bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Side‐Chain Hydrophilicity on Packing, Swelling, and Ion Interactions in Oxy‐Bithiophene Semiconductors
Authors: Siemons Nicholas , Pearce Drew , Cendra Camila , Yu Hang , Tuladhar Sachetan M. , Hallani Rawad K. , Sheelamanthula Rajendar , LeCroy Garrett S. , Siemons Lucas , White Andrew J. P. , McCulloch Iain , Salleo Alberto , Frost Jarvist M. , Giovannitti Alexander , Nelson Jenny
Published: August 2022

Exchanging hydrophobic alkyl‐based side chains to hydrophilic glycol‐based side chains is a widely adopted method for improving mixed‐transport device performance, despite the impact on solid‐state packing and polymer‐electrolyte interactions being poorly understood. Presented here is a molecular dynamics (MD) force field for modeling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals. MD simulations, coupled with X‐ray diffraction (XRD), show that alkoxylated polythiophenes will pack with a “tilted stack” and straight interdigitating side chains, whilst their glycolated counterpart will pack with a “deflected stack” and an s‐bend side‐chain configuration. MD simulations reveal water penetration pathways into the alkoxylated and glycolated crystals—through the π‐stack and through the lamellar stack respectively. Finally, the two distinct ways triethylene glycol polymers can bind to cations are revealed, showing the formation of a metastable single bound state, or an energetically deep double bound state, both with a strong side‐chain length dependence. The minimum energy pathways for the formation of the chelates are identified, showing the physical process through which cations can bind to one or two side chains of a glycolated polythiophene, with consequences for ion transport in bithiophene semiconductors.
Microstructured BN Composites with Internally Designed High Thermal Conductivity Paths for 3D Electronic Packaging
Authors: He Hongying , Peng Weixiang , Liu Junbo , Chan Xin Ying , Liu Shike , Lu Li , Le Ferrand Hortense
Published: August 2022

Miniaturized and high‐power‐density 3D electronic devices pose new challenges on thermal management. Indeed, prompt heat dissipation in electrically insulating packaging is currently limited by the thermal conductivity achieved by thermal interface materials (TIMs) and by their capability to direct the heat toward heat sinks. Here, high thermal conductivity boron nitride (BN)‐based composites that are able to conduct heat intentionally toward specific areas by locally orienting magnetically functionalized BN microplatelets are created using magnetically assisted slip casting. The obtained thermal conductivity along the direction of alignment is unusually high, up to 12.1 W m−1 K−1, thanks to the high concentration of 62.6 vol% of BN in the composite, the low concentration in polymeric binder, and the high degree of alignment. The BN composites have a low density of 1.3 g cm−3, a high stiffness of 442.3 MPa, and are electrically insulating. Uniquely, the approach is demonstrated with proof‐of‐concept composites having locally graded orientations of BN microplatelets to direct the heat away from two vertically stacked heat sources. Rationally designing the microstructure of TIMs to direct heat strategically provides a promising solution for efficient thermal management in 3D integrated electronics.
Inkjet‐Printed Narrow‐Channel Mesoporous Oxide‐Based n‐Type TFTs and All‐Oxide CMOS Electronics
Authors: Devabharathi Nehru , Pradhan Jyoti Ranjan , Priyadarsini Sushree Sangita , Brezesinski Torsten , Dasgupta Subho
Published: August 2022

Oxide semiconductors are becoming the materials of choice for modern‐day display industries. The performance of solution‐processed oxide thin film transistors (TFTs) has also improved dramatically over the last few years. However, while oxygen deficient n‐type semiconductors can demonstrate excellent electronic transport, the performance of p‐type materials has remained unsatisfactory. Consequently, only the n‐type semiconductor‐based pseudo‐complementary metal oxide semiconductor (CMOS) technology has attracted tremendous interests recently; yet, the high power dissipation remains a problem. Here, this work demonstrates all‐oxide CMOS invertors with high‐performance narrow‐channel n‐type TFTs, which can compensate for the limited carrier mobility of the p‐type transistors. These n‐type TFTs are fabricated with polymer‐templated mesoporous In2O3 and with a device geometry that allows near‐vertical current transport, thereby rendering the TFT channel lengths to be equal to the semiconductor film thickness (≈50 nm). Unprecedented On‐current (1.02 mA µm−1) and transconductance (950 µS µm−1) are achieved. The CuO‐based p‐type TFTs also show a device mobility of no less than 0.5 cm2 V−1 s−1. The printed all‐oxide CMOS inverters are found to operate at very low supply voltages and demonstrate sharp transfer curves with maximum signal gain of 31 and low power dissipation of only 4 nW, at a supply voltage of 1 V.
Symmetric Thin Films Based on Silicon Materials for Angle‐Insensitive Full‐Color Structural Colors
Authors: Feng Kun , Li Qingyuan , Liu Jintong , Guan Peng , Yuan Jinliang , Cai Guangshi , Chen Nan , Bu Yikun
Published: August 2022

Here, reflective full‐color structural colors with symmetrical thin film structures made from all silicon‐based materials are demonstrated. Considering practical application scenarios, the five‐layer reflection enhancement unit located in the core of the device is composed of amorphous silicon (a‐Si) and SiO2. Because of the large refractive index difference, the high reflection efficiency can be achieved, and the highest peak reflectivity of the sample can reach 89%. On both sides of the device, the same anti‐reflection (AR) unit composed of SiOx and SiO2 is deposited, which can significantly reduce the reflection of non‐target wavelength and enhance the color purity of the device. Meanwhile, the thin thickness of the absorbing materials provides the better angular insensitivity and the device shows a stable color appearance in the range of 0–60°. Based on the idea of symmetrical structure, a variety of angular insensitive structural colors can be realized. The scheme is simple in structure and material, which provides the feasibility for mass production. Particularly, the symmetry of the structure makes structural colors have unique advantages and the potential to be widely applied in the color paint fields of printing, decoration, and counterfeit detection.
Stable Flexible Transparent Electrodes for Localized Heating of Lab‐on‐a‐Chip Devices
Authors: Papanastasiou Dorina T. , Sekkat Abderrahime , Nguyen Viet Huong , Jiménez Carmen , Muñoz‐Rojas David , Bruckert Franz , Bellet Daniel
Published: August 2022

In situ biological observations require stable, accurate, and local temperature control of specimen. Several heating elements are coupled with microfluidic systems, but few of them are transparent to visible light and therefore compatible with microscopic observation. Traditional transparent electrodes, such as indium tin oxide, still suffer from high fabrication cost and brittleness, which is not fully compatible to emerging microfluidic devices. Here, a lightweight, low‐cost, flexible transparent heater based on percolating silver nanowire networks, protected with a transparent zinc oxide film, for the in situ monitoring of biological experiments is proposed. Using the fluorescence of dyes bound to double‐stranded DNA to monitor its temperature in situ, it is demonstrated that such nanocomposites allow rapid and reproducible heating under low applied voltage. Furthermore, selective heating is achieved in different zones of the same microchannel or for adjacent microchannels of the chip heating at different temperatures, with a single transparent heater and bias.
Advances in Emerging Photonic Memristive and Memristive‐Like Devices
Authors: Wang Wenxiao , Gao Song , Wang Yaqi , Li Yang , Yue Wenjing , Niu Hongsen , Yin Feifei , Guo Yunjian , Shen Guozhen
Published: August 2022

Possessing the merits of high efficiency, low consumption, and versatility, emerging photonic memristive and memristive‐like devices exhibit an attractive future in constructing novel neuromorphic computing and miniaturized bionic electronic system. Recently, the potential of various emerging materials and structures for photonic memristive and memristive‐like devices has attracted tremendous research efforts, generating various novel theories, mechanisms, and applications. Limited by the ambiguity of the mechanism and the reliability of the material, the development and commercialization of such devices are still rare and in their infancy. Therefore, a detailed and systematic review of photonic memristive and memristive‐like devices is needed to further promote its development. In this review, the resistive switching mechanisms of photonic memristive and memristive‐like devices are first elaborated. Then, a systematic investigation of the active materials, which induce a pivotal influence in the overall performance of photonic memristive and memristive‐like devices, is highlighted and evaluated in various indicators. Finally, the recent advanced applications are summarized and discussed. In a word, it is believed that this review provides an extensive impact on many fields of photonic memristive and memristive‐like devices, and lay a foundation for academic research and commercial applications.
Positively Charged Pt‐Based Nanoreactor for Efficient and Stable Hydrogen Evolution
Authors: Feng Kun , Xu Jiabin , Chen Yufeng , Li Shuo , Kang Zhenhui , Zhong Jun
Published: August 2022

Positively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state‐of‐the‐art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe‐PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X‐ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni‐based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H+, while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe‐PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm−2 and exhibits a high mass activity of 10.93 A mgPt−1 (at 100 mV). Most importantly, it only needs an ultra‐low overpotential of 193 mV to achieve a high current density of 1000 mA cm−2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large‐scale industrial application in the future.
Identification of serum microRNAs as potential diagnostic biomarkers for detecting precancerous lesions of gastric cancer
Authors: Otsu Hajime , Nambara Sho , Hu Qingjiang , Hisamatsu Yuichi , Toshima Takeo , Takeishi Kazuki , Yonemura Yusuke , Masuda Takaaki , Oki Eiji , Mimori Koshi
Published: August 2022

Aim

Gastric mucosal changes associated with chronic gastritis are known to be precancerous lesions of gastric cancer. We aimed to identify individuals with a high risk of gastric cancer by detection of microRNAs (miRNA) in the blood as biomarkers.

Methods

Of 1206 individuals screened, 144 who were positive for Helicobacter pylori (H. pylori) by the serum antibody test and who underwent endoscopy were the subjects of this study. For the gross assessment of mucosal inflammation, we applied the Kimura–Takemoto classification, in which normal mucosa was defined as grade 0, and atrophy was categorized as grade 1 (C‐1 and C‐2), grade 2 (C‐3 and O‐1), and grade 3 (O‐2 and O‐3). Serum samples were divided into two phases and used for miRNA microarray profiling. We compared the expression of miRNAs in grade 3 mucosa and other grades. Expression in gastric cancer was confirmed with TCGA data.

Results

miR‐196b‐3p was significantly upregulated, and miR‐92a‐2‐5p was downregulated (P < .05 and q < 0.2). TCGA data showed a high expression of miR‐196b‐3p in gastric cancer cases (P < .001). Comparing grade 3 and the others, the area under the receiver operating characteristic curve using the detected miRNAs was as high as about 0.7. Furthermore, the combination of miRNAs resulted in higher accuracy. In terms of the significance of the combinatory mRNAs, the combination of three miRNAs (miR‐196b‐3p, miR‐92a‐2‐5p, and miR‐6791‐3p) revealed high sensitivity and specificity, with the area under the curve exceeding 0.8.

Conclusion

The identified combinatory miRNAs may represent promising biomarkers of precancerous lesions in gastric cancer.
Reductive Al−B σ‐Bond Formation in Alumaboranes: Facile Scission of Polar Multiple Bonds
Authors: Güven Zeynep , Denker Lars , Wullschläger Daniela , Pablo Martínez Juan , Trzaskowski Bartosz , Frank René
Published: August 2022

We present facile access to an alumaborane species with electron precise Al−B σ‐bond. The reductive rearrangement of 1‐(AlI2), 8‐(BMes2) naphthalene (Mes=2,4,6‐Me3C6H2) affords the alumaborane speciescyclo‐(1,8‐C10H6)‐[1‐Al(Mes)(OEt2)‐8‐B(Mes)] with a covalent Al−B σ‐bond. The Al−B σ‐bond performs the reductive scission of multiple bonds: S=C(NiPrCMe)2affords the naphthalene bridged motif B−S−Al(NHC), NHC=N‐heterocyclic carbene, while O=CPh2is deoxygenated to afford an B−O−Al bridged species with incorporation of the remaining ≡CPh2fragment into the naphthalene scaffold. The reaction with isonitrile Xyl‐N≡C (Xyl=2,6‐Me2C6H4) proceeds via a proposed (amino boryl) carbene species; which adds a second equivalent of isonitrile to ultimately form the Al−N−B bridged speciescyclo‐(1,8‐C10H6)‐[1‐Al(Mes)‐N(Xyl)‐8‐B{C(Mes)=C−N−Xyl}] with complete scission of the C≡N triple bond. The latter reaction is supported with isolated intermediates and by DFT calculations.
A new heterotrimetallic sandwich‐like CuII–LaIII–CuII (3d–4f–3d) cluster as a model anticancer drug in interaction with FS‐DNA and BSA and as a new artificial catalyst for catecholase activity
Authors: Keshavarzian Elahe , Asadi Zahra , Poupon Morgane , Dusek Michal , Rastegari Banafsheh
Published: August 2022

A new heterotrimetallic sandwich‐like CuII–LaIII–CuII cluster, [(valpn)2Cu2La(NO3)2]NO3(H2O)1.8, (H2valpn = 1,3‐propanediylbis(2‐iminomethylene‐6‐methoxy‐phenol)), was synthesized by the reaction of [Cu(valpn)] with La (NO3)3.6H2O (1:1 M ratio) at room temperature. The resulted cluster was characterized by X‐ray diffraction, UV–Vis and IR spectroscopy, and elemental analysis (CHN). The crystal structure of the cluster revealed that La(III) ion was sandwiched between two [Cu(valpn)] moieties and located in the open compartments of two copper Schiff base complexes and being surrounded by 12 oxygen atoms. This cluster complex, as a model anticancer drug, was investigated in interaction with fish sperm deoxyribonucleic acid (FS‐DNA) using docking study and experimental methods such as fluorescence and UV–Vis spectroscopy, circular dichroism spectroscopy (CD), cyclic voltammetry (CV), viscosity measurements, and agarose gel electrophoresis. These investigations suggested intercalative interaction between the cluster complex and FS‐DNA. Plasma proteins are other targets for the anticancer drugs, so the cluster–bovine serum albumin (BSA) interaction was also investigated. For evaluating the binding, Stern–Volmer constants (KSV) and the number of binding sites (n) were calculated. It was proposed that the electrostatic interaction was the main force in the cluster–BSA binding. Cytotoxic activity was assayed by MTT assay toward LACaP, MCF‐7, and HeLa cancer cell lines. The IC50 values of the cluster for HeLa and LACaP cell lines were lower than for MCF‐7 cell lines. The docking studies were also performed for cluster–BSA and cluster–DNA interactions. The cluster was also investigated as an artificial enzyme in catechol oxidase activity, and kinetics of the oxidation of 3,5‐di‐tert‐butylcatechol catalyzed by the cluster was studied.
Enzyme activity inhibition properties of new cellulose nanocrystals from Citrus medica L. pericarp: A perspective of cholesterol lowering
Authors: Kalhori Fateme , Yazdyani Helya , Khademorezaeian Fatemeh , Hamzkanloo Negar , Mokaberi Parisa , Hosseini Sare , Chamani Jamshidkhan
Published: August 2022

As a waste material, the amazing potential of cellulose nanocrystals (CNCs) isolated from Citrus medica L. pericarp in being a natural resource of lingo‐cellulosic products has never been investigated before. In the present study, an alkaline pretreatment and a two‐step bleaching procedure were applied to conduct the desired acid hydrolysis by the usage of 64% sulfuric acid at 50°C for 105 min. The extracted CNCs were distinguished through the means of transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), atomic force microscopy (AFM), Fourier‐transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), zeta potential, and energy‐dispersive X‐ray spectroscopy (EDX). The elimination of peaks, which were accountable for the inducement of hemicelluloses and lignin, was confirmed by the FTIR results and were also validated by the outcomes of XRD that proved the gentle removal of non‐cellulosic components. The morphology and size of CNCs were indicated through the FESEM and TEM results. In addition, the spherical forms of synthesized CNCs were observed with a diameter of 46 nm throughout the FESEM images, while displaying a value of 42.54 nm as well due to TEM micrographs. The obtained zeta potential displayed a reasonable negative surface charge for CNCs. Furthermore, the cytotoxicity assessment of this product on fibroblast cells was performed to study their susceptibility for bio‐medical and cosmetic industrial applications, which resulted in the lack of exhibiting any cytotoxic effects. In conformity to the outcomes of TEM and FESEM, the results of AFM revealed a fine dispersion and spherical form of cellulose nanoparticles. The interaction between HMG‐CoA reductase and CNC was studied by the usage of multi‐spectroscopic methods and enzyme kinetics to explore the binding mechanism of HMG‐CoA reductase–CNC system. Reduced catalytic activity of the occurrence of changes in the secondary structure of HMG‐CoA reductase was as a result of interacting with CNC causing a reduction in its catalytic activity.
“Guide” of muscone modification enhanced brain‐targeting efficacy and anti‐glioma effect of lactoferrin modified DTX liposomes
Authors: Qi Na , Duan Wenjuan , Gao Duan , Ma Ningzhu , Zhang Jianguo , Feng Jianfang , Li Aimin
Published: August 2022

Glioma is one of the most aggressive malignant diseases for human health. It is difficult to resect completely due to their invasiveness. The targeted delivery, as a noninvasive approach, is a major strategy for the development of treatments for brain tumors. Lactoferrin (Lf) receptors are over‐expressed in both brain endothelial cells and glioma cells. Macromolecular Lf modified nanoparticles have been shown to enhance the brain targeting. Muscone is a “guide” drug that have been demonstrated to promote liposomes into the brain by modification. To further enhance the brain‐targeting efficacy of Lf modified carriers, we designed that Lf and muscone dual‐modified liposomes cross blood–brain barrier (BBB) and target to brain for enhanced docetaxel (DTX) brain delivery. The results showed that we successfully prepared Lf and muscone dual‐modified liposomes (Lf‐LP‐Mu‐DTX), the number of Lf molecules connected to the surface of per liposome was 28. Lf‐LP‐Mu‐DTX increased uptake in both U87‐MG cells and hCMEC/D3 cells, enhanced penetration of U87‐MG tumor spheroid and in vitro BBB model, had better in vitro and in vivo anti‐tumor effects. In conclusion, “guide” of muscone modification enhanced brain‐targeting efficacy of Lf modified liposomes, Lf and muscone dual‐modified docetaxel loaded liposomes present a potential brain‐targeting drug delivery system for use in the future treatment of gliomas.
Cationic Gold(II) Complexes: Experimental and Theoretical Study**
Authors: Mehara Jaya , Koovakattil Surendran Adarsh , van Wieringen Teun , Setia Deeksha , Foroutan‐Nejad Cina , Straka Michal , Rulíšek Lubomír , Roithová Jana
Published: August 2022

Gold(II) complexes are rare, and their application to the catalysis of chemical transformations is underexplored. The reason is their easy oxidation or reduction to more stable gold(III) or gold(I) complexes, respectively. We explored the thermodynamics of the formation of [AuII(L)(X)]+complexes (L=ligand, X=halogen) from the corresponding gold(III) precursors and investigated their stability and spectral properties in the IR and visible range in the gas phase. The results show that the best ancillary ligands L for stabilizing gaseous [AuII(L)(X)]+complexes are bidentate and tridentate ligands with nitrogen donor atoms. The electronic structure and spectral properties of the investigated gold(II) complexes were correlated with quantum chemical calculations. The results show that the molecular and electronic structure of the gold(II) complexes as well as their spectroscopic properties are very similar to those of analogous stable copper(II) complexes.
Vibrational Circular Dichroism Unravels Supramolecular Chirality and Hydration Polymorphism of Nucleoside Crystals
Authors: Krupová Monika , Leszczenko Patrycja , Sierka Ewa , Emma Hamplová Sára , Pelc Radek , Andrushchenko Valery
Published: August 2022

Vibrational circular dichroism (VCD) spectroscopy has been widely used to study (bio)molecules in solution. However, its solid‐state applications have been restricted due to experimental limitations and artifacts. Having overcome some of them, the first VCD study of nucleoside crystals is now presented. A two‐orders‐of‐magnitude enhancement of VCD signal was observed due to high molecular order in the crystals and resulting supramolecular chirality. This allowed to obtain high‐quality VCD spectra within minutes using minute amounts of samples. The VCD technique is extremely sensitive in detecting changes in a crystal order and is able to distinguish different hydration states of crystals. This elevates it to a new level, as a fast and efficient tool to study chiral crystalline samples. This study demonstrates that VCD is capable of near‐instantaneous detection of hydration polymorphs and crystal degradation, which is of substantial interest in pharmaceutical industry (quality and stability control).
Dioxygen Activation by Redox‐Active Bis(aldimine) Ligand Bridged Diruthenium Complex Possessing Singlet Ground State
Authors: Biswas Mitrali , Dey Sanchaita , Das Abhishek , Kanti Paine Tapan , Panda Sanjib , Kumar Lahiri Goutam
Published: August 2022

The unexplored ‘actor’ behavior of redox‐active bis(aldimine) congener, p‐phenylene‐bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2} (acac= acetylacetonate). Reaction under aerobic condition led to the one‐pot generation of dinuclear complexes with unperturbed L1, imino‐carboxamido (L2−), and bis(carboxamido) (L32−)‐bridged isovalent {RuII(μ‐L1)RuII}, 1/ {RuIII(μ‐L32−)RuIII}, 3 and mixed‐valent {RuII(μ‐L2−)RuIII}, 2. Authentication of the complexes along with the redox non‐innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2/3.
[Nb@Ge13/14]3−: New Family Members of Ge‐Based Intermetalloid Clusters
Authors: Huang Ya‐Shan , Xue Yuan , Muñoz‐Castro Alvaro , Popov Ivan A. , Sun Zhong‐Ming
Published: August 2022

During the past two decades, single‐atom‐centered medium‐sized germanium clusters [M@Gen] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas‐phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13‐/14‐vertex Ge clusters [Nb@Ge13]3− (1) and [Nb@Ge14]3− (2), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3‐connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p‐AOs with the endohedral Nb 4d‐AOs through three/four‐center two‐electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1. Low occupancies of the direct two‐center two‐electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency.
Multigram Synthesis of a Combustion‐Relevant δ‐Ketohydroperoxide through Sulfonylhydrazine Substitution
Authors: Ke Yan‐Ting , Gall Bradley K. , Dewey Nicholas S. , Rotavera Brandon , Ferreira Eric M.
Published: August 2022

A synthesis of a δ‐ketohydroperoxide is described, addressing potential functional‐group compatibilities in these elusive species relevant to combustion and atmospheric chemistries. The hydroperoxide is installed via sulfonylhydrazine substitution, which was found to be more effective than displacement of secondary halides. As part of this protocol, it was observed that 1,2‐dimethoxyethane is an advantageous medium for the reaction, avoiding the formation of a tetrahydrofuran hydroperoxide side product. This discovery facilitated the multigram synthesis (6 steps, 41 % yield overall) and discrete characterization of the target δ‐ketohydroperoxide.
A Vicinal Diol Approach for the Total Synthesis of Molestin E, ent‐Sinulacembranolide A and ent‐Sinumaximol A
Authors: Hoff Oskar , Kratena Nicolas , Aynetdinova Daniya , Christensen Kirsten E. , Donohoe Timothy J.
Published: August 2022

In this work an approach for the synthesis of furanocembranoid natural products containing the C‐7,8‐diol moiety is disclosed. This culminated in the first total synthesis of the natural product molestin E, together with ent‐sinulacembranolide A and ent‐sinumaximol A as well as a thorough exploration of their chemistry. Late‐stage ring‐closure of the C‐7,8‐diols to the corresponding epoxides was also demonstrated. Key features of this synthetic strategy include a stereoselective Baylis‐Hillman reaction, ring‐closing metathesis and Shiina macrolactonisation. Chiral‐pool materials were deployed to ensure the desired absolute stereochemistry which was confirmed by late‐stage single crystal X‐ray diffraction.
Bypass control of heat exchanger network under uncertainty
Authors: Manchikatla Chaitanya , Li Zukui , Huang Biao
Published: August 2022

The dynamic control of the heat exchanger network is important for developing energy‐efficient and safe industrial processes. In such a system, the control is achieved through the bypass stream around the heat exchanger. This work aims to track the setpoint temperature of the mixed stream by manipulating the bypass fraction of the cold stream around the heat exchanger. The implemented control is in a non‐linear model predictive control (NMPC) framework. The first‐principles model of a shell and a tube heat exchanger is used. The orthogonal collocation technique is used to discretize the first‐principles model into the system of algebraic equations. In this work, uncertainty is also considered in the inlet temperature of the hot stream. The uncertain optimal control problem is dealt with by using a scenario tree‐based approximation along with the affine policy‐based method. The results show that, under different scenarios of uncertainty, the controlled variable efficiently tracks the setpoint. In comparison, considering the same scenarios of uncertainty used, the deterministic optimization approach shows significant deviation in the controlled variable from the setpoint as time passes.
Utilization of Oil Red O staining for assessing aspiration risk in lung transplant patients: A multidisciplinary prospective study with clinical practice insights
Authors: Torous Vanda F. , Basler Debra , McEnery Caroline , Astor Todd , Ly Amy
Published: August 2022

Background

Gastroesophageal reflux disease with microaspiration has been associated with graft dysfunction in lung transplant patients. Identifying patients with aspiration is clinically important because it enables implementation of appropriate interventions like antireflux therapy. Oil Red O (ORO) staining with determination of the lipid‐laden macrophage index (LLMI) has been proposed as a noninvasive surrogate marker in the detection of aspiration. The aim of this study was to prospectively evaluate clinical utilization of ORO staining in the assessment of aspiration risk.

Methods

All transbronchial surgical pathology biopsies obtained in lung transplant patients undergoing routine surveillance from August 2020 through November 2021 were included in this study. Clinical team members prospectively ascertained the aspiration risk category (ARC) of each patient both before and after biopsy findings and recorded reasons for change in ARC.

Results

A total of 132 transbronchial biopsies with concurrent LLMI were included in the study. LLMI was low in 51 cases (38.6%), including 21 of the 54 cases (38.9%) where aspiration was suggested based on the transbronchial biopsy findings. In total, 19 cases (14.4%) underwent a change in ARC post‐biopsy including 10 that were upgraded and nine cases that were downgraded. Transbronchial biopsy findings were noted as the reason for change in ARC in the majority (15/19; 79%) of cases; only a minority (2/19; 10.5%) were due to the LLMI. Notably, 16 cases (12.1%) had a low LLMI with high‐risk post‐biopsy ARC and nine cases (6.8%) had a high LLMI with low‐risk post‐biopsy ARC.

Conclusions

This study observed that clinical evaluation for aspiration relied more heavily on transbronchial biopsy findings. Although LLMI may retain clinical utility in some scenarios, reevaluation of the clinical value of ORO testing would be prudent.
Laser Photoreduction of Graphene Aerogel Microfibers: Dynamic Electrical and Thermal Behaviors
Authors: Hunter Nicholas , Karamati Amin , Xie Yangsu , Lin Huan , Wang Xinwei
Published: August 2022

This work reports the dynamic behaviors of graphene aerogel (GA) microfibers during and after continuous wave (CW) laser photoreduction. The reduction results in one‐order of magnitude increase in the electrical conductivity. The experimental results reveal the exact mechanisms of photoreduction as it occurs: immediate photochemical removal of oxygen functional groups causing a sharp decrease in electrical resistance and subsequent laser heating that facilitates thermal rearrangement of GO sheets towards more graphene‐like domains. X‐ray and Raman spectroscopy analysis confirm that photoreduction removes virtually all oxygen and nitrogen containing functional groups. Interestingly, a dynamic period immediately following the end of laser exposure shows a slow, gradual increase in electrical resistance, suggesting that a proportion of the electrical conductivity enhancement from photoreduction is not permanent. A two‐part experiment monitoring the resistance changes in real‐time before and after photoreduction is conducted to investigate this critical period. The thermal diffusivity evolution of the microfiber is tracked and shows an improvement of 277 % after all photoreduction experiments. A strong linear coherency between thermal diffusivity and electrical conductivity is also uncovered. This is the first known work to explore both the dynamic electrical and thermal evolution of a GO‐based aerogel during and after photoreduction.
How does multi‐agent govern corporate greenwashing? A stakeholder engagement perspective from “common” to “collaborative” governance
Authors: Wang Wei , Sun Ziyuan , Zhu Weixing , Ma Lin , Dong Yuting , Sun Xiao , Wu Fengzhi
Published: August 2022

Greenwashing is an obstacle to the sustainable development of society, but the current governance of greenwashing is still a “common” governance, not a “collaborative” governance. Accordingly, this study focuses on the three stakeholders of greenwashing governance: company, media and government. Using a sample of listed companies that have published social responsibility reports from 2014 to 2018, this study analyzes the influence mechanism of media reports on greenwashing and discusses the moderating role of government regulation and mediating role of internal supervision. This study finds that internal supervision plays a hiding role in the process of media reports reducing greenwashing, but government regulation has a weakening effect on this hiding effect, showing a “common” governance. Simultaneously, this “common” governance is heterogeneous across time (i.e., corporate life cycle), space (i.e., spatial spillovers) and environment (i.e., the uncertainty of corporate external policies). However, when the cooperation between the government and the media is strengthened, the hiding behavior of the companies is suppressed and the performance of greenwashing governance is improved, so that “collaborative” governance is achieved. Against this backdrop, this study provides a macro‐to‐micro governance policy framework for corporate greenwashing from the four dimensions of strategy, systems, tools, and information to achieve “collaborative” governance. This study enriches the research on the corporate greenwashing governance and has practical implications for the government, media and other stakeholders.
Raciolinguistic policy assemblages and white supremacy in teacher education
Authors: Cushing Ian
Published: August 2022

Raciolinguistic ideologies are sets of beliefs about language which frame racialised communities as displaying linguistic deficiencies which require remediation. These ideologies are tethered to European colonialism and white supremacist logics which have long been normalised and actively written into teacher education policy in England. In this article I argue that raciolinguistic ideologies are integral to the contemporary, state‐crafted policy assemblage that pre‐service teachers and teacher educators must navigate, including the Teachers' Standards, the Core Content Framework and various documents produced by Ofsted, the schools inspectorate. I argue that this policy assemblage represents a form of hostile governance which is attempting to derail and curtail anti‐racist efforts. I show how raciolinguistic ideologies surface under guises of career advancement, pedagogical excellence, scientific objectivity, research validity and social justice. These guises operate to coerce pre‐service teachers and teacher educators to reproduce raciolinguistic ideologies in their own practice, reduce professional agency and place responsibility on low‐income and racialised communities to modify their language towards idealised whiteness. The article ends with some proposals for how teacher educators might find cracks in this oppressive system, in locating spaces for resistance which seek to undo harmful and colonial ideologies about language in the struggle against white supremacy.
Prediabetes and osteoporotic fracture risk: A meta‐analysis of prospective cohort studies
Authors: Ji Songjie , Jiang Xu , Han Huijun , Wang Cong , Wang Chao , Yang Dan
Published: August 2022

Background

Diabetes confers an increased risk of fracture. However, whether prediabetes is also a risk factor of osteoporotic fracture has not been comprehensively examined. We performed a meta‐analysis to evaluate the relationship between prediabetes and osteoporotic fracture risk.

Methods

This meta‐analysis included relevant prospective cohort studies from Medline, Embase, and Web of Science databases. A random‐effect model after incorporation of the intra‐study heterogeneity was selected to pool the results. Subgroup analyses were applied to evaluate the influences of study characteristics on relationship between prediabetes and osteoporotic fracture risk.

Results

Eight studies including 33,136 community dwelling adult patients were included, and 7429 (22.4%) patients were prediabetic. Prediabetes was not independently associated with a higher risk of osteoporotic fracture compared with normoglycemia (adjusted risk ratio: 1.03, 95% confidence interval: 0.88–1.21, P = 0.69, I2 = 42%). Sensitivity limited to the elderly population showed consistent results (RR: 1.10, 95% CI: 0.91–1.24, P = 0.15, I2 = 0%). Subgroup analysis suggested that prediabetes defined by HbA1c (approximately 5.7%–6.4%) was associated with a higher risk of osteoporotic fracture (RR: 1.24, 95% CI: 1.01–1.53, P = 0.04), but not that defined by impaired fasting glucose or impaired glucose tolerance (P = 0.60). Sex, follow‐up duration, and adjustment of bone mineral density did not significantly affect the outcome.

Conclusions

Current evidence does not support that prediabetes is independently associated with osteoporotic fracture risk. Different definitions of prediabetes may affect the association between prediabetes and osteoporotic fracture risk.
Discrepancies between validated GC‐FID and UHPLC‐DAD methods for the analysis of Δ‐9‐THC and CBD in dried hemp flowers
Authors: Duchateau Céline , De Leersnijder Cedric , Barhdadi Sophia , Canfyn Michaël , De Braekeleer Kris , Deconinck Eric
Published: August 2022

Herbal products for smoking containing cannabidiol (CBD) are available as “low‐tetrahydrocannabinol cannabis products” in most EU countries. In Belgium, Δ9‐tetrahydrocannabinol (THC) content of these products must be less than 0.2% w/w, which is also the limit for agricultural hemp. For agricultural hemp, the official and only valid method for European regulators is gas‐chromatography coupled to flame ionization detector (GC‐FID). There is no such method, for smoking products. Many of these herbal for smoking products are analyzed as part of their quality control and have certificate of analysis. During surveillance by official labs, discrepancies were seen between the official results and the certificate of analysis. In this study, a GC‐FID method based on the European method and an ultra‐high‐performance liquid chromatography coupled to diode array detection (UHPLC‐DAD) method were validated and applied for samples analysis in order to investigate these discrepancies. The GC‐FID method shows better results for the validation parameters; notably, it has β‐expectation tolerance limits within 10% with a β value of 95% while the validated UHPLC‐DAD method has β‐expectation tolerance limits within 15% with a β value of 90%. Furthermore, the other parameters evaluated are generally better with the GC‐FID method. The statistic t test shows that the difference between both methods was significantly different for total‐THC, but not significantly different for the total‐CBD. The authors state that, as for agricultural hemp, the GC‐FID method is to be preferred for the analysis of THC and CBD in products for smoking.
Detectability of oxandrolone, metandienone, clostebol and dehydrochloromethyltestosterone in urine after transdermal application
Authors: Gessner Lina , Thevis Mario , Rothschild Markus Alexander , Jübner Martin
Published: August 2022

Situations of both, intentional and inadvertent or accidental doping, necessitate consideration in today's doping controls, especially in the light of the substantial consequences that athletes are facing in case of so‐called adverse analytical findings. The aim of this study was to investigate, whether a transdermal uptake of doping substances would be possible. In addition to the period of detectability of the particular substances or respective characteristic metabolites, the possibility of deducing the route of administration by metabolite patterns was also assessed. Twelve male subjects were included in the study. Four common anabolic androgenic steroids (AAS) were dissolved in dimethylsulfoxide to facilitate transdermal administration on different skin regions. One half of the test persons received only oxandrolone (17α‐methyl‐2‐oxa‐4,5α‐dihydrotestosterone), and the other half were applied a mixture of oxandrolone, metandienone (17β‐hydroxy‐17α‐methylandrosta‐1,4‐dien‐3‐one), clostebol (4‐chlorotestosterone‐17β‐acetate) and dehydrochloromethyltestosterone (DHCMT). Urine samples were collected 1 h, 6 h and one sample per day for the next 14 consecutive days. Measurements were conducted on a tandem‐gas chromatography–mass spectrometry (GC‐MS/MS) or tandem‐liquid chromatography–MS/MS (LC‐MS/MS) system. Substance findings were obtained at least 1 day after application on nearly all skin locations. The results indicated inter‐individual variability in detection windows, also varying between the different analytes and possible impact of skin location and skin thickness, respectively. Nevertheless, a rapid and rather long detectability of all substances (or respective metabolites) was given, in some cases within hours after administration and for up to 10–14 days. Hence, the transdermal application or exposure to the investigated AAS is a plausible scenario that warrants consideration in anti‐doping.
Clinical impacts of sacubitril/valsartan on patients eligible for cardiac resynchronization therapy
Authors: Huang Hsin‐Ti , Huang Jin‐Long , Lin Po‐Lin , Lee Ying‐Hsiang , Hsu Chien‐Yi , Chung Fa‐Po , Liao Chia‐Te , Chiou Wei‐Ru , Lin Wen‐Yu , Liang Huai‐Wen , Chang Hung‐Yu
Published: August 2022

Aims

Sacubitril/valsartan (SAC/VAL) has been used in patients with heart failure and reduced ejection fraction (HFrEF), and cardiac resynchronization therapy (CRT) could benefit the HFrEF patients with wide QRS durations. This study aimed to evaluate the clinical impacts of SAC/VAL on reverse cardiac remodelling in CRT‐eligible and CRT‐ineligible HFrEF patients with different QRS durations.

Methods and results

The TAROT‐HF study was a multicentre, observational study enrolling patients who initiated SAC/VAL from 10 hospitals since 2017. Patients with baseline left ventricular ejection fraction (LVEF) ≤ 35% were classified into two groups: (i) Group 1: CRT‐eligible group, patients with left bundle branch block (LBBB) morphology plus QRS duration ≥130 ms or non‐LBBB morphology plus QRS duration ≥150 ms; and (ii) Group 2: CRT‐ineligible group. Propensity score matching was performed to adjust for confounders, and 1168 patients were analysed. Baseline characteristics were comparable between the two groups. The improvements in LVEF and left ventricular end‐systolic volume index (LVESVi) were more significant in Group 2 than in Group 1 after 1 year SAC/VAL treatment (LVEF: 8.4% ± 11.3% vs. 4.5% ± 8.1%, P < 0.001; change percentages in LVESVi: −14.4% ± 25.9% vs. −9.6% ± 23.1%, P = 0.004). LVEF improving to ≥50% in Groups 1 and 2 constituted 5.2% and 20.2% after 1 year SAC/VAL treatment (P < 0.001). Multivariate analyses showed that wide QRS durations were negatively associated with the reverse cardiac remodelling in these HFrEF patients with SAC/VAL treatment.

Conclusion

Despite SAC/VAL treatment, wide QRS durations are associated with lower degrees of left ventricular improvement than narrow ones in the HFrEF patients. Optimal intervention timing for the CRT‐eligible patients requires further investigation.
A review on characterization of supercapacitors and its efficiency analysis for different charging methods and applications
Authors: Pattnaik S. , Kumar M. R. , Mishra S. K. , Gautam S. P.
Published: August 2022

The dependence on renewable energy to solve the major energy issues related to global warming and shortage of energy resources is increasing drastically. This has led to high level awareness of proper energy storage and management. In this regard, supercapacitors have evolved as an efficient energy storage solution and hence successfully employed in several applications. This is attributed to its high‐power density, superior performance, and extended maintenance‐free lifetime. Also, it is known for low equivalent series resistance, that means, only a small amount of energy is lost while its charging/discharging even at high current. As a result, it has developed a lot of inquisitiveness among the research community of recent past for further exploration of different aspects of supercapacitors, ranging from material science, modeling and characterizations, engineering applications, and so forth. This review article aims at putting forth an exclusive study of their characterization of supercapacitor for different charging methods and applications. Further, the prime focus is given to the efficiency estimation of supercapacitors which is very essential as it denotes the amount of energy loss or the utilizable state of charge. The analysis has been carried out based on different charging methods and applications, which is essential for improving overall system reliability and performance. The purpose is to organize all important research carried out in this domain till date and to stimulate further insights for effective energy storage and management.
Effect of slopes on rainfall interception by leaf litter under simulated rainfall conditions
Authors: Zhao Longshan , Meng Ping , Zhang Jinsong , Zhang Jinxin , Sun Shoujia , He Chunxia
Published: August 2022

Rainfall interception is one of the main hydrological functions of leaf litter. However, the effect of slope on the interception capacity of leaf litter has received little attention. The objectives of this study were to determine the capacities of leaf litters to intercept rainwater under different slopes (i.e., flat ground at 0° and inclined slopes at 5°, 15°, 25° and 35°) and to analyse the ways in which the slope affects the interception capacity of leaf litter. Under a simulated rainfall intensity of 50 mm/h, litter flows (i.e., infiltration flow, slope flow and lateral flow) through three types of leaf litter (i.e., Pinus massoniana needleleaves and Osmanthus fragrans and Magnolia grandiflora broadleaves) were measured. The leaf litter biomass per unit area was 0.5 kg/m2 in the experimental box, and the interception capacity was calculated using the difference between rainfall and litter flow. The results show that the interception capacity of broadleaves was greater than that of needleleaves. The effect of slope was more pronounced than that of leaf shape because the rainwater stored on the leaf surfaces contributed to the generation of litter flow as the slope increased. The rainfall amount intercepted by each leaf litter decreased with increasing slope, and changes in the proportion of rainfall interception by leaf litter with increasing rainfall duration can be described by an exponential function (R2 > 0.80, p < 0.001). The maximum dynamic interception capacity (Cmax) and effective interception capacity (Cmin) of the three leaf litter types decreased as the slope increased. Statistical analyses show that 15° is a critical slope threshold that influences rainfall interception by leaf litter and litter flow. When the slope was greater than 15°, leaf litter interception capacities significantly decreased and the level of litter flow significantly increased. Therefore, slope affects the interception capacity of leaf litter and this impact should be considered in the estimation of litter interception storage on an inclined slope.