bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Conversion of CO2 to Methane Using Nickel‐Functionalized Mesoporous SBA‐1 with 3D Cage‐Type Porous Structure
Authors: Ismaili Arsh , Sathish C. I. , Kumar Ayush , Li Zhixuan , Joseph Stalin , Vinu Ajayan 
Published: December 2024

AbstractDeveloping efficient heterogeneous catalysts for activating CO2 is of considerable interest for achieving carbon neutrality. Therefore, many researchers have devoted a lot of effort to design and develop various porous materials‐based catalysts for CO2 conversion. Catalysts with high activity and stability for CO2 conversion are crucial for easy commercialization, but it remains a significant challenge to develop these catalysts. Herein, we report the fabrication of Ni‐functionalized mesoporous silica with 3D mesoporous structure, cage‐type pores, and different Ni contents for achieving enhanced CO2 methanation and stability. The highly ordered mesoporous structure of SBA‐1 offers a high surface area (1315 m2 g−1) that helps to anchor a significant amount of nickel nanoparticles. Insight into the structure of the catalyst and fine‐tuning of metal‐support interaction were in‐depth, characterized by the combination of X‐ray diffraction, electron imaging, and spectroscopic tools. The prepared Ni‐functionalized SBA‐1 materials exhibit an ordered mesoporous structure and the specific surface area decreases with increasing the concentration of the Ni on the porous channels of SBA‐1. The optimized Ni‐functionalized SBA‐1 yielded 80.1% conversion with a CH4 selectivity of 96.9% at a gas hourly space velocity (GHSV) of 21,000 mLgcat−1h−1 under the optimized reaction conditions. Temperature‐programmed surface reaction (TPSR) studies suggest a mechanism involving CO2 dissociation into CO. The Ni‐loaded SBA‐1 catalyst demonstrated remarkable stability over five consecutive 24 h cycles, indicating its promising potential for practical application in sustainable energy production and greenhouse gas mitigation.
Chromite–Zeolite Catalysts for Syngas Conversion to Hydrocarbons: Insights into Oxide–Zeolite Interactions
Authors: Kull Tobias , Dahlhues Johannes , Wilmsen Andrea , Lohmann Heiko , Zeidler‐Fandrich Barbara , Apfel Ulf‐Peter 
Published: December 2024

AbstractA key challenge in modern society is developing the sustainable processes for producing vital chemicals, such as hydrocarbons, from renewable raw materials. The OX‐ZEO process, which uses bifunctional catalysts to convert syngas into hydrocarbons, offers a potential alternative to the nonsustainable cracking process. Combining oxide materials with zeolites enables the direct synthesis of various hydrocarbon products with high selectivity. However, challenges remain, particularly regarding carbon monoxide (CO) conversion and unwanted carbon dioxide (CO2) generation. This study explores the impact of bimetallic chromites combined with H‐MOR zeolite on the reaction outcome. Comparative experiments using only the oxide versus the bifunctional catalyst revealed a clear link between the methanol synthesis activity of the oxide and the overall activity in the OX‐ZEO process. Furthermore, catalytic tests with monometallic oxides paired with H‐MOR highlighted the role of the oxide's crystal structure in syngas conversion. These findings offer insights into the oxide–zeolite interactions, enabling the development of improved catalyst combinations that enhance the CO conversion, reduce CO2 formation, and maintain high product selectivity.
A Palladium Tetraiodide Supported Catalyst for the Oxidative Carbonylation of β‐Amino Alcohols to 2‐Oxazolidinones
Authors: Ziccarelli Ida , Mancuso Raffaella , Novello Mariangela , De Salvo Alex , Calabrese Carla , Valentino Laura , Pettignano Alberto , Gruttadauria Michelangelo , Giacalone Francesco , Gabriele Bartolo 
Published: December 2024

AbstractA novel PdI42−‐supported catalyst, based on imidazolium‐functionalized polyhedral oligomeric silsesquioxanes (POSS) functionalized with imidazolium arms grafted on amorphous silica, is prepared through a straightforward synthetic procedure allowing to accede to high local concentration spots of palladium sites surrounding the POSS core. The hybrid material was fully characterized by thermogravimetric analysis coupled with differential scanning calorimetry (TGA–DSC), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and X‐ray photoelectron spectroscopy (XPS). This material was successfully used as heterogeneous catalyst for the oxidative carbonylation of β‐amino alcohols to 2‐oxazolidinones as well as 2‐aminopyridin‐3‐ol to oxazolo[4,5‐b]pyridin‐2(3H)‐one under relatively mild conditions (100 °C for 3 h under 40 atm of a 4:1 mixture CO–air) in DME as the solvent and with aerobic oxygen as the simplest external oxidant, with the formation of water as benign coproduct. The catalyst could be successfully recycled up to four times, before beginning to undergo partial deactivation due to palladium reduction, as evidenced by XPS and TEM. ICP–OES analysis of some representative products evidenced a low metal contamination (palladium content <1 ppm), making our approach interesting for applications in the life science field, where a high degree of purity is required.
Three‐Component Synthesis of β‐Ketosulfonamides via Visible‐Light‐Mediated Generation of Sulfamoyl Radicals
Authors: Hofman Kamil , Friedrich Marius , Manolikakes Georg 
Published: December 2024

AbstractIn this study, we report a photoredox‐catalyzed, visible‐light‐mediated three‐component synthesis of β‐ketosulfonamides from silyl enol ethers, N‐aminopyridinium salts, and the sulfur dioxide (SO2) surrogate DABSO (1,4‐diazabicyclo[2.2.2]octane·bis (sulfur dioxide) adduct). Eosin Y is used as readily available and cost‐efficient organic photoredox catalyst. This method is based on the photochemical generation of sulfamoyl radicals as key intermediates from N‐aminopyridinium salts as nitrogen radical precursors and DABSO as an easy‐to‐handle, solid SO2 source. Trapping of the in situ‐generated sulfamoyl radicals with silyl enol ethers affords pharmaceutically relevant β‐ketosulfonamides in 63%–91% yields.
Impact of Double‐π‐Bridge on Bis(Triarylamine)‐Based Organic Mixed‐Valence System: A Case Study of Diaza[1.1](4,4”)ortho‐Terphenylophane Radical Cation
Authors: Yoshida Koshi , Takasaki Fumiya , Uebe Masashi , Seki Shu , Ito Akihiro 
Published: December 2024

AbstractA bis(triarylamine) (BTA) radical cation, bridged by two o‐terphenylene moieties, was prepared and characterized to explore the impact of the double‐π‐bridge on the intramolecular charge/spin transfer process in the 2‐site organic mixed‐valence (MV) compound. Spectroscopic analyses on optically and thermally assisted intervalence charge‐transfer (IVCT) processes revealed that the doubly π‐bridging enhanced the charge delocalization between two nitrogen redox‐active centers, whereas the electronic coupling was not so strengthened, in comparison with the singly π‐bridging reference compound.
Water Microdroplets Promote Spontaneous Oxidation of Amino Acid‐ and Peptide‐related Thiols to Disulfide Bonds
Authors: Zhang Hong , Wang Yanjie , Yang Jiamin , Ju Yun , He Jing , Niu Yuqing , Liu Yaqi , Hou Wenhao , Qiao Lina , Jiang Jie 
Published: December 2024

AbstractDisulfide bonds (S−S) play a critical role in modern biochemistry, organic synthesis and prebiotic chemistry. Traditional methods for synthesizing disulfide bonds often rely on oxygen, alkali, and metal catalysts. Herein, thiol groups involved in amino acids and peptides were spontaneously converted into symmetrical and unsymmetrical disulfide bonds within water microdroplets, without the need for catalysts or oxygen, and under room temperature. Water microdroplets displayed improved selectivity for disulfide bond formation, with minimal production of other oxidative species. Mechanistic investigations revealed that hydroxyl radicals (⋅OH) present on the water microdroplet surface facilitated the oxidation process. Thiols were firstly oxidized to thiyl radicals (RS⋅), which subsequently coupled to form disulfide bonds. This study highlights the potential of microdroplet chemistry as an efficient and mild approach for constructing disulfide bonds.
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

AbstractIn 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

ZusammenfassungErst 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

AbstractThis 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

AbstractIron‐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

AbstractThe 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

AbstractMetal‐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.
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

AbstractIn 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

AbstractIn 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

AbstractIn 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

AbstractEfficient 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

ABSTRACTInvestigating 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.