bluuebunny/crossref_metadata_2025_split huggingface dataset:
Constructing Fully‐Active and Ultra‐Active Sites in High‐Entropy Alloy Nanoclusters for Hydrazine Oxidation‐Assisted Electrolytic Hydrogen Production
Authors: Feng Guang , Pan Yue , Su Dong , Xia Dingguo 
Published: December 2023

AbstractThe development of sufficiently high‐efficiency systems and effective catalysts for electrocatalytic hydrogen production is of great significance but challenging. Here, high‐entropy alloy nanoclusters (HEANCs) with full‐active sites and super‐active sites are innovatively constructed for hydrazine oxidation‐assisted electrolytic hydrogen production. The HEANCs show an average size of only seven atomic layers (1.48 nm). As the catalysts for both hydrogen evolution reaction (HER) and hydrazine oxidation reaction, the HEANC/C exhibits the best‐level performance among reported electrocatalysts. Especially, the HEANC/C achieves an ultrahigh mass activity of 12.85 A mg−1noble metals at −0.07 V and overpotential of only 9.5 mV for 10 mA cm−2 for alkaline HER. Further, with HEANC/C as both anode and cathode catalysts, an overall hydrazine oxidation‐assisted splitting (OHzS) electrolyzer shows a record mass activity of 250.2 mA mg−1catalysts at 0.1 V and only requires working voltages of 0.025 and 0.181 V to reach 10 and 100 mA cm−2, respectively, outperforming those of overall water‐splitting system and other reported chemicals‐assisted hydrogen production systems. Active site libraries including 72 sites on HEANC surface are originally constructed by theoretical calculations, revealing that all sites on HEANC surface are effective active sites for OHzS; especially some are super‐active sites, endowing the best‐level performance of HEANC/C.
Silk Fibroin‐Regulated Nanochannels for Flexible Hydrovoltaic Ion Sensing
Authors: Ge Changlei , Wang Yongfeng , Wang Mingxu , Zheng Zhuo , Wang Shuqi , Kong Yaping , Gao Qiang , Liu Mengyuan , Sun Fuqin , Li Lianhui , Zhang Ting 
Published: December 2023

AbstractThe evaporation‐induced hydrovoltaic effect based on ion‐selective nanochannels can theoretically be employed for high‐performance ion sensing; yet, the indeterminate ion‐sensing properties and the acquisition of high sensing performance are rarely explored. Herein, a controllable nanochannel regulation strategy for flexible hydrovoltaic devices with highly sensitive ion‐sensing abilities is presented across a wide concentration range. By multiple dip‐coating of silk fibroin (SF) on an electrospinning nylon‐66 nanofiber (NNF) film, the surface polarity enhancement, the fibers size regulation with a precision of ≈25 nm, and the nanostructure firm binding are achieved simultaneously. The resultant flexible freestanding hydrovoltaic device exhibits an open circuit voltage up to 4.82 V in deionized water, a wide ion sensing range of 10−7 to 100 m, and ultrahigh sensitivity as high as 1.37 V dec−1, which is significantly higher than the sensitivity of the traditional solid‐contact ion‐selective electrodes (SC‐ISEs). The fabricated flexible ion‐sensitive hydrovoltaic device is successfully applied for wearable human sweat electrolyte sensing and for environmental trace‐ion monitoring, thereby confirming the potential application of the hydrovoltaic effect for ion sensing.
Computational Design of Synthetic Optical Barcodes in Microdroplets
Authors: Kawasaki Fumiko , Mimori Takahiro , Mori Yuka , Aburatani Hiroyuki , Yachie Nozomu , Sato Issei , Ota Sadao 
Published: December 2023

AbstractBarcodes are useful for identifying objects across time, space, and information modalities. However, materializing and decoding optical and multimodal barcodes on microscopic objects remains difficult despite the increasing need for multiplexed cell analysis. Here, a computational design of randomly combinatorial is presented, yet decodable barcodes in microdroplets. The design is based on a novel Real2Sim2Real framework: it first collects experimental images of optically distinct microparticles, then simulates massive combinatorial images by randomly assembling the imaged particles to train a neural network‐based decoder. It is demonstrated that the decoder, even though trained via simulation, accurately identifies the randomly assembled particles in real hydrogel microdroplets. It also shows that the microdroplets with an additional DNA barcoding functionality are applicable to individually link independently measured microscopic images and transcriptome profiles of pooled single cells.
Intrinsically Stretchable and Healable Polymer Semiconductors
Authors: Xue Xiang , Li Cheng , Shangguan Zhichun , Gao Chenying , Chenchai Kaiyuan , Liao Junchao , Zhang Xisha , Zhang Guanxin , Zhang Deqing 
Published: December 2023

AbstractIn recent decades, polymer semiconductors, extensively employed as charge transport layers in devices like organic field‐effect transistors (OFETs), have undergone thorough investigation due to their capacity for large‐area solution processing, making them promising for mass production. Research efforts have been twofold: enhancing the charge mobilities of polymer semiconductors and augmenting their mechanical properties to meet the demands of flexible devices. Significant progress has been made in both realms, propelling the practical application of polymer semiconductors in flexible electronics. However, integrating excellent semiconducting and mechanical properties into a single polymer still remains a significant challenge. This review intends to introduce the design strategies and discuss the properties of high‐charge mobility stretchable conjugated polymers. In addition, another key challenge faced in this cutting‐edge field is maintaining stable semiconducting performance during long‐term mechanical deformations. Therefore, this review also discusses the development of healable polymer semiconductors as a promising avenue to improve the lifetime of stretchable device. In conclusion, challenges and outline future research perspectives in this interdisciplinary field are highlighted.
Multi‐Scale Volumetric Dynamic Optoacoustic and Laser Ultrasound (OPLUS) Imaging Enabled by Semi‐Transparent Optical Guidance
Authors: Nozdriukhin Daniil , Kalva Sandeep Kumar , Özsoy Cagla , Reiss Michael , Li Weiye , Razansky Daniel , Deán‐Ben Xosé Luís 
Published: December 2023

AbstractMajor biological discoveries are made by interrogating living organisms with light. However, the limited penetration of un‐scattered photons within biological tissues limits the depth range covered by optical methods. Deep‐tissue imaging is achieved by combining light and ultrasound. Optoacoustic imaging exploits the optical generation of ultrasound to render high‐resolution images at depths unattainable with optical microscopy. Recently, laser ultrasound has been suggested as a means of generating broadband acoustic waves for high‐resolution pulse‐echo ultrasound imaging. Herein, an approach is proposed to simultaneously interrogate biological tissues with light and ultrasound based on layer‐by‐layer coating of silica optical fibers with a controlled degree of transparency. The time separation between optoacoustic and ultrasound signals collected with a custom‐made spherical array transducer is exploited for simultaneous 3D optoacoustic and laser ultrasound (OPLUS) imaging with a single laser pulse. OPLUS is shown to enable large‐scale anatomical characterization of tissues along with functional multi‐spectral imaging of chromophores and assessment of cardiac dynamics at ultrafast rates only limited by the pulse repetition frequency of the laser. The suggested approach provides a flexible and scalable means for developing a new generation of systems synergistically combining the powerful capabilities of optoacoustics and ultrasound imaging in biology and medicine.
Circularly Polarized Phosphorescence of Benzils Achieved by Chiral Supramolecular Polymerization
Authors: Guang Longyu , Lu Yi , Zhang Yifei , Liao Rui , Wang Feng 
Published: December 2023

AbstractIn current approaches for circularly polarized phosphorescent materials, the crystallization of chiral phosphors suffers from poor processability, while integrating them into an amorphous polymer matrix results in unsatisfactory chiroptical signals due to the absence of chirality communication. Here, we have developed an innovative strategy through chiral supramolecular polymerization of benzil phosphors facilitated by intermolecular hydrogen bonds. The inherent film‐forming capabilities of non‐covalent supramolecular polymers obviate the need for an external polymer matrix. The pronounced helical asymmetry of benzil phosphors resulting from chiral supramolecular polymerization leads to enhanced circularly polarized phosphorescence compared to their non‐hydrogen‐bonded counterparts. The circularly polarized phosphorescent signals can be further modulated by varying the location of stereogenic centers or introducing halogen bonding to benzils. Incorporation of platinum(II) phosphor into the benzil supramolecular polymers induces both chirality and triplet‐to‐triplet energy transfer, leading to a change in circularly polarized phosphorescent color from yellow to red. In summary, chiral supramolecular polymerization of phosphors represents a novel and effective approach to circularly polarized phosphorescent materials.
Die Totalsynthese von Isoxeniolid A**
Authors: Betschart Leo , Altmann Karl‐Heinz 
Published: December 2023

AbstractIsoxeniolid A ist ein hochgespanntes marines Diterpenoid aus der Familie der Xenicane. Es steht repräsentativ für eine Unterfamilie von Xenicanen, deren 9‐gliedriger Ring eine allylische Hydroxygruppe aufweist; derartige Xenicane wurden bisher nicht als Zielmoleküle von Totalsynthesen verfolgt. Wir beschreiben hier die erste asymmetrische Totalsynthese eines derartigen Xenicans, nämlich des Isoxeniolid A. Dabei lag der Schlüssel zum Aufbau des besonders herausfordernden E‐konfigurierten Cyclononenrings in einer diastereoselektiven intramolekularen Nozaki–Hiyama—Kishi‐Reaktion. Andere wichtige Transformationen waren eine enzymatische Desymmetrisierung zur Kontrolle der absoluten Stereochemie, eine diastereoselektive Cuprat‐Addition und die Verwendung eines bifunktionalen Vinylsilan‐Bausteins. Unsere Synthesestrategie ermöglicht auch den Zugang zur enantiomeren Form des Naturstoffs sowie prinzipiell zu einer Vielzahl anderer natürlicher Xenicane und synthetischer Analoga für Struktur‐Aktivitäts‐Untersuchungen.
Pt/MnO Interface Induced Defects for High Reverse Water Gas Shift Activity
Authors: Szenti Imre , Efremova Anastasiia , Kiss János , Sápi András , Óvári László , Halasi Gyula , Haselmann Ulrich , Zhang Zaoli , Morales‐Vidal Jordi , Baán Kornélia , Kukovecz Ákos , López Núria , Kónya Zoltán 
Published: December 2023

AbstractThe implementation of supported metal catalysts heavily relies on the synergistic interactions between metal nanoparticles and the material they are dispersed on. It is clear that interfacial perimeter sites have outstanding skills for turning catalytic reactions over, however, high activity and selectivity of the designed interface‐induced metal distortion can also obtain catalysts for the most crucial industrial processes as evidenced in this paper. Herein, the beneficial synergy established between designed Pt nanoparticles and MnO in the course of the reverse water gas shift (RWGS) reaction resulted in a Pt/MnO catalyst having ≈10 times higher activity compared to the reference Pt/SBA‐15 catalyst with >99 % CO selectivity. Under activation, a crystal assembly through the metallic Pt (110) and MnO evolved, where the plane distance differences caused a mismatched‐row structure in softer Pt nanoparticles, which was identified by microscopic and surface‐sensitive spectroscopic characterizations combined with density functional theory simulations. The generated edge dislocations caused the Pt lattice expansion which led to the weakening of the Pt−CO bond. Even though MnO also exhibited an adverse effect on Pt by lowering the number of exposed metal sites, rapid desorption of the linearly adsorbed CO species governed the performance of the Pt/MnO in the RWGS.
Palladium‐Catalyzed Carbonylative Multicomponent Fluoroalkylation of 1,3‐Enynes: Concise Construction of Diverse Cyclic Compounds
Authors: Kuai Chang‐Sheng , Teng Bing‐Hong , Wu Xiao‐Feng 
Published: December 2023

AbstractMulticomponent reactions, particularly those entailing four or more reagents, have presented a longstanding challenge due to the inherent complexities associated with balancing reactivity, selectivity, and compatibility. In this study, we describe a palladium‐catalyzed multi‐component fluoroalkylative carbonylation of 1,3‐enynes. A series of products featuring three active functional groups‐allene, fluoroalkyl, and carboxyl, were efficiently and selectively integrated in a single chemical operation. Furthermore, more intricate fluoroalkyl‐substituted pyrimidinones can be constructed by simply altering the 1,3‐bisnucleophilic reagent. This approach also provides a valuable strategy for the late‐stage modification of naturally occurring molecules and concise construction of diverse cyclic compounds.
Total Synthesis of Isoxeniolide A**
Authors: Betschart Leo , Altmann Karl‐Heinz 
Published: December 2023

AbstractIsoxeniolide A is a highly strained xenicane diterpenoid of marine origin. This natural product is representative for a subfamily of xenicanes incorporating an allylic hydroxy group in the nine‐membered ring; members of this xenicane subfamily so far have not been targeted by total synthesis. Herein, we describe the first asymmetric total synthesis of isoxeniolide A. Key to forming the challenging E‐configured cyclononene ring was a diastereoselective intramolecular Nozaki–Hiyama–Kishi reaction. Other important transformations include an enzymatic desymmetrization for absolute stereocontrol, a diastereoselective cuprate addition and the use of a bifunctional vinyl silane building block. Our strategy also permits access to the enantiomer of the natural product and holds potential to access a multitude of xenicane natural products and analogs for structure–activity relationship studies.
Diaryltriazolium Photoswitch: Reaching a Millisecond Cycloreversion with High Stability and NIR Absorption
Authors: Kolarski Dušan , Steinbach Pit , Bannwarth Christoph , Klaue Kristin , Hecht Stefan 
Published: December 2023

AbstractThe exceptional thermal stability of diarylethene closed isomers enabled many applications but also prevented utilization in photochromic systems that require rapid thermal reversibility. Herein, we report the diaryltriazolium (DAT+) photoswitch undergoing thermal cycloreversion within a few milliseconds and absorption of the closed form in the near‐infrared region above 900 nm. Click chemistry followed by alkylation offers modular and fast access to the electron‐deficient DAT+ scaffold. In addition to excellent fatigue resistance, the introduced charge increases water solubility, rendering this photoswitch an ideal candidate for exploring biological applications.
Stress‐induced dynamics of glassy vitrimers with fast bond exchange rate
Authors: Pandya Harsh , Perego Alessandro , Khabaz Fardin 
Published: December 2023

AbstractVitrimers are dynamic covalent networks, showing considerable promise in self‐healing and reprocessability applications. In this work, molecular simulations are used to study the shear stress‐induced dynamics of vitrimers in the glassy regime and compare their response with that of permanent networks, providing valuable insights into the macroscopic properties of these networks. Results show that vitrimers undergo bond exchange reactions induced by the application of the shear stress, and these events result in accelerated dynamics and subsequently, higher shear compliance of vitrimer compared to the thermoset. When the applied shear stress is high and deformation enters the nonlinear regime, the vitrimer network shows large shear creep compliance and enhanced non‐affine dynamics. Furthermore, the analysis of the self‐particle dynamics demonstrates that the dynamical behavior of vitrimers is highly heterogeneous at short observation times under low and intermediate stress values, while they become homogeneous in the regime of the shear compliance where it shows significantly higher compliance than the permanent network. The significance of the rate of deformation on the dynamics of glassy vitrimers is successfully demonstrated.
Splitting for strength: Manipulating polymerization reactor split ratios to control mechanical and rheological properties in bimodal polyethylene resins
Authors: Jandaghian Mohammad Hossein , Sepahi Abdolhannan , Hosseini Shahin , Esmaeilzade Romina , Nikzinat Ehsan , Masoori Maryam , Afzali Kamal 
Published: December 2023

AbstractThis study integrates advanced mathematical modeling and experimental methodologies to investigate the simultaneous impact of modifications in the split ratio and molecular weight (MW) of chains on the rheological and mechanical properties of bimodal polyethylene (BiPE) resins. The outcomes underscored the viability of fine‐tuning the molecular weight distribution (MWD) of a BiPE resin by augmenting the MW of high molecular weight (HMW) chains while simultaneously diminishing their proportion in the final alloy formulation. In addition, the experimental results illuminated the prospect of attaining a targeted melt flow index for the final polymers by elevating the MW of HMW chains alongside an increase in the proportion of low molecular weight chains. Significantly, these adjustments resulted in remarkable enhancements in the shear thinning index and strain hardening modulus of the fabricated resins.
Evaluation of mitochondrial stress following ultraviolet radiation and 5G radiofrequency field exposure in human skin cells
Authors: Patrignoni Lorenza , Hurtier Annabelle , Orlacchio Rosa , Joushomme Alexandre , Poulletier de Gannes Florence , Lévêque Philippe , Arnaud‐Cormos Delia , Revzani Hamid Reza , Mahfouf Walid , Garenne André , Percherancier Yann , Lagroye Isabelle 
Published: December 2023

AbstractWhether human cells are impacted by environmental electromagnetic fields (EMF) is still a matter of debate. With the deployment of the fifth generation (5G) of mobile communication technologies, the carrier frequency is increasing and the human skin becomes the main biological target. Here, we evaluated the impact of 5G‐modulated 3.5 GHz radiofrequency (RF) EMF on mitochondrial stress in human fibroblasts and keratinocytes that were exposed for 24 h at specific absorption rate of 0.25, 1, and 4 W/kg. We assessed cell viability, mitochondrial reactive oxygen species (ROS) production, and membrane polarization. Knowing that human skin is the main target of environmental ultraviolet (UV), using the same read‐out, we investigated whether subsequent exposure to 5G signal could alter the capacity of UV‐B to damage skin cells. We found a statistically significant reduction in mitochondrial ROS concentration in fibroblasts exposed to 5G signal at 1 W/kg. On the contrary, the RF exposure slightly but statistically significantly enhanced the effects of UV‐B radiation specifically in keratinocytes at 0.25 and 1 W/kg. No effect was found on mitochondrial membrane potential or apoptosis in any cell types or exposure conditions suggesting that the type and amplitude of the observed effects are very punctual.
Combined in vitro/in silico approaches, molecular dynamics simulations and safety assessment of the multifunctional properties of thymol and carvacrol: A comparative insight
Authors: Akermi Sarra , Smaoui Slim , Chaari Moufida , Elhadef Khaoula , Gentile Rocco , Hait Milan , Roymahapatra Gourisankar , Mellouli Lotfi 
Published: December 2023

AbstractBioactive compounds derived from medicinal plants have acquired immense attentiveness in drug discovery and development. The present study investigated in vitro and predicted in silico the antibacterial, antifungal, and antiviral properties of thymol and carvacrol, and assessed their safety. The performed microbiological assays against Pseudomonas aeruginosa, Escherichia coli, Salmonella enterica Typhimurium revealed that the minimal inhibitory concentration values ranged from (0.078 to 0.312 mg/mL) and the minimal fungicidal concentration against Candida albicans was 0.625 mg/mL. Molecular docking simulations, stipulated that these compounds could inhibit bacterial replication and transcription functions by targeting DNA and RNA polymerases receptors with docking scores varying between (−5.1 to −6.9 kcal/mol). Studied hydroxylated monoterpenes could hinder C. albicans growth by impeding lanosterol 14α‐demethylase enzyme and showed a (ΔG=−6.2 and −6.3 kcal/mol). Computational studies revealed that thymol and carvacrol could target the SARS‐Cov‐2 spike protein of the Omicron variant RBD domain. Molecular dynamics simulations disclosed that these compounds have a stable dynamic behavior over 100 ns as compared to remdesivir. Chemo‐computational toxicity prediction using Protox II webserver indicated that thymol and carvacrol could be safely and effectively used as drug candidates to tackle bacterial, fungal, and viral infections as compared to chemical medication.
Programmed cell death 4: A novel player in the pathogenesis of polycystic ovary syndrome
Authors: Zarezadeh Reza , Abbasi Khadijeh , Aboutalebi Vand Beilankouhi Elmira , Navali Nazli , Hakimi Parvin , Fattahi Amir , Farzadi Laya 
Published: December 2023

AbstractPolycystic ovary syndrome (PCOS) is a pathological condition recognized by menstrual cycle irregularities, androgen excess, and polycystic ovarian morphology, affecting a significant proportion of women of childbearing age and accounting for the most prevalent cause of anovulatory sterility. In addition, PCOS is frequently accompanied by metabolic and endocrine disturbances such as obesity, dyslipidemia, insulin resistance, and hyperinsulinemia, indicating the multiplicity of mechanisms implicated in the progression of PCOS. However, the exact pathogenesis of PCOS is yet to be elucidated. Programmed cell death 4 (PDCD4) is a ubiquitously expressed protein that contributes to the regulation of various cellular processes, including gene expression, cell cycle progression, proliferation, and apoptosis. Despite some disparities concerning its exact cellular effects, PDCD4 is generally characterized as a protein that inhibits cell cycle progression and proliferation and instead drives the cell into apoptosis. The apoptosis of granulosa cells (GCs) is speculated to take a major part in the occurrence and progression of PCOS by ceasing antral follicle development and compromising oocyte competence. Given the possible involvement of GC apoptosis in the progression of PCOS, as well as the contribution of PDCD4 to the regulation of cell apoptosis and the development of metabolic diseases, the current review aimed to discuss whether or how PDCD4 can play a role in the pathogenesis of PCOS by affecting GC apoptosis.
Formation of Bridged Disulfide in Epidithiodioxopiperazines
Authors: Fan Jie , Wei Peng‐Lin , Yin Wen‐Bing 
Published: December 2023

AbstractEpidithiodioxopiperazine (ETP) alkaloids, featuring a 2,5‐diketopiperazine core and transannular disulfide bridge, exhibit a broad spectrum of biological activities. However, the structural complexity has prevented efficient chemical synthesis and further clinical research. In the past few decades, many achievements have been made in the biosynthesis of ETPs. Here, we discuss the biosynthetic progress and summarize them as two comprehensible metabolic principles for better understanding the complex pathways of α, α′‐ and α, β′‐disulfide bridged ETPs. Specifically, we systematically outline the catalytic machineries to install α, α′‐ and α, β′‐disulfide by flavin‐containing oxygenases. This concept would contribute to the medical and industrial applications of ETPs.