bluuebunny/crossref_metadata_2025 huggingface dataset:
Suppressing Defects‐Induced Non‐Radiative Recombination for Activating the Near‐Infrared Photoactivity of Red Polymeric Carbon Nitride
Authors: Zhang Guoqiang , Huang Wei , Xu Yangsen , Li Yongliang , He Chuanxin , Ren Xiangzhong , Zhang Peixin , Mi Hongwei
Published: September 2023

Many cases of light absorption modification exceeding 700 nm or near‐infrared (NIR) light are reported for capturing more than half of the solar energy, however, very few modifications can produce NIR photoactivity due to the inevitably introduced defects‐induced non‐radiative recombination. Here, taking four kinds of C/O co‐doped red polymeric carbon nitride as examples, defect‐repairing is carried out using alkali metal molten‐salts (LiCl/NaCl and LiCl/KCl) or solid‐salt (KCl) to activate their NIR photoactivity. The defect repair results from the passivation of alkali metal valence electron pairing and the formation of crystalline polyheptazine imide structure with more complete polymerization. More importantly, it sharply eliminates bulk defects (such as carbon vacancy and nitrogen vacancy) introduced by C/O co‐doping. Since structural defects are inevitably introduced in most photocatalysts during expanding light absorption, this proposed strategy is bound to be universal in suppressing defects‐induced non‐radiative recombination to activate NIR photoactivity.
Tough Yet Reversible Hydrogel Adhesives with Cooperative Energy Dissipation for Multifunctional Wearable Sensors
Authors: Lu Gang , Zhu Qi , Ma Rui , He Wei , Wu Jun
Published: September 2023

Achieving robust yet reversible adhesion between hydrogels and diverse substrates is of great importance and technically challenging. A family of phase‐segregated hydrogel adhesives with cooperative energy dissipation is reported. The resultant hydrogels display abundant nano‐aggregates comprising hydrophobic clusters and hydrogen‐bonded nanocrystals for efficient dissipation, and accumulated interfacial physical bonding like hydrogen bonding and hydrophobic interactions for intrinsic adhesion work, thus synergistically leading to super tough yet reversible adhesion. Additionally, the size of nano‐aggregates can be well‐tuned by varying time of solvent exchange followed by dry‐annealing and swelling, thus enabling switchable mechanical robustness and water content as well as unprecedented interfacial toughness exceeding 3300 J m−2 on the polyhydric surfaces. Multifunctional stretchable and pressure sensors with high sensitivity and ionic conductivity are also demonstrated.
Strong and Ultratough Ionogel Enabled by Ingenious Combined Ionic Liquids Induced Microphase Separation
Authors: Tie Jianfei , Mao Zhiping , Zhang Linping , Zhong Yi , Xu Hong
Published: September 2023

Ionogels have become a popular material in flexible electronics and soft robotics based on their excellent ionic conductivity, environmental tolerance, and electrochemical stability. However, it remains a challenge to develop an ionogel integrated with high strength, toughness, self‐healing, and adhesion. Herein, a novel strategy is established to design a high‐strength (0.97 MPa) and tensile (980%), excellent crack insensitivity, self‐healing ionogel based on the cosolvent method. By virtue of differential interactions between the specific polymer and various ionic liquids with gradient polarity, cosolvent systems are employed to achieve high‐performance ionogels by a simple one‐step polymerization. Gel permeation chromatography, atomic force microscopy, time‐domain nuclear magnetism, and density functional theoretical calculation are used to analyze the reasons. Microphase separation can be induced by hydrone or stretching to enhance strength of the ionogel. Therefore, ionogels can be assembled as strain and temperature sensors to monitor human movement and person's body temperature with a low detection threshold (0.1 °C) in extreme environments. This concept creates a new path to achieve soft materials with high performance, and provide a prospective strategy to regulate the in situ microphase change and performance of the resulting ionogel via the one‐step polymerization.
Cellular Mechanisms Driving the Distinct Behavior of Trichocyte Keratins in Wound Healing
Authors: Li Wenfeng , Qing Rui , Zhang Haojie , Wang Ziwei , Yuan Yuhan , Wang Lili , Deng Jia , Wang Bochu , Hao Shilei
Published: September 2023

Trichocyte keratins hold significant promise in accelerating wound healing. Yet it is difficult to discriminate characteristics and mechanisms from their subtypes because of the high sequence homology. Here,  the distinct wound healing properties in terms of wound closure rate, epidermal regeneration and angiogenesis of 17 kinds of human hair keratins is reported. Each trichocyte keratin shows distinct behaviors with unique advantages. Amongst all, recombinant keratin (RK) 33B, RK34, RK39 and RK84 show the highest efficiency in wound closure acceleration, and RK34, RK37 and RK81 presented the strongest angiogenic performance. Furthermore, transcriptomic analysis revealed the regulatory mechanisms of trichocyte keratins in the proliferation and migration of keratinocyte and blood vessel generation. Finally, the keratins with strong re‐epithelialization and angiogenic performances significantly accelerate wound closure in a diabetic rat model established in‐house. The findings provide a panorama view of trichocyte keratin performance in wound healing and that may harbor potential for finely tailored keratin development and precision applications.
Bifunctional Bidentate Organic Additive toward High Brightness Pure Red Quasi‐2D Perovskite Light‐Emitting Diodes
Authors: Rui Hongsong , Wu Xiaoming , Qiu Yuan , Liu Xuguang , Bu Shixiao , Cao Huanqi , Yin Shougen
Published: September 2023

Quasi‐2D perovskites have attracted extraordinary attention for applications in solution‐processable light‐emitting diodes (LEDs). However, the performance of quasi‐2D perovskite LEDs (PeLEDs) is limited by the wide n phases distribution and the inevitable defects in the emitting films. Herein, a novel bidentate organic molecule ethyl thiooxamate (ETO) with two different electron‐rich functional moieties (C═O and C═S) as an additive is introduced in antisolvent ethyl acetate (EA) to achieve high quality quasi‐2D perovskite (PEA2CsPb2I7) films. The unsaturated Pb defects caused by iodine vacancy (VI) and Pb‐I (PbI) antisite can be simultaneously passivated though the synergistic action of the C═O and C═S moieties. Meanwhile, suppressing the formation of large n phases results in a more concentrated n phases distribution and improves the cascade energy transfer for boosting the excitons’ radiative recombination. As a result, the fabricated 656 nm pure red PeLEDs show a high maximum luminance of 6483 cd m−2 and a high peak external quantum efficiency of 20.73% with a CIE coordinate of (0.705, 0.293). The optimal device exhibits the superior performances to the reported red quasi‐2D PeLEDs at ≈640–690 nm. This work provides a guidance for rational designing of multidentate organic molecules toward high performance quasi‐2D PeLEDs.
Multifunctional Hydrogels for the Healing of Diabetic Wounds
Authors: Xiang Tao , Guo Qianru , Jia Lianghao , Yin Tianyu , Huang Wei , Zhang Xinyu , Zhou Shaobing
Published: September 2023

The healing of diabetic wounds is hindered by various factors, including bacterial infection, macrophage dysfunction, excess proinflammatory cytokines, high levels of reactive oxygen species, and sustained hypoxia. These factors collectively impede cellular behaviors and the healing process. Consequently, this review presents intelligent hydrogels equipped with multifunctional capacities, which enable them to dynamically respond to the microenvironment and accelerate wound healing in various ways, including stimuli ‐responsiveness, injectable self‐healing, shape ‐memory, and conductive and real‐time monitoring properties. The relationship between the multiple functions and wound healing is also discussed. Based on the microenvironment of diabetic wounds, antibacterial, anti‐inflammatory, immunomodulatory, antioxidant, and pro‐angiogenic strategies are combined with multifunctional hydrogels. The application of multifunctional hydrogels in the repair of diabetic wounds is systematically discussed, aiming to provide guidelines for fabricating hydrogels for diabetic wound healing and exploring the role of intelligent hydrogels in the therapeutic processes.
Electrochemically Responsive 3D Nanoarchitectures
Authors: Hamidinejad Mahdi , Wang Heng , Sanders Kate A , De Volder Michael
Published: September 2023

Responsive nanomaterials are being developed to create new unique functionalities such as switchable colors and adhesive properties or other programmable features in response to external stimuli. While many existing examples rely on changes in temperature, humidity, or pH, this study aims to explore an alternative approach relying on simple electric input signals. More specifically, 3D electrochromic architected microstructures are developed using carbon nanotube–Tin (Sn) composites that can be reconfigured by lithiating Sn with low power electric input (≈50 nanowatts). These microstructures have a continuous, regulated, and non‐volatile actuation determined by the extent of the electrochemical lithiation process. In addition, this proposed fabrication process relies only on batch lithographic techniques, enabling the parallel production of thousands of 3D microstructures. Structures with a 30–97% change in open‐end area upon actuation are demonstrated and the importance of geometric factors in the response and structural integrity of 3D architected microstructures during electrochemical actuation is highlighted.
Asymmetric Π‐Bridge Engineering Enables High‐Permittivity Benzo[1,2‐B:4,5‐b′]Difuran‐Conjugated Polymer for Efficient Organic Solar Cells
Authors: Gao Yueyue , Xiao Zuo , Cui Minghuan , Saidaminov Makhsud I. , Tan Furui , Shang Luwen , Li Wanpeng , Qin Chaochao , Ding Liming
Published: September 2023

Organic solar cells (OSCs) exhibit complex charge dynamics, which are closely correlated with the dielectric constant (ɛr) of photovoltaic materials. In this work, a series of novel conjugated copolymers based on benzo[1,2‐b:4,5‐b′]difuran (BDF) and benzotriazole (BTz) is designed and synthesized, which differ by the nature of π‐bridge from one another. The PBDF‐TF‐BTz with asymmetric furan and thiophene π‐bridge demonstrates a larger ɛr of 4.22 than PBDF‐dT‐BTz with symmetric thiophene π‐bridge (3.15) and PBDF‐dF‐BTz with symmetric furan π‐bridge (3.90). The PBDF‐TF‐BTz also offers more favorable molecular packing and appropriate miscibility with non‐fullerene acceptor Y6 than its counterparts. The corresponding PBDF‐TF‐BTz:Y6 OSCs display efficient exciton dissociation, fast charge transport and collection, and reduced charge recombination, eventually leading to a power conversion efficiency of 17.01%. When introducing a fullerene derivative (PCBO‐12) as a third component, the PBDF‐TF‐BTz:Y6:PCBO‐12 OSCs yield a remarkable FF of 80.11% with a high efficiency of 18.10%, the highest value among all reported BDF‐polymer‐based OSCs. This work provides an effective approach to developing high‐permittivity photovoltaic materials, showcasing PBDF‐TF‐BTz as a promising polymer donor for constructing high‐performance OSCs.
An Enhanced Interlayer Construction Strategy for High‐Frequency Copper Clad Laminates: Resolving the Contradiction between Signal Loss and Adhesion
Authors: Mei Xiaokang , Yang Shu , Lei Jiang , Li Qinyuan , Li Kaikai , Xie Yingxi , Yao Yunpeng , Lu Longsheng
Published: September 2023

In high‐frequency printed circuit boards (PCBs), there is an inherent contradiction between minimizing signal loss and maximizing adhesion strength. To tackle this issue, this work presents a simple approach by developing an enhanced interlayer through a two‐step process involving anodization/APTES (3‐aminopropyltriethoxysilane) treatment. The anodization yields micro/nano oxide structures with low surface roughness, thereby reducing the skin effect. One side of the enhanced interlayer is mechanically anchored and chemically bonded to copper foils, while the other side is coupled with bismaleimide/triazine‐based resins (BT resins), significantly augmenting the adhesion strength. Eight‐layer PCBs manufactured employing this method exhibit an insertion loss of −1.3553 dB in−1 at 32 GHz. Compared to two conventional brown oxide methods, the insertion loss is reduced by 7.80% and 3.24%, respectively, with a more substantial reduction observed at higher frequencies. The peel strength of samples ranges from 0.554 to 0.589 N mm−1, demonstrating maximum enhancements of 34.78% and 164.13% in comparison to the two brown oxide methods, respectively. Moreover, eight‐layer PCBs undergo lead‐free reflow soldering tests, solder float tests, and thermal fatigue tests without encountering any failures. Consequently, the proposed method holds significant practical significance in addressing the challenge associated with low signal loss and high adhesion strength in high‐frequency PCBs.
Appearance of a Photoinduced Hidden State in the Electron Donor–Acceptor Type Metal–Organic Framework (NPr4)2[Fe2(Cl2An)3]
Authors: Banu Samiran , Kato Mone , Takubo Kou , Okimoto Yoichi , Koshihara Shinya , Iwano Kaoru , Kosaka Wataru , Miyasaka Hitoshi , Ishikawa Tadahiko
Published: September 2023

Electron donor–acceptor (DA)‐type metal–organic frameworks (MOFs) with valence instability are promising molecular materials for the design of photo‐responsive and electronic/magnetic functional materials. Here, ultrafast photoinduced dynamics in a DA‐type layered MOF that exhibits a charge‐transfer (CT)‐type phase transition are reported: (NPr4)2[Fe2(Cl2An)3], where NPr4+ = tetra‐n‐propylammonium and Cl2An2− = 2,5‐dichloro‐3,6‐dihydroxo‐1,4‐benzoquinonate. At room temperature (300 K: RT), ultrafast photoinduced CT between the Fe and Cl2An ions induces a sensitive change in the state associated with the valence instability from a single‐chain, electron‐correlated state to a new photoinduced, structurally modulated state. In the photoinduced state, two absorption bands are observed, one on the higher‐energy side of the CT band and the other in the mid‐IR range. This strongly implies that the local inversion center on the Cl2An ion that exists in the initial state disappears instantly upon photoexcitation, causing an ultrafast change in the lattice structure due to the softening of rigid bonds. This has never been realized in thermal excitation. These findings demonstrate that a new electronic state with a unique lattice structure—i.e., a photoinduced hidden state—appears in this MOF system at ultra‐high speed (within 110 fs) upon photoexcitation at RT.
Prediction of Piezoelectric Tile Performance in Flat and Mountainous Terrains Through Deep Neural Network
Authors: Adhikari Jitendra , Singh Kamalpreet , Sagar Anjani Kumar , Sharma Vikki Kumar , Kumar Rajeev , Jain Satish Chandra
Published: September 2023

Piezoelectric tiles harvest mechanical vibrations and convert them into electrical energy, making them an attractive energy‐harvesting technology. However, their performance is heavily influenced by the terrain where they are installed. Traditional experimental methods for predicting their performance on different terrains are time‐consuming, so a computational approach is necessary to improve efficiency. To address this, a machine learning‐based approach is proposed using Artificial Neural network (ANN) and Deep neural network (DNN) with the Tanh activation function to predict piezoelectric tile performance in diverse terrains. The models are trained on an experimental dataset consisting of four terrains, including Flat terrain (FT) and Hilly Terrain (HT) 1, 2, 3 with road angles of 0, 3, 6, and 10 degrees. A finite element model is also established to optimize the piezoelectric tile and estimate the suitable parameter range to prevent damage to the tile during experiments. The results indicate that the DNN model performs better than the ANN model, achieving high accuracy in predicting piezoelectric tile performance on different terrains. These findings suggest that machine learning can provide a time and cost‐effective way for predicting the performance of piezoelectric tiles in varied terrains, thereby facilitating betters installation and maintenance decisions for piezoelectric tile systems.
Cu‐Catalyzed Enantioselective Reductive Coupling of 1,3‐Dienes and Carboxylic Acid Anhydrides
Authors: Lu Wenxin , Chong Qinglei , Meng Fanke
Published: September 2023

Catalytic chemo‐, regio‐ and enantioselective construction of allyl‐Cu complexes generated from a Cu−H addition to trans‐1,3‐dienes followed by in situ addition to anhydrides to construct homoallylic alcohols is presented. This method is distinguished by a characteristic pathway to generate enantiomerically enriched allyl‐Cu species, which react with a wide range of anhydrides in high chemo‐, regio‐ and stereoselectivity. Functionalization of homoallylic alcohol products provides useful building blocks which are otherwise difficult to obtain.
Covariance in human limb joint articular morphology
Authors: Horbaly Haley
Published: September 2023

Objectives

Limb synovial joints exhibit complex shapes that must accommodate often‐antagonistic demands of function, mobility, and stability. These demands presumably dictate coordination among joint articular shapes, but the structure of morphological covariance within and among joints is unknown. This study analyzes the human shoulder, elbow, hip, and knee to determine how articular covariance is structured in relation to joint structure, accessory cartilage, and function.

Materials and Methods

Surface models were created from the CT scans of 200 modern skeletons from the University of Tennessee Donated Skeletal Collection. Three‐dimensional landmarks were collected on the shoulder, elbow, hip, and knee joints. Two‐block partial least squares were conducted to determine associations between surfaces of conarticular shapes, functionally analogous articulations, and articulations belonging to the same bone.

Results

Except for the components of the shoulder, all conarticular pairs exhibit covariance, though the strength of these relationships appears unrelated to the amount of accessory cartilage in the joint. Only the analogous articulations of the humerus and femur exhibit significant covariance, but it is unlikely that this pattern is due to function alone. Stronger covariance within the lower limb than the upper limb is consistent broader primate patterns of within‐limb integration.

Discussion

With the exception of the elbow, complementary joint function does not appear to promote strong covariance between articulations. Analogous humeral and femoral surfaces are also serially homologous, which may result in the articular associations observed between these bones. Broadly, these patterns highlight the indirect relationship between joint congruence and covariance.
Variation in human limb joint articular morphology
Authors: Horbaly Haley , Hubbe Mark , Sylvester Adam D. , Steadman Dawnie Wolfe , Auerbach Benjamin M.
Published: September 2023

Objectives

Synovial joints in human limbs strike a balance between mobility, stability, and articular fit, yet little is known about how these conflicting demands pattern intraspecific variation in articular shape. In this study, we use geometric morphometrics to establish the apportionment and magnitude of morphological variance of the articular surfaces of the human shoulder, elbow, hip, and knee. We hypothesize that variances will be comparable between articulating surfaces within a joint and will be larger in joints with smaller ranges of motion, given their plurality of functional demands.

Materials and Methods

Three‐dimensional landmarks were taken on the articular surfaces of the glenohumeral, humeroulnar, acetabulofemoral, and tibiofemoral joints from CT scans of 200 skeletons from the University of Tennessee Donated Skeletal Collection (84 females, 116 males). Root mean‐squared distances between articulations calculated from Procrustes shape coordinates were used to determine variance distributions.

Results

We found no difference in variances for each articular surface between the sexes or between left and right articular surfaces. A high range of motion is associated with greater morphological variance; however, this pattern is largely driven by the concave articular surfaces of each joint, which consistently exhibit statistically greater variance than their convex counterparts.

Discussion

The striking pattern of differential variance between articulating morphologies points to potential disparities in development between them. Consistently higher variance in concave surfaces may relate to chondral modeling theory for the formation of joints. Establishing intraspecific morphological variance patterns is a first step in understanding coordinated evolution among articular features.
Mechanisms of Biomolecular Self‐Assembly Investigated Through In Situ Observations of Structures and Dynamics
Authors: Schmid Sakshi Yadav , Lachowski Kacper , Chiang Huat Thart , Pozzo Lilo , De Yoreo Jim , Zhang Shuai
Published: September 2023

Biomolecular self‐assembly of hierarchical materials is a precise and adaptable bottom‐up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning‐based approaches, multiparametric characterization, and high‐throughput methods can boost the development of biomolecular self‐assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self‐assembly and to inspire the next generation of biomimetic materials.
Einbau von (Bioaktiven) Äquatorialen Liganden in Platin(IV)‐Komplexe
Authors: Kastner Alexander , Schueffl Hemma , Yassemipour Patrick A. , Keppler Bernhard K. , Heffeter Petra , Kowol Christian R.
Published: September 2023

Platin(IV)‐Prodrugs sind aufgrund ihrer erhöhten Tumorselektivität und geringeren Nebenwirkungen äußerst interessante Alternativen zu Platin(II)‐Antitumortherapeutika. Im Gegensatz zur gängigen Theorie haben wir kürzlich beobachtet, dass äquatoriale Liganden von z. B. Oxaliplatin(IV)‐Komplexen unter Bildung von [(DACH)Pt(OHeq)2(OAcax)2] hydrolysiert werden können. In der hier vorgestellten Arbeit untersuchten wir die Reaktivität und synthetische Verwendbarkeit dieses Komplexes, als Vorstufe für die Entwicklung neuartiger Platin(IV)‐Komplexe, welche mit herkömmlichen Methoden nicht zugänglich sind. Tatsächlich war es möglich die äquatorialen Hydroxidoliganden z. B. durch ein oder zwei monodentate Biotin‐Liganden, die unter Standardmethoden oxidiert werden würden, zu ersetzen. Die gebildeten Komplexe erwiesen sich als sehr stabil und zeigten auch nach der Reduktion eine langsame Ligandenfreisetzung, eine ideale Eigenschaft für lang zirkulierende zielgerichtete Strategien. Daraufhin wurden zwei Platin(IV)‐Komplexe mit äquatorialen Maleimiden, für die Bindung an Serumalbumin als natürlichen Nanocarrier, synthetisiert. Die Komplexe zeigten im Vergleich zu Oxaliplatin eine stark verlängerte Plasmahalbwertszeit und eine deutlich verbesserte Antitumoraktivität in vivo. Zusammenfassend ermöglicht diese neu entwickelte Syntheseplattform den einfachen und gezielten Einbau äquatorialer Liganden in Platin(IV)‐Komplexe. Des Weiteren können verschiedene (bioaktive) Einheiten koordiniert werden, wodurch sogar zielgerichtete dreifach‐wirksame Platin(IV)‐Prodrugs mit nur einem Platinzentrum möglich wären.
Enhanced Metal‐Support Interactions Boost the Electrocatalytic Water Splitting of Supported Ruthenium Nanoparticles on a Ni3N/NiO Heterojunction at Industrial Current Density
Authors: Liu Rui , Sun Mingzi , Liu Xiangjian , Lv Zunhang , Yu Xinyu , Wang Jinming , Liu Yarong , Li Liuhua , Feng Xiao , Yang Wenxiu , Huang Bolong , Wang Bo
Published: September 2023

Developing highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure‐induced‐strategy to optimize the metal‐support interaction (MSI) and the EWS activity of Ru‐Ni3N/NiO. Density functional theory (DFT) calculations firstly predicted that the Ni3N/NiO‐heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru‐Ni3N/NiO compared to Ru‐Ni3N and Ru‐NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof‐of‐concept, the Ru‐Ni3N/NiO catalyst with a 2D Ni3N/NiO‐heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which exhibited excellent HER and OER activity with overpotentials of 190 mV and 385 mV at 1000 mA cm−2, respectively. Furthermore, the Ru‐Ni3N/NiO‐based EWS device can realize an industrial current density (1000 mA cm−2) at 1.74 V and 1.80 V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000 h (@ 500 mA cm−2) in alkaline pure water.
Sulfur Changes the Electrochemical CO2 Reduction Pathway over Cu Electrocatalysts
Authors: Liang Shuyu , Xiao Jiewen , Zhang Tianyu , Zheng Yue , Wang Qiang , Liu Bin
Published: September 2023

Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g., ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR.
Dithienoazepine‐Based Near‐Infrared Dyes: Janus‐Faced Effects of a Thiophene‐Fused Structure on Antiaromatic Azepines
Authors: Murai Masahito , Enoki Takahiro , Yamaguchi Shigehiro
Published: September 2023

We here disclose that the incorporation of thiophene rings into a seven‐membered 8π azepine in a fused fashion produces a useful antiaromatic core for near‐infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno‐fused derivatives with electron‐accepting groups adopt flat conformations in the ground state. The dithieno‐fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red‐shifted relative to those of the dibenzo‐fused congeners. Theoretical study revealed two contradictory effects of the less‐aromatic thiophene‐fused structure, i.e., the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron‐accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution.
Novel core–shell magnetic nanoparticles@Zeolitic imidazolate with glycerol‐nickel for the synthesis of dihydropyrimidinones
Authors: Poursattar Marjani Ahmad , Asadzadeh Fatemeh , Danandeh Asl Aria
Published: September 2023

The present study reported a novel and eco‐friendly synthesis of Fe3O4@ZIF‐8@Glycerol‐Ni nanocatalyst via a multistep process. The as‐prepared catalyst was used due to its high efficiency, low cost, and biocompatibility for the fabrication of dihydropyrimidinones by Biginelli multicomponent reactions of aryl aldehyde, ethyl acetoacetate, and urea under ambient status. X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), Brunauer‐Emmet‐Teller (BET), vibrating sample magnetometry (VSM), scanning electron microscopy and energy dispersive X‐ray (SEM‐EDS), inductively coupled plasma (ICP), elemental mapping analysis (EMA), thermogravimetric analysis (TGA), Raman, and transmission electron microscopy (TEM) techniques were successfully utilized to evaluate the nanocatalyst. The advent of the peaks confirmed the presence of nickel on the catalyst's surface due to the oxygen and nickel, and the nanoparticle size is 10–15 nm. Eventually, nano‐heterogeneous catalyst exhibits high performance as well as good selectivity in the synthesis of dihydropyrimidinones. Also, it can be recycled up to multiple fresh runs with no significant loss of catalytic efficiency.
Neurovascular description in the South American plains vizcacha, Lagostomus maximus (Chinchilloidea, Caviomorpha). A study involving evolutionarily related species of Caviomorpha and Muroidea
Authors: Schmidt Alejandro Raúl , Inserra Pablo Ignacio Felipe , Giacchino Mariela , Ferraris Sergio , Lange Fernando , Figueredo Ramiro Vidal , Halperin Julia , Vitullo Alfredo Daniel , Dorfman Verónica Berta
Published: September 2023

Oxygenated blood is required for the adequate metabolic activity of the brain. This is supplied by the circle of Willis (CoW) and the vertebrobasilar and carotid systems. The CoW ensures blood flow in case of arterial stenosis or occlusion. Different animal models have been explored for the CoW morphological and functional study. This work aims to characterize the vascular architecture of the CoW of the plains vizcacha, Lagostomus maximus (Suborder: Hystricomorpha), and to compare it with evolutionarily related species of Caviomorpha and Muroidea. The blood supply in adult plains vizcachas was studied using latex cerebrovascular casts and angiography. A caudo‐rostral flow direction was determined, beginning in the spinal and vertebral arteries and converging in the basilar artery which bifurcates in the carotid‐basilar communication in the caudal communicating arteries. In the first third of its course, the caudal cerebral arteries project laterally, and the middle and rostral cerebral arteries bifurcate from their rostral terminal segment, supplying the temporo‐parietal and frontal cortex. The CoW architecture is mainly conserved between rodent species. Likewise, the small neurovascular variations observed could be considered phylogenetic morphological variations more than evolutionary adaptations. The absence of the rostral communicating artery that generates the rostral open architecture of the CoW in the vizcacha as in the other analyzed species, supports the need for a revision of the CoW classical function as a security system. Finally, this work supports the importance of expanding our understanding of brain anatomy among species, which may contribute to a better understanding of functional neuroanatomy.
Advances in the extracellular signal‐regulated kinase signaling pathway in silkworms, Bombyx mori (Lepidoptera)
Authors: Lv Jun‐Li , Zheng Kai‐Yi , Wang Xue‐Yang , Li Mu‐Wang
Published: September 2023

Signaling pathways regulate the transmission of signals during organism growth and development, promoting the smooth and accurate completion of numerous physiological and biochemical reactions. The extracellular signal‐regulated kinase (ERK) signaling pathway is an essential pathway involved in regulating various physiological processes, such as cell proliferation, differentiation, adhesion, migration, and more. This pathway also contributes to several important physiological processes in silkworms, including protein synthesis, reproduction, and immune defense against pathogens. Organizing related studies on the ERK signaling pathway in silkworms can provide a better understanding of its mechanism in Lepidopterans and develop a theoretical foundation for improving cocoon production and new strategies for pest biological control.
Jellyfish‐type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity
Authors: Lin Xin‐Cheng , Cui Yun‐Shu , Xie Si‐Jun , Chen Dong‐Ping , Zhai Dan‐Dan , Shi Zhang‐Jie
Published: September 2023

Di‐ and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5‐disubstituted pyrazolate‐bridged ligand LH5 with two [N2N]2−‐type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf2(μ‐1,1‐N3)2(N3)2][Na(THF)4] 3 and [LHf2(μ‐1,1‐N3)2(N3)2][Na(2,2,2‐Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes. The reactivity of 3 under reduction conditions was conducted, leading to a formation of a tetranuclear hafnium imido complex [L1Hf2(μ1‐NH)(N3){μ2‐K}]2 5. DFT calculations revealed that the mixed imido azide 5 was generated via an intramolecular C−H insertion from a putative dinuclear HfIV‐nitridyl intermediate.
Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent
Authors: Li Chenxin , Hinz Alexander
Published: September 2023

Phosphaketenes of divalent group 14 compounds can potentially serve as precursors for the synthesis of heavy multiple‐bond systems. We have employed the dtbpCbz substituent (dtbpCbz=1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazolyl) to prepare such phosphaketenyltetrylenes [(dtbpCbz)EPCO] (E=Ge, Sn, Pb). While the phosphaketenyltetrylenes are stable at ambient conditions, they can be readily decarbonylated photolytically. For the germylene and stannylene derivatives, dimeric diphosphene‐type products [(dtbpCbz)EP]2 (E=Ge, Sn) were obtained. In contrast, photolysis of the phosphaketenylplumbylene, via isomerisation of the [(dtbpCbz)PbP] intermediate to [(dtbpCbz)PPb], afforded an unsymmetric and incompletely decarbonylated product [(dtbpCbz)2Pb2P2CO] formally comprising a [(dtbpCbz)PPb] and a [(dtbpCbz)PbPCO] moiety.
Exploring the therapeutic potential of naturally occurring piceatannol in non‐communicable diseases
Authors: Gandhi Himanshu , Mahant Shikha , Sharma Abhishek Kumar , Kumar Deepak , Dua Kamal , Chellappan Dinesh Kumar , Singh Sachin Kumar , Gupta Gaurav , Aljabali Alaa A. A. , Tambuwala Murtaza M. , Kapoor Deepak N.
Published: September 2023

Piceatannol is a naturally occurring hydroxylated resveratrol analogue that can be found in a variety of fruits and vegetables. It has been documented to have a wide range of beneficial effects, including anti‐inflammatory, antioxidant, anti‐aging, anti‐allergic, antidiabetic, neuroprotective, cardioprotective, and chemopreventive properties. Piceatannol has significantly higher antioxidant activity than resveratrol. Piceatannol has been shown in preclinical studies to have the ability to inhibit or reduce the growth of cancers in various organs such as the brain, breast, lung, colon, cervical, liver, prostate, and skin. However, the bioavailability of Piceatannol is comparatively lower than resveratrol and other stilbenes. Several approaches have been reported in recent years to enhance its bioavailability and biological activity, and clinical trials are required to validate these findings. This review focuses on several aspects of natural stilbene Piceatannol, its chemistry, and its mechanism of action, and its promising therapeutic potential for the prevention and treatment of a wide variety of complex human diseases.
CUR(E)ating a new approach to study fungal effectors and enhance undergraduate education through authentic research
Authors: Li Gengtan , McWilliams Mai , Rodrigues Matheus , Mearkle Benjamin , Jaafar Nader , Golla Vivek , Yu Houlin , Yang He , Ayhan Dilay Hazal , Allen Kelly , Martínez‐Soto Domingo , Springer Amy , Ma Li‐Jun
Published: September 2023

Course‐based Undergraduate Research Experiences (CUREs) integrate active, discovery‐based learning into undergraduate curricula, adding tremendous value to Biochemistry and Molecular Biology (BMB) education. There are multiple challenges in transforming a research project into a CURE, such as the readiness of students, the time commitment of the instructor, and the productivity of the research. In this article, we report a CURE course developed and offered in the University of Massachusetts Amherst BMB Department since 2018 that addresses these challenges. Our CURE focuses on fungal effectors which are proteins secreted by a destructive pathogenic fungus Fusarium oxysporum, one of the top five most devastating plant pathogens. By studying this group of proteins, students are connected to real‐world problems and participate in the search for potential solutions. A 3‐week “standard Boot Camp” is implemented to help students familiarize themselves with all basic techniques and boost their confidence. Next, molecular cloning, a versatile technique with modularity and repeatability, is used as the bedrock of the course. Our past 5 years of experience have confirmed that we have developed a novel and feasible CURE protocol. Measurable progress documented by students who took this course includes stimulated active learning and increased career trajectory to pursue hypothesis‐based research to address societal needs. In addition, data generated through the course advance ongoing lab research. Collectively, we encourage the implementation of CURE among research‐intensive faculty to provide a more inclusive research experience to undergraduate students, an important element in predicting career success.
Residue levels and risk assessment of acetamiprid–pyridaben mixtures in cabbage under various open field conditions
Authors: Dong Bizhang , Hu Jiye
Published: September 2023

Acetamiprid and pyridaben are highly efficient insecticides widely used to protect leafy vegetables against various pests, such as Phyllotreta striolata, but analyses of their residual behaviors applied in mixtures in cabbage fields are primarily lacking. Herein, field trials were performed by spraying 50% acetamiprid–pyridaben wettable powder (50% WP) once at a dose of 150 g of active ingredient per hectare in 12 representative provinces of China under Good Agricultural Practices. The residues of acetamiprid and pyridaben were detected using modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) and liquid chromatography–tandem mass spectrometry, together with an assessment of their dietary risks. The average recoveries of the two insecticides were 84.6–104%, and the relative standard deviations were 0.898–10.1%. The residual concentrations of acetamiprid and pyridaben at the preharvest interval of 7 days were <0.364 and 0.972 mg/kg, respectively, and less than their maximum residue limits in cabbage (0.5 mg/kg for acetamiprid and 2 mg/kg for pyridaben) in China. The chronic and acute risk values of acetamiprid and pyridaben were 0.0787–33.3%, implying acceptable health hazards to Chinese consumers. In conclusion, applying 50% WP in cabbage fields under Good Agricultural Practices is acceptable. These results provide essential data for using mixtures of acetamiprid and pyridaben in cabbage fields.
rTMS targeted to the secondary somatosensory cortex influences sleep in CRPS patients, as measured with the OURA ring
Authors: Vanhanen Jukka , Kujala Jan , Liljeström Mia , Kalso Eija , Virkkala Jussi , Harno Hanna
Published: September 2023

Introduction

Chronic pain associates with various sleep problems. Patients with complex regional pain syndrome (CRPS) often report impaired sleep, but objective measurements of sleep in CRPS patients are scarce. Neuromodulation with repetitive transcranial magnetic stimulation (rTMS) can alleviate pain and improve sleep. Secondary somatosensory cortex (S2) is a possible rTMS target for the treatment of chronic pain, but the effect of S2‐targeted rTMS on sleep is unknown.

Methods

This randomized, sham‐controlled trial assessed the effect of S2‐targeted rTMS on sleep in patients with CRPS. Patients (n = 31) received either S2‐targeted rTMS (10 Hz) or sham stimulation for 3 weeks. The effect of treatment on sleep was assessed with validated questionnaires, with a sleep and pain diary, and with a consumer‐grade sleep tracker, the Oura ring. In addition to an ordinary univariate analysis of the results, we conducted multivariate testing of the Oura data using linear discriminant analysis (LDA).

Results

S2‐targeted rTMS decreased sleep restlessness that significantly differed between the rTMS and sham stimulation patient groups (p = .028). In the multivariate analysis of the Oura data, LDA classification accuracy to separate the rTMS and sham groups exceeded 95% confidence level in four out of the seven tested models. In the subjective evaluation of sleep, the effect of rTMS and sham did not differ.

Conclusion

S2‐targeted rTMS influenced sleep in patients with CRPS. Improved sleep may enhance CRPS symptom alleviation and be of clinical importance. A univariate analysis could separate the rTMS and sham treatments. The multivariate analysis revealed that including multiple sleep‐related parameters can be beneficial when analyzing rTMS effects on sleep. As sleep is related both to pain and quality of life, and sleep rTMS can be directly affected by rTMS, objective monitoring of sleep in various future rTMS trials could be fruitful.
Analyzing drivers of sustainable project‐driven supply chains: A fuzzy Delphi methodology–grey relational analysis approach
Authors: Shishodia Anjali , Sharma Rohit , M.R. Pavithra , Mathiyazhagan K.
Published: September 2023

A sustainable project‐driven supply chain (SPDSC) refers to integrating sustainability into project management to improve the sustainability performance of projects. Integrating sustainability and supply chain management is any project‐based organization's most significant performance‐related challenge. Therefore, the present study explores the drivers that can effectively tackle supply chain issues in managing projects undertaken in construction contracting firms for long‐term sustainability. Sixteen critical drivers were considered through a rigorous literature review and fuzzy Delphi method (FDM) for construction contracting firms. Then, selected drivers were used to analyze established construction contracting firms using a grey relational analysis (GRA) technique. The results highlight that construction contracting firms (CCFs) considered the drivers of sustainable use of resources, energy and eco‐efficiency, and environmental impact assessment; stakeholder engagement and social impact; and supply chain collaboration dimensions need to be improved for enhancing the sustainability of PDSCs. This study's contribution is twofold: It quantifies the identified set of critical drivers relevant to SPDSCs; it offers the CCFs a practical toolkit for sustainable project deliverables.
Ping‐pong snaring of a totally dislodged stent across left main ostium: “All is not lost”
Authors: Restivo Attilio , Stanzione Alessio , Maffeo Diego , Buono Andrea
Published: September 2023

Undeployed stent loss is a rare but potentially serious complication of percutaneous coronary intervention. Its management is not assisted by well‐defined guidelines, and it is made even more difficult when the dislodged stent is not protected by in situ guidewire. In this work, we present the case of a total stent loss with a crushed device protruding out of the left main. In this hopeless circumstance, an innovative ping‐pong technique was used to contralaterally perform a successful stent retrieval.
Bioinspired Hydrophobicity for Enhancing Electrochemical CO2 Reduction
Authors: Bai Jingwen , Wang Wenshuo , Liu Jian
Published: September 2023

Electrochemical carbon dioxide reduction (CO2R) is a promising pathway for converting greenhouse gasses into valuable fuels and chemicals using intermittent renewable energy. Enormous efforts have been invested in developing and designing CO2R electrocatalysts suitable for industrial applications at accelerated reaction rates. The microenvironment, specifically the local CO2 concentration (local [CO2]) as well as the water and ion transport at the CO2–electrolyte–catalyst interface, also significantly impacts the current density, Faradaic efficiency (FE), and operation stability. In nature, hydrophobic surfaces of aquatic arachnids trap appreciable amounts of gases due to the “plastron effect”, which could inspire the reliable design of CO2R catalysts and devices to enrich gaseous CO2. In this review, starting from the wettability modulation, we summarize CO2 enrichment strategies to enhance CO2R. To begin, superwettability systems in nature and their inspiration for concentrating CO2 in CO2R are described and discussed. Moreover, other CO2 enrichment strategies, compatible with the hydrophobicity modulation, are explored from the perspectives of catalysts, electrolytes, and electrolyzers, respectively. Finally, a perspective on the future development of CO2 enrichment strategies is provided. We envision that this review could provide new guidance for further developments of CO2R toward practical applications.
Chiral recognition mechanism studies of Tyr‐Arg‐Phe‐Lys‐NH2 tetrapeptide on crown ether‐based chiral stationary phase
Authors: Upmanis Toms , Sevostjanovs Eduards , Kažoka Helena
Published: September 2023

Even though chiral recognition for crown‐ether CSPs is generally understood, on a molecular level, exact mechanisms for the resolution are still unclear. Furthermore, short peptide analytes often contain multiple amino moieties capable of binding to the crown ether selector. In order to extend the understanding in chiral recognition mechanisms, polar organic mode separation of Tyr‐Arg‐Phe‐Lys‐NH2 tetrapeptide llll/dddd enantiomers on S‐ and R‐(3,3′‐diphenyl‐1,1′‐binaphthyl)‐20‐crown‐6 stationary phases was studied with 50‐mM perchloric acid in methanol as mobile phase. Deviation from the generally acceptable 1:1 stoichiometry was supported by mass spectroscopy analysis of the formed complexes between tetrapeptide enantiomer and crown ether selectors, which revealed adducts possessing 1:1, 1:2, and 1:3 stoichiometry. Further investigation of complexation induced shifts by NMR indicated on different binding mechanisms between llll/dddd enantiomers of Tyr‐Arg‐Phe‐Lys‐NH2 and crown ether selectors. Enantioselective proton shifts were observed in studied tetrapeptide tyrosine and phenylalanine residues exclusively for llll enantiomer upon binding with S‐(3,3′‐diphenyl‐1,1′‐binaphthyl)‐20‐crown‐6 selector (and dddd enantiomer with R‐(3,3′‐diphenyl‐1,1′‐binaphthyl)‐20‐crown‐6 selector), indicating that these two amino acid residues contribute to chiral recognition. The obtained results were in agreement with the LC data.