bluuebunny/crossref_metadata_2025 huggingface dataset:
Simultaneous Interfacial Modification and Crystallization Control by Biguanide Hydrochloride for Stable Perovskite Solar Cells with PCE of 24.4%
Authors: Xiong Zhuang , Chen Xiao , Zhang Bo , Odunmbaku George Omololu , Ou Zeping , Guo Bing , Yang Ke , Kan Zhipen , Lu Shirong , Chen Shanshan , Ouedraogo Nabonswende Aida Nadege , Cho Yongjoon , Yang Changduk , Chen Jiangzhao , Sun Kuan
Published: December 2021

Interfacial modification, which serves multiple roles, is vital for the fabrication of efficient and stable perovskite solar cells. Here, a multifunctional interfacial material, biguanide hydrochloride (BGCl), is introduced between tin oxide (SnO2) and perovskite to enhance electron extraction, as well as the crystal growth of the perovskite. The BGCl can chemically link to the SnO2 through Lewis coordination/electrostatic coupling and help to anchor the PbI2. Better energetic alignment, reduced interfacial defects, and homogeneous perovskite crystallites are achieved, yielding an impressive certified power conversion efficiency (PCE) of 24.4%, with an open‐circuit voltage of 1.19 V and a drastically improved fill factor of 82.4%. More importantly, the unencapsulated device maintains 95% of its initial PCE after aging for over 500 h at 20 °C and 30% relative humidity in ambient conditions. These results suggest that the incorporation of BGCl is a promising strategy to modify the interface and control the crystallization of the perovskite, toward the attainment of highly efficient and stable perovskite solar cells as well as other perovskite‐based electronics.
A “Pre‐Constrained Metal Twins” Strategy to Prepare Efficient Dual‐Metal‐Atom Catalysts for Cooperative Oxygen Electrocatalysis
Authors: Liu Ming , Li Na , Cao Shoufu , Wang Xuemin , Lu Xiaoqing , Kong Lingjun , Xu Yunhua , Bu Xian‐He
Published: December 2021

Dual‐metal‐atom‐center catalysts (DACs) are a novel frontier in oxygen electrocatalysis, boasting functional and electronic synergies between contiguous metal centers and higher catalytic activities than single‐atom‐center catalysts. However, the definition and catalytic mechanism of DACs configurations remain unclear. Here, a “pre‐constrained metal twins” strategy is proposed to prepare contiguous FeN4 and CoN4 DACs with homogeneous conformations embedded in a N‐doped graphitic carbon (FeCo‐DACs/NC). A programmable phthalocyanines dimer is used as a structural moiety to anchor the bimetallic sites (containing Co and Fe) in a metal–organic framework (MOF) to achieve delocalized dispersion before pyrolysis. The resultant FeCo‐DACs/NC exhibits excellent electrochemical performance in oxygen electrocatalysis and rechargeable Zn–air batteries. Theoretical calculations demonstrate that the synergetic interaction of adjacent metals optimizes the d‐band center position of metal centers and balances the free energy of the *O intermediate, thereby improving the oxygen electrocatalytic activity. This work opens up an avenue for the rational design of DACs with tailored electronic structures and uniform geometric configurations.
POM Anolyte for All‐Anion Redox Flow Batteries with High Capacity Retention and Coulombic Efficiency at Mild pH
Authors: Yang Le , Hao Yahui , Lin Jiande , Li Ke , Luo Siheng , Lei Jie , Han Yanhong , Yuan Ruming , Liu Guokun , Ren Bin , Chen Jiajia
Published: December 2021

A highly soluble Li5BW12O40 cluster delivers 2 e− redox reaction with fast electron transfer rates (2.5 × 10−2 cm s−1) and high diffusion coefficients (≈2.08 × 10−6 cm2 s−1) at mild pH ranging from 3 to 8. In‐operando aqueous‐flowing Raman spectroscopy and density functional theory calculations reveal that Raman shift changing of {BW12} clusters is due to the bond length changing between W‐Ob‐W and W‐Oc‐W at different redox states. The structure changing and redox chemistry of Li5BW12O40 are highly reversible, which makes the Li5BW12O40 cluster versatile to construct all‐anion aqueous redox flow batteries (RFBs). The cation‐exchange Nafion membrane will also repel the cross permeability of the anion redox couples. Consequently, by coupling with Li3K[Fe(CN)6] catholyte, the aqueous RFB can be operated at pH 8 with a capacity retention up to 95% and an average Coulombic efficiency more than 99.79% over 300 cycles within 0 to 1.2 V. Meanwhile, Li5BW12O40 cluster can also be paired with LiI catholyte to form aqueous RFBs at pH 7 and pH 3, the capacity retention of 94% and 90% can be realized over 300 cycles within 0 to 1.3 V.
Programmable Matter: The Nanoparticle Atom and DNA Bond
Authors: Samanta Devleena , Zhou Wenjie , Ebrahimi Sasha B. , Petrosko Sarah Hurst , Mirkin Chad A.
Published: December 2021

Colloidal crystal engineering with DNA has led to significant advances in bottom‐up materials synthesis and a new way of thinking about fundamental concepts in chemistry. Here, programmable atom equivalents (PAEs), comprised of nanoparticles (the “atoms”) functionalized with DNA (the “bonding elements”), are assembled through DNA hybridization into crystalline lattices. Unlike atomic systems, the “atom” (e.g., the nanoparticle shape, size, and composition) and the “bond” (e.g., the DNA length and sequence) can be tuned independently, yielding designer materials with unique catalytic, optical, and biological properties. In this review, nearly three decades of work that have contributed to the evolution of this class of programmable matter is chronicled, starting from the earliest examples based on gold‐core PAEs, and then delineating how advances in synthetic capabilities, DNA design, and fundamental understanding of PAE‐PAE interactions have led to new classes of functional materials that, in several cases, have no natural equivalent.
Recent Advances in Design of Electrocatalysts for High‐Current‐Density Water Splitting
Authors: Luo Yuting , Zhang Zhiyuan , Chhowalla Manish , Liu Bilu
Published: December 2021

Electrochemical water splitting technology for producing “green hydrogen” is important for the global mission of carbon neutrality. Electrocatalysts with decent performance at high current densities play a central role in the industrial implementation of this technology. This field has advanced immensely in recent years, as witnessed by many types of catalysts designed and synthesized toward industriallyrelevant current densities (>200 mA cm–2). By discussing recent advances in this field, several key aspects are summarized that affect the catalytic performance for high‐current‐density electrocatalysis, including dimensionality of catalysts, surface chemistry, electron transport path, morphology, and catalyst‐electrolyte interplay. The multiscale design strategy that considers these aspects comprehensively for developing high‐current‐density electrocatalysts are highlighted. The perspectives on the future directions in this emerging field are also put forward.
Commensurate Stacking Phase Transitions in an Intercalated Transition Metal Dichalcogenide
Authors: Yang Xiaohui , Bao Jin‐Ke , Lou Zhefeng , Li Peng , Jiang Chenxi , Wang Jialu , Sun Tulai , Liu Yabin , Guo Wei , Ramakrishnan Sitaram , Kotla Surya Rohith , Tolkiehn Martin , Paulmann Carsten , Cao Guang‐Han , Nie Yuefeng , Li Wenbin , Liu Yang , van Smaalen Sander , Lin Xiao , Xu Zhu‐An
Published: December 2021

Intercalation and stacking‐order modulation are two active ways in manipulating the interlayer interaction of transition metal dichalcogenides (TMDCs), which lead to a variety of emergent phases and allow for engineering material properties. Herein, the growth of Pb‐intercalated TMDCs–Pb(Ta1+xSe2)2, the first 124‐phase, is reported. Pb(Ta1+xSe2)2 exhibits a unique two‐step first‐order structural phase transition at around 230 K. The transitions are solely associated with the stacking degree of freedom, evolving from a high‐temperature (high‐T) phase with ABC stacking and R3m symmetry to an intermediate phase with AB stacking and P3m1, and finally to a low‐temperature (low‐T) phase again with R3msymmetry, but with ACB stacking. Each step involves a rigid slide of building blocks by a vector [1/3, 2/3, 0]. Intriguingly, gigantic lattice contractions occur at the transitions on warming. At low‐T, bulk superconductivity with Tc ≈ 1.8 K is observed. The underlying physics of the structural phase transitions are discussed from first‐principle calculations. The symmetry analysis reveals topological nodal lines in the band structure. The results demonstrate the possibility of realizing higher‐order metal‐intercalated phases of TMDCs and advance the knowledge of polymorphic transitions, and may inspire stacking‐order engineering in TMDCs and beyond.
A Vertical PN Diode Constructed of MoS2/CsPbBr3 Heterostructure for High‐Performance Optoelectronics
Authors: Xu Jiao , Li Jing , Wang Hengshan , He Chengyu , Li Jianliang , Bao Yanan , Tang Huayi , Luo Huaidong , Liu Xiaochi , Yang Yiming
Published: December 2021

To boost the performance of perovskite‐based optoelectronic devices, 2D materials, which have high carrier mobilities and diverse band structures, are preferably chosen to integrate with perovskites. Up to now, 2D materials/perovskites heterostructured photodetectors are commonly based on parallel or lateral heterojunction. The former usually confronts the problem of large dark current, and the latter's optoelectronic performance is hard to be further improved, limited to the large resistance of perovskites. Here, a vertical PN diode, based on MoS2/CsPbBr3 heterostructure, is demonstrated, where the CsPbBr3 is sandwiched by MoS2 and bottom Au electrode, and carriers’ transit distance in CsPbBr3 is hence shortened to flake's thickness. Due to appropriate band alignment between MoS2 and CsPbBr3, efficient carriers’ separation and transfer at junction area are confirmed by scanning photocurrent microscopy. The influence of thickness of MoS2 and CsPbBr3 on light absorption is simulated with finite‐difference time‐domain method. The vertical PN diode shows remarkable optoelectronic figures‐of‐merit, including large photoresponsivity (1.51 A W−1), low dark current (≈10−13 A), and fast response (34/39 mS). In addition, when operated at VD = 0 V, the device still exhibits distinct power‐dependent response, indicating its potentiality for self‐powered photodetection.
4D Printing of Plasmon‐Encoded Tunable Polydimethylsiloxane Lenses for On‐Field Microscopy of Microbes
Authors: Mariani Stefano , Corsi Martina , Paghi Alessandro , La Mattina Antonino A. , Strambini Lucanos , Frontini Francesco P. , Giuseppe Graziano Di , Barillaro Giuseppe
Published: December 2021

Here the 4D printing of a magnifying polydimethylsiloxane (PDMS) lens encoded with a tunable plasmonic rejection filter is reported. The lens is formed by moldless printing of PDMS pre‐polymer on a nanostructured porous silicon (PSi) templating layer. A nanometer‐thick plasmonic filter is integrated on the lens surface by in situ synthesis of Ag and Au nanoparticles (NPs) with programmed density. The filter can be designed to reject light at the plasmonic resonance wavelength of the NPs with an optical density tunable from 0 to 3 and retreive light at longer wavelengths with a pass‐to‐stop band ratio tunable from 0 to 60 dB. Swelling of PDMS in hexane and ether is used to change the NP density on the lens surface and modulate, in turn, the transmittance properties of the NP‐decorated lens over 3 orders of magnitude. The plasmon‐encoded lens is coupled to a commercial smartphone demonstrating: shaping of the emission spectrum of a white light‐emitting diode to tune the color from yellow to purple; real‐time bright‐field and fluorescence microscopy of living microbes in water, namely, the auto‐fluorescent green alga Chlorogonium sp. and the ciliated protozoan Euplotes daidaleos.
Surface‐Dependent Properties and Tunable Photodetection of CsPbBr3 Microcrystals Grown on Functional Substrates
Authors: Abiedh Khouloud , Dhanabalan Balaji , Kutkan Seda , Lauciello Simone , Pasquale Lea , Toma Andrea , Salerno Marco , Arciniegas Milena P. , Hassen Fredj , Krahne Roman
Published: December 2021

All‐inorganic metal halide perovskites are highly attractive materials for optoelectronics and are typically implemented as thin films, nanocrystals, and single crystals with macroscopic and millimeter‐size dimensions. Single crystals with regular shapes in the micrometer range are less explored and present an interesting alternative when a well‐defined and spatially localized response is desired. Here, CsPbBr3 microcrystals are fabricated by simple and fast drop‐casting of a precursor solution on several substrates that for the growth process are heated to temperatures in the range from 80 to 150 °C. The microcrystals have a cubic shape and feature a pyramidal cavity on their top surface that forms due to faster growth at the edges once the growing crystal is attached to the substrate. Distinct heterogeneity in the photoluminescence (PL) and conductivity of the different facets are measured by µ‐PL and conductive atomic force microscopy experiments. Toward device applications, the authors contact single microcrystals on conductive substrates mechanically with a micromanipulator tip. They observe diode‐like current–voltage curves and good photodetector functionality, obtaining a high responsivity of 150–300 A W−1 in the blue–green spectral region under forward bias, and a sharp detection band centered around 540 nm with peak responsivity close to 0.7 A W−1 under reverse bias.
LectinOracle: A Generalizable Deep Learning Model for Lectin–Glycan Binding Prediction
Authors: Lundstrøm Jon , Korhonen Emma , Lisacek Frédérique , Bojar Daniel
Published: December 2021

Ranging from bacterial cell adhesion over viral cell entry to human innate immunity, glycan‐binding proteins or lectins are abound in nature. Widely used as staining and characterization reagents in cell biology and crucial for understanding the interactions in biological systems, lectins are a focal point of study in glycobiology. Yet the sheer breadth and depth of specificity for diverse oligosaccharide motifs has made studying lectins a largely piecemeal approach, with few options to generalize. Here, LectinOracle, a model combining transformer‐based representations for proteins and graph convolutional neural networks for glycans to predict their interaction, is presented. Using a curated data set of 564,647 unique protein–glycan interactions, it is shown that LectinOracle predictions agree with literature‐annotated specificities for a wide range of lectins. Using a range of specialized glycan arrays, it is shown that LectinOracle predictions generalize to new glycans and lectins, with qualitative and quantitative agreement with experimental data. It is further demonstrated that LectinOracle can be used to improve lectin classification, accelerate lectin directed evolution, predict epidemiological outcomes in the context of influenza virus, and analyze whole lectomes in host–microbe interactions. It is envisioned that the herein presented platform will advance both the study of lectins and their role in (glyco)biology.
Dual‐Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications
Authors: Pedersen Angus , Barrio Jesús , Li Alain , Jervis Rhodri , Brett Dan J. L. , Titirici Maria Magdalena , Stephens Ifan E. L.
Published: December 2021

Electrochemical clean energy conversion and the production of sustainable chemicals are critical in the journey to realizing a truly sustainable society. To progress electrochemical storage and conversion devices to commercialization, improving the electrocatalyst performance and cost are of utmost importance. Research into dual‐metal atom catalysts (DACs) is rising in prominence due to the advantages of these sites over single‐metal atom catalysts (SACs), such as breaking scaling relationships for the adsorption energy of reaction intermediates and synergistic effects. This review provides an examination of the fundamental theoretical principles and experimental electrochemical performance of DACs in idealized half cells, as well as fuel cells, before proceeding to analyze the methods used for producing and identifying DACs. Current challenges and potential future research directions of DACs are also discussed.
Rechargeable Batteries of the Future—The State of the Art from a BATTERY 2030+ Perspective
Authors: Fichtner Maximilian , Edström Kristina , Ayerbe Elixabete , Berecibar Maitane , Bhowmik Arghya , Castelli Ivano E. , Clark Simon , Dominko Robert , Erakca Merve , Franco Alejandro A. , Grimaud Alexis , Horstmann Birger , Latz Arnulf , Lorrmann Henning , Meeus Marcel , Narayan Rekha , Pammer Frank , Ruhland Janna , Stein Helge , Vegge Tejs , Weil Marcel
Published: December 2021

The development of new batteries has historically been achieved through discovery and development cycles based on the intuition of the researcher, followed by experimental trial and error—often helped along by serendipitous breakthroughs. Meanwhile, it is evident that new strategies are needed to master the ever‐growing complexity in the development of battery systems, and to fast‐track the transfer of findings from the laboratory into commercially viable products. This review gives an overview over the future needs and the current state‐of‐the art of five research pillars of the European Large‐Scale Research Initiative BATTERY 2030+, namely 1) Battery Interface Genome in combination with a Materials Acceleration Platform (BIG‐MAP), progress toward the development of 2) self‐healing battery materials, and methods for operando, 3) sensing to monitor battery health. These subjects are complemented by an overview over current and up‐coming strategies to optimize 4) manufacturability of batteries and efforts toward development of a circular battery economy through implementation of 5) recyclability aspects in the design of the battery.
Scalable Inkjet Printing of Electrochromic Smart Windows for Building Energy Modulation
Authors: Chen Jingwei , Tan Alvin Wei Ming , Eh Alice Lee-Sie , Lee Pooi See
Published: December 2021

Electrochromic smart windows are promising for green buildings due to energy efficiency, long optical memory effect, and tunable optical transmission. However, their wide application in buildings is impeded by challenges in scalability, cost‐effectiveness, and limited optical contrast. Quantitative field study of energy savings enabled by electrochromic smart windows in buildings is also lacking. Herein, with the established inkjet printing procedures, electrochromic smart windows (900 cm2) are fabricated. With large optical contrast (≈60%), fast switching kinetics (tc = 43 s, tb = 70 s), and long optical memory retention (transmittance <10% for 7 h), when installed onto the outdoor testbed, these electrochromic smart windows can effectively reduce the internal temperature, especially in summer tropical weather. The energy savings brought by electrochromic smart windows are found to be higher in sunny days than in rainy days. Specifically in a sunny day, the heat gain reduction can reach 42.3%, and for a comfortable targeted indoor temperature of 25 °C, the cooling load savings can be 28.9% compared to regular double‐glazing units‐based reference testbed. This study demonstrates the scalability of inkjet printing technique for fabricating large‐area electrochromic devices and the substantial energy savings obtained from testbed results.
SFGAN: Unsupervised Generative Adversarial Learning of 3D Scene Flow from the 3D Scene Self
Authors: Wang Guangming , Jiang Chaokang , Shen Zehang , Miao Yanzi , Wang Hesheng
Published: December 2021

Scene flow tracks the 3D motion of each point in adjacent point clouds. It provides fundamental 3D motion perception for autonomous driving and server robot. Although red green blue depth (RGBD) camera or light detection and ranging (LiDAR) capture discrete 3D points in space, the objects and motions usually are continuous in the macroworld. That is, the objects keep themselves consistent as they flow from the current frame to the next frame. Based on this insight, the generative adversarial networks (GAN) is utilized to self‐learn 3D scene flow without ground truth. The fake point cloud is synthesized from the predicted scene flow and the point cloud of the first frame. The adversarial training of the generator and discriminator is realized through synthesizing indistinguishable fake point cloud and discriminating the real point cloud and the synthesized fake point cloud. The experiments on Karlsruhe Institute of Technology and Toyota Technological Institute (KITTI) dataset show that our method realizes promising results. Just as human, the proposed method can identify the similar local structures of two adjacent frames even without knowing the ground truth scene flow. Then, the local correspondence can be correctly estimated, and further the scene flow is correctly estimated. An interactive preprint version of the article can be found here:https://www.authorea.com/doi/full/10.22541/au.163335790.03073492.
How long does a transvaginal ultrasound examination for endometriosis take in comparison to a routine transvaginal ultrasound examination?
Authors: Deslandes Alison , Parange Nayana , Childs Jessie T. , Osborne Brooke , Panuccio Catrina , Croft Anthea , Bezak Eva
Published: December 2021

Introduction

This study aimed to determine the additional time needed to perform an endometriosis transvaginal ultrasound (eTVUS) compared to routine transvaginal ultrasound (rTVUS).

Methods

A retrospective case–control study was performed. The study group included 199 eTVUS performed between September 2019 and September 2020. The control group comprised 105 consecutive rTVUS studies performed in the same time period. The time stamps on the ultrasound images of all cases in both groups were reviewed to determine the time taken to perform each study. Mean, median, minimum and maximum scan times for both groups were calculated as was percentage difference between scan times. A two‐tailed, unpaired t‐test of the normalised data and a Mann–Whitney U test assessing time difference of scans between two groups were performed with P value <0.05 considered statistically significant.

Results

Performing eTVUS took significantly longer than rTVUS with increases in the mean (8.4 vs 13.8 min, 64%), median (7 vs 12 min, 71%), minimum (4 vs 7 min, 75%) and maximum (19 vs 42 min, 121%) scan times. The Mann–Whitney U test indicated a statistically significant difference in the median scan times (5.0, CI 4.0–6.0), P < 0.001. An independent t‐test of the normalised data revealed a significantly larger mean scan time for eTVUS than rTVUS, Mean = 9.05 95%CI [13.17–4.94], t(302) = 4.327, P < 0.001.R2= 0.583.

Conclusion

Endometriosis transvaginal ultrasound added an average 5.4 min to rTVUS, which is statistically significant. For ultrasound departments wanting to offer this technique, doubling the scan time allocated to perform a transvaginal ultrasound (TVUS) is suggested.
Alzheimer's disease biomarkers in Black and non‐Hispanic White cohorts: A contextualized review of the evidence
Authors: Gleason Carey E. , Zuelsdorff Megan , Gooding Diane C. , Kind Amy J. H. , Johnson Adrienne L. , James Taryn T. , Lambrou Nickolas H. , Wyman Mary F. , Ketchum Fred B. , Gee Alexander , Johnson Sterling C. , Bendlin Barbara B. , Zetterberg Henrik
Published: December 2021

Black Americans are disproportionately affected by dementia. To expand our understanding of mechanisms of this disparity, we look to Alzheimer's disease (AD) biomarkers. In this review, we summarize current data, comparing the few studies presenting these findings. Further, we contextualize the data using two influential frameworks: the National Institute on Aging–Alzheimer's Association (NIA‐AA) Research Framework and NIA's Health Disparities Research Framework. The NIA‐AA Research Framework provides a biological definition of AD that can be measured in vivo. However, current cut‐points for determining pathological versus non‐pathological status were developed using predominantly White cohorts—a serious limitation. The NIA's Health Disparities Research Framework is used to contextualize findings from studies identifying racial differences in biomarker levels, because studying biomakers in isolation cannot explain or reduce inequities. We offer recommendations to expand study beyond initial reports of racial differences. Specifically, life course experiences associated with racialization and commonly used study enrollment practices may better account for observations than exclusively biological explanations.
A Nanographene‐Based Two‐Dimensional Covalent Organic Framework as a Stable and Efficient Photocatalyst
Authors: Jin Enquan , Fu Shuai , Hanayama Hiroki , Addicoat Matthew A. , Wei Wenxin , Chen Qiang , Graf Robert , Landfester Katharina , Bonn Mischa , Zhang Kai A. I. , Wang Hai I. , Müllen Klaus , Narita Akimitsu
Published: December 2021

Synthesis of covalent organic frameworks (COFs) with desirable organic units furnishes advanced materials with unique functionalities. As an emerging class of two‐dimensional (2D) COFs, sp2‐carbon‐conjugated COFs provide a facile platform to build highly stable and crystalline porous polymers. Herein, a 2D olefin‐linked COF was prepared by employing nanographene, namely, dibenzo[hi,st]ovalene (DBOV), as a building block. The DBOV‐COF exhibits unique ABC‐stacked lattices, enhanced stability, and charge‐carrier mobility of ≈0.6 cm2 V−1 s−1inferred from ultrafast terahertz photoconductivity measurements. The ABC‐stacking structure was revealed by the high‐resolution transmission electron microscopy and powder X‐ray diffraction. DBOV‐COF demonstrated remarkable photocatalytic activity in hydroxylation, which was attributed to the exposure of narrow‐energy‐gap DBOV cores in the COF pores, in conjunction with efficient charge transport following light absorption.
Catalysis‐Enabled Concise and Stereoselective Total Synthesis of the Tricyclic Prostaglandin D2 Metabolite Methyl Ester
Authors: Sims Hunter S. , de Andrade Horn Pedro , Isshiki Ryota , Lim Melissa , Xu Yan , Grubbs Robert H. , Dai Mingji
Published: December 2021

A concise and stereoselective total synthesis of the clinically relevant tricyclic prostaglandin D2 metabolite (tricyclic‐PGDM) methyl ester in racemic form was accomplished in eight steps from a readily available known cyclopentene‐diol derivative. The synthesis features a nickel‐catalyzed Ueno–Stork‐type dicarbofunctionalization to generate two consecutive stereocenters, a palladium‐catalyzed carbonylative spirolactonization to build the core oxaspirolactone, and a Z‐selective cross‐metathesis to introduce the (Z)‐3‐butenoate side chain, a group challenging to introduce through traditional Wittig protocols and troublesome for the two previous total syntheses. A general Z‐selective cross‐metathesis protocol to construct (Z)‐β,γ‐unsaturated esters was also developed that has broad functional group tolerance and high stereoselectivity. Additionally, our synthesis already accumulated 75 mg of valuable material for an 18O‐tricyclic‐PGDM‐based assay used in clinical settings for inflammation.
Asymmetrical‐Dendronized TADF Emitters for Efficient Non‐doped Solution‐Processed OLEDs by Eliminating Degenerate Excited States and Creating Solely Thermal Equilibrium Routes
Authors: Li Chensen , Harrison Alastair K. , Liu Yuchao , Zhao Zhennan , Zeng Cheng , Dias Fernando B. , Ren Zhongjie , Yan Shouke , Bryce Martin R.
Published: December 2021

The mechanism of thermally activated delayed fluorescence (TADF) in dendrimers is not clear. We report that fully‐conjugated or fully‐nonconjugated structures cause unwanted degenerate excited states due to multiple identical dendrons, which limit their TADF efficiency. We have synthesized asymmetrical “half‐dendronized” and “half‐dendronized‐half‐encapsulated” emitters. By eliminating degenerate excited states, the triplet locally excited state is ≥0.3 eV above the lowest triplet charge‐transfer state, assuring a solely thermal equilibrium route for an effective spin‐flip process. The isolated encapsulating tricarbazole unit can protect the TADF unit, reducing nonradiative decay and enhancing TADF performance. Non‐doped solution‐processed devices reach a high external quantum efficiency (EQEmax) of 24.0 % (65.9 cd A−1, 59.2 lm W−1) with CIE coordinates of (0.24, 0.45) with a low efficiency roll‐off and EQEs of 23.6 % and 21.3 % at 100 and 500 cd m−2.
One‐Pot Construction of Sulfur‐Rich Thermoplastic Elastomers Enabled by Metal‐Free Self‐Switchable Catalysis and Air‐Assisted Coupling
Authors: Zhu Xiao‐Feng , Yang Guan‐Wen , Xie Rui , Wu Guang‐Peng
Published: December 2021

Construction of well‐defined sulfur‐rich macromolecules in a facile manner is an interesting but challenging topic. Herein, we disclose how to readily construct well‐defined triblock sulfur‐rich thermoplastic elastomers via a self‐switchable isothiocyanate/episulfide copolymerization and air‐assisted oxidative coupling strategy. During self‐switchable polymerization, alternating copolymerization of isothiocyanate and episulfide occurs initially due to the lower energy barrier for isothiocyanate insertion with respect to successive episulfide ring‐opening. After exhaustion of isothiocyanate, ring‐opening polymerization of episulfide begins, providing diblock polymers. Subsequent exposure of the reaction to air leads to a transformation of diblock copolymers into triblock thermoplastic elastomers. This protocol can be extended to diverse isothiocyanates and episulfides, allowing fine‐tuning of the performance of the produced sulfur‐rich thermoplastic elastomers.
COVID‐19 infection in a child following liver transplantation
Authors: Sindwani G. , Abhinaya S. V. , Arora M. K. , Pamecha V. , Lal B. B.
Published: December 2021

COVID‐19 infection immediately after liver transplantation presents a unique and challenging situation. In this report, we present the case of an 11‐year‐old girl who underwent emergency living donor liver transplantation for acute liver failure. After an uneventful intra‐operative course, the patient was transferred to the intensive care unit. On the second postoperative day, the patient developed unexplained severe hypoxia. A polymerase chain reaction test was positive for SARS‐CoV‐2 virus and a hypercoagulable state was indicated by laboratory investigations. Despite therapies such as mechanical ventilation and therapeutic anticoagulation, further clinical deterioration occurred. On the seventh postoperative day, the patient’s pupils were fully dilated bilaterally and unreactive to light, and brain death was later confirmed. This report highlights unique challenges pertaining to oxygenation, coagulation and immunosuppression after liver transplantation in a child with COVID‐19. Hypoxia of unknown origin in the postoperative period should prompt consideration of COVID‐19 as a possible cause.
Structural characterization, spectroscopic studies, and molecular docking studies on metal complexes of new hexadentate cyclic peptide ligand
Authors: Moustafa Gaber , Sabry Eman , Zayed Ehab M. , Mohamed Gehad G.
Published: December 2021

New cyclic peptide ligand (L), 4,7,17,20‐tetrabenzyl‐2,5,8,16,19,22‐hexaoxo‐3,6,9,15,18,21‐hexaaza‐1(1,3)‐benzenacyclodocosaphane‐10‐carboxylic acid (BOABCA), was prepared using the recommended method. The ligand (L) and its complexes have been proven by using elemental analyses, molar conductivity, and magnetic moment measurements. The structural properties of the title compounds were explored using spectroscopy (1H NMR, ultraviolet [UV]–visible, and Fourier transform infrared [FT‐IR]) and mass spectrometry. The thermal decomposition of the ligand and its complexes are measured by thermal analysis (thermogravimetry [TG] and derivative thermogravimetry [DTG]) technique. The ligand (L) acts as neutral hexadentate with NNOOOO coordination sites and coordinating to the metal ions via the two nitrogen and four oxygen atoms. Bond lengths, bond angles, and quantum chemical characteristics have been established for the ligand and its complexes. The scanning electron microscope (SEM) analysis confirmed the presence of Fe(III) and Ni(II) complexes in nanostructure. The structural formula for the examined cyclic peptide ligand was optimized using Gaussian09 program. The energy gaps and other relevant theoretical parameters were computed applying the DFT/B3LYP technique. Antibacterial properties of the BOABCA ligand (L) and its transition metal complexes have been evaluated. In vitro biological properties for BOABCA ligand (L) and its transition metal complexes were carried out against Gram(+) bacteria (Bacillis subtilis and Staphylococcus aureus) and Gram(−) bacteria (Escherichia coli and Pseudomonas aeruginosa) employing agar diffusion method. The results showed that title compounds are biologically active than the parent BOABCA ligand. Molecular docking has shown favorable interaction between the title compounds and crystal structure of 3t88‐E. coli, 3ty7‐S. aureus, 5h67‐B. subtilis, and 5i39‐P. aeruginosa receptors.
Polyacrylamide/carboxymethyl chitosan double‐network hydrogels with high conductivity and mechanical toughness for flexible sensors
Authors: Zeng Runpeng , Lu Shuxin , Qi Chuyi , Jin Lele , Xu Jinbao , Dong Zhixian , Lei Caihong
Published: December 2021

Conductive hydrogels are ideal candidate materials for flexible sensors, but the integration of satisfactory mechanical performances with high conductivity to meet the requirements for practical applications remains a challenge. Herein, a tough ionically conductive polyacrylamide (PAAm)/carboxymethyl chitosan (CMCs) double‐network (DN) hydrogel is fabricated via in situ polymerization of acrylamide in CMCs aqueous solution, followed by ferric chloride (FeCl3) solution immersing. The PAAm/CMCs‐Fe3+ DN hydrogel demonstrates satisfactory mechanical properties, including sufficient tensile strength (~440 kPa), prominent stretchability (~715%), high toughness (~1658 kJ m−3), and excellent fatigue resistance, as well as superb conductivity up to 3.1 S m−1. Moreover, the ionically conductive DN hydrogel‐based sensors exhibit high sensitivity in a broad strain window (0%–700%) and can accurately, and repeatedly monitor the motions of body joints, such as finger and wrist, exhibiting great potential in applications of flexible sensors.
Occupancy modelling confirms the first extirpation of a freshwater fish from one of the world's largest river systems
Authors: Wedderburn Scotte D. , Whiterod Nick S. , Vilizzi Lorenzo
Published: December 2021

Numerous human‐induced changes to freshwater ecosystems are implicated in the loss of biodiversity, including fish extinctions. Dams and weirs have profoundly altered the ecological character of the Murray–Darling Basin (MDB), one of the world's largest river systems, which discharges at the mouth of the River Murray in South Australia.

These impacts are evident in the Ramsar‐listed final reaches of the river, where regulation, drought, and flow reductions over recent decades have led to the collapse of freshwater fish populations, including Yarra pygmy perch (Nannoperca obscura), which is Endangered on the International Union for Conservation of Nature Red List of Threatened Species.

Nannoperca obscura occurs in several major catchments in south‐eastern Australia, but the genetically unique population in the MDB only inhabits wetlands near the terminus of the River Murray where wild populations were last recorded in 2008 approaching the end of a prolonged drought.

This study involved repeated surveys targeting N. obscura to evaluate its occupancy in the MDB while accounting for imperfect detection. The surveys failed to find N. obscura despite regular detection of the closely related southern pygmy perch (Nannoperca australis), which provides a proxy for the congener.

This study presents strong evidence that N. obscura is absent in the survey region, thereby inferring the first freshwater fish extirpation from the MDB. The outcomes of this study should prompt responses required to aid the species' population recovery and present a reliable approach to confirm the status of freshwater fishes for conservation management.
Design, synthesis, anticancer, and docking of some S‐ and/or N‐heterocyclic derivatives as VEGFR‐2 inhibitors
Authors: El‐Adl Khaled , Abdel‐Rahman Adel A.‐H. , Omar Asmaa M. , Alswah Mohamed , Saleh Nashwa M.
Published: December 2021

Novel heterocyclic derivatives (4–22) were designed, synthesized, and evaluated against hepatocellular carcinoma type (HepG2) and breast cancer (MCF‐7) cells, targeting the VEGFR‐2 enzyme. Compounds 18, 10, 13, 11, and 14 were found to be the most potent derivatives against both the HepG2 and MCF‐7 cancer cell lines, with GI50 = 2.11, 2.54 µM, 3.16, 3.64 µM, 3.24, 6.99 µM, 7.41, 6.49 µM and 8.08, 10.46 µM, respectively. Compounds 18 and 10 showed higher activities against both HepG2 and MCF‐7 cells than sorafenib (GI50 = 9.18, 5.47 µM, respectively) and doxorubicin (GI50 = 7.94, 8.07 µM, respectively). Compounds 13, 11, and 14 showed higher activities than sorafenib against HepG2 cancer cells, but lower activities against MCF‐7 cells. Compounds 18, 13, and 10 were more potent than sorafenib, inhibiting vascular endothelial growth factor receptor‐2 (VEGFR‐2) at GI50 values of 0.05, 0.06, and 0.08 µM, respectively. Compound 11 inhibited VEGFR‐2 at an IC50 value of 0.10 µM, which is equipotent to sorafenib. Compound 14 inhibited VEGFR‐2 at an IC50 value of 0.11 µM, which is nearly equipotent to sorafenib. The tested compounds have more selectivity against cancer cell lines. Compounds 18, 10, 13, 11, and 14 are, respectively, 16.76, 9.24, 6.06, 2.78, and 2.85 times more toxic in HePpG2 cancer cells than in VERO normal cells. Also, compounds 18, 10, 13, 11, and 14 are, respectively, 14.07, 8.02, 2.81, 3.18, and 2.20 times more toxic in MCF‐7 than in VERO normal cells. The most active compounds, 10, 13, and 18, showed a good ADMET (absorption, distribution, metabolism, excretion, and toxicity) profile.
Biology‐oriented drug synthesis and evaluation of secnidazole esters as novel enzyme ınhibitors
Authors: Ansari Muhammad A. , Saad Syed M. , Khan Khalid M. , Salar Uzma , Taslimi Parham , Taskın‐Tok Tugba , Saleem Faiza , Jahangir Sajid
Published: December 2021

The identification of novel compounds that can inhibit physiologically and metabolically important drug targets or enzymes has prime importance in medicinal chemistry. With this aim, a range of secnidazole esters 1–30 were synthesized under the heading of biology‐oriented drug synthesis by the 1,1′‐carbonyldiimidazole‐mediated coupling reaction between secnidazole and varyingly benzoic acid derivatives. All compounds were screened for inhibitory activity against human carbonic anhydrase (hCA) I and II, acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and α‐glucosidase. The results indicate that all the synthesized compounds showed potent inhibitory activities against all targets, as compared to the standard inhibitors, revealed by IC50 values. Ki values of the secnidazole derivatives 1–30 for hCA I, hCA II, AChE, BChE, and α‐glucosidase enzymes were obtained in the ranges of 47.37–190.74, 44.38–198.21, 12.14–68.37, 8.04–61.53, and 7.78–45.91 nM, respectively. To assess the enzyme–ligand interactions, the optimized most active compounds 2, 3, 8, 9, 14, 17, and 23 were subjected to molecular docking studies with modeled AChE, BChE, hCA I, hCA II, and α‐glucosidase enzymes, where several important and key interactions were monitored with amino acid residues of each target enzyme.
3D Printed Multilayer Graphite@SiO Structural Anode for High‐Loading Lithium‐Ion Battery
Authors: He Wenjie , Chen Chenglong , Jiang Jiangmin , Chen Zhijie , Liao Haojie , Dou Hui , Zhang Xiaogang
Published: December 2021

To satisfy the increasing demand for higher energy density, the fabrication and structural designs of three‐dimensional (3D) thick electrodes have received considerable attention. In this work, cheap commercial graphite (Gt) and silicon monoxide (SiO) were chosen as raw materials. We have took advantage of the multi‐layer biscuit structure feature to the 3D Gt@GS (Gt@Gt/SiO) electrode with high loading through a modified 3D printing technology. Such a unique structure can not only effectively accommodate the volume expansion in all directions, but also provide a 3D transport channel to enhance the mobility of electrons and ions in the thick electrodes. The obtained 3D Gt@GS electrode, as a freestanding material, shows high capacity and good cycling stability. Especially, the 3D Gt@GS electrode after 120 cycles has achieved a reversible capacity of 3.52 mAh cm−2 at 3.6 mA cm−2.

In addition, we have successfully fabricated a 3D plane‐shaped batteries via a direct ink writing technology and a fused deposition technology. The heterotypic battery assembled can be utilized as an external power supply for the aircraft model. This work demonstrates that the structural battery combined with structural load and 3D printing technology is versatile enough to meet the demand of energy storage systems for high energy density.
Outcomes of prostatic urethral lift in a medically complex population at a veterans affairs hospital
Authors: Lehner Kelly , Popat Shreeya , Utech Katherine , Taylor Jennifer , Brooks Michael , Jones Jeffrey
Published: December 2021

Objective

The objective of this study is to report “real‐world” outcomes of prostatic urethral lift (PUL) in a medically complex US military veteran population while employing liberalized procedural indications.

Methods

A retrospective review was conducted of patients who underwent PUL at our institution. There were no prostatic size requirements, patients were accepted on anti‐platelet/anticoagulant therapy, no benign prostatic hyperplasia (BPH) medication washout was required, and there was no maximum post‐void residual PVR. Pre‐ and post‐operative International Prostate Symptom Score (IPSS), uroflowmetry, and PVR were recorded. Statistical comparisons were performed using simple t tests.

Results

From 2013 to 2019, 91 patients underwent PUL. Mean age was 70 (range 55–92) years. The majority of our patients were classified as American Society of Anesthesiologists (ASA) class 3 versus the general population at ASA class 2. Post‐operatively, IPSS decreased by an average of 43% (23 to 13, p < 0.001). There was a mean 41% decrease in PVR (179 to 101 cc, p = 0.009), which was durable for a follow‐up of up to 54 months. Maximum urinary flow rate improved by an average of 32% (9.3 to 12.3 cc/s, p = 0.003), which was also durable throughout follow‐ up. Forty‐four patients required catheterization pre‐operatively and 16 required catheterization post‐operatively. Therefore, 27 patients (61.4%) were rendered catheter‐free by PUL. Thirty‐nine patients were taking antiplatelet medications peri‐operatively, and 13 took anticoagulants. Only one patient (on warfarin) experienced hematuria requiring re‐admission with catheter placement.

Conclusions

PUL produced effective and durable results in our veteran population, including in patients with significant pre‐operative bladder decompensation and those on antiplatelets/anticoagulants.
Transgenerational adverse effects of valproate? A patient report from 90 affected families
Authors: Martin Marine , Hill Catherine , Bewley Susan , MacLennan Alastair H. , Braillon Alain
Published: December 2021

Background

Valproate use during pregnancy increases risk in malformations and neurodevelopmental disorders. Data from the experimental setting in mice showed valproate is a direct inhibitor of histone deacetylase, inducing histone hyperacetylation, histone methylation, and DNA demethylation causing congenital malformations with an epigenetic inheritance. We investigated potential transgenerational adverse effects of valproate.

Methods

We questioned 108 individuals (from 90 families) suffering complications due to valproate exposure in utero who were parents themselves (85 women and 23 men) about the occurrence of malformations and neurodevelopmental disorders in their children. All were member of Aide aux Parents d'Enfants souffrants du Syndrome de l'AntiConvulsivant (APESAC), a charity created in 2011 to provide personal assistance and support to families suffering complications due to valproate exposure during pregnancy.

Results

Among their 187 children they reported 43 (23%) children with malformation(s) (26 hand or foot malformations; 15 dysmorphic facial features; 10 renal/urologic malformations; 6 spina bifida; 4 cardiac malformation; 2 craniosynostosis; 2 cleft lip and palate) and 82 (44%) children with neurodevelopmental disorders (63 problematic behaviors and autism; 41 psychomotor disorders; 16 language problems; 16 attention deficit; 5 mental retardation). Only 88 (47%) children had neither malformation nor developmental disorders.

Conclusion

These data add to the need for funding pharmacoepidemiological investigations of epigenetic inheritance caused by drugs causing malformations or neurodevelopmental disorders. Individuals exposed in utero to valproate must be informed about the risk, so they can consider fertility options, antenatal diagnosis, and adequate early surveillance.
Improvement of acetyl‐CoA supply and glucose utilization increases l‐leucine production in Corynebacterium glutamicum
Authors: Wang Yingyu , Xu Jianzhong , Jin Zhengyu , Xia Xiaole , Zhang Weiguo
Published: December 2021

Background

l‐Leucine is an important essential amino acid with multiple industrial applications, whose market requirements cannot be met because of the low productivity.

Main Methods and Major Results

In this study, a strain of Corynebacterium glutamicum with high l‐leucine yield was constructed to enhance its acetyl‐CoA supply and glucose utilization. One copy of leuA under the control of a strong promoter was incorporated into the C. glutamicum genome. Then, acetyl‐CoA supply was increased by the integration of a terminator in front of gltA and by the heterogeneous overexpression of acetyl‐CoA synthetase (ACS) and deacetylase (CobB) derived from Escherichia coli. Next, the transcriptional regulator sugR was deleted to enhance glucose uptake via a phosphotransferase‐mediated route. In fed‐batch fermentation performed in a 5‐L reactor, l‐leucine production of 40.11 ± 0.73 g L−1 was achieved under the optimized conditions, with an l‐leucine yield and productivity of 0.25 g g−1 glucose and 0.59 g L−1 h−1, respectively.

Conclusions and Implications

These results represent a significant improvement in the l‐leucine production of C. glutamicum, indicating that the process possesses high potential for industrial application. These strategies can be also expanded to enable the production of other value‐added biochemicals derived from the intermediates of central carbon metabolism.
Barrett's esophagus: The pathomorphological and molecular genetic keystones of neoplastic progression
Authors: Maslyonkina Ksenia S. , Konyukova Alexandra K. , Alexeeva Darya Y. , Sinelnikov Mikhail Y. , Mikhaleva Liudmila M.
Published: December 2021

Barrett's esophagus is a widespread chronically progressing disease of heterogeneous nature. A life threatening complication of this condition is neoplastic transformation, which is often overlooked due to lack of standardized approaches in diagnosis, preventative measures and treatment. In this essay, we aim to stratify existing data to show specific associations between neoplastic transformation and the underlying processes which predate cancerous transition. We discuss pathomorphological, genetic, epigenetic, molecular and immunohistochemical methods related to neoplasia detection on the basis of Barrett's esophagus. Our review sheds light on pathways of such neoplastic progression in the distal esophagus, providing valuable insight into progression assessment, preventative targets and treatment modalities. Our results suggest that molecular, genetic and epigenetic alterations in the esophagus arise earlier than cancerous transformation, meaning the discussed targets can help form preventative strategies in at‐risk patient groups.