterococcus was the most common etiologic agent and was isolated in 50% of cases; only one fungal infection was identified, a mixed infection with Candida. Thirty‐day mortality was 14% in SOT patients, significantly higher versus no deaths in non‐SOT (P =.037). Conclusions: The present study illustrates a change in epidemiology of IE in SOT patients characterized by IE that generally occurs more than one‐year post‐transplant, is due to bacterial infection rather than fungus, and appears to be health care associated. Multicenter studies are merited to explore transplant‐specific risk factors for IE in the special population of SOT patients. [ABSTRACT FROM AUTHOR]

Acute myeloid leukemia (AML) is a heterogeneous disease marked by the presence of several driver mutations and molecular subgroups even in a single patient. The genetic and molecular heterogeneity is also reflected by a progressive shift from a morphologic classification to one informed by causative genomic changes. Cytogenetic results and somatic mutations are increasingly being utilized to guide use of intensive chemotherapy and low‐intensity chemotherapy, particularly among older adults. Utilization of next‐generation sequencing in AML has led to increasing use of targeted treatments for actionable mutations. Quantitative real‐time polymerase chain reaction‐based mutational analysis and multicolor flow cytometry offer sensitive assays that can detect minimal residual disease (MRD). Several studies have shown that MRD negativity, as defined by specified cutoff values, is highly prognostic with potential therapeutic implications. The last 3 years mark an unprecedented history in the drug development in AML with approval of 8 new drugs and large portfolio of ongoing early and late‐phase trials of several promising drugs. Multiple combinatorial trials of approved agents and approval of newer agents in the future will continue to change the therapeutic landscape of AML. [ABSTRACT FROM AUTHOR]

Photovoltaic power‐conversion systems can harvest energy from sunlight almost perpetually whenever sunrays are accessible. Meanwhile, as indispensable energy storage units used in advanced technologies such as portable electronics, electric vehicles, and renewable/smart grids, batteries are energy‐limited closed systems and require constant recharging. Fusing these two essential technologies into a single device would create a sustainable power source. Here, it is demonstrated that such an integrated device can be realized by fusing a rear‐illuminated single‐junction perovskite solar cell with Li4Ti5O12‐LiCoO2 Li‐ion batteries, whose photocharging is enabled by an electronic converter via voltage matching. This design facilitates a straightforward monolithic stacking of the battery on the solar cell using a common metal substrate, which provides a robust mechanical isolation between the two systems while simultaneously providing an efficient electrical interconnection. This system delivers a high overall photoelectric conversion‐storage efficiency of 7.3%, outperforming previous efforts on stackable integrated architectures with organic–inorganic photovoltaics. Furthermore, converter electronics facilitates system control with battery management and maximum power point tracking, which are inevitable for efficient, safe, and reliable operation of practical loads. This work presents a significant advancement toward integrated photorechargeable energy storage systems as next‐generation power sources. [ABSTRACT FROM AUTHOR]

The political economy literature on post‐disaster reconstruction tends to contrast 'disaster capitalism' narratives denouncing the predatory character of neoliberal rebuilding, and 'building back better' policies supporting market‐driven reconstruction. This article seeks to provide a more nuanced account, developing the concept of 'disaster financialization' through a case study of household‐level changes experienced through processes of post‐earthquake reconstruction in Nepal. The concept of disaster financialization describes not only the integration of disaster‐affected households into the cash‐based logic of reconstruction instituted by donors and government authorities, but also the financialization of their lives, social relations and subjectivities. It is a transitive process involving a shift into financialized mechanisms of disaster prevention, adaptation and recovery. Analysing contrasting experiences across three earthquake‐affected districts in Nepal, this study proposes disaster financialization as an integrative term through which to understand the simultaneous acceleration of monetization, the leveraging of cash incentives by donors and government to 'build back better', and the flurry of financial transactions associated with reconstruction processes. While some aspects of disaster financialization have had negative social impacts, such as debt‐related anxieties and a breakdown of voluntary labour exchanges hurting the most vulnerable, the process has taken on variegated forms, with equally variegated effects, reflecting household characteristics and interactions with financial institutions. [ABSTRACT FROM AUTHOR]

Two new examples of structurally characterized β‐diketiminate analogues i.e., conjugated bis‐guanidinate (CBG) supported palladium(II) complexes, [LPdX]2; [L= {(ArHN)(ArN)–C=N–C=(NAr)(NHAr)}; Ar = 2,6‐Et2‐C6H3], X = Cl (1), Br (2) have been reported. The synthesis of complexes 1–2 was achieved by two methods. Method A involves deprotonation of LH by nBuLi followed by the treatment of LLi (insitu formed) with PdCl2 in THF, which afforded compound 1 in good yield (75 %). In Method B, the reaction between free LH and PdX2 (X = Cl or Br) in THF allowed the formation of complexes 1 (Yield 73 %) and 2 (Yield 52 %), respectively. Moreover, these complexes were characterized thoroughly by several spectroscopic techniques (1H, 13C NMR, UV/Vis, FT‐IR, and HRMS), including single‐crystal X‐ray structural and elemental analyses. In addition, we tested the catalytic activity of these complexes 1–2 for the hydroboration of carbonyl compounds with pinacolborane (HBpin). We observed that compound 1 exhibits superior catalytic activity when compared to 2. Compound 1 efficiently catalyzes various aldehydes and ketones under solvent‐free conditions. Furthermore, both inter‐ and intramolecular chemoselectivity hydroboration of aldehydes over other functionalities have been established. [ABSTRACT FROM AUTHOR]

In recent years, hybrid perovskite solar cells (HPSCs) have received considerable research attention due to their impressive photovoltaic performance and low‐temperature solution processing capability. However, there remain challenges related to defect passivation and enhancing the charge carrier dynamics of the perovskites, to further increase the power conversion efficiency of HPSCs. In this work, the use of a novel material, phenylhydrazinium iodide (PHAI), as an additive in MAPbI3 perovskite for defect minimization and enhancement of the charge carrier dynamics of inverted HPSCs is reported. Incorporation of the PHAI in perovskite precursor solution facilitates controlled crystallization, higher carrier lifetime, as well as less recombination. In addition, PHAI additive treated HPSCs exhibit lower density of filled trap states (1010 cm−2) in perovskite grain boundaries, higher charge carrier mobility (≈11 × 10−4 cm2 V−1 s), and enhanced power conversion efficiency (≈18%) that corresponds to a ≈20% improvement in comparison to the pristine devices. [ABSTRACT FROM AUTHOR]

Multiple sclerosis (MS) is a chronic inflammatory and neurodegenerative disease leading to gray matter atrophy and brain network reconfiguration as a response to increasing tissue damage. We evaluated whether white matter network reconfiguration appears subsequently to gray matter damage, or whether the gray matter degenerates following alterations in white matter networks. MRI data from 83 patients with clinically isolated syndrome and early relapsing–remitting MS were acquired at two time points with a follow‐up after 1 year. White matter network integrity was assessed based on probabilistic tractography performed on diffusion‐weighted data using graph theoretical analyses. We evaluated gray matter integrity by computing cortical thickness and deep gray matter volume in 94 regions at both time points. The thickness of middle temporal cortex and the volume of deep gray matter regions including thalamus, caudate, putamen, and brain stem showed significant atrophy between baseline and follow‐up. White matter network dynamics, as defined by modularity and distance measure changes over time, were predicted by deep gray matter volume of the atrophying anatomical structures. Initial white matter network properties, on the other hand, did not predict atrophy. Furthermore, gray matter integrity at baseline significantly predicted physical disability at 1‐year follow‐up. In a sub‐analysis, deep gray matter volume was significantly related to cognitive performance at baseline. Hence, we postulate that atrophy of deep gray matter structures drives the adaptation of white matter networks. Moreover, deep gray matter volumes are highly predictive for disability progression and cognitive performance. [ABSTRACT FROM AUTHOR]

Background: Migraine pathophysiology is complex and probably involves cortical and subcortical alterations. Structural and functional brain imaging studies indicate alterations in the higher order visual cortex in patients with migraine. Arterial spin labeling magnetic resonance imaging (ASL‐MRI) is a non‐invasive imaging method for assessing changes in cerebral blood flow (CBF) in vivo. Objective: To examine if interictal CBF differs between patients with episodic migraine (EM) with or without aura and healthy controls (HC). Methods: We assessed interictal CBF using 2D pseudo‐continuous ASL‐MRI on a 3 Tesla Philips scanner (University Hospital Zurich, Switzerland) in EM (N = 17, mean age 32.7 ± 9.9, 13 females) and HC (N = 19, mean age 31.0 ± 9.3, 11 females). Results: Compared to HC, EM showed exclusively hyperperfusion in the right MT+ and Cohen's d effect size was 0.99 (HC mean CBF ± SD: 33.1 ± 5.9 mL/100 g/minutes; EM mean CBF: 40.9 ± 9.4 mL/100 g/minutes). EM with aura (N = 13, MwA) revealed hyperperfusion compared to HC in the right MT+ and superior temporal gyrus. For MT, Cohen's d effect size was 1.34 (HC mean CBF ± SD: 33.1 ± 5.9 mL/100 g/minutes; MwA mean CBF: 43.3 ± 8.6 mL/100 g/minutes). For the superior temporal gyrus, Cohen's d effect size was 1.28 (HC mean CBF ± SD: 40.1 ± 4.9 mL/100 g/minutes; MwA mean CBF: 47.4 ± 6.4 mL/100 g/minutes). In EM, anxiety was positively associated with CBF in the parietal operculum and angular gyrus. Conclusions: Our results suggest that extrastriate brain regions probably involved in cortical spreading depression are associated with CBF changes in the interictal state. We conclude that ASL‐MRI is a sensitive method to identify local neuro‐functional abnormalities in CBF in patients with EM in the interictal state. [ABSTRACT FROM AUTHOR]

Background: Deep brain stimulation (DBS) is an effective evidence-based therapy for dystonia. However, no unequivocal predictors of therapy responses exist. We investigated whether patients optimally responding to DBS present distinct brain network organization and structural patterns.Methods: From a German multicenter cohort of 82 dystonia patients with segmental and generalized dystonia who received DBS implantation in the globus pallidus internus, we classified patients based on the clinical response 3 years after DBS. Patients were assigned to the superior-outcome group or moderate-outcome group, depending on whether they had above or below 70% motor improvement, respectively. Fifty-one patients met MRI-quality and treatment response requirements (mean age, 51.3 ± 13.2 years; 25 female) and were included in further analysis. From preoperative MRI we assessed cortical thickness and structural covariance, which were then fed into network analysis using graph theory. We designed a support vector machine to classify subjects for the clinical response based on individual gray-matter fingerprints.Results: The moderate-outcome group showed cortical atrophy mainly in the sensorimotor and visuomotor areas and disturbed network topology in these regions. The structural integrity of the cortical mantle explained about 45% of the DBS stimulation amplitude for optimal response in individual subjects. Classification analyses achieved up to 88% of accuracy using individual gray-matter atrophy patterns to predict DBS outcomes.Conclusions: The analysis of cortical integrity, informed by group-level network properties, could be developed into independent predictors to identify dystonia patients who benefit from DBS. © 2019 The Authors. Movement Disorders published by Wiley Periodicals, Inc. on behalf of International Parkinson and Movement Disorder Society. [ABSTRACT FROM AUTHOR]

Purpose: We present a classifier for automatically selecting a lesion border for dermoscopy skin lesion images, to aid in computer‐aided diagnosis of melanoma. Variation in photographic technique of dermoscopy images makes segmentation of skin lesions a difficult problem. No single algorithm provides an acceptable lesion border to allow further processing of skin lesions. Methods: We present a random forests border classifier model to select a lesion border from 12 segmentation algorithm borders, graded on a "good‐enough" border basis. Morphology and color features inside and outside the automatic border are used to build the model. Results: For a random forests classifier applied to an 802‐lesion test set, the model predicts a satisfactory border in 96.38% of cases, in comparison to the best single border algorithm, which detects a satisfactory border in 85.91% of cases. Conclusion: The performance of the classifier‐based automatic skin lesion finder is found to be better than any single algorithm used in this research. [ABSTRACT FROM AUTHOR]

This paper explores a vertical product differentiation model with a licensing arrangement between a multinational firm with superior technology and a domestic firm with obsolete technology. We find that a subsidy provided by the domestic country's government to the domestic firm to assist with the licensing arrangement is welfare enhancing for the domestic country. Furthermore, both the multinational firm and the domestic country are better off under royalty than under fixed fee licensing. These findings stand in contrast to earlier results in the literature. [ABSTRACT FROM AUTHOR]