bluuebunny/crossref_metadata_2025 huggingface dataset:
Electronic Tuning of CO2 Interaction by Oriented Coordination of N‐Rich Auxiliary in Porphyrin Metal–Organic Frameworks for Light‐Assisted CO2 Electroreduction
Authors: Xin Zhifeng , Dong Xue , Wang Yi‐Rong , Wang Qian , Shen Kejing , Shi Jing‐Wen , Chen Yifa , Lan Ya‐Qian
Published: May 2023

The efficient CO2 electroreduction into high‐value products largely relies on the CO2 adsorption/activation or electron‐transfer of electrocatalysts, thus site‐specific functionalization methods that enable boosted related interactions of electrocatalysts are much desired. Here, an oriented coordination strategy is reported to introduce N‐rich auxiliary (i.e., hexamethylenetetramine, HMTA) into metalloporphyrin metal organic frameworks (MOFs) to synthesize a series of site‐specific functionalized electrocatalysts (HMTA@MOF‐545‐M, M = Fe, Co, and Ni) and they are successfully applied in light‐assisted CO2 electroreduction. Noteworthy, thus‐obtained HMTA@MOF‐545‐Co presents approximately two times enhanced CO2 adsorption‐enthalpy and electrochemical active surface‐area with largely decreased impedance‐value after modification, resulting in almost twice higher CO2 electroreduction performance than its unmodified counterpart. Besides, its CO2 electroreduction performance can be further improved under light‐illumination and displays superior FECO (≈100%), high CO generation rate (≈5.11 mol m−2 h−1 at −1.1 V) and energy efficiency (≈70% at −0.7 V). Theoretical calculations verify that the oriented coordination of HMTA can increase the charge density of active sites, almost doubly enhance the CO2 adsorption energy, and largely reduce the energy barrier of rate determining step for the boosted performance improvement. This work might promote the development of modifiable porous crystalline electrocatalysts in high‐efficiency CO2 electroreduction.
Ultraflexible Organic Active Matrix Sensor Sheet for Tactile and Biosignal Monitoring
Authors: Karner‐Petritz Esther , Petritz Andreas , Uemura Takafumi , Namba Naoko , Araki Teppei , Sekitani Tsuyoshi , Stadlober Barbara
Published: May 2023

Flexible sensors are currently the subject of intensive research, as they allow cost‐effective and environmentally friendly production of large‐area, flexible, and when fabricated on ultrathin substrates, highly conformable devices. Among many intriguing applications, tactile and biosignal monitoring, where lightweight sensors with high wearing comfort are particularly interesting, is focused on here. The required spatiotemporal resolution of the signals is achieved by integrating the sensors in an active matrix configuration. Organic ferroelectric transducers of high uniformity, characterized, for example, by a sensitivity spread of only 1.5%, are combined with similarly uniform ultralow noise level organic thin film transistors operating below 5 V, showing, for example, a threshold voltage variation of just 0.13 V, in a 12 × 12 sensor array. The transistors transition frequency of up to 160 kHz (saturation range) and 17 kHz (linear range) allows for a high spatiotemporal resolution of ≈3 mm at a frame rate of 1400 fps. The thickness of only 2.8 µm renders the organic active matrix sensor sheet ultraflexible and therefore virtually imperceptible on the human skin. Real‐time monitoring of tactile modes in a subset of 8 × 3 pixels and of the pulse wave including heart rate and blood pressure using four sensors of the matrix is demonstrated.
A Competitive n‐Type OECT Material via Copolymerization of Electron Deficient Building Blocks
Authors: Erhardt Andreas , Hochgesang Adrian , McNeill Christopher R. , Thelakkat Mukundan
Published: May 2023

The classical acceptor motifs diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) are copolymerized to yield the acceptor–acceptor polymer “Poly(DPP‐TPD).” The fundamental design idea is to maximize the electron affinity (EA), thus increasing the ambient stability of the reduced state against oxygen and water while ensuring high ion compatibility through the incorporation of hydrophilic oligoethylene glycol N‐substituents. Additionally, a highly planarized polymer structure is anticipated, due to the extended noncovalent interactions (conformational locking) between the carbonyl oxygen and the thiophene protons. Cyclic voltammetry, spectroelectrochemistry, ultraviolet photoelectron spectroscopy, ultraviolet‐visible absorption spectroscopy, and organic field effect transistor (OFET) characterization demonstrate the suitability for n‐type organic electrochemical transistor (OECT) devices. High EA, ionization potential, and good electron mobility (µe(OFET)) are shown, in addition to the electrochemical reduction of polymer films in aqueous electrolyte. In n‐type OECTs, poly(DPP‐TPD) demonstrates a moderate threshold voltage of Vth = 0.58 V and an outstanding µC* value of 7.62 F cm−1 V−1 s−1. Cycling studies consisting of pulsed on‐ and off‐switching of the device at gate voltages between Vg = 0.6–0.8 V in the saturation regime reveal high stability for more than 2700 cycles with rapid switching kinetics.
Multi‐Dimensional Characterization of Battery Materials
Authors: Ziesche Ralf F. , Heenan Thomas M. M. , Kumari Pooja , Williams Jarrod , Li Weiqun , Curd Matthew E. , Burnett Timothy L. , Robinson Ian , Brett Dan J. L. , Ehrhardt Matthias J. , Quinn Paul D. , Mehdi Layla B. , Withers Philip J. , Britton Melanie M. , Browning Nigel D. , Shearing Paul R.
Published: May 2023

Demand for low carbon energy storage has highlighted the importance of imaging techniques for the characterization of electrode microstructures to determine key parameters associated with battery manufacture, operation, degradation, and failure both for next generation lithium and other novel battery systems. Here, recent progress and literature highlights from magnetic resonance, neutron, X‐ray, focused ion beam, scanning and transmission electron microscopy are summarized. Two major trends are identified: First, the use of multi‐modal microscopy in a correlative fashion, providing contrast modes spanning length‐ and time‐scales, and second, the application of machine learning to guide data collection and analysis, recognizing the role of these tools in evaluating large data streams from increasingly sophisticated imaging experiments.
Ultrahigh‐Capacity Rocksalt Cathodes Enabled by Cycling‐Activated Structural Changes
Authors: Ahn Juhyeon , Giovine Raynald , Wu Vincent C. , Koirala Krishna Prasad , Wang Chongmin , Clément Raphaële J. , Chen Guoying
Published: May 2023

Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li1.1Mn0.8Ti0.1O1.9F0.1, an ultrahigh capacity of ≈320 mAh g−1 (energy density of ≈900 Wh kg−1) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn4+ and Li+ vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn4+ reduction, along with Li+ insertion transform the structure to a partially ordered DRX phase with a β′‐LiFeO2‐type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high‐Mn DRXbut also provide guidance for the future development of Mn‐based, high‐energy density oxide, and oxyfluoride cathode materials.
High Fill Factor CsPbI2Br Perovskite Solar Cells Via Crystallization Management
Authors: Jeong Min Ju , Jeon Soo Woong , Kim Sung Yong , Noh Jun Hong
Published: May 2023

Inorganic CsPbI2Br perovskite has a substantial potential for triple‐junction tandem solar cells as a top subcell, however it exhibits relative instability in the air compared with organic‐inorganic perovskites as well as significantly lower efficiency than the theoretical efficiency limit. To further enhance the air‐stability and efficiency of CsPbI2Br‐based perovskite solar cells (PSCs), it is vitally crucial to improve the crystallinity and passivate the defects within films that accelerate the phase transformation to the photo‐inactive phase in the air. Here, it is reported that crystallization management via incorporating sodium formate (NaFo) in a CsPbI2Br perovskite solution effectively leads to enlarged grain size and the reduced trap density. The Na+ cation and HOOC− anion produce a synergistic effect for engineering the defects by acting as cation and pseudo‐halide anion passivators, respectively. As a result, the NaFo‐incorporating device shows an improved power conversion efficiency (PCE) of 17.7% with a fill factor (FF) of 84.5%. To the best of the authors' knowledge, this progressive FF value is the highest value among CsPbI2Br‐based PSCs reported thus far. In addition, the NaFo‐incorporated device shows improved air stability compared to the control device, retaining over 95% of its initial PCE for 1000 hours under 10% relative humidity at room temperature without any encapsulation.
A Bithiazole‐Substituted Donor for High‐Efficiency Thick Ternary Organic Solar Cells via Regulation of Crystallinity and Miscibility
Authors: Zou Wentao , Han Chenyang , Zhang Xu , Qiao Jiawei , Yu Jifa , Xu Huajun , Gao Huanhuan , Sun Yanna , Kan Yuanyuan , Hao Xiaotao , Lu Guanghao , Yang Yingguo , Gao Ke
Published: May 2023

Organic solar cells (OSCs) with thick active layers exhibit great potential for future roll‐to‐roll mass production. However, increasing the thickness of the active layer generally leads to unfavorable morphology, which decreases the device's performance. Therefore, it is a critical challenge to achieve OSCs with high efficiency and thick film simultaneously. Herein, a small molecular donor, ZW1, incorporating a bithiazole unit along with a thiophene group as a π‐bridge is reported. ZW1 with high crystallinity is employed to fabricate D18:ZW1:Y6 ternary devices, which enhances the crystallization, optimizes the morphology, and suppresses bimolecular recombination. Additionally, ZW1 shows better miscibility with D18, resulting in the preferred vertical phase distribution. As a result, an outstanding power conversion efficiency (PCE) of 18.50% is realized in ternary OSCs with 120 nm active layer thickness. Importantly, the thick ternary OSCs attain a high PCE of 16.67% (thickness ≈300 nm), significantly higher than the corresponding binary devices (13.50%). The PCE of 16.67% is one of the highest values for thick‐film OSCs reported to date. This work demonstrates that the incorporation of highly crystalline small‐molecule donors into ternary OSCs, possessing good miscibility with host materials, presents an effective strategy for fabricating highly efficient thick OSCs.
Carbon sequestration and water management in Texas—One size does not fit all
Authors: Bell Jourdan , DeLaune Paul B. , Fischer Bart L. , Foster Jamie L. , Lewis Katie L. , McCarl Bruce A. , Outlaw Joe L.
Published: May 2023

Climate‐smart agriculture (CSA) is an integrated approach to sustainably meeting food, fiber, and feed production needs. The technical and socioeconomic feasibility of different CSA strategies depends on local conditions, and there is no one‐size‐fits‐all approach. Here, we review two key aspects of CSA with a focus on Texas: soil C sequestration and water management. Carbon sequestration potential is highly variable across Texas as it depends on local biophysical conditions and soil management practices in place, for example, tillage and cover crops. Grasslands also have an important role to play in C sequestration. Important co‐benefits of effective soil management for C sequestration, such as reduced CO2 emissions, enhanced soil structure, and increased microbial activity, can positively impact soil fertility and productivity. The economic and political realities of C sequestration will have a strong influence on the implementation of technically feasible strategies. The major challenge for water management is the sustainable allocation of increasingly scarce resources. Expanded irrigation is a short‐term solution, but in many cases, the existing water supply is insufficient to meet future demand. A drying Texas, and aquifer depletion, portends lower future supplies. The Panhandle, Llano Estacado, and Rio Grande regions have the greatest projected gaps between future supply and demand. Increasing water‐use efficiency and using drought‐tolerant crops are important management goals and precision agriculture with site‐specific management measures could help improve drought resiliency. Texas’ geographic diversity is reflected in the variety of agricultural commodities produced by the state, and CSA activities are likely to be equally diverse.
Influence of seed rate and row spacing on seed multiplication factor and yield of durum wheat in Ethiopia
Authors: Megerssa Shitaye Homma , Geleta Tesfaye , Bekele Nigusu
Published: May 2023

Optimum seeding rate and row spacing are important for uniform crop establishment and harvest of quality seed. Field experiment was conducted at three locations in 2014 and 2015 to study the influence of seed rate and row spacing on seed multiplication factor and yield of durum wheat. Triplicate split plot design was used. The highest seed yield was found at a seed rate of 125 kg ha−1 with a row spacing of 10 cm in 2014 but not significant with the seed rates of 100 kg ha−1 at 10 cm spacing, 75 kg ha−1 at 20 cm row spacing in 2014, and 150 kg ha−1 at 10 cm row spacing in 2015 at Debre Zeit. At Chefe Donsa, the highest seed yield (4.75 ton) was harvested at a seed rate of 100 kg ha−1. At Minjar, seed yield was not affected by seeding rate. Seed multiplication factor was higher at a seed rate of 50 kg ha−1 and spacing of 20 cm at Debre Zeit. At Chefe Donsa, the highest seed multiplication ratio (97.3) was observed in 2015 at a seed rate of 50 kg ha−1 with row spacing of 30 cm. Seed multiplication factor decreased with increasing seed rate at all testing locations. Sowing of 100 kg seeds per hectare with 20 cm spacing gave optimum seed yield over the testing locations. With limited seed availability of nucleus seed, 50 and 75 kg ha−1 with a spacing of 20 cm is appropriate to upsurge seed multiplication ratio.
A new hybrid quantitative structure property relationships‐support vector regression (QSPR‐SVR) approach for predicting the solubility of drug compounds in supercritical carbon dioxide
Authors: Euldji Imane , Belghait Aicha , Si‐Moussa Cherif , Benkortbi Othmane , Amrane Abdeltif
Published: May 2023

The purpose of this work was to compare the performance of 7 meta‐heuristics algorithms namely: Dragonfly (DA), Ant Lion (ALO), Grey Wolf (GWO), Artificial Bee Colony (ABC), Particle Swarm (PSO), Whale (WAO), and a hybrid Particle Swarm with Grey Wolf (HPSOGWO) optimizers in terms of fine‐tuning hyper‐parameters of a hybrid quantitative structure property relationships (QSPR)‐support vector regression (SVR) for the prediction of molar fraction solubilities of drug compounds in supercritical carbon dioxide (SC‐CO2). A dataset of 168 drug compounds, 13 inputs, and 4490 experimental data points was used to achieve the goal. All 7 models were statistically and graphically approved while the HPSOGWO‐SVR was found to over‐perform with an average absolute relative deviation (AARD) of 0.706% and an AIC of −14,434,249. The model was subjected to an external test (validation) using 160 experimental data points that were not used in the training and the test set. The overall results proved that the obtained model has good predictivity ability and robustness.
The first Gondwanan Euphorbiaceae fossils reset the biogeographic history of the Macaranga‐Mallotus clade
Authors: Wilf Peter , Iglesias Ari , Gandolfo María A.
Published: May 2023

Premise

The spurge family Euphorbiaceae is prominent in tropical rainforests worldwide, particularly in Asia. There is little consensus on the biogeographic origins of the family or its principal lineages. No confirmed spurge macrofossils have come from Gondwana.

Methods

We describe the first Gondwanan macrofossils of Euphorbiaceae, represented by two infructescences and associated peltate leaves from the early Eocene (52 Myr ago [Ma]) Laguna del Hunco site in Chubut, Argentina.

Results

The infructescences are panicles bearing tiny, pedicellate, spineless capsular fruits with two locules, two axile lenticular seeds, and two unbranched, plumose stigmas. The fossils' character combination only occurs today in some species of the Macaranga‐Mallotus clade (MMC; Euphorbiaceae), a widespread Old‐World understory group often thought to have tropical Asian origins. The associated leaves are consistent with extant Macaranga.

Conclusions

The new fossils are the oldest known for the MMC, demonstrating its Gondwanan history and marking its divergence by at least 52 Ma. This discovery makes an Asian origin of the MMC unlikely because immense oceanic distances separated Asia and South America 52 Ma. The only other MMC reproductive fossils so far known are also from the southern hemisphere (early Miocene, southern New Zealand), far from the Asian tropics. The MMC, along with many other Gondwanan survivors, most likely entered Asia during the Neogene Sahul‐Sunda collision. Our discovery adds to a substantial series of well‐dated, well‐preserved fossils from one undersampled region, Patagonia, that have changed our understanding of plant biogeographic history.
Triplications of chromosome 1p36.3, including the genes GABRD and SKI, are associated with a developmental disorder and a facial gestalt
Authors: Pelgrims Elise , Lynch Sally Ann , Hannes Laurens , Hoffer Mariëtte J. V. , Melotte Cindy , Van Haeringen Arie , Swillen Ann , Breckpot Jeroen
Published: May 2023

Triplication of chromosomal region 1p36.3 is a rare genomic rearrangement. In this report, we delineate the phenotypic spectrum associated with 1p36.3 triplications. We describe four patients with microtriplications of variable size, but with a strong phenotypic overlap, and compare them to previously described patients with an isolated triplication or duplication of this region. The 1p36.3 triplication syndrome is associated with a distinct phenotype, characterized by global developmental delay, moderate intellectual disability, seizures, behavioral problems, and specific facial dysmorphic features, including ptosis, hypertelorism, and arched eyebrows. The de novo occurrence of these microtriplications demonstrates the reduced reproductive fitness associated with this genotype, in contrast to 1p36.3 duplications which are mostly inherited and can be associated with similar facial features but with a less severe developmental phenotype. The shared triplicated region encompasses four disease‐related genes of which GABRD and SKI are most likely to contribute to the phenotype.
Recent Advances in Indole Synthesis and the Related Alkylation
Authors: Ma Jie , Feng Rong , Dong Zhi‐Bing
Published: May 2023

The derivatives of indoles are very useful intermediates in pharmaceuticals and organic synthesis. The efficient synthesis of the indole blocks and related functionalizations, especially the alkylation of indoles are hot topics in recent years. This review will focus on the following two aspects: i) new developments for the synthesis of indoles which was catalyzed by transition metals, the alkylation of indoles, including the one on N1‐position, C2‐position, as well as C3‐position. 1. Introduction 2. Synthesis of indoles catalyzed by various metals 2.1. Synthesis of indoles by palladium catalysts 2.2. Synthesis of indoles by other metal catalysts 3. Alkylation of indoles 3.1. N1‐alkylation of indoles 3.2. C2‐alkylation of indoles 3.3. C3‐alkylation of indoles
Reducing stress and stereotypic behaviors in captive female pygmy slow lorises (Nycticebus pygmeaus)
Authors: Alejandro Josue , Yamanashi Yumi , Nemoto Kei , Mouri Keiko , Huang Ching‐wen , Bercovitch Fred B. , Huffman Michael A.
Published: May 2023

Improving captive conditions of pygmy slow lorises (Nekaris and Nijman have recently suggested that the pygmy slow loris should be called the pygmy loris and is distinctive enough to warrant a new genus, Xanthonycticebu) (Nycticebus pygmeaus) poses many challenges because detailed aspects of their lives in the wild are incomplete. This hinders efforts to replicate sustainable environments for them. To improve their well‐being in captivity, eight rescued female pygmy slow lorises at the Japan Monkey Center (JMC) were socially housed in two types of groups following their solitary housing: two pairs and one group of four individuals. They spent much of their time in affiliative behaviors, as well as sharing sleeping sites after placement in a social group. The purpose of my study was to examine whether social housing helped in reducing stress by comparing fecal glucocorticoids and stereotypic behaviors when housed alone and when with conspecifics. Overall, the levels of fecal glucocorticoids were significantly lower when socially housed than when kept alone. One individual exhibited stereotypic behavior when housed alone, but this behavior disappeared after social housing. These findings support recent evidence that pygmy slow lorises are social animals and will benefit from group housing in captivity. We conclude that social housing of pygmy slow lorises improves their well‐being by reducing stress levels, and that their group housing in captivity can provide dividends for the conservation of this endangered nocturnal primate because lorises intended for release should find it easier to adapt to natural conditions.
Hybrid Bacteria System with Nanomaterials for Tumor Therapy
Authors: Zhang Qinyi , Ma Xiaotu , Zhao Xiao
Published: May 2023

Recently, bacteria‐mediated therapy has been widely applied for tumor treatments owing to some inherent features of bacteria. With further advancements in genetic engineering and nanotechnology, natural bacteria are endowed with extra capacities of rational genetic reprogramming, spatiotemporally precise manipulation, and some other exogenous characteristics. Hybrid bacteria systems leverage versatile nanomaterials to modify the surface of bacteria, which exhibit great potential in solving the existed problems of traditional bacteria therapy, further greatly improving the tumor therapeutic efficacy. Therefore, hybrid bacteria–based therapeutic platforms present a promising strategy for tumor therapy, which raise increasing attentions. In this review, hybrid bacteria systems for tumor therapy based on different types of chassis bacteria and other related organisms are introduced, and methodologies of nanomaterial‐modified bacteria are systemically expounded. Moreover, the promises of hybrid bacteria as drug delivery vesicles for cancer therapy, other disease therapy, bioimaging, and diagnosis are further discussed, followed by the elaboration on their perspectives and challenges in clinical translation.
Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites
Authors: Criado‐Gonzalez Miryam , Alegret Nuria , Fracaroli Alejandro M. , Mantione Daniele , Guzmán‐González Gregorio , Del Olmo Rafael , Tashiro Kentaro , Tomé Liliana C. , Picchio Matias L. , Mecerreyes David
Published: May 2023

Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water‐free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid‐derived low‐molecular‐weight gelator (LMWG) was found to self‐assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4‐ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self‐healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.
Multi‐Domain versus Single‐Domain: A Magnetic Field is Not a Must for Promoting Spin‐Polarized Water Oxidation
Authors: Ge Jingjie , Ren Xiao , Chen Riccardo Ruixi , Sun Yuanmiao , Wu Tianze , Ong Samuel Jun Hoong , Xu Zhichuan J.
Published: May 2023

The reaction kinetics of spin‐polarized oxygen evolution reaction (OER) can be enhanced by ferromagnetic (FM) catalysts under an external magnetic field. However, applying a magnetic field necessitates additional energy consumption and creates design difficulties for OER. Herein, we demonstrate that a single‐domain FM catalyst without external magnetic fields exhibits a similar OER increment to its magnetized multi‐domain one. The evidence is given by comparing the pH‐dependent increment of OER on multi‐ and single‐domain FM catalysts with or without a magnetic field. The intrinsic activity of a single‐domain catalyst is higher than that of a multi‐domain counterpart. The latter can be promoted to approach the former by the magnetization effect. Reducing the FM catalyst size into the single‐domain region, the spin‐polarized OER performance can be achieved without a magnetic field, illustrating an external magnetic field is not a requirement to reap the benefits of magnetic catalysts.
Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin‐Frameworks for Enhanced Shape‐Selectivity Catalysis
Authors: Zhang Weijie , Lu Zhou , Wojtas Lukasz , Chen Yu‐Sheng , Baker Alexander A. , Liu Yi‐Sheng , Al‐Enizi Abdullah M. , Nafady Ayman , Ma Shengqian
Published: May 2023

One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape‐selectivity of product by the confined spatial environment. The success of shape‐selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal‐organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape‐selectivity for the reactions. For this purpose, a series of binding site‐accessible metal metalloporphyrin‐frameworks (MMPFs) have been investigated to shed light on the nature of enzyme‐mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.
Frenkel Defect‐modulated Anti‐thermal Quenching Luminescence in Lanthanide‐doped Sc2(WO4)3
Authors: Wei Yang , Pan Yue , Zhou Enlong , Yuan Ze , Song Hao , Wang Yilin , Zhou Jie , Rui Jiahui , Xu Mengjiao , Ning Lixin , Liu Zhanning , Wang Hongyu , Xie Xiaoji , Tang Xiaobin , Su Haiquan , Xing Xianran , Huang Ling
Published: May 2023

Although large amount of effort has been invested in combating thermal quenching that severely degrades the performance of luminescent materials particularly at high temperatures, not much affirmative progress has been realized. Herein, we demonstrate that the Frenkel defect formed via controlled annealing of Sc2(WO4)3:Ln (Ln=Yb, Er, Eu, Tb, Sm), can work as energy reservoir and back‐transfer the stored excitation energy to Ln3+ upon heating. Therefore, except routine anti‐thermal quenching, thermally enhanced 415‐fold downshifting and 405‐fold upconversion luminescence are even obtained in Sc2(WO4)3:Yb/Er, which has set a record of both the Yb3+‐Er3+ energy transfer efficiency (>85 %) and the working temperature at 500 and 1073 K, respectively. Moreover, this design strategy is extendable to other hosts possessing Frenkel defect, and modulation of which directly determines whether enhanced or decreased luminescence can be obtained. This discovery has paved new avenues to reliable generation of high‐temperature luminescence.
Atomically Precise Defective Copper Nanocluster Catalysts for Highly Selective C−C Cross‐Coupling Reactions
Authors: Nematulloev Saidkhodzha , Sagadevan Arunachalam , Alamer Badriah , Shkurenko Aleksander , Huang Renwu , Yin Jun , Dong Chunwei , Yuan Peng , Yorov Khursand E. , Karluk Azimet A. , Mir Wasim J. , Hasanov Bashir E. , Nejib Hedhili Mohamed , Halappa Naveen M. , Eddaoudi Mohamed , Mohammed Omar F. , Rueping Magnus , Bakr Osman M.
Published: May 2023

Point defects in nanoparticles have long been hypothesized to play an important role in governing the particle's electronic structure and physicochemical properties. However, single point defects in material systems usually exist with other heterogeneities, obscuring the chemical role of the effects. Herein, we report the synthesis of novel atomically precise, copper hydride nanoclusters (NCs), [Cu28H10(C7H7S)18(TPP)3] (Cu28; TPP: triphenylphosphine; C7H7S: o‐thiocresol) with a defined defect in the gram scale via a one‐pot reduction method. The Cu28 acts as a highly selective catalyst for C−C cross‐couplings. The work highlights the potential of defective NCs as model systems for investigating individual defects, correlating defects with physiochemical properties, and rationally designing new nanoparticle catalysts.
Mucin‐Inspired Single‐Chain Polymer (MIP) Fibers as Potent SARS‐CoV‐2 Inhibitors
Authors: Bej Raju , Nie Chuanxiong , Ludwig Kai , Ahmadi Vahid , Trimpert Jakob , Adler Julia M. , Povolotsky Tatyana L. , Achazi Katharina , Kagelmacher Marten , Vidal Ricardo Martin , Dernedde Jens , Kaufer Benedikt B. , Haag Rainer
Published: May 2023

Mucins are the key component of the defensive mucus barrier. They are extended fibers of very high molecular weight with diverse biological functions depending strongly on their specific structural parameters. Here, we present a mucin‐inspired nanostructure, produced via a synthetic methodology to prepare methacrylate‐based dendronized polysulfates (MIP‐1) on a multi gram‐scale with high molecular weight (MW=450 kDa) and thiol end‐functionalized mucin‐inspired polymer (MIP) via RAFT polymerization. Cryo‐electron tomography (Cryo‐ET) analysis of MIP‐1 confirmed a mucin‐mimetic wormlike single‐chain fiber structure (length=144±59 nm) in aqueous solution. This biocompatible fiber showed promising activity against SARS‐CoV‐2 and its mutant strain, with a remarkable low half maximal (IC50) inhibitory concentration (IC50=10.0 nM). Additionally, we investigate the impact of fiber length on SARS‐CoV‐2 inhibition by testing other functional polymers (MIPs) of varying fiber lengths.
All‐Solid‐State Rechargeable Air Batteries Using Dihydroxybenzoquinone and Its Polymer as the Negative Electrode
Authors: Yonenaga Makoto , Kaiwa Yusuke , Oka Kouki , Oyaizu Kenichi , Miyatake Kenji
Published: May 2023

A proof‐of‐concept study was conducted on an all‐solid‐state rechargeable air battery (SSAB) using redox‐active 2,5‐dihydroxy‐1,4‐benzoquinone (DHBQ) and its polymer (PDBM) and a proton‐conductive polymer (Nafion). DHBQ functioned well in the redox reaction with the solid Nafion ionomer at 0.47 and 0.57 V vs. RHE, similar to that in acid aqueous solution. The resulting air battery exhibited an open circuit voltage of 0.80 V and a discharge capacity of 29.7 mAh gDHBQ−1 at a constant current density (1 mA cm−2). With PDBM, the discharge capacity was much higher, 176.1 mAh gPDBM−1, because of the improved utilization of the redox‐active moieties. In the rate characteristics of the SSAB‐PDBM, the coulombic efficiency was 84 % at 4 C, which decreased to 66 % at 101 C. In a charge/discharge cycle test, the capacity remaining after 30 cycles was 44 %, which was able to be significantly improved, to 78 %, by tuning the Nafion composition in the negative electrode.
Atroposelective Silylation of 1,1′‐Biaryl‐2,6‐diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution
Authors: Zhu Min , Jiang Hua‐Jie , Sharanov Illia , Irran Elisabeth , Oestreich Martin
Published: May 2023

A desymmetrizing silylation of aromatic diols is reported. The previously unknown asymmetric silyl ether formation of phenol derivatives is achieved by applying List's counteranion directed silylation technique. A silylium‐ion‐like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi) enables enantioselective discrimination of achiral 1,1′‐biaryl‐2,6‐diols. The enantioselectivity of that desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding, again achiral bissilylated diol.
Cluster Light‐Emitting Diodes Containing Copper Iodine Cube with 100 % Exciton Utilization Using Host‐Cluster Synergy
Authors: Zhang Nan , Li Ying , Han Sanyang , Wei Ying , Hu Huan , Huo Ran , Duan Chunbo , Zhang Jing , Han Chunmiao , Xie Guohua , Xu Hui
Published: May 2023

Clusters combine the advantages of organic molecules and inorganic nanomaterials, which are promising alternatives for optoelectronic applications. Nonetheless, recently emerged cluster light‐emitting diodes require further excited state optimization of cluster emitters, especially to reduce population of the cluster‐centered triplet quenching state (3CC). Here we report that redox‐active ligands enhance reverse intersystem crossing (RISC) of Cu4I4 cluster for triplet‐to‐singlet conversion, and thermally activated delayed fluorescence (TADF) host can provide an external RISC channel. It indicates that the complementarity between TADF host and cluster in RISC transitions gives rise to 100 % triplet conversion efficiency and complete singlet exciton convergence, rendering 100‐fold increased singlet radiation rate constant and tenfold decreased triplet non‐radiation rate constant. We achieve a photoluminescence quantum yield of 99 % and a record external quantum efficiency of 29.4 %.
Rough FTO electrode interface effect upon ferroelectric switching dynamics in Ag/P(VDF‐HFP)/FTO capacitor structures
Authors: Roy Jyotirmoy , Joseph Bekcy , Gangineni R. B.
Published: May 2023

Rough FTO electrode interface effect upon the characteristic ferroelectric polarization parameters and switching dynamics in Ag/P(VDF‐HFP)/FTO junctions is systematically evaluated by varying electric field amplitude and frequency. Structural and microstructural studies confirm the ferroelectric phase formation of P(VDF‐HFP) on FTO surface. Tilted rectangular P‐E loops have been recorded in the applied fields ranging over 156.25–468.75 MV/m measured between 250 mHz and 5 Hz frequency ranges. Giant saturation of 21.7 μC/cm2 and remnant polarization of 34.9 μC/cm2 has been noted at low frequencies due to the influence of high electric field induced leakage currents. The coercive field, saturation and remnant polarization response with increase in electric field amplitude and frequency of the applied signal are well fitted with classic domain growth model proposed by Kolmogorov‐Avrami‐Ishibashi. A switching time scales of 32.2–693 ms has been observed for forward switching while for backward switching it is noted as 22.1–618.8 ms, when measured at frequencies from 5 Hz to 250 mHz. Furthermore, the tilted P‐E loops are attributed to the excessive leakage currents due to the high surface roughness of FTO bottom electrode.
Association of adverse childhood experiences with adulthood multiple sclerosis: A systematic review of observational studies
Authors: Rehan Syeda Tayyaba , Khan Zayeema , Shuja Syed Hasan , Salman Afia , Hussain Hassan ul , Abbasi Muhammad Saif , Razak Sufyan , Cheema Huzaifa Ahmad , Swed Sarya , Surani Salim
Published: May 2023

Introduction

Adverse childhood experiences (ACEs) are proposed to increase the risk of developing multiple sclerosis (MS) later in life. This systematic review aimed to explore the correlation between ACEs and MS development, age of onset, quality of life in MS patients and MS relapse rates.

Methods

We searched a total of six databases in June 2022 and retrieved the relevant studies. The population included adult (18+) individuals who either had been diagnosed or were at risk for developing MS and also had exposure to ACEs. Our primary outcomes include the risks of MS development, age of MS onset, and MS relapse rate in patients who were exposed to different types of ACEs.

Results

A total of 11 studies were included in our review. A study reported that among 300 women diagnosed with MS, 71 (24%) reported a history of childhood abuse; moreover, with further research, it was concluded that ACEs were associated with the development of MS. Abuse that occurred 2–3 times per week was associated with an 18.81‐fold increased risk of having MS when compared to the unexposed sample. The relapse rate of MS was found to be substantially greater in severe cases of ACEs compared to individuals who did not report any ACEs.

Conclusions

Results support a significant association between ACEs and the development of MS; individuals with a positive history of ACEs develop MS symptoms earlier. Moreover, the severity of ACEs is also linked with increased relapse rates of MS.
Qualitative and quantitative plaque enhancement on high‐resolution vessel wall imaging predicts symptomatic intracranial atherosclerotic stenosis
Authors: Huang Li‐Xin , Wu Xiao‐Bing , Liu Yi‐Ao , Guo Xin , Ye Jie‐Shun , Cai Wang‐Qing , Wang Sheng‐Wen , Luo Bin‐
Published: May 2023

Background and purpose

Intracranial atherosclerotic stenosis (ICAS) is a major cause of ischemic stroke (IS), and high‐resolution vessel wall imaging (HR‐VWI) can be used to assess the plaque characteristics of ICAS. This study aimed to qualitatively and quantitatively assess plaque enhancement of ICAS and to investigate the relationship between plaque enhancement, plaque morphological features, and IS.

Methods

Data from adult patients with ICAS from April 2018 to July 2022 were retrospectively collected, and all patients underwent HR‐VWI examination. Plaque enhancement was qualitatively and quantitatively assessed, and the plaque‐to‐pituitary stalk contrast ratio (CR) indicated the degree of plaque enhancement. Plaque characteristics, such as plaque burden and area, were quantitatively measured using HR‐VWI. Furthermore, receiver‐operating characteristic (ROC) analysis was performed to assess the ability of CR to discriminate plaque enhancement. The patients were divided into a symptomatic ICAS group and an asymptomatic ICAS group according to the clinical and imaging characteristics. Univariate and multivariate analyses were performed to investigate which factors were significantly associated with plaque enhancement and symptomatic ICAS. The plaque burden and CR were compared using linear regression.

Results

A total of 91 patients with ICAS were enrolled in this study. ICAS plaque burden was significantly associated with plaque enhancement (p = .037), and plaque burden was linearly positively correlated with CR (R = 0.357, p = .001). ROC analysis showed that the cutoff value of CR for plaque enhancement was 0.56 (specificity of 81.8%). Both plaque enhancement and plaque burden were significantly associated with symptomatic ICAS, and only plaque enhancement was an independent risk factor after multivariate analysis.

Conclusion

Plaque burden was an independent risk factor for plaque enhancement and showed a linear positive correlation with CR. The cutoff value of CR for plaque enhancement was 0.56, and CR ≥ 0.56 was significantly associated with symptomatic ICAS, which was independently associated with plaque enhancement.
Customized flexible hollow microneedles for psoriasis treatment with reduced‐dose drug
Authors: Ren Yingjie , Li Junshi , Chen Yiwen , Wang Jing , Chen Yuxuan , Wang Zhongyan , Zhang Zhitong , Chen Yufeng , Shi Xiaoyi , Cao Lu , Zhang Jiayan , Dong Huang , Yan Cong , Li Zhihong
Published: May 2023

Microneedles, especially hollow microneedles (HMNs), play an important role in drug delivery, but most of the current HMNs are manufactured based on silicon microfabrication (lithography, etching, etc.), which are slightly conservative due to the lack of low‐cost, batch‐scale and customized preparation approach, especially for the HMNs with flexible substrate. For the first time, we propose the use of a high‐precision 3D printed master mold followed by a dual‐molding process for the preparation of HMNs with different shapes, heights, and inner and outer diameters to satisfy different drug delivery needs. The 3D printed master mold and negative mold can be reused, thereby significantly reducing the cost. HMNs are based on biocompatible materials, such as heat‐curing polymers or light‐curing resins. The thickness and rigidity/flexibility characteristics of the substrate can be customized for different applications. The drug delivery efficiency of the fabricated HMNs was verified by the in situ treatment of psoriasis on the backs of mice, which required only a 0.1‐fold oral dose to achieve similar efficacy, and the associated side effects and drug toxicity were reduced. Thus, this dual‐molding process can reinvigorate HMNs development.
Transcriptomic features reveal molecular signatures associated with recombinant adeno‐associated virus production in HEK293 cells
Authors: Wang Yongdan , Fu Qiang , Lee Yong Suk , Sha Sha , Yoon Seongkyu
Published: May 2023

The development of gene therapies based on recombinant adeno‐associated viruses (rAAVs) has grown exponentially, so the current rAAV manufacturing platform needs to be more efficient to satisfy rising demands. Viral production exerts great demand on cellular substrates, energy, and machinery; therefore, viral production relies heavily on the physiology of the host cell. Transcriptomics, as a mechanism‐driven tool, was applied to identify significantly regulated pathways and to study cellular features of the host cell for supporting rAAV production. This study investigated the transcriptomic features of two cell lines cultured in their respective media by comparing viral‐producing cultures with non‐producing cultures over time in parental human embryonic kidney cells (HEK293). The results demonstrate that the innate immune response signaling pathways of host cells (e.g., RIG‐I‐like receptor signaling pathway, Toll‐like receptor signaling pathway, cytosolic DNA sensing pathway, JAK‐STAT signaling pathway) were significantly enriched and upregulated. This was accompanied by the host cellular stress responses, including endoplasmic reticulum stress, autophagy, and apoptosis in viral production. In contrast, fatty acid metabolism and neutral amino acid transport were downregulated in the late phase of viral production. Our transcriptomics analysis reveals the cell‐line independent signatures for rAAV production and serves as a significant reference for further studies targeting the productivity improvement in the future.
Friends and safeguarding: Young people's views about safety and to whom they would share safety concerns
Authors: Russell Douglas H. , Higgins Daryl J.
Published: May 2023

Child sexual abuse prevention strategies typically focus on teaching children ‘protective behaviours’, including telling a ‘trusted adult’. However, disclosure rates are low, and we know little about who they tell. We analysed data from over 3400 young people aged 10–18. After viewing hypothetical unsafe scenarios involving either an adult or peer, participants were asked whether – and whom – they would tell someone if such a situation occurred. Most (83.9 per cent) said they would tell someone about concerns involving an adult; fewer (79.3 per cent) would tell if they encountered an unsafe situation with a peer. Across adult and peer scenarios, participants were most likely to say they would approach their mother (about concerning behaviour of an adult, 68.7 per cent; or a peer, 63.1 per cent), a friend (64.4; 57.9 per cent) or their father (52.2; 48.9 per cent). Those most likely to tell a friend were girls and older children. Children in out‐of‐home care and community welfare organisations were less likely to tell someone about concerning behaviour from a peer/friend than in other organisational contexts. Although organisations must train staff in supporting young people who raise concerns or make disclosures, it is vital to consider the role of parents and other young people in hearing about concerns and building their capacity to respond appropriately.
Transitioning from military to civilian life: The Ohio story
Authors: Shankle Shawnice , Hibler David , Caven Gwen , Krause‐Parello Cheryl A. , Duffy Sonia A.
Published: May 2023

Veterans often experience difficulties transitioning from military to civilian life. This secondary qualitative analysis explored Ohio Veterans' and Veterans' health stakeholders priorities (N = 41) for care when transitioning from military to civilian life. Ten, 90‐minute focus groups were conducted. Barriers to becoming a civilian included not being adequately prepared for transition and being unable to access resources (e.g., “They [the military] prepare you for combat. Nobody prepares you for discharge; nobody tells you how to get care.”). Barriers to physical health focused on gaps in care (e.g., “it took all day to get care”). Mental health barriers included stigma and posttraumatic stress disorder (PTSD; e.g., “When I say Veteran what do you think? 'Homeless Vet' or a 'Ticking Time Bomb'”; “PTSD… let's talk about what it really is and reduce stigma”). Financial/educational barriers included the inability to afford healthcare co‐payments, delayed receipt of service‐connected disability, and educational benefits, (e.g., “[Veterans] will stop taking medications … because they have a bill or co‐pay they need to pay”). Policy makers, community leaders, and healthcare professionals can use these data to enhance programmes that facilitate Veterans transitioning from military to civilian life.
The mental health crisis: New data on teen girls
Authors: Walters Anne S.
Published: May 2023

In February of this year, the CDC released sobering data: nearly three in five teen girls experienced sadness and hopelessness in 2021. This is double the number of boys and represents an almost 60% increase as well as the highest level over the past 10 years. Further, nearly one in three considered death by suicide, an increase of almost 60% over the past 10 years. One in five girls was the victim of sexual violence in the past year, an increase of 20% since 2017. Moreover, finally, one in 10 have been forced to have sex, an increase of 27% since 2019. These numbers are noted to be even higher in LBGTQ+ and minority populations of girls.