bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of 3‐Methylidene‐2,3‐dihydropyrroles via Formal 1,2‐Enamine Migration/Cyclization Cascade of Rhodium Carbenes
Authors: Jie Yuchen , Hu Huiqin , Xu Ze‐Feng , Duan Shengguo , Li Chuan‐Ying
Published: January 2023

3‐Methylidene‐2,3‐dihydropyrroles with an ester or keto group at the C4 position were obtained in moderate to good yields from enamine‐tethered triazoles in the presence of a rhodium(II) catalyst. A formal 1,2‐enamine migration/cyclization cascade triggered by formation of an α‐amino carbene is proposed to illustrate the mechanism. The valuable exocyclic double bond showed distinctive reactivity, which is very useful for further introduction of functional groups. The dihydropyrrole is stable under neutral, weakly acidic, or weakly basic conditions.

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B−N Coordinated Phenanthroimidazole‐Based Zinc‐Salen as a Photocatalyst for the Synthesis of Oxazolidinones using Carbon Dioxide as a C1 Source under Mild Reaction Conditions
Authors: Nayak Prakash , Chandrasekar Murali Anna , Rao Velpuri Venkateswara , Chandrasekhar Vadapalli , Venkatasubbaiah Krishnan
Published: January 2023

Cycloaddition of carbon dioxide (CO2) with aziridine catalyzed by a zinc‐salen having B−N coordinated phenanthroimidazole motif as a photocatalyst (1), at 1 bar CO2 pressure and room temperature under solvent free condition is presented. The photocatalyst exhibited excellent selectivity and tolerates a variety of substituted aziridines, and successfully produces the corresponding oxazolidinones at mild conditions.

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Comparing self‐reported obstructive airway disease in firefighters with and without World Trade Center exposure
Authors: Mueller Alexandra K. , Singh Ankura , Webber Mayris P. , Hall Charles B. , Prezant David J. , Zeig‐Owens Rachel
Published: January 2023

Background

The degree to which routine, non‐World Trade Center (WTC) firefighting exposures contribute to the WTC exposure‐obstructive airway disease (OAD) relationship is unknown. Our objective was to compare the frequency of self‐reported OAD diagnoses in WTC‐exposed firefighters from the Fire Department of the City of New York (FDNY) compared with non‐WTC‐exposed firefighters from other cities and the general population.

Methods

A total of 9792 WTC‐exposed male FDNY firefighters and 3138 non‐WTC‐exposed male firefighters from Chicago, Philadelphia, and San Francisco who were actively employed on 9/11/01 and completed a health questionnaire were included. Logistic regression estimated odds ratios of self‐reported asthma and COPD diagnoses in firefighters (WTC‐exposed vs. non‐WTC‐exposed; all firefighters vs. general population), adjusting for age, race, smoking status, and last medical visit.

Results

WTC‐exposed firefighters were, on average, younger on 9/11 (mean ± SD = 40.2 ± 7.4 vs. 44.1 ± 9.1) and less likely to report ever‐smoking (32.9% vs. 41.8%) than non‐WTC‐exposed firefighters. Odds of any OAD and asthma were 4.5 and 6.3 times greater, respectively, in WTC‐exposed versus non‐WTC‐exposed. Odds of COPD were also greater in WTC‐exposed versus non‐WTC‐exposed, particularly among never‐smokers. Compared with the general population, WTC‐exposed firefighters had greater odds of both asthma and COPD, while the nonexposed had lower odds of asthma and greater odds of COPD.

Conclusions

Odds ratios for OAD diagnoses were greater in WTC‐exposed firefighters versus both non‐WTC‐exposed and the general population after adjusting for covariates. While asthma and other OADs are known occupational hazards of firefighting, WTC exposure significantly compounded these adverse respiratory effects.
How do Australian policymakers frame the causes of and policy solutions to poverty? A critical examination of Anti‐Poverty Week parliamentary debates from 2012 to 2021
Authors: Mendes Philip , Roche Steven
Published: January 2023

In recent decades, poverty has increasingly been marginalised in Australian policy discourse. One strategy used by social justice advocates to revitalise a poverty policy agenda has been the annual Anti‐Poverty Week campaign, which aims to stimulate community debate around policy innovations to relieve poverty. This paper analyses the Commonwealth parliamentary debates around Anti‐Poverty Week for 10 years from 2012 to 2021. We analyse and compare how politicians from three political parties – the Liberal and National Party Coalition, the Australian Labor Party and The Australian Greens – identified the key statistics for and groups in poverty, their sources of evidence, the consequences of poverty for those affected, the causes of poverty including whether or not disadvantage was linked to wider structural inequities, and the framing of poverty and potential policy solutions. Some conclusions are drawn from these findings about potential strategies for reinvigorating the poverty debate.
Isolierung eines anellierten 1,4‐Distibabenzol‐Diradikaloids
Authors: Steffenfauseweh Henric , Rottschäfer Dennis , Vishnevskiy Yury V. , Neumann Beate , Stammler Hans‐Georg , Szczepanik Dariusz W. , Ghadwal Rajendra S.
Published: January 2023

Die erste 1,4‐Distabenzol‐1,4‐diid‐Verbindung [(ADC)Sb]2 (5) auf der Basis eines anionischen Dicarbens (ADC) (ADC=PhC{N(Dipp)C}2, Dipp=2,6‐iPr2C6H3) wird als bordeauxroter Feststoff berichtet. Verbindung 5, die einen zentralen sechsgliedrigen C4Sb2‐Ring mit formalen SbI‐Atomen aufweist, kann als ein Basen‐stabilisiertes cyclisches Bis‐Stibiniden betrachtet werden, in dem jedes der Sb‐Atome zwei freie Elektronenpaare trägt. 5 geht eine 2e‐Oxidation mit Ph3C[B(C6F5)4] ein und bildet [(ADC)Sb]2[B(C6F5)4]2 (6) als ziegelroten Feststoff. Jedes der Sb‐Atome von 6 hat ein ungepaartes Elektron und ein freies Elektronenpaar. Die offenschalige Singulett‐Diradikal‐Lösung (broken‐symmetry) für (6)2+ ist um 2.13 kcal mol−1 stabiler als die geschlossenschalige Singulett‐Lösung. Der diradikalische Charakter von (6)2+ beträgt nach SS‐CASSCF (state‐specific complete active space self‐consistent field) und UHF (unrestricted Hartree‐Fock) 39 % bzw. 36 %. Die Behandlung von 6 mit (PhE)2 ergibt [(ADC)Sb(EPh)]2[B(C6F5)4]2 (7‐E) (E=S oder Se). Die Reaktion von 5 mit (cod)Mo(CO)4 führt zu [(ADC)Sb]2Mo(CO)4 (8).
Ferroelectric and relaxor ferroelectric activities of the P(VDF‐TrFE) and its blends synthesized by (SiMe3)3SiHhydrogenation process
Authors: Wang Rong , Xia Weimin , Zhang Xiaofang , Xi Yuanyuan
Published: January 2023

A group of ferroelectric polyvinylidene‐trifluoroethylene (P(VDF‐TrFE)) with 6, 9, 20, and 50 mol% trifluoroethylene (TrFE) is synthesized by an hydrogenation process using a new catalyst (SiMe3)3SiH from polyvinylidene‐chlorotrifluoroethylene. We find the crystalline region of hydrogenated P(VDF‐TrFE) 80/20 mol% isβcrystal phase predominant, which is responsible to the favorable ferroelectric property. Moreover, polyvinylidene fluoride (PVDF) blending is used to fabricate the ferroelectric and relaxor ferroelectric properties of P(VDF‐TrFE) 80/20 mol%. Interestingly, with the increasing of PVDF content, PVDF/P(VDF‐TrFE) has three successional conversion stages of ferroelectricity, antiferroelectricity, and relaxor ferroelectricity, respectively, indicating that theβcrystal domains in hydrogenated P(VDF‐TrFE) films gradually reduces with the introduction of PVDF. Otherwise, after an unidirectional stretching process, the ferroelectricity of relaxor PVDF/P(VDF‐TrFE) blend film is reformed. As such, the maximum polarization (Pm) and remnant polarization (Pr) of stretched PVDF/P(VDF‐TrFE) with 90 wt% PVDF reached to 13.8 and 7.5 μC/cm2under 200 MV/m, respectively. Thus, the three methods proposed in this work including fabricating configuration by changing TrFE content, physical blending by introduction of PVDF, and simple stretching can modify the ferroelectric performances of this hydrogenated P(VDF‐TrFE), which also provides a reference of application of this polymer on ferroelectric areas.
Multifractal cross‐correlation analysis between CME and Planetary K‐index time series
Authors: Chattopadhyay Anirban , Khondekar Mofazzal H.
Published: January 2023

This research aims to examine the multiscale‐multifractal correlation properties between the geomagnetic storm and coronal mass ejection (CME) occurrences by analyzing the CME linear speed and Planetary K‐index time series data. The relevant data for both CME and geomagnetic storm occurrences were obtained from the Solar and Heliospheric Observatory mission's LASCO and the NOAA Space Weather Prediction Center, respectively, for the same period (February 1999 to December 2007). We performed MultiFractal cross‐correlation Detrended Fluctuation Analysis (MFXDFA) and Multifractal cross‐correlation Detrending Moving average Analysis (MFXDMA) to investigate and quantify the possible cross‐correlation between the two natural events. The MFXDFA technique is also compared to the backward MFXDMA algorithm's performance. The change in the degree of cross‐correlation over time has been investigated, and the findings are quantitatively analyzed. The existence of significant power‐law cross‐correlations has been discovered within all scaling orders. Furthermore, we also find evident persistence of cross‐correlation with substantial Hurst exponents. In addition, it has been observed that long‐term cross‐correlation has a more considerable degree of multifractality and persistence than short‐term cross‐correlation.
Light vector meson photoproduction in ultraperipheral heavy‐ion collisions at the LHC within the Reggeometric Pomeron approach
Authors: Jenkovszky László , Rocha Érison S. , Machado Magno V. T.
Published: January 2023

By using the Reggeometric Pomeron model for vector meson production which successfully describes the high energy lepton‐nucleon data, we analyze the light meson production in ultra‐peripheral heavy‐ion collisions at the Large Hadron Collider (LHC). The rapidity distributions for ρ and ϕ photoproduction in lead–lead, xenon–xenon and oxygen– oxygen collisions are investigated.
CRISPR‐interceded CHO cell line development approaches
Authors: Amiri Shahin , Adibzadeh Setare , Ghanbari Samaneh , Rahmani Behnaz , Kheirandish Mohammad H. , Farokhi‐Fard Aref , Dastjerdeh Mansoureh S. , Davami Fatemeh
Published: January 2023

For industrial production of recombinant protein biopharmaceuticals, Chinese hamster ovary (CHO) cells represent the most widely adopted host cell system, owing to their capacity to produce high‐quality biologics with human‐like posttranslational modifications. As opposed to random integration, targeted genome editing in genomic safe harbor sites has offered CHO cell line engineering a new perspective, ensuring production consistency in long‐term culture and high biotherapeutic expression levels. Corresponding the remarkable advancements in knowledge of CRISPR‐Cas systems, the use of CRISPR‐Cas technology along with the donor design strategies has been pushed into increasing novel scenarios in cell line engineering, allowing scientists to modify mammalian genomes such as CHO cell line quickly, readily, and efficiently. Depending on the strategies and production requirements, the gene of interest can also be incorporated at single or multiple loci. This review will give a gist of all the most fundamental recent advancements in CHO cell line development, such as different cell line engineering approaches along with donor design strategies for targeted integration of the desired construct into genomic hot spots, which could ultimately lead to the fast‐track product development process with consistent, improved product yield and quality.
Business models for sustainability and firms' external relationships—A systematic literature review with propositions and research agenda
Authors: Stål Herman I. , Riumkin Ivan , Bengtsson Maria
Published: January 2023

Increased focus on sustainability has made firms' value creation increasingly boundary spanning and complex. This begs the question of how business model research describes firm's external relationships, motivating us to undertake a systematic literature review. In analyzing 49 articles, we discuss and problematize four conceptualizations of external relationships—collaboration, alliances, networks, and ecosystems—arriving at nine propositions that clarify their meaning and refer to either firm‐centric or collective business models for sustainability. In combining these findings with review results from conventional business model research we identify three main blind spots in extant business model for sustainability research, regarding coopetition, wider inter‐organizational and sustainability tensions, and power. Based on these blind spots, we sketch a research agenda that could theorize business models for sustainability without neglecting their inherent tensions and contradictions.
Awe and guilt: Desirability and feasibility appeals in social media green campaigns
Authors: Kim Seeun , Childs Michelle L. , Baek Tae Hyun
Published: January 2023

As the world has become increasingly concerned about environmental plastic pollution, private and public sectors remain devoted to creating effective green marketing campaigns on social media platforms. Drawing upon construal level theory and appraisal tendency theory, this research examines the interaction effect of green ad appeals and two distinct emotions—awe and guilt—on consumers' social media engagement and pro‐environmental intentions. The findings from two experimental studies demonstrate that when individuals experience awe, desirability (vs. feasibility) message appeals generate stronger engagement in social media green campaigns. In contrast, it was found that when individuals experience guilt, feasibility (vs. desirability) message appeals enhance social media engagement and pro‐environmental behaviors more effectively. This research offers novel theoretical contributions to the existing body of literature and provides practical insights by suggesting that awe and guilt act as moderators leading to greater consumer responses when used with matching social media messages promoting green campaigns.
Targeted treatment of refractory primitive neuroectodermal tumor arising from an immature teratoma with crizotinib leading to a sustained response
Authors: Snyder Benjamin M. , Lion Alex H. , Helvie Amy E. , Marshall Mark S. , Ferguson Michael J.
Published: January 2023

Here we present a case of metastatic PNET which arose from an immature teratoma that was refractory to standard Ewing sarcoma chemotherapy. This PNET was determined to have elevated levels of ALK protein via IHC. The patient was treated with crizotinib on a palliative basis with a sustained response.
Recurrent urinary tract infection associated with SGLT‐2 inhibitor in type 2 diabetes mellitus patient: A case report
Authors: Hazique Mohammad , Surana Arihant , Sinha Mehul , Anand Ayush
Published: January 2023

A high index of clinical suspicion of urinary tract infections due to empagliflozin use should be maintained in T2DM patients to avoid progression to life‐threatening condition.
Streptococcus‐related acute suppurative thyroiditis in a COVID‐19‐positive child: A rare case report
Authors: Maleki Elham , Iranmanesh Kimia , Najafzadeh Mohammad Javad , Baniasad Amir
Published: January 2023

In this case report, we present a 10‐year‐old girl with acute suppurative thyroiditis (AST) symptoms, such as fever, sore throat, and swelling in the suprasternal region, who had a positive PCR test for COVID‐19. The result of the secretions culture obtained from the abscess drainage was positive for nonhemolytic Streptococcus.
Green Synthesis and Analytical Characterization of Core‐Shell Copper Sub‐Microparticles
Authors: Sportelli Maria Chiara , Picca Rosaria Anna , Izzi Margherita , Cioffi Nicola
Published: January 2023

This study demonstrates a simple and reproducible approach to synthesize green core‐shell copper sub‐microparticles stabilized by poly(n‐vinyl)pyrrolidone (PVP). Cu@PVP colloids were here prepared using copper sulfate pentahydrate as precursor and glucose as reducing agent. The presence of PVP in the synthetic medium eliminates the need for an inert atmosphere during the process, thus simplifying the whole method. Both the morphology and the spectroscopic properties of Cu@PVP colloids were investigated by transmission electron microscopy, and infrared, UV‐Vis and X‐ray photoelectron spectroscopies. Size distributions and average shell thickness were obtained by statistical analysis on TEM micrographs, and spectroscopies demonstrated the formation of a PVP layer around the copper core. The produced colloids were employed in composite thin films for potential antimicrobial application, in association with a highly‐recyclable polymer: polycarbonate (4,4’‐(1‐methylethylidene)bis(phenol)).
Templating Influence of Regulated Inorganic Framework in Two‐Dimensional Ferroelastic Perovskites: (C3H5CH2NH3)2[MCl4] (M=Mn and Cd)
Authors: Yin Ti‐Jian , Xu Ke , He Lei , Meng Xin , Xu Yan , Men Jin‐Tiao , Mu Jie , Ye Qiong , Shi Ping‐Ping
Published: January 2023

The remarkable material stability and structural diversity of two‐dimensional (2D) organic‐inorganic hybrid perovskites (OIHPs) constitute a vast available library of versatile materials. In particular, ferroelastic property, for which the spontaneous strain can be transformed by applying mechanical stress, is very promising for extensive nanotechnological applications. However, integrating ferroelastic property into 2D OIHPs is still in its infancy. Herein, we designed two new 2D OIHPs (C3H5CH2NH3)2[MCl4] (M=Mn for 1 and Cd for 2), which undergo reversible ferroelastic phase transitions with an Aizu expression 4/mmmFmmm. The templating influence of the more distorted inorganic framework on the disordering of organic cations and the stronger hydrogen bonds has a key role in the striking improvement of Curie temperature from 246 K in 1 to 273 K in 2. Meanwhile, the minimized alteration of structural motif ensures the well maintaining of the ferroelastic performance in the forms of crystals and thin films, as demonstrated by the identifiable evolution of domain structures. This work will provide a fertile new ground for enlarging the limited number of 2D ferroelastic OIHPs with better practical utility.
Gold Teflates Revisited: From the Lewis Superacid [Au(OTeF5)3] to the Anion [Au(OTeF5)4]−
Authors: Winter Marlon , Peshkur Natallia , Ellwanger Mathias A. , Pérez‐Bitrián Alberto , Voßnacker Patrick , Steinhauer Simon , Riedel Sebastian
Published: January 2023

A new synthetic access to the Lewis acid [Au(OTeF5)3] and the preparation of the related, unprecedented anion [Au(OTeF5)4]−with inorganic or organic cations starting from commercially available and easy‐to‐handle gold chlorides are presented. In this first extensive study of the Lewis acidity of a transition‐metal teflate complex by using different experimental and quantum chemical methods, [Au(OTeF5)3] was classified as a Lewis superacid. The solid‐state structure of the triphenylphosphine oxide adduct [Au(OPPh3)(OTeF5)3] was determined, representing the first structural characterization of an adduct of this highly reactive [Au(OTeF5)3]. Therein, the coordination environment around the gold center slightly deviates from the typical square planar geometry. The [Au(OTeF5)4]−anion shows a similar coordination motif.
Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing NpV and the Uranyl Peroxide Nanocluster U60Ox30
Authors: Smith Kyson R. , Ilavsky Jan , Hixon Amy E.
Published: January 2023

Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U60Ox30, [((UO2)(O2))60(C2O4)30]60−, and neptunium(V) as a function of neptunium concentration. Ultra‐small and small angle X‐ray scattering were used to observe these interactions in the aqueous phase, and X‐ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U60Ox30 when the neptunium concentration is≤10 mM, whereas (NpO2)2C2O4 ⋅ 6H2O(cr) and studtite ultimately form at 15–25 mM neptunium. The latter result suggests that neptunium coordinates with the bridging oxalate ligands in U60Ox30, leaving metastable uranyl peroxide species in solution. This is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.
Dendrite‐Free Engineering toward Efficient Zinc Storage: Recent Progress and Future Perspectives
Authors: Miao Ling , Zhang Jinmao , Lv Yaokang , Gan Lihua , Liu Mingxian
Published: January 2023

Zinc‐based energy storage has lately gained popularity due to natural abundance, operational safety, high energy density. Unfortunately, dendrite growth is a common and intractable issue faced in existing zinc‐ion batteries to shorten cycle lifespan/stability. This review summarizes recent progress in assembly component (e. g., anode, electrolyte, separator) engineering for dendrite‐free zinc‐ion batteries. First, diversiform strategies of Zn surface modification and Zn host design are presented to shield the fundamental adverse effect aroused by uneven zinc deposition on the anode. Then, subtle deployments of electrolyte constituents are illustrated to optimize the Zn2+solvation structure for ultimate dendrite control and Coulombic efficiency elevation in aqueous systems and beyond (e. g., eutectic electrolytes). Furthermore, rational manipulation of advanced separators and the upgrade of zinc metal‐free Zn2+‐storage devices are briefly discussed to explore the dendrite‐free and high‐level Zn2+‐storage. Finally, challenges and perspectives are proposed to offer research inspirations toward safe, high‐efficiency and long‐lifespan zinc storage.
Process Engineering and Glycosyltransferase Improvement for Short Route Chemoenzymatic Total Synthesis of GM1 Gangliosides
Authors: Yu Hai , Zhang Libo , Yang Xiaohong , Bai Yuanyuan , Chen Xi
Published: January 2023

Large‐scale synthesis of GM1, an important ganglioside in mammalian cells especially those in the nervous system, is needed to explore its therapeutic potential. Biocatalytic production is a promising platform for such a purpose. We report herein the development of process engineering and glycosyltransferase improvement strategies to advance chemoenzymatic total synthesis of GM1. Firstly, a new short route was developed for chemical synthesis of lactosylsphingosine from the commercially available Garner's aldehyde. Secondly, two glycosyltransferases including Campylobacter jejuni β1–4GalNAcT (CjCgtA) and β1–3‐galactosyltransferase (CjCgtB) were improved on their soluble expression in E. coli and enzyme stability by fusing with an N‐terminal maltose binding protein (MBP). Thirdly, the process for enzymatic synthesis of GM1 sphingosines from lactosylsphingosine was engineered by developing a multistep one‐pot multienzyme (MSOPME) strategy without isolating intermediate glycosphingosines and by adding a detergent, sodium cholate, to the later enzymatic glycosylation steps. Installation of a desired fatty acyl chain to GM1 glycosphingosines led to the formation of target GM1 gangliosides. The combination of glycosyltransferase improvement with chemical and enzymatic process engineering represents a significant advance in obtaining GM1 gangliosides containing different sialic acid forms by total chemoenzymatic synthesis in a short route and with high efficiency.
Design and Analysis of Charge‐Reduced Refrigerant Cycles Using R290
Authors: Schnabel Lena , Methler Timo , Hassan Abdelrahman H. , Dankwerth Clemens , Maciá José María Gonzálvez
Published: January 2023

R290 is one of the most promising refrigerants for heat pumps and cooling processes working in a temperature range of –15 to 70 °C. The nearly neglectable global warming potential and attractive thermodynamic properties allow the design of climate‐friendly and efficient refrigeration systems and heat pumps. However, R290 is flammable, and the use of charge‐reduced components and designs should be the first central step to reduce safety risks. Whereas the prediction of heat capacity, temperatures and pressure drops are sufficiently precise the prediction of refrigerant charge is not very accurate when using computer‐aided design tools. The article presents a method to enhance accuracy for refrigerant cycles with less than 500 g of R290.
Tales from the Other Side: An Exploratory Study of the Effects of Third‐party Enforced Psychological Contract Breach Risk on Breachers and their Relationships During a Work‐to‐rule Teacher Strike
Authors: Michaud James , Somogyvari Gabor
Published: January 2023

Little research has been done on psychological contract breach situations from the perspective of the breacher, including situations in which potential breach actions were enforced by a third‐party. This exploratory study aims to see how enforced breach affects the breacher, their reactions to the situation, and their relationships with community stakeholders. Semi‐structured long‐form interviews with Canadian teachers whose union decided to go on a work‐to‐rule strike, risking relational breaches with school community stakeholders, were undertaken. Teachers experienced negative emotions and engaged in breach mitigating actions. Implications include being aware of the negative effects on unwilling breachers and the relationships with the source of breaches, and the possibility of mitigating breaches while still removing obligations if breachers engage in mitigating actions.
Spatial PD‐L1, immune‐cell microenvironment, and genomic copy‐number alteration patterns and drivers of invasive‐disease transition in prospective oral precancer cohort
Authors: William William N. , Zhang Jianjun , Zhao Xin , Parra Edwin R. , Uraoka Naohiro , Lin Heather Y. , Peng S. Andrew , El‐Naggar Adel K. , Rodriguez‐Canales Jaime , Song Jaejoon , Gillenwater Ann M. , Wistuba Ignacio I. , Myers Jeffrey N. , Gold Kathryn A. , Ferrarotto Renata , Hwu Patrick , Davoli Teresa , Lee J. Jack , Heymach John V. , Papadimitrakopoulou Vassiliki A. , Lippman Scott M.
Published: January 2023

Background

Studies of the immune landscape led to breakthrough trials of programmed death‐1 (PD‐1) inhibitors for recurrent/metastatic head and neck squamous cell carcinoma therapy. This study investigated the timing, influence of somatic copy‐number alterations (SCNAs), and clinical implications of PD‐L1 and immune‐cell patterns in oral precancer (OPC).

Methods

The authors evaluated spatial CD3, CD3/8, and CD68 density (cells/mm2) and PD‐L1 (membranous expression in cytokeratin‐positive intraepithelial neoplastic cells and CD68) patterns by multiplex immunofluorescence in a 188‐patient prospective OPC cohort, characterized by clinical, histologic, and SCNA risk factors and protocol‐specified primary end point of invasive cancer. The authors used Wilcoxon rank‐sum and Fisher exact tests, linear mixed effect models, mediation, and Cox regression and recursive‐partitioning analyses.

Results

Epithelial, but not CD68 immune‐cell, PD‐L1 expression was detected in 28% of OPCs, correlated with immune‐cell infiltration, 9p21.3 loss of heterozygosity (LOH), and inferior oral cancer‐free survival (OCFS), notably in OPCs with low CD3/8 cell density, dysplasia, and/or 9p21.3 LOH. High CD3/8 cell density in dysplastic lesions predicted better OCFS and eliminated the excess risk associated with prior oral cancer and dysplasia. PD‐L1 and CD3/8 patterns revealed inferior OCFS in PD‐L1 high intrinsic induction and dysplastic immune‐cold subgroups.

Conclusion

This report provides spatial insight into the immune landscape and drivers of OPCs, and a publicly available immunogenomic data set for future precancer interrogation. The data suggest that 9p21.3 LOH triggers an immune‐hot inflammatory phenotype; whereas increased 9p deletion size encompassing CD274 at 9p24.1 may contribute to CD3/8 and PD‐L1 depletion during invasive transition. The inferior OCFS in PD‐L1‐high, immune‐cold OPCs support the development of T‐cell recruitment strategies.
Culturing and Imaging Glioma Stem Cells in 3D Collagen Matrices
Authors: Cowan James M. , Juric Matey , Petrie Ryan J.
Published: January 2023

Methods to maintain human glioma stem cells as neurosphere cultures and image their dynamic behavior in 3D collagen matrices are described. Additional approaches to monitor glioma stem cell differentiation into mesenchymal‐type cells, along with example data are included. Together, these approaches enable glioma stem cell differentiation to be controlled while maintaining the cells in culture, as well as allowing cell dynamics to be captured and analyzed. These methods should be helpful for those seeking to understand the molecular mechanisms driving the invasion of glioma cells through three‐dimensional environments. © 2023 Wiley Periodicals LLC.

Basic Protocol 1: Culturing human glioma stem cells as neurospheres

Basic Protocol 2: Inducing GSC adherence and monitoring their differentiation into mesenchymal cells

Support Protocol 1: Preparing fibronectin‐coated dishes for cell microscopy

Basic Protocol 3: Embedding GSCs in a 3D collagen matrix to study their invasive behavior

Support Protocol 2: Phase‐contrast imaging with a tiled matrix to study cell migration in a 3D gel
Analysis of full reference quality metrics for image transmission over a MIMO OWC channel under varying turbulent conditions
Authors: Gill Harpuneet Singh , Singh Maninder Lal , Singh Mandeep , Priyanka  , Kaur Sehajpal , Kaur Hardeep
Published: January 2023

The integrated OWC‐PON architecture has a potential to overcome the limitations of existent RF technology and eliminate the last mile bottleneck in geographically constrained access networks thus providing real sense broadband from core to user. However, phenomenon such as atmospheric turbulence causes performance degradation in such systems. In the dissemination of multimedia services, the performance is the ultimate quality as perceived by end user's visual senses. To ascertain this quality in quantitative terms, full reference quality metrics are employed for communication purposes. This paper deals with classification, evaluation and analysis of various image quality assessment metrics for image transmission over OWC channel under varying turbulent conditions. The performance enhancement in terms of these metrics is investigated by deploying MIMO diversity reception. Moreover, a prediction model for SSIM is developed and compared for both SISO and MIMO links. The results show an improvement in IQA metrics with diversity reception. SSIM can be predicted in terms of log of refractive index structure parameter by a fourth order polynomial model for both SISO and MIMO receptions under all regimes of turbulence. The goodness of the fit statistics is presented along with the models to provide for their accuracy and reliability.
A retrospective multicenter study comparing the punctures to B2 and B3 in endoscopic ultrasound–guided hepaticogastrostomy
Authors: Sekine Masanari , Hashimoto Yusuke , Shibuki Taro , Okumura Kei , Kobori Ikuhiro , Miyagaki Aki , Sasaki Yoshihiro , Takano Yuichi , Matsumoto Keita , Mashima Hirosato
Published: January 2023

Objectives

In recent years, endoscopic ultrasound–guided hepaticogastrostomy (EUS–HGS) has been performed as an important salvage option for failed endoscopic retrograde cholangiopancreatography for biliary drainage. However, technical issues, such as puncture site (bile duct of segment 3 [B3] or bile duct of segment 2 [B2]), dilation method, stent selection, and procedural safety, need to be resolved for the optimization of EUS–HGS. The present study was to compare the safety, difficulty, and technical and functional success between biliary access via B2 and B3 during EUS–HGS.

Methods

We conducted a retrospective investigation of 161 consecutive EUS–HGS cases across a total of 6 facilities, including those at our hospital. The patients were divided into two groups according to the successful drainage route: the puncture to B2 (P‐B2) or the puncture to B3 (P‐B3). We compared the technical and functional success rates, technical difficulty, and adverse events between the two groups. We also conducted a subgroup analysis to show the factors related to the procedure time.

Results

There were 92 cases in the P‐B2 group and 69 cases in the P‐B3 group. There were no significant differences in the technical success, functional success, or adverse events between the groups; however, the procedure time was significantly shorter in P‐B2 cases than in P‐B3 cases. The multivariate analysis showed that the puncture site was the only factor related to the procedure time.

Conclusions

Based on these findings, P‐B2 appears useful and safe. P‐B2 is as effective as P‐B3 and was able to be performed in a shorter period of time. The B2 approach can be considered a useful option for EUS–HGS.
3D Grid of Carbon Tubes with Mn3O4‐NPs/CNTs Filled in their Inner Cavity as Ultrahigh‐Rate and Stable Lithium Anode
Authors: Zhang Shiping , Han Fangming , Pan Qijun , Lin Dou , Zhu Xiaoguang , Shao Cheng , Zhang Gaixia , Wang Zhaoming , Sun Shuhui , Meng Guowen
Published: January 2023

Transition metal oxides are regarded as promising candidates of anode for next‐generation lithium‐ion batteries (LIBs) due to their ultrahigh theoretical capacity and low cost, but are restricted by their low conductivity and large volume expansion during Li+ intercalation. Herein, we designed and constructed a structurally integrated 3D carbon tube (3D‐CT) grid film with Mn3O4 nanoparticles (Mn3O4‐NPs) and carbon nanotubes (CNTs) filled in the inner cavity of CTs (denoted as Mn3O4‐NPs/CNTs@3D‐CT) as high‐performance free‐standing anode for LIBs. The Mn3O4‐NPs/CNTs@3D‐CT grid with Mn3O4‐NPs filled in the inner cavity of 3D‐CT not only afford sufficient space to overcome the damage caused by the volume expansion of Mn3O4‐NPs during charge and discharge processes, but also achieves highly efficient channels for the fast transport of both electrons and Li+ during cycling, thus offering outstanding electrochemical performance (865 mAh g−1 at 1 A g−1 after 300 cycles) and excellent rate capability (418 mAh g−1 at 4 A g−1) based on the total mass of electrode. The unique 3D‐CT framework structure would open up a new route to the highly stable, high‐capacity, and excellent cycle and high‐rate performance free‐standing electrodes for high‐performance Li‐ion storage.
Biomarker signature and pathophysiological pathways in patients with chronic heart failure and metabolic syndrome
Authors: van der Hoef Camilla C.S. , Boorsma Eva M. , Emmens Johanna E. , van Essen Bart J. , Metra Marco , Ng Leong L. , Anker Stefan D. , Dickstein Kenneth , Mordi Ify R. , Dihoum Adel , Lang Chim C. , van Veldhuisen Dirk J. , Lam Carolyn S.P. , Voors Adriaan A.
Published: January 2023

Aim

The comorbidities that collectively define metabolic syndrome are common in patients with heart failure. However, the role of metabolic syndrome in the pathophysiology of heart failure is not well understood. We therefore investigated the clinical and biomarker correlates of metabolic syndrome in patients with heart failure.

Methods and results

In 1103 patients with heart failure, we compared the biomarker expression using a panel of 363 biomarkers among patients with (n = 468 [42%]) and without (n = 635 [58%]) metabolic syndrome. Subsequently, a pathway overrepresentation analysis was performed to identify key biological pathways. Findings were validated in an independent cohort of 1433 patients with heart failure of whom 615 (43%) had metabolic syndrome. Metabolic syndrome was defined as the presence of three or more of five criteria, including central obesity, elevated serum triglycerides, reduced high‐density lipoprotein cholesterol, insulin resistance and hypertension. The most significantly elevated biomarkers in patients with metabolic syndrome were leptin (log2 fold change 0.92, p = 5.85 × 10−21), fatty acid‐binding protein 4 (log2 fold change 0.61, p = 1.21 × 10−11), interleukin‐1 receptor antagonist (log2 fold change 0.47, p = 1.95 × 10−13), tumour necrosis factor receptor superfamily member 11a (log2 fold change 0.35, p = 4.16 × 10−9), and proto‐oncogene tyrosine‐protein kinase receptor Ret (log2 fold change 0.31, p = 4.87 × 10−9). Network analysis identified 10 pathways in the index cohort and 6 in the validation cohort, all related to inflammation. The primary overlapping pathway in both the index and validation cohorts was up‐regulation of the natural killer cell‐mediated cytotoxicity pathway.

Conclusion

Metabolic syndrome is highly prevalent in heart failure and is associated with biomarkers and pathways relating to obesity, lipid metabolism and immune responses underlying chronic inflammation.
Bridging strategies and cardiac replacement outcomes in patients with acute decompensated heart failure‐related cardiogenic shock
Authors: Varshney Anubodh S. , Berg David D. , Zhou Guohai , Sinnenberg Lauren , Hirji Sameer , DeFilippis Ersilia M. , Mallidi Hari R. , Morrow David A. , Rinewalt Daniel , Givertz Michael M.
Published: January 2023

Aims

To describe outcomes associated with bridging strategies in patients with acute decompensated heart failure‐related cardiogenic shock (ADHF‐CS) bridged to durable left ventricular assist device (LVAD) or heart transplantation (HTx).

Methods and results

Durable LVAD or HTx recipients from 2014 to 2019 with pre‐operative ADHF‐CS were identified in the Society of Thoracic Surgeons Adult Cardiac Surgery Database and stratified by bridging strategy. The primary outcome was operative or 30‐day post‐operative mortality. Secondary outcomes included post‐operative major bleeding. Exploratory comparisons between bridging strategies and outcomes were performed using overlap weighting with and without covariate adjustment. Among 9783 patients with pre‐operative CS, 8777 (89.7%) had ADHF‐CS. Medical therapy (n = 5013) was the most common bridging strategy, followed by intra‐aortic balloon pump (IABP; n = 2816), catheter‐based temporary mechanical circulatory support (TMCS; n = 417), and veno‐arterial extracorporeal membrane oxygenation (VA‐ECMO; n = 465). Mortality was highest in patients bridged with VA‐ECMO (22%), followed by catheter‐based TMCS (10%), IABP (9%), and medical therapy (7%). Adverse post‐operative outcomes were more frequent in LVAD recipients compared with HTx recipients.

Conclusion

Among patients with ADHF‐CS bridged to HTx or durable LVAD, the highest rates of death and adverse events during index hospitalization were observed in those bridged with VA‐ECMO, followed by catheter‐based TMCS, IABP, and medical therapy. Patients who received durable LVAD had higher rates of post‐operative complications compared with HTx recipients. Prospective trials are needed to define optimal bridging strategies in patients with ADHF‐CS.
N‐terminal pro‐B‐type natriuretic peptide and high‐sensitivity troponin T hold diagnostic value in cardiac amyloidosis
Authors: Vergaro Giuseppe , Castiglione Vincenzo , Aimo Alberto , Prontera Concetta , Masotti Silvia , Musetti Veronica , Nicol Martin , Cohen Solal Alain , Logeart Damien , Georgiopoulos Georgios , Chubuchny Vladyslav , Giannoni Alberto , Clerico Aldo , Buda Gabriele , Patel Kiara N. , Razvi Yousuf , Patel Rishi , Wechalekar Ashutosh , Lachmann Helen , Hawkins Philip N. , Passino Claudio , Gillmore Julian , Emdin Michele , Fontana Marianna
Published: January 2023

Aims

Cardiac amyloidosis (CA) is associated with an elevation of natriuretic peptides and troponins, predicting outcome. Nevertheless, the diagnostic yield of these biomarkers has not been extensively investigated. This study aimed to evaluate the diagnostic performance for CA of N‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP) and high‐sensitivity troponin T (hs‐TnT).

Methods and results

Patients with suspected CA (n = 1149) underwent a diagnostic work‐up in three centres in Italy, France (n = 343, derivation cohort), and United Kingdom (n = 806, validation cohort). Biomarker values with either 100% sensitivity or ≥95% specificity were selected as rule‐out/rule‐in cut‐offs, respectively. In the derivation cohort, 227 patients (66%) had CA, and presented with higher NT‐proBNP and hs‐TnT. NT‐proBNP 180 ng/L and hs‐TnT 14 ng/L were selected as rule‐out cut‐offs, and hs‐TnT 86 ng/L as rule‐in cut‐off. NT‐proBNP <180 ng/L or hs‐TnT <14 ng/L were found in 7% of patients, and ruled out CA without false negatives. In the validation cohort, 20% of patients (2% false negatives) had NT‐proBNP <180 ng/L or hs‐TnT <14 ng/L, and 10% showed both biomarkers below cut‐offs (0.5% false negatives). These cut‐offs refined CA prediction when added to echocardiographic scores in patients with a haematologic disease or an increased wall thickness. In the validation cohort, the 86 ng/L hs‐TnT cut‐off ruled in 20% of patients (2% false positives). NT‐proBNP and hs‐TnT cut‐offs retained their rule‐out and rule‐in performance also in cohorts with CA prevalence of 20%, 10%, 5% and 1% derived from the original cohort through bootstrap analysis.

Conclusions

Cardiac biomarkers can refine the diagnostic algorithm in patients with suspected CA. NT‐proBNP <180 ng/L and hs‐TnT <14 ng/L reliably exclude the diagnosis, both in the overall population and subgroups referred for either AL‐CA or cardiac (pseudo)hypertrophy.
Transcatheter edge‐to‐edge repair for secondary mitral regurgitation with third‐generation devices in heart failure patients – results from the Global EXPAND Post‐Market study
Authors: Orban Mathias , Rottbauer Wolfgang , Williams Mathew , Mahoney Paul , von Bardeleben Ralph Stephan , Price Matthew J. , Grasso Carmelo , Lurz Philipp , Zamorano Jose L. , Asch Federico M. , Maisano Francesco , Kar Saibal , Hausleiter Jörg
Published: January 2023

Aims

Mitral valve transcatheter edge‐to‐edge repair is a guideline‐recommended treatment option for patients with secondary mitral regurgitation (SMR). The purpose of this analysis was to report contemporary real‐world outcomes in SMR patients treated with third‐generation MitraClip systems.

Methods and results

EXPAND is a prospective, multicentre, international, single‐arm study with 1041 patients treated for mitral regurgitation (MR) with MitraClip NTR/XTR, with 30‐day and 1‐year follow‐up. All echocardiograms were analysed by an independent echocardiographic core lab. Study outcomes included procedural outcomes, durability of MR reduction, and major adverse events including all‐cause mortality and heart failure hospitalizations (HFH). A subgroup of 413 symptomatic patients (age 74.7 ± 10.1 years, 58% male) with severe SMR were included. MR reduction to MR ≤ 1+ and MR ≤ 2+ was achieved in 93.0% and 98.5% of patients, respectively, which was sustained at 1‐year follow‐up. All‐cause mortality was 17.7% at 1‐year‐ follow‐up, and the combined endpoint of all‐cause mortality or first HFH occurred in 34% of patients. This combined endpoint was significantly less frequently observed in MR ≤ 1+ patients (Kaplan–Maier estimates: 29.7% vs. 69.6% for MR ≤ 1+ vs. MR  ≥ 2 +; p < 0.0001). New York Heart Association (NYHA) functional class improved significantly from baseline (NYHA ≤ II: 17%) to 1‐year follow‐up (NYHA ≤ II: 78%) (p < 0.0001). While MR reduction was comparable between NTR‐only vs. XTR‐only treated patients, less XTR clips were required for achieving MR reduction.

Conclusions

Under real‐world conditions, optimal sustained MR reduction to MR ≤ 1+ was achieved in a high percentage of patients with third‐generation MitraClip, which translated into symptomatic improvement and low event rates. These results appear to be comparable with recent randomized clinical trials.
Antigen clearance at the peak of the primary immune response induces experimental autoimmune encephalomyelitis
Authors: Zheng Peiguo , Wei Xufeng , Cao Xuezhen , Ma Panhong , Dong Rui , Tang Hongwei , Meng Xianchun , Liu Xinjing , Zhang Cai , Zhang Shuijun , Ming Liang
Published: January 2023

Autoimmune demyelinating diseases can be induced by an immune response against myelin peptides; however, the exact mechanism underlying the development of such diseases remains unclear. In experimental autoimmune encephalomyelitis, we found that the clearance of exogenous myelin antigen at the peak of the primary immune response is key to the pathogenesis of the disease. The generation of effector T cells requires continuous antigen stimulation, whereas redundant antigen traps and exhausts effector T cells in the periphery, which induces resistance to the disease. Moreover, insufficient antigenic stimulation fails to induce disease efficiently owing to insufficient numbers of effector T cells. When myelin antigen is entirely cleared, the number of effector T cells reaches a peak, which facilitates infiltration of more effector T cells into the central nervous system. The peripheral antigen clearance initiates the first wave of effector T cell entry into the central nervous system and induces chronic inflammation. The inflamed central nervous system recruits the second wave of effector T cells that worsen inflammation, resulting in loss of self‐tolerance. These findings provide new insights into the mechanism underlying the development of autoimmune demyelinating diseases, which may potentially impact future treatments.
Synthesis of Low Silica SAPO‐34 by In Situ Pretreatment and Its Catalytic Performance in the Methanol‐to‐Olefins (MTO) Reaction
Authors: Guo Lei , Zhu Weiping , Xing Aihua , Li Fei
Published: January 2023

A series of low‐silica SAPO‐34 molecular sieves with a tunable silica content were synthesized through a facile in situ pretreatment strategy under different pretreatment condition. The effects of the pretreatment condition on the crystal phases, chemical composition, morphology and acidity of SAPO‐34 were characterized by XRD, XRF, SEM, N2 adsorption‐desorption, NH3‐TPD and 29Si MAS NMR. The obtained low‐silica SAPO‐34 exhibits higher catalytic performance in the MTO reaction than conventional SAPO‐34 due to the moderate acidity and larger surface areas. Sample S4 with a Si content of Si/(Si+Al+P)=0.053 showed the prolonged catalytic lifetime of 204 min and remarkably improved selectivity for ethylene and propylene reaching up to 86.58 %, which was 34 % and 4.16 % higher than the reference sample.
Manganese‐Catalyzed Transfer Hydrodebromination of Aryl Bromides with Ethanol
Authors: Wen Xiaoting , Gong Yingjie , Niu Shuodong , Luo Tianjun , Xi Hui , Liu Weiping
Published: January 2023

A convenient PNP pincer manganese catalyzed transfer hydrogenation of bromides to corresponding debrominated aryl compounds using ethanol as the hydrogen sources is reported. Importantly, the application of biomass‐derived ethanol highlights the sustainability of the methodology. The use of 6‐phenyl substituted triazine‐based PiprN5Pipr manganese pincer catalyst allows for the debromination of various aryl bromides with good yields. Notably, the process also occurs with bromides derived from several classes of natural products and bioactive compounds, such as citronellol, diacetone fructose, cholesterol, and vitamin E.
Flexible Synthesis of Benzofuranones from ortho‐Alkynyl Phenols or Benzofurans
Authors: Du Wenqian , Yang Rongjie , Wu Jiawen , Xia Zhonghua
Published: January 2023

Benzofuranones are attractive synthetic targets in medicinal and natural products. The cycloisomerization of o‐alkynyl phenol to benzofuran‐3(2H)‐one is reported here using gold(I) and Selectfluor. This benzofuranone can also be obtained from benzofuran without a gold catalyst. This study presents two appealing synthetic methods for benzofuran‐3(2H)‐ones that use readily available starting materials, have high chemoselectivity and operate under very mild conditions.