bluuebunny/crossref_metadata_2025 huggingface dataset:
Lumineszenz‐ und Längenkontrolle in nicht‐chelatisierten d8‐metallosupramolekularen Polymeren vermittelt durch Metall‐Metall‐Wechselwirkungen
Authors: Matern Jonas , Maisuls Iván , Strassert Cristian A. , Fernández Gustavo
Published: June 2022

Supramolekulare Polymere (SPs) von d8‐Übergangsmetallkomplexen haben aufgrund ihrer vielseitigen photophysikalischen Eigenschaften, die sich u. a. aus Metall‐Metall‐Wechselwirkungen ergeben, an Bedeutung gewonnen. Bislang ist das molekulare Design jedoch auf Komplexe mit chelatisierenden Liganden beschränkt, aufgrund ihrer vorteilhaften Präorganisation und starken Ligandenfeldaufspaltungen. In diesem Manuskript berichten wir über einzigartige Metall‐Metall‐Wechselwirkungen und eine bemerkenswerte3MMLCT‐Lumineszenz in SPs eines nicht chelatisierten PtII‐Komplexes, welche durch den Aggregationspfad kontrolliert werden können. Unter kinetischer Kontrolle induzieren selbstkomplementäre Bisamid‐H‐Bindungsmotive eine schnelle Selbstorganisation zu nicht‐emissiven H‐Aggregaten (1A). Unter thermodynamischen Bedingungen hingegen führt eine effizientere Liganden‐Koplanarisierung zu stärker stabilisierten SP1Bmit ausgedehnten Pt⋅⋅⋅Pt‐Wechselwirkungen und bemerkenswert langer3MMLCT‐Lumineszenz (τ77 K=0.26 ms). Die Metall‐Metall‐Wechselwirkungen konnten anschließend genutzt werden, um die Länge der emittierenden SPs durch Keim‐vermitteltes SP‐Wachstum zu kontrollieren.
Luminescence and Length Control in Nonchelated d8‐Metallosupramolecular Polymers through Metal‐Metal Interactions
Authors: Matern Jonas , Maisuls Iván , Strassert Cristian A. , Fernández Gustavo
Published: June 2022

Supramolecular polymers (SPs) of d8transition metal complexes have received considerable attention by virtue of their rich photophysical properties arising from metal‐metal interactions. However, thus far, the molecular design is restricted to complexes with chelating ligands due to their advantageous preorganization and strong ligand fields. Herein, we demonstrate unique pathway‐controllable metal‐metal‐interactions and remarkable3MMLCT luminescence in SPs of a non‐chelated PtIIcomplex. Under kinetic control, self‐complementary bisamide H‐bonding motifs induce a rapid self‐assembly into non‐emissive H‐type aggregates (1A). However, under thermodynamic conditions, a more efficient ligand coplanarization leads to superiorly stabilized SP1Bwith extended Pt⋅⋅⋅Pt interactions and remarkably long3MMLCT luminescence (τ77 K=0.26 ms). The metal‐metal interactions could be subsequently exploited to control the length of the emissive SPs using the seeded‐growth approach.
A novel bioderived AB2‐type monomer from castor oil derivative for the preparation of fully biobased hyperbranched polyesters
Authors: Shan Pengjia , Lu Hengyu , Chen Ning , Liu Hongzhi , Zhang Xianhui , Liu Xiaohuan
Published: June 2022

Designing biobased hyperbranched polyesters from vegetable oil has been attracting considerable interests from academic industrial communities. Herein, a novel fully biobased hyperbranched polyester (HBPE) was prepared by self‐condensation of AB2‐type bioderived monomer based on methyl ricinoleate (MR), a castor oil‐derived renewable chemical. The reaction conditions were optimized to obtain the AB2‐type monomer in a high conversion ratio (up to 87%). The self‐condensation of AB2‐type monomers was carried out in the presence of two kinds of transesterification catalysts (Ti(OBu)4 versus Zn(Ac)2), among which Ti(OBu)4 was found to be more efficient one and yield higher molecular weights in the range of 5800~11,500 g/mol. The resulting HBPEs were characterized in terms of Fourier transform infrared spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. The degree of branching was calculated to be 0.33~0.39. Thermal analysis revealed that the as‐prepared HBPEs were amorphous with tunable glass transition temperatures ranging from −44.8 to −24.6°C. All the prepared HBPEs exhibited good thermal stability with the maximum onset decomposition temperature (Tonset) up to 294.6°C. These structural features and properties of resulting biobased HBPEs enabled them to act as a potential ‘greener’ additive for polymers.
Characterization and expression profiling of serine protease inhibitors in the yellow mealworm Tenebrio molitor
Authors: Li Guang‐Ya , Yang Lin , Xiao Kai‐Ran , Song Qi‐Sheng , Stanley David , Wei Shu‐Jun , Zhu Jia‐Ying
Published: June 2022

Serine protease inhibitors (SPIs) act in diverse biological processes in insects such as immunity, development, and digestion by preventing the unwanted proteolysis. So far, the repertoire of genes encoding SPIs has been identified from few insect species. In this study, 62 SPI genes were identified from the genome of the yellow mealworm, Tenebrio molitor. According to their modes of action, they were classified into three families, serpin (26), canonical SPI (31), and α‐macroglobulins (A2M) (5). These SPIs feature eight domains including serpin, Kazal, TIL, Kunitz, WAP, Antistasin, pacifastin, and A2M. In total, 39 SPIs contain a single SPI domain, while the others encode at least two inhibitor units. Based on the amino acids in the cleaved reactive sites, the abilities of these SPIs to inhibit trypsin, chymotrypsin, or elastase‐like enzymes are predicted. The expression profiling based on the RNA‐seq data showed that these genes displayed stage‐specific expression patterns during development, suggesting to us their significance in development. Some of the SPI genes were exclusively expressed in particular tissues such as hemocyte, fat body, gut, ovary, and testis, which may be involved in biological processes specific to the indicated tissues. These findings provide necessary information for further investigation of insect SPIs.
PGE2 mediation of egg development in Western flower thrip, Frankliniella occidentalis
Authors: Choi Du‐Yeol , Kim Yonggyun
Published: June 2022

Eicosanoids mediate various insect physiological processes, including reproduction. Especially, the eicosanoid prostaglandin E2 (PGE2) is known to mediate oocyte development in some insects. The explosive reproductive potential of the Western flower thrips, Frankliniella occidentalis, damages various agricultural crops. However, little is known about the underlying physiological processes of egg development in this pest. This study found that treatment with aspirin (ASP) (a specific cyclooxygenase (COX) inhibitor) used to inhibit PGE2 biosynthesis during ovarian development significantly suppressed the reproduction of female F. occidentalis. However, the addition of PGE2 to ASP‐treated females significantly rescued the suppressed reproduction. PGE2 was detected in growing ovarian follicles in an immunofluorescence assay. The hypothetical biosynthetic machinery of PGE2 was predicted from the F. occidentalis genome and included phospholipase A2 (PLA2), COX‐like peroxidase (POX), and PGE2 synthase (PGES). Three specific PLA2s were highly expressed in female adults during active oogenesis. Specific POX and PGES genes also showed high expression during active oogenesis. The adverse effect of ASP treatment on oogenesis was observed in follicle formation in the germarium where the follicle numbers in an ovariole were decreased, which resulted in hypotrophied ovaries. This impairment was rescued by the addition of PGE2. ASP treatment also significantly inhibited chorion formation and suppressed gene expression associated with choriogenesis, which included chorion protein, mucin, and yellow while it did not inhibit vitellogenin gene expression. However, the addition of PGE2 induced the expression of the target genes suppressed by ASP treatment and rescued chorion formation. These results suggest that PGE2 mediated ovarian development by affecting follicle formation and choriogenesis in F. occidentalis.
A model predictive control approach for angle tracking of steer‐by‐wire system with nonlinear transmission ratio
Authors: Shi Qin , Wei Yujiang , Xie Dong , Li Feilong , Song Ke , He Lin
Published: June 2022

Steer‐by‐wire for full self‐driving vehicles requires rapid angle tracking in the process of steering, making steering system stability paramount. This is particularly challenging for steering wheels accurately without handwheel, for which road feedback information is scarce. While much of the research on steer‐by‐wire has focused on improving the stability of vehicle dynamics, comparatively little is known about the angle tracking control of steer‐by‐wire system for full self‐driving vehicle. Here, we discuss a series of studies on the steering dynamics model and nonlinear transmission ratio of steering system that, collectively, design an angle tracking approach of how the model predictive control algorithm steers the front wheels precisely. The designed approach has been downloaded into a steering control unit and tested by some steering cycles in a steering test bench to fully realize angle tracking control of steer‐by‐wire system in practical engineering.
The diurnal cycle of the lightning potential index over the Mexican tropical continental region during tropical cyclone Bud
Authors: Clouthier‐Lopez Jorge , Barrón‐Fernández Ricardo , Salas‐de‐León David Alberto
Published: June 2022

Atmospheric processes over the Mexican continental territory can be influenced by the occurrence of tropical cyclones (TCs) over the adjacent oceans. Furthermore, the Mexican territory is characterized by the presence of diurnal cycles of lightning. The Lightning Potential Index (LPI), that is a measure of the potential for charge generation and separation that leads to lightning production in convective storms, was assessed for the diurnal variability of lightning that exhibited a strong diurnal cycle over the Mexican continental territory when TC Bud was over the adjacent eastern Pacific Ocean. The assessment, from 0000 UTC 10 June to 2000 UTC 15 June 2018, used the Weather Research and Forecasting (WRF) model with a new hybrid terrain‐following sigma‐pressure vertical coordinate. Two ensembles with various cumulus and microphysical parameterizations were performed with a grid spacing of 2 km. In one ensemble, sea surface temperature (SST) was prescribed from the Real‐time global (RTG) SST analysis product and allowed to evolve interactively with the modeled atmosphere. Then, all the ensemble members were compared against available observations from the World Wide Lightning Location Network (WWLLN) to evaluate which model configurations perform best. It is not known if the LPI is capable of reproducing diurnal cycles of lightning over tropical regions; and the results allow gaining an understanding of the LPI when it reproduces the observed diurnal variability of lightning over land. The ensemble members that had better performances were those that included the prescribed SST.
Unraveling the role of biofuels in road transport under rapid electrification
Authors: Cavalett Otavio , Cherubini Francesco
Published: June 2022

Biofuels have been the predominant option for climate change mitigation in road transport for decades, but the recent expansion of electric vehicles may bring into question their key role. In this work we model the energy use and life‐cycle emissions of road transport activities until 2050 in Norway, a country with a rapid growth in vehicle fleet electrification, to investigate the role that biofuels can play in climate change mitigation, and assess the implications for air pollution and human health. The mitigation benefits from biofuels peak around 2030 at 3.1 ± 0.45 MtCO2eq. year−1, approximately 30% of today's road transport emissions. The largest specific emission savings are achieved from biofuels in trucks and vans, for which the penetration of electric vehicles is slower. These results are consistent under different time horizons and climate metrics. The average impacts on human health are also decreased, but the uncertainty ranges for some biofuels options overlap with those of fossil fuels. Complementary and integrated strategies combining high electrification rates of the vehicle fleet with targeted applications of biofuels can increase the mitigation of road transport emissions. © 2022 The Authors. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.
Review of the state of science and evaluation of currently available in silico prediction models for reproductive and developmental toxicity: A case study on pesticides
Authors: Weyrich Anastasia , Joel Madeleine , Lewin Geertje , Hofmann Thomas , Frericks Markus
Published: June 2022

Background

In silico methods for toxicity prediction have increased significantly in recent years due to the 3Rs principle. This also applies to predicting reproductive toxicology, which is one of the most critical factors in pesticide approval. The widely used quantitative structure–activity relationship (QSAR) models use experimental toxicity data to create a model that relates experimentally observed toxicity to molecular structures to predict toxicity. Aim of the study was to evaluate the available prediction models for developmental and reproductive toxicity regarding their strengths and weaknesses in a pesticide database.

Methods

The reproductive toxicity of 315 pesticides, which have a GHS classification by ECHA, was compared with the prediction of different in silico models: VEGA, OECD (Q)SAR Toolbox, Leadscope Model Applier, and CASE Ultra by MultiCASE.

Results

In all models, a large proportion (up to 77%) of all pesticides were outside the chemical space of the model. Analysis of the prediction of remaining pesticides revealed a balanced accuracy of the models between 0.48 and 0.66.

Conclusion

Overall, predictions were only meaningful in rare cases and therefore always require evaluation by an expert. The critical factors were the underlying data and determination of molecular similarity, which offer great potential for improvement.
Influence of the anti‐oestrogens tamoxifen and letrozole on thyroid function in women with early and advanced breast cancer: A systematic review
Authors: Marina Djordje , Rasmussen Åse Krogh , Buch‐Larsen Kristian , Gillberg Linn , Andersson Michael , Schwarz Peter
Published: June 2022

Introduction

Breast cancer (BC) is a common type of cancer in women. Advances in therapy options have resulted in higher overall survival rates but side effects of cancer treatment are increasingly in the spotlight. The beneficial effects of anti‐oestrogen therapy with tamoxifen and letrozole in the prevention of BC recurrence are well documented. While the most common side‐effects of this therapy are well‐defined, less is known about its effects on thyroid function. In women treated for early BC, an average of 1–5 kg weight gain has been observed after treatment with chemotherapy/anti‐oestrogens. We aim to evaluate the current knowledge on the side effects of tamoxifen and letrozole treatments on thyroid function, followed by its potential influence on the observed weight gain.

Methods

We searched PubMed and found 16 publications on thyroid function and tamoxifen treatment in pre‐ and post‐menopausal women with early‐ and advanced BC, whereas five publications on letrozole treatment in post‐menopausal women with advanced BC.

Results

According to the current literature, there is an overall tendency towards a mild and transient thyroid dysfunction, that is, subclinical hypothyroidism in tamoxifen‐treated patients. Only one publication reported further significant changes in thyroid hormones beyond one year of tamoxifen treatment. No significant changes in thyroid function have been observed among letrozole‐treated patients.

Conclusion

Tamoxifen‐treated patients can develop mild and transient thyroid dysfunction within the first 12 months, yet further significant changes in thyroid function beyond one year of tamoxifen treatment have been reported in a single study. There is no evidence of thyroid dysfunction in letrozole‐treated patients. Current literature does not focus on subclinical hypothyroidism as a possible cause of weight gain in patients with BC. Subgrouping of BC patients and studies with a longer observation of thyroid hormones and weight changes during and after anti‐oestrogen treatment are needed to further elucidate how anti‐oestrogens affect thyroid function.
Ultrasound features of pregnancy‐associated breast cancer: A retrospective observational analysis
Authors: Jafari Maryam , Abbasvandi Fereshteh , Nazeri Elahe , Olfatbakhsh Asiie , Kaviani Ahmad , Esmaeili Rezvan
Published: June 2022

Pregnancy‐associated breast cancer (PABC) is a poor prognosis in women, and the mortality rate is higher in this subgroup of patients than in non‐PABC. This study aims to assess clinicopathological and ultrasound features of patients with PABC. Of 75 patients with breast cancer, 31 cases were in lactating, or pregnancy phase and 44 patients had no recent history of pregnancy/lactation at the time of cancer detection. The available pathological characteristics and ultrasound findings of the PABC and non‐PABC groups were compared. The analysis of ultrasound findings demonstrated that the percentages of antiparallel orientation (p = 0.04) and heterogeneous internal echo pattern (p = 0.002) were higher in the PABC group. The final Breast Imaging Reporting and Data System (BI‐RADS) assessment in the two groups was significantly different (p = 0.008). In this study, most PABCs were BI‐RADS 4c or 5; compared with age‐matched non‐PABC cases. There were significant differences in ER (p = 0.03), receptor groups (p = 0.007), and tumor grade (p = 0.02) in PABC compared to non‐PABC group. To conclude, radiologists should be careful about ultrasound findings of PABC and recommend core needle biopsy in suspected cases.
Modeling craftspeople for cultural heritage: A case study
Authors: Cadi Yazli Nedjma , Baka Evangelia , Magnenat‐Thalmann Nadia , Kaplanidi Danae , Partarakis Nikolaos , Karuzaki Effie , Zidianakis Manos , Pattakos Andreas , Zabulis Xenophon
Published: June 2022

Intangible heritage is often linked to human actions and performances. The use of digital humans (DHs) for its digital representation and therefore its preservation, allows reframing the way to transmit and deal with content that is difficult to visualize. To that end, the digital human becomes an important element establishing the connection between the action, the objects, the knowledge, and the environment. In this article, we describe the development of DHs acting as practitioners and storytellers for traditional craft processes within virtual environments. We present the process and the tasks involved in modeling, designing, and animating DHs, detailing the underlying technological background. Animations were completely based on real humans' motion extraction while working on the corresponding craft. As a result, we present the different DHs models created for three specific heritage crafts: mastic cultivation, glass blowing, and silk weaving as well as an AR application, built to augment exhibits of the Chios Mastic Museum. This article is a practical description of the steps to model and animate virtual humans. The work aims to bring a methodology for achieving DHs creation for CH applications.
Insight into the Potential of Meehania fargesii var. Radicans against Hp‐Induced Gastric Carcinoma Based on Phytochemical and Molecular Docking Studies
Authors: Zhou GuangXin , Song Ce , Liu XuePeng , Zhao JiaMing , Meng DaLi
Published: June 2022

We used UV‐guided method to isolate and identify 12 secondary metabolites from Meehania fargesii var. Radicans for the first time, including eight triterpenoids (1–8), two phenylpropanoid derivatives (9–10) and two flavone glycosides (11–12). Their structures were identified by NMR spectroscopic methods, as well as literature comparison. The identified compounds and positive drugs (amoxicillin, omeprazole and clarithromycin) were further analyzed for their in silico docking interactions with HtrA using igemdock. Docking studies revealed the high binding affinity of phytochemicals at significant sites with HtrA, compounds 11 and 12 exhibiting stronger binding ability than standard drug, 1 and 3–10 demonstrating comparable docking capacity to standard drugs. The chemotaxonomic relationships were carried out to exploring the possibilities of other medicinal plants against Hp‐induced gastric carcinoma. The results demonstrated there are closely chemotaxonomic similarity among several genera of the Lamiaceae family as well as among Lamiaceae, Actinidiaceae and Rosaceae families, indicating a similar chemical compositions and anti‐Hp‐induces gastric carcinoma activity among them.
Immobilized Eosin Y for the Photocatalytic Oxidation of Tetrahydroisoquinolines in Flow
Authors: Herbrik Fabian , Rossi Sergio , Sanz Miguel , Puglisi Alessandra , Benaglia Maurizio
Published: June 2022

A new easy‐to‐synthesize solid supported Eosin Y and its application in the building of a catalytic continuous flow reactor is reported. The fluidic device was employed to perform tertiary amines in‐flow photooxidations followed by a nucleophile addition, with overall productivity increased by one order magnitude. When using the iminium‐ions in situ generated or in a telescoped fashion, the resulting Mannich‐products were isolated with high diastereoselectivity and up to 90 % enantioselectivity, simply using air as terminal oxidant.
Revealing the Promotion Effects of Nb on Alkali Resistance of FeVO4/TiO2 Catalysts for NOx Reduction
Authors: Li Shuangxi , Hu Weiwei , Xu Ziqiang , Yu Huijun , Lan Tianwei , Han Lupeng , Zhang Dengsong
Published: June 2022

FeVO4‐based catalysts with a wide temperature window and high SO2 tolerance have attracted increasing attention for the selective catalytic reduction of NOx with NH3. However, the alkali‐resistance of FeVO4‐based catalysts is still challenging. In this study, the K‐resistance of FeVO4/TiO2 was markedly improved via the Nb modification. It was demonstrated that the adsorption and reactivity of NH3/NH4+ and NOx species on K poisoned FeVO4/TiO2 both decreased, which restrained the process of Langmuir‐Hinshelwood reaction path. As a comparison, more adsorption of NH3/NH4+ species and the higher reactivity with gaseous NO maintain the process of Eley‐Rideal reaction path, leading to a satisifactory SCR activity. This work demonstrated an effective route to improve alkali‐resistance via modulating reactivity and reaction path of adsorbed NH3/NH4+ and NOx species over Nb modified vanadate catalysts, which presented a new point for the development of high‐performance alkali‐resistant SCR catalysts.
Transition Metal‐Free Catalytic C−H Silylation of Terminal Alkynes with bis(Trimethylsilyl)acetylene Initiated by KHMDS
Authors: Kuciński Krzysztof , Hreczycho Grzegorz
Published: June 2022

Commercially available and inexpensive potassium bis(trimethylsilyl)amide (KHMDS) serves as an efficient transition metal‐free catalyst for the catalytic sp C−H silylation of several terminal alkynes including two pharmaceuticals. Overall, the presented system allows the synthesis of various attractive silylacetylenes under mild conditions, making this approach an environmentally benign and sustainable alternative to existing synthetic solutions.
C−H and Si−H Activation Reactions at Ru/Ga Complexes: A Combined Experimental and Theoretical Case Study on the Ru−Ga Bond
Authors: Muhr Maximilian , Bühler Raphael , Liang Hao , Gilch Jonas , Jandl Christian , Kahlal Samia , Saillard Jean‐Yves , Gemel Christian , Fischer Roland A.
Published: June 2022

Treatment of [Ru(COD)(MeAllyl)2] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to reactive intermediates which activate Si−H or C−H bonds, respectively. The product complexes [Ru(GaCp*)3(SiEt3)H3] (1) and [Ru(GaCp*)3(C7H7)H3] (2) are formed with HSiEt3or with toluene as the solvent, respectively. While1was isolated and fully characterized by NMR, MS, IR and SC‐XRD,2was too labile to be isolated and was observed and characterized in situ by using mass spectrometry, including labelling experiments for the unambiguous assignment of the elemental composition. The structural assignment was confirmed by DFT calculations. The relative energies of the four isomers possible upon toluene activation at theortho‐,meta‐,para‐ and CH3‐positions have been determined and point to aromatic C−H activation. The Ru−Ga bond was analyzed by EDA and QTAIM and compared to the Ru−P bond in the analogue phosphine compound. Bonding analyses indicate that the Ru‐GaCp* bond is weaker than the Ru‐PR3bond.
Nickel‐Catalyzed Electroreductive Syntheses of Triphenylenes Using ortho‐Dihalobenzene‐Derived Benzynes
Authors: Li Zhao‐Ming , Shuai Bin , Ma Cong , Fang Ping , Mei Tian‐Sheng
Published: June 2022

Comprehensive Summary

Electrochemical nickel‐catalyzed syntheses of triphenylenes by a) reductive trimerization of ortho‐dibromobenzenes or ortho‐bromoarylsulfurofluoridates, or b) reductive cross‐coupling of ortho‐dibromobenzenes to 2,2’‐diiodobiphenyls, are described. The former provides a practical means for the construction of triphenylene derivatives in up to 87% isolated yield at room temperature. For 1,2‐dihalo‐3‐methylbenzenes and related ortho‐trisubstituted substrates, trimerizations proceed with high substrate‐controlled regioselectivity for the non‐C3h symmetric triphenylene isomer.
Quantifying the hidden impact of COVID‐19 pandemic: The cytology perspective
Authors: Yousefi Elham , Cibas Edmund S. , Mito Jeffrey K.
Published: June 2022

Background

The burden of the COVID‐19 pandemic is often enumerated in lives lost, but the strain on health care resources and mobility limitations contributed to the burden of non–COVID related disease. In this study, we evaluated the impact of the pandemic through a time series review of cytology samples.

Methods

Pathology reports for all cytology specimens received from January 2019 through April 2021 at our institution were reviewed. Time series analysis was performed using moving averages, time trend analysis, cross‐correlation, and tests of homogeneity.

Results

During the first peak of the pandemic (March–June 2020), breakpoint analysis showed a downward shift in the number of gynecologic (−89.4%) and non‐gynecologic (−70.4%) cytology specimens within a week of declaration of an emergency. Cross‐correlation analysis showed a relationship between sample numbers and COVID‐19 cases during the initial phase of the pandemic (April–June 2020). During the second surge (October 2020–April 2021), despite the higher incidence of COVID‐19, there was a smaller impact on cytology samples (−20.1% and − 24.8% for gynecologic and non‐gynecologic samples, respectively). During the first 3 months of the pandemic, 154 fewer malignant cases were identified compared with the prior year. Although specimen numbers slowly returned to baseline following the first wave of the pandemic, the earlier decline in malignant diagnoses was not offset during the study period.

Conclusions

The deleterious effects of COVID‐19 extend beyond direct mortality attributed to the disease. The significant decrease in diagnostic cytology specimens during this period has profound implications including delayed care and missed disease.
Novel insights on [1,2]oxazolo[5,4‐e]isoindoles on multidrug resistant acute myeloid leukemia cell line
Authors: Labbozzetta Manuela , Barreca Marilia , Spanò Virginia , Raimondi Maria Valeria , Poma Paola , Notarbartolo Monica , Barraja Paola , Montalbano Alessandra
Published: June 2022

A series of [1,2]oxazolo[5,4‐e]isoindole derivatives was evaluated against HL‐60 cell line and its multidrug resistance (MDR) variant, HL‐60R, resistant to doxorubicin and to other P‐gp substrates by overexpressing the efflux pump. They displayed antiproliferative activities, with IC50 values ranging from 0.02 to 5.5 µM. In particular, the newly synthesized compound 4k produced synergistic effects in terms of cell growth inhibition and cell death induction either in combination with a Vinca alkaloid, Vinblastine, and a Taxane, Paclitaxel in HL‐60R cells. The study of the mechanism of action indicated that all compounds showed antimitotic activity through inhibition of tubulin polymerization. Thus, [1,2]oxazoles could represent a valuable tool to overcome MDR mechanism, confirming the potential use of this class of compounds.
Multiple‐region,N‐mixture community model to assess associations of riparian area, fragmentation, and species richness
Authors: Fogarty Frank A. , Yen Jian D. L. , Fleishman Erica , Sollmann Rahel , Ke Alison
Published: June 2022

The associations of habitat area and fragmentation with species richness long have been major topics within community ecology. Recent discussion has focused on properly assessing fragmentation independent of habitat area (fragmentation per se), and on whether fragmentation has significant negative or positive associations with species richness. We created a novel, multiple‐region, N‐mixture community model (MNCM) to examine the relations of riparian area and fragmentation with species richness of breeding birds in mountain ranges within the Great Basin, Nevada, USA. Our MNCM accounts for imperfect detection in count data at the survey‐point level while allowing comparisons of species richness among regions in which those points are embedded. We used individual canyons within mountain ranges as regions in our model and measured riparian area and the Normalized Landscape Shape Index, a metric of fragmentation that is independent of total riparian area. We found that riparian area, but not its fragmentation, was a primary predictor of canyon‐level species richness of both riparian obligates and all species. The relationship between riparian area and riparian obligate species richness was nonlinear: canyons with ≥25 ha woody riparian vegetation had relatively high species richness, whereas species richness was considerably lower in canyons with <25 ha. Our MNCM can be used to calculate other metrics of diversity that require abundance estimates. For example, Simpson's evenness of riparian obligate species had a weak negative association with riparian area and was not associated with fragmentation. Projections of future riparian contraction suggested that decreases in species richness are likely to be greatest in canyons that currently have moderate (~10–25 ha) amounts of riparian vegetation. Our results suggest that if a goal of management is to maximize the species richness of breeding birds in montane riparian areas in the Great Basin, it may be more effective to focus on total habitat area than on fragmentation of patches within canyons, and that canyons with at least moderate amounts of riparian vegetation should be prioritized.
Histopathological and epigenetic changes in myocardium associated with cancer therapy‐related cardiac dysfunction
Authors: Terada Chiyoko‐Ikeda , Onoue Kenji , Fujii Tomomi , Itami Hiroe , Morita Kohei , Uchiyama Tomoko , Takeda Maiko , Nakagawa Hitoshi , Nakano Tomoya , Baba Youichirou , Amemiya Kisaki , Saito Yoshihiko , Hatakeyama Kinta , Ohbayashi Chiho
Published: June 2022

Aims

Cancer therapy‐related cardiac dysfunction (CTRCD) is commonly reported, but its histopathology, mechanisms, and risk factors are not known. We aimed to clarify the histopathology and mechanisms of CTRCD to identify risk factors.

Methods and results

We performed myocardial histopathological studies on 13 endomyocardial biopsies from CTRCD patients, 35 autopsied cancer cases with or without cardiac dysfunction, and controls without cancer (10 biopsies and 9 autopsies). Cardiotoxicity risk scores were calculated based on medication; and patient‐related risk factors, fibrosis, and cardiomyocyte changes were scored; and p53 and H3K27ac histone modification were evaluated by histological score (H‐score). In the biopsy cases, all histopathological changes and the p53 evaluation were significantly higher in the CTRCD group than in the controls [p53 H‐score; 63 (9.109) vs. 33 (5.099), P < 0.05]. In patients with a short time between drug and disease onset (<4.2 years), fibrosis and p53 positively correlated (r = 0.76, P < 0.05), and in those with late onset disease (>4.2 years), cellular abnormalities and p53 trended to a positive correlation and cardiotoxicity risk scores and p53 positively correlated (r = 0.95, P < 0.05). A year after biopsy, the short‐term group had significant recovery of ejection fraction compared with the long‐term group (P < 0.05). The CTRCD group had a significantly worse overall survival prognosis than the control group [hazard ratio 7.61 (95% confidence interval 1.30–44.6), P < 0.05]. Autopsy cases with cancer treatment also had a high grade of histopathological changes, with even more severe changes in patients with cardiac dysfunction, and had increased p53 and H3K27ac expression levels, compared with controls. H‐scores of p53 and H3K27ac showed a positive correlation in the CTRCD group in biopsy cases (r = 0.62, P < 0.05) and a positive correlation in autopsy cases.

Conclusions

Our results indicate distinct morphological characteristics in myocardial histopathology associated with CTRCD. p53 and H3K27ac histone modification could be sensitive markers of CTRCD and suggest a mechanistic involvement of epigenetic changes.
D‐dimer and outcomes in hospitalized heart failure patients across the ejection fraction phenotypes
Authors: Huang Liyan , Liang Lin , Tian Pengchao , Zhao Lang , Chen Yuyi , Huang Yan , Zhou Qiong , Zhai Mei , Zhang Yuhui , Ambrosio Giuseppe , Zhang Jian
Published: June 2022

Aims

The prognostic significance of D‐dimer in hospitalized heart failure (HF) patients is incompletely characterized. We aimed to assess the association of D‐dimer levels on admission with adverse events at follow‐up in patients hospitalized with HF across all ejection fraction (EF) phenotypes.

Methods and results

Consecutive patients hospitalized from December 2006 to December 2017 for HF with D‐dimer and EF values available (n = 1795) were enrolled. Associations between D‐dimer and all‐cause death were examined at 1‐year follow‐up. Median age was 57 years, 73.4% were male, and the majority (72.1%) were in New York Heart Association Classes III–IV. EF was reduced in 53.3% (HFrEF), mildly reduced in 16.3% (HFmrEF), and preserved in 30.4% (HFpEF). Median (interquartile range) D‐dimer on admission was 0.56 (0.27–1.295) μg/mL FEU (fibrinogen‐equivalent unit) in the whole cohort, 0.64 (0.28–1.48) μg/mL FEU in HFrEF, 0.50 (0.27–1.03) μg/mL FEU in HFmrEF, and 0.495 (0.25–1.10) μg/mL FEU in HFpEF (P = 0.001). At 1‐year follow‐up, higher D‐dimer (D‐dimer ≥0.56 μg/mL FEU) independently predicted all‐cause death in total cohort [hazard ratio (HR) 1.55; 95% confidence interval (CI), 1.15–2.1], in HFrEF (HR, 1.49; P = 0.039), and in HFpEF (HR, 2.06; P = 0.033). However, no relationship was found for HFrEF or HFmrEF when D‐dimer was treated as quartiles. In sensitivity analysis, quantitatively similar but more pronounced association between D‐dimer and all‐cause death was observed in total cohort and HFpEF cohort.

Conclusions

In hospitalized HF patients, higher D‐dimer concentration was a significant and independent predictor of 1‐year all‐cause mortality. Across all HF phenotypes, this effect was most evident in HFpEF patients.
Clinical implications of left atrial changes after optimization of medical therapy in patients with heart failure
Authors: Inciardi Riccardo M. , Pagnesi Matteo , Lombardi Carlo M. , Anker Stefan D. , Cleland John G. , Dickstein Kenneth , Filippatos Gerasimos S. , Lang Chim C. , Ng Leong L. , Pellicori Pierpaolo , Ponikowski Piotr , Samani Nilesh J. , Zannad Faiez , van Veldhuisen Dirk J. , Solomon Scott D. , Voors Adriaan A. , Metra Marco
Published: June 2022

Aims

Limited data exist regarding the prognostic relevance of changes in left atrial (LA) dimensions in patients with heart failure (HF). We assessed changes in LA dimension and their relation with outcomes after optimization of guideline‐directed medical therapy (GDMT) in patients with new‐onset or worsening HF.

Methods and results

Left atrial diameter was assessed at baseline and 9 months after GDMT optimization in 632 patients (mean age 65.8 ± 12.1 years, 22.3% female) enrolled in BIOSTAT‐CHF. LA adverse remodelling (LAAR) was defined as an increase in LA diameter on transthoracic echocardiography between baseline and 9 months. After the 9‐month visit, patients were followed for a median of 13 further months. LAAR was observed in 247 patients (39%). Larger baseline LA diameter (odds ratio [OR] 0.90; 95% confidence interval [CI] 0.87–0.93; p < 0.001) and up‐titration to higher doses of angiotensin‐converting enzyme inhibitors or angiotensin receptor blockers (ACEi/ARBs) (OR 0.56; 95% CI 0.34–0.92; p = 0.022) were independently associated with lower likelihood of LAAR. LAAR was associated with an increased risk of the composite of all‐cause mortality or HF hospitalization (log‐rank p = 0.007 and adjusted hazard ratio 1.73, 95% CI 1.22–2.45, p = 0.002). The association was more pronounced in patients without a history of atrial fibrillation (p for interaction = 0.009).

Conclusion

Among patients enrolled in BIOSTAT‐CHF, LAAR was associated with an unfavourable outcome and was prevented by ACEi/ARB up‐titration. Changes in LA dimension may be a useful marker of response to treatment and improve risk stratification in patients with HF.
Hybridization of Palladium Nanoparticles with Aromatic‐Rich SU‐101 Metal‐Organic Framework for Effective Transfer Hydrogenation
Authors: Krishnaveni Valle , Esclance DMello Marilyn , Basavaiah Keloth , Samsonu Dasi , Rambhia Dheer A. , Kalidindi Suresh Babu
Published: June 2022

Metal‐organic frameworks (MOFs) are crystalline porous materials with designable pores. In this study, we loaded Pd nanoparticles onto π‐electron rich pores of ellagic acid based SU‐101 MOF (Bi2O(H2O)2(C14H2O8) ⋅ nH2O) in order to surround Pd active sites with π‐electron rich environment. The material has been explored for the transformation of 4‐Nitro phenol (4‐NP) to 4‐Amino phenol (4‐AP) using ammonia borane (AB). AB acted as efficient transfer hydrogenation agent compared to NaBH4 because of its ability to transfer hydrogens at milder conditions. AB is safer and easy to handle compared to molecular hydrogen or NaBH4. The Pd NPs are loaded on to SU‐101 using two methodologies. One by supporting preformed Pd NPs onto MOF surface (Pd‐WCGA/SU‐101) and the other by wet impregnation method (Pd/SU‐101). The later method yields a material with strong interaction between Pd and SU‐101. The Pd/SU‐101 exhibited superior activity for 4‐NP reduction (turn over frequency=2421 h−1) using AB due to an enrichment of 4‐NP around Pd active sites by π‐electron rich pore environment.
Diphenylprolinol Silyl Ether Catalyzed Asymmetric Formal Carbo [3+3] Cycloaddition Reaction of Isopropylidenemalononitrile and α,β‐Unsaturated Aldehyde
Authors: Umekubo Nariyoshi , Han Xiaolei , Mori Naoki , Hayashi Yujiro
Published: June 2022

Enantioselective formal carbo [3+3] cycloaddition reaction of isopropylidenemalononitrile (1) and α,β‐unsaturated aldehyde, catalyzed by diphenylprolinol silyl ether, was developed. The reaction is a domino Michael/aldol‐type reaction, followed by Al2O3‐mediated dehydration to afford 5‐substituted cyclohexene derivatives possessing a methylene‐malononitrile moiety, with excellent enantioselectivity.
Potential Application of Carbon‐based Electrical Sensor for the Highly Sensitive Diltiazem HCl Quantification in its Pharmaceutical Products and Biological Samples
Authors: Mohamed Marwa El Badry , Heakal Fakiha El‐Taib
Published: June 2022

Diltiazem (DTZ) hydrochloride, a calcium channel blocker compound, is a very well‐known drug used by many clinicians to treat important diseases playing a role in increased morbidity and mortality among adults worldwide, namely hypertension, cardiac arrhythmia, and ischemic heart disease (angina pectoris). These diseases are a common public health concern, implying that the construction of a specific, accurate, and simple sensor for DTZ determination is needed. Herein, an innovative, portable, and sensitive modified carbon paste electrode (MCPE) was seamlessly developed based on the affordable green compound N‐bromosuccinimide (NBS) as a sensing material and tricresyl phosphate as a solvent mediator for the voltammetric determination of DTZ. The proposed NBS‐MCPE exhibited an excellent electrocatalytic activity towards the oxidation of DTZ molecules in a phosphate buffer solution of pH 5.0 in presence of 20 μM sodium dodecyl sulfate to improve the developed sensor performance. The sensor was found to respond linearly to the DTZ drug over a wide concentration ranging from 1 μM to 300 μM with a low limit of detection. LSV and EIS measurements were also used to scrutinize our sensor, in addition to using scanning electron microscopy and energy dispersive X‐ray analysis techniques for its surface morphology inspection before and after soaking in the drug‐containing solution. The applicability of the proposed sensor for the rapid, sensitive, and selective determination of DTZ in pharmaceutical preparation and human urine samples was assessed and the obtained results were compared with that of the reported HPLC analytical method.
Blue hydrogen must be done properly
Authors: Pettersen Jostein , Steeneveldt Rosetta , Grainger David , Scott Tyler , Holst Louise‐Marie , Hamborg Espen Steinseth
Published: June 2022

Future energy scenarios include both green and blue hydrogen, as both are needed to scale up decarbonized energy supply. A transition to renewable energy is predicted over time, but the urgency we are facing cannot be met by renewable energy alone. For blue hydrogen production, the overall greenhouse gas (GHG) emissions are primarily affected by emissions from natural gas production, processing, and transport (CO2 and methane), as well as process efficiency and carbon capture ratio. Few complete and updated analyses are available that cover the entire blue hydrogen value chain with the best available technology for process facilities, as well as the proper design, operation, and maintenance of all relevant systems and infrastructure. This paper analyses the GHG intensity of blue hydrogen, using recent data as well as input from technology providers on state‐of‐the‐art gas reforming technologies. Data are primarily based on natural gas production and transport in the North Sea Basin, with gas export from the Norwegian continental shelf to continental Europe or the United Kingdom, and with blue hydrogen production either in Norway or near pipeline landfall in the European Union or United Kingdom. Some data related to potential blue hydrogen production in the US Appalachian region are also given. The data show that the properly designed and operated value chains for blue hydrogen supply, with minimal emissions from natural gas supply and high carbon capture in hydrogen production, will give a major reduction in GHG emissions from energy end‐use. GHG footprint for end‐users based on blue hydrogen will typically be 80%–90% lower than for direct supply and use of natural gas.
Contextualizing social networks: The role of person–organization fit in the network–job performance relationship
Authors: Soltis Scott M. , Dineen Brian R. , Wolfson Mikhail A.
Published: June 2022

While scholars have attended to the performance implications of employee embeddedness in social networks within the workplace, less research accounts for the interface of employee and organizational values in enabling employees to leverage these networks. Network perspectives on employee performance acknowledge that certain informal network positions create resources that are beneficial for performance while simultaneously creating demands that may diminish or erode these benefits. Leveraging a Job Demands‐Resources (JD‐R) perspective, we suggest that person–organization (PO) fit—the perceived congruence between individual and organizational values—will play a crucial role in shaping the performance effects of demands and resources inherently generated by workplace relationships. Results suggest that PO fit moderates relationships between network positions and individual job performance. Specifically, we find that having many friendships or being heavily sought out for advice enhances performance for those with higher levels of PO fit. Supplemental analyses highlight that incoming friendships or advice ties that are cross‐functional are still beneficial for those among the highest in PO fit, but also that these same network positions can be detrimental for employees who are among the lowest in PO fit. These results contribute to a more nuanced understanding of the demands and resources generated by informal networks and how the translation of these features into performance is contingent upon the extent to which an employee identifies with organizational values.
Role of electromagnetic analysis in radiative immiscible Newtonian and non‐Newtonian fluids through a microchannel with chemical reactions
Authors: Gajbhiye Sneha , Warke Arundhati , Katta Ramesh
Published: June 2022

The study of an immiscible fluid plays a significant role in the field of petroleum extraction, blood flow in arteries, hydrology, manufacturing process, and reservoir mechanics. These phenomena include immiscible fluids of different densities and viscosities in the same channel. Due to the various practical applications, in the current study, the generalized Couette flow of two immiscible fluids (Newtonian and non‐Newtonian fluids) of different viscosities between two infinite parallel plates under the presence of constant pressure gradient and electroosmosis is addressed. The effects such as electromagnetohydrodynamics, zeta potential, Joule heating, thermal radiation, modified Darcy's law, and chemical reaction have been also considered into account. The dimensional system of equations has been nondenationalized with suitable dimensionless quantities. The resulting nondimensional system of coupled flow equations has been solved analytically. The solutions for the velocity, temperature, and concentration have been presented. The effect of various pertinent fluid flow parameters has been displayed graphically. The current study concludes that both the velocity and temperature profiles decrease with the increase in Hartmann number and radiation parameter, whereas an increase in chemical reaction parameter uplifts the concentration of both fluids.