bluuebunny/crossref_metadata_2025 huggingface dataset:
Broadband Terahertz Metalenses Based on Printed Circuit Board Fabrication
Authors: Qi Chu , He Xiaoluo , Ren Bowen , Wong Alex M. H.
Published: January 2024

Metalenses have provided a good solution to the bulkiness of conventional refractive lenses. Due to the subwavelength feature sizes of the metalens structure, the increasing fabrication difficulties at high frequencies limit its application in the terahertz and optical regime. Moreover, the deeply subwavelength features of the metasurface unit cells usually make the cells strongly resonant, which limits the bandwidth of the metalens. In this paper the usage of aggressive discretization in a metalens design is investigated, and it is found that aggressive discretization can lead to the usage of weakly resonant and relatively large unit cells, which leads to excellent broadband performance and dramatically relaxes the feature size tolerance of the metalens. For examples, two terahertz focusing metalenses are designed which feature large numerical apertures (NA = 0.86), diffraction‐limited focusing over a broad bandwidth (240–400 GHz, or 50% bandwidth), and minimum feature sizes of 0.1 mm. These tolerance‐relaxed terahertz metalenses are successfully constructed using conventional printed‐circuit‐board fabrication technology. The experimental measurements validate the simulated performances. Compared to existing terahertz meta‐devices based on micro‐fabrication or nano‐fabrication technologies, this paper opens door to a kind of high‐quality terahertz metasurfaces featuring low‐cost, rapid, and established fabrication.
Four‐Dimensional Design Space of High‐Q Second‐Order Distributed Feedback Perovskite Lasers
Authors: Annavarapu Nirav , Goldberg Iakov , Hamdad Sarah , Elkhouly Karim , Puybaret Renaud , Sabuncuoglu Tezcan Deniz , Genoe Jan , Gehlhaar Robert , Heremans Paul
Published: January 2024

Second‐order distributed feedback (DFB) resonators are widely used for thin‐film lasers as they combine low lasing thresholds with ease of manufacturing. Here, the grating design parameters are varied to map the lasing characteristics of lead halide perovskite films deposited on a single substrate that contains hundreds of high‐quality silicon nitride surface gratings. The lowest lasing threshold (≈130 µJ cm−2) is identified through the aid of near‐field and far‐field imaging spectroscopy in a four‐dimensional design space composed of grating period, duty cycle, active layer thickness, and cavity length. Moreover, it is shown that antisymmetric modes support high‐quality lasing (Q up to ≈10800) in the second‐order DFBs. The multi‐dimensional experimental analysis is accompanied by a thorough theoretical study with a semi‐empirical model based on coupled wave equations, which is used to investigate the lasing characteristics beyond the manufacturing range. The results can be applied to a broad range of thin‐film DFB resonators, enabling the design of more complex laser stack configurations including light‐emitting devices for current‐injection lasing.
Antimony Doped Hybrid Zinc Halide Crystals with Tunable Light Emission and Long‐Term Stability
Authors: Zhang Yaqing , Jiang Yan , Zhang Qi , Liu Qingyi , Guo Weiping , Zhang Wei , Li Lingyun , Feng Ya‐Nan , Yu Yan
Published: January 2024

As a class of emerging photoluminescent materials, hybrid halide crystals have drawn research attention for their potential application in the fields of light‐emitting, security, and waveguide. Nevertheless, hybrid halide crystals containing antimony with long‐term stability and tunable light emission are still increasingly in demand. In this work, serial new hybrid halide crystals (BZA)2ZnCl4·2H2O:xSb3+ (x = 0–0.2, x represents the reaction ratio) and (BZA)2SbCl5 are synthesized (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine). In (BZA)2ZnCl4·2H2O:xSb3+ crystals, Sb3+ cations replace partial Zn2+ cations to form [SbCl4]− tetrahedron. Red light emission caused by the substitution of Sb3+ for Zn2+ enhances as the doping rate increases, resulting in the tunable emission from light blue to pink and finally to dark red. There are two kinds of Sb3+ in (BZA)2SbCl5 crystal. Sb(1) has a sixfold coordination with Cl to form a [Sb(1)Cl5]∞ 1D zigzag chain. Sb(2) atom adopts a fivefold coordination with Cl and is separated from each other by BZA+ cations. (BZA)2SbCl5 crystal shows bright orange‐yellow light emission with a photoluminescence quantum yield of 45%. Moreover, the organic–inorganic hybrid metal halide crystals containing antimony have excellent long‐term stability, with phase and luminescence keeping nearly unchanged after more than six months in ambient air.
The Modulation of the Optical Properties of Low‐Dimensional Hybrid Perovskite by Using Anchoring Groups and Biaxial Strain: A First‐Principles Study
Authors: Xue Ruixing , Chen Chengbing , Long Pan , Liu Shaohua , Xiao Jianrong , Dai Xueqiong , Wang Zhiyong
Published: January 2024

In this paper, using CsMA2Sn2I7 as an example, first‐principles calculations are performed to thoroughly investigate the crystal structures, electronic properties, and optical properties of 11 representative anchoring group/low‐dimensional hybrid perovskite systems. The results show that the addition of benzene, 4‐iodoaniline, aniline, and benzenethiol anchoring groups causes a blueshift phenomenon in the absorption spectra of CsMA2Sn2I7 perovskite. Furthermore, the involvement of the benzoic acid anchoring group has a minimal effect on the absorption spectra of the CsMA2Sn2I7 hybrid perovskites, which show better absorption intensity only in the ultraviolet. The addition of other anchoring groups leads to varying degrees of redshift in the absorption spectra of CsMA2Sn2I7 perovskite, which not only enhances absorption intensity but also lends to the improvement of the absorption efficiency in the visible range. In addition, the bandgap can be tuned by applying biaxial strain, which further effectively modulates the absorption intensity of the adsorption systems in different optical bands. Therefore, the selection of suitable anchoring groups has great potential for modulating the photovoltaic performance of organic–inorganic hybrid perovskites, which is helpful for the application of organic–inorganic perovskites in photovoltaics.
Modeling the Coupled Mass‐Heat Transport in Lennard–Jones‐Like Binary Mixtures by Approach‐to‐Equilibrium Molecular Dynamics
Authors: Cappai Antonio , Colombo Luciano , Melis Claudio
Published: January 2024

A general theoretical framework to address the coupled heat‐mass transport and predict the corresponding Soret and Dufour coefficients is presented. It is shown that by starting from microscopical definitions of heat and mass currents, conservation laws dictate the form of the differential equations governing the time evolution of the temperature and mass density profiles along the sample. The present theoretical device is finally validated using as benchmark system a two‐component Lennard–Jones (LJ) liquid system, for which generalized diffusivities are estimated in different reduced temperature and density regions of phase diagram.
SUMOylation of TEAD1 Modulates the Mechanism of Pathological Cardiac Hypertrophy
Authors: Shi Xin , Dang Xuening , Huang Zhenyu , Lu Yanqiao , Tong Huan , Liang Feng , Zhuang Fei , Li Yi , Cai Zhaohua , Huo Huanhuan , Jiang Zhaolei , Pan Changqing , Wang Xia , Gu Chang , He Ben
Published: January 2024

Pathological cardiac hypertrophy is the leading cause of heart failure and has an extremely complicated pathogenesis. TEA domain transcription factor 1 (TEAD1) is recognized as an important transcription factor that plays a key regulatory role in cardiovascular disease. This study aimed to explore the role of TEAD1 in cardiac hypertrophy and to clarify the regulatory role of small ubiquitin‐like modifier (SUMO)‐mediated modifications. First, the expression level of TEAD1 in patients with heart failure, mice, and cardiomyocytes is investigated. It is discovered that TEAD1 is modified by SUMO1 during cardiac hypertrophy and that the process of deSUMOylation is regulated by SUMO‐specific protease 1 (SENP1). Lysine 173 is an essential site for TEAD1 SUMOylation, which affects the protein stability, nuclear localization, and DNA‐binding ability of TEAD1 and enhances the interaction between TEAD1 and its transcriptional co‐activator yes‐associated protein 1 in the Hippo pathway. Finally, adeno‐associated virus serotype 9 is used to construct TEAD1 wild‐type and KR mutant mice and demonstrated that the deSUMOylation of TEAD1 markedly exacerbated cardiomyocyte enlargement in vitro and in a mouse model of cardiac hypertrophy. The results provide novel evidence that the SUMOylation of TEAD1 is a promising therapeutic strategy for hypertrophy‐related heart failure.
A Robust Biomimetic Superhydrophobic Coating with Superior Mechanical Durability and Chemical Stability for Inner Pipeline Protection
Authors: Zang Xuerui , Bian Jiang , Ni Yimeng , Zheng Weiwei , Zhu Tianxue , Chen Zhong , Cao Xuewen , Huang Jianying , Lai Yuekun , Lin Zhiqun
Published: January 2024

Durable superhydrophobic anti‐erosion/anticorrosion coatings are highly demanded across various applications. However, achieving coatings with exceptional superhydrophobicity, mechanical strength, and corrosion resistance remains a grand challenge. Herein, a robust microstructure coating, inspired by the cylindrical structures situated on the surface of conch shell, for mitigating erosion and corrosion damages in gas transportation pipelines is reported. Specifically, citric acid monohydrate as a pore‐forming agent is leveraged to create a porous structure between layers, effectively buffering the impact on the surface. As a result, the coating demonstrates remarkable wear resistance and water repellency. Importantly, even after abrasion by sandpaper and an erosion loop test, the resulting superhydrophobic surfaces retain the water repellency. The design strategy offers a promising route to manufacturing multifunctional materials with desired features and structural complexities, thereby enabling effective self‐cleaning and antifouling abilities in harsh operating environments for an array of applications, including self‐cleaning windows, antifouling coatings for medical devices, and anti‐erosion/anticorrosion protection, among other areas.
Advanced Tuneable Micronanoplatforms for Sensitive and Selective Multiplexed Spectroscopic Sensing via Electro‐Hydrodynamic Surface Molecular Lithography
Authors: Gomes Paulo De Carvalho , Hin‐Chu Martin , Rickard Jonathan James Stanley , Goldberg Oppenheimer Pola
Published: January 2024

Micro‐ and nanopatterning of materials, one of the cornerstones of emerging technologies, has transformed research capabilities in lab‐on‐a‐chip diagnostics. Herein, a micro‐ and nanolithographic method is developed, enabling structuring materials at the submicron scale, which can, in turn, accelerate the development of miniaturized platform technologies and biomedical sensors. Underpinning it is the advanced electro‐hydrodynamic surface molecular lithography, via inducing interfacial instabilities produces micro‐ and nanostructured substrates, uniquely integrated with synthetic surface recognition. This approach enables the manufacture of design patterns with tuneable feature sizes, which are functionalized via synthetic nanochemistry for highly sensitive, selective, rapid molecular sensing. The development of a high‐precision piezoelectric lithographic rig enables reproducible substrate fabrication with optimum signal enhancement optimized for functionalization with capture molecules on each micro‐ and nanostructured array. This facilitates spatial separation, which during the spectroscopic sensing, enables multiplexed measurement of target molecules, establishing the detection at minute concentrations. Subsequently, this nano‐plasmonic lab‐on‐a‐chip combined with the unconventional computational classification algorithm and surface enhanced Raman spectroscopy, aimed to address the challenges associated with timely point‐of‐care detection of disease‐indicative biomarkers, is utilized in validation assay for multiplex detection of traumatic brain injury indicative glycan biomarkers, demonstrating straightforward and cost‐effective micro‐ and nanoplatforms for accurate detection.
Dry Laser‐Induced Graphene Fractal‐like ECG Electrodes
Authors: Houeix Yann , Gerardo Denice , Romero Francisco J. , Toral Víctor , Hernandez Lidia , Rivadeneyra Almudena , Castillo Encarnación , Morales Diego P. , Rodriguez Noel
Published: January 2024

Fractal‐like geometries applied to biosignal‐electrodes design show great potential for enhancing the signal acquisition of sensing systems. This study reports a novel approach for flexible, silver‐free, and dry fractal‐like electrodes based on Laser‐Induced Graphene (LIG) obtained through laser photothermal processing of a commercial polyimide film. This one‐step mask‐less manufacturing process enables the simple fabrication of natural and optimized fractal‐like shapes inspired by actual snowflake patterns. To ensure a reliable and standardized connection to the measurement unit, the electrodes are equipped with a snap terminal. The electrodes are structurally characterized using various techniques including Scanning Electron Microscopy (SEM), Raman spectroscopy, and X‐ray Photoelectron Spectroscopy (XPS). By benchmarking the performance of these electrodes against Ag/AgCl wet commercial electrodes and LIG electrodes shaped as commercial ones, a heart rate‐monitoring accuracy of over 96.8% is achieved, with high specificity, positive prediction, and sensitivity, surpassing the 95.8% achieved by conventional commercial electrodes. These results demonstrate the efficacy of fractal‐based designs in combination with LIG‐based transduction, offering flexible and cost‐effective electrocardiogram (ECG) electrodes with improved performance compared to traditional wet electrodes.
Self‐Regulating Interfacial Space Charge through Polyanion Repulsion Effect towards Dendrite‐Free Polymer Lithium‐Metal Batteries
Authors: Cui Manying , Gao Na , Zhao Wenshan , Zhao Hongyang , Cao Zhenjiang , Qin Yanyang , Gao Guoxin , Xi Kai , Su Yaqiong , Ding Shujiang
Published: January 2024

Uncontrolled transport of anions leads to many issues, including concentration polarization, excessive interface side reactions, and space charge‐induced lithium dendrites at the anode/electrolyte interface, which severely deteriorates the cycling stability of lithium metal batteries. Herein, an asymmetrical polymer electrolyte modified by a boron‐containing single‐ion conductor (LiPVAOB), is designed to inhibit the nonuniform aggregation of free anions in the vicinity of the lithium anode through the repulsion effect improving the lithium‐ion transference number to 0.63. This LiPVAOB exerts a repulsion interaction with free anions even at a long distance and a selective effect for free anions transport, which diminishes uneven aggregation of free anions at the interface and suppresses space charges‐induced lithium dendrites growth. Consequently, the assembled Li||Li cell delivers an ultra‐long cycle for over 5400 h. The Li||LiFePO4 cell exhibits outstanding cycle performance with a capacity retention of 93% over 4500 cycles. In particular, the assembled high‐voltage Li||Li1.2Ni0.2Mn0.6O2 cell (charged to 4.8 V) exhibits good cycle stability with a high specific capacity of 245 mAh g−1. This designed polymer electrolyte provides a promising strategy for regulating ion transport to inhibit space charge‐induced lithium dendrite growth for high‐performance lithium metal batteries.
Dithiophosphoric Acids for Polymer Functionalization
Authors: Bao Jianhua , Kang Kyung‐Seok , Molineux Jake , Bischoff Derek J. , Mackay Michael E. , Pyun Jeffrey , Njardarson Jon T.
Published: January 2024

Dithiophosphoric acids (DTPAs) are an intriguing class of compounds that are sourced from elemental sulfur and white phosphorus and are prepared from the reaction of phosphorus pentasulfide with alcohols. The electrophilic addition of DTPAs to alkenes and unsaturated olefinic substrates is a known reaction, but has not been applied to polymer synthesis and polymer functionalization. We report on the synthesis and application of DTPAs for the functionalization of challenging poly‐enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring‐opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly‐ene materials after direct electrophilic addition reactions to the polymer backbone introducing DTPAs as side chain groups. The resulting materials possess both enhanced optical and flame retardant properties vs the poly‐ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di‐functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios.
Stabilizing Ni‐rich Single‐crystalline LiNi0.83Co0.07Mn0.10O2 Cathodes using Ce/Gd Co‐doped High‐entropy Composite Surfaces
Authors: Li Jing , Yang Hui , Deng Qiang , Li Wanming , Zhang Qimeng , Zhang Zihan , Chu Youqi , Yang Chenghao
Published: January 2024

Ni‐rich layered oxides are promising lithium‐ion batteries (LIBs) cathode materials for their high reversible capacity, but they suffer from fast structural degradation during cycling. Here, we report the Ce/Gd incorporated single‐crystalline LiNi0.83Co0.07Mn0.10O2 (SC‐NCM) cathode materials with significantly enhanced cycling stability. The Gd ions are adequately incorporated in SC‐NCM while Ce ions are prone to aggregate in the outer surface, resulting in the formation of a high‐entropy zone in the near‐surface of SC‐NCM, including a Gd doped LiCeO2 (LCGO) shell and Ce/Gd dopant‐concentrated layer. The high‐entropy zone can effectively inhibit the oxygen evolution and prevent the formation of oxygen vacancies. Meanwhile, it leads to a greatly improved H2‐H3 phase transformation reversibility and mitigated stress/strain caused by Li‐ion extraction/insertion during (de)lithiation process. The synergetic effects of reduced oxygen vacancies concentration and mitigated stress/strain can effectively prevent the in‐plane migration of TM ions, lattice planar gliding as well as the formation of intragranular nanocracks. Consequently, Ce/Gd incorporated SC‐NCM (SC‐NCM@CG2) delivers a high initial discharge specific capacity of 219.7 mAh g−1 at 0.1 C and an excellent cycling stability with a capacity retention of 90.2 % after 100 cycles at 1.0 C.
Lithiophilic Covalent Organic Framework as Anode Coating for High‐Performance Lithium Metal Batteries
Authors: Wu Xinyu , Zhang Shuoqing , Xu Xiaoyi , Wen Fuxiang , Wang Hanwen , Chen Hongzheng , Fan Xiulin , Huang Ning
Published: January 2024

The growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well‐aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one‐dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF−Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm−2, which can be well retained up to 400 cycles. Meanwhile, the Li‐COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries.
Ambient Catalytic Spinning of Polyethylene Nanofibers
Authors: Wu Ruikai , Lenz Tim M. , Alfayez Fayez Abdullah S , Zhao Ruohan , Rupper Patrick , Perret Edith , Lehner Sandro , Jovic Milijana , Gaan Sabyasachi , Rieger Bernhard , Heuberger Manfred
Published: January 2024

A novel single‐atom Ni(II) catalyst (Ni‐OH) is covalently immobilized onto the nano‐channels of mesoporous Santa Barbara Amorphous (SBA)‐15 particles and isotropic Anodized Aluminum Oxide (AAO) membrane for confined‐space ethylene extrusion polymerization. The presence of surface‐tethered Ni complexes (Ni@SBA‐15 and Ni@AAO) is confirmed by the inductively coupled plasma‐optical emission spectrometry (ICP‐OES) and X‐ray photoelectron spectroscopy (XPS). In the catalytic spinning process, the produced PE materials exhibit very homogeneous fibrous morphology at nanoscale (diameter: ~50 nm). The synthesized PE nanofibers extrude in a highly oriented manner from the nano‐reactors at ambient temperature. Remarkably high Mw (1.62×106 g mol−1), melting point (124 °C), and crystallinity (41.8 %) are observed among PE samples thanks to the confined‐space polymerization. The chain‐walking behavior of surface tethered Ni catalysts is greatly limited by the confinement inside the nano‐channels, leading to the formation of very low‐branched PE materials (13.6/1000 C). Due to fixed supported catalytic topology and room temperature, the filaments are expected to be free of entanglement. This work signifies an important step towards the realization of a continuous mild catalytic‐spinning (CATSPIN) process, where the polymer is directly synthesized into fiber shape at negligible chain branching and elegantly avoiding common limitations like thermal degradation or molecular entanglement.
Invertebrate diversity associated with a shallow rhodolith bed in the Mediterranean Sea (Mar Piccolo of Taranto, south‐east Italy)
Authors: Pierri Cataldo , Longo Caterina , Falace Annalisa , Gravina Maria F. , Gristina Michele , Kaleb Sara , Lazic Tamara , Lisco Stefania , Moretti Massimo , Putignano Matteo , Ravisato Miriam , Trani Roberta , Dadamo Marco , Albano Paolo G.
Published: January 2024

Rhodoliths, formed by free‐living coralline algae, are distributed worldwide, and the rhodolith beds (RBs) that they form are recognized as structurally complex habitats. In the Mediterranean, they are generally distributed in the mesophotic zone, at depths of 30–100 m; so far, only a few shallow RBs (<2 m) have been reported (e.g. Îles Kuriat, Tunisia, and Stagnone Marsala, Italy).

Here a shallow‐water RB located in the Mar Piccolo of Taranto (south‐eastern Italy, Mediterranean Sea) is described. The diversity of associated invertebrates, the rhodolith‐forming algal species, the type of sediments, and the bed extent are characterized.

The RB investigated extends over 5 ha at depths of 0.5–1.5 m. The rhodoliths vary in shape and size, from pralines to large spherical structures, and are formed by a single species, Neogoniolithon brassica‐florida, growing around nuclei of both natural and anthropogenic origin. The associated fauna consisted of 158 taxa, 79 (50%) of which were new basin records. The associated diversity was approximately twice that of the underlying and nearby sediments.

The structural complexity of the RBs promotes biodiversity and provides shelter, food, and a breeding ground for numerous species, including seahorses, which are a conservation priority in this basin.
Calprotectin Impairs Platelet Survival in Patients With Primary Antiphospholipid Syndrome
Authors: Hoy Claire K. , NaveenKumar Somanathapura K. , Navaz Sherwin A. , Sugur Kavya , Yalavarthi Srilakshmi , Sarosh Cyrus , Smith Tristin , Kmetova Katarina , Chong Emily , Peters Noah F. , Rysenga Christine E. , Norman Gary L. , Figueroa‐Parra Gabriel , Nelson Dava , Girard Jennifer , Ahmed Asra Z. , Schaefer Jordan K. , Gudjonsson Johann E. , Kahlenberg J. Michelle , Madison Jacqueline A. , Knight Jason S. , Crowson Cynthia S. , Duarte‐García Alí , Zuo Yu
Published: January 2024

Objective

While thrombosis and pregnancy loss are the best‐known clinical features of antiphospholipid syndrome (APS), many patients also exhibit “extra‐criteria” manifestations, such as thrombocytopenia. The mechanisms that drive APS thrombocytopenia are not completely understood, and no clinical biomarkers are available for predicting antiphospholipid antibody (aPL)–mediated thrombocytopenia. Calprotectin is a heterodimer of S100A8 and S100A9 that is abundant in the neutrophil cytoplasm and released upon proinflammatory neutrophil activation. Here, we sought to evaluate the presence, clinical associations, and potential mechanistic roles of circulating calprotectin in a cohort of primary APS and aPL‐positive patients.

Methods

Levels of circulating calprotectin were determined in plasma by the QUANTA Flash chemiluminescent assay. A viability dye‐based platelet assay was used to assess the potential impact of calprotectin on aPL‐mediated thrombocytopenia.

Results

Circulating calprotectin was measured in 112 patients with primary APS and 30 aPL‐positive (without APS criteria manifestations or lupus) patients as compared to patients with lupus (without APS), patients with unprovoked venous thrombosis (without aPL), and healthy controls. Levels of calprotectin were higher in patients with primary APS and aPL‐positive patients compared to healthy controls. After adjustment for age and sex, calprotectin level correlated positively with absolute neutrophil count (r = 0.41, P < 0.001), positively with C‐reactive protein level (r = 0.34, P = 0.002), and negatively with platelet count (r = −0.24, P = 0.004). Mechanistically, we found that calprotectin provoked aPL‐mediated thrombocytopenia by engaging platelet surface toll‐like receptor 4 and activating the NLRP3‐inflammasome, thereby reducing platelet viability in a caspase‐1‐dependent manner.

Conclusion

These data suggest that calprotectin has the potential to be a functional biomarker and a new therapeutic target for APS thrombocytopenia.

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Quantitative assessment of the potential of optimal estimation for aerosol retrieval from geostationary weather satellites in the frame of the iAERUS‐GEO algorithm
Authors: Georgeot Adèle , Ceamanos Xavier , Attié Jean‐Luc
Published: January 2024

Satellite remote sensing enables the study of atmospheric aerosols at large spatial scales, with geostationary platforms making this possible at sub‐daily frequencies. High‐temporal‐resolution aerosol observations can be made from geostationary data by using robust numerical inversion methods such as the widely‐used optimal estimation (OE) theory. This is the case of the instantaneous Aerosol and surfacE Retrieval Using Satellites in GEOstationary orbit (iAERUS‐GEO) algorithm, which successfully retrieves aerosol optical depth (AOD) maps from the Meteosat Second Generation weather satellite based on a simple implementation of the OE approach combined with the Levenberg–Marquardt method. However, the exact gain in inversion performances that can be obtained from the multiple and more advanced possibilities offered by OE is not well documented in the current literature. Against this background, this article presents the quantitative assessment of OE for the future improvement of the iAERUS‐GEO algorithm. To this end, we use a series of comprehensive experiments based on AOD maps retrieved by iAERUS‐GEO using different OE implementations, and ground‐based observations used as reference data. First, we assess the varying importance in the inversion process of satellite observations and a priori information according to the content of satellite aerosol information. Second, we quantify the gain of AOD estimation in log space versus linear space in terms of accuracy, AOD distribution and number of successful retrievals. Finally, we evaluate the accuracy improvement of simultaneous AOD and surface reflectance retrieval as a function of the regions covered by the Meteosat Earth's disk.
Enzymatic properties of ornithine decarboxylase from Clostridium aceticum DSM1496
Authors: Tan Qian , Gou Linbo , Fan Tai‐Ping , Cai Yujie
Published: January 2024

Clostridium aceticum DSM1496 is an acid‐resistant strain in which ornithine decarboxylase (ODC) plays a crucial role in acid resistance. In this study, we expressed ODC derived from C. aceticum DSM1496 in Escherichia coli BL21 (DE3) and thoroughly examined its enzymatic properties. The enzyme has a molecular weight of 55.27 kDa and uses pyridoxal‐5′‐phosphate (PLP) as a coenzyme with a Km = 0.31 mM. ODC exhibits optimal activity at pH 7.5, and it maintains high stability even at pH 4.5. The peak reaction temperature for ODC is 30°C. Besides, it can be influenced by certain metal ions such as Mn2+. Although l‐ornithine serves as the preferred substrate for ODC, the enzyme also decarboxylates l‐arginine and l‐lysine simultaneously. The results indicate that ODC derived from C. aceticum DSM1496 exhibits the ability to produce putrescine, cadaverine, and agmatine through decarboxylation. These polyamines have the potential to neutralize acid in an acidic environment, facilitating the growth of microorganisms. These significant findings provide a strong basis for further investigation into the acid‐resistant mechanisms contributed by ODC.
Preclinical Evaluation of Azabenzimidazole‐Based PET Radioligands for γ‐8 Dependent Transmembrane AMPA Receptor Regulatory Protein Imaging
Authors: Chen Jiahui , Li Yinlong , Yu Qingzhen , Patel Jimmy S. , Zhou Xin , Zhang Kuo , Rong Jian , Zhao Chunyu , Chaudhary Ahmad F. , Zhang Wei , Bi Chunyang , Song Zhendong , Davenport April T. , Daunais James B. , Haider Achi , Collier Lee , Yuan Hongjie , Liang Steven
Published: January 2024

AMPA glutamate receptors (AMPARs) play a pivotal role in excitatory neurotransmission, particularly in the hippocampus where the TARP γ‐8 subunit is enriched and serves as a target for emerging anti‐epileptic drugs. To enable in vivo visualization of TARP γ‐8 distribution and expression by positron emission tomography (PET), this study focuses on the development of novel 18F‐labeled TARP γ‐8 inhibitors and their corresponding precursors, stemming from the azabenzimidazole scaffold. The resulting radioligands [18F]TARP‐2204 and [18F]TARP‐2205 were successfully synthesized with acceptable radiochemical yield, high molar activity, and excellent radiochemical purity. In vitro autoradiography demonstrates high level of specific binding of [18F]TARP‐2205 to TARP γ‐8 in both rat and nonhuman primate brain tissues. However, unexpected radiodefluorination in PET imaging studies of rodents emphasizes the need for further structural refinement. This work serves as an excellent starting point for the development of future 18F‐labeled TARP γ‐8 PET tracers, offering valuable insights into medicinal chemistry design, radiosynthesis and subsequent PET evaluation.
How many Mutations are needed to Evolve the Chemical Makeup of a Synthetic Cell?
Authors: Lefèvre‐Morand Rodrigue Yves Louis , Nikel Pablo Iván , Acevedo‐Rocha Carlos G.
Published: January 2024

The chemical evolution of a synthetic cell endowed with a synthetic amino acid as building block, analog to tryptophan, required the emergence of key mutations in genes involved in, inter alia, the general stress response, amino acid metabolism, stringent response, and chemotaxis. Understanding adaptation mechanisms to non‐canonical biomass components will inform strategies for engineering synthetic metabolic pathways and cells.
Ginsenoside Rg3 overcomes tamoxifen resistance through inhibiting glycolysis in breast cancer cells
Authors: Zhao Wenhui , Ma Jianli , Zhang Qingyuan , Zhang Han , Ma Wenjie , Li Shuo , piao Ying , Zhao Shu , Dai Shaochun , Tang Dabei
Published: January 2024

Tamoxifen (TAM) resistance poses a significant clinical challenge in human breast cancer and exhibits high heterogeneity among different patients. Rg3, an original ginsenoside known to inhibit tumor growth, has shown potential for enhancing TAM sensitivity in breast cancer cells. However, the specific role and underlying mechanisms of Rg3 in this context remain unclear. Aerobic glycolysis, a metabolic process, has been implicated in chemotherapeutic resistance. In this study, we demonstrate that elevated glycolysis plays a central role in TAM resistance and can be effectively targeted and overcome by Rg3. Mechanistically, we observed upregulation of 6‐phosphofructo‐2‐kinase/fructose‐2,6‐bisphosphatase 3 (PFKFB3), a key mediator of glycolysis, in TAM‐resistant MCF‐7/TamR and T‐47D/TamR cells. Crucially, PFKFB3 is indispensable for the synergistic effect of TAM and Rg3 combination therapy, which suppresses cell proliferation and glycolysis in MCF‐7/TamR and T‐47D/TamR cells, both in vitro and in vivo. Moreover, overexpression of PFKFB3 in MCF‐7 cells mimicked the TAM resistance phenotype. Importantly, combination treatment significantly reduced TAM‐resistant MCF‐7 cell proliferation in an in vivo model. In conclusion, this study highlights the contribution of Rg3 in enhancing the therapeutic efficacy of TAM in breast cancer, and suggests that targeting TAM‐resistant PFKFB3 overexpression may represent a promising strategy to improve the response to combination therapy in breast cancer.
The use of silicon in the membrane electrode assembly of fuel cells
Authors: Antolini Ermete
Published: January 2024

Silicon, silicon‐based and Si‐containing materials are widely used and play different roles in fuel cells. These materials have been used overall in polymer electrolyte membrane fuel cells, but also in solid oxide fuel cells and phosphoric acid fuel cells. The most used Si compounds in fuel cells are SiO2 and SiC. In this work an overview of the use of Si‐based and Si‐containing materials in the membrane electrode assembly of fuel cells is presented.
From Small‐Area Observations to Insight: Surface‐Feature‐Extrapolation of Anodes for Alkaline Oxygen Evolution Reaction
Authors: Jain Adarsh , Vinayakumar Vineetha , Olean‐Oliveira André , Marcks Christian , Chatwani Mohit , Mechler Anna K. , Andronescu Corina , Segets Doris
Published: January 2024

In this study, we developed a statistical framework, named multistage data quantification (MSDQ), to evaluate representative surface characteristics such as surface roughness, surface area, and homogeneity score of cobalt oxide‐based anodes, and contributing to a deeper insight into the quality of the anode surface. Atomic force microscopy (AFM) was employed to capture the surface morphology of two anodes that have a comparable loading of cobalt oxide but exhibit distinct morphological features. Application of MSDQ exposed notable disparities in surface characteristics across these anodes, underlining the critical importance of MSDQ in precise surface characterization. Specifically, surface roughness, surface area and homogeneity score effectively elucidated the disparities in electrocatalytic activity for the oxygen evolution reaction (OER), as quantified through scanning droplet cell (SDC) measurements. By conducting a systematic comparative analysis, the respective contributions of the extrinsic surface characteristics of the anodes to the intrinsic electrocatalytic material property could be differentiated and quantified. Applications of our findings range from benchmarking of anodes to optimization of anode manufacturing processes.
Mechanistic Insights into the electron‐transfer driven substrate activation by [4Fe‐4S]‐dependent Enzymes
Authors: Wei Wen‐Jie , Liao Rong‐Zhen
Published: January 2024

[4Fe‐4S]‐dependent enzymes catalyze many different types of biological reactions. The quantum chemical cluster approach and the combined quantum mechanics/molecular mechanics approach, with the broken symmetry approach, are powerful tools for understanding the reaction mechanism in enzymes. This review discusses examples of the computational studies on [4Fe‐4S]‐dependent enzymes, focusing on the electron‐transfer driven substrate activation.
A Rational Design of Electrochemically and Photophysically Tunable Triarylamine Luminophores by Consecutive (Pseudo‐)Four‐Component Syntheses
Authors: Kohlbecher Regina , Müller Thomas J. J.
Published: January 2024

The concatenation of Suzuki coupling and two‐fold Buchwald‐Hartwig amination in sequentially palladium‐catalyzed consecutive multicomponent syntheses paves a concise, convergent route to diversely functionalized para‐biaryl‐substituted triarylamines (p‐bTAAs) from simple, readily available starting materials. An extensive library of p‐bTAAs permits comprehensive investigations of their electronic properties by absorption and emission spectroscopy, cyclic voltammetry, and quantum chemical calculations, which contribute to a deep understanding of their electronic structure. The synthesized p‐bTAAs exhibit tunable fluorescence from blue to yellow upon photonic excitation with quantum yields up to 98 % in solution and 92 % in the solid state. Furthermore, a pronounced bathochromic shift of the emission maxima by increasing solvent polarity indicates positive emission solvatochromism. Aggregation‐induced enhanced emission (AIEE) in dimethyl sulfoxide (DMSO)/water mixtures causes the formation of intensely blue fluorescent aggregates. Cyclic voltammetry shows reversible first and second oxidations of p‐bTAAs at low potentials, which are tunable by variation of the introduced para substituents. 3D Hammett plots resulting from the correlation of oxidation potentials and emission maxima with electronic substituent parameters emphasize the rational design of tailored p‐bTAAs with predictable electrochemical and photophysical properties.
Versatile Spectroscopic Cell for Operando Studies in Heterogeneous Catalysis Using Tender X‐ray Spectroscopy in Fluorescence Mode
Authors: Suarez Orduz H. A. , Heck S.‐L. , Dolcet P. , Watier Y. , Casapu M. , Grunwaldt J.‐D. , Glatzel P.
Published: January 2024

The design and commissioning of a cell suitable for operando studies using high‐energy‐resolution fluorescence‐detected X‐ray absorption near‐edge structure (HERFD‐XANES) spectroscopy in the tender X‐ray regime is reported. The cell is optimized for measurements within the energy range of 1.5 keV to 4.5 keV. It has a plug‐flow geometry and can be used for sieved powder samples, analogous to reactors employed for laboratory tests. The functionality of the spectroscopic cell is demonstrated in the area of emission control using CO oxidation as target reaction over 1 wt.% Rh/γ‐Al2O3 as catalyst. We show how HERFD‐XANES at the Rh L3‐edge captures variations in the noble metal structure resulting from the interaction with the support material and reactant molecules. Moreover, distinct structural changes were identified along the catalyst bed as a function of temperature and local gas mixture.
Pharmacokinetics, Bioequivalence, and Safety Evaluation of Two Oral Formulations of Calcium Dobesilate Capsules in Healthy Chinese Volunteers Under Fasting and Fed Conditions
Authors: Wang Yanrong , Liu Ying , Tang Liyuan , Gao Jie , LI Hongmin , Dai Xinya , Chen Ran , Wang Fengqin
Published: January 2024

To determine the pharmacokinetics (PK), safety, and bioequivalence profiles of 0.5‐g calcium dobesilate capsules in both fasting and fed states for the test drug and reference drug. A randomized‐sequence, single‐dose, open‐label, 2‐period crossover study was conducted in fasted and fed healthy Chinese volunteers (Chinese Clinical Trials Registry identifier: CTR202000268‐01). The fasting and fed studies, both involving 24 subjects, were conducted. A single dosage of either the reference or the test preparation was given to each eligible subject in a 1:1 ratio, followed by a 7‐day rest interval before the administration of the alternative formulation. After taking the capsules, plasma samples were taken for 48 hours, and using liquid chromatography‐tandem mass spectrometry, the calcium dobesilate level was determined. The PK parameters evaluated in the study included the maximum serum concentration (Cmax), area under the plasma concentration‐time curve (AUC) from time 0 to the last quantifiable concentration, AUC from time 0 to infinity, half‐life, time to Cmax, and terminal elimination rate constant. In addition, the safety evaluation encompassed monitoring fluctuations in vitals (temperature, pulse, and blood pressure) and laboratory tests (urinalysis, hepatic function, blood biochemistry, and hematology), as well as recording the emergence of adverse events (AEs). The geometric mean ratio (GMR) of the test/reference medications was used to assess bioequivalence by determining if the 90% confidence intervals of the GMR fell within the predefined range of 80%‐125%. AEs were assessed as safety end points. The study included 48 healthy Chinese volunteers (with n = 24 each for the fasting and the fed conditions), and no subjects dropped out for any reason. The differences in the PK metrics for the test and reference drugs for both conditions were insignificant (P > .05). For bioequivalence, irrespective of whether the food was consumed or not, the range of the 90% confidence intervals of the GMR for Cmax, AUC from time 0 to the last quantifiable concentration, and AUC from time 0 to infinity was between 80% and 125%. In the experiment, no serious AEs were recorded. Our findings revealed that the calcium dobesilate capsules used as the reference and the test drugs were both bioequivalent. Irrespective of whether the healthy Chinese volunteers consumed food or not, the PK and safety profiles were comparable.
Prediction of M3B4‐type MBenes as Promising Catalysts for CO2 Capture and Reduction
Authors: Li Mingxia , Zhang Yaoyu , Gao Dongyue , Li Ying , Yu Chao , Fang Yi , Huang Yang , Tang Chengchun , Guo Zhonglu
Published: January 2024

The rational design of novel catalysts with high activity and selectivity for carbon dioxide reduction reaction (CO2RR) is highly desired. In this work, we have extensive investigations on the properties of two‐dimensional transition metal borides (MBenes) to achieve efficient CO2 capture and reduction through first‐principles calculations. The results show that all the investigated M3B4‐type MBene exhibit remarkable CO2 capture and activation abilities, which proved to be derived from the lone pair of electrons on the MBene surface. Then, we emphasize that the investigated MBenes can further selectively reduce activated CO2 to CH4. Moreover, a new linear scaling relationship of the adsorption energies of potential‐determining intermediates (*OCH2O and *HOCH2O) versus ΔG(*OCHO) has been established, where the CO2RR limiting potentials on MBenes are determined by the different fitting slopes of ΔG(*OCH2O) and ΔG(*HOCHO), allowing significantly lower limiting potentials to be achieved compared to transition metals. Especially, two promising CO2RR catalysts (Mo3B4 and Cr3B4 MBene) exist quite low limiting potentials of −0.48 V and −0.66 V, as well as competitive selectivity concerning hydrogen evolution reactions have been identified. Our research results make future advances in CO2 capture by MBenes easier and exploit the applications of Mo3B4 and Cr3B4 MBenes as novel CO2RR catalysts.
Charge‐Transfer Modulation of Emissivity in Polarized Diketopyrrolopyrroles
Authors: Kumar G. Dinesh , Banasiewicz Marzena , Hu Wei‐Hsu , Hany Roland , Vakuliuk Olena , Nüesch Frank , Deperasińska Irena , Gryko Daniel T.
Published: January 2024

Strongly polarized donor‐acceptor‐donor′ diketopyrrolopyrroles, differing in the type of key donor moiety, were designed and synthesized to examine how this affects the non‐radiative decay. Dyes possessing less electron‐rich N‐carbazolyl substituents are characterized by strong yellow emission from a locally excited (LE) state, whereas replacing this donor with more electron‐rich N‐phenothiazinyl substituent changes the relative position of charge‐transfer (CT) and LE states, leading to weaker, reddish‐orange fluorescence. As a result, there is solvent‐dependent charge‐transfer emission shifted to as far as 700 nm. The opening of the intersystem crossing channel to the triplet state possessing CT character is the most likely cause of the fluorescence quantum yield variation in some cases. These results reveal that the fate of molecules in their excited state can be fine‐tuned by very small structural changes.
Recommendations call for screening before, during, and after pregnancy
Authors: Knopf Alison
Published: January 2024

The most common pregnancy complication, and the leading cause of preventable maternal mortality, are perinatal mental health problems. Sometimes, clinicians don't want to screen for something because they don't know what to do if the results are positive: but in the case of perinatal depression, there are treatments, according to a new study.
Setting‐zero analysis for multistage amplifier design
Authors: Lei Junqing , Wu Chenjian
Published: January 2024

A setting‐zero analysis method is presented to facilitate the prediction of zeros in multistage amplifiers. The main objective of this method is to simplify the analysis process of such amplifiers while improving the overall performance, and the feasibility is confirmed by various examples presented in this paper. By proposing a single‐capacitor cascode Miller compensation three‐stage amplifier using setting‐zero analysis, this paper has theoretically verified that the addition of a grounding second‐stage compensation capacitor is unnecessary. Measurement results show that this amplifier consumes a current of 38 μA at a 1.2 V supply voltage, with a 103 dB open‐loop gain. When driving a 1 nF load capacitor, this design achieves 1.88 MHz gain bandwidth and 73° phase margin, with a 3.33 V/μs average slew rate and an average 1% settling time of 0.40 μs under the unity‐gain configuration.
ICH Q14‐inspired novel approach to establish an SFC‐based purity method for carbamazepine
Authors: Schmidt Alexander H. , Stanic Mijo , Parr Maria Kristina
Published: January 2024

The proposed ICH Q14 guideline “Analytical procedure development” describes science and risk‐based approaches for development and maintenance of analytical procedures suitable for the assessment of the quality of drug substances and drug products. As a case study, the systematic development and validation of a supercritical fluid chromatography (SFC)‐based purity method for carbamazepine is presented. Systematic analytical quality by design (AQbD) principles were applied using the software package Fusion QbD to the method development approach. The relationship between chromatographic parameters and the responses of interest were examined to improve the reliability of the method by understanding, reducing, and controlling sources of variability. Method performance qualification in terms of method robustness was finally carried out with the parameters that were classified as critical after method development and a validation study met previously set acceptance criteria. The developed SFC purity method for carbamazepine demonstrated readiness as a viable alternative to the official HPLC method published in the Ph.Eur. with improved peak resolution, improved peak symmetry, and faster analysis times (3 min vs. 80 min for the official method). Its inherent reliability illustrates the superiority of AQbD in method development and application for drug quality assurance.