bluuebunny/crossref_metadata_2025 huggingface dataset:
Blade‐Coating (100)‐Oriented α‐FAPbI3 Perovskite Films via Crystal Surface Energy Regulation for Efficient and Stable Inverted Perovskite Photovoltaics
Authors: Feng Wenhuai , Liu Xudong , Liu Gengling , Yang Guo , Fang Yuxuan , Shen Jinliang , Jin Bowen , Chen Xi , Huang Yu‐Hua , Wang Xu‐Dong , Wu Congcong , Yang Shaopeng , Wu Wu‐Qiang
Published: July 2024

Photoactive black‐phase formamidinium lead triiodide (α‐FAPbI3) perovskite has dominated the prevailing high‐performance perovskite solar cells (PSCs), normally for those spin‐coated, conventional n‐i‐p structured devices. Unfortunately, α‐FAPbI3 has not been made full use of its advantages in inverted p‐i‐n structured PSCs fabricated via blade‐coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites during film formation. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol % of N‐aminoethylpiperazine hydroiodide (NAPI) additive into α‐FAPbI3 crystal‐derived perovskite ink, which enabled the formation of highly‐oriented α‐FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade‐coated α‐FAPbI3 perovskite films via combining a series of in‐situ characterizations and theoretical calculations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb−I framework help to reduce the surface energy of (100) crystal plane by 42 %, retard the crystallization rate and lower the formation energy of α‐FAPbI3. Benefited from multifaceted advantages of promoted charge extraction and suppressed non‐radiative recombination, the resultant blade‐coated inverted PSCs based on (100)‐oriented α‐FAPbI3 perovskite films realized promising efficiencies up to 24.16 % (~26.5 % higher than that of the randomly‐oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3‐based inverted PSCs fabricated via scalable deposition methods.
3D Lead‐Organoselenide‐Halide Perovskites and their Mixed‐Chalcogenide and Mixed‐Halide Alloys
Authors: Li Jiayi , Wang Yang , Saha Santanu , Chen Zhihengyu , Hofmann Jan , Misleh Jason , Chapman Karena W. , Reimer Jeffrey A. , Filip Marina R. , Karunadasa Hemamala I.
Published: July 2024

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se−), which occupies both the X− and A+ sites in the prototypical ABX3 perovskite. The new organoselenide‐halide perovskites: (SeCYS)PbX2 (X=Cl, Br) expand upon the recently discovered organosulfide‐halide perovskites. Single‐crystal X‐ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide‐halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid‐state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV–straddling the ideal range for tandem solar cells or visible‐light photocatalysis. The comprehensive description of the average and local structures, and how they can fine‐tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid‐state and organo‐main‐group chemistry.
Functional Group‐Driven Competing Mechanism in Electrochemical Reaction and Adsorption/Desorption Processes toward High‐Capacity Aluminum‐Porphyrin Batteries
Authors: Jiao Shuqiang , Han Xue , Jiang Li‐Li , Du Xueyan , Huang Zheng , Li Shijie , Wang Wei , Wang Mingyong , Liu Yunpeng , Song Wei‐Li
Published: July 2024

Nonaqueous organic aluminum batteries are considered as promising high‐safety energy storage devices due to stable ionic liquid electrolytes and Al metals. However, the stability and capacity of organic positive electrodes are limited by their inherent high solubility and low active organic molecules. To address such issues, here porphyrin compounds with rigid molecular structures present stable and reversible capability in electrochemically storing AlCl2+. Comparison between the porphyrin molecules with electron‐donating groups (TPP‐EDG) and with electron‐withdrawing groups (TPP‐EWG) suggests that EDG is responsible for increasing both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, resulting in decreased redox potentials. On the other hand, EWG is associated with decreasing both HOMO and LUMO energy levels, leading to promoted redox potentials. EDG and EWG play critical roles in regulating electron density of porphyrin π bond and electrochemical energy storage kinetics behavior. The competitive mechanism between electrochemical redox reaction and de/adsorption processes suggests that TPP‐OCH3 delivers the highest specific capacity ~171.8 mAh g−1, approaching a record in the organic Al batteries.
p–d Orbital Hybridization in Ag‐based Electrocatalysts for Enhanced Nitrate‐to‐Ammonia Conversion
Authors: Wu Guanzheng , Zhang Wuyong , Yu Rui , Yang Yidong , Jiang Jiadi , Sun Mengmiao , Du Aijun , He Wenhui , Dai Lei , Mao Xin , Chen Zhening , Qin Qing
Published: July 2024

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate‐to‐ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p–d orbital hybridization via doping p‐block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn‐doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH3 at −0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3±14.1 mg h−1 mgcat.−1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere‐level current density of 1.1 A cm−2 with an NH3 yield of 78.6 mg h−1 cm−2, during which NH3 can be further extracted to prepare struvite as high‐quality fertilizer. A mechanistic study reveals that a strong p–d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate‐determining step for NH3 synthesis, which as a general principle, can be further extended to Bi‐ and In‐doped Ag catalysts. Moreover, when integrated into a Zn‐nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L−1, high power density of 18.1 mW cm−2, and continuous NH3 production.
Catalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes via Sequential Povarov Reaction and Aromatizations
Authors: Yu Shaoze , Yuan Mengyao , Xie Wansen , Ye Zidan , Qin Tianren , Yu Na , Yang Xiaoyu
Published: July 2024

Inherently chiral calix[4]arenes represent a unique type of chiral molecules with significant applications, yet their catalytic enantioselective synthesis remains largely underexplored. We report herein the catalytic enantioselective synthesis of inherently chiral calix[4]arenes through the sequential organocatalyzed enantioselective Povarov reaction and aromatizations. The chiral phosphoric acid catalyzed three‐component Povarov reaction involving amino group‐substituted calix[4]arenes, aldehydes and (di)enamides desymmetrized the prochiral calix[4]arene substrates, which was followed by various aromatization methods, resulting in a diverse array of novel quinoline‐containing calix[4]arenes with good yields and high enantioselectivities (up to 75 % yield, 99 % ee). The large‐scale enantioselective synthesis and diverse derivatizations of the chiral calix[4]arene products highlight the value of this method. Furthermore, preliminary exploration into their photophysical and chiroptical properties demonstrate the potential applications of these novel calix[4]arene molecules.
Development of biobased, sustainable and environmentally friendly glycerol ester rosins for the production of thermoplastic road marking paint
Authors: Yılmaz Bilge , Deniz İlhan , Fazlı Hilal , Bekircan Olcay , Gültekin Ergün , Pranovich Andrey
Published: July 2024

In recent years, natural rosin derivatives have gained significant importance in the production of sustainable bio‐based materials, including thermoplastic road marking paint (TRMP). This study evaluates the use of sustainable natural glycerol ester rosins as bio‐based binders in TRMP formulations, specifically focusing on pine, wood, and tall oil rosins. Various analytical techniques, such as FT‐IR, TGA, MALDI‐TOF‐MS and GPC‐HPLC, were utilized to analyze both unmodified and glycerol ester rosins. Standard tests, including acid number (mg KOH/g) ASTM D 465‐05 and softening point (°C) ASTM E 28‐99, were also conducted on the samples. The optimum synthesis conditions for glycerol ester rosins (GER) were determined as follows: a rosin/glycerol molar ratio of 2.54, catalyst/rosin weight ratio of 0.5%, and antioxidant/rosin weight ratio of 1.0%. GPC‐HPLC analysis revealed average esterification reaction yields of over 90.85%. Furthermore, TRMPs underwent various tests, including gloss factor (β), chromaticity coordinates (x, y), UVB aging, and softening point (°C). The results demonstrated that GERs exhibited superior performance, especially in the UVB aging test, with all TRMPs classified as UV1 type. These findings highlight the promising potential of GERs derived from different types of rosins in producing sustainable, environmentally friendly, and bio‐based next‐generation TRMPs.
Genetically Proxied Interleukin‐13 Inhibition Is Associated With Risk of Psoriatic Disease: A Mendelian Randomization Study
Authors: Zhao Sizheng Steven , Hyrich Kimme , Yiu Zenas , Barton Anne , Bowes John
Published: July 2024

Objective

Inhibitors of the interleukin 13 (IL‐13) pathway, such as dupilumab, are licensed for atopic dermatitis and asthma. Adverse events resembling psoriatic disease after dupilumab initiation have been reported, but evidence is limited to case reports with uncertain causality. We aimed to investigate whether genetically mimicked IL‐13 inhibition (IL‐13i) is associated with risk of psoriatic arthritis (PsA) and psoriasis.

Methods

We instrumented IL‐13i using a protein‐coding variant in the IL13 gene, rs20541, that is associated with circulating eosinophil count (biomarker of IL‐13i) at genome‐wide significance in a study of 563,946 individuals. Outcome genetic data were taken from studies of PsA, psoriasis, and related spondyloarthritis traits in up to 10,588 cases and 209,287 controls. Colocalization analysis was performed to examine genetic confounding. We additionally used circulating IgE as a biomarker to test whether associations were replicated, both in the test and in an independent genetic dataset. We also replicated analyses using individual‐level data from the UK Biobank.

Results

Genetically proxied IL‐13i was associated with increased risk of PsA (odds ratio [OR] 37.39; 95% confidence interval [95% CI] 11.52–121.34; P = 1.64 × 10−9) and psoriasis (OR 20.08; 95% CI 4.38–92.01; P = 1.12 × 10−4). No consistent associations were found for Crohn disease, ulcerative colitis, ankylosing spondylitis, or iritis. Colocalization showed no strong evidence of genetic confounding for psoriatic disease. Results were replicated using circulating IgE for the exposure, using independent outcome data and using individual‐level data.

Conclusion

We provide supportive genetic evidence that IL‐13i is linked to increased risk of PsA and psoriasis. Physicians prescribing IL‐13 inhibitors should be vigilant for these adverse events.

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Heparosan biosynthesis in recombinant Bacillus megaterium: Influence of N‐acetylglucosamine supplementation and kinetic modeling
Authors: Nehru Ganesh , Balakrishnan Rengesh , Swaminathan Nivedhitha , Tadi Subbi Rami Reddy , Sivaprakasam Senthilkumar
Published: July 2024

Heparosan, an unsulfated polysaccharide, plays a pivotal role as a primary precursor in the biosynthesis of heparin—an influential anticoagulant with diverse therapeutic applications. To enhance heparosan production, the utilization of metabolic engineering in nonpathogenic microbial strains is emerging as a secure and promising strategy. In the investigation of heparosan production by recombinant Bacillus megaterium, a kinetic modeling approach was employed to explore the impact of initial substrate concentration and the supplementation of precursor sugars. The adapted logistic model was utilized to thoroughly analyze three vital parameters: the B. megaterium growth dynamics, sucrose utilization, and heparosan formation. It was noted that at an initial sucrose concentration of 30 g L−1 (S1), it caused an inhibitory effect on both cell growth and substrate utilization. Intriguingly, the inclusion of N‐acetylglucosamine (S2) resulted in a significant 1.6‐fold enhancement in heparosan concentration. In addressing the complexities of the dual substrate system involving S1 and S2, a multi‐substrate kinetic models, specifically the double Andrew's model was employed. This approach not only delved into the intricacies of dual substrate kinetics but also effectively described the relationships among the primary state variables. Consequently, these models not only provide a nuanced understanding of the system's behavior but also serve as a roadmap for optimizing the design and management of the heparosan production method.
Can Prussian Blue Analogues be Holy Grail for Advancing Post‐Lithium Batteries?
Authors: Palaganas Mecaelah S. , Garcia Jayson S. , Sanglay Giancarlo Dominador D. , Sapanta Lora Monique E. , Limjuco Lawrence A. , Ocon Joey D.
Published: July 2024

The recent classification of lithium as a critical raw material surged the research and development (R&D) of post‐lithium batteries (PLBs). The larger cation charge carriers of these PLBs consequently entailed extensive materials R&D for battery components, especially cathode. Prussian Blue (PB) and its analogues (PBAs) have emerged as promising cathode materials for PLBs due to their desirable characteristics, including a three‐dimensional open framework structure that facilitates fast ion diffusion for both monovalent (Li+, Na+, K+) and multivalent (Mg2+, Ca2+, Zn2+, Al3+) ions, stable framework structures, electrochemical tunability, availability of widely used precursors, and ease of synthesis. Our comprehensive review reveals that several challenges are yet to be addressed in employing PBAs as cathode materials for PLBs, viz., vacancies, crystal water, side reactions, and conductivity issues. This review paper provides an exhaustive survey of material development, including the mitigation strategies of the challenges in employing PBAs as cathode materials for advancing PLBs (i. e., sodium‐ion batteries (SIBs), potassium‐ion batteries (KIBs), magnesium‐ion batteries (MIBs), calcium‐ion batteries (CIBs), zinc‐ion batteries (ZIBs), aluminum‐ion batteries (AIBs)) towards commercialization.
Indications and added value of videourodynamics in men with spinal cord injury
Authors: Françot Marc , Lefevre Chloé , Reiss Bénédicte , Lefort Marc , Karam Georges , Rigaud Jerome , Le Normand Loic , Ruffion Alain , Perrouin‐Verbe Brigitte , Perrouin‐Verbe Marie‐Aimee
Published: July 2024

Purpose

The primary aim of this study was to evaluate the indications and additional information provided by videourodynamic study (VUDS) over urodynamic studies (UDS) in men with spinal cord injury (SCI) and neurogenic lower urinary tract dysfunction (NLUTD). The secondary aim was to determine the added value of VUDS and its impact on bladder management.

Materials and Methods

Single‐centre retrospective study of all men with SCI who underwent VUDS between 2011 and 2021. Participant characteristics, clinical data and indications for UDS and VUDS as well as bladder management were recorded. The added value of VUDS was defined as additional information not provided by standard UDS that impacted on bladder management (choice of voiding mode, surgical indication or type of surgery).

Results

Eighty‐eight men with a median age of 52 years were included. In 20 men who were unable to perform self‐catheterisation, the VUDS clarified the nature and extent of the obstruction and enabled targeted surgery to achieve reflex bladder emptying in all of them. VUDS also clarified the type and level of obstruction in 28 patients, enabling targeted surgery in 24. In 11 men, VUDS was performed as part of the preoperative assessment for a Brindley procedure or after this operation if a complication occurred during follow‐up to confirm the need for further surgery or to target surgical revision. Overall, VUDS had added value in 59 patients (67%).

Conclusions

VUDS had added value over UDS in specific situations; the additional information provided impacted on bladder management in men with SCI and NLUTD.
Partial atrioventricular canal defect and aortic coarctation associated with variants in GDF1 and NOTCH1 genes: A case report
Authors: Putotto Carolina , Masci Marco , Magliozzi Monia , Novelli Antonio , Marino Bruno , Digilio Maria Cristina , Toscano Alessandra
Published: July 2024

Background

A peculiar subgroup of patients with partial or complete atrioventricular canal defect exhibits a spectrum of left‐sided obstructions including right ventricular dominance and aortic coarctation. The association of atrioventricular canal defect with left‐sided obstructions is found in several genetic syndromes; however, the molecular basis of nonsyndromic atrioventricular canal defect with aortic coarctation is still poorly understood. Although some candidate genes for nonsyndromic atrioventricular canal defect are known, a complex oligogenic inheritance determined in some cases by the co‐occurrence of multiple variants has also been hypothesized.

Case Report

We describe a nonsyndromic infant with mesocardia with viscero‐atrial situs solitus, partial atrioventricular canal defect, mild right ventricular dominance, and coarctation of the aorta. Next generation sequencing genetic testing revealed variants in two genes, GDF1 and NOTCH1, previously reported in association with atrioventricular canal defect and left‐sided obstructive lesions, respectively.

Conclusion

The present report could support the hypothesis that the co‐occurrence of cumulative variants may be considered as genetic predisposing risk factor for specific congenital heart defects.
Optical discrimination of pathological red blood cells
Authors: Vergari Michele , Niccolini Benedetta , Pitocco Dario , Rizzi Alessandro , Ciasca Gabriele , de Spirito Marco , Gavioli Luca
Published: July 2024

Fast diagnostic methods are crucial to reduce the burden on healthcare systems. Currently, detection of diabetes complications such as neuropathy requires time‐consuming approaches to observe the correlated red blood cells (RBCs) morphological changes. To tackle this issue, an optical analysis of RBCs in air was conducted in the 250–2500 nm range. The distinct oscillations present in the scattered and direct transmittance spectra have been analyzed with both Mie theory and anomalous diffraction approximation. The results provide information about the swelling at the ends of RBCs and directly relate the optical data to RBCs morphology and deformability. Both models agree on a reduction in the size and deformability of RBCs in diabetic patients, thus opening the way to diabetes diagnosis and disease progression assessment.
Plasma metabolites and inflammatory proteins profiling predict outcome of Fufang Duzhong Jiangu granules treating Kashin–Beck disease
Authors: Deng Xingxing , Niu Hui , Zhang Qian , Wen Jinfeng , Zhao Yijun , Naren Gaowa , Liu Huan , Guo Xiong , Zhang Feng , Wu Cuiyan
Published: July 2024

To investigate predictive biomarkers that could be used to identify patients’ response to treatment, plasma metabolomics and proteomics analyses were performed in Kashin–Beck disease (KBD) patients treated with Fufang Duzhong Jiangu Granules (FDJG). Plasma was collected from 12 KBD patients before treatment and 1 month after FDJG treatment. LC–MS and olink proteomics were employed for obtaining plasma metabolomics profiling and inflammatory protein profiles. Patients were classified into responders and non‐responders based on drug efficacy. Enrichment analyses of differential metabolites and proteins of the responders at baseline and after treatment were conducted to study the mechanism of drug action. Differential metabolites and proteins between the two groups were screened as biomarkers to predict the drug efficacy. The receiver operating characteristic curve was used to evaluate the prediction accuracy of biomarkers. The changes in metabolites and inflammatory proteins in responders after treatment reflected the mechanism of FDJG treatment for KBD, which may act on glycerophospholipid metabolism, d‐glutamine and d‐glutamate metabolism, nitrogen metabolism and NF‐kappa B signaling pathway. Three metabolites were identified as potential predictors: N‐undecanoylglycine, β‐aminopropionitrile and PC [18:3(6Z,9Z,12Z)/20:4(8Z,11Z,14Z,17Z)]. For inflammatory protein, interleukin‐8 was identified as a predictive biomarker to detect responders. Combined use of these four biomarkers had high predictive ability (area under the curve = 0.972).
Exploring coopetition and value‐based networks in business models for sustainability—A case study of the specialty coffee industry in Colombia
Authors: Rodríguez Angélica , Alcalde‐Heras Henar , Iñigo Edurne A.
Published: July 2024

Drawing on coopetition‐based and values‐based business model networks, we explore competitors' coevolutionary interactions to drive sustainability. Using a specialty coffee industry case study in Colombia, we propose an analytical framework for collaboration, leveraging resources to transform neglected industry values. We apply the congruence analysis method to compare theoretical expectations with empirical findings, providing rigorous evidence. Our study reveals that developing values‐based networks through coopetition allows collective problem resolution and offers new opportunities for value creation. This research contributes to coopetition and values‐based network theories, emphasizing practical implications for sustainability‐focused business models. By highlighting competitor collaboration intricacies, our study enhances our understanding of the dynamics of local markets.
Investigating the Potential of 2‐Ethylbutyl‐(Phenoxy)phosphoryl‐D‐Alaninate Against RNA‐Dependent RNA Polymerase (RdRp) of SARS‐CoV‐2
Authors: Yadav Sandeep , Kumar Durgesh , Chopra Haritma , Bhatt Ishita , Gabba Ritu , Chaudhary Ankita , SINGH PRASHANT
Published: July 2024

There was an emergency call globally when COVID‐19 was detected in December 2019. The SARS‐CoV‐2 virus, a modified virus, is what causes this contagious disease. Although research is being conducted throughout the world, the main target is still to find the promising candidate to target RNA‐dependent RNA polymerase (RdRp) to provide possible drug against COVID‐19. Aim of this work is to find a molecule to inhibit the translational process of viral protein synthesis. Density Functional Theory calculations revealed information about the formation of the desired ligand (RD). Molecular docking of RD with RdRp was performed and compared with some reported molecules and the data revealed that RD had the best docking score with RdRp (−6.7 kcal/mol). Further, molecular dynamics (MD) simulations of RD with RdRp of SARS‐CoV‐2 revealed the formation of stable complex with a maximum number of seven hydrogen bonds. Root mean square deviations values are in acceptable range and root mean square fluctuations has less fluctuation indicate stable complex formation. Further, based on MM‐GBSA calculation, RD formed a stable complex with RdRp of nCoV with ΔG° of −12.28 kcal·mol−1.
Salvage endoscopic nasopharyngectomy in locally recurrent carcinoma adjacent to the internal carotid artery—A case report
Authors: Karamitsou Paraskevi , Poutoglidis Alexandros , Karamitsou Aikaterini , Papargyriou Georgia‐Evangelia , Leventi Argyro , Georgalas Christos
Published: July 2024

Key Clinical Message

In cases adjacent to critical structures, such as the internal carotid artery, surgeons should meticulously explore the feasibility of surgery before declaring the neoplasm unresectable.

Salvage treatment for locally recurrent carcinoma of the nasopharynx constitutes a unique challenge. Surgery remains the gold standard treatment modality. Endoscopic nasopharyngectomy is considered a safe and feasible procedure overcoming the morbidities of an open surgery. Tumor adjacency to the internal carotid artery (ICA) is not an absolute contradiction for the endoscopic approach. Even in cases adjacent to critical structures, surgeons should meticulously explore the feasibility of surgery before declaring the neoplasm unresectable. We present the case of a 56‐year‐old male with locally recurrent adenoid cystic carcinoma (AdCC) of the nasopharynx adjacent to the ICA treated with endoscopic nasopharyngectomy.
Gastrokine 1 transferred by gastric cancer exosomes inhibits growth and invasion of gastric cancer cells in vitro and in vivo
Authors: Tian Lingling , Tang Li , Li Xu , Huang Liuye
Published: July 2024

In gastric cancer, gastrokine 1 (GKN1) is a potential theragnostic marker while the related mechanisms remain elusive. Exosomes mediate intercellular communications via transferring various molecules, yet there are limited research studies on the specific cargos of gastric cancer exosomes and the associated mechanisms in this disease. In the present study, AGS and N87‐C cells were transfected with an overexpressed GKN1 plasmid, followed by extraction of exosomes. The study utilized gastric cancer cell lines and a xenograft mouse model to investigate the functional significance of exosomal GKN1. Cell proliferation, metastasis, and apoptosis were assessed through CCK‐8, Transwell, and flow cytometry assays, respectively. The study further explored the mechanism of exosomal GKN1 and its interaction with the PI3K/AKT/mTOR signaling pathways, including immunofluorescence and western blot analyses. Exosomal GKN1 was observed to suppress cell proliferation and invasion while enhancing apoptosis. This effect was attributed to the modulation of key proteins involved in cellular processes, including Ki‐67, MMP‐9, Bcl‐2, Bax, caspase‐3, and caspase‐9, ultimately impacting the PI3K/AKT/mTOR signaling pathway. The findings suggest that exosomal GKN1 exerts inhibitory effects on gastric cancer cell growth and invasion through the regulation of the PI3K/AKT/mTOR signaling cascade, both in experimental cell cultures and animal models.
Nitrogen, Fluorine, and Phosphorus Tri‐Doped Porous Carbon with High Electrical Conductivity as an Excellent Metal‐Free Electrocatalyst for Oxygen Reduction Reaction
Authors: Takada Ryuji , Narimatsu Kotaro , Taniguchi Yurika , Yang Xinran , Miyake Koji , Uchida Yoshiaki , Nishiyama Norikazu
Published: July 2024

Today's oxygen reduction reaction (ORR) depends on the precious metal Pt‐based catalysts, limiting the large commercialization of promising energy conversion technologies such as proton exchange membrane fuel cells (PEMFCs) and metal‐air batteries. Therefore, the rational design of low‐cost and highly efficient electrocatalysts for ORR is strongly desired. Herein, we report a porous carbon doped with nitrogen, fluorine, and phosphorus (N, F, P tri‐doped carbon) prepared via only a heating process using low‐cost glycine, ammonium fluoride, and phytic acid as precursors. X‐ray photoelectron spectroscopy (XPS) analysis revealed the existence of pyridinic‐N and the co‐existence of graphitic‐N and oxidized graphitic‐P, which can be active sites, with semi‐ionic C−F bonds highly boosting ORR activity. Remarkably, the resultant N, F, P tri‐doped carbon exhibited outstanding activity for the ORR with an onset potential comparable to that of commercial 20 wt % Pt/C catalyst, the half‐wave potential superior to that of the Pt/C catalyst, and the electron transfer number close to 4.
Exploiting Archaeal/Thermostable Enzymes in Synthetic Chemistry: Back to the Future?
Authors: Kudalkar Gaurav P. , Tiwari Virendra K. , Berkowitz David B.
Published: July 2024

Billions of years of evolution have led to the selection of (hyper)thermophiles capable of flourishing at elevated temperatures. The corresponding native (hyper)thermophilic enzymes retain their tertiary and quaternary structures at near‐boiling water temperatures and naturally retain catalytically competent conformational dynamics under these conditions. And yet, while hyper/thermophilic enzymes offer special opportunities in biocatalysis and in hybrid bio/chemocatalytic approaches to modern synthesis in both academia and industry, these enzymes remain underexplored in biocatalysis. Among the strategic advantages that can be leveraged in running biocatalytic transformations at higher temperatures are included more favorable kinetics, removal of volatile byproducts to drive reactions forward, improved substrate solubility and product separation, and accelerated stereodynamics for dynamic kinetic resolutions. These topics are discussed and illustrated with contemporary examples of note, in sections organized by stratagem. Finally, the reader is alerted in particular to archaeal enzymes that have proven useful in non‐natural synthetic chemistry ventures, and at the same time is referred to a rich area of archaea whose genomes have been sequenced but whose enzymatic activities of interest have not yet been mined. Though hyperthermophilic archaea are among the most ancient of organisms, their enzymes may hold the key to many future innovations in biocatalytic chemistry–perhaps we really do need to go ‘back to the future’.
Ambient Semi‐Hydrogenation of Terminal Alkynes with NaBH4 Catalyzed by Palladium Nanowires
Authors: Wang Ying , Ji Mengyuan , Wu Guohao , Wang Yawen , Zhang Yanhua
Published: July 2024

The semi‐hydrogenation of terminal alkynes is achieved with sodium borohydride (NaBH4) as the reductant and palladium nanowires (PdNWs) as the catalysts under ambient conditions. The reaction proceeds smoothly in the presence of only 0.32 mol % of PdNWs, giving the hydrogenated products with up to 98 % overall yields, in which 97 % are semi‐hydrogenated products. Under the optimal reaction conditions, both aromatic and aliphatic terminal alkynes have been successfully converted to the corresponding olefins with high efficiency and good selectivity. This method promotes the hydrogenation of terminal alkynes under mild conditions and opens up a window for the application of metal nanowires in organic syntheses.
Patients with glioblastoma: A tale of health care access and genetic ancestry
Authors: Asfaw Zerubabbel K. , Hernandez‐Marquez Gianina C. , Germano Isabelle M.
Published: July 2024

The incidence of glioblastoma, previously described as a disease predominantly affecting non‐Hispanic White patients, was higher among non‐White patients in the authors' recent study in which the racial/ethnical composition of the patients was representative of the overall population. These findings offer an opportunity to accurately redefine the patient population of patients with glioblastoma bearing the burden of this disease in the United States.
Stability and Surface Functionalization of Plasmonic Group 4 Transition Metal Nitrides
Authors: Shea Dreenan , Karaballi Reem A. , Jee Samantha , Dasog Mita
Published: July 2024

Plasmonic transition metal nitrides (TMNs) have emerged as a low‐cost and thermally and chemically robust alternatives to noble metals. While their superior thermal properties have been established, their chemical properties on the nanoscale haven't been as well investigated. Herein, the oxidative stability over time under ambient conditions and colloidal stability as function of pH was explored for plasmonic TiN, ZrN, and HfN nanoparticles. It was discovered that the TMN nanoparticles made via solid‐state method had a narrow pH stability range between 2–3. Under highly acidic conditions, the particles underwent dissolution and at pH ≥4, they aggregate and precipitate from the solution. Additionally, TiN nanoparticles had poor oxidative stability and oxidized to TiO2 after ~40 days. 3‐Aminopropyltriethoxysilane (APTES) and dimethylsilane coated TMNs were synthesized to yield water and organic solvent dispersible particles, respectively. These functionalized colloidal suspensions showed enhanced oxidative stability over 60 days and the APTES coating widened the pH stability window of TMNs to include physiological pH. This study shows that surface functionalization using M−O−Si linkages (where M=Ti, Zr, or Hf) can greatly enhance the stability, dispersibility and therefore applicability of plasmonic TMN nanoparticles.
Photostability of Phenoxazine Derivatives
Authors: Goll Felix D. , Welscher Philipp J. , Bodenmüller Franz , Blinder Rémi , Jelezko Fedor , Ziener Ulrich
Published: July 2024

Phenoxazine is a commonly used molecular building block, for example in optoelectronic applications and pharmaceuticals. However, it is highly susceptible to rapid photodegradation, especially in halogenated solvents. In the present study, we identify the degradation products in both halogenated and non‐halogenated solvents by UV/Vis absorption, NMR spectroscopy and mass spectrometry. We also propose a substitution strategy aimed at effectively suppressing the high photoreactivity. Kinetic studies show that the quantum yield of photodegradation φ differs by a factor of more than 1000 between trisubstituted derivatives and N‐substituted phenoxazine.
Computational Design of Bidentate Hypervalent Iodine Catalysts in Halogen Bond‐Mediated Organocatalysis
Authors: O'Brien James , Melnyk Nika , Lee Rico Shing , James Michael , Trujillo Cristina
Published: July 2024

In recent years, halogen bond‐based organocatalysis has garnered significant attention as an alternative to hydrogen‐based catalysis, capturing considerable interest within the scientific community. This transition has witnessed the evolution of catalytic scaffolds from monodentate to bidentate architectures, and from monovalent to hypervalent species. In this DFT‐based study, we explored a bidentate hypervalent iodine(III)‐based system that has already undergone experimental validation. Additionally, we explore various functionalisations (‐CF3, ‐CH3, ‐tBu, ‐OH, ‐OMe, ‐NO2, ‐CN) and scaffold modifications, such as sulfur oxidation, theoretically proposed for an indole‐based Michael addition. The investigated systems favour bidentate O‐type binding, underlining the importance of ligand coordination in catalytic activity. Electron‐deficient scaffolds exhibited stronger binding and lower activation energies, indicating the pivotal role of electronic properties for σ‐hole‐based catalysis. Of these groups, Lewis‐base‐like moieties formed stabilising intramolecular interactions with hypervalent iodines when in the ortho‐position. Furthermore, inductive electron withdrawal was deemed more effective than mesomeric withdrawal in enhancing catalytic efficacy for these systems. Lastly, increasing sulfur oxidation was theoretically proven to improve catalytic activity significantly.
Metal‐Organic Frameworks for Enhanced Hydrogen Generation from Syngas: A Density Functional Theory Approach
Authors: Gopalsamy Karuppasamy , Singh Chandrodai Pratap , Krishnamurty Sailaja , Babarao Ravichandar
Published: July 2024

Although methane poses environmental concerns, it is employed in hydrogen production processes such as steam‐methane reforming (SMR), which has an issue of by‐products released. Initiatives are being pursued to address CO and CO2 emissions using carbon capture methods, with the goal of minimizing environmental harm while improving pure hydrogen generation from syngas. In this study, porous coordination network (PCN‐250) has been studied for its selective adsorption property towards CO, CO2 and H2O as syngas mixture to obtain pure hydrogen. For this purpose, the trimetallic cluster node Fe2M (where Fe2 represents the 3+ oxidation state and M is Cr(II), Mn(II), Fe(II), Co(II), Ni(II), and Zn(II)) has been considered. Fe(III) in combination with metal atoms like Cr(II), Co(II), or Ni(II) has been found to exhibit enhanced adsorption properties towards CO, CO2 and H2O. The molecule with the strongest interaction was found to be H2O over Fe(III)2Zn(II) cluster and weakest interaction was found between H2 and Fe(III)2Ni(II). Charge transfer, natural bond orbital (NBO) and spin density analyses reveal the electronic structural properties of this combination, leading to enhanced adsorption of CO and CO2.
Oronasal Fistula Closure and Defect Reconstruction: Two Case Reports Using Periodontal Plastic Surgery Principles
Authors: Chacon Gerardo , Alrmali Abdusalam , Mandil Obada , Rodriguez Héctor , Rodriguez José , Al‐misurati Anas , Wang Hom‐Lay
Published: July 2024

Objectives

Oronasal fistulas are common sequelae following cleft lip and palate surgery and can significantly impact a patient's quality of life. They result from various factors, including surgical techniques, tissue management, and patient‐specific factors. This case report explores the modern approach to oronasal fistula closure using periodontal plastic surgery principles.

Materials and Methods

The report presents two cases of patients with oronasal fistulas due to previous maxillofacial surgical intervention. These patients underwent microsurgical procedures that involved partial flap thickness preparation of the fistula areas, the use of connective tissue grafts from the palate, and meticulous suturing techniques to ensure graft integrity. The procedures were performed in stages, and postoperative care was provided.

Results

Both cases demonstrated successful fistula closure and graft survival. The patients reported improvements in breathing, speech, aesthetics, and quality of life. The second case also included guided bone regeneration and implant placement.

Conclusions

Oronasal fistulas resulting from maxillofacial surgery can be effectively treated using periodontal plastic surgery techniques, significantly improving patients' quality of life and aesthetic outcomes. This approach represents a valuable addition to the existing repertoire of oronasal fistula closure methods.
A Cross‐Sectional Survey of the Use of Clear Aligners by General Dentists in Australia
Authors: Meade Maurice J. , Weir Tony
Published: July 2024

Objectives

The primary aim of the investigation was to survey clear aligner therapy (CAT) use among general dentists in Australia. A secondary aim was to evaluate the factors that influenced general dentists in Australia not to provide CAT.

Material and Methods

General dentists registered with the Australian Health Practitioner Regulation Agency were invited to participate in a structured cross‐sectional electronic survey. The survey covered demographics, preferred CAT systems and practices, relevant treatment planning and retention protocols, patient‐reported CAT issues, pertinent respondent opinions, and reasons for not providing CAT. Descriptive statistics were computed via GraphPad Prism v10 (GraphPad Software Inc., La Jolla, CA, USA).

Results

Most of the 264 (n = 172; 65.2%) respondents indicated that they provided CAT. The majority (n = 82; 58.6%) reported that they treated between 1 and 20 patients with CAT annually. Invisalign was the most used system (n = 83; 61.2%), with 55 (41.7%), indicating that they used more than one system. Most (n = 124; 98.4%) were comfortable using CAT for mild crowding, whereas 73.4% (n = 94) were not comfortable in treating severe crowding with CAT. The median (IQR) number of patients per respondent treated with extraction of a permanent incisor or premolar was 0 (0). Issues regarding tooth positions were reportedly always or mostly in need of change in the initial treatment plan by 68.7%. Problems regarding patient compliance with CAT wear protocols (n = 67; 45.6%) and the predictability of treatment outcomes (n = 31; 21.1%) were the most identified themes of the free‐text comments. Over 80% of those who did not provide CAT indicated that they preferred to refer to an orthodontist for management.

Conclusion

Almost two‐thirds of the respondents provided CAT. Invisalign was the most used system. The majority use CAT combined with nonextraction treatment. Most of those who did not provide CAT preferred to refer to an orthodontist for patient management.
Oral Hygiene With Neutral Electrolyzed Water and Systemic Therapy Increases Gastric Helicobacter pylori Eradication and Reduces Recurrence
Authors: Urrutia‐Baca Victor Hugo , Paz‐Michel Brenda Astrid , Calderon‐Porras Alma Nidia , Valle Jany Ariadne Jiménez‐Del , Alvarez‐Fernández Wendy Jazmin , Mervitch‐Sigal Nicolas , Rodríguez‐León Mario Alfredo , De La Garza‐Ramos Myriam Angelica
Published: July 2024

Objectives

Helicobacter pylori gastric infection strongly correlates with gastric diseases such as chronic gastritis, functional dyspepsia, and complications such as peptic ulcers and gastric cancer. In developing countries, systemic therapies are not usually successful due to elevated antibiotic resistance. Additionally, oral H. pylori infection and periodontal disease correlate with gastric treatment failures. This study aimed to explore the effect of an integral therapy, comprising oral hygiene and concomitant systemic treatment, to increase the eradication of gastric infection and recurrences.

Materials and Methods

A prospective, randomized, four‐arm, parallel‐group, open‐label clinical trial was conducted to investigate the efficacy of integral therapy to eradicate gastric H. pylori infection and avoid recurrences in double‐positive (real‐time PCR oral and gastric infection) patients. Oral hygiene involved mouthwash with neutral electrolyzed water (NEW), with or without periodontal treatment. One hundred patients were equally distributed into four groups: NS, NS‐PT, NEW, and NEW‐PT. All patients had concomitant systemic therapy and additionally, the following oral treatments: mouthwash with normal saline (NS), periodontal treatment and mouthwash with normal saline (NS‐PT), mouthwash with NEW (NEW), and periodontal treatment and mouthwash with NEW (NEW‐PT). Gastric and oral infection and symptoms were evaluated one and four months after treatments.

Results

Integral therapy with NEW‐PT increased gastric eradication rates compared with NS or NS‐PT (84%−96% vs. 20%−56%; p < 0.001). Even more, a protective effect of 81.2% (RR = 0.1877; 95% CI: 0.0658−0.5355; p = 0.0018) against recurrences and 76.6% (RR = 0.2439; 95% CI: 0.1380−0.4310; p < 0.001) against treatment failure (eradication of infection and associated symptoms) was observed in patients from the NEW and NEW‐PT groups.

Conclusions

Implementation of oral hygiene and systemic treatment can increase the eradication of gastric infection, associated symptoms, and recurrences. NEW is recommended as an antiseptic mouthwash due to its efficacy and short‐ and long‐term safety.
Intelligent reflecting surface‐aided D2D‐enabled coordinated multipoint NOMA systems over Nakagami‐m fading channels
Authors: Ravishankar Simhadri , Selvaraj M. D.
Published: July 2024

The future wireless communication networks (beyond 5G) are intended to provide seamless connectivity, higher data rates, and lower latency. The intelligent reflecting surface (IRS) promises extended network coverage. The non‐orthogonal multiple access (NOMA) technique provides higher spectral efficiency and supports a larger number of users. In general, the cell‐edge users far from the base station are affected by severe fading, which may result in an outage. To overcome this issue, we propose an IRS‐aided device‐to‐device (D2D)‐enabled two cells coordinated NOMA system in which a common cell‐edge user acts as D2D receiver. The cell‐edge user receives the signals from near users, IRSs, and both base stations to achieve better diversity. We analyze the outage probability of cell‐edge user, while all the fading channels are assumed Nakagami‐
and obtain a closed‐form expression at higher signal‐to‐noise ratios. We develop an algorithm to find the ergodic capacity of the cell‐edge user. We validate the mathematical expressions with simulation results and see a substantial improvement in outage performance over the existing systems.
Cytomorphologic comparison of upper urinary tract urothelial carcinomas and renal cell carcinomas on urine cytology
Authors: Ng Joanna K. M. , Li Joshua J. X.
Published: July 2024

Introduction

Compared to urothelial carcinomas (UCs), the cytomorphology of renal cell carcinomas (RCCs) is underdescribed. This study aims to investigate whether UCs and RCCS of the upper urinary tract can be differentiated cytologically, and to identify distinguishing cytomorphological features.

Methodology

Consecutive urine cytology specimens with atypical/C3, suspicious/C4 or malignant/C5 diagnoses matched with a nephrectomy or ureterectomy specimen with UC or RCC over a 15‐year period were reviewed for cellularity, architecture, background composition and cytomorphologic features.

Results

Totally 132 specimens were retrieved, comprising 24 RCCs and 108 UCs. Clear cell RCC (CCRCC) (n = 18) was the most common RCC. Urine cytology specimens from UC showed a trend of higher cellularity (p = 0.071) against RCC and was significant in subgroup analysis with CCRCC (p < .001). Epithelial structures in sheets, tubules, and papillae were exclusive in specimens of UC (p < .05). For background features, squamous cells were more common for RCC (p = .006) including CCRCC (p = .003), whereas polymorphs (p = .011) and necrotic material (p = .010) were associated with UC. Average nuclear size was larger and nuclear size variation (p < .001) and nuclear‐cytoplasmic ratio (p = .001) were greater in UC (p = .001) than RCC. Comparing RCC to high‐grade UCs only, nuclear‐cytoplasmic ratio maintained statistical significance (p = .006) while average nuclear size showed a trend (p = .063).

Conclusion

A clean background free of tumor necrosis and polymorphs, and the lack of complex tumor fragments favors RCC. UCs also display larger nuclear size, higher nuclear size variation and nuclear‐cytoplasmic ratio. These cytomorphological features with corroboration of clinical/radiological findings, can aid in raising a diagnosis of RCC.