bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigation and Modeling of the Electrical Bias Stress in Electrolyte‐Gated Organic Transistors
Authors: Segantini Matteo , Ballesio Alberto , Palmara Gianluca , Zaccagnini Pietro , Frascella Francesca , Garzone Giovanna , Marasso Simone Luigi , Cocuzza Matteo , Parmeggiani Matteo
Published: May 2022

Electrolyte‐gated organic transistors (EGOTs) are emerging as an important tool in advanced biosensing applications. However, their widespread exploitation is still limited by their poor operational stability. In order to understand the causes of this unreliability, the proposed study focuses on the influence of electrical bias stress (EBS) on EGOTs operating in aqueous electrolytes. Poly(3‐hexylthiophene) (P3HT)‐ and poly[3‐(5‐carboxypentyl)thiophene)] (P3CPT)‐based transistors are studied under the application of a bias in the continuous and pulse mode. Combining electrical and spectroscopic characterizations, it is possible to ascribe the performance variation of P3HT devices to backbone rearrangements induced by side chain oxidation, hydration, and interfacial electrochemical doping at the semiconductor/electrolyte interface, while the presence of polar side chains in P3CPT enhances the oxidative degradation of the polymer throughout the bulk of the film. The charge‐trapping model based on a stretched exponential is commonly exploited for the description of EBS in solid dielectric organic field‐effect transistors (OFETs). The same model is here applied to fit liquid dielectric EGOT behavior. The extracted material parameters are in good agreement with those found in the literature for P3HT‐based OFETs. Finally, a novel improvement of the model is proposed to allow reproducing P3CPT data by accounting for its different degradation process.
Combining Experimental and Theoretical Techniques to Gain an Atomic Level Understanding of the Defect Binding Mechanism in Hard Carbon Anodes for Sodium Ion Batteries
Authors: Surta T. Wesley , Koh Edward , Li Zhifei , Fast Dylan B. , Ji Xiulei , Greaney P. Alex , Dolgos Michelle R.
Published: May 2022

Sodium ion batteries (NIBs) are an attractive alternative to lithium‐ion batteries in applications that require large‐scale energy storage due to sodium's high natural abundance and low cost. Hard carbon (HC) is the most promising anode material for NIBs; however, there is a knowledge gap in the understanding of the sodium binding mechanism that prevents a rational design of HC. This study tunes sucrose‐derived HC via synthesis temperature then evaluates the structural, physical, and electrochemical properties. Neutron total scattering is used to generate structural models by fitting pair distribution functions (PDF) with a combination of molecular dynamics and reverse Monte Carlo methods. From this model, the number and type of structural features are identified, quantified, and correlated to the galvanostatic charge/discharge. A method of PDF “fingerprinting” binding sites using Na probe atoms is developed and analyzing these PDFs reveals an atomistic view of ion binding sites responsible for “defect” storage mechanisms. Combining these techniques results in an atomic‐level study that provides a big picture of the Na‐binding mechanism in NIBs, which allows for more precise tuning of the structure–property relationships in the future. The methodologies developed will also enable new strategies for the analysis of amorphous functional materials.
Facilitating connection to enhance college student well‐being: Evaluation of an experiential group program
Authors: Costello Meghan A. , Nagel Alison G. , Hunt Gabrielle L. , Rivens Ariana J. , Hazelwood Olivia A. , Pettit Corey , Allen Joseph P.
Published: May 2022

This randomized controlled trial examined the impact of The Connection Project, an experiential, relationship‐focused intervention designed to improve school belongingness and decrease symptoms of depression and loneliness among new college students. Participants were 438 first‐year and transfer students (232 treatment, 206 waitlist‐control) at a medium‐sized, 4years, predominantly White public university in the Southeastern United States. At postintervention, the treatment group reported significant relative increases in school belonging and significant relative reductions in levels of loneliness and depressive symptoms in comparison to waitlist‐controls. Program effects were stronger for students from marginalized racial or ethnic backgrounds, students from lower socioeconomic status households, and transfer students. Results are interpreted as suggesting the utility of experiential, peer‐support prevention programming to promote college students' well‐being, particularly college students who hold identities that are traditionally disadvantaged in this context.
Systematic use of phenotype evidence in clinical genetic testing reduces the frequency of variants of uncertain significance
Authors: Johnson Britt , Ouyang Karen , Frank Lauren , Truty Rebecca , Rojahn Susan , Morales Ana , Aradhya Swaroop , Nykamp Keith
Published: May 2022

Guidelines for variant interpretation include criteria for incorporating phenotype evidence, but this evidence is inconsistently applied. Systematic approaches to using phenotype evidence are needed. We developed a method for curating disease phenotypes as highly or moderately predictive of variant pathogenicity based on the frequency of their association with disease‐causing variants. To evaluate this method's accuracy, we retrospectively reviewed variants with clinical classifications that had evolved from uncertain to definitive in genes associated with curated predictive phenotypes. To demonstrate the clinical validity and utility of this approach, we compared variant classifications determined with and without predictive phenotype evidence. The curation method was accurate for 93%–98% of eligible variants. Among variants interpreted using highly predictive phenotype evidence, the percentage classified as pathogenic or likely pathogenic was 80%, compared with 46%–54% had the evidence not been used. Positive results among individuals harboring variants with highly predictive phenotype‐guided interpretations would have been missed in 25%–37% of diagnostic tests and 39%–50% of carrier screens had other approaches to phenotype evidence been used. In summary, predictive phenotype evidence associated with specific curated genes can be systematically incorporated into variant interpretation to reduce uncertainty and increase the clinical utility of genetic testing.
Optochemical Control of Immune Checkpoint Blockade via Light‐Triggered PD‐L1 Dimerization
Authors: Liu Yuwei , Long Kaiqi , Kang Weirong , Wang Tianyi , Wang Weiping
Published: May 2022

The blockade of PD‐1/PD‐L1, which serves to “release the brake” of tumor immunity, represents a promising approach for treating various malignancies. However, the systemic immune‐related side effects significantly undermine its therapeutic efficacy. To address this dilemma, a photoactivatable and biocompatible prodrug cBMS‐1 based on the concept of photopharmacology is reported. The prodrug exhibits negligible toxicity but exerts effective PD‐1/PD‐L1 axis inhibition upon light irradiation, holding promising potential to achieve local activation of immune responses in clinical settings.
Strukturaufklärung eines chiralen in situ erzeugten hypervalenten Iod‐Komplexes mittels VCD‐Spektroskopie
Authors: Golub Tino P. , Abazid Ayham H. , Nachtsheim Boris J. , Merten Christian
Published: May 2022

Die Struktur von in situ erzeugten chiralen Aryl‐λ3‐iodanen, die unter oxidativen Reaktionsbedingungen erhalten wurden, konnte bisher nicht mit experimentellen Techniken beobachtet werden. Deren vorgeschlagene Strukturen beruhen nahezu ausschließlich auf DFT‐Berechnungen. In diesem Beitrag etablieren wir die Schwingungszirkulardichroismus‐Spektroskopie (VCD) als eine experimentelle Technik zur Verifizierung von DFT‐berechneten chiralen Iodanstrukturen. Für einen chiralen Triazol‐substituierten Iodoaren‐Katalysator wird ein bisher unbeschriebenes kationisches chirales Iodan identifiziert, dass eine intramolekulare N‐I‐Wechselwirkung aber keine signifikanten Wechselwirkungen mit Tosylat oder m‐Chlorbenzoesäure als potenzielle anionische Liganden aufweist. Stattdessen wurde eine Aggregation dieser Substrate festgestellt, die zur Bildung eines nicht‐koordinierenden anionischen wasserstoffgebundenen Komplexes führte. Die Bedeutung der VCD‐Spektroskopie als entscheidende experimentelle Methode zum Nachweis der kationischen Spezies wird auch durch die Tatsache unterstrichen, dass unser ursprünglicher Strukturvorschlag, der rein auf DFT‐Berechnungen basierte, widerlegt werden konnte.
Enhancement of mechanical properties of ultra‐high molecular weight polyethylene nanocomposites without losing thermal stability
Authors: Tenório Soares Igor , de Muniz Almeida Clara , de Maru Moraes Marcia Marie , de Fátima Vieira Marques Maria
Published: May 2022

This study involves the development of individual and hybrid nanocomposites and their structural, thermal, and mechanical characterization, using wear‐resistant fillers like aluminum oxide (Al2O3) and boron carbide (B4C) in a high‐performance polymer, namely, ultra‐high molecular weight polyethylene (UHMWPE). Nanocomposites were produced by ball milling followed by hot‐pressing molding, using vitamin E as an antioxidant agent. Fourier transform infrared spectroscopy and x‐ray diffractometry revealed no interaction at the molecular level between the phases. Optical microscopy evidenced a network formed by the nanoparticles surrounding the polymeric grains in the nanocomposites structure. Field emission scanning electron microscopy and confocal Raman spectroscopy helped understand this morphology. The mixing process results in a polymeric powder covered by the nanometric particles with a superficial interaction. Thermogravimetric analysis and differential scanning calorimetry were able to show the stability of the polymeric matrix, even with the presence of the nanofillers, which is possible due to the nanocomposites' structure. The produced nanocomposites present enhancement of their mechanical properties as compared to the pure polymer, evidenced by indentation tests. This work shows that UHMWPE can be manipulated to suit industrial applications that demand good mechanical reinforcement without losing thermal stability.
Recent Advances in Post‐polymerization Modifications on Polypeptides: Synthesis and Applications
Authors: Li Yue , Chang Rong , Chen Yong‐Xiang
Published: May 2022

Polypeptides, a kind of very promising biomaterial, have shown a wide range of applications due to their excellent biocompatibility, easy accessibility, and structural variability. To synthesize polypeptides with desired functions, post‐polymerization modification (PPM) plays an important role in introducing novel chemical structure on their side‐chains. The key to PPM strategy is to develop highly selective and efficient reactions that can couple the additional functional moieties with pre‐installed side‐chain functionalities on polypeptides. In this minireview, classic PPM approaches and their recent progresses are summarized and categorized into five sections, including various reactions on unsaturated alkyl, oxygen‐, nitrogen‐, sulfur‐containing and other special functional groups. In addition, we also highlight the applications of the resultant structure‐diversified polypeptides in the field of biomaterial.
Optimizing Atomically Dispersed Metal Electrocatalysts for Hydrogen Evolution: Chemical Coordination Effect and Electronic Metal Support Interaction
Authors: Jiang Su , Xue Dongping , Zhang Jia‐Nan
Published: May 2022

Hydrogen has emerged as a green and sustainable fuel to meet the demand for future global energy. Distinct from steam reforming, electrochemical water splitting, especially powered by renewables, has been considered as a promising technique for scalable production of high‐purity hydrogen with no carbon emission. Its commercialization depends on accelerating reaction kinetics and thus reduction of hydrogen cost, requiring electrocatalysts that are efficient, economical, and capable of stable and sustained hydrogen production. Atomically dispersed metal carbon‐based catalysts (ADMCs) have attracted extensive attention due to their high atom utilization, abundant accessible active sites, fast mass transfer, and well‐defined and tunable structures as ideal models for commercialized hydrogen production catalysts. However, boosting the performances of ADMCs for HER still requires new‐captions of rational structural design. In this review, starting from the recently developed strategies of ADMCs synthesis, the microenvironment regulation of active sites of ADMCs are systematically summarized and discussed, such as atomically metal doping, synergetic atomically doping and ADMCs supported nanocrystals. With attention on the catalytic mechanisms and structure‐activity relationships ranging from chemical coordination effects and electronic metal‐support interaction, the active origin of ADMCs in the electrocatalytic hydrogen evolution reaction is discussed. Finally, the review outlooks the remaining challenges and emerging research topics in the future, including long service life, amplification preparation techniques, high‐output alkaline water electrolysis, seawater electrolysis for hydrogen production and large current density hydrogen evolution. The new insights and knowledge into these aspects will be helpful for filling the existing gaps between scientific communities and industries and open up opportunities for bringing this promising technology into reality.
The endocannabinoid system in borderline personality disorder and antisocial personality disorder: A scoping review
Authors: Ho Wilson , Kolla Nathan J.
Published: May 2022

Individuals with borderline personality disorder (BPD) or antisocial personality disorder (ASPD) are overrepresented in forensic settings. Yet, despite the burden these disorders place on healthcare and criminal justice systems, there remains a lack of evidence‐based pharmacological treatments. Epidemiological data have shown that comorbid cannabis use disorders are common in BPD and ASPD. ∆9‐Tetrahydrocannabinol, the primary psychoactive constituent of cannabis, is an exogenous cannabinoid that stimulates the endocannabinoid system (ECS). Hence, an investigation of the ECS in these conditions is warranted. This scoping review screened 105 records and summarized the extant research on the ECS in ASPD (n = 69) and BPD (n = 61) participants. Preliminary results suggest that alterations of the ECS may be present in these disorders. Although research examining the ECS in personality disorders is still in its infancy, more research is warranted given initial positive findings.
An Excel‐based approach for designing stepped driveshafts for mobility devices and a study of its use in a design of machine elements course
Authors: Darnal Aryabhat , Fisseler Matthew , Benjamin Chandler C. , Srinivasa Arun R.
Published: May 2022

The aim of this paper is to describe a new MS Excel‐based approach for designing driveshafts for stiffness and fatigue strength. We analyze the efficacy of the approach in engaging students in an iterative design process and higher‐level qualitative decision‐making activities in an undergraduate class at Texas A&M University. Compared to conventional fixed cross‐section frames and trusses, there are few tools (barring Finite Element Packages) that facilitate rapid design evaluations of stepped shafts. The approach is based on a novel use of singularity functions to obtain explicit solutions for stepped shafts under concentrated loads. This approach allows for relatively easy implementation into Excel without the need for any numerical integration or other forms of approximation. Currently, the tedious calculations involved in the design of stepped shafts prevent instructors from exploring iterative changes in driveshaft design. The Excel tool that we have developed allows instructors and students to focus on iterative decision‐making. With this tool, open‐ended design questions are assigned even in exams since the entire iterative process takes less than 15–20 min. Student surveys and analysis of exam answers reveal that students have gained a considerable capability to make design decisions. They also indicate areas where improvement in design thinking is needed.
A practical framework RNMF for exploring the association between mutational signatures and genes using gene cumulative contribution abundance
Authors: Li Zhenzhang , Liang Haihua , Zhang Shaoan , Luo Wen
Published: May 2022

Background

Mutational signatures are somatic mutation patterns enriching operational mutational processes, which can provide abundant information about the mechanism of cancer. However, understanding of the pathogenic biological processes is still limited, such as the association between mutational signatures and genes.

Methods

We developed a simple and practical R package called RNMF (https://github.com/zhenzhang‐li/RNMF) for mutational signature analysis, including a key model of cumulative contribution abundance (CCA), which was designed to highlight the association between mutational signatures and genes and then applying it to a meta‐analysis of 1073 individuals with esophageal squamous cell carcinoma (ESCC).

Results

We revealed a number of known and previously undescribed SBS or ID signatures, and we found that APOBEC signatures (SBS2* and SBS13*) were closely associated with PIK3CA mutation, especially the E545k mutation. Furthermore, we found that age signature is closely related to the frequent mutation of TP53, of which R342* is highlighted due to strongly linked to age signature. In addition, the CCA matrix image data of genes in the signatures New, SBS3*, and SBS17b* were helpful for the preliminary evaluation of shortened survival outcome. These results can be extended to estimate the distribution of mutations or features, and study the potential impact of clinical factors.

Conclusions

In a word, RNMF can successfully achieve the correlation analysis of mutational signatures and genes, proving a strong theoretical basis for the study of mutational processes during tumor development.
Lifting the curtain on cultural values, materialism and luxury consumption: Evidence from Jordan
Authors: Shammout Eyad , D'Alessandro Steven , Small Felicity , Nayeem Tahmid
Published: May 2022

The demand for luxury goods is growing in new emerging markets. However, there is still minimal research on the influence of culture and materialism on consumers' purchasing behaviour for luxury goods in these markets. Data were collected using an online survey from 532 luxury customers in Jordan. This research provides empirical evidence that adds to brand luxury studies by investigating the relationship between cultural orientations (vertical–horizontal), dimensions of individualism and collectivism with materialism and other interpersonal factors influencing materialism and luxury purchase intentions. The findings show that materialism is highly correlated with vertical orientations. Moreover, the relationship between materialism and purchase intentions is not significant but mediated by the bandwagon effect and status consumption. This suggests that Jordanian consumers buy luxury products to help support their social status and keep up with trends within their social groups. For marketing management strategy, to encourage purchases, communication strategies should emphasise the social value of the purchase.
Understanding high‐involvement product purchase through an innovative machine learning approach: A case of housing type choice
Authors: Amarasinghe Arachchige Jaliya , Quach Sara , Roca Eduardo , Liu Benjamin , Liew Alan Wee‐Chung , Earl George
Published: May 2022

Adopting the conservation of resources theory, this research explores the joint influence of multiple factors affecting the choice of housing, an instance of a high involvement product. We develop an innovative Machine Learning approach to identify the most significant set of factors affecting consumers' housing choices. It was found that housing choices were primarily bound by energy resources and secondarily by other personal, conditional, and object resources. The study identified 25 key factors, many of which previous studies have not explored. The new factors include government payments, vehicle possession, time living with children, marriage duration, current location duration, and health conditions. The results suggest that joint effects of factors are more prominent than individual effects in influencing the choice of high‐involvement products. Further, the study suggests that ML methods are more robust than traditional methods and can be applied to analyse other types of high involvement products. The findings can assist real estate investors, policymakers and other stakeholders to understand sophisticated market behaviours to develop better and tailored housing strategies.
Give where you live: A social network analysis of charitable donations reveals localized prosociality
Authors: Chapman Cassandra M. , Louis Winnifred R. , Masser Barbara M. , Hornsey Matthew J. , Broccatelli Chiara
Published: May 2022

Millions of charities compete for donations, yet no empirical study has examined patterns of shared giving behavior across the nonprofit sector. To understand which types of charities are more likely to share donors, we conducted a social network analysis using behavioral data from 1,504,848 donors to 52 large charities in Australia. Three hypotheses were tested, which considered how patterns of shared donations may be determined by charity sub‐type (e.g., health, social services, religious), type of beneficiaries (i.e., humans, animals, the environment), or geographic focus (i.e., international, national, regional). Overall, results indicate that patterns of shared giving are strongly shaped by geography: international charities typically share donors, as do charities operating in the same local region. Some—albeit inconsistent—evidence also emerged to support the notion that sub‐type may be an organizing principle for donation distributions, but little support was found for the idea that beneficiaries influence shared giving patterns. A key managerial implication is that the practice of supporter list swapping may be most beneficial when lists are shared between organizations that both operate in the same geographic region rather than between organizations that both operate as the same sub‐type of charity or both share similar beneficiaries.
Effects of arbutin on glucose uptake by glucose transporter 4 (GLUT4) and its cytoprotective properties in L6 skeletal muscle cell line
Authors: Gholami Bahnemiri Mehdi , Nouri Hamid Reza , Zabihi Ebrahim , Sadeghi Farzin , Pouramir Mahdi
Published: May 2022

It has been well known that oxidative stress and increased intracellular reactive oxygen species (ROS) have a pivotal role in disrupting the insulin signaling pathways leading to cellular insulin resistance. In this study, we evaluated arbutin's effects on glucose uptake by GLUT4 and cytoprotective properties in the L6 skeletal muscle cell line. The effect of arbutin and tertiary butyl hydrogen peroxide (t‐BHP) on glucose uptake in cultured L6 cells was investigated by flow cytometry. We also evaluated gene expression levels of GLUT1 and GLUT4 in the L6 cells by quantitative real‐time polymerase chain reaction analysis. The results from the study demonstrated that the optimum ROS generation occurred 3 h after 100 µM t‐BHP treatment and pretreatment with arbutin (500 and 1000 µM) significantly inhibited the t‐BHP induced ROS generation (p < .05). Our result indicated that 3 h pretreatment of L6 cells with 1000 μM of arbutin before 50 μM t‐BHP significantly increased glucose uptake than the 50 μM t‐BHP alone group (p < .05). Our findings may suggest that an increase in the uptake of 2‐NBDG by L6 cells with arbutin pretreatment can be associated with increased expression of GLUT4 and GLUT1 under oxidative stress.
Case report: PICC line for a toddler with bilateral bidirectional Glenn shunt, Fontan circulation, and persistent left superior vena cava
Authors: Tran Huong Thi Mai , Tran Dien Minh , Nguyen Truong Ly Thinh , Nguyen Nguyet Thi , Nguyen Mai Thi , Ngo Huyen Thanh
Published: May 2022

Performing peripherally inserted central catheters for children with bilateral bidirectional Glenn shunt, Fontan circulation, and persistent left superior vena cava differs from those with normal central venous anatomy. This study presents two PICC procedures for a toddler with this condition to demonstrate an accurate PICC approach for such children.
Gram‐Scale Production of GDP‐β‐l‐fucose with Multi‐Enzyme Cascades in a Repetitive‐Batch Mode
Authors: Frohnmeyer Hannes , Rueben Simon , Elling Lothar
Published: May 2022

Guanosine 5’‐diphospho‐β‐l‐fucose (GDP‐Fuc) is an important and expensive nucleotide sugar only available in low quantities. We established two processes for the gram‐scale production of GDP‐Fuc with multi‐enzyme cascades. We used the bifunctional enzyme fucokinase/GDP‐fucose pyrophosphorylase from Bacteroides fragilis either with an ATP‐regeneration system using polyphosphate or an excess of ATP. The optimized enzyme modules were scaled up to a 20 mL repetitive‐batch production with 15 and 12 repetitive batches for ATP‐regeneration and ATP excess, respectively. With ATP‐regeneration a final product amount of 1.1 g (31 % yield) GDP‐Fuc was obtained. The production process with ATP excess reached 1.6 g (57 % yield). Exceptional high total turnover numbers of 27 gP*gE−1 and 31 gP*gE−1, as well as space‐time‐yields of 0.083 gp*L−1*h−1 and 0.217 gp*L−1*h−1 were reached for each process respectively. Furthermore, we established a product purification protocol that enables a 95 % removal of free phosphates from the product solution, to ease further purification.
Halogenation and Nucleophilic Quenching: Two Routes to E−X Bond Formation in Cobalt Triple‐Decker Complexes (E=As, P; X=F, Cl, Br, I)
Authors: Garbagnati Anna , Piesch Martin , Seidl Michael , Balázs Gábor , Scheer Manfred
Published: May 2022

The oxidation of [(Cp’’’Co)2(μ,η2 : η2‐E2)2] (E=As (1), P (2); Cp’’’=1,2,4‐tri(tert‐butyl)cyclopentadienyl) with halogens or halogen sources (I2, PBr5, PCl5) was investigated. For the arsenic derivative, the ionic compounds [(Cp’’’Co)2(μ,η4 : η4−As4X)][Y] (X=I, Y=[As6I8]0.5 (3 a), Y=[Co2Cl6‐nIn]0.5 (n=0, 2, 4; 3 b); X=Br, Y=[Co2Br6]0.5 (4); X=Cl, Y=[Co2Cl6]0.5 (5)) were isolated. The oxidation of the phosphorus analogue 2 with bromine and chlorine sources yielded the ionic complexes [(Cp’’’Co)2(μ‐PBr2)2(μ‐Br)][Co2Br6]0.5 (6 a), [(Cp’’’Co)2(μ‐PCl2)2(μ‐Cl)][Co2Cl6]0.5 (6 b) and the neutral species [(Cp’’’Co)2(μ‐PCl2)(μ‐PCl)(μ,η1 : η1‐P2Cl3] (7), respectively. As an alternative approach, quenching of the dications [(Cp’’’Co)2(μ,η4 : η4‐E4)][TEF]2 (TEF=[Al{OC(CF3)3}4]−, E=As (8), P (9)) with KI yielded [(Cp’’’Co)2(μ,η4 : η4‐As4I)][I] (10), representing the homologue of 3, and the neutral complex [(Cp’’’Co)(Cp’’’CoI2)(μ,η4 : η1‐P4)] (11), respectively. The use of [(CH3)4N]F instead of KI leads to the formation of [(Cp’’’Co)2(μ‐PF2)(μ,η2 : η1 : η1‐P3F2)] (12) and 2, thereby revealing synthetic access to polyphosphorus compounds bearing P−F groups and avoiding the use of very strong fluorinating reagents, such as XeF2, that are difficult to control.
Synthesis and Exploitation of the Biological Profile of Novel Guanidino Xylofuranose Derivatives**
Authors: Fortuna Andreia , Gonçalves‐Pereira Rita , Costa Paulo J. , Jorda Radek , Vojáčková Veronika , Gonzalez Gabriel , Heise Niels V. , Csuk René , Oliveira M. Conceição , Xavier Nuno M.
Published: May 2022

The synthesis and biological evaluation of novel guanidino sugars as isonucleoside analogs is described. 5‐Guanidino xylofuranoses containing 3‐O‐saturated/unsaturated hydrocarbon or aromatic‐containing moieties were accessed from 5‐azido xylofuranoses via reduction followed by guanidinylation with N,N′‐bis(tert‐butoxycarbonyl)‐N′′‐triflylguanidine. Molecules comprising novel types of isonucleosidic structures including 5‐guanidino 3‐O‐methyl‐branched N‐benzyltriazole isonucleosides and a guanidinomethyltriazole 3′‐O‐dodecyl xylofuranos‐5′‐yl isonucleoside were accessed. The guanidinomethyltriazole derivative and a 3‐O‐dodecyl (N‐Boc)guanidino xylofuranose were revealed as selective inhibitors of acetylcholinesterase (Ki=22.87 and 7.49 μM, respectively). The latter also showed moderate antiproliferative effects in chronic myeloid leukemia (K562) and breast cancer (MCF‐7) cells. An aminomethyltriazole 5’‐isonucleoside was the most potent molecule with low micromolar GI50 values in both cells (GI50=6.33 μM, 8.45 μM), similar to that of the drug 5‐fluorouracil in MCF‐7 cells. Moreover, the most bioactive compounds showed low toxicity in human fibroblasts, further indicating their interest as promising lead molecules.
Sulfur‐Containing Silsesquioxane Derivatives Obtained by the Thiol‐ene Reaction: Synthesis and Thermal Degradation
Authors: Pakuła Daria , Przekop Robert E. , Brząkalski Dariusz , Frydrych Miłosz , Sztorch Bogna , Marciniec Bogdan
Published: May 2022

This article presents the synthesis of new derivatives of octa(3‐thiopropyl)silsesquioxane (SSQ‐8SH) via thiol‐ene reaction with simple olefins bearing alkyl groups as well as methoxysilyl, substituted aryl or fluoroalkyl groups. All products were characterized by 1H NMR, 13C NMR, 29Si NMR, FTIR, GPC, MALDI‐TOF‐MS, as well as thermal analysis (TGA) to confirm their structures, purity and thermal stability, and finally give some insight into their thermal degradation pathway. In some of the structures obtained, the T5% values take place at high temperatures and are close to 230 °C. The thiol‐ene reaction allowed to obtain 7 new compounds with high yield (>92 %), no by‐products and in a relatively short time (24 h). All products are characterized by high conversion >99 %. New derivatives can find potential use as modifiers of plastics to improve their certain properties for example hydrophobicity or thermo‐oxidative stability.
Paradoxical tensions in faculty identity and allegiance
Authors: Freebairn‐Smith Laura
Published: May 2022

In the inaugural column, I introduced the concept of paradoxical tensions — critical, unresolvable tensions that all leaders, including those in academia, must balance. All organizations are balancing an array of paradoxical tensions in every decision, even in the design of their offices: privacy versus camaraderie, freedom of speech versus civility, legal risks versus innovation, work–life balance versus output, the organization's needs versus the needs of science. Leaders and managers are the fulcrum for balancing these tensions.
Successful management of pyriform sinus cyst and fistula using endoscopic electrocauterization
Authors: Kawakubo Naonori , Obata Satoshi , Yoshimaru Koichiro , Miyoshi Kina , Izaki Tomoko , Tajiri Tatsuro
Published: May 2022

Objectives

Pyriform sinus cyst (PSC) and pyriform sinus fistula (PSF) is a rare congenital malformation that arises from the third or fourth branchial structure. In our study, we describe the safety and the utility of endoscopic electrocauterization against PSC/PSF.

Methods

We retrospectively reviewed the records of patients who underwent endoscopic electrocauterization for PSC/PSF at our hospital. The internal opening of the fistula was identified under general anesthesia using a flexible endoscope (XQ‐260 or H‐290; Olympus, Tokyo, Japan), and the DualKnifeJ (KD‐655L; Olympus) was used to ablate the internal opening.

Results

We experienced three PSF and three PSC patients. The postoperative course was uneventful in all cases. The patients declared no pain in the neck, and there were no cases showing recurrent nerve paralysis. Five in six cases (83%), the closure of fistula was archived in the first cauterization. One case (16.6%) required repeated cauterization. No recurrence was found during the follow‐up period ( median: 1 year) in any cases.

Conclusions

Owing to its rarity in neonates, the diagnosis and treatment of PSC remains complicated and not clearly described. Complete removal of the fistula and the cyst with or without affected thyroid tissue was previously the most commonly used treatment. From our experience, we believe that endoscopic electrocauterization can be the first choice not only for PSF but also for neonatal PSC. In conclusion, endoscopic electrocauterization is feasible even for neonatal PSC. Further investigations including multicenter analyses are needed.
A new cannabinoid receptor 1 selective agonist evading the 2021 “China ban”: ADB‐FUBIATA
Authors: Deventer Marie H. , Van Uytfanghe Katleen , Vinckier Inge M. J. , Reniero Fabiano , Guillou Claude , Stove Christophe P.
Published: May 2022

Following the class‐wide ban of synthetic cannabinoid receptor agonists (SCRAs) in China, SCRAs carrying new core and linker structures, aimed at circumventing the recent Chinese generic legislation, have appeared on the recreational drug market. A very recent example is (S)‐2‐(2‐(1‐(4‐fluorobenzyl)‐1H‐indol‐3‐yl)acetamido)‐3,3‐dimethylbutanamide (ADB‐FUBIATA), which is structurally closely related to the potent SCRA ADB‐FUBICA, but carries an additional methylene in the linker region of the molecule. ADB‐FUBIATA has recently been identified in seized materials in China, Russia, the United States, and also Belgium; however, its pharmacological characteristics were unknown. The aim of this study was to evaluate the intrinsic cannabinoid receptor (hCB1 and hCB2) activation potential of this previously unknown substance via two distinct yet similar in vitro β‐arrestin2 recruitment assays, based on the NanoLuc Binary Technology®. At CB1, a potency of 635 nM (EC50) was found, with an efficacy (Emax) of 141% relative to the reference compound CP55,940. On the other hand, ADB‐FUBIATA had almost no activity at CB2, indicative of a clear CB1 selectivity. Interestingly, this activation pattern differs markedly from that observed for ADB‐FUBICA, which was previously found to be potent and efficacious at both cannabinoid receptors. Additionally, the bioassays were applied to a seized powder containing ADB‐FUBIATA, as analytically confirmed by high‐performance liquid chromatography coupled to diode‐array detection (HLPC‐DAD), gas chromatography coupled to mass spectrometry (GC‐MS), liquid chromatography couple to time‐of‐flight mass spectrometry (LC‐QTOF‐MS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR). The EC50 and Emax values obtained for this powder were very similar to those of the ADB‐FUBIATA analytical standard, suggesting a high purity of the powder, although analytical techniques did reveal that the sample was not entirely pure.
Diets maintained in a changing world: Does land‐use intensification alter wild bee communities by selecting for flexible generalists?
Authors: Peters Birte , Keller Alexander , Leonhardt Sara Diana
Published: May 2022

Biodiversity loss, as often found in intensively managed agricultural landscapes, correlates with reduced ecosystem functioning, for example, pollination by insects, and with altered plant composition, diversity, and abundance. But how does this change in floral resource diversity and composition relate to occurrence and resource use patterns of trap‐nesting solitary bees? To better understand the impact of land‐use intensification on communities of trap‐nesting solitary bees in managed grasslands, we investigated their pollen foraging, reproductive fitness, and the nutritional quality of larval food along a land‐use intensity gradient in Germany. We found bee species diversity to decrease with increasing land‐use intensity irrespective of region‐specific community compositions and interaction networks. Land use also strongly affected the diversity and composition of pollen collected by bees. Lack of suitable pollen sources likely explains the absence of several bee species at sites of high land‐use intensity. The only species present throughout, Osmia bicornis (red mason bee), foraged on largely different pollen sources across sites. In doing so, it maintained a relatively stable, albeit variable nutritional quality of larval diets (i.e., protein to lipid (P:L) ratio). The observed changes in bee–plant pollen interaction patterns indicate that only the flexible generalists, such as O. bicornis, may be able to compensate the strong alterations in floral resource landscapes and to obtain food of sufficient quality through readily shifting to alternative plant sources. In contrast, other, less flexible, bee species disappear.
Recent change in spatial distribution of the European flat oyster (Ostrea edulis) inferred from field data and empirical models of living oysters and empty shells
Authors: Bergström Per , Thorngren Linnea , Lindegarth Mats
Published: May 2022

Marine coastal areas are increasingly affected by human activities resulting in changes in species and habitat distributions. Understanding these patterns and its causes and consequences is important for conservation and restoration of such changing habitats. One habitat that has been heavily affected by human use are the North Sea oyster beds which once were abundant but have lost large parts of its coastal distribution due to overexploitation. Based on data of living and dead assemblages of Ostrea edulis collected using video transects, we used an ensemble modeling technique to model and predict current and recent distribution of O. edulis along the Swedish west coast where its distribution is, in relative terms, still rather unaffected. We could detect a recent change in the distribution of O. edulis along the coast which to a large extent could be attributed to a change in depth distribution, suggesting that the population of O. edulis have a slightly shallower distribution today than in the past. Although a potential mismatch between living and dead assemblages, caused by a complex combination of biological and environmental conditions, needs to be considered in the interpretations drawn, it may be a way around the lack of suitable background data in management decisions. This provides important information for management and conservation of the native oyster beds. Furthermore, this study illustrates a method for identifying recent changes in species distribution using dead assemblages of bivalves.
Interfacial Engineering of Defect‐Rich and Multi‐Heteroatom‐Doped Metal–Organic Framework‐Derived Manganese Fluoride Anodes to Boost Lithium Storage
Authors: Tan Xiaohong , Liu Jiawei , Huang Jiating , Li Yilin , Zeb Akif , Lin Xiaoming
Published: May 2022

Manganese fluoride (MnF2) is a high‐performance lithium‐ion battery anode material with an excellent structural stability, low synthesis cost, and better manufacturing convenience. However, its low theoretical capacity (577 mAh g−1), weak conductivity of fluoride, and poor recyclability limit its practical application. Fortunately, oxygen vacancies (Ov) and heteroatomic doping are among the most promising strategies to modulate the inherent reduced electronic conductivity and kinetic response of electrode materials in order to boost their lithium storage capacity. Herein, self‐templating, self‐optimizing, and self‐supporting metal–organic framework template approach with the introduction of oxygen vacancies by substitution of exogenous heteroatoms is proposed, where triple heteroatom‐doped (N, O, and F) carbon‐encapsulated MOF‐derived manganese fluoride (Ov‐ZMF@NOFs) microstructures are designed. Interestingly, the exogenously introduced triple heteroatomic carbon matrix forms a fluffy three‐dimensional mechanical structure, interlaced conducting networks, efficient conducting pathways, and intense electrochemical dynamics at the periphery of the manganese fluoride nanoparticles. Benefiting from the above‐mentioned features, the Ov‐ZMF@NOFs exhibit expected electrochemical properties with ultra‐long recyclability (high reversible capacity of 419 mAh g−1 at 6 A g−1) and good rate performance (capacity of 232 mAh g−1 at a current density of 16 A g−1). Theoretical calculations underline the essential contribution of multiple heteroatoms doping in boosting the electrode conductivity and reducing the lithium‐ion migration energy barrier. Combining controllable vacancy engineering and heteroatom doping technology at the nanoscale provides a new philosophy and concept for the design and fabrication of next‐generation high‐energy lithium‐ion battery materials.
Factors associated with health‐related quality of life in heart failure in 23 000 patients from 40 countries: results of the G‐CHF research programme
Authors: Johansson Isabelle , Balasubramanian Kumar , Bangdiwala Shrikant , Mielniczuk Lisa , Hage Camilla , Sharma Sanjib Kumar , Branch Kelley , Zhu Jun , Kragholm Kristian , Sliwa Karen , Alla Francois , Yonga Gerald , Roy Ambuj , Orlandini Andres , Grinvalds Alex , McCready Tara , Pogosova Nana , Störk Stefan , McMurray John J.V. , Conen David , Yusuf Salim ,   on behalf of the G‐CHF Investigators
Published: May 2022

Aims

To examine clinical and social correlates of health‐related quality of life (HRQL) in patients with heart failure (HF) from high‐ (HIC), upper middle‐ (UMIC), lower middle‐ (LMIC) and low‐income (LIC) countries.

Methods and results

Between 2017 and 2020, 23 292 patients with HF (32% inpatients, 61% men) from 40 countries were enrolled in the Global Congestive Heart Failure study. HRQL was recorded at baseline using the Kansas City Cardiomyopathy Questionnaire (KCCQ)‐12. In a cross‐sectional analysis, we compared age‐ and sex‐adjusted mean KCCQ‐12 summary scores (SS: 0–100, higher = better) between patients from different country income levels. We used multivariable linear regression examining correlations (estimated coefficients) of KCCQ‐12‐SS with sociodemographic, comorbidity, treatment and symptom covariates. The adjusted model (37 covariates) was informed by univariable findings, clinical importance and backward selection. Mean age was 63 years and 40% of patients were in New York Heart Association (NYHA) class III–IV. Average HRQL was 55 SD 27. It was 62.5 (95% confidence interval [CI] 62.0–63.1) in HIC, 56.8 (56.1–57.4) in UMIC, 48.6 (48.0–49.3) in LMIC, and 38.5 (37.3–39.7) in LICs (p < 0.0001). Strong correlates (estimated coefficient [95% CI]) of KCCQ‐12‐SS were NYHA class III versus class I/II (−12.1 [−12.8 to −11.4] and class IV versus class I/II (−16.5 [−17.7 to −15.3]), effort dyspnoea (−9.5 [−10.2 to −8.8]) and living in LIC versus HIC (−5.8 [−7.1 to −4.4]). Symptoms explained most of the KCCQ‐12‐SS variability (partial R2 = 0.32 of total adjusted R2 = 0.51), followed by sociodemographic factors (R2 = 0.12). Results were consistent in populations across income levels.

Conclusion

The most important correlates of HRQL in HF patients relate to HF symptom severity, irrespective of country income level.
Whole blood transcriptomic profiling identifies molecular pathways related to cardiovascular mortality in heart failure
Authors: Nath Mintu , Romaine Simon P.R. , Koekemoer Andrea , Hamby Stephen , Webb Thomas R. , Nelson Christopher P. , Castellanos‐Uribe Marcos , Papakonstantinou Manolo , Anker Stefan D. , Lang Chim C. , Metra Marco , Zannad Faiez , Filippatos Gerasimos , van Veldhuisen Dirk J. , Cleland John G. , Ng Leong L. , May Sean T. , Marelli‐Berg Federica , Voors Adriaan A. , Timmons James A. , Samani Nilesh J.
Published: May 2022

Aims

Chronic heart failure (CHF) is a systemic syndrome with a poor prognosis and a need for novel therapies. We investigated whether whole blood transcriptomic profiling can provide new mechanistic insights into cardiovascular (CV) mortality in CHF.

Methods and results

Transcriptome profiles were generated at baseline from 944 CHF patients from the BIOSTAT‐CHF study, of whom 626 survived and 318 died from a CV cause during a follow‐up of 21 months. Multivariable analysis, including adjustment for cell count, identified 1153 genes (6.5%) that were differentially expressed between those that survived or died and strongly related to a validated clinical risk score for adverse prognosis. The differentially expressed genes mainly belonged to five non‐redundant pathways: adaptive immune response, proteasome‐mediated ubiquitin‐dependent protein catabolic process, T‐cell co‐stimulation, positive regulation of T‐cell proliferation, and erythrocyte development. These five pathways were selectively related (RV coefficients >0.20) with seven circulating protein biomarkers of CV mortality (fibroblast growth factor 23, soluble ST2, adrenomedullin, hepcidin, pentraxin‐3, WAP 4‐disulfide core domain 2, and interleukin‐6) revealing an intricate relationship between immune and iron homeostasis. The pattern of survival‐associated gene expression matched with 29 perturbagen‐induced transcriptome signatures in the iLINCS drug‐repurposing database, identifying drugs, approved for other clinical indications, that were able to reverse in vitro the molecular changes associated with adverse prognosis in CHF.

Conclusion

Systematic modelling of the whole blood protein‐coding transcriptome defined molecular pathways that provide a link between clinical risk factors and adverse CV prognosis in CHF, identifying both established and new potential therapeutic targets.
Examining the relationship between autistic spectrum disorder characteristics and structural brain differences seen in anorexia nervosa
Authors: Halls Daniel , Leppanen Jenni , Kerr‐Gaffney Jess , Simic Mima , Nicholls Dasha , Mandy William , Williams Steven , Tchanturia Kate
Published: May 2022

Cortical differences have been reported in Anorexia Nervosa (AN) compared with healthy controls (HC); however, it is unclear if Autism Spectrum Disorder (ASD) characteristics are related to these cortical differences. The aim of this study was to examine if structural measures were correlated to ASD traits in AN. In total 184 female participants participated in the study; 57 acutely underweight AN participants (AAN), 59 weight‐restored participants (WR) and 68 HC. Participants underwent structural magnetic resonance imaging as well as completing the Autism Diagnostic Observation schedule, second edition to examine ASD characteristics. Group differences in curvature, gyrification, surface area, thickness, global grey matter and white matter were measured. Correlation and regression analysis were conducted to examine the relationship between cortical measures and ASD characteristics. Two decreased gyrification clusters in the right post central and supramarginal gyrus and decreased global grey matter were observed in the AAN group compared to HC and WR. No correlations between ASD traits and structural measures existed. Our results suggest structural differences seen in individuals with AN do not appear to be related to ASD characteristics.
Towards a new semantic middleware for service description, discovery, selection, and composition in the Internet of Things
Authors: Berrani Samir , Yachir Ali , Djamaa Badis , Mahmoudi Said , Aissani Mohamed
Published: May 2022

The emergence of the Internet of Things (IoT) allows the integration of everyday devices such as tags, sensors, and actuators into the Internet. IoT also provides handy and automatic techniques to interoperate ad‐hoc, heterogeneous, and mobile networks and simplify data sharing among devices by abstracting their capabilities as services. Nevertheless, the large number and heterogeneity of encompassed networks/devices and the diversity of the offered resources/services make the IoT service description, discovery, selection, and composition a challenging task. To deal with these issues, we introduce, in this article, a semantic middleware for IoT applications based on service composition. Such a solution supports the semantic description of IoT resources, including services and user requests, and provides a modular, end‐to‐end, and loosely coupled request resolution process that comprises a context‐aware service discovery, a semantic service selection, and an automatic lightweight service composition. The proposal is illustrated and extensively evaluated on a restricted smart‐city scenario. Obtained results show that the proposed service discovery, selection, and composition sub‐processes improve the scalability of equivalent state‐of‐the‐art solutions by around 15, 20, and 40, respectively.