bluuebunny/crossref_metadata_2025 huggingface dataset:
Sex‐specific effects of environmental temperature during gestation on fluctuating asymmetry in deciduous teeth
Authors: Moes Emily , Kuzawa Christopher W. , Edgar Heather J. H.
Published: April 2024

Objectives

External environmental heat exposure during gestation impacts the physiology of human development in utero, but evidence for these impacts has not yet been explored in dentition. We examined deciduous teeth for fluctuating asymmetry (FA), a measure of developmental instability, together with gestational environmental temperature data drawn from historical weather statistics.

Materials and Methods

We measured dental casts from the longitudinal Burlington Growth Study, representing 172 participants (ages 3–6 years) with health records. FA was calculated from crown dimensions and intercuspal distances that develop during gestation. Multiple regression separated by sex (nfemale = 81) examined the effects of mean temperatures in each trimester, controlling for birth year.

Results

In females, increased temperatures during the first trimester are significantly associated with an increase in FA (p = 0.03), specifically during the second and third prenatal months (p = 0.03). There is no relationship between temperature and FA for either sex in the second or third trimesters, when enamel is formed.

Discussion

Dental instability may be sensitive to temperature in the first trimester in females during the scaffolding of crown shape and size in the earliest stages of tooth formation. Sexual dimorphism in growth investment strategies may explain the differences in results between males and females. Using enduring dental characteristics, these results advance our understanding of the effects of temperature on fetal physiology within a discrete period.
Engineering of Halide Methyltransferase BxHMT through Dynamic Cross‐Correlation Network Analysis
Authors: Gao Chun‐Yu , Yang Gui‐Ying , Ding Xu‐Wei , Xu Jian‐He , Cheng Xiaolin , Zheng Gao‐Wei , Chen Qi
Published: April 2024

Halide methyltransferases (HMTs) provide an effective way to regenerate S‐adenosyl methionine (SAM) from S‐adenosyl homocysteine and reactive electrophiles, such as methyl iodide (MeI) and methyl toluene sulfonate (MeOTs). As compared with MeI, the cost‐effective unnatural substrate MeOTs can be accessed directly from cheap and abundant alcohols, but shows only limited reactivity in SAM production. In this study, we developed a dynamic cross‐correlation network analysis (DCCNA) strategy for quickly identifying hot spots influencing the catalytic efficiency of the enzyme, and applied it to the evolution of HMT from Paraburkholderia xenovorans. Finally, the optimal mutant, M4 (V55T/C125S/L127T/L129P), exhibited remarkable improvement, with a specific activity of 4.08 U/mg towards MeOTs, representing an 82‐fold increase as compared to the wild‐type (WT) enzyme. Notably, M4 also demonstrated a positive impact on the catalytic ability with other methyl donors. The structural mechanism behind the enhanced enzyme activity was uncovered by molecular dynamics simulations. Our work not only contributes a promising biocatalyst for the regeneration of SAM, but also offers a strategy for efficient enzyme engineering.
N‐(Sulfonio)Sulfilimine Reagents: Non‐Oxidizing Sources of Electrophilic Nitrogen Atom for Skeletal Editing
Authors: Heilmann Tobias , Lopez‐Soria Juan M. , Ulbrich Johannes , Kircher Johannes , Li Zhen , Worbs Brigitte , Golz Christopher , Mata Ricardo A. , Alcarazo Manuel
Published: April 2024

The one‐pot synthesis of λ4‐dibenzothiophen‐5‐imino‐N‐dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh2(esp)2 (esp=α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid) generating a Rh‐coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good yields. We assumed that after formation of the corresponding N‐sulfonio aziridine, a ring expansion occurs via selective C−C bond cleavage and concomitant elimination of dibenzothiophene. Unexpectedly, a similar protocol transforms 1‐arylcyclobutenes into 1‐cyano‐1‐arylcyclopropanes. Our calculations indicate that aziridination is not favored in this case; instead, sulfilimine‐substituted cyclobutyl carbocations are initially formed, and these evolve to the isolated cyclopropanes via ring contraction. Both procedures are operationally simple, tolerate a range of functional groups, including oxidation‐sensitive alcohols and aldehydes, and enable the convenient preparation of valuable 15N‐labelled products. These results demonstrate the potential of 1 to provide alternative pathways for the selective transfer of N‐atoms in organic molecules.
Isla del Fraile. Reconstructing Coastal Dynamics in Southeastern Spain Through Underwater Archaeological Survey
Authors: Quevedo Alejandro , Aragón Enrique , de Dios Hernández García Juan , Rodríguez Pandozi Javier , Mukai Tomoo , Segura Alicia , Bellviure Joel , Muñoz Yesares Ricardo
Published: April 2024

A new archaeological research project analyses the history of Isla del Fraile (Águilas, Spain), a small island off the coast occupied since at least Roman times. Its isolation means that the sea has always conditioned its connectivity and relationship with land. Despite some underwater studies carried out in previous decades, its underwater surroundings, El Hornillo Bay, continue to be relatively unexplored. In parallel to the excavation work on the island's surface, an underwater survey was carried out in the area, which is known for its archaeological wealth. The objectives of this paper are to study the underwater contexts associated with the archaeological site, to determine whether there were any ports or anchorages and to analyse the phases of greatest activity in the bay between Antiquity and the Modern Age. New data are provided, and earlier finds, either previously unpublished or from private donations, are also reviewed. The findings are discussed and related to their local and interregional contexts. The main purpose is to offer a new contribution to the study of the maritime cultural landscape of the Western Mediterranean through a region underrepresented by research.
Residential load forecasting based on symplectic geometry mode decomposition and GRU neural network with attention mechanism
Authors: Lu Yuting , Wang Gaocai , Huang Xianfei , Wu Man
Published: April 2024

Short‐term residential load forecasting plays an increasingly important role in modern smart grids, with its main challenge being the high volatility and uncertainty of load curves. This article proposes a hybrid Symplectic Geometry Mode Decomposition‐Gated Recurrent Unit with Attention Mechanism (SGMD‐GRUAM) model for hourly residential load forecasting. First, SGMD is used to decompose the residential load and obtain a series of stable subsequences. Then, the Pearson correlation coefficient is used to select features related to each subsequence, such as weather factors. Next, a GRUAM prediction model is constructed for each subsequence. Finally, the final load prediction value is obtained by superimposing the previous component sequences and eliminating the noise sequence. The experiment uses the public dataset from UMass for a case study and compares it with benchmark models such as ARIMA and EEDM‐GRUAM. The experimental results show that the proposed SGMD‐GRUAM model has significant advantages in terms of prediction performance.
Agar‐Based Interface for Suppressing Parasitic Reactions toward High‐Performance Aqueous Zn‐Ion Batteries
Authors: Qu Yi‐Fan , Liu Xin , Qian Jia‐Wei , Chen Jingwei , Chen Li‐Feng
Published: April 2024

With advantages including high capacity, intrinsic safety and low cost, aqueous zinc‐ion batteries (AZIBs) are ideal electrochemical energy storage devices for large‐scale and portable energy storage. However, the development of AZIBs suffers from tricky challenges, such as the notorious Zn dendrite growth and severe parasitic reactions. Herein, as a low‐cost and nontoxic biomass, agar is adopted to construct an interface layer on Zn foil to mitigate side reactions and induce uniform Zn deposition on Zn anodes. The interaction between Zn2+ and polar functional groups of agar can regulate Zn2+ distribution and promote Zn2+ desolvation, thus simultaneously achieving homogenous Zn deposition and suppressed hydrogen evolution reaction. Meanwhile, SO42− anions are blocked from contacting Zn surface due to electrostatic repulsion, greatly restraining corrosion and passivation. Consequently, Zn||A‐Cu asymmetric cell operates normally for 590 cycles with an average coulombic efficiency of 99.5 %, suggesting good reversibility of Zn plating/stripping. Notably, A‐Zn symmetric cell exhibits a long lifespan of 1100 h at 2 mA cm−2. Furthermore, the A‐Zn||NVO full cell displays a superb capacity retention of 94.8 % after 3600 cycles at 5 A g−1. This work offers a novel interface modification method for constructing stable and dendrite‐free anodes of AZIBs.
Urolithin A affects cellular migration and modulates matrix metalloproteinase expression in colorectal cancer cells
Authors: El‐Wetidy Mohammad S. , Rady Mohamad I. , Rady Islam , Helal Hamed
Published: April 2024

Colorectal cancer (CRC) is the world's second most common gastrointestinal malignancy. Preventing tumor cell proliferation and dissemination is critical for patient survival. Polyphenols have a variety of health advantages and can help prevent cancer. The current study examined different cellular activities of the gut‐microbiota metabolite urolithin A (UA) on several colon cancer cell lines. The results revealed that UA suppressed cell growth in a dose‐ and time‐dependent manner. In the current investigation, UA substantially affected cell migration in the wound‐healing experiment and greatly decreased the number of colonies generated in each CRC cell culture. UA decreased cellular migration in CRC cells 48 h after treatment, which was significant (p < .001) compared to the migration rate in untreated cells. When compared to untreated cells, UA slowed the process of colony formation by reducing the number of colonies or altering their morphological shape. The western blot analysis investigation revealed that UA inhibits cellular metastasis by lowering the expression levels of matrix metalloproteinases 1 and 2 (MMP1 and MMP2) by more than 43% and 41% (p < .001) in HT29, 28% and 149% (p < .001) in SW480, and 90% and 74% (p < .001) in SW620, respectively, at a 100 µM dosage of UA compared to the control. Surprisingly, at a 100 µM dosage of UA, the expression levels of the tissue inhibitor of metalloproteinases 1 (TIMP1) were elevated in HT29, SW480, and SW620 cells treated with 100 µM of UA by more than 89%, 57%, and 29%, respectively. Our findings imply that UA has anticancer properties and might be used therapeutically to treat CRC. The findings provided the first indication of the influence of UA on cellular migration and metastasis in colon cancer cells. All of these data showed that UA might be used as an adjuvant therapy in the treatment of various forms of CRC.
Application of Sublimation in the Synthesis and Crystal Growth of Organosulfones
Authors: Alaa Eldin Refat Lamis , Karpinska Jolanta , Konda Saidulu , Simmie John M. , Murphy Paul V. , McArdle Patrick , Erxleben Andrea
Published: April 2024

The solvent‐free elimination of sulfinic acid and aromatization of 1,6‐trans‐substituted bis(arylsulfone) trienes is reported. It is shown that sublimation can be used as a ‘green’ method to combine the thermal transformation of six trienes and the crystal growth of the resulting 4‐(phenylsulfonyl)biphenyls. When the sublimation conditions are carefully controlled, high quality single crystals of the 4‐(phenylsulfonyl)biphenyls are obtained. Theoretical modelling of the reaction using the simplified triene Ph‐(CH)6‐SO2H showed that the cyclization is energetically feasible and that the complete conversion is possible during the timescale of the sublimation. At temperatures slightly higher than the optimum sublimation temperature two of the trienes transformed into 1,4‐cyclohexadienes that did not eliminate phenylsulfinic acid. A reaction mechanism involving a 1,3‐hydrogen shift induced by free PhS• radicals is proposed for the formation of the 1,4‐cyclohexadienes.
Conformational and Electronic Variations in 1,2‐ and 1,5a‐Cyclophellitols and their Impact on Retaining α‐Glucosidase Inhibition
Authors: Ofman Tim P. , Heming Jurriaan J. A. , Nin‐Hill Alba , Küllmer Florian , Moran Elisha , Bennett Megan , Steneker Roy , Klein Anne‐Mei , Ruijgrok Gijs , Kok Ken , Armstrong Zach W. B. , Aerts Johannes M. F. G. , van der Marel Gijsbert A. , Rovira Carme , Davies Gideon J. , Artola Marta , Codée Jeroen D. C. , Overkleeft Herman S.
Published: April 2024

Glycoside hydrolases (glycosidases) take part in myriad biological processes and are important therapeutic targets. Competitive and mechanism‐based inhibitors are useful tools to dissect their biological role and comprise a good starting point for drug discovery. The natural product, cyclophellitol, a mechanism‐based, covalent and irreversible retaining β‐glucosidase inhibitor has inspired the design of diverse α‐ and β‐glycosidase inhibitor and activity‐based probe scaffolds. Here, we sought to deepen our understanding of the structural and functional requirements of cyclophellitol‐type compounds for effective human α‐glucosidase inhibition. We synthesized a comprehensive set of α‐configured 1,2‐ and 1,5a‐cyclophellitol analogues bearing a variety of electrophilic traps. The inhibitory potency of these compounds was assessed towards both lysosomal and ER retaining α‐glucosidases. These studies revealed the 1,5a‐cyclophellitols to be the most potent retaining α‐glucosidase inhibitors, with the nature of the electrophile determining inhibitory mode of action (covalent or non‐covalent). DFT calculations support the ability of the 1,5a‐cyclophellitols, but not the 1,2‐congeners, to adopt conformations that mimic either the Michaelis complex or transition state of α‐glucosidases.
Azophosphines: Synthesis, Structure and Coordination Chemistry
Authors: Jordan Emma J. , Calder Ethan D. E. , Adcock Holly V. , Male Louise , Nieger Martin , Slootweg J. Chris , Jupp Andrew R.
Published: April 2024

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus‐containing analogues of triazenes are underexplored but offer great potential as flexible and small bite‐angle ligands. This manuscript explores the synthesis and characterisation of a family of air‐stable azophosphine‐borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.
Versatile Ce(III)‐Terephthalic Acid@Au Metal Organic Frameworks for ROS Elimination and Photothermal Sterilization
Authors: Wang Jing , Wei Xue , Chen Jian , Zhang Jing , Guo Yanzhen , Xin Yongjuan
Published: April 2024

Nanozymes have been widely used for treating reactive oxygen species (ROS) caused diseases. However, the ROS‐dependent antibacterial property is inevitably damaged during the process of scavenging ROS, which is unfavorable for the treatment of diseases related to both ROS accumulation and bacterial infections. To address the issues, biomedical materials with both ROS‐elimination ability and ROS‐independent antibacterial capacity are fabricated via in situ depositing spherical Au nanoparticles (Au NPs) on rough surface of metal organic frameworks composed of Ce(III) and terephthalic acid (Ce‐BDC@Au MOFs). The synthesized Ce‐BDC@Au MOFs show multi‐enzymatic activities owing to the reversible conversion between Ce3+ and Ce4+, and can significantly scavenge ROS in cells. The deposition of spherical Au NPs on surface of Ce‐BDC MOFs causes Au NPs to come close proximity for forming plasmon resonance coupling, inducing the resonance wavelength of Au NPs red shifted to NIR region. Based on this, Ce‐BDC@Au MOFs show good photothermal conversion efficiency under NIR laser (808 nm) irradiation. Benefitting from rough surface and photothermal conversion ability, Ce‐BDC@Au MOFs have high antibacterial efficiency against staphylococcus aureus through both mechanically damaging and photothermal destruction. This strategy is biosafety and effectiveness for treating diseases related to both ROS accumulation and bacterial infections.
Effects of Quinidine or Rifampin Co‐administration on the Single‐Dose Pharmacokinetics and Safety of Rilzabrutinib (PRN1008) in Healthy Participants
Authors: Rask‐Madsen Christian , Katragadda Suresh , Li Mengyao , Ucpinar Sibel , Chinn Leslie , Arora Puneet , Smith Patrick
Published: April 2024

This open‐label, phase 1 study was conducted with healthy adult participants to evaluate the potential drug‐drug interaction between rilzabrutinib and quinidine (an inhibitor of P‐glycoprotein [P‐gp] and CYP2D6) or rifampin (an inducer of CYP3A and P‐gp). Plasma concentrations of rilzabrutinib were measured after a single oral dose of rilzabrutinib 400 mg administered on day 1 and again, following a wash‐out period, after co‐administration of rilzabrutinib and quinidine or rifampin. Specifically, quinidine was given at a dose of 300 mg every 8 hours for 5 days from day 7 to day 11 (N = 16) while rifampin was given as 600 mg once daily for 11 days from day 7 to day 17 (N = 16) with rilzabrutinib given in the morning of day 10 (during quinidine dosing) or day 16 (during rifampin dosing). Quinidine had no significant effect on rilzabrutinib pharmacokinetics. Rifampin decreased rilzabrutinib exposure (the geometric mean of Cmax and AUC0‐∞ decreased by 80.5% and 79.5%, respectively). Single oral doses of rilzabrutinib, with or without quinidine or rifampin, appeared to be well tolerated. These findings indicate that rilzabrutinib is a substrate for CYP3A but not a substrate for P‐gp.
Two‐Dimensional Sc2CCl2/XSe2(X=Mo, Pt) van der Waals Heterojunctions: Promising Photocatalytic Hydrogen Evolution Materials
Authors: Zeng Qionghui , Xu Liang , Xiong S.X. , Zhang Ying , Cao Lei , Tao Ji , Li Zhengquan , Wang Ling‐Ling , Dong Kejun
Published: April 2024

In the field of photocatalysis, new heterojunction materials are increasingly explored to achieve efficient energy conversion and environmental catalysis under visible light and sunlight. This paper presents a study on two newly constructed two‐dimensional van der Waals heterojunctions, Sc2CCl2/MoSe2 and Sc2CCl2/PtSe2, using density‐functional theory. The study includes a systematic investigation of their geometrical structure, electronic properties, and optical properties. The results indicate that both heterojunctions are thermodynamically, kinetically, and mechanically stable. Additionally, Bader charge analysis reveals that both heterojunctions exhibit typical type II band properties. However, the band gap of the Sc2CCl2/MoSe2 heterojunction is only 1.18 eV, which is insufficient to completely cross the reduction and oxidation (REDOX) potential of 1.23 eV, whereas the band gap of Sc2CCl2/PtSe2 heterojunction is 1.49 eV, which is theoretically capable for water decomposition. The subsequent calculation of the Sc2CCl2/PtSe2 heterojunction demonstrate excellent hole carrier mobility and high efficiency light absorption in the visible light range, facilitating the separation of photogenerated electrons and holes. More importantly, Sc2CCl2/PtSe2 vdW type II heterojunction can achieve full water decomposition from pH 1 to pH 4, and its thermodynamic feasibility is confirmed by Gibbs free energy results. The aim of this study is to develop materials and analyses that will result in optoelectronic devices that are more efficient, stable, and sustainable.
How territoriality and sociality influence the habitat selection and movements of a large carnivore
Authors: Hansen K. Whitney , Ranc Nathan , Morgan John , Jordan Neil R. , McNutt J. Weldon , Wilson Alan , Wilmers Christopher C.
Published: April 2024

While territoriality is one of the key mechanisms influencing carnivore space use, most studies quantify resource selection and movement in the absence of conspecific influence or territorial structure. Our analysis incorporated social information in a resource selection framework to investigate mechanisms of territoriality and intra‐specific competition on the habitat selection of a large, social carnivore. We fit integrated step selection functions to 3‐h GPS data from 12 collared African wild dog packs in the Okavango Delta and estimated selection coefficients using a conditional Poisson likelihood with random effects. Packs selected for their neighbors' 30‐day boundary (defined as their 95% kernel density estimate) and for their own 90‐day core (defined as their 50% kernel density estimate). Neighbors' 30‐day boundary had a greater influence on resource selection than any habitat feature. Habitat selection differed when they were within versus beyond their neighbors' 30‐day boundary. Pack size, pack tenure, pup presence, and seasonality all mediated how packs responded to neighbors' space use, and seasonal dynamics altered the strength of residency. While newly‐formed packs and packs with pups avoided their neighbors' boundary, older packs and those without pups selected for it. Packs also selected for the boundary of larger neighboring packs more strongly than that of smaller ones. Social structure within packs has implications for how they interact with conspecifics, and therefore how they are distributed across the landscape. Future research should continue to investigate how territorial processes are mediated by social dynamics and, in turn, how territorial structure mediates resource selection and movement. These results could inform the development of a human–wildlife conflict (HWC) mitigation tool by co‐opting the mechanisms of conspecific interactions to manage space use of endangered carnivores.
Aluminum Complexes Supported by Ph2P‐Functionalized Anilido‐Pyridine Ligand Platform: Synthesis, Structure and Evaluation as Frustrated Lewis Pairs
Authors: Chandramohan Kavin Raj Kumar , Abdalghani Issam , Roisnel Thierry , Kirillov Evgueni
Published: April 2024

A simple direct condensation of 2,6‐bis(phenylamino)pyridine (1) and ClPPh2 under basic conditions allowed straightforward synthesis of the new multidentate Ph2P‐substituted anilido‐pyridine proligands 2 a and 2 b. Proligand 2 a was used in σ‐bond metathesis reactions with Me3Al affording either dinuclear product 3 a‐Al2 or mononuclear 4 a‐Al, depending on the reaction conditions. These complexes were authenticated by X‐ray crystallography, NMR spectroscopy and microanalysis. The analysis of the interaction between Me2Al and Ph2P fragments in 4 a‐Al was performed by structural and computational studies. The reactivity of 4 a‐Al was preliminary assessed in several representative reactions.
Synthesis of Asymmetric Variants in a Dinucleating Ligand Family and Application for Dinuclear Copper(II) Complexes
Authors: Siebe Lena , Butenuth Christoph , Köhler Antonia , Stammler Anja , Oldengott Jan , Bögge Hartmut , Glaser Thorsten
Published: April 2024

We developed a dinucleating ligand system with two identical tetradentate coordination compartments and varying terminal donors. Here, we report the synthesis of two differently asymmetric dinucleating ligands: the ligand selma (=4,7,10‐trimethyl‐1,1,10‐tris(2‐pyridylmethyl)‐1,4,7,10‐tetraazadecane) with one N3‐ and one N4‐ and the ligand susan
(=4,7‐dimethyl‐1,1‐bis(6‐methylpyridine‐2‐yl‐methyl)‐10,10‐bis(2‐pyridylmethyl)‐1,4,7,10‐tetraazadecane) with two different N4‐coordination compartments. The initial synthesis of the ligand selma based on extending dipicolylamine with 2‐(methylamino)ethyl units in repeated reductive aminations. Synthesis of 1‐trifluoroacetyl‐4,7‐dimethyl‐1,4,7,10‐tetraazadecane allowed the synthesis of both ligands selma and susan
. To study the influence of the terminal donors, the CuII chloride complexes of selma and susan
and the two symmetric susan and susan6−Me were synthesized. The introduction of the 6‐methyl substituents on the pyridines increases the bond lengths, reduces the electron donation, and shifts the reduction potentials anodically. The large 6‐methyl substituents enforce a meridional coordination of the dipicolylamine subunits, while it is mainly facial without the 6‐methyl substituents. Analysis of the solid‐state structures and the d‐d transitions in solution demonstrate a flat potential energy surface for the 5‐coordinate polyhedra. Analysis of d‐d transitions and reduction potentials indicate that the properties of the CuIICuII complexes are additive for but cooperative for selma reflecting the difference of these asymmetric dinucleating ligands.
Application of the Photo‐Fries Reaction as a Key Step in the Preparation of Valuable Aryloxyethyl Selenocyanates
Authors: Lucena Valentin , Hernán Szajnman Sergio , Bautista Rodriguez Juan , Mauricio Bonesi Sergio
Published: April 2024

A multistep sequence leads to the preparation of a series of aryl selenocyanate WC‐9 homologues, which are interesting compounds with potential biological activity against Trypanosoma cruzi, the etiological agent of Chagas disease. The synthetic sequence involves the application of the photo‐Fries rearrangement reaction as a key step for the preparation of a series of 2‐hydroxyphenones bearing alkyl chains of different length and a phenyl group. These intermediates are obtained upon direct irradiation (254 nm) of 4‐phenoxyphenyl esters in different solvents at room temperature. Then, reaction of the 2‐hydroxyphenones with 2‐(2‐bromoethoxy)tetrahydro‐2H‐pyran followed by acid deprotection, tosylation (or mesylation) reaction and, finally, nucleophilic attack with potassium selenocyanate provides the target aryloxyethyl selenocyanate homologues in good yields.
Direct Introduction of an Acetyl Group at the α‐Carbon Atom of an Arene Ring through an Amide Photo‐Fries Rearrangement upon Exposure to UV Light
Authors: Kim Myeonggeuk , Na Ha‐Na , Shen Liu‐lan , Jeong Jin Hyun
Published: April 2024

We employed an amide photo‐Fries rearrangement for the synthesis benzoheterocyclic compounds and found that direct acylation of the α‐carbon atom in an arene ring can occur upon exposure to ultraviolet (UV) light. In this reaction, the N‐acetyl group of amides underwent rearrangement to the α‐position across the bridgehead carbon atom under UV−C light. The reaction conditions were gentle and safe. Moreover, this reaction proves to be more convenient for selectively manipulating benzoheterocyclic compounds in comparison to traditional approaches involving Lewis acid catalysts or anionic reagents.
Construction of an electrochemical platform with carbon nanotubes and aluminium doped zinc oxide nanoparticles for the sensitive determination of sunset yellow
Authors: Omar Abdullah Bikhtiyar , Teker Tuğçe , Aslanoglu Mehmet
Published: April 2024

Sunset yellow, a synthetic colorant and used to improve the texture and the appearance of food samples, can adversely affect humans. The development of a sensitive method to analyse food products for the accurate determination of sunset yellow is of importance for the level of risk to human health and thus food safety. The present study aimed to prepare a voltammetric method for the precise detection of sunset yellow content in a commonly consumed powdered beverage and pharmaceutical products. For this purpose, a sensitive method utilizing a voltammetric platform was constructed by modifying a glassy carbon electrode (GCE) with carbon nanotubes (MWCNTs) and aluminium doped zinc oxide (AZO). Cyclic voltammetry (CV) and electrochemical impedance spectroscopic (EIS) measurements indicated that the proposed voltammetric platform (GCE/MWCNTs/AZO) possessed high electro‐active surface area and lower value of charge transfer resistance (Rct) and therefore, could serve as a promising sensing material. The GCE/MWCNTs/AZO system improved voltammetric behaviour of sunset yellow at an accumulation time of 210 s and indicated good electrocatalytic activity due to high synergistic effect between MWCNTs and AZO nanoparticles. This method of analysis exhibited a dynamic working range from 4.0×10−9 to 7.5×10−6 M with a limit of detection (LOD) of 9.5×10−10 M for sunset yellow. The GCE/MWCNTs/AZO system was successfully utilized for the electroanalysis of beverages and pharmaceuticals for detection of sunset yellow. Voltammetric measurements indicate that the GCE/MWCNTs/AZO system enables good accuracy and high precision for the determination of sunset yellow.
Option pricing with dynamic conditional skewness
Authors: Liang Fang , Du Lingshan
Published: April 2024

In this paper, we develop a discrete‐time affine option‐pricing model that explicitly incorporates the dynamics of conditional skewness. The new proposed model features different dynamics for conditional skewness and variance. To stress the difference in information, we use alternative realized measures constructed from high‐frequency historical returns to update skewness and variance dynamics. By Fourier inversion, we derive closed‐form option valuation formulas. Empirically, the flexibility that the model offers for conditional skewness as well as high‐frequency information from the underlying asset contribute to superior performance upon benchmark models using S&P 500 index options. Overall, the joint modeling of dynamic conditional skewness and realized measures leads to an out‐of‐sample gain of 12.25% in pricing accuracy. The improvements are more pronounced for deep in‐the‐money calls, options with shorter maturities, and during highly volatile periods.
VIX option pricing through nonaffine GARCH dynamics and semianalytical formula
Authors: Liu Junting , Wang Qi , Zhang Yuanyuan
Published: April 2024

This paper develops analytical approximations for volatility index (VIX) option pricing under nonaffine generalized autoregressive conditional heteroskedasticity (GARCH) models as advocated by Christoffersen et al. We obtain the approximation formulae for pricing VIX options and then evaluate their performance with three expansions under four empirically well‐tested models. Our numerical experiments find that the weighted expansion generated by the fat‐tailed weighting kernel can significantly reduce approximation error over the Gram‐Charlier expansion; the Taylor expansion of conditional moments can lead to divergence for parameters with certain high persistence in the affine GARCH, nonlinear asymmetric GARCH, and Glosten‐Jagannathan‐Runkle GARCH models, while surviving during high persistence in the exponential GARCH.
Trading commodity ETFs: Price behavior, investment insights, and performance analysis
Authors: Hadad Elroi , Malhotra Davinder , Nippani Srinivas
Published: April 2024

This study analyzes the risk‐adjusted performance of commodity exchange‐traded funds (ETFs) across diverse market conditions. Examining monthly returns from December 2004 to June 2022, our findings suggest that commodity ETFs underperformed US stocks, indicating limited diversification benefits. However, we document positive α during turbulent market periods like the COVID‐19 crisis, signifying potential resilience. Furthermore, our factor regressions reveal that shifts in the global commodity price index and disposable personal income significantly influence commodity ETFs' excess returns, pointing to broader economic and income‐related trends. Commodity ETFs exhibit lower Value‐at‐Risk and Expected Shortfall compared to stock market indices, indicating reduced downside risk exposure for investors. Given the increasing popularity of commodity ETFs, these insights hold substantial significance for market participants.
Surface electromyography‐based biofeedback can facilitate recovery from total knee arthroplasty
Authors: Armshaw Brennan , Vaidya Manish , Mehta Sacheen
Published: April 2024

Knee osteoarthritis is among the most prevalent chronic diseases. Total knee arthroplasty is a common solution that effectively addresses the continued structural degeneration of the articular cartilage. However, effective physical therapy is critical for recovery. Despite participating in physical therapy, many patients fail to recover. This study investigated the potential efficacy of a behaviorally informed approach to surface electromyographic biofeedback following total knee arthroplasty relative to the clinical standard, neuromuscular electrical stimulation. The surface electromyographic biofeedback procedure incorporated improved techniques for establishing a baseline and individualized and adjusting criteria for feedback. The findings suggest some advantages for surface electromyographic biofeedback over neuromuscular electrical stimulation in quadriceps strength, range of motion, functional recovery, and quality of life. Behaviorally informed surface electromyographic biofeedback holds promise for total knee arthroplasty recovery and these data suggest considerable room for collaboration between behavior analysts and physical therapists.
Role of high‐volume plasmapheresis in the management of paediatric acute liver failure
Authors: Hilberath Johannes , Camelli Vittoria , Hofer Christiane , Hartleif Steffen , Nadalin Silvio , Peters Maren , Kumpf Matthias , Bevot Andrea , Zirngibl Matthias , Weitz Marcus , Sturm Ekkehard
Published: April 2024

Objectives

Paediatric acute liver failure (PALF) is a life‐threatening disease. Management aims to support hepatic regeneration or to bridge to liver transplantation. High‐volume plasmapheresis (HVP) removes protein‐bound substances, alleviates inflammation, and improves survival in adult acute liver failure. However, experience with HVP in PALF is limited. Aim of this study is to report on feasibility, safety, efficacy and outcomes of HVP in PALF.

Methods

Retrospective observational study in children with PALF. HVP was performed upon identification of negative prognostic indicators, in toxic aetiology or multiorgan failure (MOF). Exchanged volume with fresh‐frozen plasma corresponded to 1.5–2.0 times the patient's estimated plasma volume. One daily cycle was performed until the patient met criteria for discontinuation, that is, liver regeneration, liver transplantation, or death.

Results

Twenty‐two children with PALF (body weight 2.5–106 kg) received 1–7 HVP cycles. No bleeding or procedure‐related mortality occurred. Alkalosis, hypothermia and reduction in platelets were observed. Haemolysis led to HVP termination in one infant. Seven children (32%) survived with their native livers, 13 patients (59%) underwent liver transplantation. Two infants died due to MOF. Overall survival was 86%. International normalization ratio (INR), alanine aminotransaminases (ALT), bilirubin and inotropic support were reduced significantly (p < 0.05) after the first HVP‐cycle (median): INR 2.85 versus 1.5; ALT 1280 versus 434 U/L; bilirubin 12.7 versus 6.7 mg/dL; norepinephrine dosage 0.083 versus 0.009 µg/kg/min. Median soluble‐interleukin‐2‐receptor dropped significantly following HVP (n = 7): 2407 versus 950 U/mL (p < 0.02).

Conclusions

HVP in PALF is feasible, safe, improves markers of liver failure and inflammation and is associated with lowering inotropic support. Prospective and controlled studies are required to confirm efficacy of HVP in PALF.
Esophago‐gastric junction findings on high resolution impedance manometry in children with esophageal atresia
Authors: Tan Tanny Sharman P. , Senior Nicholas D. , Comella Assia , McCall Lisa , Hutson John M. , Finch Sue , Safe Mark , Teague Warwick J. , Omari Taher I. , King Sebastian K.
Published: April 2024

Objectives

Using high resolution impedance manometry (HRIM), this study characterized the esophago‐gastric junction (EGJ) dynamics in children with esophageal atresia (EA).

Method

Esophageal HRIM was performed in patients with EA aged less than 18 years. Objective motility patterns were analyzed, and EGJ data reported. Controls were pediatric patients without EA undergoing investigations for consideration of fundoplication surgery.

Results

Seventy‐five patients (M:F = 43:32, median age 1 year 3 months [3 months–17 years 4 months]) completed 133 HRIM studies. The majority (64/75, 85.3%) had EA with distal tracheo‐esophageal fistula. Compared with controls, liquid swallows were poorer in patients with EA, as evident by significant differences in distension pressure emptying and bolus flow time (BFT). The integrated relaxation pressure for thin liquid swallows was significantly different between EA types, as well as when comparing patients with EA with and without previous esophageal dilatations. The BFT for solid swallows was significantly different when compared with EA types.

Conclusions

We have utilized HRIM in patients with EA to demonstrate abnormalities in their long‐term EGJ function. These abnormalities correlate with poorer esophageal compliance and reduced esophageal peristalsis across the EGJ. Understanding the EGJ function in patients with EA will allow us to tailor long‐term management to specific patients.
Formula modifications to the Crohn's disease exclusion diet do not impact therapy success in paediatric Crohn's disease
Authors: Landorf Emma , Hammond Paul , Abu‐Assi Rammy , Ellison Samuel , Boyle Terry , Comerford Annabel , Couper Richard
Published: April 2024

Objectives

The Crohn's disease exclusion diet (CDED) + partial enteral nutrition (PEN) is an emerging diet used to induce clinical remission in children with active Crohn's disease (CD). This study aims to determine the effectiveness of using the CDED+PEN to induce clinical remission in an Australian group of children with active CD using different PEN formulas and incorporating patient dietary requirements.

Methods

We retrospectively collected data from children (both newly diagnosed and with existing CD while on therapy) with active CD (Paediatric Crohn's Disease Activity Index [PCDAI] ≥10) and biochemical evidence of active disease (elevated C‐reactive protein [CRP], erythrocyte sedimentation rate [ESR] or faecal calprotectin [FC]) who completed at least phase 1 (6 weeks) of the CDED+PEN to induce clinical remission. Data were collected at baseline, Week 6 and Week 12. The primary endpoint was clinical remission at Week 6 defined as PCDAI < 10.

Results

Twenty‐four children were included in phase 1 analysis (mean age 13.8 ± 3.2 years). Clinical remission at Week 6 was achieved in 17/24 (70.8%) patients. Mean PCDAI, CRP, ESR and FC decreased significantly after 6 weeks (p < 0.05). Formula type (cow's milk based, rice based, soy based) did not affect treatment efficacy. A greater than 50% decrease in FC was achieved in 14/21 (66.7%) patients who completed phase 1 and 12/14 (85.7%) patients who completed phase 2 of the CDED+PEN.

Conclusions

Formula modifications to the CDED+PEN do not impact the expected treatment efficacy in Australian children with active luminal CD.
The prevalence and predictors of metabolic dysfunction‐associated steatotic liver disease and fibrosis/cirrhosis among adolescents/young adults
Authors: Perumpail Brandon J. , Manikat Richie , Wijarnpreecha Karn , Cholankeril George , Ahmed Aijaz , Kim Donghee
Published: April 2024

Objectives

We investigated the current prevalence of metabolic dysfunction‐associated steatotic liver disease (MASLD) and fibrosis/cirrhosis and identified at‐risk populations for MASLD and MASLD‐related fibrosis among US adolescents and young adults in the United States.

Methods

Utilizing the National Health and Nutrition Examination Survey 2017−2020, the prevalence of MASLD and fibrosis/cirrhosis was assessed via controlled attenuation parameter (CAP) score and liver stiffness measurements by transient elastography in participants aged 12−29 years with at least one cardiometabolic criteria and absence of other chronic liver disease. Multivariable logistic regression was performed to determine predictors of MASLD and MASLD‐related fibrosis.

Results

The overall prevalence of MASLD was 23.9% (95% confidence interval [CI]: 21.3−26.5 for CAP ≥ 263 dB/m) and 17.3% (95% CI: 14.7−20.0 for ≥285 dB/m), respectively. The prevalence of fibrosis and cirrhosis in MASLD was 11.0% and 3.1%, respectively. When categorized by age, the prevalence of MASLD varied from 16.8% (of which 6.2% [fibrosis], 1.8% [cirrhosis]) in early and middle adolescents (12−17 years), to 25.5% (11.8% [fibrosis], 4.8% [cirrhosis]) in late adolescents and young adults (18−24 years), and to 30.4% (of which 13.2% [fibrosis] and 2.1% [cirrhosis]) in older young adults (25−29 years). The independent predictors for MASLD included male sex, Hispanic, non‐Hispanic Asian, body mass index, and low HDL‐cholesterol. In contrast, diabetes and body mass index were associated with an increased risk of fibrosis in individuals with MASLD.

Conclusions

The prevalence of MASLD and related fibrosis in adolescents and young adults in the United States has reached a significant level, with a substantial proportion of cirrhosis.
Catabolism of phenolics from grape peel and its effects on gut microbiota during in vitro colonic fermentation
Authors: Cui Wenyu , Chen Fuchun , Sun Zhaoyue , Cui Caifang , Xu Ben , Shen Weijun , Wan Fachun , Cheng Anwei
Published: April 2024

BACKGROUND

Grape peels, the main by‐products of wine processing, are rich in bioactive ingredients of phenolics, including proanthocyanidins, flavonoids and anthocyanins. Phenolics have the function of regulating intestinal microbiota and promoting intestinal health. From the perspective of the dietary nutrition of grape peel phenolics (GPP), the present study aimed to investigate the influence of GPP on the composition and metabolism of human gut microbiota during in vitro fermentation.

RESULTS

The results indicated that GPP could decrease pH and promote the production of short‐chain fatty acids. ACE and Chao1 indices in GPP group were lower than that of the Blank group. GPP enhanced the levels of Lachnospiraceae UCG‐004, Bacteroidetes and Roseburia, but reduced the Firmicutes/Bacteroidetes ratio. Kyoto Encyclopedia of Proteins and Genome enrichment pathways related to phenolic acid metabolism mainly included flavonoid, anthocyanin, flavone and flavonol biosynthesis. Gut microbiota could accelerate the release and breakdown of phenolic compounds, resulting in a decrease in the content of hesperetin‐7‐O‐glucoside, delphinidin‐3‐O‐glucoside and cyanidin‐3‐rutinoside etc. In vitro antibacterial test found that GPP increased the diameters of the inhibition zones of Escherichia coli and Staphylococcus aureus in a dose‐dependent manner.

CONCLUSION

The results of the present study revealed that GPP might be a potential prebiotic‐like to prevent diseases by improving gut health. The findings could provide a theoretical basis for the potential to exploit GPP as dietary nutrition to maintain intestinal function. © 2024 Society of Chemical Industry.
Exploring the flavor changes in mung bean flour through Lactobacillus fermentation: insights from volatile compounds and non‐targeted metabolomics analysis
Authors: Xue Yuqi , Chen Jie , Wang Lei , Wang Yuwen , Xu Fei
Published: April 2024

BACKGROUND

Mung beans are highly nutritious but their leguminous flavor limits their development. Lactic acid bacteria (LAB) fermentation can decrease unwanted bean flavors in legumes and enhance their flavor. This study examined the influence of Lactobacillus fermentation on the flavor characteristics of mung bean flour (MBF) using volatile compounds and non‐targeted metabolomics.

RESULTS

Lactobacillus plantarum LP90, Lactobacillus casei LC89, and Lactobacillus acidophilus LA85 eliminated 61.37%, 48.29%, and 43.73%, respectively, of the primary bean odor aldehydes from MBF. The relative odor activity value (ROAV) results showed that fermented mung bean flour (FMBF) included volatile chemicals that contributed to fruity, flowery, and milky aromas. These compounds included ethyl acetate, hexyl formate, 3‐hydroxy‐2‐butanone, and 2,3‐butanedione. The levels of amino acids with a fresh sweet flavor increased significantly by 93.89, 49.40, and 35.27% in LP90, LC89, and LA85, respectively. A total of 49 up‐regulated and 13 down‐regulated significantly differential metabolites were annotated, and ten metabolic pathways were screened for contributing to the flavor. The correlation between important volatile compounds and non‐volatile substances relies on two primary metabolic pathways: the citric acid cycle pathway and the amino acid metabolic system.

CONCLUSION

The flavor of MBF was enhanced strongly by the process of Lactobacillus fermentation, with LP90 having the most notable impact. These results serve as a reference for identifying the flavor of FMBF. © 2024 Society of Chemical Industry.
When to ditch the ladder and take the elevator: The Anderson SArcoma Risk of Complications (A‐SARC) score to guide reconstructive decision‐making in extremity soft tissue sarcoma patients
Authors: Mericli Alexander F. , Elmorsi Rami , Camacho Luis , Hassan Abbas , Krijgh David D. , Tilney Gordon , Lyu Heather , Traweek Raymond S. , Witt Russell G. , Roubaud Margaret S. , Roland Christina L.
Published: April 2024

Background

The reconstructive ladder relies mostly on defect size and depth to determine reconstructive technique, however, in actuality, many more variables ultimately inform reconstructive decision making, especially regarding extremity soft tissue sarcoma (eSTS) defects. The purpose of this study was to describe eSTS patients who will most optimally benefit from an advanced method of reconstruction (defined as a pedicled regional flap or free flap) and to create a simple risk assessment scale that can be employed in clinical practice.

Study Design

A single‐institution retrospective cohort study examined patients undergoing resection of soft tissue sarcoma affecting the upper or lower extremities between 2016 and 2021. We categorized patients who required a pedicled or free flap as having had advanced reconstruction, and all other techniques were considered simple reconstruction. A regression was used to create a risk scale to guide reconstructive decision‐making.

Results

The following variables were identified as independent predictors of complications and used to create our risk scale: lower extremity tumor location, preoperative radiotherapy, tumor bed excision, male sex, hypertension, and tumor volume. Intermediate and high‐risk patients reconstructed using simple techniques had significantly greater overall complication rates compared to those reconstructed with advanced techniques. Major complications were significantly greater in low‐risk patients reconstructed with advanced techniques.

Conclusions

To minimize postoperative wound complications, low‐risk patients should receive simple methods of reconstruction, whereas high‐risk patients should be reconstructed using advanced techniques.