bluuebunny/crossref_metadata_2025 huggingface dataset:
Electroacupuncture reactivates estrogen receptors to restore the neuroprotective effect of estrogen against cerebral ischemic stroke in long‐term ovariectomized rats
Authors: Ma Yulong , Niu Erlong , Xie Fei , Liu Min , Sun Miao , Peng Ye , Guo Hang
Published: September 2021

Background

Stroke is a sexually dimorphic disease and a leading cause of death and disability. Estrogen replacement therapy (ERT) confers beneficial neuroprotective effects if administered within a widely accepted time window called the “critical period.” However, very few studies have explored the idea of modulating the critical period to enable long‐term post‐menopausal women to regain more benefits from estrogen therapy. Here, motivated by previous findings that electroacupuncture could both alter estrogen metabolism and induce significant tolerance against stroke, it was explored whether EA could restore estrogen's neuroprotection against cerebral ischemia in long‐term ovariectomized (OVX) rats.

Methods

We implemented 1 week(w)‐EA pretreatment on OVX‐10w or OVX‐20w rats, and tested the expression of estrogen receptors, and detected the ERT's neuroprotection against stroke induced by middle cerebral artery occlusion (MCAO).

Results

We found that the expression levels of phospho‐ERα‐S118 and estrogen receptor β (ERβ) in the striatum of OVX‐10w rats were significantly decreased and ERT's neuroprotection was abolished in the OVX‐10w rats. However, EA‐1w pretreatment could significantly recover the expression levels of phospho‐ERα‐S118 and ERβ, and also restored the neuroprotective effects of ERT in OVX‐10w rats. However, EA‐1w pretreatment could not restore the expression of estrogen receptors and ERT's neuroprotection in OVX‐20w rats.

Conclusion

Taken together, our study indicates that EA may be an easy intervention that can restore the efficacy of estrogen therapy during the “critical period,” which has the potential to improve the stroke outcomes of an enormous number of long‐term post‐menopausal women. However, the time‐sensitive influences for how EA and estrogen metabolism interact with each other should be considered.
Comprehensive analysis of pan‐cancer reveals potential of ASF1B as a prognostic and immunological biomarker
Authors: Hu Xinyao , Zhu Hua , Zhang Xiaoyu , He Xiaoqin , Xu Ximing
Published: September 2021

Background

Anti‐silencing function 1 (ASF1) is a conserved histone H3–H4 chaperone protein. ASF1B, a paralog of ASF1, acts by promoting cell proliferation and influencing cell cycle progression. Although there is some evidence demonstrating that ASF1B plays a key role in the development, progression, and prognosis of certain cancers, there are no pan‐cancer analyses of ASF1B.

Methods

We used a range of bioinformatics approaches to investigate the predictive role of ASF1B, including its correlation with prognosis, tumor mutational burden (TMB), microsatellite instability (MSI), tumor microenvironment (TME), and immune cell infiltration, in diverse cancer types.

Results

We found that ASF1B was highly expressed in 22 cancers and was negatively correlated with the prognosis of multiple major cancer types. Furthermore, ASF1B expression was correlated with TMB in 21 cancers and with MSI in 7 cancers. We found that ASF1B was coexpressed with genes encoding immune activators, immune suppressors, major histocompatibility complexes, chemokines, and chemokine receptors. We further found that the role of ASF1B in the infiltration of different types of immune cells varied across tumor types. ASF1B may potentially affect several key immune‐related pathways, such as those involved in antigen processing and presentation, natural killer cell‐mediated cytotoxicity, and autoimmune thyroid disease.

Conclusions

Our findings show that ASF1B may serve as a prognostic marker and potential immunotherapeutic target for several malignancies due to its role in tumorigenesis and immune infiltration.
Unravelling the Selectivity of 6,7‐Dimethyl Quinoxaline Analogs for Kinase Inhibition: An Insight towards the Development of Alzheimer's Therapeutics
Authors: Kumar Jain Arvind , Gupta Arindam , Karthikeyan C. , Trivedi Piyush , Dutt Konar Anita
Published: September 2021

Untangling the most selective kinase inhibitors via pharmacological intervention remains one of the challenging affairs to date. In accordance to this drift, herein we describe the design and synthesis of a set of new heterocyclic analogs consisting of 6,7‐dimethyl Quinoxaline, appended to a connector, employing Schiff base strategy (Compounds I–IX). The compounds were characterized by various spectroscopic techniques and the kinase inhibition assay were performed on few prime members of the CMGC family namely the GSK3β, DYRK1A and CLK1 receptors, respectively, that have been known to be directly involved in hyperphosphorylation of Tau. Interestingly the biological evaluation results revealed that Compounds IV and V, with bromo/chloro functionalities in the aromatic core were advantaged of being highly selective towards the target GSK3β over others. To strengthen our analysis, we adopted molecular modelling studies, where compounds IV/V were redocked in the same grid 4AFJ, as that of the reference ligand, 5‐aryl‐4‐carboxamide‐1,3‐oxazole. Surprisingly, our investigation underpinned that for both the compounds IV/V, a primary H‐bonding existed between the designed molecules (IV/V) and Val 135 residue in the receptor GSK3β, in line with the reference ligand. We attribute this interaction to instigate potency in the compounds. Indeed the other non‐covalent interaction, between the derivative's aromatic nucleus and Arg 141/Thr 138 in the receptor GSK3β, might have been responsible for enhancing the selectivity in the targets. Overall, we feel that the present work depicts a logical demonstration towards fine tuning the efficacy of the inhibitors through systematic adjustment of electron density at appropriate positions in the aromatic ring be it the main quinoxaline or the other aromatic nucleus. Thus this pathway offers a convenient strategy for the development of efficient therapeutics for diversified neurodegenerative diseases like that of Alzheimer's.
Boosting the Electrocatalytic Activity of Fe−Co Dual‐Atom Catalysts for Oxygen Reduction Reaction by Ligand‐Modification Engineering
Authors: Li Lei , Li Yameng , Huang Rao , Cao Xinrui , Wen Yuhua
Published: September 2021

Development of high‐efficiency and low‐cost electrocatalysts as the platinum substitute for the oxygen reduction reaction (ORR) is of significance for electrochemical energy conversion and storage devices, such as fuel cells and rechargeable batteries. Here we report graphene‐based nitrogen‐coordinated Fe−Co dual‐atom catalysts (referred to as FeCoN6) with markedly enhanced ORR activity by ligand‐modification. By density functional theory calculations, we thoroughly investigated the ORR activity of three preferred FeCoN6 isomers (denoted as FeCoN6‐I, FeCoN6‐II, and FeCoN6‐III) and their complexes with the ligands of ORR intermediates such as *O, *OH, and *O2. Our results reveal that these ligands cause the apparent shift of d‐orbitals of metal atoms toward the Fermi level to modulate the adsorption strength for reaction intermediates, thereby significantly improving the ORR activity of FeCoN6 complexes. Notably, FeCoN6‐I(OH) and FeCoN6‐I(O2) with the lowest overpotential of ∼0.23 V possessed the best ORR activity, which are superior to pristine FeCoN6 and available Pt catalysts. These results not only build on the fundamental understanding of the catalytic mechanism of ligand modified dual‐atom catalysts but also provide a new strategy to develop highly efficient ORR electrocatalysts by ligand‐modification engineering.
Hydrogen Production by Methane Pyrolysis in a Molten‐Metal Bubble Column
Authors: Zaghloul Nada , Kodama Satoshi , Sekiguchi Hidetoshi
Published: September 2021

Hydrogen was produced by methane pyrolysis in a molten‐metal bubble column reactor. The proposed reactor improves heat transfer to the reactant gas and allows the separation of solid carbon due to the density difference between the molten metal and produced carbon. The effects of the temperature of the molten metal and metal type on the process were studied. The kinetic parameters were estimated by using a semi‐numerical model of two reactors in series developed for the system. Molten tin, as reaction medium, showed improved kinetic parameters compared to those of the conventional tubular reactor. Tin‐copper and tin‐nickel alloys were also used as molten media to study the effect of catalytically active metals. The produced carbon was analyzed to examine its morphology and purity.
How to Look for Compounds: Predictive Screening and in situ Studies in Na−Zn−Bi System
Authors: Gvozdetskyi Volodymyr , Wang Renhai , Xia Weiyi , Zhang Feng , Lin Zijing , Ho Kai‐Ming , Miller Gordon , Zaikina Julia V.
Published: September 2021

Here, the combination of theoretical computations followed by rapid experimental screening and in situ diffraction studies is demonstrated as a powerful strategy for novel compounds discovery. When applied for the previously “empty” Na−Zn−Bi system, such an approach led to four novel phases. The compositional space of this system was rapidly screened via the hydride route method and the theoretically predicted NaZnBi (PbClF type, P4/nmm) and Na11Zn2Bi5 (Na11Cd2Sb5 type, P
) phases were successfully synthesized, while other computationally generated compounds on the list were rejected. In addition, single crystal X‐ray diffraction studies of NaZnBi indicate minor deviations from the stoichiometric 1 : 1 : 1 molar ratio. As a result, two isostructural (PbClF type, P4/nmm) Zn‐deficient phases with similar compositions, but distinctly different unit cell parameters were discovered. The vacancies on Zn sites and unit cell expansion were rationalized from bonding analysis using electronic structure calculations on stoichiometric “NaZnBi”. In‐situ synchrotron powder X‐ray diffraction studies shed light on complex equilibria in the Na−Zn−Bi system at elevated temperatures. In particular, the high‐temperature polymorph HT‐Na3Bi (BiF3 type, Fm
m) was obtained as a product of Na11Zn2Bi5 decomposition above 611 K. HT‐Na3Bi cannot be stabilized at room temperature by quenching, and this type of structure was earlier observed in the high‐pressure polymorph HP‐Na3Bi above 0.5 GPa. The aforementioned approach of predictive synthesis can be extended to other multinary systems.
A Water Soluble Pd2L4 Cage for Selective Binding of Neu5Ac
Authors: Schaapkens Xander , van Sluis Roy N. , Bobylev Eduard O. , Reek Joost N. H. , Mooibroek Tiddo J.
Published: September 2021

The sialic acid N‐acetylneuraminic acid (Neu5Ac) and its derivatives are involved in many biological processes including cell‐cell recognition and infection by influenza. Molecules that can recognize Neu5Ac might thus be exploited to intervene in or monitor such events. A key obstacle in this development is the sparse availability of easily prepared molecules that bind to this carbohydrate in its natural solvent; water. Here, we report that the carbohydrate binding pocket of an organic soluble [Pd2L4]4+ cage could be equipped with guanidinium‐terminating dendrons to give the water soluble [Pd2L4][NO3]16 cage 7. It was shown by means of NMR spectroscopy that 7 binds selectively to anionic monosaccharides and strongest to Neu5Ac with Ka=24 M−1. The cage had low to no affinity for the thirteen neutral saccharides studied. Aided by molecular modeling, the selectivity for anionic carbohydrates such as Neu5Ac could be rationalized by the presence of charge assisted hydrogen bonds and/or the presence of a salt bridge with a guanidinium solubilizing arm of 7. Establishing that a simple coordination cage such as 7 can already selectively bind to Neu5Ac in water paves the way to improve the stability, affinity and/or selectivity properties of M2L4 cages for carbohydrates and other small molecules.
Water‐Assisted Chemical Route Towards the Oxygen Evolution Reaction at the Hydrated (110) Ruthenium Oxide Surface: Heterogeneous Catalysis via DFT‐MD and Metadynamics Simulations
Authors: Creazzo Fabrizio , Luber Sandra
Published: September 2021

Notwithstanding that RuO2 is a promising catalyst for the oxygen evolution reaction (OER), a plethora of fundamental details on its catalytic properties are still elusive, severely limiting its large‐scale deployment. It is also established experimentally that corrosion and wettability of metal oxides can, in fact, enhance the catalytic activity for OER owing to the formation of a hydrated surface layer. However, the mechanistic interplay between surface wettability, interfacial water dynamics and OER across RuO2, and what degree these processes are correlated are still debated. Herein, spin‐polarized Density Functional Theory Molecular Dynamics (DFT‐MD) simulations, coupled with advanced enhanced sampling methods in the well‐tempered metadynamics framework, are applied to gain a global understanding of RuO2 aqueous interface (explicit water solvent) in catalyzing the OER, and hence possibly help in the design of novel catalysts in the context of photochemical water oxidation. The present study quantitatively assesses the free‐energy barriers behind the OER at the (110)‐RuO2 catalyst surface revealing plausible pathways composing the reaction network of the O2 evolution. In particular, OER is investigated at room temperature when such a surface is exposed to both gas‐phase and liquid‐phase water. Albeit a unique efficient pathway has been identified in the gas‐phase OER, a surprisingly lowest‐free‐energy‐requiring reaction route is possible when (110)‐RuO2 is in contact with explicit liquid water. By estimating the free‐energy surfaces associated to these processes, we reveal a noticeable water‐assisted OER mechanism which involves a crucial proton‐transfer‐step assisted by the local water environment. These findings pave the way toward the systematic usage of DFT‐MD coupled with metadynamics techniques for the fine assessment of the activity of catalysts, considering finite‐temperature and explicit‐solvent effects.
On the Origin of the Non‐Planarity in Biarylsilyloxonium Ions
Authors: Fernandes Anthony J. , Robert Frederic , Landais Yannick , Künzler Sandra , Müller Thomas
Published: September 2021

The structure determination of a series of biphenylsilyloxonium cations through NMR and XRD studies, supported by DFT calculations was carried out, allowing to get insights into the origin of the oxygen pyramidalization in biphenyl and binaphthylsilyl oxoniums. Low barrier of inversion in the oxygenyl series points toward a key role of the biaryl axis in the inversion of configuration at the oxygen center.
Computational Study of Bridge Splitting, Aryl Halide Oxidative Addition to PtII, and Reductive Elimination from PtIV: Route to Pincer‐PtII Reagents with Chemical and Biological Applications
Authors: Canty Allan J. , Ariafard Alireza , van Koten Gerard
Published: September 2021

Density functional theory computation indicates that bridge splitting of [PtIIR2(μ‐SEt2)]2 proceeds by partial dissociation to form R2Pta(μ‐SEt2)PtbR2(SEt2), followed by coordination of N‐donor bromoarenes (L‐Br) at Pta leading to release of PtbR2(SEt2), which reacts with a second molecule of L‐Br, providing two molecules of PtR2(SEt2)(L‐Br‐N). For R=4‐tolyl (Tol), L‐Br=2,6‐(pzCH2)2C6H3Br (pz=pyrazol‐1‐yl) and 2,6‐(Me2NCH2)2C6H3Br, subsequent oxidative addition assisted by intramolecular N‐donor coordination via PtIITol2(L‐N,Br) and reductive elimination from PtIV intermediates gives mer‐PtII(L‐N,C,N)Br and Tol2. The strong σ‐donor influence of Tol groups results in subtle differences in oxidative addition mechanisms when compared with related aryl halide oxidative addition to palladium(II) centres. For R=Me and L‐Br=2,6‐(pzCH2)2C6H3Br, a stable PtIV product, fac‐PtIVMe2{2,6‐(pzCH2)2C6H3‐N,C,N)Br is predicted, as reported experimentally, acting as a model for undetected and unstable PtIVTol2{L‐N,C,N}Br undergoing facile Tol2 reductive elimination. The mechanisms reported herein enable the synthesis of PtII pincer reagents with applications in materials and bio‐organometallic chemistry.
Investigation of CO2 Orientational Dynamics through Simulated NMR Line Shapes**
Authors: Melix Patrick , Heine Thomas
Published: September 2021

The dynamics of carbon dioxide in third generation (i. e., flexible) Metal‐Organic Frameworks (MOFs) can be experimentally observed by 13C NMR spectroscopy. The obtained line shapes directly correlate with the motion of the adsorbed CO2, which in turn are readily available from classical molecular dynamics (MD) simulations. In this article, we present our publicly available implementation of an algorithm to calculate NMR line shapes from MD trajectories in a matter of minutes on any current personal computer. We apply the methodology to study an effect observed experimentally when adsorbing CO2 in different samples of the pillared layer MOF Ni2(ndc)2(dabco) (ndc=2,6‐naphthalene‐dicarboxylate, dabco=1,4‐diazabicyclo‐[2.2.2]‐octane), also known as DUT‐8(Ni). In 13C NMR experiments of adsorbed CO2 in this MOF, small (rigid) crystals result in narrower NMR line shapes than larger (flexible) crystals. The reasons for the higher mobility of CO2 inside the smaller crystals is unknown. Our ligand field molecular mechanics simulations provide atomistic insight into the effects visible in NMR experiments with limited computational effort.
Impact of SARS‐CoV‐2 Infection (COVID‐19) on Cytochromes P450 Activity Assessed by the Geneva Cocktail
Authors: Lenoir Camille , Terrier Jean , Gloor Yvonne , Curtin François , Rollason Victoria , Desmeules Jules Alexandre , Daali Youssef , Reny Jean‐Luc , Samer Caroline Flora
Published: September 2021

Coronavirus disease 2019 (COVID‐19), caused by severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection, is a severe acute respiratory syndrome with an underlying inflammatory state. We have previously demonstrated that acute inflammation modulates cytochromes P450 (CYPs) activity in an isoform‐specific manner. We therefore hypothesized that COVID‐19 might also impact CYP activity, and thus aimed to evaluate the impact of acute inflammation in the context of SARS‐CoV‐2 infection on the six main human CYPs activity. This prospective observational study was conducted in 28 patients hospitalized at the Geneva University Hospitals (Switzerland) with a diagnosis of moderate to severe COVID‐19. They received the Geneva phenotyping cocktail orally during the first 72 hours of hospitalization and after 3 months. Capillary blood samples were collected 2 hours after cocktail administration to assess the metabolic ratios (MRs) of CYP1A2, 2B6, 2C9, 2C19, 2D6, and 3A. C‐reactive protein (CRP), interleukin 6 (IL‐6), and tumor necrosis factor‐α (TNF‐α) levels were also measured in blood. CYP1A2, CYP2C19, and CYP3A MRs decreased by 52.6% (P = 0.0001), 74.7% (P = 0.0006), and 22.8% (P = 0.045), respectively, in patients with COVID‐19. CYP2B6 and CYP2C9 MRs increased by 101.1% (P = 0.009) and 55.8% (P = 0.0006), respectively. CYP2D6 MR variation did not reach statistical significance (P = 0.072). As expected, COVID‐19 was a good acute inflammation model as mean serum levels of CRP, IL‐6, and TNF‐α were significantly (P < 0.001) higher during SARS‐CoV‐2 infection. CYP activity are modulated in an isoform‐specific manner by SARS‐CoV‐2 infection. The pharmacokinetics of CYP substrates, whether used to treat the disease or as the usual treatment of patients, could be therefore clinically impacted.
New Diglyme‐based Gel Polymer Electrolytes for Na‐based Energy Storage Devices
Authors: Babu Binson , Enke Marcel , Prykhodska Sofiia , Lex‐Balducci Alexandra , Schubert Ulrich S. , Balducci Andrea
Published: September 2021

This work presents for the first time a new diglyme‐based gel polymer (DOBn‐GPE) suitable for Na‐based energy storage devices. The DOBn‐GPE, which contains a methacrylate‐based polymer, exhibited an excellent high ionic conductivity (2.3 mS cm−1 at 20 °C), broad electrochemical stability (>5.0 V), and high mechanical stability. DOBn‐GPE could be successfully used for the realization of Na‐ion capacitors, sodium‐metal batteries, and sodium‐ion batteries, displaying performance comparable with those of systems containing liquid electrolytes at room temperature and at 60 °C. The results of these investigation indicated that the development of diglyme‐based gel polymer electrolytes represents a promising strategy for the realization of advanced Na‐based energy storage devices.
Season of prescribed fire determines grassland restoration outcomes after fire exclusion and overgrazing
Authors: Novak Erin N. , Bertelsen Michelle , Davis Dick , Grobert Devin M. , Lyons Kelly G. , Martina Jason P. , McCaw W. Matt , O'Toole Matthew , Veldman Joseph W.
Published: September 2021

Fire exclusion and mismanaged grazing are globally important drivers of environmental change in mesic C4 grasslands and savannas. Although interest is growing in prescribed fire for grassland restoration, we have little long‐term experimental evidence of the influence of burn season on the recovery of herbaceous plant communities, encroachment by trees and shrubs, and invasion by exotic grasses. We conducted a prescribed fire experiment (seven burns between 2001 and 2019) in historically fire‐excluded and overgrazed grasslands of central Texas. Sites were assigned to one of four experimental treatments: summer burns (warm season, lightning season), fall burns (early cool season), winter burns (late cool season), or unburned (fire exclusion). To assess restoration outcomes of the experiment, in 2019, we identified old‐growth grasslands to serve as reference sites. Herbaceous‐layer plant communities in all experimental sites were compositionally and functionally distinct from old‐growth grasslands, with little recovery of perennial C4 grasses and long‐lived forbs. Unburned sites were characterized by several species of tree, shrub, and vine; summer sites were characterized by certain C3 grasses and forbs; and fall and winter sites were intermediate in composition to the unburned and summer sites. Despite compositional differences, all treatments had comparable plot‐level plant species richness (range 89–95 species/1000 m2). At the local‐scale, summer sites (23 species/m2) and old‐growth grasslands (20 species/m2) supported greater richness than unburned sites (15 species/m2), but did not differ significantly from fall or winter sites. Among fire treatments, summer and winter burns most consistently produced the vegetation structure of old‐growth grasslands (e.g., mean woody canopy cover of 9%). But whereas winter burns promoted the invasive grass Bothriochloa ischaemum by maintaining areas with low canopy cover, summer burns simultaneously limited woody encroachment and controlled B. ischaemum invasion. Our results support a growing body of literature that shows that prescribed fire alone, without the introduction of plant propagules, cannot necessarily restore old‐growth grassland community composition. Nonetheless, this long‐term experiment demonstrates that prescribed burns implemented in the summer can benefit restoration by preventing woody encroachment while also controlling an invasive grass. We suggest that fire season deserves greater attention in grassland restoration planning and ecological research.
Clinical significance of new‐onset atrial fibrillation in patients with hypertrophic cardiomyopathy
Authors: Kubo Toru , Baba Yuichi , Ochi Yuri , Hirota Takayoshi , Yamasaki Naohito , Kawai Kazuya , Yamamoto Katsuhito , Kondo Fumiaki , Bando Kanji , Yamada Eisuke , Furuno Takashi , Yabe Toshikazu , Doi Yoshinori L. , Kitaoka Hiroaki
Published: September 2021

Aims

There is limited information about the clinical significance of atrial fibrillation (AF), particularly new‐onset AF, in patients with hypertrophic cardiomyopathy (HCM) in a community‐based patient cohort. This study was carried out to clarify the prevalence and prognostic impact of AF in Japanese HCM patients.

Methods and results

In 2004, we established a cardiomyopathy registration network in Kochi Prefecture as a prospective study, and finally, 293 patients with HCM were followed. In the patients' cohort, we recently reported the clinical outcomes including mortality and HCM‐related morbid events. HCM‐related adverse cardiovascular events were defined in the following: (i) sudden cardiac death (SCD)‐relevant events including SCD, spontaneous sustained ventricular tachycardia, and appropriate implantable cardioverter defibrillator discharge; (ii) heart failure (HF) events with the composite of HF death and hospitalization for HF; and (iii) embolic events included embolic stroke‐related death and admission for embolic events. In the present study, we focused on AF and conducted a detailed investigation. At registration, the mean age of the patients was 63 ± 14 years, and 86 patients (29%) had documented AF including paroxysmal AF. Patients with AF at registration were characterized by worse clinical profiles including more advanced age, more symptomatic, more advanced left ventricular, and left atrial remodelling at registration. During a mean follow‐up period of 6.1 ± 3.2 years, a total of 77 HCM‐related adverse events occurred, and the presence of AF at registration was associated with an increased risk of HCM‐related adverse events, particularly heart failure events. During the follow‐up period, an additional 31 patients (11%) had documentation of AF for the first time, defined as new‐onset AF, with an annual incidence of approximately 1.8%, and finally, a total of 117 patients (40%) showed AF. The presence of palpitation and enlarged left atrial diameter, particularly left atrial diameter ≥50 mm, at registration were significant predictors of new‐onset AF. Importantly, the incidence of overall HCM‐related adverse events was further higher in patients with new‐onset AF observed from AF onset than in patients with AF at registration.

Conclusions

In our HCM registry in an aged Japanese community, a significant proportion developed AF. The presence of AF, particularly new‐onset AF, was associated with increased incidence of HCM‐related events. AF may not be just a marker of disease stage but an important trigger of adverse events.
Thermally‐Induced Spin‐Crossover in Fe1‐xTx(pyrazine)[Fe(CN)5NO] with T=Co, Ni – Effects of Iron Atom Dilution
Authors: Avila Yosuan , Terrero Ricardo , Crespo Paula M. , Díaz‐Paneque Luis A. , González Marlene , Ávila Manuel , Reguera Edilso
Published: September 2021

2D ferrous nitroprusside with the pyrazine molecule as a pillar between adjacent layers shows a thermally induced spin‐crossover behavior. This supposes that the energy gap between the high and low spin states is the order of kT in the temperature region where such a spin transition is observed. If a fraction of the iron atoms involved in that transition is progressively replaced by a second metal, to form a solid solution (alloy), the thermal effect could be modified due to the iron atom dilution, but such behavior also depends on the bonding properties of the ligands for the iron atom and of the NO and CN interaction in the interlayer region. This hypothesis was the idea that motivated the preparation of the titled systems of solid solutions and their study from magnetic and Mössbauer data recorded at different temperatures in the range of 5–300 K, complemented with XRD, Raman, and IR measurements. Co and Ni were considered to form the solid solutions under study because they form isostructural solids in the parent 3D coordination polymers. For both metals, the formed solids show a spin‐crossover effect for all the compositions range but from a certain degree of dilution for the iron atom, above 75 % substitution by the second metal, the thermal hysteresis almost disappears. This suggests that from that dilution degree, the spin transition involves structural changes at the local coordination environment for the iron atom but not for the entire solid framework. This hypothesis is properly supported by the recorded Raman and Mössbauer spectra. The presence of Co and Ni atoms in the solid solutions results in higher stability for the entropy‐driven high spin state. This is appreciated as lower values for T↓HS,1/2, and T↑LS,1/2 corresponding to the temperatures where the subscript 1/2 indicates the temperature where 50 % of the metal centers have changed their spin state.
Metal Coordinated Tri‐ and Tetraborane Analogues
Authors: Kar Sourav , Bairagi Subhash , Kar Ketaki , Roisnel Thierry , Dorcet Vincent , Ghosh Sundargopal
Published: September 2021

A series of triborane and tetraborane analogues have been isolated and structurally characterized utilizing chalcogenatoborate ligands Li[BH3(EPh)] (E=S or Se). Thermolysis of [Cp*TaCl4] in the presence of Li[BH3(SPh)] afforded bimetallic tantallaheteroborane [(Cp*Ta)2(μ‐η3:η3‐B2H4S)(μ‐η2:η2‐SBH3)] (1) and hexasulfido trimetallic complex [(Cp*Ta)3(μ‐S)4(μ‐SPh)2] (2). Compound1is a fused ditantallaheteroborane, in which both di‐ and triborane analogues are stabilized by two tantalum atoms. In an attempt to synthesize the selenium analogues of1and2, room‐temperature reaction of [Cp*TaCl4] with Li[BH3(SePh)] was carried out, which afforded bimetallic tantallaheteroborane [(Cp*Ta)2{μ‐η3:η3‐B3H6(SePh)}{μ‐SePh}2] (3), monometallic tantallaheteroboranes [Cp*Ta(SePh)2{B4H8‐n(SePh)n}] (4: n=0,5: n=1), and trimetallic species [(Cp*Ta)3(μ‐Se)4{μ‐Se2(Se)}] (6). Compound3is the rarest example of triborane analogue {B3H6(SePh)} in the coordination sphere of two tantalum atoms. Whereas compounds4and5are examples of unsaturated metallaheteroboranes, in which the tetraborane analogues are stabilized in the coordination sphere of tantalum. One of the unique features of3and5is the presence of terminal B‐SePh. Compound6has similar Ta3Se6trisbutterfly core as that of2with additional bridging selenide unit. All the compounds have been characterized by NMR spectroscopy, mass spectrometry, IR spectroscopy and single‐crystal X‐ray diffraction studies.
A Novel Flexible Electrochemical Ascorbic Acid Sensor Constructed by Ferrocene Methanol doped Multi‐walled Carbon Nanotube Yarn
Authors: Wang Yue , Wu Jinping , Yang Tian , Wang Zhong , Hasebe Yasushi , Lv Tianhang , Zhang Zhiqiang
Published: September 2021

An ascorbic acid (AA) electrochemical sensor was fabricated by ferrocene methanol (Fc−OH) modified multi‐walled carbon nanotube yarn (CNTY). The prepared sensor (Fc−OH/CNTY) exhibited outstanding flexibility, highly stretchability, excellent bendability and obviously electrocatalytic activity for oxidation of ascorbic acid. The morphology of Fc−OH/CNTY was evaluated by scanning electron microscope. The electrochemical behaviour of Fc−OH/CNTY sensor was studied by cyclic voltammetry and amperometry measurements. Moreover, the influence of Fc−OH concentration, applied potential and electrolyte solution pH were also investigated to obtain the best sensor performance. The prepared sensor exhibited a wide linear range from 3 μM to 3.0 mM toward AA, and a detection limit of 1.32 μM (S/N=3). It also possessed a good lifetime and a fast response speed (2.83 s). In addition, the Fc−OH/CNTY sensor remained 90 % and 60 % of its initial activity after 100 and 500 times bending, respectively, which indicated a potential application on flexible, implantable and/or wearable electrochemical sensors.
Are Fragrance Encapsulates Taken Up by Aquatic and Terrestrial Invertebrate Species?
Authors: Kuehr Sebastian , Windisch H. , Schlechtriem C. , Leon G. , Gasparini G. , Gimeno S.
Published: September 2021

The uptake potential of fragrance encapsulates by aquatic or terrestrial organisms was investigated. Because of their size of <5 mm and their polymeric nature, fragrance encapsulates fall under the Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection definition of microplastics. After use, fragrance encapsulates enter the sewer system and reach the sewage treatment plant (STP), where >90% of them are likely to be removed by sorption to the sludge. When the STP-generated sludge is used as fertilizer for agricultural soils, this may lead to potential exposure of terrestrial invertebrates to fragrance encapsulates, especially those feeding on particles of a similar size as the fragrance encapsulates. Two aquatic (Corbicula fluminea [water exposure] and Hyalella azteca [water and dietary exposure]) and one terrestrial invertebrate (Eisenia andrei [soil exposure]) species were exposed to 50 mg/L (or mg/kg) double fluorescence-labeled fragrance encapsulates (diameter 5–50 µm). The results showed that fragrance encapsulates are available to aquatic and terrestrial invertebrates but that species-specific differences regarding the ability to ingest fragrance encapsulates may exist. The benthic grazer H. azteca showed no ingestion of fragrance encapsulates, whereas the capsules were readily ingested and egested by the unselective freshwater filter feeder C. fluminea as well as the terrestrial decomposer E. andrei. No signs of bioaccumulation of fragrance encapsulates were indicated by microscopic assessment. Environ Toxicol Chem 2022;41:931–943. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
A Mechanically Flexible Superhydrophobic Rock Wool Modified with Reduced Graphene Oxide‐Chloroperene Rubber for Oil‐Spill Clean‐Up
Authors: Davardoostmanesh Maryam , Ahmadzadeh Hossein
Published: September 2021

The leakage of industrial oil and organic wastewater discharge has caused serious damage to the natural environment and ecology. Therefore, implementation of a low‐cost and high‐performance adsorbent material is of great significant. This work reports the preparation of superhydrophobic rock wool (RW) for efficient clean‐up of oil and organic solvents. The modified RW is prepared by coating a commercial RW with reduced graphene oxide (RGO) nanosheets under hydrothermal treatment. To improve the adhesion between the RGO nanosheets and RW, a film of chloroperene rubber is deposited on the RW surface followed by modification with RGO. The modified RW possesses superhydrophobicity and superoleophilicity with a water contact angle of 152.4°, and it is used for separation of oil–water mixture. The modified RW exhibits excellent mechanical elasticity and durability when compared with commercial one, and the adsorbed oils are recycled by simple squeezing. Its oil adsorption capacities are maintained above 95%, after several compression cycles. Importantly, the modified RW exhibits excellent photothermal properties which are beneficial for the separation of high‐viscosity oils. Owing to low costs, versatility, and scalability in production, the modified RW can be regarded as a suitable choice for large‐scale oil/water separation.
Genetic risks, adolescent health, and schooling attainment
Authors: Amin Vikesh , Behrman Jere R. , Fletcher Jason M. , Flores Carlos A. , Flores‐Lagunes Alfonso , Kohler Hans‐Peter
Published: September 2021

We provide new evidence on the effect of adolescent health behaviors/outcomes (obesity, depression, smoking, and attention deficit hyperactivity disorder [ADHD]) on schooling attainment using the National Longitudinal Study of Adolescent to Adult Health. We take two different approaches to deal with omitted variable bias and reverse causality. Our first approach attends to the issue of reverse causality by estimating the effect of health polygenic scores (PGSs) on schooling. Second, we estimate the effect of adolescent health using sibling fixed‐effects models that control for unmeasured genetic and family factors shared by siblings. We use the PGSs as additional controls in the sibling fixed‐effects models to reduce concerns about residual confounding from sibling‐specific genetic differences. We find consistent evidence across both approaches that being genetically predisposed to smoking and smoking regularly in adolescence reduces schooling attainment. Estimates for depression are more imprecise, but also suggest that a high genetic risk of depression and adolescent depression reduce schooling attainment. We find mixed evidence for ADHD. Our estimates suggest that having a high genetic risk for ADHD reduces grades of schooling, but we do not find any statistically significant negative effects of ADHD. Finally, we find no consistent evidence for a detrimental effect of obesity on schooling attainment.
Wilson’s Disease: An Analysis of Health Care Use and Cost Burden of Commercially Insured Adults in the United States
Authors: Rustgi Vinod K. , Gupta Kapil , Tait Christopher , Bhurwal Abhishek , Kabaria Savan , Catalano Carolyn , Li You , Minacapelli Carlos D.
Published: September 2021

The economic and health care use burdens of Wilson’s disease (WD) are unknown. In this study, we aimed to quantify this health care resource use and economic burden. We performed a retrospective case‐control analysis of individuals in the Truven Health MarketScan Commercial Claims database (2007‐2017). Using propensity scores, 424 WD cases were matched 1:1 to chronic liver disease (CLD) controls without WD. Total and service‐specific parameters, expressed in monthly averages, were quantified for the 6‐month pre‐WD diagnosis versus the 12‐month period after diagnosis. Wilcoxon signed‐rank tests and McNemar tests were used to examine incremental differences in burden between cases and controls. Adjusted multivariable generalized linear regression models were used to compare health care burdens. Relative to the 6‐month pre‐WD diagnosis, the 12 months after diagnosis had more claims per patient (2.87 vs. 3.35; P < 0.0001) and increased per patient health care costs (US $2,089 vs. US $3,887; P < 0.0001). WD cases incurred US $1,908 more in total unadjusted costs compared to controls in the 12‐month postindex date monthly averages. The increase in claims was primarily due to outpatient visits (1.62 vs. 1.82) and pharmaceutical claims (1.11 vs. 1.37). Cases also had higher health care costs for inpatient admissions (US $559 vs. US $1,264), outpatient visits (US $770 vs. US $1,037), and pharmaceutical claims (US $686 vs. US $1,489). Conclusion: WD is associated with significant health care cost and use burdens driven by increased inpatient admissions, outpatient visits, and pharmaceutical claims.
Predictors of Jaundice Resolution and Survival After Endoscopic Treatment of Primary Sclerosing Cholangitis
Authors: Eaton John E. , Haseeb Abdul , Rupp Christian , Eusebi Leonardo H. , van Munster Kim , Voitl Robert , Thorburn Douglas , Ponsioen Cyriel Y. , Enders Felicity T. , Petersen Bret T. , Abu Dayyeh Barham K. , Baron Todd H. , Chandrasekhara Vinay , Gostout Christopher J. , Levy Michael J. , Martin John , Storm Andrew C. , Dierkhising Ross , Kamath Patrick S. , Gores Gregory J. , Topazian Mark
Published: September 2021

The benefit of endoscopic retrograde cholangiopancreatography (ERCP) for the treatment of primary sclerosing cholangitis (PSC) remains controversial. To identify predictors of jaundice resolution after ERCP and whether resolution is associated with improved patient outcomes, we conducted a retrospective cohort study of 124 patients with jaundice and PSC. These patients underwent endoscopic biliary balloon dilation and/or stent placement at an American tertiary center, with validation in a separate cohort of 102 patients from European centers. Jaundice resolved after ERCP in 52% of patients. Median follow‐up was 4.8 years. Independent predictors of jaundice resolution included older age (P = 0.048; odds ratio [OR], 1.03 for every 1‐year increase), shorter duration of jaundice (P = 0.059; OR, 0.59 for every 1‐year increase), lower Mayo Risk Score (MRS) (P = 0.025; OR, 0.58 for every 1‐point increase), and extrahepatic location of the most advanced biliary stricture (P = 0.011; OR, 3.13). A logistic regression model predicted jaundice resolution with area under the receiver operator characteristic curve of 0.67 (95% confidence interval, 0.5‐0.79) in the validation set. Independent predictors of death or transplant during follow‐up included higher MRS at the time of ERCP (P < 0.0001; hazard ratio [HR], 2.33 for every 1‐point increase), lower total serum bilirubin before ERCP (P = 0.031; HR, 0.91 for every 1 mg/dL increase), and persistence of jaundice after endoscopic therapy (P = 0.003; HR, 2.30). Conclusion: Resolution of jaundice after endoscopic treatment of biliary strictures is associated with longer transplant‐free survival of patients with PSC. The likelihood of resolution is affected by demographic, hepatic, and biliary variables and can be predicted using noninvasive data. These findings may refine the use of ERCP in patients with jaundice with PSC.
Primary treatment and recent survival trends in patients with primary diffuse large B‐cell lymphoma of central nervous system, 1995–2016: A population‐based SEER analysis
Authors: Chen Cui , Sun Peng , Sun Xiao‐Qing , Chen Shao‐Yong , Hang Yang  , Wang Yu , Li Zhi‐Ming
Published: September 2021

This retrospective cohort study aimed to evaluate primary treatment and recent survival trends in patients with primary diffuse large B‐cell lymphoma of central nervous system (CNS) from 1995 to 2016. Using the SEER data, patients diagnosed with non‐HIV‐associated primary central nervous system lymphoma (PCNSL)–diffuse large B‐cell lymphoma (DLBCL) aged ⩾18 years between 1995 and 2016 were identified. The year of diagnosis was divided into the time period‐1 (1995–2002), the time period‐2 (2003–2012), and the time period‐3 (2013–2016). Chi‐square tests, the Kaplan–Meier method, log‐rank test, and Cox regression model were used in the analysis. Overall, 3760 patients were included. Both the use of radiotherapy alone and the application of combined chemoradiotherapy decreased significantly, following the wider use of chemotherapy alone during 1995–2016. There was a significant improvement in PCNSL cause‐specific survival (CSS) (period‐1: 13 months vs. period‐2: 19 months vs. period‐3: 41 months, p < 0.001). Survival of patients aged above 70 years did not change from the time period‐1 to the time period‐2 (p = 0.101). However, there was an increase in CSS from the time period‐2 to the time period‐3 in the elderly patients (period‐2: 5 months vs. period‐3: 9 months, p < 0.001). On multivariable analyses, diagnosed in the time period‐3 was significantly and independently associated with better CSS (hazard ratio 0.577, 95% confidence interval 0.506–0.659, p < 0.001). Our analysis shows the use of radiotherapy in the treatment of PCNSL has waned over the study span. There was a significant improvement in CSS during 1995–2016, which reflected developments in treatment over time. The elderly patient population also gained a significant CSS benefit in the most recent period.
Role of neutrophils in acute viral infection
Authors: Ma Yuan , Zhang Yue , Zhu Liuluan
Published: September 2021

Neutrophils play multiple roles in acute viral infections. They restrict viral replication and diffusion through phagocytosis, degranulation, respiratory burst, secretion of cytokines, and the release of neutrophil extracellular traps, as well as, activate the adaptive immune response. However, the overactivation of neutrophils may cause tissue damage and lead to poor outcomes. Additionally, some characteristics and functions of neutrophils, such as cell number, lifespan, and antiviral capability, can be influenced while eliminating viruses. This review provides a general description of the protective and pathological roles of neutrophils in acute viral infection.
Understanding immunotherapy terminology: An analysis of provider‐patient conversations
Authors: Blee Shannon , Rosenberg Bari , Switchenko Jeffrey M. , Hianik Rachel , Thomson Mary Catherine , Dixon Margie , Bilen Mehmet Asim , Pentz Rebecca D.
Published: September 2021

Background

Immunotherapy terminology is complex and can be difficult for patients to understand, threatening informed consent. The aims of this exploratory study are to determine whether patients understand immunotherapy terminology and if the provider defining the term improves patient understanding. Good patient/provider communication is important for good informed consent, patient adherence to treatment and patient outcomes.

Methods

Conversations between oncology providers and patients discussing immunotherapy were observed (n = 39), and technical terms used were noted. With consent, patients were interviewed post‐conversation to assess their understanding of these terms (n = 39). Comparisons of the terms were conducted using chi‐square tests, Fisher's exact tests, or ANOVA where appropriate.

Results

“Immunotherapy” was the most difficult for participants to understand with 48.7% (19/39) correctly defining immunotherapy. “Immunotherapy agents” was understood 53.8% (14/26) of the time. “Immune system” was well understood 88.5% (23/26). Providers defined immunotherapy in 97.4% of conversations. There was no correlation between having immunotherapy defined in the conversation, and the likelihood of a correct definition (p = 0.487). “Immune system” was defined in 92.3% of conversations (n = 26), and defining it in the conversation was correlated with increased patient understanding (p = 0.009).

Conclusion

Our results indicate that patients have difficulty understanding some immunotherapy terminology. Since patient understanding of key terminology is crucial for informed consent and patient care, it is essential to implement interventions to improve understanding.
Recent progress in terahertz modulation using photonic structures based on two‐dimensional materials
Authors: Wang Ziming , Qiao Jie , Zhao Shuqi , Wang Shilei , He Chuan , Tao Xutang , Wang Shanpeng
Published: September 2021

Terahertz (THz) technology has attracted great attention in the past few decades for its unique applications in various fields, including spectroscopy, noninvasive detection, wireless communications, and imaging. In parallel to this, the practical, fast, and broadband modulation of THz waves is becoming indispensable. Two‐dimensional (2D) materials exhibit unusual optical and electrical properties, which has prompted tremendous interest and significant advances in THz modulation. This review provides the recent progress in 2D materials‐based THz modulators, outlining the operating principles, including all‐optical, electro‐optic, magneto‐optic, and other exotic mechanisms. We focus on the recent advances in THz modulation by the designed photonic structures, such as heterostructure, metamaterial, capacitor, optical cavity, and waveguide integration. Lastly, we discussed the challenges and opportunities for 2D materials‐based THz modulators and presented our prospects for the future development.

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Photoluminescence of P3HT:PCBM bulk heterojunction thin films and effect of external electric field
Authors: Narra Sudhakar , Tsai Shuo‐En , Awasthi Kamlesh , Rana Shailesh , Diau Eric Wei‐Guang , Ohta Nobuhiro
Published: September 2021

Steady‐state and time‐resolved photoluminescence (PL) and electrophotoluminescence (E‐PL) have been recorded for bulk heterojunction samples of thin films of regio‐regular poly(3‐hexylthiophene) (P3HT) and methyl [6,6]‐phenyl‐C61‐butanoate (PCBM). The PL spectra of the bulk heterojunction samples showed a monotonic decrease of PL quantum yield with increased PCBM content in the film. The PL decay was measured with both a femtosecond up‐conversion technique and a time‐correlated single‐photon‐counting technique. The mechanism of PL quenching deviated from a simple Stern‐Volmer equation, explained in terms of an apparent static quenching with a sphere‐of‐action model and dynamic quenching. With increased content of PCBM, the static quenching played a dominant role. Upon application of an electric field, the E‐PL spectra of both P3HT and bulk heterojunction samples showed an enhanced quantum yield and incremented lifetime of PL of P3HT. The long‐range electron transfer from P3HT to PCBM was retarded upon application of an electric field; the field‐induced change increased with increasing PCBM content.