bluuebunny/crossref_metadata_2025 huggingface dataset:
Structural Instability Stimulated Heteroatoms Co‐Doping of 2D Quaternary Semiconductor for Optoelectronic Applications
Authors: Park Se Yeon , Seo Dong‐Bum , Choi Hyuk , Lee Ju Hyeok , Lee Do Hyung , Kim Jin , Kang Saewon , Yim Soonmin , Kim Eui‐Tae , Lee Sun Sook , Yoon Dae Ho , Kim Hyun You , Song Wooseok , An Ki‐Seok
Published: December 2023

Although the structural and electrical engineering of transition metal dichalcogenides using atomic doping or doping‐induced phase modulation can be used to attain high‐performance and wavelength‐tunable optoelectronic devices, accessible substitutional doping to overcome the large lattice mismatch between the host and guest atom‐related bonding states remains elusive. This study corroborates an innovative synthetic route for molybdenum disulfide (MoS2)‐derived two‐dimensional (2D) quaternary semiconductors substitutionally doped with Re and O using a solution‐based large‐area compatible approach combined with the thermal evaporation of dopants. The substitutional doping of Re into MoS2 crystals with a large lattice mismatch is effectively accomplished by adopting structurally unstable host films, resulting in the large‐scale synthesis of 2D quaternary multi‐layers with a Re doping concentration >10%. Comprehensive spectroscopic and microscopic evaluations are performed to determine the efficacy of the host films with structural instability for the synthesis of 2D RexMo(1‐x)O2yS2(1‐y) quaternary multi‐layers. The capability of the quaternary semiconductor for versatile nanophotonic devices is validated by ascertaining the simultaneous enhancement of the photoelectrical properties with wide‐range optical absorption and photoelectrochemical properties, as compared with those of their binary counterparts.
Exploiting Laser‐Induced Oxidation Phase Diagrams for Multifunctional Titania Thin Films
Authors: Austin Drake , Everhart Brian , Khurshid Farheen , Muthu Jeyavelan , Pelton Anthony , Altvater Michael , Smith Morgen , Post Susanna , Miesle Paige , Muratore Christopher , Rao Rahul , Hofmann Mario , Amama Placidus , Glavin Nicholas
Published: December 2023

Local laser‐induced oxidation is an extremely valuable technique to perform high‐throughput optimization across multidimensional parameter sets. In this work, a versatile method is presented for the synthesis of titanium dioxide (TiO2) thin‐films with varying crystalline structures through the use of localized, visible, continuous‐wave laser‐processing. By controlling the laser intensity and the exposure time, the conversion of amorphous titanium disulfide (a‐TiS2) precursor films into distinct phases of TiO2 is achieved and a laser‐induced oxidation phase diagram is constructed with the resulting material phases, including anatase, rutile, and black TiO2. By utilizing the dependence of phase formation on the rate and duration of laser energy input, mixtures of anatase and rutile phases are fabricated with controlled spatial arrangements. Photocatalytic properties of the synthesized films are evaluated using the degradation of nitrogen oxide (NOx) gas under UV illumination and an organic dye under white‐light illumination, revealing that mixtures of anatase and rutile phases demonstrate superior photocatalytic activity. The laser‐induced oxidation method highlighted showcases a strategy for precisely tailored phase composition for directly tunable properties, paving the way for in‐depth studies into structure‐property relationships in photocatalysis and other applications of metal oxide films.
Mg‐Doped Porous Silicon Derived from Silica Aerogels for Fast and Stable Zinc‐Ion Hybrid Capacitors with High Capacitance
Authors: Deng Shengyuan , Li Jiawen , Zewdie Getasew Mulualem , Jiang Xiaodi , Ji Mingze , Shen Jun , Gao Guohua , Wu Guangming , Bao Zhihao , Kang Hong Seok
Published: December 2023

Zinc‐ion hybrid capacitors (ZICs) are of interest for their optimal balance between power and energy density. Among the cathode materials, silicon is particularly attractive due to its abundance and potential compatibility with the microelectronics industry. However, silicon‐based materials exhibit specific capacitances far below 100 mF cm−2 because of their inherently low electronic and ionic transport, making them less competitive than other nanomaterials such as carbon and MXenes. In this study, state‐of‐the‐art silicon‐based ZICs using Mg‐doped porous silicon (PSi) derived from silica aerogels are constructed. The improved electronic conductivity achieved by Mg doping, combined with enhanced ion diffusion promoted by the porous structure, results in excellent electrochemical properties of the ZIC. Consequently, the prepared ZIC exhibits a specific capacitance of 106.1 mF cm−2 at 0.2 mA cm−2 with remarkable cyclic stability (92% retention after 20 000 cycles). Additionally, the pouch ZICs using gel electrolytes demonstrate good rate capability and a long lifespan, indicating significant potential for practical applications. These results underscore the potential of heteroatom‐doped PSi as a cathode for ZICs.
Long‐cycling Zinc Metal Anodes Enabled by an In Situ Constructed ZnO Coating Layer
Authors: Ren Qingqing , Tang Xinyue , He Kun , Zhang Congmin , Wang Wei , Guo Yaqing , Zhu Zixuan , Xiao Xiaofen , Wang Shun , Lu Jun , Yuan Yifei
Published: December 2023

Suppressing dendrite growth in zinc (Zn) anodes for aqueous Zn batteries remains a significant challenge. Modifying the Zn/electrolyte interface stands out as one of the most promising strategies to tackle this problem. In this study, a nanometer‐thick ZnO coating layer with a uniform concave surface geometry is in situ constructed to modify the Zn anode for the first time. The chemical bond formed between the ZnO layer and the Zn foil enhances the structural stability of the synthesized ZnO modified‐Zn anode. Finite element simulations indicate that the ZnO coating layer facilitates uniform electric field distribution and zinc flux on the Zn electrode. In situ optical observations unveil how the modification interface regulates zinc plating behaviors on the Zn anode. Impressively, the symmetrical ZnO‐Zn cell displays a remarkable cycling stability of 1765 h at a current density of 5 mA cm−2 with an areal capacity of 1 mAh cm−2. Even when subjected to a very high current density of 50 mA cm−2, it maintains stable operation over 3800 cycles. This success highlights the immense application potential of the rationally tailored ZnO‐Zn anode.
Near‐Field Coupling Induced Less Chiral Responses in Chiral Metamaterials for Surface‐Enhanced Vibrational Circular Dichroism
Authors: Xu Cheng , Ren Zhihao , Zhou Hong , Zhou Jingkai , Li Dongxiao , Lee Chengkuo
Published: December 2023

Chiral metamaterials play vital roles in manipulating the circular polarization of electromagnetic waves. Although planar chiral metamaterials are believed to have no true/intrinsic chirality, the design of structural anisotropy can still create enormous circular dichroism, while the mechanism is fully explored. Here, for the first time, it is observed that strong near‐field coupling induces less chiral response in chiral metamaterials. Selective exposure methods to manipulate the near‐field coupling strength, and experimentally validate the circular dichroism difference from tailored near‐field coupling effect are leveraged, which provides strong evidence for the assumption and can be utilized for the structural design framework. Besides, using the enhanced near‐field (over 750‐fold), surface‐enhanced vibrational circular dichroism (SEVCD) for glucose enantiomers, which shows a larger‐than‐one normalized sensitivity compared with metamaterials with chiral response is demonstrated. Furthermore, The potential of SEVCD by detecting a broadband signal using arrayed metamaterials is explored. These findings pave the way toward chiroptical nanophotonic designs for potential biomedical and healthcare applications.
Versatile Structural Engineering of Metal–Organic Frameworks Enabling Switchable Catalytic Selectivity
Authors: Li Zhixi , Yao Bingqing , Cheng Chuanqi , Song Meina , Qin Yutian , Wan Yue , Du Jing , Zheng Chaoyang , Xiao Liyun , Li Shaopeng , Yin Peng‐Fei , Guo Jun , Liu Zhengqing , Zhao Meiting , Huang Wei
Published: December 2023

The structure engineering of metal–organic frameworks (MOFs) forms the cornerstone of their applications. Nonetheless, realizing the simultaneous versatile structure engineering of MOFs remains a significant challenge. Herein, a dynamically mediated synthesis strategy to simultaneously engineer the crystal structure, defect structure, and nanostructure of MOFs is proposed. These include amorphous Zr‐ODB nanoparticles, crystalline Zr‐ODB‐hz (ODB = 4,4′‐oxalyldibenzoate, hz = hydrazine) nanosheets, and defective d‐Zr‐ODB‐hz nanosheets. Aberration‐corrected scanning transmission electron microscopy combined with low‐dose high‐angle annular dark‐field imaging technique vividly portrays these engineered structures. Concurrently, the introduced hydrazine moieties confer self‐reduction properties to the respective MOF structures, allowing the in situ installation of catalytic Pd nanoparticles. Remarkably, in the hydrogenation of vanillin‐like biomass derivatives, Pd/Zr‐ODB‐hz yields partially hydrogenated alcohols as the primary products, whereas Pd/d‐Zr‐ODB‐hz exclusively produces fully hydrogenated alkanes. Density functional theory calculations, coupled with experimental evidence, uncover the catalytic selectivity switch triggered by the change in structure type. The proposed strategy of versatile structure engineering of MOFs introduces an innovative pathway for the development of high‐performance MOF‐based catalysts for various reactions.
“Spark” PtMnIr Nanozymes for Electrodynamic‐Boosted Multienzymatic Tumor Immunotherapy
Authors: Li Danyang , Ha Enna , Zhou Zhenli , Zhang Jingge , Zhu Yaoyao , Ai Fujin , Yan Li , He Shuqing , Li Lei , Hu Junqing
Published: December 2023

Multienzyme‐mimicking redox nanozymes capable of efficient reactive oxygen species (ROS) generation and cellular homeostasis disruption are highly pursued for cancer therapy. However, it still faces challenges from the complicate tumor microenvironment (TME) and high chance for tumor metastasis. Herein, well‐dispersed PtMnIr nanozymes are designed with multiple enzymatic activities, including catalase (CAT), oxidase (OXD), superoxide dismutase (SOD), peroxidase (POD), and glutathione peroxidase (GPx), which continuously produce ROS and deplete glutathione (GSH) concurrently in an “inner catalytic loop” way. With the help of electrodynamic stimulus, highly active “spark” species (Ir3+ and Mn3+) are significantly increased, resulting in an effective cascade enzymatic and electrodynamic therapy. Moreover, the cyclic generation of ROS can also facilitate ferroptosis and apoptosis in tumor cells, boosting synergistic therapy. Importantly, lung metastasis inhibition is found, which confirms efficient immunotherapy by the combined effect of immunogenic cell death (ICD) and Mn2+‐induced cyclic guanosine monophosphate (GMP)–adenosine monophosphate (AMP) synthase (cGAS)–stimulator of interferon genes (cGAS–STING) pathway, contributing great potential in the treatment of malignant tumors.
Negative Enthalpy Variation Drives Rapid Recovery in Thermoplastic Elastomer
Authors: Chen Haiming , Sun Zaizheng , Lu Kai , Liu Jinming , He Chaobin , Mao Dongsheng
Published: December 2023

The mechanism behind the resilience of polymeric materials, typically attributed to the well‐established entropy elasticity, often ignores the contribution of enthalpy variation (ΔH), because it is based on the assumption of an ideal chain. However, this model does not fully account for the reduced resilience of thermoplastic polyurethane (TPU) during long‐range deformation, which is mainly caused by the dynamics of physical crosslink networks. Such reduction is undesirable for long‐range stretchable TPU considering its wide application range. Therefore, a negative ΔH effect is established in this work to facilitate instant recovery in long‐range stretchable TPU, achieved by constructing a reversible interim interface via strain‐induced phase separation. Consequently, the newly constructed dual soft segmental TPU shows resilience efficiency exceeding 95%, surpassing many synthetic high‐performance TPUs with typical efficiencies below 80%, and comparable to biomaterials. Moreover, a remarkable hysteresis loop with a ratio exceeding 50%, makes it a viable candidate for applications such as artificial ligaments or buffer belts. The research also clarifies structural factors influencing resilience, including the symmetry of the dual soft segments and the content of hard segments, offering valuable insights for the design of highly resilient long‐range stretchable elastomers.
Polyelectrolyte Complexation of Chitosan and WS2 Nanotubes
Authors: Magee Eimear , Xie Fengwei , Farris Stefano , Dsouza Andrea , Constantinidou Chrystala , Zak Alla , Tenne Reshef , McNally Tony
Published: December 2023

The inclusion of tungsten disulphide nanotubes (WS2 NTs) in chitosan, plasticized with glycerol, facilitates the formation of a polyelectrolyte complex. The glycerol interrupts the intramolecular hydrogen bonding between chitosan chains allowing positively charged protonated amines of chitosan to form a complex with negatively charged oxygen ions chemisorbed to the tungsten atoms in defects. These interactions, with the unique mechanical and chemical properties of WS2 NTs, result in a chitosan film with superior properties relative to unfilled chitosan. Even at low WS2 NT loadings (≤1 wt%), the Young's modulus (E) increases by 59%, tensile strength (σ) by 40% and tensile toughness by 74%, compared to neat chitosan, without sacrificing ductility. Addition of highly dispersed WS2 NTs significantly improves the gas barrier properties of chitosan, with a 50% reduction in oxygen permeability, while the addition of both glycerol and WS2 NTs to chitosan effectively reduces the carbon dioxide permeability by 80% and the water vapor transmission rate by 90%. The intrinsic antimicrobial efficacy of chitosan against both Gram‐positive and Gram‐negative bacteria is enhanced on inclusion of WS2 NTs. Polyelectrolyte complexation of WS2 NTs and glycerol‐plasticized chitosan provides a cost‐effective, sustainable route to biodegradable films with desirable mechanical, gas barrier properties, and antimicrobial efficacy suitable for food packaging applications.
Carbon Monoxide Reduction Reaction to Produce Multicarbon Products in Acidic Electrolytes Using Gas Diffusion Electrode Loaded with Copper Nanoparticles
Authors: Kurihara Ryo , Nagita Kaito , Ohashi Keitaro , Mukouyama Yoshiharu , Harada Takashi , Nakanishi Shuji , Kamiya Kazuhide
Published: December 2023

The synthesis of multi‐carbon products (C2+) by electrochemical CO2 reduction reaction (CO2RR) is a promising technology that will contribute to the realization of a carbon‐neutral society. In particular, efficient CO2RR to produce C2+ in acidic electrolytes is desirable because the conversion of CO2 to inert (bi)carbonate can be suppressed under acidic conditions, thereby increasing the efficiency of substrate CO2 utilization. Herein, since C2+ products are produced via the dimerization of carbon monoxide, an intermediate in CO2RR, the focus is on the carbon monoxide reduction reaction (CORR). A gas diffusion electrode loaded with copper nanoparticles is used in acidic electrolytes to investigate the conditions necessary for efficient C2+ production. The faradaic efficiency and partial current density for C2+ production attained 75% and 280 mA cm−2 in a pH 2.0 solution, and they reached up to 66% and 260 mA cm−2 even in a pH 1.0 solution. Numerical simulations showed that increasing the alkalinity of the electrode surface to greater than pH 7 by consuming protons is necessary to facilitate the production of C2+ during the CORR. When the desired level of alkalinity is achieved, the concentration and type of alkali cations present at the electrode surface have an impact on the selectivity for C2+ production.
Scintillation Performance of Mn(II)‐Doped Cs2NaBiCl6 Double Perovskite Nanocrystals for X‐Ray Imaging Applications
Authors: Varnakavi Naresh , Rajavaram Ramaraghavulu , Gupta Kiran , Cha Pil‐Ryung , Lee Nohyun
Published: December 2023

Lead‐free halide perovskite‐based X‐ray scintillators with high light yield (LY) and low detection limit (LOD) have become a growing subject of research interest due to their promising application in a wide range of areas, from security to healthcare. Herein, a modified hot injection method is employed to synthesize Mn(II)‐doped Cs2NaBiCl6 double perovskite nanocrystals (DPNCs) and to examine their scintillating properties for application in X‐ray imaging and detection. The Mn(II)‐doped Cs2NaBiCl6 DPNCs exhibit a broad orange photoluminescence (PL) band at 586 nm with a PL quantum yield of 10.6%, attributed to the 4T2g(4G) → 6A1g(6S) transition of Mn2+. Temperature‐dependent PL and time‐resolved PL spectra of 4.04% Mn(II)‐doped Cs2NaBiCl6 demonstrate that the orange emission intensity initially reaches a maximum and subsequently decreases, while the decay lifetimes monotonically decrease with increasing temperature. This inconsistency can be due to the effect of the [MnCl6]4− octahedra and electron‐phonon coupling at elevated temperatures. Further, 0.05 mm thick Cs2NaBiCl6:4.04%Mn@poly(methyl methacrylate) scintillator film is synthesized with an LY of 28,350 photons MeV−1 and a LOD of 45.2 nGyair s−1. Additionally, this film demonstrates good X‐ray imaging performance with a spatial resolution of 14.76 line pairs (lp) mm−1 and shows exceptional stability under prolonged X‐ray exposure.
Enhanced Fibrillar Network and Molecular Crystallization via Volatile Solid Additives Enable Efficient Near‐Infrared Organic Photodetectors
Authors: Quan Huilei , Wu Xuefei , Fink Zachary , Zhong Wenkai , Luo Xuanang , Li Meijing , Su Huimin , Lan Linfeng , Huang Fei , Ying Lei
Published: December 2023

Controlling the phase separation and domain purity of organic semiconductors to form well‐developed nanoscale morphology optimization in the bulk‐heterojunction active layer is critical yet challenging for building high‐performance organic photodetectors. Herein, an effective morphology controlling method by applying a small molecule IC‐Br as the solid additive is demonstrated, which can effectively restrict the overmix of the PTzBI‐Si:IEICO‐4F in the process of film formation. The film processed with IC‐Br formed well‐developed nanoscale phase separation with bi‐continuous interpenetrating networks, which exhibited enhanced π–π stacking and the improved domain purity of the IEICO‐4F phase, resulting in a significant decrease in the density of the trap state compared to the pristine film. Consequently, the device processed with IC‐Br additive enabled a high specific detectivity of 3.8 × 1013 Jones at 860 nm under −0.1 V associated with the improved linear dynamic range and response speed, indicating the strong visible‐to‐near infrared detecting capability and potential for practical applications. The morphology optimization strategy established in this work may offer unprecedented opportunities to build state‐of‐the‐art OPDs.
A Sprayable Electrically Conductive Edible Coating for Piezoresistive Strain Sensing
Authors: Annese Valerio Francesco , Cataldi Pietro , Galli Valerio , Coco Giulia , Damasceno João Paulo Vita , Keller Alex , Kumaresan Yogeenth , Rossi Pietro , Ilic Ivan K. , Kwak Bokeon , Kubota Lauro Tatsuo , Athanassiou Athanassia , Rossiter Jonathan , Floreano Dario , Caironi Mario
Published: December 2023

Edible electronics leverages the electronic properties of food‐derived materials to deliver safer technologies that can be degraded (or digested) in the environment (or body) at the end‐of‐life. Sensors will be central to future smart edible robots, and edible strain sensors are particularly interesting as they can transduce deformation, providing real time feedback of the movement. Yet, to date edible strain sensors have been limited to the use of ionic conductive hydrogels, resulting in sensors not directly suitable for direct current operation and therefore not compatible with existing edible batteries. Here, the first edible strain sensor based on electronic conduction made of a novel conductive ink sprayed over an edible substrate is presented. The ink formulation consists of activated carbon (conductor), Haribo gummy bears (binder), and water−ethanol mixture (dispersant). The ink, deposited on multiple substrates by spray deposition, produces edible electrically conductive composite coatings with resistivity of ≈50 Ω cm. The coatings were used as a piezoresistive layer to fabricate strain sensors with gauge factors of 19−92 suitable for direct current operation. As a proof‐of‐concept of future edible systems, the sensor is validated by integrating it within a gelatin actuator to produce a sensorized gripper powered by an edible battery.
The Zn Deposition Mechanism and Pressure Effects for Aqueous Zn Batteries: A Combined Theoretical and Experimental Study
Authors: Li Yuyin , Musgrave Charles B. , Yang Moon Young , Kim Minho M. , Zhang Kenan , Tamtaji Mohsen , Cai Yuting , Tang Tsz Wing , Wang Jun , Yuan Bin , Goddard William A. , Luo Zhengtang
Published: December 2023

A new reactive force field based on quantum mechanical data for describing formation of the Zn electrode‐electrolyte interface (EEI) chemistry in aqueous zinc‐ion batteries (ZIBs) is developed. This is the first demonstration in which Reactive Molecular Dynamics (RMD) simulation is used to follow the Zn reduction and anode structural evolution at the EEI. It is found that under axial pressure, Zn dendrite formation is inhibited. This is associated with accelerated ion transport and reduction while increasing preference towards horizontal (002) plane growth. Pressure‐induced desolvation of Zn ions within the electric double layer, which promotes faster reduction kinetics is observed. It is found that axial pressure stabilizes adatoms on the (002) plane by decreasing axial atom stress during nucleation and by increasing favorable lateral adatom diffusion, which reduces atomic scale dendrite formation. Finally, these are confirmed results by experimental characterization and electrochemical tests.
Reproductive physiology with emphasis on endometrial cycles of woolly and uakari monkeys—A literature review
Authors: Pereira Thyago Habner de Souza , Mayor Pedro , Evangelista Janaina Serra Azul Monteiro , Lima Ana Kelen Felipe , de Andrade Rafael dos Santos , Monteiro Frederico Ozanan Barros
Published: December 2023

The ability of a species to withstand human impact depends on its life history characteristics, including social, ranging, and reproductive activity. The genera Lagothrix and Cacajao are more susceptible to anthropic action than small‐sized primates due to their slower life histories, more restricted geographical ranges, and lower population densities. This narrative literature review aimed to gather scientific information available from the last 60 years on the reproductive biology of females of the genera Lagothrix and Cacajao. Most studies on the genus Lagothrix, mainly focused on L. lagothricha and L. l. poeppigii, present important advances on reproductive strategies, reproductive productivity, functional morphology and physiology, including seasonality, sexual cycle, gestation and fetal development in captive and free‐living populations. Contrary, there is much less known about the reproductive biology of the genus Cacajao, with studies on free‐living C. calvus and C. melanocephalus highlighting reproductive behavior, and basic description of the sexual cycle, gestation, and lactation. Unfortunately, the morphology of the female genital organs is only described in C. calvus, and there is still scarce information about the menstrual activity and the placenta. This literature review encourages primatologists, morphophysiologists, reproductive specialists, and ecologists to conduct comprehensive studies of these species to better understand the gaps in knowledge about reproduction, their relationship with their environment, including climatic and social variables. Understanding the integrative reproductive biology of these species will be a clue for improving the assessment of the resilience capacity of free‐living populations and, consequently, establishing more appropriate management programs, and for the development of ex situ management techniques for the conservation of the species.
Hydrated [3+2] Cyclotelomerization of Butafulvenes to Create Multiple Contiguous Fully Substituted Carbon Centers
Authors: Zhou Bo‐Chao , Chen Bing‐Zhi , Song Ting‐Ting , Yang Yang , Zhang Li‐Ming , Ji Ding‐Wei , Wan Boshun , Chen Qing‐An
Published: December 2023

The construction of multiple continuous fully substituted carbon centers, which serve as unique structural motif in natural products, is a challenging topic in organic synthesis. Herein, we report a hydrated [3+2] cyclotelomerization of butafulvenes to create contiguous fully substituted carbon backbone. In the presence of scandium triflate, all‐carbon skeleton with spiro fused tricyclic ring can be constructed in high diastereoselectivity by utilizing butafulvene as the synthon. Mechanistic studies suggest that this atom‐economic reaction probably proceeds through a synergistic process containing butafulvenes dimerization and nucleophilic attack by water. In addition, the tricyclic product can undergo a series of synthetic derivatizations, which highlights the potential applications of this strategy. The recyclability of Sc(OTf)3 has also been demonstrated to show its robust performance in this hydrated cyclotelomerization.
Coupling Electrochemical Sulfion Oxidation with CO2 Reduction over Highly Dispersed p‐Bi Nanosheets and CO2‐Assisted Sulfur Extraction
Authors: Teng Xue , Shi Kai , Chen Lisong , Shi Jianlin
Published: December 2023

We report herein an electrocatalytic CO2 reduction‐coupled sulfion oxidation system for the co‐productions of valuable formate and sulfur at much enhanced atom utilization. Specifically, an organic ligand‐assisted two‐step reconstruction approach has been developed to fabricate the highly dispersed p‐Bi nanosheets (p‐Bi NSs) for cathodic CO2 reduction reaction (CO2RR), and meanwhile porous Co−S nanosheets (Co−S NSs) was applied for anodic sulfion oxidation reaction (SOR). Significantly high Faradaic Efficiencies of about 90 % for formate production by CO2RR in a wide potential range from −0.6 V to −1.1 V, and excellent SOR performances including an ultra‐low onset potential of about 0.2 V and recycle capacity of S2− in the 0.1 M and 0.5 M S2− solutions, have been simultaneously achieved. In the meantime, both the structure transformation of the catalysts and the reaction pathways are explored and discussed in detail. A two‐electrode CO2RR||SOR electrolyzer equipped with above electrocatalysts has been established, which features as low as about 1.5 V to run the electrolyzer at 100 mA cm−2, manifesting extremely lowered electricity consumption in comparison to conventional CO2RR system. Moreover, a sulfur separation approach has been proposed by using CO2, which is efficient, environmentally friendly and cost effective with value‐added NaHCO3 be obtained as the byproduct.
Difficult‐to‐Treat Psoriatic Arthritis: A Conceptual Approach
Authors: Fagni Filippo , Motta Francesca , Schett Georg , Selmi Carlo
Published: December 2023

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A review on the upstream production and downstream purification of mannosylerythritol lipids
Authors: Valkenburg André D. , Ncube Mellisa Z. , Teke George M. , van Rensburg Eugéne , Pott Robert W. M.
Published: December 2023

Biosurfactants are natural compounds with remarkable surface‐active properties that may offer an eco‐friendly alternative to conventional surfactants. Among them, mannosylerythritol lipids (MELs) stand out as an intriguing example of a glycolipid biosurfactant. MELs have been used in a variety of sectors for various applications, and are currently commercially produced. Industrially, they are used in the pharmaceutical, cosmetic, food, and agricultural industries, based on their ability to reduce surface tension and enhance emulsification. However, despite their utility, their production is comparatively limited industrially. From a bioprocessing standpoint, two areas of interest to improve the production process are upstream production and downstream (separation and purification) product recovery. The former has seen a significant amount of research, with researchers investigating several production factors: the microbial species or strain employed, the producing media composition, and the production strategy implemented. Improvement and optimization of these are key to scale‐up the production of MELs. On the other hand, the latter has seen comparatively limited work presented in the literature. For the most part traditional separation techniques have been employed. This systematic review presents the production and purification methodologies used by researchers by comprehensively analyzing the current state‐of‐the‐art with regards the production, separation, and purification of MELs. By doing so, the review presents different possible approaches, and highlights some potential areas for future work by identifying opportunities for the commercialization of MELs.
Rational design of transaminases based on comparative analysis of catalytically active and distance‐free modes of the high‐energy intermediate state
Authors: Yi Xiaomin , Yu Hongwei , Ye Lidan
Published: December 2023

Bioproduction of chiral amines is limited by low transaminase (TA) activity on nonnatural substrates, leading to the need for protein engineering. To address the challenge of quickly and precisely identifying the engineering targets, a strategy was proposed based on analyzing the mode changes in the high‐energy intermediate state (H‐state) of the substrate–enzyme complex during catalysis. By substituting the residues with minimal structural changes in catalytically active mode (A‐mode) and distance‐free mode (F‐mode) of the H‐state complex with more conserved ones to stabilize it, a TA mutant M5(T295C/L387A/V436A) with 121.9‐fold higher activity for synthesizing the (S)‐Rivastigmine precursor (S)‐1‐(3‐methoxyphenyl)ethylamine was created. The applicability of this strategy was also validated by engineering another TA for 1.52‐fold higher activity and >99% selectivity toward (R)‐3‐amino‐1‐butanol biopreparation. The much higher stereoselectivity of the mutant compared with the wild type (28.3%) demonstrated that this strategy is not only advantageous in engineering enzyme activity but also applicable for modulating stereoselectivity.
Urticaria pigmentosa and systemic mastocytosis
Authors: Keow Jonathan , Chin‐Yee Benjamin , Hsia Cyrus C. , Robertson Kara
Published: December 2023

Key Clinical Message

Additional investigations for systemic involvement should be initiated once the diagnosis of cutaneous mastocytosis has been established in an adult patient. A serum tryptase can serve as a screening test for systemic mastocytosis, and persistent elevations should prompt further investigations, such as bone marrow studies.

Urticaria pigmentosa (UP) is the most common form of cutaneous mastocytosis, presenting as a wide variety of macroscopic appearances. Cutaneous mastocytosis in pediatric patients usually does not present with systemic involvement, but more than half of adult patients with cutaneous mastocytosis demonstrate systemic involvement. Currently, there is no guidance surrounding systemic testing in patients with UP. A 50‐year‐old Caucasian male was referred to the Clinical Immunology and Allergy clinic with a history of a rash. He initially presented to hospital 12 years prior with group A beta hemolytic streptococcus bacteremia treated with multiple different antibiotics. One week following discharge, he developed erythematous brown spots on his right leg which were flat, non‐pruritic, and not painful. The rash later expanded to his trunk and extremities. A skin biopsy performed 2 years prior to referral to our clinic demonstrated urticaria pigmentosa. The CD117 immunohistochemical stain showed increased perivascular and interstitial mast cells in the superficial dermis. Darier's sign was negative on physical examination, and venom testing was also negative. Although he had no symptoms of systemic involvement, his serum tryptase was elevated at 47.6 ng/mL in the context of normal kidney and liver function. A skeletal survey was normal, and an abdominal ultrasound ruled out splenomegaly. Bone marrow biopsy demonstrated a mild increase in paratrabecular and perivascular atypical mast cells, in keeping with systemic mastocytosis. Adult patients with cutaneous mastocytosis have a high likelihood of having an underlying systemic mast cell disorder. Therefore, any patient presenting with characteristic skin findings should be investigated as having a cutaneous manifestation of systemic mastocytosis. This case demonstrates the utility of serum tryptase and its role in triggering additional investigations and guiding appropriate therapy.
The superiority of TiO2 hollow microspheres over nanoparticles upon integration into a coating formulation for VOC removal
Authors: Golbarg Sara , Garcia Alicia Gutierrez , Velázquez‐Palenzuela Amado , Dam‐Johansen Kim , Christensen Jakob Munkholt
Published: December 2023

Heterogeneous photocatalysis is a promising technology for the abatement of pollutants in the air. Practical application of this technology requires the incorporation of the photocatalyst into a coating formulation. The coating can subsequently be applied on surfaces with a large geometric area, promoting various catalytic reactions. Photocatalysts, such as TiO2, appear to be most active in the form of nanoparticles. However, there is a rising concern regarding the adverse health effects of the nano‐sized particles. In this study, we investigate the photocatalytic oxidation of isopropanol, a common VOC, and demonstrate that a water‐based acrylic coating containing TiO2 micrometer‐sized hollow spheres can outperform a nanoparticle‐based coating by a factor of 10 in the rate of isopropanol removal. The porous shell structure of TiO2 hollow microspheres enables a three‐dimensional surface porosity within the coating film, thereby enhancing the access to the active catalytic surface. Our findings underscore the importance of the catalyst morphology for practical applications of photocatalytic materials when integrated into a coating formulation.
Noncatalytic Reductive Deiodination of Thyroid Hormones. Electrochemistry and Quantum Chemical Calculations
Authors: Romańczyk Piotr P. , Kurek Stefan S.
Published: December 2023

Noncatalytic processes may occur spontaneously leading often to undesired products. Electrochemical measurements provide data for thermodynamic calculations. Cyclic voltammetry of thyroxine (T4) and 3,3’,5‐triiodothyronine (T3) in N,N‐dimethylformamide (DMF) and alkaline aqueous solutions of pH 10–14 on glassy carbon electrodes yielded the values of redox potentials for the reduction leading to deiodination of those thyroid hormones under noncatalytic conditions. The first step of T4 deiodination occurs in DMF at −1.93 V vs. Fc+/Fc and for T3 at −1.95 V, which was confirmed by quantum‐chemical calculations at DFT and DLPNO‐CCSD(T) levels. In alkaline aqueous solutions, owing to poor solubility of these compounds, it was possible to determine only approximate values equal to −1.6 to −1.7 V vs. Ag/AgCl for the first step of deiodination. The reduction potentials do not depend on pH under these conditions. As shown by calculations, further steps exhibit very close reduction potentials. The radicals formed as products of concerted dissociative electron transfer to T4 and T3 are relatively kinetically stable which leads to side reactions initiated by radicals in uncatalyzed deiodination processes.
Metal Activation Produces Different Reaction Environments for Intermediates during Oxidative Addition
Authors: Hanada Erin M. , Lou Hanyun , McShea Patrick J. , Blum Suzanne A.
Published: December 2023

Commercial zinc metal powder requires activation for consistent and reliable use as a reductant in the formation of organozinc reagents from organohalides, and for the avoidance of supplier and batch‐to‐batch variability. However, the impact of activation methods on the reaction environments of subsequent intermediates has been unknown. Herein, a fluorescence lifetime imaging microscopy (FLIM) method is developed to bridge this knowledge gap, by imaging and examining reaction intermediates on zinc metal that has been activated by pretreatment through different common methods (i. e., by chemical activation with TMSCl, dibromoethane, or HCl; or by mechanical activation). The group of chemical activating agents, previously thought to act similarly by removing oxide layers, are here shown to produce markedly different reaction environments experienced by subsequent oxidative‐addition intermediates from organohalides – data uniquely available through FLIM's ability to detect small quantities of intermediates in situ coupled with its microenvironmental sensitivity. These different microenvironments potentially give rise to different rates of formation, subsequent solubilization, and reactivity, despite the shared “[RZnX]” molecular structure of these intermediates. This information revises models for methods development for oxidative addition to currently sluggish metals beyond zinc by establishing diverse outcomes for pretreatment activation methods that were previously considered similar.
Are “Carbon Dots” Always Carbon Dots? Evidence for Their Supramolecular Nature from Structural and Dynamic Studies in Solution and in the Pure Solid
Authors: Sousa Diogo A. , Berberan‐Santos Mário N. , Prata José V.
Published: December 2023

Invited for the cover of this issue are José Prata and co‐workers at Instituto Superior de Engenharia de Lisboa and Instituto Superior Técnico. The image depicts a model for the supramolecular nature of carbon dots. Read the full text of the article at 10.1002/chem.202302955.
The differences between patients with nonalcoholic fatty liver disease (NAFLD) and those without NAFLD, as well as predictors of functional coronary artery ischemia in patients with NAFLD
Authors: Li Wen‐Jing , Xu Hong‐Wei
Published: December 2023

Background

Nonalcoholic fatty liver disease (NAFLD) is a chronic liver disease associated with metabolic syndrome. It is the most common cause of cryptogenic cirrhosis. The disease is also involved in the occurrence and development of type 2 diabetes and atherosclerosis and can directly affect the outcome of patients with coronary heart disease. Therefore, the focus of treatment of nonalcoholic fatty liver disease has also begun to focus on the treatment of risk factors for atherosclerotic heart disease. In this study, we investigated the difference between patients with coronary artery stenosis combined with NAFLD and those without NAFLD and evaluated the predictive factors and value of functional coronary artery ischemia in patients with NAFLD.

Hypothesis

Many clinical factors (such as age, BMI, hyperglycemia) and imaging parameters (such as CACS grade) in the NAFLD group were different from those in the non‐NAFLD group. The predictive model combined with multiple influencing factors has a good value in predicting coronary artery ischemia in patients with NAFLD.

Methods

We collected the clinical and imaging data of patients who underwent coronary computed tomography angiography and coronary artery calcification score (CACS) scans between January and June 2023. A total of 392 patients were included and divided into the NAFLD group and the non‐NAFLD group. Based on CT fractional flow reserve (CT‐FFR), patients with NAFLD were divided into CT‐FFR ≤ 0.08 group and CT‐FFR > 0.08 group.

Results

Significant differences were observed between the non‐NAFLD and NAFLD groups in terms of age, body mass index, hyperglycemia, hyperlipidemia, triglyceride, high‐density lipoprotein, coronary artery disease‐reporting and data system (CAD‐RADS) classification, CACS classification, number of diseased coronary arteries, and CT‐FFR ≤ 0.80 ratio (p < .05). The CAD‐RADS and CACS classifications can independently predict functional coronary artery ischemia in NAFLD patients. The combined use of CAD‐RADS and CACS classifications resulted in an area under the curve of 0.819 (95% confidence interval: 0.761–0.876) for predicting coronary artery ischemia in NAFLD patients, which was higher than the individual classification methods (CAD‐RADS: 0.762, CACS: 0.742) (p = .000).

Conclusions

There are differences between patients with coronary artery stenosis and NAFLD and those without NAFLD. The CAD‐RADS classification and CACS classification can economically and efficiently predict functional coronary artery ischemia in patients with NAFLD, which has crucial value in clinical diagnosis and treatment.
Abatement of Volatile Organic Compounds Employing a Thermoplastic Nano‐Photocatalyst Layered on a Glass Reactor
Authors: Vento Fabiana , Nicosia Angelo , Fiorenza Roberto , Scirè Salvatore , Pellegrino Anna Lucia , Mezzina Lidia , Raciti Giulia , Mineo Placido
Published: December 2023

Industrial development and urbanization have increased the emission of Volatile Organic Compounds (VOCs) into the atmosphere, causing environmental and health risks. Several approaches are used for their abatement, including chemical, thermo‐ and photo‐catalytic oxidations, but they are not fully satisfactory. In this work, a thermoplastic TiO2‐based photo‐catalyst was used as a coating layer of a glass‐reactor. Solar‐triggered photocatalytic degradation of ethanol, toluene, and acetone (used as model VOCs) highlights the better performance of the coated photoreactor than that of TiO2 nanopowder. The influence of the pollutant flow rate on the photodegradation performance of the system was also investigated, revealing an inverse relationship between degradation and flow rates. The experimental data suggest that our approach provides a cost‐effective and efficient way to boost the abatement of VOCs, useful for further industrial‐scale applications. The morphology and the compositional homogeneity of the nanocomposite coating were addressed through Field Emission Scanning Electron Microscopy coupled with Energy Dispersive X‐ray Analysis.
Evaluating the predictive performance of presence–absence models: Why can the same model appear excellent or poor?
Authors: Abrego Nerea , Ovaskainen Otso
Published: December 2023

When comparing multiple models of species distribution, models yielding higher predictive performance are clearly to be favored. A more difficult question is how to decide whether even the best model is “good enough”. Here, we clarify key choices and metrics related to evaluating the predictive performance of presence–absence models. We use a hierarchical case study to evaluate how four metrics of predictive performance (AUC, Tjur's R2, max‐Kappa, and max‐TSS) relate to each other, the random and fixed effects parts of the model, the spatial scale at which predictive performance is measured, and the cross‐validation strategy chosen. We demonstrate that the very same metric can achieve different values for the very same model, even when similar cross‐validation strategies are followed, depending on the spatial scale at which predictive performance is measured. Among metrics, Tjur's R2 and max‐Kappa generally increase with species' prevalence, whereas AUC and max‐TSS are largely independent of prevalence. Thus, Tjur's R2 and max‐Kappa often reach lower values when measured at the smallest scales considered in the study, while AUC and max‐TSS reaching similar values across the different spatial levels included in the study. However, they provide complementary insights on predictive performance. The very same model may appear excellent or poor not only due to the applied metric, but also how predictive performance is exactly calculated, calling for great caution on the interpretation of predictive performance. The most comprehensive evaluation of predictive performance can be obtained by evaluating predictive performance through the combination of measures providing complementary insights. Instead of following simple rules of thumb or focusing on absolute values, we recommend comparing the achieved predictive performance to the researcher's own a priori expectations on how easy it is to make predictions related to the same question that the model is used for.
Constructed rock riffles increase habitat heterogeneity but not biodiversity in streams constrained by urban impacts
Authors: Walsh Christopher J. , Webb J. Angus , Gwinn Daniel C. , Breen Peter F.
Published: December 2023

Riffles are heterogeneous habitats that support diverse assemblages in natural streams. They are often constructed as part of stream restoration practice, including in degraded urban stream ecosystems, despite larger scale limits to ecological state. Such restoration practices fail to consider ecological theory, and their outcomes have rarely been robustly monitored and assessed. We assessed the effects of constructed rock riffles on habitat heterogeneity and on macroinvertebrate assemblages in six urban streams (4%–32% effective imperviousness). We compared habitat heterogeneity, and taxon abundance and richness of the six streams before and after (1 and 5 years) riffle construction and in three control streams without riffles. Riffles increased habitat heterogeneity. In contrast, macroinvertebrate assemblages in all streams were dominated by tolerant, cosmopolitan, and invasive taxa before and after riffle construction. Riffles reduced the abundance and richness of tolerant taxa in less urbanized streams and increased their richness in more urban streams. These changes had no effect on measures of biodiversity. Urban stormwater runoff can affect the degree to which rock riffles increase habitat heterogeneity through sediment transport and increased physical disturbance. In highly urban streams, increased habitat heterogeneity is likely to primarily favor cosmopolitan species that can tolerate frequent chemical and physical disturbance. Riffle construction may reduce the abundance of cosmopolitan species and increase the abundance of more sensitive species, but only if catchment‐scale impacts of urban stormwater runoff are adequately controlled. Robust experiments such as this add to general understanding of the effectiveness of restoration practice, reducing the need for ubiquitous monitoring of restoration projects.
Autonomic nervous modulation: early treatment for pulmonary artery hypertension
Authors: Xueyuan Liu , Yanping Xu , Jiaoqiong Guan , Yuehui Yin
Published: December 2023

Pulmonary artery hypertension (PAH) is a chronic vascular disease defined by the elevation of pulmonary vascular resistance and mean pulmonary artery pressure, which arises due to pulmonary vascular remodelling. Prior research has already established a link between the autonomic nervous system (ANS) and PAH. Therefore, the rebalancing of the ANS offers a promising approach for the treatment of PAH. The process of rebalancing involves two key aspects: inhibiting an overactive sympathetic nervous system and fortifying the impaired parasympathetic nervous system through pharmacological or interventional procedures. However, the understanding of the precise mechanisms involved in neuromodulation, whether achieved through medication or intervention, remains insufficient. This limited understanding hinders our ability to determine the appropriate timing and scope of such treatment. This review aims to integrate the findings from clinical and mechanistic studies on ANS rebalancing as a treatment approach for PAH, with the ultimate goal of identifying a path to enhance the safety and efficacy of neuromodulation therapy and improve the prognosis of PAH.