bluuebunny/crossref_metadata_2025 huggingface dataset:
L‐Proline Derived Thioamide Small Organic Molecule for the α‐Stereoselective Synthesis of 2‐Deoxyglycosides
Authors: Tiwari Ashwani , Khanam Ariza , Kumar Ashwani , Lal Mohan , Kumar Mandal Pintu
Published: July 2023

L‐Prolinethioamide catalyzes direct stereoselective glycosylation of glycal donors to access 2‐deoxyglycosides under moderate reaction conditions. This proposed glycosylation protocol produced the desired products in up to 88% yield and shows greater tolerance of glycosyl acceptors and a broad substrate scope with better stereoselectivity. This method is also applicable for less nucleophilic acceptors such as phenol. In addition, 1,1′‐linked trehalose‐type analogues can also be accessed through this methodology. Further, mechanistic studies suggest that, in this glycosylation, L‐prolinethioamide operates via Brønsted acid/base catalysis.
Single‐Atom Cobalt‐Catalyzed Transfer Hydrogenation of Azides and One‐Pot Synthesis of Pyrroles
Authors: Panja Dibyajyoti , Sau Anirban , Thakur Seema D. , Dey Sadhan , Sahu Rajib , Kundu Sabuj
Published: July 2023

In this work, a single‐atom cobalt‐catalyzed transfer hydrogenation (TH) of azides is reported under mild conditions (at 30 °C in 30 min) using NH2NH2 ⋅ H2O as the hydrogen source. Employing this protocol, a wide range of azides were transformed to their corresponding amines. This methodology was extended towards the synthesis of several important N‐substituted pyrroles from azides in one‐pot manner. The control experiments suggested, the transfer hydrogenation favoured by electron withdrawing substituents and one‐pot pyrrole synthesis favoured by electron‐donating substituents. The recyclability test revealed the catalysts could be recycled up to 7th times without significant loss in the catalytic activity.
Visible Light‐Driven, Persulfate‐Mediated Hydrocarboxylation of Vinylsulfones
Authors: Pálvölgyi Ádám Márk , Scharinger Fabian , Bauhoff Thomas , Bica‐Schröder Katharina
Published: July 2023

We report a visible light‐mediated approach for the radical hydrocarboxylation of vinylsulfone derivatives. Using cheap and easily accessible sodium formate as C1‐source and K2S2O8 as reagent, a set of vinylsulfone substrates could be efficiently hydrocarboxylated in aqueous medium without any additional catalyst or reagent; and the concept could be also applied for direct hydroacylations, hydroalkylations and hydrophosphorylations. The control experiments clearly indicated that the reaction proceeds via radical mechanism without the generation of electron donor‐acceptor (EDA) complexes; supporting the working model of K2S2O8‐initiated in situ formation of CO2 radical anion.
Substituent‐Controlled Regiodivergent Palladium‐Catalyzed Annulative Dearomatization of Phenols toward Skeletally Diverse Spirocyclohexadienones
Authors: Mao Hui‐Lin , Yu Jun , Shen Yi‐Ting , Li Qiuyun , Hao Wen‐Juan , Jiang Bo
Published: July 2023

A palladium‐catalyzed intermolecular dearomative formal [4+2] annulation of phenols with propargyl electrophiles is reported, enabling substituent‐controlled regiodivergent synthesis of a wide range of skeletally diverse spirocyclohexadienones with good yields. The regiodivergence could be precisely controlled by adjusting the steric hindrance of O‐ and N‐substituents from binucleophilic substrates, where substrates with an O‐nucleophilic site were converted into spiro[chromane‐4,1′‐cyclohexane]‐2′,5′‐dien‐4′‐ones with complete regioselectivity and (Z)‐selectivity, whereas N‐nucleophiles enabled a different regiodivergent process to access spiro[cyclohexane‐1,4′‐quinoline]‐2,5‐dien‐4‐ones.
Responsive Regulation of Energy Transfer in Lanthanide‐Doped Nanomaterials Dispersed in Chiral Nematic Structure
Authors: Luo Yuxia , Liu Qingdi , He Ping , Li Liang , Zhang Zhao , Li Xinping , Bao Guochen , Wong Ka‐Leung , Tanner Peter A. , Jiang Lijun
Published: July 2023

The responsive control of energy transfer (ET) plays a key role in the broad applications of lanthanide‐doped nanomaterials. Photonic crystals (PCs) are excellent materials for ET regulation. Among the numerous materials that can be used to fabricate PCs, chiral nematic liquid crystals are highly attractive due to their good photoelectric responsiveness and biocompatibility. Here, the mechanisms of ET and the photonic effect of chiral nematic structures on ET are introduced; the regulation methods of chiral nematic structures and the resulting changes in ET of lanthanide‐doped nanomaterials are highlighted; and the challenges and promising opportunities for ET in chiral nematic structures are discussed.
Ultra‐Tough Self‐Healing Hydrogel via Hierarchical Energy Associative Dissipation
Authors: Zhao Zhi , Li Yurong , Wang Haibin , Shan Yupeng , Liu Xuemei , Wu Mengfei , Zhang Xinping , Song Xiaoyan
Published: July 2023

Owing to high water content and homogeneous texture, conventional hydrogels hardly reach satisfactory mechanical performance. Tensile‐resistant groups and structural heterogeneity are employed to fabricate tough hydrogels. However, those techniques significantly increase the complexity and cost of material synthesis, and have only limited applicability. Here, it is shown that ultra‐tough hydrogels can be obtained via a unique hierarchical architecture composed of chemically coupled self‐assembly units. The associative energy dissipation among them may be rationally engineered to yield libraries of tough gels with self‐healing capability. Tunable tensile strength, fracture strain, and toughness of up to 19.6 MPa, 20 000%, and 135.7 MJ cm⁻3 are achieved, all of which exceed the best known records. The results demonstrate a universal strategy to prepare desired ultra‐tough hydrogels in predictable and controllable manners.
Designing Electrolytes With Controlled Solvation Structure for Fast‐Charging Lithium‐Ion Batteries
Authors: Kautz David J. , Cao Xia , Gao Peiyuan , Matthews Bethany E. , Xu Yaobin , Han Kee Sung , Omenya Fredrick , Engelhard Mark H. , Jia Hao , Wang Chongmin , Zhang Ji‐Guang , Xu Wu
Published: July 2023

Recharging battery‐powered electric vehicles (EVs) in a similar timeframe as those used for refueling gas‐powered internal combustion vehicles is highly desirable for rapid penetration of the EV market. It is well known that the electrolyte in a battery plays a critical role in fast‐charging capability of the battery because it determines the rate of ion transport together with its derived electrode/electrolyte interphases on both cathode and anode of the battery. In this study, the effects of contents of salt, coordinating solvent, and noncoordinating diluent on salt dissociation degree and electrolyte ionic conductivity are investigated, and a controlled solvation structure electrolyte is developed to improve the lithium ion mobility and conductivity in the electrolyte and to enhance the kinetics and stability of the electrode/electrolyte interphases in the battery. This electrolyte enables fast‐charging capability of high energy density lithium‐ion batteries (LIBs) at up to 5 C rate (12‐min charging), which significantly outperforms the state‐of‐the‐art electrolyte. The controlled solvation structure sheds light on the future electrolyte design for fast‐charging LIBs.
Intraspecific variation of long bone cross‐sectional properties in Pan troglodytes troglodytes and Gorilla gorilla gorilla
Authors: Cosman Miranda Nicole , MacLatchy Laura M. , Schlecht Stephen H. , Devlin Maureen J.
Published: July 2023

Objectives

Morphological intraspecific variation is due to the balance between skeletal plasticity and genetic constraint on the skeleton. Osteogenic responses to external stimuli, such as locomotion, have been well documented interspecifically across the primate order, but less so at the intraspecific level. Here, we examine the differences in cross‐sectional variability of the femur, humerus, radius, and tibia in Pan troglodytes troglodytes versus Gorilla gorilla gorilla. We investigate whether there are sex, species, bone, and trait differences in response to variable body size and locomotion.

Materials and Methods

Adult male and female P. t. troglodytes and G. g. gorilla long bones from the Cleveland Museum of Natural History were scanned with a peripheral quantitative computer tomography system. Scans were taken at the midshaft of each bone according to functional bone length. Coefficients of variation were used to provide a size‐independent measure of variation. We applied a Bonferroni correction to account for the multiple pairwise tests.

Results

There were limited significant differences between males and females, however, females tended to be more variable than males. Variation in Gorilla, when significant, was greater than in Pan, although significant differences were limited. There were no differences between bone variability in male and female Gorilla, and female Pan.

Discussion

Increased female variability may be due to more variable locomotor behavior, particularly during periods of pregnancy, lactation, and caring for an offspring compared to consistent locomotion over the life course by males. Body size may be a contributing factor to variability; more work is needed to understand this relationship.
Optimizing the timing of biologic and surgical therapy for patients with refractory chronic rhinosinusitis with nasal polyposis (CRSwNP)
Authors: Garvey Emily , Naimi Bita , Duffy Alexander , Hannikainen Paavali , Kahn Chase , Farquhar Douglas , Rosen Marc , Rabinowitz Mindy , Toskala Elina , Nyquist Gurston
Published: July 2023

Introduction

Chronic rhinosinusitis with nasal polyposis (CRSwNP) is often treated with endoscopic sinus surgery (ESS); however, patients may require revision surgery due to recurrence. To date, no studies have compared outcomes for combined surgery and biologic therapy for CRSwNP compared with biologic therapy alone.

Methods

Retrospective case–control study of CRSwNP patients who underwent ESS while on dupilumab or mepolizumab (ESS‐biologic cohort) compared with CRSwNP patients on biologic therapy (biologic‐only controls). Cohorts were matched according to indication, aspirin‐exacerbated respiratory disease (AERD), sinonasal outcome test‐22 (SNOT‐22), and total polyp scores.

Results

Sixteen patients underwent ESS while on biologic therapy (13 dupilumab and 3 mepolizumab). Sixteen patients were biologic‐only controls. There were no significant differences between indication, baseline SNOT‐22 scores, polyp scores, and AERD status between cohorts. Patients underwent surgery a median of 33 days after starting biologic therapy. After 12 months of follow‐up, the total polyp score for the ESS‐biologic cohort decreased from 4.73 to 0.09 compared with a decrease from 5.22 to 3.38 for the biologic‐only controls (95% confidence interval [CI] of difference: −5.37 to −1.38, Cohen's d: 2.40, p = 0.005). In the ESS‐dupilumab subanalysis, the ESS‐dupilumab cohort had a significant reduction in polyp burden from 4.85 to 0.00 compared with 4.88 to 3.50 for the controls (95% CI of difference: −5.68 to −1.32, Cohen's d: −1.69, p = 0.009).

Conclusion

In CRSwNP patients, combined ESS and biologic therapy results in a significant and sustained decrease in polyp burden compared with biologic therapy alone. Larger studies are warranted to further examine the impact of combined therapy.
Automatisierte Generierung von Mikrokinetiken für heterogen katalysierte Reaktionen unter Berücksichtigung korrelierter Unsicherheiten**
Authors: Kreitz Bjarne , Lott Patrick , Studt Felix , Medford Andrew J. , Deutschmann Olaf , Goldsmith C. Franklin
Published: July 2023

Die Studie stellt eine ab initio basierte Methode für die automatische Konstruktion von detaillierten Mikrokinetiken vor, welche korrelierte Unsicherheiten in allen energetischen Parametern und Schätzroutinen berücksichtigt. Hierfür wurden innerhalb des Unsicherheitsraums des BEEF‐vdW Funktionals 2000 Mikrokinetiken für die Oxidationsreaktionen repräsentativer Abgasemissionen von stöchiometrischen Verbrennungsmotoren auf Pt(111) generiert und durch Multiskalenmodellierung mit Experimenten verglichen. Das Ensemble der Simulationsergebnisse unterstreicht die Bedeutung der Berücksichtigung von Unsicherheiten. Innerhalb dieses Ensembles ist es möglich, eine Mikrokinetik zu identifizieren, welche mit den experimentellen Daten übereinstimmt. Diese Mikrokinetik lässt sich auf ein einziges Austausch‐Korrelations‐Funktional zurückführen und legt nahe, dass Pt(111) das aktive Zentrum für die Oxidation leichter Kohlenwasserstoffe sein könnte. Die Studie bietet einen universellen Rahmen für die automatisierte Konstruktion von Reaktionsmechanismen unter Berücksichtigung korrelierter Unsicherheiten und ermöglicht eine DFT‐basierte Optimierung der Mikrokinetik auch für andere heterogen katalysierte Systeme.
Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties**
Authors: Kreitz Bjarne , Lott Patrick , Studt Felix , Medford Andrew J. , Deutschmann Olaf , Goldsmith C. Franklin
Published: July 2023

The study presents an ab‐initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF‐vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first‐principles‐based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange‐correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT‐constrained microkinetic model optimization for other heterogeneously catalyzed systems.
Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy
Authors: Manna Samir , Paul Swagata , Kong Wang‐Yeuk , Aich Debasis , Sahoo Rupam , Tantillo Dean J. , Panda Santanu
Published: July 2023

Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π‐systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3‐dienes in good yield and up to 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z‐vinyl heteroarenes for different heteroarenes under identical conditions. Density functional theory (DFT) investigations unveil the mechanistic dichotomy between olefin and heteroarene activation followed by 1,2‐migration, leading to E or Z‐vinyl heteroarenes respectively. We also report a previously unknown reversal of stereoselectivity by using 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an electrophile. The Zweifel olefination using a boronate complex that carries two different olefins was previously unexplored due to significant challenges associated with the site‐selective activation of olefins. We have solved this problem and reported the site‐selective activation of olefins for the stereoselective synthesis of 1,3‐dienes.
Catalytic water oxidation mediated by copper‐triazolylpyridine complexes
Authors: Zhao Si‐Yang , Zhu Xue‐Ling , Wang Xue‐Han , Cao Yuan‐Yang , Li Qing‐An , Qin Shu‐Yi , Wang Tian‐Shun , Zhang Hua‐Xin
Published: July 2023

Water oxidation reaction (WOR) is a rather sluggish process in the water splitting that hampers the extraction of hydrogen gas from water in a large scale. It is highly desirable to develop low‐cost WOR catalysts to increase the efficacy. Herein two Cu(II) complexes [Cu (DTEL)2]n(ClO4)2n (1) and [Cu(DTE)2(ClO4)2] (2) of two triazolylpyridines, 1‐(2‐hydroxy)‐4‐(2‐pyridyl)1,2,3‐triazole (DTEL) and 1‐(2‐acetoxymethyl)‐4‐(2‐pyridyl)1,2,3‐triazole (DTE), have been synthesized and characterized. The X‐ray diffraction analysis revealed that the copper centers of 1 and 2 adopted the octahedral coordination geometry with four N atoms from two DTEL or DTE ligands in the equatorial plane. The two axial sites were weakly ligated by the hydroxyl group of DTEL or perchlorate. Both complexes 1 and 2 were homogenous molecular catalysts boosting the WOR in pH 9.0 phosphate buffer solution with the overpotentials being 568 and 478 mV, rate constants (kcat) of 0.1 and 0.39 s−1, and Faradaic efficiencies of 90% and 93%, respectively. The pendant substituent on the two triazolylpyridine ligands DTEL and DTE apparently influenced the catalysis. A mechanism for the catalytic WOR mediated by 1 and 2 was suggested on the basis of the experimental data. This work illustrated that triazolylpyridines were promising scaffolds for forming metal complexes working as WOR catalysts.
Crystallization and polymorphic behaviors of cocoa butter alternatives: A review
Authors: Ramos Ramos María Regina , García Londoño Víctor Alonso , Borroni Virginia , Candal Roberto Jorge , Herrera María Lidia
Published: July 2023

Although cocoa butter (CB) has remarkable physical properties, its high price, growing difficulties, and increased consumption have been the main incentive to explore alternatives to replace or improve it. The potential of fats systems obtained from tropical butters, mixtures of them with vegetable oils, or marine fats as cocoa butter equivalent (CBE), extender (CBEx), substitute (CBS), replacer (CBR), or improver (CBI) have been deeply investigated and their physical chemical properties have been compared to those of CB. The TAGs composition of fats systems is a key factor that determines fats crystallization and polymorphic behaviors, and the suitability for an application. Fats with high concentrations of the TAGs StOSt, StOA, or StOB and low concentrations of POP compared to CB show some incompatibility with CB as analyzed by iso‐solid diagrams and a more complex polymorphic behavior. The presence of low melting TAGs such as POO, StOO, and AOO also leads to significant differences in physical behavior compared to CB. In those fats systems, co‐crystallization and polymorphic transitions of co‐existing solid solutions were reported. A few of the studied fat systems may behave as CBE. However, most of them have potential as CBS, CBR, CBEx or CBI in confectionery products. Studies reported the relevance of fractionation and interesterification processes to modify TAGs composition and the need of finding the right processing conditions and additives to extend fats applications.
Application of molecular dynamics simulations in interface interaction of clay: Current status and perspectives
Authors: Chen Jun , Chu Xinxia , Cheng Yali , Shu Qingdong , Ling Yunjia , Shang Huanhuan , Min Fanfei
Published: July 2023

To understand the research progress of molecular dynamics (MD) method in the field of clay minerals, the application of MD in the interface interaction of clay minerals is reviewed in this paper. MD simulations have become the indispensable means to study mineral interface effects. Clay minerals are common associated minerals with hydrophilic surface, the ease of argillization, negative electricity, and the ability of forming impurities and defects. They are widely concerned in the fields of mine wastewater treatment, fine clay mineral flotation, shale oil and gas exploitation, and so forth. In addition, clay minerals are considered as natural adsorbents due to their large specific surface area, but their complex interface interactions hinder their effective utilization. Therefore, it is particularly important to reveal the interaction mechanism of clay interface at the atomic/molecular level by means of software simulation technology. In this review, our focus is on the applications of MD method in the field of clay mineral interface interaction, such as clay/gas interface, clay/water interface, agents and clay/water interface, and mineral particle and clay/water interface. Furthermore, the history and shortcomings of MD simulation are summarized. The research and effective utilization of clay interface are summarized and prospected as well.
LoCoLotive: In silico mining for low‐copy nuclear loci based on target capture probe sets and arbitrary reference genomes
Authors: Lautenschlager Ulrich , Scheunert Agnes
Published: July 2023

Premise

Universal target enrichment probe kits are used to circumvent the individual identification of loci suitable for phylogenetic studies in a given taxon. Under certain circumstances, however, target capture can be inefficient and costly, and lower numbers of marker loci may be sufficient. We therefore propose a computational pipeline that enables the easy identification of a subset of promising candidate loci for a taxon of interest.

Methods and Results

Target sequences used for probe design are filtered based on an assembled reference genome, resulting in presumably intron‐containing single‐copy loci as present in the reference taxon. The applicability of the proposed approach is demonstrated based on two probe kits (universal and family‐specific) in combination with several publicly available reference genomes.

Conclusions

Guided by commercial probe kits, LoCoLotive enables fast and cost‐efficient marker mining. Its accuracy mainly depends on the quality of the reference genome and its relatedness to the taxa under study.
Memorandum: Korrosionsschutz im Konstruktiven Ingenieurbau
Authors: Keßler Sylvia , Beck Matthias , Harnisch Jörg , Angst Ueli M.
Published: July 2023

Einer der maßgebenden Werkstoffe im Konstruktiven Ingenieurbau ist Stahl in Form von Baustahl, Betonstahl, Befestigungstechnik etc. Stahl bietet eine hohe Festigkeit in Kombination mit beliebiger Formbarkeit, guter Verarbeitbarkeit und Schweißbarkeit. Um das Potenzial von Stahl auszuschöpfen, ist das Wissen über dessen maßgebenden Schädigungsmechanismus – die Korrosion – essenziell, um Korrosionsprozesse durch konsequente Planung verhindern oder bestehende Korrosionsschäden bewerten und instand setzen zu können. Das Ziel dieses Hochschulmemorandums ist es, die Grundlagen der Kompetenzentwicklungen im Bereich des Korrosionsschutzes des Konstruktiven Ingenieurbaus zu legen, zu diskutieren und weiterzuentwickeln. Aufgrund der zunehmend dynamischen Entwicklungen im Bauingenieurwesen (z. B. durch Digitalisierung, Nachhaltigkeitsvorgaben, neue Fertigungsmethoden, längere Lebensdauern von Bauwerken) ist die Bereitschaft einer stetigen Reflexion und Weiterentwicklung unumgänglich, um langfristig eine hohe Qualität im Korrosionsschutz konstruktiver Ingenieurbauwerke sicherstellen zu können. Das hier vorliegende Memorandum ist in Zusammenarbeit mit dem Arbeitskreis „Korrosionsschutz im konstruktiven Ingenieurbau“ der Gesellschaft für Korrosionsschutz e. V. (GfKORR) und dem bauforumstahl e. V. entstanden.
Nonlinear state estimation as tool for online monitoring and adaptive feed in high throughput cultivations
Authors: Kemmer Annina , Fischer Nico , Wilms Terrance , Cai Linda , Groß Sebastian , King Rudibert , Neubauer Peter , Cruz Bournazou M. Nicolas
Published: July 2023

Robotic facilities that can perform advanced cultivations (e.g., fed‐batch or continuous) in high throughput have drastically increased the speed and reliability of the bioprocess development pipeline. Still, developing reliable analytical technologies, that can cope with the throughput of the cultivation system, has proven to be very challenging. On the one hand, the analytical accuracy suffers from the low sampling volumes, and on the other hand, the number of samples that must be treated rapidly is very large. These issues have been a major limitation for the implementation of feedback control methods in miniaturized bioreactor systems, where observations of the process states are typically obtained after the experiment has finished. In this work, we implement a Sigma‐Point Kalman Filter in a high throughput platform with 24 parallel experiments at the mL‐scale to demonstrate its viability and added value in high throughput experiments. The filter exploits the information generated by the ammonia‐based pH control to enable the continuous estimation of the biomass concentration, a critical state to monitor the specific rates of production and consumption in the process. The objective in the selected case study is to ensure that the selected specific substrate consumption rate is tightly controlled throughout the complete Escherichia coli cultivations for recombinant production of an antibody fragment.
Elucidating the mechanisms underlying the anti‐hyperlipidemic effects of Laportea bulbifera using integrated serum metabolomics and network pharmacology
Authors: Shi Qingxin , Lin Yuqi , Huang Lu , Jin Shuna , Huang Rongzeng , Zhang Lijun , Song Chengwu , Xu Lei , Zhang Shiying
Published: July 2023

Hyperlipidemia is a chronic metabolic disorder characterized by alterations in lipid metabolism as well as other pathways. Laportea bulbifera, an indigenous medicinal plant of Chinese herbal medicine, exhibits therapeutic effects on hyperlipidemia, but the mechanisms remain unclear. This study investigated the potential mechanisms underlying the anti‐hyperlipidemic effects of L. bulbifera using an integrated strategy based on metabolomics and network pharmacology methods that were established to investigate the potential mechanism of anti‐hyperlipidemia effect of L. bulbifera. First, the therapeutic effects of L. bulbifera on body weight reduction and biochemical indices were assessed. Next, 18 significant metabolites distinguishing the control and model groups were identified based on serum metabolomics and multivariate analyses. Then, a compound–target network was constructed by linking L. bulbifera and hyperlipidemia using network pharmacology. Three metabolic pathways involved in treating hyperlipidemia were identified. Finally, five crucial targets were selected by constructing a bionetwork starting from the compounds and ending in the metabolites. This study established an integrated strategy based on metabolomics coupled with network pharmacology and revealed the mechanism underlying the protective effects of L. bulbifera against hyperlipidemia for the first time.
Serum soluble immune checkpoint levels predict cervical lymph node metastasis of differentiated thyroid carcinoma patients
Authors: Shao Yi , Gui Xinru , Wang Yuxin , Sheng Lei , Sun Dong , Zeng Qingdong , Wang Huayang
Published: July 2023

Background

Cervical lymph node metastasis (CLNM) is common in patients with differentiated thyroid carcinoma (DTC); however, the efficiency to distinguish CLNM before surgery is limited. T cell exhaustion, characterized by the overexpression of immune checkpoints, plays a critical role in the immune evasion of tumors. The aim of this study is to analyze the association between serum levels of soluble immune checkpoints (sICs) and CLNM in DTC patients.

Methods

Levels of sICs in serum of 71 DTC patients and 56 healthy volunteers were analyzed by ELISA. Peripheral blood mononuclear cells and cervical lymph nodes of DTC patients were isolated and their expression of sICs were analyzed. Lymphocytes in cervical lymph nodes were analyzed for immune checkpoints expression and transcription of exhaustion‐associated factors. 30 out of 71 DTC patients were followed up from 3 to 9 months after the operation, and postoperative sTIM‐3 were analyzed.

Results

Four sICs, including LAG‐3, PD‐1, PD‐L1, and TIM‐3, were increased in DTC patients. All four sICs exhibited higher sensitivity at discriminating CLNM than cervical ultrasound. In the patient‐matched comparison, higher sTIM‐3 levels were observed in tumor‐involved lymph nodes (TILNs) than in normal lymph nodes (nLNs). T lymphocytes in TILNs had higher TIM‐3 surface expression and increased secretion of sTIM‐3 than those in patient‐matched nLNs. Finally, postoperative serum sTIM‐3 levels were decreased in DTC patients with CLNM compared to their preoperative levels.

Conclusion

Serum levels of sICs, especially sTIM‐3, could help to predict CLNM and provide evidence for surgical decision‐making in DTC.
Isolation of Two Plasticizers, Bis(2‐ethylhexyl) Terephthalate and Bis(2‐ethylhexyl) Phthalate, from Capparis spinosa L. Leaves
Authors: Kdimy Ayoub , Kim Seong Jong , Ali Zulfiqar , Khan Md Imdadul H. , Tripathi Siddharth K. , El Hajjaji Souad , Le Hoang V.
Published: July 2023

Many plants have been known to be contaminated and accumulate plasticizers from the environment, including water sources, soil, and atmosphere. Plasticizers are used to confer elasticity and flexibility to various fiber and plastic products. Consumption of plasticizers can lead to many adverse effects on human health, including reproductive and developmental toxicity, endocrine disruption, and cancer. Herein, we report for the first time that two plasticizers, bis(2‐ethylhexyl) terephthalate (DEHT) and bis(2‐ethylhexyl) phthalate (DEHP), have been isolated from the leaves of Capparis spinosa L. (the caper bush), a plant that is widely used in food seasonings and traditional medicine. 297 mg/kg of DEHT and 48 mg/kg of DEHP were isolated from dried and grounded C. spinosa L. leaves using column chromatography and semi‐preparative high‐performance liquid chromatography. Our study adds to the increase in the detection of plasticizers in our food and medicinal plants and to the alarming concern about their potential adverse effects on human health.
Synthesis of Imidazole‐2,3‐dihydrothiazole Compounds as VEGFR‐2 Inhibitors and Their Support with in Silico Studies
Authors: Osmaniye Derya , Bozkurt Nurnehir Baltacı , Kurban Berkant , Yardımcı Gamze Benli , Ozkay Yusuf , Kaplancıklı Zafer Asım
Published: July 2023

In this study, 12 novel 2‐((1‐(4‐(1H‐imidazol‐1‐yl)phenyl)ethylidene)hydrazineylidene)‐3‐ethyl‐4‐(substitutephenyl)‐2,3‐dihydrothiazole derivatives were obtained. Among these compounds, 2‐((1‐(4‐(1H‐imidazol‐1‐yl)phenyl)ethylidene)hydrazineylidene)‐4‐([1,1′‐biphenyl]‐4‐yl)‐3‐ethyl‐2,3‐dihydrothiazole (4h) was chosen as the most active derivative in the series. According to the MTT results, compounds 4h and 4k showed activity with IC50=4.566±0.246 μM and IC50=4.537±0.463 μM, respectively. Unlike other derivatives, compound 4h carries a phenyl ring in the 4th position of the phenyl ring. This bulky group allowed the compound to settle in the enzyme active site. Dynamic studies show that the stability of the compound does not change over 40 ns. RMSD, RMSF and Rg parameters all remained within acceptable limits. The uninterrupted aromatic hydrogen bonding of the enzyme active site with the important amino acids Cys919, Glu885 and Asp1046 proves the inhibitory potential of compound 4h on the VEGFR‐2 enzyme. It is thought that more active compounds will be reached with the derivatives to be synthesized starting from compound 4h.
Soft‐textured wheat with high protein content and strength is suitable for making hot‐press tortillas
Authors: Ma Fengyun , Baik Byung‐Kee
Published: July 2023

Background and Objectives

Soft‐textured wheat with low damaged starch content, low product discoloration, and varying protein strength has the potential to be suitable for making tortillas if the required flour characteristics are known and selected for. Eastern US soft winter (ESW) wheat varieties were evaluated to identify the characteristics required for making tortillas in comparison to five commercial tortilla flours (CTFs).

Findings

ESW wheat flours had lower protein, damaged starch and ash contents, and polyphenol oxidase activity than CTFs and produced larger and brighter‐colored tortillas. Lactic acid solvent retention capacity (LA‐SRC) showed a strong association with tortilla quality attributes. Seven ESW wheat flours with LA‐SRC greater than 115.6% produced tortillas comparable with CTF tortillas in rollability scores.

Conclusions

ESW wheat, with high protein content and strength, appears to be suitable for making tortillas. The lower damaged starch content and polyphenol oxidase activity in ESW wheat when compared with hard wheat flour would be advantageous because ESW wheat would require less water for dough preparation and would produce larger and brighter‐colored tortillas.

Significance and Novelty

These results prove that the selected ESW wheat flours are desirable for making tortillas and provide guidance for selecting ESW wheat for making tortillas.
A Note on Modeling the Effects of Surfactants on Bubble‐Induced Turbulence
Authors: Ma Tian , Liao Yixiang , Hessenkemper Hendrik , Lucas Dirk , Bragg Andrew D.
Published: July 2023

Recent experimental results reveal that with rising concentration of surfactants, the generated bubble‐induced turbulence (BIT) increases as well, although the bubbles rise slower. Herein, it is shown that this phenomenon has not be considered so far in the standard Reynolds‐averaged Navier‐Stokes (RANS) modeling for BIT, using the Ansatz with source terms added to the transport equation of turbulent kinetic energy and dissipation, respectively. Some problematic issues related to the common concepts for closure of the liquid‐phase turbulence kinetic energy equation are also discussed. Furthermore, this issue is demonstrated by simulating the experiments using two‐fluid approach.
Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries
Authors: Sockwell A. Kirstin , Sweet Teagan F. M. , Barth Brodie , Isbill Sara B. , DiBlasi Nicole A. , Szymanowski Jennifer E. S. , Sigmon Ginger E. , Oliver Allen G. , Miskowiec Andrew J. , Burns Peter C. , Hixon Amy E.
Published: July 2023

Invited for the cover of this issue is the group of Amy Hixon at the University of Notre Dame. The image depicts the newly identified structure of a PuIV oxalate sheet compared to the historically assumed structure. Read the full text of the article at 10.1002/chem.202301164.
Circular dichroism and UV–Vis detection of UV‐induced damage to nucleic acids
Authors: Dowling Reed C. , Carroll Gregory T. , Kirschman David L. , Masthay Mark B. , Mammana Angela
Published: July 2023

In this report, we demonstrate that CD spectroscopy can be used as a tool to detect changes to DNA upon irradiation with UV light. We follow the spectroscopic response of DNA samples irradiated at selected exposure times with both CD and UV–Vis spectroscopy. We analyzed four different nucleic acids to evaluate the effect of the sequence on photodegradation. Only one polymer, calf thymus DNA, was a natural nucleic acid and contained all four nucleobases. The other three were synthetic polymers and contained only one type of base pair: poly (deoxyadenylic‐deoxythymidylic) acid [poly (dA‐dT)2] and poly (deoxyadenylic acid) · poly (deoxythymidylic acid) [poly (dA) · poly (dT)], which contained only adenine and thymine; poly (deoxyguanylic‐deoxycytidylic) acid [poly (dG‐dC)2], which contained only guanine and cytosine. CD and UV–Vis spectra showed sequence dependent changes. In particular, poly (dA) · poly (dT) undergoes changes more rapidly than the other sequences investigated. The CD spectrum of poly (dA) · poly (dT) gradually undergoes an inversion, suggesting a change in helicity, before disappearing due to the unfolding of the double strand.
Noncontrast cardiac computed tomography‐derived mitral annular calcification scores in mitral valve disease
Authors: Hou Jie , Sun Yu , Wang Huishan , Zhang Libo , Shi Jinglong , You Hongrui , Zhang Rongrong , Yang Benqiang
Published: July 2023

Background and Aims

Mitral annular calcification (MAC) by computed tomography (CT) is reported as an independent predictor of poor outcomes. However, it currently remains unclear if quantitative MAC parameters provide more value for mitral valve disease (MVD) management, therefore, we examined the prognostic value of MAC scores using noncontrast cardiac‐CT in MVD patients.

Methods

Between January 2020 and December 2021, we prospectively enrolled 300 consecutive patients with MVD (MAC‐present = 80 and MAC‐absent = 220) undergoing preoperative cardiac‐CT and mitral valve (MV) surgery. Noncontrast cardiac‐CT images were used to qualitatively detect MAC (present or absent) and evaluate MAC scores. For analyses, we also collected baseline clinical data, intraoperative conversion (from MV repair to MV replacement), and follow‐up arrhythmia data.

Results

Compared with the MAC‐absent group, MAC‐present patients were older (62 ± 7 vs. 58 ± 9 years, p < .001), mostly women (55% vs. 39.5%, p = .017), and also had aortic valve calcification (57.5% vs. 23.2%, p < .001), mitral stenosis (82.5% vs. 61.8%, p < .001), atrial fibrillation (30% vs. 11.8%, p < .001), and larger left atrial end‐diastolic dimension (LADD, 49 [44–56] versus 46 [41–50], p = .001]. Furthermore, MAC‐present patients underwent more MV replacements (61.8% vs. 82.5%, p = .001) and experienced a higher intraoperative conversion prevalence (11.8% vs. 61.3%, p < .001). Multiple logistic regression analyses showed that the female gender (odds ratio [OR]/95% confidence interval [CI]/p = 2.001/1.042–3.841/0.037) and MAC scores (OR/95% CI/p = 10.153/4.434–23.253/p < .001) were independent predictors of intraoperative conversion. During a follow‐up of 263 ± 134 days, MAC‐present patients had more arrhythmias (42.5% vs. 9.5%, p < .001). Also, MAC‐scores (hazard ratio [HR]/95% CI/p = 6.841/3.322–14.089/p < .001) and LADD (HR/95% CI/p = 1.039/1.018–1.060/p < .001) were independently associated with arrhythmias by Cox regression analyses.

Conclusions

Noncontrast cardiac CT‐derived MAC‐scores showed a high risk for intraoperative conversion and follow‐up arrhythmias in MVD‐patients.
Sports cardiology: A glorious past, a well‐defined present, a bright future
Authors: D'Ascenzi Flavio , Ragazzoni Gian L. , Boncompagni Alex , Cavigli Luna
Published: July 2023

The attention towards sports cardiology has dramatically grown after the introduction of preparticipation screening and the need for specific education on electrocardiogram interpretation in athletes, given the differences between athletes and the general population. The present article stresses the need for specific skills, knowledge, and clinical expertise in sports cardiology, which are essential for appropriately screening competitive athletes to prevent sudden cardiac death and avoid overdiagnosis. However, disqualification from sports competitions may lead to sports inactivity, and athletes may enter a gray zone where little or no information is provided about what they can or cannot do to stay active. However, modern sports cardiology cannot neglect the patient's needs and the importance of the safe practice of regular exercise. In this context, the personalized exercise prescription plays a crucial role in the core curriculum and the clinical activity of professionals involved in sports cardiology programs. Given its specificities, sports cardiology requires a formal education plan for medical school students and all residents. Additional education and practice are required for young colleagues who want to focus their professional lives on sports cardiology. The future directions of emerging modern sports cardiology should not neglect the importance of a scientific community that works together, designing multicenter international outcomes‐based research to address the many remaining areas of uncertainty.
Association between the systemic immune‐inflammation index and outcomes among atrial fibrillation patients with diabetes undergoing radiofrequency catheter ablation
Authors: Zhao Zhihao , Jiang Baoping , Zhang Fengyun , Ma Ruicong , Han Xiao , Li Chengzong , Zhang Chaoqun , Wang Zhirong , Yang Yu
Published: July 2023

Purpose

To investigate the relationship between the incidence of atrial fibrillation (AF) recurrence and the levels of the systemic immune‐inflammatory index (SII, platelet × neutrophil/lymphocyte ratio) in patients with AF and diabetes mellitus (DM) undergoing after radiofrequency catheter ablation (RFCA).

Patients and Methods

Preoperative SII levels were determined in AF patients with DM undergoing RFCA. Restricted cubic splines were used to determine the correlation between SII and the risk of AF recurrence. Multivariate‐adjusted logistic regression models were constructed to determine the relationship between SII levels and AF recurrence. The predictive value of the clinical model and combined with the SII index was estimated by the area under the receiver‑operating characteristic curve, net reclassification improvement (NRI), and integrated discrimination improvement (IDI).

Results

A total of 204 patients with AF and DM who underwent RFCA in our hospital were included. Seventy‐seven patients had AF recurred during a mean follow‐up of 20 months. Restricted cubic spline analysis showed that when SII ≥ 444.77 × 109/L, there was a positive correlation with the incidence of AF recurrence. In addition, adding the SII to the predictive model for AF recurrence after RFCA in patients with DM and AF could contribute to an increase in C‐statistics (0.798 vs. 0.749, p = .034). After SII was incorporated into the clinical model, the comprehensive discrimination and net reclassification tended to improve (IDI and NRI > 0, p < .05).

Conclusion

SII was independently and positively associated with recurrence after the first catheter ablation in patients with DM and AF.
Proton beam radiotherapy versus transarterial chemoembolization for hepatocellular carcinoma: Results of a randomized clinical trial
Authors: Bush David A. , Volk Michael , Smith Jason C. , Reeves Mark E. , Sanghvi Samrat , Slater Jerry D. , deVera Michael
Published: July 2023

Background

This study compares survival rates, recurrence patterns, toxicity, and treatment cost in patients with hepatocellular carcinoma (HCC) treated with either transarterial chemoembolization (TACE) or proton beam radiotherapy (PBT).

Methods

Subjects with untreated HCC meeting Milan or San Francisco transplant criteria were recruited. Subjects were randomized to receive PBT (n = 36) or TACE (n = 40). Proton therapy was administered in 15 fractions over 3 weeks to a total dose of 70.2 Gy. TACE was repeated until complete or maximal response. The primary outcome measure was overall survival (OS). Secondary end points were progression‐free survival (PFS), local control (LC), toxicity, and cost.

Results

Of the 76 randomized patients, 74 were assessed for outcome measures. The 2‐year OS for PBT versus TACE was similar at 68%, 95% confidence interval (CI), 0.54–0.86, and 65%, 95% CI, 0.52–0.83 (p = .80), however, median PFS was improved for PBT versus TACE (not reached vs. 12 months, p = .002). LC was improved with PBT versus TACE (hazard ratio, 5.64; 95% CI, 1.78–17.9, p = .003). Days of posttreatment hospitalization were 24 for PBT and 166 for TACE (p < .001). Total mean cost per patient for treatment and posttreatment care revealed a 28% cost savings for PBT.

Conclusions

PBT and TACE yielded similar OS for treatment of HCC, but PFS and LC were improved with PBT compared to TACE. Patients treated with PBT required fewer courses of treatment, fewer posttreatment hospitalization days, and reduced cost of treatment compared to TACE. These data support the use of PBT as a viable treatment alternative to TACE for patients with HCC within transplant criteria.
Integrated bidirectional converter with voltage equalizer for energy storage system
Authors: Yang Xiaoguang , Zhao Xiaobing , Liu Jietao
Published: July 2023

In energy storage systems, a voltage equalizer is always needed. The voltage equalizers often include a DC‐DC converter. In this paper, the DC‐DC converter in the voltage equalizer is saved by integrating the voltage equalization circuit into the bidirectional converter of the battery system, thus simplifying the system. The voltage equalization circuit in the integrated system is composed of a LC resonant circuit and a voltage multiplier, which has the advantages of simplicity and low complexity. This paper presents the design process based on the analysis model, which enables the equalizer to obtain the optimal parameter configuration. Test results show the proposed LC‐SVM can automatically realize voltage balance between energy storage cells without additional control.
From bench to bedside: The role of cough hypersensitivity in chronic cough
Authors: Drake Matthew G. , McGarvey Lorcan P. , Morice Alyn H.
Published: July 2023

Background

Chronic cough is a burdensome condition characterized by persistent cough lasting longer than 8 weeks. Chronic cough can significantly affect quality of life, physical function and productivity, with many people troubled with a cough that lasts for months or even years. People with chronic cough commonly report a persistent urge to cough with frequent bouts of coughing triggered by innocuous stimuli, which has led to the concept of cough hypersensitivity.

Main body

Both central and peripheral neural pathways regulate cough, and although mechanisms driving development of cough hypersensitivity are not fully known, sensitization of these neural pathways contributes to excessive cough triggering in cough hypersensitivity. Effective therapies that control chronic cough are currently lacking. Recent therapeutic development has focused on several ion channels and receptors involved in peripheral activation of cough (e.g., transient receptor potential channels, P2 × 3 receptors and voltage‐gated sodium channels) or central cough processing (e.g., neurokinin‐1 [NK‐1] receptors and nicotinic acetylcholine receptors).

Conclusion

These targeted therapies provide novel insights into mechanisms underlying cough hypersensitivity and may offer new treatment options for people with chronic cough. In this review, we explore preclinical and clinical studies that have improved our understanding of the mechanisms responsible for chronic cough and discuss the most promising targeted approaches to date, including trials of P2 × 3‐receptor antagonists and NK‐1–receptor antagonists.
Childhood pilomatrixoma mimicking malignant small round blue cell tumor with positivity for CD99: Potential pitfall in cytology
Authors: Singh Brijdeep , Srinivasan Radhika , Bansal Deepak , Rohilla Manish , Dey Pranab , Saikia Uma Nahar , Nada Ritambhra
Published: July 2023

Pilomatrixoma is a relatively rare benign skin appendageal tumor, often presenting in the pediatric age group as a nodular lesion and most commonly involving the head and neck, making it amenable to primary fine needle aspiration (FNA) diagnosis. We report the clinical and histopathological findings of two cases of pilomatrixoma in children, both of which were initially misdiagnosed as small round blue cell tumors due to high cellularity and misinterpretation of the proliferating basaloid cells. Histopathology revealed basal cell proliferation and mitoses indicating that they were progressive, early lesions. The first case showed membranous positivity for CD99 which prompted a diagnosis of Ewing sarcoma. Awareness of the morphological spectrum including positivity for CD99 and careful evaluation of cell block histology could have averted the misdiagnosis. Pilomatrixoma should be included as an important differential diagnosis when faced with primitive‐appearing cells on FNA, especially in children with mass lesions in the head and neck region.