bluuebunny/crossref_metadata_2025 huggingface dataset:
Novel 2‐substituted thioquinazoline‐benzenesulfonamide derivatives as carbonic anhydrase inhibitors with potential anticancer activity
Authors: Abdel‐Mohsen Heba T. , Omar Mohamed A. , Petreni Andrea , Supuran Claudiu T.
Published: September 2022

A novel series of 2‐thioquinazoline‐benzenesulfonamide hybrids were designed as carbonic anhydrase (CA) inhibitors. The design approach relies on molecular hybridization between the benzenesulfonamide scaffold as a Zn2+ binding group and 2‐substituted thioquinazolines as a tail. Assaying the thioquinazoline‐benzenesulfonamide conjugates against four different CA isoforms revealed that compounds 12f and 12p are the most potent derivatives. They exhibit Ki = 0.09 and 0.05 µM on CA II, 0.32 and 0.47 µM on CA IX, and 0.58 and 0.46 µM on CA XII, respectively. In addition, 12p demonstrated high selectivity for CA II over CA I with selectivity index (SI) = 92, and slightly higher specificity for CA II over CA IX and CA XII with SI = 9.40 and 9.20, respectively. The synthesized compounds were screened for their cytotoxic activity at 10 µM concentration and derivatives 12o, 12n, and 12f turned out to be the most potent ones from the synthesized series; they exhibit mean growth inhibition % values of 89.38%, 58.75%, and 54.71%, respectively, while 12p demonstrated moderate activity against the NCI cancer cell lines, with mean growth inhibition % = 29.62%. The analysis of the MCF‐7 cell cycle after treatment with 5.0 µM of 12f displayed that it arrests the cell cycle at the G2/M phase. Molecular docking simulation of the thioquinazoline‐benzenesulfonamide hybrids in the CA II active site rationalized the potent activity to the settlement of the sulfonamide moiety at the depth of the CA II active site and its stabilization by performing the important interactions with the Zn2+ ion as well as with the key amino acids Thr199 and/or Thr200, while the thioquinazoline moiety with different (un)substituted phenyl tails is stabilized by the formation of various hydrogen bonding and hydrophobic interactions with the surrounding amino acids in the binding site.
Mechanistic Target of Rapamycin Inhibition Prevents Coronary Artery Remodeling in a Murine Model of Kawasaki Disease
Authors: Stock Angus T. , Parsons Sarah , D'Silva Damian B. , Hansen Jacinta A. , Sharma Varun J. , James Fiona , Starkey Graham , D'Costa Rohit , Gordon Claire L. , Wicks Ian P.
Published: September 2022

Objective

Remodeling of the coronary arteries is a common feature in severe cases of Kawasaki disease (KD). This pathology is driven by the dysregulated proliferation of vascular fibroblasts, which can lead to coronary artery aneurysms, stenosis, and myocardial ischemia. We undertook this study to investigate whether inhibiting fibroblast proliferation might be an effective therapeutic strategy to prevent coronary artery remodeling in KD.

Method

We used a murine model of KD (induced by the injection of the Candida albicans water‐soluble complex [CAWS]) and analyzed patient samples to evaluate potential antifibrotic therapies for KD.

Results

We identified the mechanistic target of rapamycin (mTOR) pathway as a potential therapeutic target in KD. The mTOR inhibitor rapamycin potently inhibited cardiac fibroblast proliferation in vitro, and vascular fibroblasts up‐regulated mTOR kinase signaling in vivo in the CAWS mouse model of KD. We evaluated the in vivo efficacy of mTOR inhibition and found that the therapeutic administration of rapamycin reduced vascular fibrosis and intimal hyperplasia of the coronary arteries in CAWS‐injected mice. Furthermore, the analysis of cardiac tissue from KD fatalities revealed that vascular fibroblasts localizing with inflamed coronary arteries up‐regulate mTOR signaling, confirming that the mTOR pathway is active in human KD.

Conclusion

Our findings demonstrate that mTOR signaling contributes to coronary artery remodeling in KD, and that targeting this pathway offers a potential therapeutic strategy to prevent or restrict this pathology in high‐risk KD patients.
Production and Application of Biomaterials Based on Polyvinyl alcohol (PVA) as Wound Dressing
Authors: Jin Sung Giu
Published: September 2022

The development of ideal wound dressing with excellent properties, such as exudate absorption capacity, drug release control ability, and increased wound healing, is currently a major requirement for wound healing. Polyvinyl alcohol (PVA) is a biodegradable semi‐crystalline synthetic polymer that has been used in the field of biotechnology such as tissue regeneration, wound dressing, and drug delivery systems. In recent years, PVA‐based wound dressing materials have received considerable attention due to their excellent properties such as biodegradability, biocompatibility, non‐toxicity and low cost. PVA can be used as a wound dressing material to create the necessary moist wound environment, improve the physical properties of the dressing, and increase the wound healing rates. In addition, PVA can also be mixed with other organic and inorganic materials and can be used for drug delivery and wound healing. This review article addresses the role of biomaterials based on PVA mixed with other ingredients for wound dressing. It also focuses on its recent use in wound dressings as carriers of active substances.
A Stable Metal‐azolate Framework with Cyclic Tetracopper(I) Clusters for Highly Selective Electroreduction of CO2 to C2 Products
Authors: Liu Yuan‐Yuan , Wang Zhi‐Shuo , Liao Pei‐Qin , Chen Xiao‐Ming
Published: September 2022

It is of great significance for constructing electrocatalysts with accurate structures and compositions to pinpoint the active sites, thereby improving the C2 products (C2H4, C2H5OH and CH3COOH) selectivity during electrocatalytic CO2 reduction raction. Here, we report a tetracopper(I) cluster‐based metal‐organic framework that exhibits long‐term stability and remarkable performance for electroreduction CO2 towards C2 products in an H‐type cell with a maximum Faradaic efficiency (FE) of 72%, and delivers a current density of 350 mA cm−2 with a FE(C2) up to 46% in a flow cell device, outperforming most of the Cu‐based electrocatalysts such as Cu derivatives and Cu nanostructured materials. Importantly, no obvious degradation was observed at 350 mA cm–2 over 20 hours of continuous operation, strengthening the practicability. In‐situ infrared spectroscopy analysis showed the cooperative effect of adjacent Cu(I) ions in tetracopper(I) cluster may promote the C−C coupling to generate C2 products.
Child language and autism diagnosis impact hierarchical temporal structure of parent–child vocal interactions in early childhood
Authors: Boorom Olivia , Alviar Camila , Zhang Yumeng , Muñoz Valerie A. , Kello Christopher T. , Lense Miriam D.
Published: September 2022

Timing is critical to successful social interactions. The temporal structure of dyadic vocal interactions emerges from the rhythm, timing, and frequency of each individuals' vocalizations and reflects how the dyad dynamically organizes and adapts during an interaction. This study investigated the temporal structure of vocal interactions longitudinally in parent–child dyads of typically developing (TD) infants (n = 49; 9–18 months; 48% male) and toddlers with ASD (n = 23; 27.2 ± 5.0 months; 91.3% male) to identify how developing language and social skills impact the temporal dynamics of the interaction. Acoustic hierarchical temporal structure (HTS), a measure of the nested clustering of acoustic events across multiple timescales, was measured in free play interactions using Allan Factor. HTS reflects a signal's temporal complexity and variability, with greater HTS indicating reduced flexibility of the dyadic system. Child expressive language significantly predicted HTS (ß = −0.2) longitudinally across TD infants, with greater dyadic HTS associated with lower child language skills. ASD dyads exhibited greater HTS (i.e., more rigid temporal structure) than nonverbal matched (d = 0.41) and expressive language matched TD dyads (d = 0.28). Increased HTS in ASD dyads occurred at timescales >1 s, suggesting greater structuring of pragmatic aspects of interaction. Results provide a new window into how language development and social reciprocity serve as constraints to shape parent–child interaction dynamics and showcase a novel automated approach to characterizing vocal interactions across multiple timescales during early childhood.
Adapting SIMEX to correct for bias due to interval‐censored outcomes in survival analysis with time‐varying exposure
Authors: Abrahamowicz Michal , Beauchamp Marie‐Eve , Moura Cristiano Soares , Bernatsky Sasha , Ferreira Guerra Steve , Danieli Coraline
Published: September 2022

Many clinical and epidemiological applications of survival analysis focus on interval‐censored events that can be ascertained only at discrete times of clinic visits. This implies that the values of time‐varying covariates are not correctly aligned with the true, unknown event times, inducing a bias in the estimated associations. To address this issue, we adapted the simulation‐extrapolation (SIMEX) methodology, based on assessing how the estimates change with the artificially increased time between clinic visits. We propose diagnostics to choose the extrapolating function. In simulations, the SIMEX‐corrected estimates reduced considerably the bias to the null and generally yielded a better bias/variance trade‐off than conventional estimates. In a real‐life pharmacoepidemiological application, the proposed method increased by 27% the excess hazard of the estimated association between a time‐varying exposure, representing the 2‐year cumulative duration of past use of a hypertensive medication, and the hazard of nonmelanoma skin cancer (interval‐censored events). These simulation‐based and real‐life results suggest that the proposed SIMEX‐based correction may help improve the accuracy of estimated associations between time‐varying exposures and the hazard of interval‐censored events in large cohort studies where the events are recorded only at relatively sparse times of clinic visits/assessments. However, these advantages may be less certain for smaller studies and/or weak associations.
Splice‐switch oligonucleotide‐based combinatorial platform prioritizes synthetic lethal targets CHK1 and BRD4 against MYC‐driven hepatocellular carcinoma
Authors: Thng Dexter Kai Hao , Toh Tan Boon , Pigini Paolo , Hooi Lissa , Dan Yock Young , Chow Pierce Kah‐Hoe , Bonney Glenn Kunnath , Rashid Masturah Bte Mohd Abdul , Guccione Ernesto , Wee Dave Keng Boon , Chow Edward Kai‐Hua
Published: September 2022

Deregulation of MYC is among the most frequent oncogenic drivers in hepatocellular carcinoma (HCC). Unfortunately, the clinical success of MYC‐targeted therapies is limited. Synthetic lethality offers an alternative therapeutic strategy by leveraging on vulnerabilities in tumors with MYC deregulation. While several synthetic lethal targets of MYC have been identified in HCC, the need to prioritize targets with the greatest therapeutic potential has been unmet. Here, we demonstrate that by pairing splice‐switch oligonucleotide (SSO) technologies with our phenotypic‐analytical hybrid multidrug interrogation platform, quadratic phenotypic optimization platform (QPOP), we can disrupt the functional expression of these targets in specific combinatorial tests to rapidly determine target–target interactions and rank synthetic lethality targets. Our SSO‐QPOP analyses revealed that simultaneous attenuation of CHK1 and BRD4 function is an effective combination specific in MYC‐deregulated HCC, successfully suppressing HCC progression in vitro. Pharmacological inhibitors of CHK1 and BRD4 further demonstrated its translational value by exhibiting synergistic interactions in patient‐derived xenograft organoid models of HCC harboring high levels of MYC deregulation. Collectively, our work demonstrates the capacity of SSO‐QPOP as a target prioritization tool in the drug development pipeline, as well as the therapeutic potential of CHK1 and BRD4 in MYC‐driven HCC.
Risk stratification and prognosis prediction based on inflammation‐related gene signature in lung squamous carcinoma
Authors: Zhai Wenyu , Chen Si , Duan Fangfang , Wang Junye , Zhao Zerui , Lin Yaobin , Rao Bingyu , Wang Yizhi , Zheng Lie , Long Hao
Published: September 2022

Background

Inflammation is known to have an intricate relationship with tumorigenesis and tumor progression while it is also closely related to tumor immune microenvironment. Whereas the role of inflammation‐related genes (IRGs) in lung squamous carcinoma (LUSC) is barely understood. Herein, we recognized IRGs associated with overall survival (OS), built an IRGs signature for risk stratification and explored the impact of IRGs on immune infiltration landscape of LUSC patients.

Methods

The RNA‐sequencing and clinicopathological data of LUSC patients were downloaded from The Cancer Genome Atlas (TCGA) and the Gene Expression Omnibus (GEO) database, which were defined as training and validation cohorts. Cox regression and least absolute shrinkage and selection operator analyses were performed to build an IRG signature. CIBERSORT, microenvironment cell populations‐counter and tumor immune dysfunction and rejection (TIDE) algorithm were used to perform immune infiltration analysis.

Results

A two‐IRG signature consisting of KLF6 and SGMS2 was identified according to the training set, which could categorize patients into two different risk groups with distinct OS. Patients in the low‐risk group had more anti‐tumor immune cells infiltrated while patient with high‐risk had lower TIDE score and higher levels of immune checkpoint molecules expressed. The IRG signature was further identified as an independent prognostic factor of OS. Subsequently, a prognostic nomogram including IRG signature, age, and cancer stage was constructed for predicting individualized OS, whose concordance index values were 0.610 (95% CI: 0.568–0.651) in the training set and 0.652 (95% CI: 0.580–0.724) in validation set. Time‐dependent receiver operator characteristic curves revealed that the nomogram had higher prediction accuracy compared with the traditional tumor stage alone.

Conclusion

The IRG signature was a predictor for patients with LUSC and might serve as a potential indicator of the efficacy of immunotherapy. The nomogram based on the IRG signature showed a relatively good predictive performance in survival.
Metagenomic analysis of the fecal microbiome in colorectal cancer patients compared to healthy controls as a function of age
Authors: Kharofa Jordan , Apewokin Senu , Alenghat Theresa , Ollberding Nicholas J.
Published: September 2022

Background and Aims

Colorectal cancer (CRC) incidence is increasing in young patients without a clear etiology. Emerging data have implicated the fecal microbiome in CRC carcinogenesis. However, its impact on young onset CRC is poorly defined.

Methods

We performed a meta‐analysis of fecal metagenomics sequencing data from n = 692 patients with CRC and n = 602 healthy controls from eleven studies to evaluate features of the fecal metagenome associated with CRC. We hypothesized that known carcinogenic virulence factors (colibactin, fadA) and species abundance may be differentially enriched in young CRC patients relative to older CRC patients and controls.

Results

Summary odds ratios (OR) for CRC were increased with the presence of colibactin (OR 1.92 95% CI 1.08–3.38), fadA (OR 4.57 95% CI 1.63–12.85), and F. nucleatum (OR 6.93 95% CI 3.01–15.96) in meta‐analysis models adjusted for age, gender, and body mass index. The OR for CRC for the presence of E.coli was 2.02 (0.92–4.45). An increase in the prevalence of Fusobacterium nucleatum (OR = 1.40 [1.18; 1.65]) and Escherichia coli (OR = 1.14 [1.02; 1.28]) per 10‐year increase in age was observed in models including samples from both CRC and healthy controls. Species relative abundance was differentially enriched in young CRC patients for five species‐Intestinimonas butyriciproducens, Holdemania filiformis, Firimicutues bacterium CAG 83, Bilophilia wadsworthia, and Alistipes putredinis.

Conclusion

In this study, we observed strong associations with CRC status for colibactin, fadA, and Fusobacterium nucleatum with CRC relative to controls. In addition, we identified several microbial species differentially enriched in young colorectal cancer patients. Studies targeting the young CRC patients are warranted to elucidate underlying preclinical mechanisms.
Alveolar ridge augmentation for implant placement in a growing patient
Authors: Meghil Mohamed M. , Lowry Scott , Lyons Collins , Ghaly Mira
Published: September 2022

Background

Partial edentulism in growing children due to aplasia or trauma poses a difficult situation to manage. We present a case of horizontal ridge augmentation in a growing patient who had trauma in childhood when it was too early to place implants.

Methods and Results

This patient had a history of trauma, at age 13, that resulted in mandibular fracture and loss of teeth #23–27. The definitive restorative treatment plan was postponed due to the patient's continued growth. At age 18, horizontal bone augmentation was performed in a severely resorbed anterior mandible. After 7 months of healing, 7–8 mm ridge augmentation was achieved, and three implants were placed. Soft tissue augmentation by free gingival graft was performed at implant second stage surgery 4 months later.

Conclusions

When considering the timing of implant placement in adolescents, the clinician walks a fine line between waiting as long as possible to place the implants and racing against continued resorption of the edentulous alveolar ridge. 70/30 mineralized/demineralized cortical bone allograft and injectable platelet‐rich fibrin mix combined with tenting screws and resorbable membranes are useful measures for horizontal ridge augmentation in growing patients.

Key points

Why is this case new information?

There are insufficient data available when considering implant treatment in younger patients. The present case was managed with a variation of the sausage technique described by Urban. The use of allograft, I‐PRF, and tenting screws replaced the use of autogenous bone and resulted in exceptional results.

What are the keys to the successful management of this case?

Delaying treatment until after the critical growth period has passed. Adequate flap release, tension‐free primary flap closure, and space maintenance through the use of tenting screws and tacking the membranes using tacking pins provided support for the grafted site.

What are the primary limitations to success in this case?

The continued growth may cause infra occlusion of the implant‐supported bridge.
Selected Aspects of InvasiveSolidago canadensiswith an Emphasis on Its Allelopathic Abilities: A Review
Authors: Zhu Xunzhi , Li Weijie , Shao Hua , Tang Shijie
Published: September 2022

Solidago canadensisL., native to North America, is now an invasive plant worldwide. Its abundant seeds, rapid vegetative reproduction ability, and allelopathy to other plants are the main reasons for its successful invasion. It has negative impacts on the ecological environment of the invaded area and causes a reduction in local biodiversity and economic losses of agriculture and stock farming. Each part of the plant contains a variety of allelochemicals (terpenoids, phenolics, and flavonoids), including a large number of essential oil components. These allelochemicals can be released in various ways to inhibit the growth of adjacent plants and promote their invasion; they can also affect soil properties and soil microorganisms. This article summarizes the allelopathic effects ofS. canadensison other plant species and the interaction mechanism between it and the ecosystem.
The relationship between self‐forgiveness and psychological wellbeing in prison inmates: The mediating role of mindfulness
Authors: Paleari Giorgia F. , Danioni Francesca , Pelucchi Sara , Lombrano Maria Rita , Lumera Daniel , Regalia Camillo
Published: September 2022

Background

Previous research with general population samples has consistently shown that forgiveness and mindfulness facilitate coping with distressing experiences and significantly promote mental health. No study, however, has examined their unique contribution to prisoners' psychological wellbeing nor has considered the different forms of self‐forgiveness among prisoners.

Aims

Our aim was to investigate the role of mindfulness in mediating any association between prisoners' self‐forgiveness and psychological wellbeing and to test whether any such links are moderated by years spent in prison. In this study self‐forgiveness was conceptualised as a multidimensional construct, including presence of genuine self‐forgiveness, absence of pseudo self‐forgiveness and/or absence of self‐punitiveness.

Methods

Participants were recruited from a prison in Northern Italy. Consenting men were asked to complete an anonymous self‐report questionnaire with only a researcher present.

Results

104 male prisoners (mean age 46.63 years, SD 11.38) took part. Findings were that self‐punitiveness was inversely related to well‐being, with mindfulness mediating this relationship, this while controlling for the other dimensions of self‐forgiveness and the perceived severity of the crime committed. Contrary to expectation, we found no direct relationship between genuine self‐forgiveness and well‐being, but the moderated mediation models showed that genuine self‐forgiveness was positively associated with mindfulness and, through this, had an indirect association with wellbeing, significant only for prisoners who had already spent several years in prison.

Conclusions

Our findings confirm that self‐forgiveness is a complex construct, worthy of further investigation among offenders. They suggest that forgiveness interventions for prisoners should include modules aimed at primarily reducing self‐punitive attitudes. Promotion of genuine self‐forgiveness should be tried only with awareness that this is likely to take a very long time. In such circumstances, interventions may promote energy to be invested in mindful processes with a consequent improvement in psychological wellbeing.
Eagle syndrome in the pediatric population: A case report
Authors: Tanenbaum Zachary G. , Johng Stephanie Y. , Parsa Keon M. , Russo Mark E. , Harley Earl H.
Published: September 2022

Objectives: To present a rare case of Eagle Syndrome in a pediatric patient, reminding the medical community to keep this diagnosis on their differential.
Intractable low back pain during acute exacerbation of systemic lupus erythematosus
Authors: Boulas Konstantinos A. , Nathanailidou Maria , Sitaridis Konstantinos , Filippidis Isaac , Tsiariglis Ioannis , Hatzigeorgiadis Anestis
Published: September 2022

Diagnosis of acute low back emergencies during a systemic lupus erythematosus flare necessitates high clinical suspicion and early CT.
Metastatic papillary thyroid cancer to cerebellum with incidental medullary microcarcinoma
Authors: Wang Mawson , Samra Spinder , Chou Shaun , Howle Julie , Gild Matti L. , Girgis Christian Meena
Published: September 2022

Thyroid cancer is the most common endocrine cancer, with papillary thyroid carcinoma (PTC) accounting for the majority of these cases. Cerebellar metastasis is rarely the presenting feature and confers poor prognosis. Genetic mutations in this setting are most commonly TERTp, in contrast to BRAFV600E in the majority of PTC. We report the case of an 82 year‐old male who presented with a symptomatic right cerebellar lesion and underwent surgical resection to demonstrate metastatic PTC. Extensive workup with computed tomography, neck ultrasound and FDG‐PET was suggestive of a left thyroid primary lesion, with FNA confirming PTC. However, total thyroidectomy demonstrated incidental microMTC (medullary thyroid microcarcinoma, defined as tumour <10mm) without any evidence of PTC, whereas the left level VI neck dissection demonstrated a 30mm nodule of PTC without identifiable normal thyroid or lymph node tissue.
Intraabdominal guidewire‐related perforation of the esophagus: An uncommon complication of esophageal bougienage treated by intraprocedural clip closure
Authors: Zimmer Vincent
Published: September 2022

Esophageal perforation is an uncommon, though typical complication of esophageal bougienage. However, guidewire‐related transmural injury distant from the stricture has only rarely been reported. Post‐procedural endoscopy is critical to appreciate perforation and proved instrumental in a unique clinical case with immediate clip closure.
Cutaneous involvement in relapsed multiple myeloma
Authors: Salle Valéry , Attencourt Christophe , Chevalier Marion , Semeria Lucile , Boulu Xavier , Karam Jean‐Denis , Smail Amar , Schmidt Jean , Duhaut Pierre , Dernoncourt Amandine
Published: September 2022

Cutaneous involvement in multiple myeloma with extramedullary disease is rare. We report the case of a refractory multiple myeloma patient who developed a cutaneous lesion. Histopathology revealed dermal immature plasma cell infiltrate with a lack of CD138 expression. This cutaneous location was associated with an aggressive clinical course and short survival.
Nickel Nanoparticles Immobilized on Pristine Halloysite: An Outstanding Catalyst for Hydrogenation Processes
Authors: Pérez Alonso Alejandro , Mauriés Steven , Ledeuil Jean‐Bernard , Madec Lénaïc , Pham Minh Doan , Pla Daniel , Gómez Montserrat
Published: September 2022

Nickel nanoparticles (NiNPs) immobilized on halloysite‐based supports were straightforwardly synthesized and fully characterized by different techniques with the purpose of evaluating the catalytic performance of these as‐prepared composite materials as catalysts in hydrogenation reactions. Thus, halloysite bearing amino (HAL‐NH2) and ammonium (HAL‐NEt3) groups led to less active catalytic materials in comparison with unfunctionalized halloysite supports, probably due to relative strong metal‐support interactions with amino and tetraalkylammonium functions, consequently hindering the interaction of unsaturated substrates at the surface of the catalytic material. Despite NiNPs supported on pristine halloysite provided merely agglomerates, NiNPs stabilized by quinidine on unfunctionalized halloysite (NiC) proved to be a highly effective and versatile catalyst operating at relative low temperature (25–100 °C) and metal loading (1–20 mol %Ni), very well‐adapted to reduce a large range of functions (alkenes, alkynes, ketones, aldehydes, nitro…). Moreover, NiC was able to selectively reduce substrates from biomass to yield high value‐added products, such as squalane, saturated fatty acids, furfuryl alcohol and γ‐valerolactone.
Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt‐Fe Alloy Electrocatalysts for Methanol Oxidation Performance
Authors: Wang Zhengcheng , Zhou Shangyan , Liao Wei , Zhou Qian , Chen Meida , Long Jin , Wang Qingmei
Published: September 2022

The designs of efficient and inexpensive Pt‐based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen‐doped carbon (NC) have been successfully prepared via co‐engineering of the surface composition and electronic structure. The Pt1Fe3@NC/MWCNTs catalyst with moderate Fe3+ feeding content (0.86 mA/mgPt) exhibits 2.26‐fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mgPt). Furthermore, the CO oxidation initial potential of Pt1Fe3@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti‐corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N‐doped carbon (NC) layer, the Pt1Fe3@NC/MWCNTs catalyst presents an improved MOR performance and anti‐CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.
Differential Tunneling‐Driven and Vibrationally‐Induced Reactivity in Isomeric Benzazirines
Authors: Nunes Cláudio M. , Doddipatla Srinivas , Loureiro Gonçalo F. , Roque José P. L. , Pereira Nelson A. M. , Pinho e Melo Teresa M. V. D. , Fausto Rui
Published: September 2022

Quantum mechanical tunneling of heavy‐atoms and vibrational excitation chemistry are unconventional and scarcely explored types of reactivity. Once fully understood, they might bring new avenues to conduct chemical transformations, providing access to a new world of molecules or ways of exquisite reaction control. In this context, we present here the discovery of two isomeric benzazirines exhibiting differential tunneling‐driven and vibrationally‐induced reactivity, which constitute exceptional results for probing into the nature of these phenomena. The isomeric 6‐fluoro‐ and 2‐fluoro‐4‐hydroxy‐2H‐benzazirines (3‐a and 3′‐s) were generated in cryogenic krypton matrices by visible‐light irradiation of the corresponding triplet nitrene 32‐a, which was produced by UV‐light irradiation of its azide precursor. The 3′‐s was found to be stable under matrix dark conditions, whereas 3‐a spontaneously rearranges (τ1/2 ∼64 h at 10 and 20 K) by heavy‐atom tunneling to 32‐a. Near‐IR‐light irradiation at the first OH stretching overtone frequencies (remote vibrational antenna) of the benzazirines induces the 3′‐s ring‐expansion reaction to a seven‐member cyclic ketenimine, but the 3‐a undergoes 2H‐azirine ring‐opening reaction to triplet nitrene 32‐a. Computations demonstrate that 3‐a and 3′‐s have distinct reaction energy profiles, which explain the different experimental results. The spectroscopic direct measurement of the tunneling of 3‐a to 32‐a constitutes a unique example of an observation of a species reacting only by nitrogen tunneling. Moreover, the vibrationally‐induced sole activation of the most favorable bond‐breaking/bond‐forming pathway available for 3‐a and 3′‐s provides pioneer results regarding the selective nature of such processes.
Sterically and Electronically Flexible Pyridylidene Amine Dinitrogen Ligands at Palladium: Hemilabile cis/trans Coordination and Application in Dehydrogenation Catalysis
Authors: Lentz Nicolas , Streit Yanik , Knörr Pascal , Albrecht Martin
Published: September 2022

Ligand design is crucial for the development of new catalysts and materials with new properties. Herein, the synthesis and unique hemilabile coordination properties of new bis‐pyridylidene amine (bis‐PYE) ligands to palladium, and preliminary catalytic activity of these complexes in formic acid dehydrogenation are described. The synthetic pathway to form cationic complexes [Pd(bis‐PYE)Cl(L)]X with a cis‐coordinated N,N‐bidentate bis‐PYE ligand is flexible and provides access to a diversity of PdII complexes with different ancillary ligands (L=pyridine, DMAP, PPh3, Cl, P(OMe)3). The 1H NMR chemical shift of the trans‐positioned PYE N−CH3 unit is identified as a convenient and diagnostic handle to probe the donor properties of these ancillary ligands and demonstrates the electronic flexibility of the PYE ligand sites. In the presence of a base, the originally cis‐coordinated bis‐PYE ligand adopts a N,N,N‐tridentate coordination mode with the two PYE units in mutual trans position. This cis–trans isomerization is reverted in presence of an acid, demonstrating a unique structural and steric flexibility of the bis‐PYE ligand at palladium in addition to its electronic adaptability. The palladium complexes are active in formic acid dehydrogenation to H2 and CO2. The catalytic performance is directly dependent on the ligand bonding mode, the nature of the ancillary ligand, the counteranion, and additives. The most active system features a bidentate bis‐PYE ligand, PPh3 as ancillary ligand and accomplishes turnover frequencies up to 525 h−1 in the first hour and turnover numbers of nearly 1000, which is the highest activity reported for palladium‐based catalysts to date.
Antifungal Graphene‐based Absorbers as Advanced Materials for Preventive Conservation of Cultural Objects
Authors: Gorgolis George , Messina Elena , Kotsidi Maria , Staccioli Maria Paola , Lesaria Nhuch Elsa , Di Carlo Gabriella , Schrekker Henri Stephan , Paterakis George , Koutroumanis Nikos , Galiotis Costas
Published: September 2022

The development of innovative materials for preventive conservation of cultural objects against known threats, such as fungi and volatile organic compounds (VOCs) that often exist in museums and galleries, is still challenging. In this work, graphene‐based aerogels with an ionic liquid (IL) additive were prepared, and their anti‐fungal and VOCs absorption properties were investigated. Several IL contents were evaluated and the graphene aerogel containing 10 wt.% IL was found to have the best anti‐fungal activity, preventing the aerogel contamination with Aspergillus niger. When exposed to a VOC saturated micro‐environment, this aerogel was highly suitable for the absorption of acetaldehyde, formic acid, acetic acid, and formaldehyde. This combined anti‐fungal and VOC absorption properties are prerequisites for bringing preventive conservation to a higher level.
An Extremal Problem Arising in the Dynamics of Two‐Phase Materials That Directly Reveals Information about the Internal Geometry
Authors: Mattei Ornella , Milton Graeme W. , Putinar Mihai
Published: September 2022

In two‐phase materials, each phase having a non‐local response in time, it has been found that for some driving fields the response somehow untangles at specific times, and allows one to directly infer useful information about the geometry of the material, such as the volume fractions of the phases. Motivated by this, and to obtain an algorithm for designing appropriate driving fields, we find approximate, measure independent, linear relations between the values that Markov functions take at a given set of possibly complex points, not belonging to the interval [‐1,1] where the measure is supported. The problem is reduced to simply one of polynomial approximation of a given function on the interval [‐1,1] and, to simplify the analysis, Chebyshev approximation is used. This allows one to obtain explicit estimates of the error of the approximation, in terms of the number of points and the minimum distance of the points to the interval [‐1,1]. Assuming this minimum distance is bounded below by a number greater than 1/2, the error converges exponentially to zero as the number of points is increased. Approximate linear relations are also obtained that incorporate a set of moments of the measure. In the context of the motivating problem, the analysis also yields bounds on the response at any particular time for any driving field, and allows one to estimate the response at a given frequency using an appropriately designed driving field that effectively is turned on only for a fixed interval of time. The approximation extends directly to Markov‐type functions with a positive semidefinite operator valued measure, and this has applications to determining the shape of an inclusion in a body from boundary flux measurements at a specific time, when the time‐dependent boundary potentials are suitably tailored. © 2022 Wiley Periodicals, Inc.
Free Energy Wells and Overlap Gap Property in Sparse PCA
Authors: Arous Gérard Ben , Wein Alexander S. , Zadik Ilias
Published: September 2022

We study a variant of the sparse PCA (principal component analysis) problem in the “hard” regime, where the inference task is possible yet no polynomial‐time algorithm is known to exist. Prior work, based on the low‐degree likelihood ratio, has conjectured a precise expression for the best possible (subexponential) runtime throughout the hard regime. Following instead a statistical physics‐inspired point of view, we show bounds on the depth of free energy wells for various Gibbs measures naturally associated to the problem. These free energy wells imply hitting time lower bounds that corroborate the low‐degree conjecture: we show that a class of natural MCMC (Markov chain Monte Carlo) methods (with worst‐case initialization) cannot solve sparse PCA with less than the conjectured runtime. These lower bounds apply to a wide range of values for two tuning parameters: temperature and sparsity misparametrization. Finally, we prove that the overlap gap property (OGP), a structural property that implies failure of certain local search algorithms, holds in a significant part of the hard regime. © 2022 Wiley Periodicals, Inc.
An optimal self adaptive deep neural network and spine‐kernelled chirplet transform for image registration
Authors: Senthil Pandi S. , Senthilselvi A. , Maragatharajan M. , Manju I.
Published: September 2022

Image registration is one of the image processing techniques that align more than two images of a similar scene captured under different perspectives at different intervals of time. In demographical research, the image registration process assists to study differences in the structure of brain tissue. Due to enhanced technological advancements, numerous image registration methods have been established. On the other hand, these traditional techniques face few real‐time challenges while processing huge input data. In addition to this, uncertainty analysis becomes a crucial step in medical applications which is utilized to judge whether the registration result is valuable or not. The high percentage of uncertainty than the threshold makes the registration result abnormal. Therefore, to conquer such circumstances, this research work proposed a modified spine‐kernelled chirplet transform (MCST) based optimal Self‐Adaptive Deep Neural Network (SADNN) which focuses mainly on enhancing registration accuracy by reducing the uncertainties of registration results. The experimental analysis is conducted and from the evaluation results, the proposed MCST‐based optimal SADNN technique outperforms existing techniques in terms of accuracy, specificity, sensitivity, F‐measure, and DICE values. Moreover, the proposed method achieves 97.2% accuracy for accurate image registration.
A survey on recommendation in process mining
Authors: Yari Eili Mansoureh , Rezaeenour Jalal
Published: September 2022

Recommender systems have been widely applied in several domains to make informed decisions by recommending items that might be of interest. Considering recommendation during business process execution is also highly advantageous as the efficient suggestions about possible activities or resources can impact process performance. However, the deployment of the recommendation frameworks in process mining still needs more investigations to identify the current challenges to enable the practical application of research findings and ensure a large‐scale adoption of this technique. Accordingly, a systematic review is conducted to provide a taxonomy of the published studies on process‐aware recommender systems based on specified criteria, including the type and perspective of recommendation, a list of datasets and evaluation metrics used in the setting of PARS, implementation environments, and different algorithms used in PARS. In this regard, there are various insights extracted from this study: (i) Most studies in the business process analysis domain are of descriptive and predictive nature, (ii) recommendation in process mining is an emerging research area that is being evolving; the majority of proposals relate to 2015 and after that, and (iii) due to the lack of common evaluation protocol, datasets, and metrics, most studies are validated through experiments and prototyping, with less tendency to the practical implementation of a solution regarding real scenarios.
Successive Cleavage and Reconstruction of Lignin β‐O‐4 Models and Polymer to Access Quinoxalines
Authors: Liu Yuxuan , Luo Qi , Qiang Qian , Wang Hua , Ding Yangming , Wang Chao , Xiao Jianliang , Li Changzhi , Zhang Tao
Published: September 2022

The construction of N‐heterocyclic compounds from lignin remains a great challenge due to the complex lignin structure and the involvement of multiple steps, including the cleavage of lignin C−O linkages and the formation of heterocyclic aromatic rings. Herein, the first example of KOH mediated sustainable synthesis of quinoxaline derivatives from lignin β‐O‐4 model compounds in a one‐pot fashion under transition‐metal‐free conditions has been achieved. Mechanistic studies suggested that this transformation includes highly coupled cascade steps of cleavage of C−O bonds, dehydrative condensation, sp3C−H bond oxidative activation, and intramolecular dehydrative coupling reaction. With this protocol, a wide range of functionalized quinoxalines, including an important drug compound AG1295, were synthesized from lignin β‐O‐4 model compounds and β‐O‐4 polymer, showcasing the application potential of lignin in pharmaceutical synthesis.
A novel bi‐directional high‐gain DC‐DC converter with optimum number of components
Authors: Krishna Bekkam , Karthikeyan V.
Published: September 2022

Most emerging applications of battery energy storage systems, fuel cells, and unified power supply (UPS) applications require essential bi‐directional power capability with a high conversion ratio. It supports the integration of the high‐voltage DC‐bus with an energy storage unit or fuel cell. In order to meet this requirement, this paper proposes a novel nonisolated high‐gain DC‐DC converter with bi‐directional power flow capability. This converter is configured with a hybrid structure with a combination of the switched capacitor (SC) and switched inductor (SI) techniques. Moreover, this converter can attain extreme voltage gain with less number of semiconductors and passive components. As a result, the converter cost gets reduced and achieves a wide range of voltage gain at a lesser duty ratio. Furthermore, steady‐state analysis and performance of the proposed topology and its characteristics were presented in this paper. Additionally, a detailed comparative analysis was presented with the most recent literature. Finally, a 500‐W experimental prototype has been fabricated to authorize the performance, feasibility, and analytical waveforms with experimental results.
Simultaneous wireless information and power transfer in resonant beam charging
Authors: Ali Ehab , Jibreel Nareeman , Rajab Zakariya , Younis Abdelhamid , Mesleh Raed
Published: September 2022

FSO links have attracted a significant amount of interest in the recent years driven by the paramount importance of their license‐free spectrum and ease of deployment in wireless networks. Besides, the energy harvesting (EH) paradigm allows recharging terminals via ambient and/or external sources and prolongs battery lifetime operation. Thereby, facilitating free space optical (FSO) in EH networks creates potential scenarios for the future sixth‐generation (6G) communication systems. In this study, an EH system performing simultaneous wireless information and power transfer (SWIPT) while adopting FSO and resonant beam charging (RBC), RBC–SWIPT system is thoroughly analyzed. The performance of RBC‐SWIPT system is analyzed through Monte Carlo simulations, where average bit error ratio (ABER) and energy efficiency (EE) are studied and evaluated. In addition, channel capacity is derived along with the mutual information and studied over indoor line of sight (LOS) optical channel. Monte Carlo simulation results corroborate the accuracy of the derived formulas.
Breast implant‐associated anaplastic large‐cell lymphoma: A series of two case reports diagnosed by cytopathology
Authors: Hrones Morgan , Harigopal Malini , Xu Mina , Abi‐Raad Rita
Published: September 2022

Breast implant‐associated anaplastic large‐cell lymphoma (BIA‐ALCL) is a rare T‐cell lymphoma with a good prognosis. It occurs in association with textured breast implants. Its most common presentation is a late‐onset peri‐implant effusion. We present two cases of BIA‐ALCL diagnosed by cytopathological examination of the fluid collection and describe the cytopathologic findings. Both patients were disease free after implant removal. This report highlights the contribution of the cytopathologic analysis to early diagnosis and definite treatment of BIA‐ALCL.
Emotional expression visual mismatch negativity in children
Authors: Kovarski Klara , Charpentier Judith , Houy‐Durand Emmanuelle , Batty Magali , Gomot Marie
Published: September 2022

Detection of changes in facial emotions is crucial to communicate and to rapidly process threats in the environment. This function develops throughout childhood via modulations of the earliest brain responses, such as the P100 and the N170 recorded using electroencephalography. Automatic brain signatures can be measured through expression‐related visual mismatch negativity (vMMN), which reflects the processing of unattended changes. While increasing research has investigated vMMN processing in adults, few studies have been conducted on children. Here, a controlled paradigm previously validated was used to disentangle specific responses to emotional deviants (angry face) from that of neutral deviants. Latencies and amplitudes of P100 and N170 both decrease with age, confirming that sensory and face‐specific activity is not yet mature in school‐aged children. Automatic change detection‐related activity is present in children, with a similar vMMN pattern in response to both emotional and neutral deviant stimuli to what previously observed in adults. However, vMMN processing is delayed in children compared to adults and no emotion‐specific response is yet observed, suggesting nonmature automatic detection of salient emotional cues. To our knowledge, this is the first study investigating expression‐related vMMN in school‐aged children, and further investigations are needed to confirm these results.
Alkali Metal Ion Substituted Carboxymethyl Cellulose as Anode Polymeric Binders for Rapidly Chargeable Lithium‐Ion Batteries
Authors: Byun Seoungwoo , Liu Zhu , Shin Dong Ok , Kim Kyuman , Choi Jaecheol , Roh Youngjoon , Jin Dahee , Jung Seungwon , Kim Kyung‐Geun , Lee Young‐Gi , Ringe Stefan , Lee Yong Min
Published: September 2022

The increasing demand for short charging time on electric vehicles has motivated realization of fast chargeable lithium‐ion batteries (LIBs). However, shortening the charging time of LIBs is limited by Li+ intercalation process consisting of liquid‐phase diffusion, de‐solvation, SEI crossing, and solid‐phase diffusion. Herein, we propose a new strategy to accelerate the de‐solvation step through a control of interaction between polymeric binder and solvent‐Li+ complexes. For this purpose, three alkali metal ions (Li+, Na+, and K+) substituted carboxymethyl cellulose (Li‐, Na‐, and K‐CMC) are prepared to examine the effects of metal ions on their performances. The lowest activation energy of de‐solvation and the highest chemical diffusion coefficient were observed for Li‐CMC. Specifically, Li‐CMC cell with a capacity of 3 mAh cm−2 could be charged to >95% in 10 min, while a value above >85% was observed after 150 cycles. Thus, the presented approach holds great promise for the realization of fast charging.