bluuebunny/crossref_metadata_2025 huggingface dataset:
Stepwise Modulation of Bridged Single‐Benzene‐Based Fluorophores for Materials Science
Authors: Huber Alexander , Schmidt Laura , Gatz Tim , Bublitz Jana , Rex Tobias , Sailaja Sidharth Thulaseedharen Nair , Verheggen Elisabeth , Höfmann Lea , Wölper Christoph , Strassert Cristian A. , Knauer Shirley K. , Voskuhl Jens
Published: December 2024

In recent years, researchers studying fluorogenic samples have steadily shifted from using large, expensive, poorly soluble fluorophores with complex synthetic sequences to smaller, simpler π scaffolds with low molecular weight. This research article presents an in‐depth study of the photophysical properties of five bridged single‐benzene‐based fluorophores (SBBFs) investigated for their solution and solid‐state emission (SSSE) properties. The compounds O4, N1O3, N2O2, N3O1, and N4 are derived from a central terephthalonitrile core and vary in the amount of oxygen and nitrogen bridging atoms. These minimalized emitters show full‐color tunable emission properties and exhibit moderate‐to‐high photoluminescence quantum yield values reaching up to 0.78 in dimethyl sulfoxide (DMSO). In addition to demonstrating excellent compatibility in poly(methyl methacrylate) (PMMA) films and additive manufacturing using stereolithography (SLA), white light emission was achieved in both solution and 3D‐printed materials by controlling the mixing ratio of the compounds. Employing density‐functional theory (DFT), well‐correlating theoretical absorption and emission wavelengths were calculated as average values of the different possible conformers. Furthermore, cellular internalization of the substances was accomplished using Pluronic® F‐127 nanoparticles. Overall, this study emphasizes the remarkable properties of single‐benzene‐based emitters, showcasing their accessibility and potential applications in biomedical fields and materials science.
Die Entwicklung der Drucktechniken: Von der Schreibmaschine zum 3D‐Druck
Authors: Wöhrle Dieter
Published: December 2024

Erst in der Neuzeit wurde als Druckgerät für den Heimgebrauch zunächst die mechanische Schreibmaschine entwickelt, mit der Verbreitung des Papiers als wichtigstem Bedruckstoff. Dann setzte Mitte des 19. Jahrhunderts die digitale Revolution ein, die heute unter anderem für den Heimgebrauch die bedeutendsten Drucktechniken für Ausgabe von Texten, Zahlen und Grafiken beinhalten. Beispiele sind 2D‐Drucker wie Tintenstrahl‐ und Laserdrucker. Hinzu kommen 3D‐Drucker für das Drucken von Objekten. In diesem Artikel liegt der Schwerpunkt neben dem Aufbau, der Funktionsweise auch bei den verwendeten Materialien. Auch als Unterrichtsthema in verschiedenen Jahrgangsstufen der Schule eignet sich das Themenfeld hervorragend.
Bias Selectable Dual Band Detectors Based on Vertically Aligned In2S3‐Coated ZnO Nanorod Arrays Grown on p‐GaN
Authors: Qi Yu , Li Lanfeng , Xu Yaowen , Gao Guangcheng , Yu Naisen , Wu YunFeng
Published: December 2024

This study presents the fabrication of ZnO nanotube arrays coated with vertically aligned In2S3, which were deposited onto a p‐GaN substrate using a wet chemical approach. The In2S3/ZnO/p‐GaN heterostructure‐based device showed improved photoresponse and self‐driven operation. The device based on ZnO/p‐GaN structure coupling with In2S3 nanoparticles revealed bias selectable photodetection by detecting UV and UV/visible light through bias voltage modulation. This strategy can benefit the fabrication of ZnO/GaN‐based broadband photodetector.
Fe−Ni with Chitosan via Microwave and Carboxymethyl as Electrode Materials for Supercapacitor
Authors: Zheng Dianyuan , Yao Rongbin , Sun Chengxiang , Li Jinli , Zheng Yuhang , Zhu Jianhong , Liu Cheng
Published: December 2024

Iron‐nickel double hydroxides (Fe−Ni) have been broadly synthesized for supercapacitors (SC). However, the influence of precipitant quantity on SC performance is one of the present challenges. Herein, we found that Fe0.64Ni0.36@ graphite electrodes, the open and interconnected 3D graded conductive network of carboxymethyl chitosan‐derived porous carbon (C), have achieved effective surface contact. In addition, iron and nickel reinforced redox active materials on porous carbon will undergo more redox reactions for rapid diffusion of electrolyte ions/electrons. Due to the special construction and the synergistic effect of multiple oxidation transformations, the prepared Fe0.64Ni0.36@graphite composite material exhibits a maximum capacitance of 1232 F g−1 at a current density of 1 A g−1. The prepared Fe0.64Ni0.36@graphite//Fe0.64Ni0.36@graphite symmetric supercapacitors exhibit a high energy density of 22.9 Wh kg−1 at a power density of 771 W kg−1. Particularly, the sample exhibits excellent cycling stability, retaining approximately 95.8 % capacitance after 5000 cycles.
Carbidopa and ZnCarbidopa Induce Reductive Stress in MDA‐MB‐231 Cells
Authors: Actis Dato Agustin B. , Naso Luciana G. , Martínez Valeria R. , Ferrer Evelina G. , Williams Patricia A. M.
Published: December 2024

The redox imbalance, caused by depletion or generation of reactive oxygen species (ROS), is a key mechanism by which metal complexes exert anticancer effects. Carbidopa has shown the ability to inhibit the MDA‐MB‐231 cell line, a highly aggressive triple‐negative human breast adenocarcinoma, by inducing reductive stress. The metal complex of carbidopa with zinc (ZnCarbi) was designed to modify carbidopa's structure and exhibited increased cytotoxicity against MDA‐MB‐231 cells. Interestingly, ZnCarbi selectively targets certain cancer cells, showing no impact on the viability of normal HEK293 (human embryonic kidney) cells or other cancer cell lines like A549 (human lung adenocarcinoma), LM3 (murine breast adenocarcinoma), or HCT116 (human colon cancer). Treatment with carbidopa and ZnCarbi induces reductive stress, decreases ROS levels, increases the GSH/GSSG ratio, and protects cells from H2O2‐induced death. Both compounds also cause mitochondrial damage, leading to cell death, and exhibit antimetastatic effects by inhibiting cell migration and invasion of MDA‐MB‐231 cells. Interaction studies with bovine serum albumin showed moderate binding through hydrophobic association. Overall, ZnCarbi demonstrates enhanced anticancer properties compared to carbidopa alone, highlighting its potential as an anticancer and antimetastatic compound.
Continuous Flow Synthesis and Applications of Metal‐Organic Frameworks: Advances and Innovations
Authors: Rahman Rashed , Malik Fazal , Min Hein Zaw , Huang Junrong , You Hengzhi , Zhu Yuxiang
Published: December 2024

Metal‐Organic Frameworks (MOFs) are an emerging class of solid‐state materials comprising inorganic elements and organic molecules. These hybrid materials are widely recognized for their diverse properties, rendering them indispensable in the field of organic synthesis, material science and the pharmaceutical industry. Although the traditional batch methods for MOFs synthesis are well‐developed, they often struggle with reproducibility, scalability and environmental issues. However, the development of continuous flow techniques has emerged as a promising alternative, offering more efficient mass and heat transfer, precise reaction control, greater potential for automation, improved safety, and reduced environmental impact. This review primarily focuses on advanced continuous flow synthesis of MOFs incorporating techniques such as air flow, spray drying, microwave, micro‐droplets, supercritical carbon dioxide, and ultrasound. Additionally, the recent advancements in applying MOFs as heterogeneous catalysts for various organic transformations under continuous flow conditions are discussed, categorized by the type of bond formation, including C−H bond formation (hydrogen reduction), C−C bond formation, and C−O bond formation.
Efficacy and Safety of Janus Kinase Inhibitors in Patients with Vitiligo: A Systematic Review and Meta‐Analysis
Authors: Huang Fan , Hu Dingyuan , Fan Huaying , Hu Binyi , Liu Yian , Dong Wenliang , Liu Xiangxing , Li Yanting , Yan Diqin , Ding Rui , Niu Suping , Chen Liming , Nie Xiaoyan , Fang Yi
Published: December 2024

Although several case reports and small clinical trials have reported promising outcomes with Janus kinase (JAK) inhibitors for vitiligo, high‐quality evidence and guidelines are lacking. We evaluated the efficacy and safety of JAK inhibitors for the treatment of vitiligo using a meta‐analysis of randomized controlled trials (RCTs). We searched the PubMed, Embase, and Cochrane Library databases up to August 2023, with additional studies from ClinicalTrials.gov and company websites. We assessed outcomes, including percentage improvement in total vitiligo area score index (TVASI) and facial vitiligo area score index (FVASI); the proportion of patients achieving 50% improvement in TVASI (TVASI50) and 50% and 75% improvement in FVASI (FVASI50 and FVASI75); the risk of treatment‐emergent adverse events (TEAEs), serious adverse events (SAEs), infections, and skin‐related adverse events (AEs). Five studies with 1,550 participants were included. JAK inhibitors were associated with a higher proportion of TVASI50 (relative risk [RR] 2.67, 95% confidence interval [CI] 1.24–5.78) and FVASI75 (RR 3.97, 95%CI 2.62–6.02) responders than placebo. JAK inhibitors significantly increased the risk of skin‐related AEs (RR 1.96, 95% CI 1.29–2.98) compared with placebo. However, the risk of TEAEs, SAEs, and infections was not significantly different between the JAK inhibitor and placebo groups. Subgroup analysis showed that JAK1 and JAK1/2 inhibitors were more effective than JAK3 inhibitors. However, there was insufficient evidence to suggest that the route of administration affects the efficacy and safety of JAK inhibitors in vitiligo. These findings indicate that JAK inhibitors are effective in repigmentation and well tolerated in patients with vitiligo.
Cu‐MOF‐74 as Fluorescent Probe: Selective Optical Sensor for H2S Gas
Authors: Shingole Manish , Banerjee Seemita , Modak Brindaban , Kolay Siddhartha , Mohanty Jyotirmayee , Sudarsan Vasanthakumaran
Published: December 2024

In order to address the air quality issues and industrial gas leakages effectively, gas sensors must be highly sensitive, selective, stable, cost‐effective, and with high life time. We present here a facile solvothermal method to synthesize a Cu based metal‐organic framework (Cu‐MOF‐74) and demonstrated its potential as a selective fluorescent probe for environmental H2S gas detection. Cu‐MOF‐74 based fluorescence sensor shows strong affinity towards H2S with the limit of detection as low as 7 ppm., Though Cu‐MOF‐74 based sensor exhibited high sensitivity and selectivity for H2S gas over H2, SO2 and NH3, Co‐MOF‐74 is inactive towards H2S sensing. The increased fluorescence intensity in presence of H2S gas as well as the decreased fluorescence intensity in presence of NO2 gas was investigated by experimental observation and theoretical calculation. In presence of H2S gas, interaction between Cu and sulphur atoms occur, the bond between Cu and ligand. This reduces the extent of ligand to metal charge transfer, resulting in increase in fluorescence intensity. The present attempt led to the progress of highly selective and sensitive fluorescence‐based environmental gas sensing probe using metal organic framework with a wide operating temperature ranging of 25 °C to 90 °C.
Photocatalytic Activity and Stability of Carbon Nitride‐Pyrite Composites
Authors: Kaulbersch Julian , McGuigan Scott , Timm Jana , Maggard Paul , Marschall Roland
Published: December 2024

In photocatalysis, the photoabsorber plays a crucial role in the reaction. The most important parameters are stability, cost and optical band gap. In this work, a prominent class of absorbers, namely carbon nitrides (CN), has been investigated. In the literature, CN is most often described as stable, although photodegradation has been observed. In order to retain the beneficial properties of CN while improving stability, a crystalline phase poly(triazine imide) (PTI) of carbon nitride was investigated and compared to polymeric CN in photocatalytic hydrogen generation experiments. In order to improve the charge separation for the photoinduced hydrogen evolution reaction, pyrite (FeS2) was used as a surface co‐catalyst with a loading of 1, 5 and 10 wt %. At the same time, any photodegradation products in solution were investigated by ion chromatography. Interestingly, PTI shows hardly any photocorrosion compared to defective carbon nitride, indicating its higher photostability in hydrogen evolution experiments. However, FeS2 produces ammonium as a degradation product when synthesised from nitrogen‐containing precursors. When made from nitrogen‐free precursors, FeS2 together with photostable PTI releases little ammonia, making it a photostable, earth‐abundant composite for photocatalytic hydrogen generation.
Design, Synthesis, and Chemical Characterization of Pyrene‐Substituted BODIPY Dyes
Authors: Köksoy Baybars
Published: December 2024

In this study, novel di‐ and tetra‐pyrenylated BODIPY (boron‐dipyrromethene) dyes (Bdpy2 and Bdpy4) were synthesized via the Suzuki‐Miyaura cross‐coupling reaction, incorporating pyrene units at specific positions on the BODIPY core. Comprehensive structural characterization was achieved through FT‐IR, UV‐Vis, MALDI‐mass spectrometry, and NMR techniques. The optical properties were extensively analyzed in different solvents, revealing Q‐band absorption maxima at 531 nm for Bdpy2 and 533 nm for Bdpy4 in THF, along with red‐shifted emission peaks due to increased π–π stacking interactions. Bdpy4 displayed a fluorescence quantum yield of 0.68 and a fluorescence lifetime of 3.88 ns, surpassing Bdpy2′s values of 0.61 and 3.44 ns, respectively. These improved values in Bdpy4 highlight the enhanced energy transfer efficiency provided by the additional pyrene groups. Theoretical TD‐DFT calculations supported the experimental findings, indicating effective energy transfer from pyrene to the BODIPY core. These findings suggest that the high fluorescence efficiency and extended lifetimes of pyrenylated BODIPY derivatives make them promising candidates for optoelectronic applications, including bioimaging and energy harvesting.
Aqueous Light‐Harvesting Systems Constructed from Pillar[n]Arene‐Based Supra‐Amphiphiles
Authors: Dang Xiaoman , Zhang Qiaona , Cui Fengyao , Xiao Tangxin
Published: December 2024

Efficient light energy utilization is important for a wide range of technological applications, including photoelectric conversion, photocatalysis, sensing, and bioimaging. In recent years, supramolecular light‐harvesting systems (LHSs) have attracted significant attention due to their potential applications in solar energy conversion and photochemical processes. Pillar[n]arene‐based supra‐amphiphiles, with their unique structural properties and versatile macrocyclic host–guest chemistry, offer promising platforms for constructing efficient aqueous LHSs. This Concept highlights the design, self‐assembly, and photophysical behaviour of pillar[n]arene‐based supra‐amphiphiles, focusing on their role in enhancing light absorption and energy transfer. Key strategies for improving the stability and efficiency of these systems are discussed, such as molecular tuning and environmental adaptability. The Concept also explores the challenges and future directions in optimizing these supramolecular systems for real‐world applications.
Effects of Vegetation Restoration Type on Soil Greenhouse Gas Emissions and Associated Microbial Regulation on the Loess Plateau
Authors: Zhou Jihai , Liu Daokun , Xu Shangqi , Li Xiaoping , Zheng Jiyong , Han Fengpeng , Zhou Shoubiao , Na Meng
Published: December 2024

Investigating responses of soil greenhouse gas (GHG) emissions to vegetation restoration is important for global warming mitigation. On the Loess Plateau, a wide range of vegetation restoration strategies have been implemented to control land degradation. However, the thorough quantification of soil GHG emissions triggered by different modes of vegetation restoration is insufficient. There is still a knowledge gap regarding the regulation of soil biochemical and microbial processing on soil GHG emissions. To do so, we compared responses of soil GHG emissions to various types of vegetation restoration on the Loess Plateau, and investigated the changes in soil properties as well as microbial composition and activities. We found that artificial plantation of Caragana korshinskii had low soil carbon dioxide (CO2) emission, while natural grassland had high CO2 emission. The possible explanations could be related to higher moisture and microbial biomass carbon, and greater nitrogen limitation in natural grassland, which was controlled by actinomycetes and gram‐negative bacteria. Natural grassland had low soil nitrous oxide (N2O) emission and high methane (CH4) uptake, whereas Prunus mume had high N2O emission and Medicago sativa had low CH4 uptake, respectively. Soil N2O emission could be driven by fungi and gram‐positive bacteria which were affected by N availability and dissolved organic carbon. Soil CH4 consumption was associated with anaerobic bacteria and gram‐negative bacteria which were affected by N availability and moisture. These different emissions of CO2, N2O and CH4 generated the largest total GHG emissions for plantation of Prunus mume, but the smallest total GHG emissions for natural grassland and plantation of leguminous Caragana korshinskii. Overall, our findings suggested that the restoration of natural grassland and artificial N‐fixing shrubland like Caragana korshinskii should be encouraged to alleviate GHG emissions, with the practical implications for selecting suitable modes and species to improve ecological sustainability in degraded lands.
The Influence of Native Deer on Forest Fauna—A Systematic Map
Authors: Schwegmann Sebastian , Bhardwaj Manisha , Storch Ilse
Published: December 2024

Deer are the most abundant large herbivores in temperate and boreal forests across the Northern Hemisphere. They are ecosystem engineers known to alter understory vegetation and future tree species composition by selective browsing. Also, deer have strong impacts on faunistic groups, often mediated by vegetation. The ongoing loss of faunal biodiversity in forests worldwide can be exacerbated by high deer population densities. Adapted deer management for the purpose of forest biodiversity conservation requires a holistic understanding of deer–fauna relationships. In this systematic map, we examine the existing literature assessing the effects of deer on faunal communities in boreal and temperate forests. Our aim is to synthesize currently described trends and identify research gaps for our understanding of deer as biotic drivers of forest communities. We reviewed 64 studies on how the abundance, species richness, or diversity of faunal taxa responded to different levels of deer abundance or density in forest ecosystems across the Northern Hemisphere. In total, we found almost 400 individual reported effects of nine native deer species on forest‐dwelling faunal communities. However, our systematic map reveals that comprehensive synthesis of the current literature remains a challenge. Published studies often do not report contextual data essential for comparison and meta‐analysis, for example, deer density, forest management, and predation pressure. Moreover, the methodological approaches of the included studies often only account for potential linear effects of deer on fauna, likely oversimplifying the complexity of direct and indirect effects that deer can have on their ecosystem. We recommend that multi‐level enclosure experiments be applied to assess the impact on faunal taxa. This approach combines robust causal inference with the potential straightforward comparison and replication between deer species, forest types, and system productivity, which will facilitate the utilization of the results in future research and management.
A Comparison of Digestive Strategies for Teratoscincus roborowskii With Different Diet Compositions: Digestive Enzyme Activities, Gut Microbiota, and Metabolites
Authors: Wang Ziyi , Wu Ruichen , Yang Yi
Published: December 2024

Animal gut microbiota play important roles in host immunity, nutrient metabolism, and energy acquisition. The gut microbiota and its metabolic products interact with the host in many different ways, influencing gut homoeostasis and health. Teratoscincus roborowskii is an endemic species which displays special frugivorous behavior, and it has been observed consuming grapes. To explore the effects of grape intake on the gut microbiota and metabolites of T. roborowskii, 16S rRNA sequencing and liquid chromatography mass spectrometry metabolomics were applied to investigate the gut microbiota and metabolite profiles of T. roborowskii fed with mealworms (LC group) and a mixture of mealworms and grapes (FG group). Our results demonstrated that a notable shift in microbiota composition occurred, particularly in terms of an increase in the probiotic Lactococcus in the FG group. The metabolite analysis revealed a significant enrichment of the pathways related to glucose metabolism in the FG group. In addition, the digestive enzyme activity analysis showed that the α‐amylase and cellulase activities in the FG group were significantly higher than those of the LC group, which was consistent with the food type. A strong correlation between diet, gut microbiota, and fecal metabolites was observed, which may imply that different diets promote the establishment of host intestinal adaptation strategies. Our study provides a theoretical basis for host health and the scientific captive breeding of the desert lizards T. roborowskii.
A comparative framework to develop transferable species distribution models for animal telemetry data
Authors: Cullen Joshua A. , Domit Camila , Lamont Margaret M. , Marshall Christopher D. , Santos Armando J. B. , Sasso Christopher R. , Al Ansi Mehsin , Fuentes Mariana M. P. B.
Published: December 2024

Species distribution models (SDMs) have become increasingly popular for making ecological inferences, as well as predictions to inform conservation and management. In predictive modeling, practitioners often use correlative SDMs that only evaluate a single spatial scale and do not account for differences in life stages. These modeling decisions may limit the performance of SDMs beyond the study region or sampling period. Given the increasing desire to develop transferable SDMs, a robust framework is necessary that can account for known challenges of model transferability. Here, we propose a comparative framework to develop transferable SDMs, which was tested using satellite telemetry data from green turtles (CheloniaChelonia mydas). This framework is characterized by a set of steps comparing among different models based on (1) model algorithm (e.g., generalized linear model vs. Gaussian process regression) and formulation (e.g., correlative model vs. hybrid model), (2) spatial scale, and (3) accounting for life stage. SDMs were fitted as resource selection functions and trained on data from the Gulf of Mexico with bathymetric depth, net primary productivity, and sea surface temperature as covariates. Independent validation datasets from Brazil and Qatar were used to assess model transferability. A correlative SDM using a hierarchical Gaussian process regression (HGPR) algorithm exhibited greater transferability than a hybrid SDM using HGPR, as well as correlative and hybrid forms of hierarchical generalized linear models. Additionally, models that evaluated habitat selection at the finest spatial scale and that did not account for life stage proved to be the most transferable in this study. The comparative framework presented here may be applied to a variety of species, ecological datasets (e.g., presence‐only, presence‐absence, mark‐recapture), and modeling frameworks (e.g., resource selection functions, step selection functions, occupancy models) to generate transferable predictions of species–habitat associations. We expect that SDM predictions resulting from this comparative framework will be more informative management tools and may be used to more accurately assess climate change impacts on a wide array of taxa.
Influence of the Halogen Anion Combination on the Spin Crossover Properties of Iron(II) Triazole Complexes
Authors: Sander Arthur , Kilic Maximilian Seydi , Brehme Jules , Tran Kevin , Wesemann Christoph , Renz Franz
Published: December 2024

In this paper we study a series of solid iron(II)‐triazole spin crossover complexes of the formula [Fe(NH2trz)3]Br2(x−1)Cl2x, where the counterions bromide and chloride are present in the same structure in different ratios. Thus, the spin transition temperature also changes in the temperature range between the pure complexes [Fe(NH2trz)3]Br2 and [Fe(NH2trz)3]Cl2. Since these switching temperatures of the pure complexes are rather far apart, this allows us to examine how the SCO behavior of iron(II) triazole complexes with mixed counterions changes with different ratios. To achieve this, the complexes were synthesized with both counterions simultaneously using the salts FeBr2 and FeCl2 ⋅ 4 H2O. The complexes were analyzed by IR and XRD measurements to confirm a successful synthesis. Energy dispersive X‐ray spectroscopy (EDX) was further used to validate the results and to verify a homogeneous distribution of the mixed anions in all samples. This study reveals a linear switching behavior of the complexes depending on the substitution ratio with a temperature range between the homo ionic samples.
Synthesis, Structure, Spectral and Electrochemical Properties of 5,6,7,9,10,11‐Hexaaryl Substituted Meso‐(p‐Tolyl) 3‐Pyrrolyl BODIPYs
Authors: Chauhan Pinky , Ravikanth Mangalampalli
Published: December 2024

Hexabrominated meso‐(p‐tolyl) 3‐pyrrolyl BODIPY was regioselectively synthesized by treating meso‐(p‐tolyl) 3‐pyrrolyl BODIPY with eight equivalents of Br2 in CH2Cl2 under inert atmosphere at room temperature. Five different 5,6,7,9,10,11‐hexaarylated meso‐(p‐tolyl) 3‐pyrrolyl BODIPYs were synthesized by treating 5,6,7,9,10,11‐hexabromo meso‐(p‐tolyl) 3‐pyrrolyl BODIPY with various boronic acids under Suzuki coupling conditions. The X‐ray structure obtained for hexabromo and hexaarylated 3‐pyrrolyl BODIPYs showed slightly distorted structures. Absorption spectral studies revealed that the absorption bands in hexabromo and hexaarylated 3‐pyrrolyl BODIPYs were bathochromically shifted compared to 3‐pyrrolyl BODIPY. The hexabromo 3‐pyrrolyl BODIPY was less fluorescent due to presence of heavy halogens whereas the hexaarylated 3‐pyrrolyl BODIPYs emits moderately in the region of 687–736 nm with quantum yields in the range of 0.18–0.30 and singlet state lifetimes in 2.99–4.50 ns range. The electrochemical studies revealed that hexabrominated 3‐pyrrolyl BODIPY undergo easier reduction compared to 3‐pyrrolyl BODIPY. The hexaarylated 3‐pyrrolyl BODIPYs showed one reversible/quasi‐reversible oxidation and one reversible reduction and their redox behaviour depends on the type of electron donating or electron withdrawing substituents present at the pyrrole carbons. DFT/TD‐DFT studies were in agreement with the experimental results. Group webpage: https://ravikanthlab.wixsite.com/mysite/
Ag Nanoparticles‐Modified FeVO4 Composite for Efficient Photocatalytic CO2 Reduction
Authors: Liang Xinming , Hu Shan , Bi Fuhong , Liu Zixin , Hu Huilin , Ye Jinhua , Wang Defa
Published: December 2024

Photoreduction of CO2 and H2O into fuels and value‐added chemicals is an effective solution to address global energy issues. However, developing photocatalysts with high activity and selectivity remains a major challenge. Herein, we report Ag nanoparticles (NPs) loaded FeVO4 (FVO) composite photocatalyst for highly efficient and selective photoreduction of CO2 to CO. Under a 300 W Xe lamp irradiation, the optimal Ag1‐FVO catalyst exhibits a CO yield of 255.4 μmol g−1 h−1 and a CO selectivity of 99.7 %, which are dramatically higher than those of pure FVO alone. The significantly enhanced photocatalytic performance could be attributed to Ag NPs on the surface of FVO, which improve the separation efficiency of photogenerated carriers and promote the adsorption/activation of CO2 molecules. This study suggests that modification of semiconductor photocatalysts with Ag NPs is an effective method for enhancing the CO2 photoreduction activity.
Synthesis and Exploration of the Reactivity of a 16‐Electron Half‐Sandwich Ir(III) Complex Featuring a Bifunctional O,N‐o‐Carborane Ligand
Authors: Li Jun‐Xian , Zhou Liu‐Jie , Zhang Yu‐Ping , Luo Ya‐Xiong , Wu Mian , Cui Peng‐Fei , Jin Guo‐Xin
Published: December 2024

In this work, a 16‐electron half‐sandwich Ir(III) complex (Cp*Ir(OCN−Ph‐Cl)C2B10H10, 2) featuring a bifunctional O,N‐o‐carborane ligand was synthesized, and its reactivity was thoroughly investigated. Further studies indicate that this complex could react with various donor ligands to achieve a stable 18‐electron species. Interestingly, the obtained 16‐electron complex 2 shows acid–base responsive behavior, namely reversible structural transformation between the 16‐electron complex 2 and 18‐electron complex 4 (Cp*IrCl(OCNH−Ph‐Cl)C2B10H10) with different coordination configuration. This work describes in detail the different reaction processes of half‐sandwich iridium complex and carborane ligand.
Theoretical Insights into the Oxidation of Substrates by High‐Spin Iron(III)‐Acylperoxido Complexes
Authors: Velmurugan Gunasekaran , Comba Peter
Published: December 2024

While the oxidation of organic substrates by FeIV‐oxido complexes has been studied extensively, there are only few highly reactive FeIII‐alkylperoxido complexes. We report here computational mechanistic work of a novel mononuclear nonheme FeIII‐phenylperoxido acetate complex, focusing on the splitting of the peroxide bond, the epoxidation of ethene and the hydroxylation of cyclohexane. Our results reveal that the peroxide bond undergoes homolysis, leading to the formation of an FeIV‐oxido complex. Spectroscopic evidence supports the presence of an FeIV species, aligning with the observed product distribution. Additionally, we have explored a potential sigmatropic rearrangement mechanism. However, based on the activation barriers and initial product energy levels, the FeIII rather than the FeV species is shown to be the active species in the initial step. For both, the epoxidation and hydroxylation reactions, stepwise mechanisms are proposed, involving the FeIV‐oxido species as the catalytic intermediate. The energy barriers calculated for these pathways are significantly lower than those for concerted mechanisms, involving the FeIII‐peroxido species as direct oxidant. In particular, the calculated activation barrier in the FeIV‐oxido pathway is 38 kJ/mol for the activation of the C=C bond in ethene, while the analogous step in the FeIII‐peroxido pathway is calculated to be as high as 183 kJ/mol. Our computational results indicate that the FeIV‐oxido species is the active catalyst in these oxidation reactions.
Multigram Synthesis of 3‐Azabicyclo[3.1.1]heptane Derivatives Including Bicyclic Thalidomide Analogs
Authors: Lysenko Viacheslav , Portiankin Anton , Shyshlyk Oleh , Savchenko Timur , Nazarenko Kostiantyn , Kostyuk Alexander , Golovchenko Oleksandr V. , Brovarets Volodymyr S. , Grygorenko Oleksandr O
Published: December 2024

An efficient approach to the multigram synthesis of 3‐azabicyclo[3.1.1]heptanes is described. The method relied on the intramolecular imide formation in the properly 1,3‐functionalized cyclobutane derivative. In turn, the latter compound was obtained via the diastereoselective Strecker reaction of readily accessible 3‐oxo­cyclobutanecarboxylate. The resulting synthetic intermediate – 1‐amino‐3‐azabicyclo[3.1.1]heptane‐2,4‐dione – was used to synthe­size several monoprotected bicyclic diamines valuable as building blocks for medicinal chemistry, as well as a series of bridged analogs of Thalidomide, a known anticancer drug and a component of proteolysis‐targeting chimeras (PROTACs).
A Sequential Nitro‐Michael Addition and Reductive Cyclization Cascade Reaction for Diastereoselective Synthesis of Multifunctionalized 3,3′‐pyrrolidinyl‐spirooxindoles
Authors: Nichinde Chandrakant B. , Bhati Meema , Girase Amardipsing S. , Patil Baliram R. , Chaudhari Suryakant S. , Krishna Gamidi Rama , Joshi Kavita , Kinage Anil K.
Published: December 2024

In this investigation, we elucidated, one‐pot two stage efficient synthesis of multifuctionalized spiro[oxindole −3,3′‐pyrrolidine]. The methodology proceeds via organocatalyzed nitro‐Michael addition reaction between indolylidenecyanoesters and nitroalkanes to formed nitro‐Michael adduct which transformed into multifunctionalized 3,3′‐pyrrolidinyl‐spirooxindoles by metal catalyzed reductive cyclization cascade. DFT investigations were conducted to elucidate the mechanism underlying the preferential reduction of the nitro group, with subsequent attack on the nitrile and ester groups remain inert throughout the reaction process. The approach is operationally simple, easily scalable, exhibits compatibility with readily accessible starting material and catalysts, thereby emphasizing cost‐effectiveness.
An Electrochemical Method for the Direct Sulfonylation of N‐(4‐hydroxyphenyl)‐sulfonamides with Sulfonyl Hydrazides
Authors: Li Yanan , Li Lin , Li Feiyang , Hu Shuaihu , Zhu Rui , Sun Jianan
Published: December 2024

A facile electrochemical strategy for the synthesis of sulfonylphenol derivatives from N‐(4‐hydroxyphenyl)‐sulfonamides with sulfonyl hydrazides has been successfully developed. This metal‐ and oxidant‐free protocol is suitable for aromatic, heteroaromatic and aliphatic reagents to afford the corresponding sulfonylated products in moderate to high yields under mild conditions. A gram‐scale experiment and an in vitro antibacterial assay were conducted to demonstrate the potential utility of this approach.
Utilizing N‐Hydroxylamine‐Based Active Esters for the Synthesis of Oseltamivir Amide Derivatives
Authors: Zahradníková Barbora , Mravíková Zuzana , Némethová Viktória , Polnišerová Petra , Frecer Vladimír , Mečiarová Mária , Šebesta Radovan
Published: December 2024

Functionalizing and derivatizing pharmaceuticals are essential for preparing new potentially active compounds. This work shows how active esters derived from oseltamivir carboxylate can be useful synthetic tools for accessing various amide derivatives of oseltamivir. Six hydroxylamine active esters were synthesized directly from oseltamivir carboxylate, and their utility in preparing amide derivatives was evaluated. Succinimide ester 5 e was the most efficient in terms of its preparation and in synthesizing oseltamivir derivatives.
Data‐Physical Fusion Deep Learning for Site Seismic Response Using KiK‐Net Records
Authors: Chen Su , Hu Xiaohu , Jiang Weiping , Wang Suyang , Chen Xingye , Li Xiaojun
Published: December 2024

In the realm of earthquake engineering, response spectra play a crucial role in characterizing the effects of site dynamic characteristics under seismic activity. Consequently, accurately predicting seismic response spectra is of paramount importance. We have developed a physics‐guided bidirectional long short‐term memory neural network model (Phy‐BiLSTM) that is proficient in predicting site seismic response based on bedrock records. The core principle of the Phy‐BiLSTM is to improve the alignment between the solution space and the ground truth by integrating physics knowledge obtained from the physical model. The model introduced in this study utilized the 5%‐damped response spectra, which were derived from strong ground motion records collected at the KiK‐net downhole array. The results substantiate the performance enhancement of Phy‐BiLSTM in comparison to the data‐driven BiLSTM model. Furthermore, we conduct a comparative analysis of the Phy‐BiLSTM model against traditional methods (EQ, SBSR) as well as other neural network architectures (CNN and LSTM). The result highlights the advantages of Phy‐BiLSTM in accurately predicting the site seismic response.
Practical Approach to Enhance Energy Resilience in Manufacturing Facilities
Authors: Ngongo P. K. , Almaktoof A. M. A. , Kahn M. T. E.
Published: December 2024

Both developed and developing countries are affected by the global energy problem. Over the last few decades, the industrial sector's electrical energy demand has grown exponentially, altering the supply‐and‐demand balance. The trend toward Industry 4.0 compliant production facilities necessitates a greater demand for high‐reliability power. Because severe production losses caused by power outages cannot be tolerated, an increasing number of large vital industrial processes integrate centralized high‐quality, online UPS technology onto their network to establish a grid‐to‐load link and continuously condition dirty electricity from the national grid. These facilities distribute electrical power using either an MV or LV system. Based on the integration design, investigating ways to quantify energy efficiency savings of MV versus LV UPS system is required. This paper proposes strategic and technical interventions for these systems and assesses their electrical losses and budgetary ramifications. The paper also aims to contribute to the implementation of an energy efficiency plan and help facilities close power efficiency gaps. From the results obtained, the MV UPS system offers a significant reduction in energy consumption. Compared to the LV UPS system, annual energy losses are reduced by 46% at a load factor of 65%. A significant energy improvement is expected at higher load factors and in larger facilities where longer distribution cables are used. Compared to the LV UPS system, MV UPS saves R221 509 per meter of cable length increase and R31 457 per percentage increase in load factor.
High Internal Phase Emulsions of Algae Oil Based on Rapeseed Protein via Salt Extraction Combined With Ultrafiltration
Authors: Cai Jiyang , Mei Yuqi , Yang Yunyi , Fang Suqiong , Chen Wenrong , Yang Tao , Wan Zhili , Yang Xiaoquan
Published: December 2024

Rapeseed protein, as a valuable plant protein, holds great potential as a natural emulsifier for construction of food‐grade high internal phase emulsions (HIPEs). In this work, rapeseed protein, obtained through salt extraction combined with ultrafiltration, was employed as a sole stabilizer to formulate algae oil‐based HIPEs. The effects of protein concentration and pH changes on the physicochemical properties of HIPEs are systematically evaluated. The results show that a protein concentration of 0.5 wt% is sufficient to form stable and self‐supporting HIPEs. As the protein concentration increases, the droplet size of HIPEs gradually decreases, leading to a more robust structure and enhanced stability. Compared to neutral conditions (pH 7.0), the HIPEs under acidic pH 3.5 exhibit more densely packed emulsion droplets with smaller size and more uniform distribution, contributing to superior mechanical properties (higher G′ and yield stress) as well as preferable thixotropic and creep recovery behaviors, which thereby improve their physical stability during storage, thermal processing, and freeze‐thaw cycles. Furthermore, the rapeseed protein‐stabilized HIPEs inhibit the oxidation of algae oil, especially at pH 3.5. The results of oral lubrication indicate that the reduction in the friction coefficient is mainly associated with an increase in protein concentration, with minor effect from pH variation. These findings suggest that rapeseed protein is an effective emulsifier for preparing stable and processable HIPEs, especially under acidic conditions, which have great potential for applications in semi‐solid emulsion foods or edible oil structuring.
Respiratory Protective Effects of Perilla Leave Varieties (Perilla frutescens) Against Fine Particulate Matter (PM2.5)‐induced Damage in Human Nasal Cells
Authors: Kim Min Young , Kim Jung In , Kim Sang Woo , Kim Sungup , Oh Eunyoung , Lee Jeongeun , Lee Eunsoo , An Yeon Ju , Han Chae‐Yeon , Lee Heungsu , Lee Myoung Hee
Published: December 2024

Fine particulate matter (PM2.5) is known to exacerbate chronic respiratory disorders, primarily by inducing inflammatory responses and mucus overproduction. Perilla leaves are reported to have significant health benefits, such as antioxidant, antibacterial, and antiallergic properties, attributed to phenolic compounds that vary depending on genetic diversity. In this study, flavonoid‐rich extracts (FRE) from 56 perilla leaf varieties and genetic resources were prepared and screened using a mass screening system. The screening focused on evaluating their anti‐inflammatory, mucus‐reducing, and respiratory protective effects against PM2.5‐induced damage in human nasal cells (RPMI2650). Parameters such as cell viability, nitric oxide (NO) levels, and mucus secretion factor (MUC5AC) concentrations were assessed. Among the 56 varieties, Perilla frutescens var. crispa (YCPL706), sourced from Ulleung Island, Korea, exhibited the highest cell viability (112.50%, 100 μg/mL), lowest NO concentration (9.98 μM, 100 μg/mL), and MUC5AC level (78.65 ng/mL, 100 μg/mL). Further evaluation of YCPL706 FRE demonstrated significant respiratory protective effects, including the inhibition of pro‐inflammatory cytokines (TNF‐α, IL‐6, and IL‐1β), MUC5AC, and oxidative stress factors (MDA and ROS), compared to the control cultivar Namcheon. YCPL706 also showed strong antibacterial activity against Pseudomonas aeruginosa (minimum inhibitory concentration: 5 mg/mL). These findings suggest that the genetic resource YCPL706 is a promising candidate for combating PM2.5‐induced respiratory damage due to its potent anti‐inflammatory, antioxidant, and antibacterial properties.
Single Molecule Conductance of Anthraquinone‐Based Molecular Wire: Effect of the Anchoring Group
Authors: Vavrek František , Gasior Jindřich , Šebera Jakub , Valášek Michal , Mészáros Gábor , Hromadová Magdaléna
Published: December 2024

Functional molecular electronics require molecular design that provides integrity and stability. In this work, we explored two types of single molecule devices differing in anchoring to the conducting leads. Single molecule conductance was measured by STM break junction method and the molecular conductor was composed of the redox active anthraquinone center (switching element) containing either 4‐pyridyl or p‐phenylene thioacetate anchoring groups. The experimental results were supported by quantum chemical charge transport calculations. Molecular junctions containing 4‐pyridyl anchors displayed two stable configurations with conductance values of 4.9 nS and 20 pS, respectively. Molecules anchored via p‐phenylene thioacetate groups led to one main junction configuration with conductance of 0.1 nS. Junctions employing 4‐pyridyl anchoring groups had higher junction formation probability, which in combination with lower conductance makes them better candidates for switching purposes.
Exploring the Duality of Perceptions: Insights into Uncertainties, Aversion and Appreciation Towards Algorithmic HRM
Authors: Tandon Anushree , Dhir Amandeep , Malik Ashish , Budhwar Pawan , Kaur Puneet
Published: December 2024

The human resource management (HRM) function has witnessed the rapid integration of algorithms into incumbent processes; however, significant employee resistance and aversion to algorithmic decision‐making have also been reported. Research on algorithmic HRM practices indicates an underlying duality of perceptual responses by HRM professionals towards this technology. We seek to understand how HRM professionals experience algorithmic HRM use and determine if there are bright sides to its organizational integration. We undertake a qualitative, open‐ended study based on written responses to open‐ended questions from 58 respondents in the United Kingdom and the United States of America. The data were thematically analyzed using grounded theory, which revealed four themes representing HRM professionals' overarching perspectives on why algorithmic HRM precipitates aversion or appreciation. The first two themes highlight HRM professionals' perceived subjective uncertainty regarding algorithmic HRM and its perceived negative effects on the organization. The third theme acknowledges the positive effect of algorithmic HRM, and the final theme discusses three critical coping strategies (embrace, avoid, and collaborate) that HRM professionals adopt to counteract their experienced fears. Our findings suggest that HRM professionals adopt a cautiously fearful rather than a wholly adverse outlook towards algorithmic HRM, wherein aversion and appreciation appear to emerge simultaneously. We contend this existence of a duality of perceptual responses to algorithmic HRM may be a precursor to setting a harmonious collaboration between humans and algorithms in the HRM domain, contingent on appropriate levels of oversight and governance. Implications for theory and managerial practice are also discussed.
CustOmized versus standard fundal‐height measuREments for the detection of small‐for‐gestational age fetuses in low‐risk women (CORE study): A randomized controlled trial
Authors: Ahmed Farhat ul Ain , Hanook Sharoon , Ismail Fatima , Shah Fatima , Arsalan Maaz , Lopez Garcia‐Tinajero Maria F. , Martinez‐Egea Judit , Figueras Francesc
Published: December 2024

Objective

To compare the proportion of small‐for‐gestational age (SGA) infants detected by routine care versus a growth assessment protocol using customized fundal‐height charts in low‐risk pregnancies of a developing country.

Methods

An open label randomized controlled trial was conducted at the Fatima Memorial Hospital (NUR International University, Pakistan). Low‐risk pregnant women were randomly allocated to routine care (Mcdonald's rule for fundal height measurements followed by referral for scan with discrepancy of 3 cm from gestational age and a contingency third trimester scan) or the growth assessment protocol (GAP) developed by the Perinatal Institute (UK), which consists of the use of gestation‐related optimal weight (GROW) customized charts, alongside management protocols for suspected SGA fetuses, audit tools and training. The primary prespecified outcome was the detection of SGA (defined as a birthweight <10th centile).

Results

Of the 2535 eligible women, 1884 (74%) were randomized (942 to standard care and 942 to GAP). After loss‐to‐follow‐up, 1755 women were analyzed (874 in the standard measurement group and 881 in the GAP group). The detection rate of SGA infants was higher in the GAP group (83.2% [95% CI: 74.4%–89.9%] vs. 29% [95% CI: 20.4%–38.9%], P < 0.001), at the cost of an increased false positive rate (10.4% [95% CI: 8.3%–12.7%] vs. 1.4% [95% CI: 0.7%–2.5%], P < 0.001). The diagnostic odds ratio (positive likelihood ratio/negative likelihood ratio) was 42.6 (95% CI: 24.1–75.4) in the GAP group and 28.3 (95% CI:13.6–59.1) in the standard care group.

Conclusion

In low‐risk pregnant women of a developing country, a growth assessment protocol based on customized fundal‐height charts is superior to standard measurements for the antenatal detection of SGA in newborns.
Native tissue repair of the female pelvic floor: A four‐level surgical concept
Authors: Otcenasek Michal , Borycka Katarzyna , Herman Hynek
Published: December 2024

This review describes our experience with native tissue repair of the visceral pelvic fascia, the perineum, and anal sphincters in women. We propose that complex repair of the pelvic floor should consider vaginal support in all three anatomical Delancey's levels, together with more caudal structures—the external and internal anal sphincters. Original illustrations were created to facilitate the understanding of the complex anatomy of common multi‐level defects. As the integrity of connective tissue adds to various aspects of the delicate function of the female pelvic floor, it is complete and as perfect as possible repair is a common goal of both gynecologists and colorectal specialists.