bluuebunny/crossref_metadata_2025 huggingface dataset:
Benzotriazole‐Based Polymer Acceptor for High‐Efficiency All‐Polymer Solar Cells with High Photocurrent and Low Voltage Loss
Authors: Li Xiaoming , Duan Xiaopeng , Qiao Jiawei , Li Shilin , Cai Yunhao , Zhang Jianqi , Zhang Yuan , Hao Xiaotao , Sun Yanming
Published: November 2022

The power conversion efficiencies (PCEs) of all‐polymer solar cells (all‐PSCs) have already exceeded 17%. However, the limited absorption range of an all‐polymer system results in significantly reduced short‐circuit current density (Jsc), which eventually influences the PCE improvement. To broaden the light absorption of polymer acceptors, herein, benzotriazole is introduced in the core unit of small molecule acceptors and thus two narrow‐bandgap polymer acceptors named PTz‐BO and PTz‐C11 featuring the same molecular backbone and different side‐chain length are synthesized. Compared with PTz‐C11, the PTz‐BO based‐all PSCs deliver a slightly reduced Jsc, a large open‐circuit voltage (Voc) and a low voltage loss below 0.50 V. Moreover, ternary all‐PSCs are constructed by introducing PTz‐C11 as a guest component. Benefiting from the reduced recombination, improved exciton generation and dissociation, and balanced charge transport, a high efficiency of 16.58% is obtained for the ternary all‐PSCs, with a high Jsc over 25 mA cm−2 without sacrificing the Voc. Such result represents the highest efficiency reported for benzotriazole‐based all‐PSCs in the literature thus far. This work demonstrates the great potential of benzotriazole for the synthesis of efficient narrow‐bandgap polymer acceptors.
A Pleistocene assemblage of near‐modern Papio hamadryas from the Middle Awash study area, Afar Rift, Ethiopia
Authors: Brasil Marianne F. , Monson Tesla A. , Taylor Catherine E. , Yohler Ryan M. , Hlusko Leslea J.
Published: November 2022

Objectives

The aim of this study is to assess a new assemblage of papionin fossils (n = 143) recovered from later Pleistocene sediments in the Middle Awash study area in the Afar Rift of Ethiopia.

Materials and Methods

We collected metric and qualitative data to compare the craniodental and postcranial anatomy of the papionin fossils with subspecies of modern Papio hamadryas and with Plio‐Pleistocene African papionins. We also estimated sex and ontogenetic age.

Results

The new fossils fit well within the range of morphological variation observed for extant P. hamadryas, overlapping most closely in dental size and proportions with the P. h. cynocephalus individuals in our extant samples, and well within the ranges of P. h. anubis and P. h. hamadryas. The considerable overlap in craniodental anatomy with multiple subspecies precludes subspecific diagnosis. We therefore referred 143 individuals to P. hamadryas ssp. The majority of the individuals assessed for ontogenetic age fell into middle‐ and old‐adult age categories based on the degree of dental wear. Males (26%) were better represented than females (12%) among individuals preserving the canine‐premolar honing complex.

Discussion

These new near‐modern P. hamadryas fossils provide a window into population‐level variation in the later Pleistocene. Our findings echo previous suggestions from genomic studies that the papionin family tree may have included a ghost population and provide a basis for future testing of hypotheses regarding hybridization in the recent evolutionary history of this taxon.
Mutability‐Landscape‐Guided Engineering of l‐Threonine Aldolase Revealing the Prelog Rule in Mediating Diastereoselectivity of C−C Bond Formation
Authors: Zheng Wenlong , Pu Zhongji , Xiao Lanxin , Xu Gang , Yang Lirong , Yu Haoran , Wu Jianping
Published: November 2022

l‐threonine aldolase (LTA) catalyzes C−C bond synthesis with moderate diastereoselectivity. In this study, with LTA from Cellulosilyticum sp (CpLTA) as an object, a mutability landscape was first constructed by performing saturation mutagenesis at substrate access tunnel amino acids. The combinatorial active‐site saturation test/iterative saturation mutation (CAST/ISM) strategy was then used to tune diastereoselectivity. As a result, the diastereoselectivity of mutant H305L/Y8H/V143R was improved from 37.2 %syn to 99.4 %syn. Furthermore, the diastereoselectivity of mutant H305Y/Y8I/W307E was inverted to 97.2 %anti. Based on insight provided by molecular dynamics simulations and coevolution analysis, the Prelog rule was employed to illustrate the diastereoselectivity regulation mechanism of LTA, holding that the asymmetric formation of the C−C bond was caused by electrons attacking the carbonyl carbon atom of the substrate aldehyde from the re or si face. The study would be useful to expand LTA applications and guide engineering of other C−C bond‐forming enzymes.
Synthesis of α‐Quaternary β‐Lactams via Copper‐Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross‐Coupling with Organoboronate Esters
Authors: Wang Fu‐Li , Liu Lin , Yang Chang‐Jiang , Luan Cheng , Yang Jing , Chen Ji‐Jun , Gu Qiang‐Shuai , Li Zhong‐Liang , Liu Xin‐Yuan
Published: November 2022

The copper‐catalyzed enantioconvergent radical C(sp3)−C(sp2) cross‐coupling of tertiary α‐bromo‐β‐lactams with organoboronate esters could provide the synthetically valuable α‐quaternary β‐lactams. The challenge arises mainly from the construction of sterically congested quaternary stereocenters between the tertiary alkyl radicals and chiral copper(II) species. Herein, we describe our success in achieving such transformations through the utilization of a copper/hemilabile N,N,N‐ligand catalyst to forge the sterically congested chiral C(sp3)−C(sp2) bond via a single‐electron reduction/transmetalation/bond formation catalytic cycle. The synthetic potential of this approach is shown in the straightforward conversion of the corresponding products into many valuable building blocks. We hope that the developed catalytic cycle would open up new vistas for more enantioconvergent cross‐coupling reactions.
Near‐Infrared‐Absorbing Chiral Open [60]Fullerenes
Authors: Hashikawa Yoshifumi , Sadai Shumpei , Okamoto Shu , Murata Yasujiro
Published: November 2022

Though [60]fullerene is an achiral molecular nanocarbon with Ih symmetry, it could attain an inherent chirality depending upon a functionalization pattern. The conventional chiral induction of C60 relies mainly upon a multiple addition affording a mixture of achiral and chiral isomers while their chiral function would be largely offset by the existence of pseudo‐mirror plane(s). These are major obstacles to proceed further study on fullerene chirality and yet leave its understanding elusive. Herein, we showcase a carbene‐mediated synthesis of C1‐symmetric chiral open [60]fullerenes showing an intense far‐red to near‐infrared absorption. The large dissymmetry factor of |gabs|=0.12 was achieved at λ=820 nm for circular dichroism in benzonitrile. This is, in general, unachievable by other small chiral organic molecules, demonstrating the potential usage of open [60]fullerenes as novel types of chiral chromophores.
Isolated Electron‐Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia
Authors: Zhang Huaifang , Li Yanbo , Cheng Chuanqi , Zhou Jin , Yin Pengfei , Wu Haoming , Liang Zhiqin , Zhang Jiangwei , Yun Qinbai , Wang An‐Liang , Zhu Lijie , Zhang Bin , Cao Wenbin , Meng Xiangmin , Xia Jing , Yu Yifu , Lu Qipeng
Published: November 2022

The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH3with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body‐centered cubic RuGa intermetallic compounds (i.e.,bccRuGa IMCs) via a substrate‐anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH4+yield rate of 320.6 μmol h−1 mg−1Ruwith the corresponding Faradaic efficiency of 72.3 % at very low potential of −0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron‐rich Ru atoms inbccRuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential‐determining step in NORR could be greatly reduced.
Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion
Authors: Jiang Yunzhe , Danowski Wojciech , Feringa Ben L. , Heinke Lars
Published: November 2022

Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom‐up layer‐by‐layer assembly of oriented overcrowded‐alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded‐alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light‐induced molecular rotation. Taking advantage of the thin film's transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta‐)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials.
Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen Evolution
Authors: An Li , Zhang Hong , Zhu Jiamin , Xi Shibo , Huang Bolong , Sun Mingzi , Peng Yong , Xi Pinxian , Yan Chun‐Hua
Published: November 2022

Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet(Co2)octO4 nanosheets (NSs) at fixed geometrical sites, including Mnoct, Nioct, and Nitet, to optimize the initial geometrical structure and modulate the CoCo2O4 surface from oxygen‐excess to oxygen‐deficiency. The pristine (Ni,Mn)‐(Co)tet(Co2)octO4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a current density of 10 mA cm−2. Moreover, without damaging their initial activity, the activated (Act)‐(Ni,Mn)‐(Co)tet(Co2)octO4 NSs after surface reconstruction exhibit long‐term stability of 100 h under 10 mA cm−2, 50 mA cm−2, or even 100 mA cm−2. The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.
Synthesis, modification, and adsorption properties of Yb‐MOF: Kinetic and thermodynamic studies
Authors: Yin Lili , Deng Qinsong , Ke Zhilin , Yu Qiaoling , Xiao Yu , Zhang Shuhua
Published: November 2022

In this paper, a novel Yb metal–organic frameworks {[Yb(L)(DMA)(H2O)]·(3H2O)}n(Yb‐MOF, H3Lis 4‐(N,N′‐bis(4‐carboxylbenzyl)amino)benzenesulfonic acid) was synthesized by solvothermal reaction. ModifiedYb‐MOFwas prepared by the potassium permanganate method for removing the Cu(II) and As(V) from simulated wastewater. The optimal pH value of modifiedYb‐MOFfor Cu(II) and As(V) adsorption was 5, and the optimal dosage of adsorbent was 0.04 mg/10 ml by static adsorption test. Four isothermal adsorption models (Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich models) were fitted and analyzed. The adsorption processes of Cu(II) and As(V) were consistent with Freundlich, Langmuir, and Temkin models. The highest Cu(II) and As(V) adsorption capacity are 59.418 and 81.169 mg/g, respectively. The adsorption kinetic model and thermodynamic analysis of the modifiedYb‐MOFfor Cu(II) and As(V) were studied. The results showed revealed that the pseudo‐second‐order kinetic had a higher correlation association with the Cu(II) and As(V) adsorption process, indicating that chemisorption was dominant in both processes. At 298 and 308 K, the Cu(II) and As(V) adsorption by modifiedYb‐MOFis spontaneous.
Hyaluronan‐coated poly(propylene imine) dendrimers as biomimetic nanocarriers of doxorubicin
Authors: Paolino Marco , Varvarà Paola , Saletti Mario , Reale Annalisa , Gentile Mariangela , Paccagnini Eugenio , Giuliani Germano , Komber Hartmut , Licciardi Mariano , Cappelli Andrea
Published: November 2022

A coating technology based on low molecular weight hyaluronic acid (HA) and ferulic acid (FA) was applied to the coating of low generation poly(propylene imine) dendrimers through a biocompatible hexa(ethylene glycol) spacer. The ensuing HA‐FA‐HEG‐PPID dendrimeric materials showed interesting loading capability (between 7.65% and 9.08%) regarding anticancer agent doxorubicin, and their interactions with the drug appeared to hamper the drug release in the physiological environment. Thus, the stable nanostructured loaded delivery systems were able to internalize into cells expressing the HA receptor CD44 and to demonstrate high cytotoxicity comparable to that shown by equivalent amounts of free doxorubicin. Thus, HA‐FA‐HEG‐PPID dendrimeric materials were proposed as biocompatible drug carriers capable of transporting anticancer doxorubicin to tumor cells.
Optimization of high temperature energy storage properties of PEI‐based composite dielectric based on rapid in‐situ growth of inorganic functional layer
Authors: Xu Fuping , Feng Yu , Liu Guang , Zhang Changhai , Li Changming , Chen Qingguo , Chi Qingguo
Published: November 2022

The serious deterioration of the energy density of polymer energy storage dielectrics in high temperature environment is the main reason to curb the in‐depth application of dielectric film capacitors in the field of modern electrical and electronic engineering. Here, aiming at the problem of low dielectric constant of polymer dielectric, a simple, low‐cost method is proposed to grow inorganic polar functional layer on surface of polymer film in situ, which effectively improves the polarization characteristics of polymer dielectric at high temperature. The in situ growth of Ti(OH)4 inorganic polar functional layer on surface of polyetherimide (PEI) film noteworthy to improve the energy storage performance of dielectric film. The energy storage density of 4.59 J/cm2 is obtained at 150°C and 600 MV/m, which is 1.18 times that of PEI film under the same condition. The significant enhancement of high temperature energy storage density can be attributed to introduction of functional layer, which effectively improves the dielectric properties and polarization intensity of dielectric film. Furthermore, the facile preparation method provided in this paper can be applied to various thin films under the premise of controllable cost, which is of great significance to improve the high temperature energy storage characteristics of polymer dielectric.
Infiltration of laponite: An effective approach to improve the mechanical properties and thermostability of collagen hydrogel
Authors: Li Jiao , Tian Zhenhua , Yang Huan , Duan Lian , Liu Yunfei
Published: November 2022

Rapid aggregate precipitation of collagen and laponite in solution restricted the development of corresponding hybrid materials. Herein, a facile method of immerging collagen hydrogel into laponite dispersion was adopted to prepare hybrid collagen/laponite hydrogel, avoiding the precipitation. Collagen hydrogel shrunk and water content decreased dramatically after laponite solution treatment. According to the images of Scanning electron microscopy and energy dispersive system, the uniformly dispersed laponite in collagen hydrogel was observed, demonstrating infiltration of laponite into collagen hydrogel. X‐ray photoelectron spectroscopy results revealed that coordination bonds generated between magnesium in laponite and collagen. Thermogravimetric analysis and Differential scanning calorimetry results displayed thermal decomposition temperature of collagen hydrogel increased from 321 to 342°C, and denaturation temperature rose from 43.8 to 50.8 °C after laponite infiltration. Rheological and compressive tests showed the elastic modulus, fracture stress, compressive modulus and rupture point of hydrogel treated by 10% laponite were 695.2 Pa, 253.3 kPa, 13.5 kPa and 76.7%, respectively, which were about 3.5, 5.5, 45.0, and 1.4 times larger than those of pristine collagen hydrogel. Besides, enzyme degraded rate of collagen was decelerated, and the hydrogel was still nontoxic with the infiltration of laponite. The promising data demonstrated infiltration of laponite was an effective way to fabricate collagen/laponite hybrid materials with desirable properties.
Spatial–temporal feature extraction based on convolutional neural networks for travel time prediction
Authors: Chen Abel C. H. , Yang Ya‐Ting
Published: November 2022

In recent years, some traffic information prediction methods have been proposed to provide the precise information on travel time, vehicle speed and traffic flow for highways. However, huge errors may be obtained by these methods for urban roads or alternative roads of highways. Therefore, this study proposes a travel time prediction method based on convolutional neural networks to extract important factors for the improvement of traffic information prediction. In practical experimental environments, the travel time records on No. 5 Highway and its alternative roads were collected and used to evaluate the proposed method. The results showed that the mean absolute percentage error of the proposed method was about 5.69%. Therefore, the proposed method based on deep‐learning techniques can improve the accuracy of travel time prediction.
Lowering of Electrostatic Actuator Driving Voltage and Increasing Generated Force Using Spontaneous Polarization of Ferroelectric Nematic Liquid Crystals
Authors: Nishimura Suzushi , Masuyama Satoshi , Shimizu Genichiro , Chen Chun‐Yi , Ichibayashi Taku , Watanabe Junji
Published: November 2022

Although electrostatic actuators have a simple structure and are lightweight, their range of application is limited because a high applied voltage of more than several kilovolts is required for practical use. Since the force acting between the electrodes of an electrostatic actuator is determined by the electric charge accumulated at the electrode/dielectric interface, the focus is on spontaneous polarization of ferroelectrics to increase the charge. As the ferroelectric material, a nematic liquid crystal material with a spontaneous polarization of 5 µC cm−2 is used. It is demonstrated that a force of 1.3 N is generated at an applied electric field of 0.5 MV m−1. This force is 1200 times higher than that for standard paraelectric materials with a dielectric constant of ten. Further, the generated force responds linearly to the applied voltage, whereas it is proportional to the square of the applied voltage for paraelectric materials. The actuator function of this ferroelectric is examined using a double‐helical coil electrode fabricated using a 3D printer. It can be successfully operated at a voltage of several tens of volts. Under an electric field of 0.25 MV m−1, a remarkable contraction of 6.3 mm occurs, corresponding to 19% of the original length.
Online tuning of derivative order term of variable‐order fractional proportional–integral–derivative controllers for the first‐order time delay systems
Authors: Can Kurucu Mert , Yumuk Erhan , Güzelkaya Müjde , Eksin Ibrahim
Published: November 2022

In this study, an online tuning strategy for the fractional derivative order term of the variable‐order fractional proportional–integral–derivative (PID) controller is proposed for processes with dead time. The classical step response is divided into regions, and meta‐rules are developed for each region in order to improve the control performance. To achieve the goals of the meta‐rules, a set of equations that are the functions of absolute error and model parameters are proposed to manipulate the fractional order derivative during the process. These equations can handle the changes in model parameters since the coefficients of these equations are functions of model parameters. On both simulation studies and experimental results on the active suspension system, we show that the proposed method improves the time domain performance criteria both in relation to reference tracking and load disturbance rejection. Moreover, the robustness of the proposed method has also been tested and analyzed for the dead time variation within the process.
Lean–agile–resilience–green practices adoption challenges in sustainable agri‐food supply chains
Authors: Sahu Atul Kumar , Raut Rakesh D. , Gedam Vidyadhar V. , Cheikhrouhou Naoufel , Sahu Anoop Kumar
Published: November 2022

Supply chain practitioners are striving to improve the performance of agri‐food supply chains (AFSC) due to the lack of understanding of the mutual impacts of lean, agile, resilience, and green (LARG) practices in improving the performance of AFSC. There is a lack of specific methods to assess the power of their subsequent attributes. This paper identifies 12 unique challenges related to the implementation of LARG practices under the context of AFSC. The identification of challenges and the interdependency relationships among the LARG challenges are developed using a multistage approach. The multistage approach is composed of the generalized interval‐valued trapezoidal fuzzy numbers (GIVTFNs), the degree of similarity method, and the decision‐making trial and evaluation laboratory (DEMATEL) method. The finding of the study indicates that “Lack of understanding between the customer and other stakeholder requirements” and “Lack of transparency and trust” are the most significant challenges in the cause group and are the driving elements for implementing LARG practices. Furthermore, “Lack of competitive advantages” and “Lack of monitoring and auditing the ongoing supply chain activities” fall under the effect category, which are influenced by the cause groups' challenges. The identified challenges can be controlled and handled strategically on a priority basis for successfully implementing LARG practices in the agri‐food industry. The finding of study will help practitioners to overcome the LARG challenges and to improve the overall performance of AFSC.
The quality of SMEs stakeholder communication during strategic crises: The case of Italian unlisted SMEs
Authors: Cardoni Andrea , Kiseleva Evgeniia , Bellucci Andrea
Published: November 2022

The aim of this paper is to assess small and medium‐sized enterprises' (SMEs') readiness to initiate a mature dialogue with stakeholders in the exceptional context of a strategic crisis, when information on business model sustainability has become universally material for all stakeholders. A quantitative study is carried out by developing a business model content analysis and applying it to a data sample of 109 manufacturing SMEs in Italy with annual revenues ranging from €10 to €50 million. After analyzing the literature on SMEs stakeholder communication and arguing the conflicting influences of stakeholder and legitimacy motivations in the context of a strategic crisis, three hypotheses are tested by collecting data from annual reports. Despite increased stakeholder expectations, the level of communication was limited to a minimum amount of information, demonstrating no relationship with the firms' relative size and proving a prominent influence of legitimacy motivations, with a specific relevance of legal pressures. Under the stress of the crisis, all SMEs, particularly those that were strategically and financially vulnerable, provided extremely limited information, demonstrating the tendency to conceal strategic risks and the difficulties in engaging in mature dialogue with stakeholders. To the best of our knowledge, this is the first quantitative study focusing on unlisted SMEs' sustainability communication. The paper contributes to the policymaker debate on the possibility of extending the current legal obligation on sustainability reporting and transparency to smaller businesses.
Solid Single‐Atom Catalysts in Tandem Catalysis: Lookout, Opportunities and Challenges
Authors: Rodenas Tania , Prieto Gonzalo
Published: November 2022

Tandem catalysis stands out as a major instrument towards the intensification of existing and future chemical processes. Initially formulated in the field of homogeneous catalysis, the concept relies on the single‐pot integration of two (or more) catalysts showing high specificity for mechanistically decoupled reactions, while being operational and compatible under a single set of operation conditions. Isolated metal atoms stabilized on solid carriers in single‐atom catalysts (SACs) hold the potential to reconcile the high reaction specificities of mononuclear sites in molecular catalysts with an intrinsic catalyst compartmentalization on inorganic matrices. Understandably, SACs have started to be considered as platforms in tandem catalysis. Tandem (electro)catalytic processes based on SACs have been showcased recently. While this sets excellent prospects for the expansion of this research subarea, challenges are faced, particularly as to the verification of the tandem nature of the processes.
Micellar Effects and their Relevance in Photochemistry and Photocatalysis
Authors: Brüss Linda , Jeyaseelan Rubaishan , Kürschner Julian C. G. , Utikal Martin , Næsborg Line
Published: November 2022

The encapsulation of substrates within micellar structures gives rise to a multitude of effects beyond simple solubilization in water. When incorporated in photochemical reaction design micellar media may offer possibilities to control both reactivity and selectivity. Herein, we describe various important micellar phenomena such as encapsulation, polarity differences, electrostatic interactions and hydrogen bonding, and discuss the various resulting mechanisms by which reaction outcomes can be greatly influenced. In this concept article, we showcase selected photochemical reactions to demonstrate how micellar effects can be selectively applied in reaction design.
Preparation of Micron and Submicron Particles via Spray Drying and Electrostatic Precipitation
Authors: Justen Anna , Kurth Christopher , Schaldach Gerhard , Thommes Markus
Published: November 2022

Small particles are of great interest in a variety of applications. Spray drying is a common technique for particle synthesis, but it is limited with respect to sizes below 10 μm. Therefore, a new laboratory‐scale spray dryer was designed to address this issue. A novel aerosol generator consisting of a piezo crystal in a swirl chamber was designed to obtain droplets in the low micrometer range. After drying and cooling, particles were deposited in a molten carrier, using melt electrostatic precipitation. The median particle size of three pharmaceutical drug substances was 2 μm. The size distribution was particularly narrow, with span values of about 1.1. Spray drying is a sufficient technique to produce small drug particles below 5 μm with ultrasonic atomization at high frequencies. Electrostatic precipitation in a molten carrier is a suitable method to capture these particles.
Reconstructured Electrocatalysts during Oxygen Evolution Reaction under Alkaline Electrolytes
Authors: Jia Hongnan , Yao Na , Zhu Juan , Luo Wei
Published: November 2022

The development of electrocatalysts with high‐efficiency and clear structure‐activity relationship towards the sluggish oxygen evolution reaction (OER) is essential for the wide application of water electrolyzers. Recently, the dynamic reconstruction phenomenon of the catalysts’ surface structures during the OER process has been discovered. With the help of various advanced ex situ and in situ characterization, it is demonstrated that such surface reconstruction could yield actual active species to catalyze the water oxidation process. However, the attention and studies of potential interaction between reconstructed species and substrate are lacking. This review summarizes the recent development of typical reconstructed electrocatalysts and the substrate effect. First, the advanced characterization for electrocatalytic reconstruction is briefly discussed. Then, typical reconstructed electrocatalysts are comprehensively summarized and the key role of substrate effects during the OER process is emphasized. Finally, the future challenges and perspectives of surface reconstructed catalysts for water electrolysis are discussed.
Formation, Reactivity and Decomposition of Aryl Phospha‐Enolates
Authors: Urwin Stephanie J. , Goicoechea Jose M.
Published: November 2022

Two lithium phospha‐enolates [RP=C(SiiPr3)OLi]2were prepared by reaction of triisopropyl silyl phosphaethynolate,iPr3SiPCO, with aryl lithium reagents LiR (R=Mes: 1,3,5‐trimethyl phenyl; or Mes*: 1,3,5,‐tri‐tertbutyl phenyl). Monomer/dimer aggregation of the enolates can be modulated by addition of 12‐crown‐4. Substitution of lithium for a heavier alkali metal was achieved through initial formation of a silyl enol ether, followed by reaction with KOtBu to form the corresponding potassium phospha‐enolate [MesP=C(SiiPr3)OK]2. On addition of water, the enolates are protonated to afford RP=C(SiiPr3)(OH). For the sterically less demanding system (R=Mes), this phospha‐enol rapidly tautomerises to the corresponding acyl phosphine MesP(H)C(SiiPr3)(O), which on heating extrudes CO. In contrast, bulkier phospha‐enol (R=Mes*) is stable to rearrangement at room temperature and thermally decomposes to RH andiPr3SiPCO.
The effectiveness of cognitive behavioural therapy for social anxiety disorder in routine clinical practice
Authors: Morina Nexhmedin , Seidemann Julienne , Andor Tanja , Sondern Lisa , Bürkner Paul‐Christian , Drenckhan Isabelle , Buhlmann Ulrike
Published: November 2022

Numerous randomized controlled trials have shown cognitive behaviour therapy (CBT) to be effective in treating social anxiety disorder (SAD). Yet, less is known about the effectiveness of CBT for SAD conducted by psychotherapists in training in routine clinical practice. In this study, 231 patients with SAD were treated with CBT under routine conditions and were examined at pre‐ and post‐treatment as well as at 6 and 12 months follow‐up. We applied self‐reports to assess symptoms of SAD (defined as primary outcome), depression and psychological distress (defined as secondary outcome). We conducted both completer and intent‐to‐treat analyses and also assessed the reliability of change with the reliable change index. Results revealed significant reductions in symptoms of SAD between pre‐ and post‐assessments, with effect sizes ranging from d = 0.9 to 1.2. Depending on the SAD specific questionnaire applied, 47.8% to 73.5% of the sample showed a reliable positive change, whereas 1.9% to 3.8% showed a reliable negative change. Depressive symptoms and psychological distress also decreased significantly from pre‐ to post‐assessment, with large effect sizes. Significant treatment gains regarding both primary and secondary outcomes were further observed at 6 and 12 months follow‐up. The current findings based on a large sample of patients suggest that psychotherapists in CBT training working under routine conditions can effectively treat symptoms of SAD, depression and psychological distress.
Optimized channel prediction and auction‐based channel allocation for personal cognitive networks
Authors: Jeyakanth Krishnan , Venkatakrishnan Perumalsamy , Chitra Chinnasamy
Published: November 2022

Cognitive networks are stands out as intelligent technology which evolved to enhance spectrum utilization. Secondary users are allowed to utilize the primary user's frequency bands on idling times. Identifying the idle licensed spectrum is achieved through spectrum sensing. The spectrum holes should be explored such that a suitable spectrum can be selected and allocated to the secondary users. Existing spectrum sensing and selection schemes have limitations due to interferences. Thus, an optimization algorithm based on bio‐inspired improved weed optimization was presented in this research work for enhanced channel utilization. The optimization model explores the channel characteristics and reduces the primary network interferences through its optimal solution. Further, Markov greedy‐based auction scheme was presented for channel allocation. Considering the channel capacity, delay, and switching rates the allocation is performed to enhance the overall system performance. Simulation analysis demonstrates the superior performance of the proposed model over existing techniques like particle swarm optimization and genetic algorithm.
Molecular testing in cytology
Authors: Schmitt Fernando , Yang Zhongbo , Esebua Magda
Published: November 2022

In the era of personalized medicine, molecular testing plays a critical role in patient care. The rapid advance of molecular techniques, especially next‐generation sequencing, makes molecular diagnosis feasible in daily practice. Molecular testing can be used as a valuable ancillary test to increase diagnostic sensitivity and specificity, especially in small biopsy or cytology samples. In addition, molecular testing plays an important role in selecting patients for appropriate treatment by detecting therapeutic and predictive biomarkers in tissue or cytology samples. Molecular studies can be applied in all cytology samples, sometimes with better results than histology. As molecular testing has become essential for patient care and is often requested to be performed in cytology samples, it is critical for cytopathologists to understand the basics of molecular diagnostic methods, indications for molecular testing, and how to best utilize different cytologic samples for this purpose. In this special issue, experts in various areas of cytopathology and molecular pathology review the literature and discuss the basics of molecular techniques and the application of molecular testing in various types of cytology samples. It is our hope that after reading the articles in this special issue, the readers can know better about the possibilities of molecular cytology, a very exciting field of pathology.
Sustainable Recycling of Spent Ionic Liquid Dual‐Ion Batteries
Authors: Lin Kuan-Yu , Hsieh Tsung-Lin , Wu Yi-Hao , Lin Meng-Chang
Published: November 2022

Ionic liquid (IL) dual‐ion batteries (DIBs) are widely studied as advanced electrochemical systems because of their potential nonflammability, environmental friendliness, and high working voltage. Recycling and reusing valuable IL electrolytes and metallic Ni current collectors might boost the application of IL DIBs. Herein, the preliminary results of the recycling of a spent DIB with 1,2‐dimethyl‐3‐propylimidazolium chloroaluminate (DMPI+)(AlCl4−) electrolyte are reported. Recovery rates of most components (graphite flakes, Ni current collector, and so on) of the DIB reach a range of 84–98%, whereas the IL electrolyte is only 24%. Optimistically, the cost of an IL DIB using recycled components can be reduced by around 68%. Thus, developing the recycling processes might pave the way to increase the competitiveness of IL DIBs for grid‐scale energy storage.
Extreme late onset of genetic generalized epilepsy in older adults and the elderly: A cohort study and literature review
Authors: Alzahrany Majed , Punia Vineet
Published: November 2022

Rare case reports describe genetic generalized epilepsy (GGE) starting de novo in people ≥50 years of age (older adults and the elderly). We aimed to provide comprehensive detail of electro‐clinical findings of this extremely late‐onset GGE using a retrospective, single‐center cohort design and a systematic review of the literature. People with de novo seizure onset ≥50 years of age with EEG and clinical history consistent with GGE were included. These 12 individuals (9; 75% females) with a median age of 56 years at seizure onset accounted for 7.9% of 152 older adults and the elderly with generalized epilepsy. Three patients only had absence seizures. A family history of epilepsy was present in 5 individuals. They had tried a median of 2 anti‐seizure medications. More than 90% (11 of 12) were seizure‐free for >1 year at the last follow‐up, including four requiring monotherapy. Valproate was used in only two patients and levetiracetam in 75% of them. A systematic literature review revealed six papers with 10 extreme late‐onset GGE cases. They similarly had good seizure outcomes but a majority were on valproate. Our study shows that rarely, late‐onset epilepsy can be GGE, which mostly has a good prognosis.
Relevance of field data in the assessment of structural and functional sediment connectivity in a small catchment of southern Brazilian plateau
Authors: Abatti Bruno Henrique , Zanandrea Franciele , Paul Leonardo Rodolfo , Michel Gean Paulo
Published: November 2022

Hydrological and sedimentological dynamics are controlled by hillslope‐channel (de)coupling, which is influenced by several natural and anthropogenic factors. However, studies on sediment connectivity are recent and present numerous challenges to be overcome. Furthermore, there is a need to explore and identify sediment connectivity governing processes and phenomena. In this study, hydrological monitoring and indices application were used to access aspects of sediment connectivity in a small catchment (0.89 km2), located on a plateau in southern Brazil. The indices are a combination of variables conceptually known as controllers of the spatial and temporal organization of sediment flows in the system. The application of these tools proved to be relevant for the characterization of structural and functional connectivity of the study area. The tools applied were structural index of connectivity (IC); index of hydrosedimentological connectivity (IHC), based on observed events; field connectivity index (FIC). The characterization of structural connectivity highlighted natural sinks and blankets zones as the main elements of disconnection in the catchment. The functional connectivity was evaluated for five distinct magnitude events, the results showed a higher influence of sediment availability and antecedent moisture conditions than the other structural factors. The FIC validated the theoretical indices in the study area and highlighted the importance of coupling thresholds between the numerous sediment sources in a known event.
Identifying structural VARs from sparse narrative instruments: Dynamic effects of US macroprudential policies
Authors: Budnik Katarzyna , Rünstler Gerhard
Published: November 2022

We study identification in Bayesian proxy VARs for instruments that consist of sparse qualitative observations indicating the signs of shocks in specific periods. We propose the Fisher discriminant regression and a non‐parametric sign concordance criterion as two alternative methods for achieving correct inference in this case. The former represents a minor deviation from a standard proxy VAR, whereas the non‐parametric approach builds on set identification. Our application to US macroprudential policies finds persistent declines in credit volumes and house prices together with moderate declines in GDP and inflation and a widening of corporate bond spreads after a tightening of capital requirements or mortgage underwriting standards.
Reduction in required volume of imaging data and image reconstruction time for adaptive‐illumination Fourier ptychographic microscopy
Authors: Luo Jiaxiong , Tan Haishu , Wu Ruofei , Zhu Sicong , Chen Hanbao , Zhen Junrui , Li Jiancong , Guan Caizhong , Wu Yanxiong
Published: November 2022

Fourier ptychographic microscopy (FPM) is a promising super‐resolution computational imaging technology. It stitches a series of low‐resolution (LR) images in the Fourier domain by an iterative method. Thus, it obtains a large field of view and high‐resolution quantitative phase images. Owing to its capability to perform high‐spatial bandwidth product imaging, FPM is widely used in the reconstruction of conventional static samples. However, the influence of the FPM imaging mechanism limits its application in high‐speed dynamic imaging. To solve this problem, an adaptive‐illumination FPM scheme using regional energy estimation is proposed. Starting with several captured real LR images, the energy distribution of all LR images is estimated, and select the measurement images with large information to perform FPM reconstruction. Simulation and experimental results show that the method produces efficient imaging performance and reduces the required volume of data to more than 65% while ensuring the quality of FPM reconstruction.
Bone Formation in 2D Culture of Primary Cells
Authors: Mertz Edward L. , Makareeva Elena , Mirigian Lynn S. , Leikin Sergey
Published: November 2022

Relevance of mineralized nodules in two‐dimensional (2D) osteoblast/osteocyte cultures to bone biology, pathology, and engineering is a decades old question, but a comprehensive answer appears to be still wanting. Bone‐like cells, extracellular matrix (ECM), and mineral were all reported but so were non‐bone‐like ones. Many studies described seemingly bone‐like cell‐ECM structures based on similarity to few select bone features in vivo, yet no studies examined multiple bone features simultaneously and none systematically studied all types of structures coexisting in the same culture. Here, we report such comprehensive analysis of 2D cultures based on light and electron microscopies, Raman microspectroscopy, gene expression, and in situ messenger RNA (mRNA) hybridization. We demonstrate that 2D cultures of primary cells from mouse calvaria do form bona fide bone. Cells, ECM, and mineral within it exhibit morphology, structure, ultrastructure, composition, spatial–temporal gene expression pattern, and growth consistent with intramembranous ossification. However, this bone is just one of at least five different types of cell‐ECM structures coexisting in the same 2D culture, which vary widely in their resemblance to bone and ability to mineralize. We show that the other two mineralizing structures may represent abnormal (disrupted) bone and cartilage‐like structure with chondrocyte‐to‐osteoblast transdifferentiation. The two nonmineralizing cell‐ECM structures may mimic periosteal cambium and pathological, nonmineralizing osteoid. Importantly, the most commonly used culture conditions (10mM β‐glycerophosphate) induce artificial mineralization of all cell‐ECM structures, which then become barely distinguishable. We therefore discuss conditions and approaches promoting formation of bona fide bone and simple means for distinguishing it from the other cell‐ECM structures. Our findings may improve osteoblast differentiation and function analyses based on 2D cultures and extend applications of these cultures to general bone biology and tissue engineering research. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.
Urinary neutrophil gelatinase‐associated lipocalin predicted to contrast‐associated acute kidney injury after planned percutaneous coronary intervention in elderly patients
Authors: Nguyen Duy Toan , Dao Bui Quy Quyen , Ho Viet Le Diem , Le Ha Khoa , Nguyen Huu Dung , Nguyen Trung Kien , Tran Van Duy , Nguyen Oanh Oanh , Luong Cong Thuc , Tran Duc Hung , Le Viet Thang
Published: November 2022

Aim

To determine the proportion of contrast‐associated acute kidney injury (CA‐AKI) after percutaneous coronary intervention (PCI) and the predictive value of urine neutrophil gelatinase‐associated lipocalin (uNGAL) for CA‐AKI in elderly patients with chronic coronary artery disease.

Methods

A total of 509 patients who had planned percutaneous coronary intervention (mean age was 63.58 ± 11.63 years and 63.3% of males) were divided into two groups: group 1 (n = 153; elderly patients) with ≥70 years old and group 2 (n = 356) with <70 years old. Urine NGAL was measured by the ELISA method. Clinical and laboratory data were collected on the day before intervention. CA‐AKI was defined based on Kidney Disease: Improving Global Outcomes criteria.

Results

The ratio of CA‐AKI in group 1 was 23.5% which was higher than that of group 2 (8.7%) with a p‐value < 0.001. Urine NGAL level in group 1 was significantly higher than that of group 2 [31.3 (19.16–55.13) ng/ml vs. 19.86 (13.21–29.04) ng/ml, p < 0.001]. At a cut‐off value of 44.43 ng/ml, uNGAL had a predictive value for CA‐AKI in all patients (AUC = 0.977, p < 0.001). Especially at a cut‐off value of 44.14 ng/ml, uNGAL had a predictive value for CA‐AKI in elderly patients (AUC = 0.979, p < 0.001).

Conclusions

The rate of CA‐AKI after PCI in elderly patients was 23.5%. Urine NGAL before PCI had a good predictive value for CA‐AKI in elderly patients with chronic coronary artery disease.
Clinical geneticists' views on and experiences with unsolicited findings in next‐generation sequencing: “A great technology creating new dilemmas”
Authors: van der Schoot Vyne , Damsté Carlijn , Yntema Helger G. , Brunner Han G. , Oerlemans Anke J. M.
Published: November 2022

Unsolicited findings (UFs) from diagnostic genetic testing are a subject of debate. The emerging consensus is that some UFs from genetic testing should be disclosed, but recommendations on UF disclosure generally leave room for variation in practice. This study aimed to explore clinical geneticists' views on and experiences with UFs during pretest counseling and UF disclosure. We interviewed 20 certified clinical genetics medical specialists and clinical genetics residents, working in 7 Dutch genetic centers. Participants indicated that discussing the probability of detecting UFs is an integral part of pretest counseling and informed consent. However, they expressed doubts about the degree to which this discussion should occur and about what information they should share with patients. They argued that the contents of their counseling should depend on the individual patient's capacity to understand information. These results endorse the importance of tailored pretest counseling alongside informed consent for optimal genetic consultations. While “medical actionability” is broadly accepted as an important criterion for the disclosure of UFs, participants experienced substantial uncertainty regarding this concept. This study underscores the need for further demarcation of what exactly constitutes medical actionability. Installation of an expert panel to help healthcare professionals decide what variants to disclose will support them when facing the dilemmas presented by UFs.
Extended postoperative thromboprophylaxis after pancreatic resection for pancreatic cancer is associated with decreased risk of venous thromboembolism in the minimally invasive approach
Authors: Sood Divya , Kuchta Kristine , Paterakos Pierce , Schwarz Jason L. , Rojas Aram , Choi Sung H. , Vining Charles C. , Talamonti Mark S. , Hogg Melissa E.
Published: November 2022

Background

Pancreatic ductal adenocarcinoma (PDAC) is associated with increased venous thromboembolism (VTE). We sought to compare rates of bleeding complications and VTE in patients receiving extended postoperative thromboprophylaxis (EPT) to those who did not, and identify risk factors for VTE after pancreatectomy for PDAC.

Methods

This is a retrospective review of pancreatectomies for PDAC. EPT was defined as 28 days of low molecular weight heparin. Multivariable analysis (MVA) was performed to identify independent risk factors of VTE.

Results

Of 269 patients included, 142 (52.8%) received EPT. Of those who received EPT, 7 (4.9%) suffered bleeding complications, compared to 6 (4.7%) of those who did not (p = 0.938). There was no significant difference in VTE rate at 90 days (2.8% vs. 2.4%, p = 0.728) or at 1 year (6.3% vs. 7.9%, p = 0.624). On MVA, risk factors for VTE included worse performance status, lower preoperative hematocrit, R1/R2 resection, and minimally invasive (MIS) approach. Among those who received EPT, there was no difference in VTE rate between MIS and open approach.

Conclusions

EPT was not associated with a difference in VTE risk or bleeding complications. MIS approach was associated with a higher risk of VTE; however, this was significantly lower among those who received EPT.