bluuebunny/crossref_metadata_2025 huggingface dataset:
Cyclodextrin Metal–Organic Framework Functionalized Carbon Materials with Optimized Interface Electronics and Selective Supramolecular Channels for High‐Performance Lithium–Sulfur Batteries
Authors: Sun Bingxin , Wang Dan , Jiang Yuxuan , Wang Rui , Lyu Lulu , Diao Guowang , Zhang Wang , Pang Huan
Published: November 2024

During the reaction process in lithium–sulfur batteries, Lewis acidic lithium polysulfides (LiPSs) affect ion distribution and overall electrolyte stability, degrading battery performance and product distribution (e.g., Li2S). Here, a microenvironment regulation strategy with optimized interface electronics and selective supramolecular channels, is proposed to enhance LiPS reaction kinetics through Lewis basic γ‐cyclodextrin metal–organic framework (γ‐CDMOF). To validate this concept, γ‐CDMOF is rapidly synthesized on 3D graphene foam (GF) via a microwave‐assisted method, resulting in a γ‐CDMOF/GF cathode for high‐performance Li–S batteries. A range of analytical techniques combined with density functional theory (DFT) calculations confirm that introducing a Lewis basic supramolecular microenvironment mitigates the LiPSs shuttle effect, enhances polysulfide capture, and improves sulfur redox conversion. Additionally, COMSOL simulations reveal that the γ‐CDMOF framework and oxygen sites significantly reduce volumetric expansion stress during the LiPS solid–liquid phase transition. Impressively, the γ‐CDMOF/GF cathode exhibits exceptional performance, including a high specific capacity (1253.01 mAh g⁻¹ at 0.1C), excellent rate performance (589.68 mAh g⁻¹ at 5C), and long cycle life (over 1200 cycles). This study introduces a new concept of supramolecular microenvironment regulation and interfacial interaction strategy, offering a unique approach for the development of multifunctional electrode materials.
Nitrogen‐Doped Multiwalled Carbon Nanotubes Trigger Immune Responses and Inhibit Fat Deposition
Authors: He Dalin , Xiao Xue , Hu Geng , Zhang Wenqian , Yu Guanliu , Liu Yan , Lin Yun , Lin Hai , Li Xianyao , Diao Youxiang , Tang Yi , Li Haifang
Published: November 2024

Multiwalled carbon nanotubes (MWCNTs) offer immense opportunities to deliver drugs and biomolecules to targeted tissues. However, it's unclear to their effects on fat metabolism. Here, it is demonstrated that nitrogen‐doped carboxylate‐functionalized MWCNTs (N‐MWCNTs) inhibit fat deposition both in vivo and in vitro. N‐MWCNTs <0.5 µg mL−1 do not affect the viability of HEK293 cells and adipose‐derived stem cells (ASCs). Intramuscular administration of N‐MWCNTs does not affect the body weight gain and feed intake of mice, but reduces the fat mass. In in vitro‐cultured adipocytes, N‐MWCNTs suppress fat accumulation, accompanied by decreased and increased expression of adipogenic and lipolysis genes, respectively. Transcriptome analysis further certifies the N‐MWCNT alteration of fat metabolism‐related genes. Interestingly, the internalization of N‐MWCNTs by macrophage‐like cells via Transmission electron microscopy (TEM) imaging is observed. The mRNA sequencing data also shows remarkable variation of the genes involved in the Toll‐like receptors (TLRs) pathway, exhibiting down‐ or up‐regulation of inflammatory factors, of which TNF‐α, IL‐1, IL‐7, IL‐10, and IL‐12 are decreased, whereas IL‐6 and IL‐11 are increased. In conclusion, N‐MWCNTs trigger immune responses and reduction of fat deposition.
Redox‐Neutral Cascade Trifluoromethylation of Dienes and Enynes Using a Perylene Diimide (PDI) Organophotocatalyst
Authors: Gopal Ghosh Krishna , Pal Koustav , Mallick Manasi , Das Debabrata , Sureshkumar Devarajulu
Published: November 2024

The perylene diimide (PDI) is an underexplored synthetic organic dye with significant potential in photoredox catalysis. We have developed a good chemo‐ and regioselective, atom‐economical methodology for synthesizing trifluoroethylated saturated heterocyclic derivatives and trifluoroethyl‐containing cyclobutane derivatives. This process involves the generation of trifluoromethyl radical from the Langlois (CF3SO2Na) reagent under photoredox conditions, which selectively reacts with the electron‐rich terminal double/triple bonds in the diene/enyne framework. The resulting intermediate undergoes a cascade cyclization, yielding the desired compounds in a redox‐neutral manner. Our methodology operates under very mild conditions, eliminating the need for transition metals and external oxidizing agents. It is broadly applicable across various substrates and is supported by comprehensive mechanistic insights from regular photophysical experiments.
Zinc Ion Hybrid Capacitors: Four Essential Parameters Determining Device Energy Density
Authors: Wu Jiacheng , Zhu Di , Pan Yuqi , Prabowo Justin , Wei Li , Chen Yuan
Published: November 2024

Zinc ion hybrid capacitors (ZIHCs) with Zn metal faradic and carbon capacitive electrodes have potential applications in grid‐scale energy storage systems and wearable devices. However, the high specific energy density reported in many recent studies is based on the mass of active carbon materials alone, with deficient device energy density. This perspective article discusses how four crucial parameters influence the device energy density of ZIHCs, including areal mass loading (mc) and specific capacity (Qg,c) of active carbon materials in cathodes, negative‐to‐positive electrode capacity ratio (N/P), and electrolyte‐to‐active carbon materials mass ratio (E/C). Using a representative device model, how the device energy density varies when these four parameters change is shown. Detailed analysis indicates that specific parameter windows with the four parameters within narrow ranges (e.g., mc = 10–20 mg cm−2, Qg,c > 100 mAh g−1, N/P < 20, and E/C < 5) need to be achieved simultaneously to deliver application‐relevant energy density (e.g., >30 Wh kg−1) in ZIHCs. It is hoped that these findings assist in objectively evaluating reported performance data and identifying essential issues for future research development to realize practical applications.
Neuronal Multi Unit Activity Processing with Metal Oxide Memristive Devices
Authors: Sbandati Caterina , Jiang Xiongfei , Yadav Deepika , Stathopoulos Spyros , Cohen Dana , Serb Alex , Wang Shiwei , Prodromakis Themis
Published: November 2024

Intra‐cortical brain‐machine interfaces (BMIs), able to decode neural activity in real‐time, represent a revolutionary opportunity for treating medical conditions. However, traditional systems focusing on single‐neuron spike detection require high processing rates and power, hindering the up‐scaling for neurons‐population monitoring in clinical application. An intriguing proposition is the memristive integrating sensor (MIS) approach, which uses resistive RAM (RRAM) for threshold‐based neural activity detection. MIS leverages analogue multi‐state switching properties of metal‐oxide RRAM to compress neural inputs by encoding above‐threshold events in resistance displacement, facilitating efficient data down‐sampling in the post‐processing, enabling low‐power, high‐channel systems. Initially tested on spikes and local field potentials, here MIS is adapted to process multi‐unit activity envelope (eMUA)—the envelope of entire spiking activity—which has recently been proposed as crucial input for real‐time neuro‐prosthetic control. Prior necessary modifications to the MIS for effective operation, this adaptation achieved over 95% sensitivity across two types of metal‐oxide devices: Pt/TiOx/Pt and TiN/HfOx/TiN, proving its platform‐agnostic capabilities. Furthermore, towards the integration of MIS with silicon chips, it is shown that it can reduce total system power consumption to below 1 µW, as RRAM encoding stage relaxes the signal preservation and noise requirements that challenge traditional complementary metal‐oxide‐semiconductor (CMOS) front‐ends. This eMUA‐MIS adaptation offers a viable pathway for developing more scalable and efficient BMIs for clinical use.
Long‐Channel Effects in Randomly Oriented Carbon Nanotube Thin Film Transistors
Authors: Liu Hai‐Yang , Zhang Panpan , Cao Xianmao , Zhang Yang , He Jianping , Zhu Maguang , Xiao Mengmeng , Zhang Zhiyong
Published: November 2024

Carbon nanotube (CNT) thin film transistors (TFTs) have demonstrated great potential for application in highly sensitive biosensors and large‐area electronics. However, research on the electrical behavior of long‐channel CNT TFTs is lacking; thus, the purposeful improvement in the performance of biosensors or circuits is difficult. In this study, the electrical transport characteristics of ionic‐liquid‐gate CNT TFTs with channel lengths (Lch) ranging from 10 to 400 µm are investigated. The CNT TFTs present classical drift‐diffusion transport at on‐state with a carrier mobility of around 27 cm2 V−1 s−1. In the subthreshold region of the CNT TFTs, an abnormal Lch‐dependent subthreshold swing (SS) relationship, named as the long‐channel effect (LCE)is observed, where SS worsens with increasing Lch. The existence of the junctions between the CNTs results in an unconventional density of states for carriers and a large series resistance for sharing the gate voltage; this dominates the abnormal scaling behavior in the subthreshold region by degrading the electrostatic integrity. The discovery of the abnormal LCE can aid in the construction of device models and purposefully improve the performance of CNT TFTs for biosensors and other large‐scale electronic applications.
Life History Traits of Ambassidae Fish, Chanda nama (Hamilton, 1822) From the Old Brahmaputra River of Northeastern Bangladesh
Authors: Islam Md. Fakhrul , Haque Syed Ariful , Sharker Md. Rajib , Uddin Kazi Belal , Kasif Tariq‐Al , Sarmin Most. Shakila , Rahman Md. Mizanur , Hasan Md. Sabit
Published: November 2024

The present study provides a comprehensive analysis of the population structure (length–frequency distributions), growth pattern (length–weight relationships [LWRs] and length–length relationships), physiological condition factors (allometric [KA], Fulton's [KF] and relative [KR]), relative weight (WR) and form factor (a3.0) of Chanda nama. A total of 1200 specimens were collected from the Old Brahmaputra River, northeastern Bangladesh, for 12 months by traditional fishing gear, including seine net and cast net. The total length (TL) of several individuals varied from 2.3 to 7.2 cm. The highest percentage contributed to the population's 4.0–4.5‐cm‐sized group. The LWRs indicated a positive allometric growth pattern (b > 3.0). Fulton's condition factor significantly correlated with TL and body weight (p < 0.0001). The calculated WR ranged from 67.38 to 137.64. No significant variations from 100 were found using the Wilcoxon rank test (p = 0.034), suggesting that C. nama might live there in a balanced predator–prey environment. Furthermore, the measured value for the form factor (a3.0) was 0.0105. In addition, fish with a TL of 7–8 cm should be caught since they are in good condition and have enough meat. The study's findings will greatly contribute to the efficient and enduring management of C. nama in the Old Brahmaputra River and its adjacent ecosystems.
A Multi‐Prong Approach for Monitoring Hydrilla [Hydrilla verticillate (L. fil.) Royle] in Lakes and Reservoirs
Authors: Glomb Jackson C. , Lowe Roger C. , Shelton James L. , Hamel Martin J.
Published: November 2024

Hydrilla verticillatata is an invasive aquatic macrophyte that has negatively impacted freshwater ecosystems in areas around the world. As a result, lake managers often seek ways to manage hydrilla and mitigate its spread. Having effective methods for assessing hydrilla abundance in a system is imperative, but traditional assessment methods are expensive, time consuming, and may be inaccurate. Contemporary remote sensing techniques have the potential to provide a faster and more effective means for obtaining hydrilla coverage estimates. Therefore, we set out to determine what methodologies provide the most efficient and effective approach for assessing hydrilla in a large reservoir. We used spectral indices on satellite imagery and unoccupied aerial vehicle (UAV) imagery to develop an image classification scheme for quantifying hydrilla occurrence. We also used down‐scan sonar in conjunction with the BioBase software to generate hydrilla coverage and biovolume estimates. the normalized difference vegetation index derived from 3‐m resolution multispectral satellite imagery proved effective for training an image classification, providing a reliable means at quantifying hydrilla colonization through time. The coloration index combined with UAV imagery yielded pixel values for hydrilla that were distinct from other aquatic plant species and can be used to verify results of satellite imagery. However, these methods were ineffective when hydrilla had not yet grown to maximum shoot length. In these conditions, down‐scan sonar remained a valuable assessment tool to supplement aerial remote sensing techniques. These results equip lake managers with the knowledge to make more informed decisions, quickly assess hydrilla occurrence, and develop effective management strategies.
Development and validation of a controlled heating apparatus for long‐term MRI of 3D microfluidic tumor models
Authors: Alkhadrawi Hassan , Dese Kokeb , Panchal Dhruvi M. , Pueschel Alexander R. , Freshwater Kasey A. , Stewart Amanda , Henderson Haleigh , Elkins Michael , Dave Raj T. , Wilson Hunter , Bennewitz John W. , Bennewitz Margaret F.
Published: November 2024

Conventional testing of novel contrast agents for magnetic resonance imaging (MRI) involves cell and animal studies. However, 2D cultures lack dynamic flow and in vivo MRI is limited by regulatory approval of long‐term anesthesia use. Microfluidic tumor models (MTMs) offer a cost‐effective, reproducible, and high throughput platform for bridging cell and animal models. Yet, MRI of microfluidic devices is challenging, due to small fluid volumes generating low sensitivity. For the first time, an MRI of MTMs was performed at low field strength (1 T) using conventional imaging equipment without microcoils. To enable longitudinal MRI, we developed (1) CHAMP‐3 (controlled heating apparatus for microfluidics and portability) which heats MTMs during MRI scans and (2) an MRI‐compatible temperature monitoring system. CHAMP‐3 maintained chip surface temperature at ~37°C and the media inside at ~35.5°C. Enhanced T1‐weighted MRI contrast was achieved in 3D MTMs with free manganese (Mn2+) solutions and Mn2+ labeled tumor cells.
Ceanothus: Taxonomic patterns in life history responses to fire
Authors: Keeley Jon E. , Thomas Parker V. , Zedler Paul H. , Brandon Pratt R.
Published: November 2024

Premise

Ceanothus (Rhamnaceae) is a large genus of shrubs that dominate California chaparral and are resilient to fires. Persistence is ensured by resprouting and/or seedling recruitment from dormant seed banks. Some species do both and others, the obligate seeders, are entirely dependent on seedling recruitment. The distribution of these two modes within the genus is poorly documented.

Methods

We used all available publications that document species responses to fire and filled most gaps in the literature based on extensive field studies of more than 60 recent wildfires in California.

Results

The genus is divided into two subgenera, Ceanothus and Cerastes. Ceanothus is widely considered to comprise mostly resprouting species and Cerastes to consist of only obligate seeders. The subgenus Ceanothus includes resprouting species throughout their range from the eastern United States and Midwest to western United States. Within the California Floristic Province (CFP), a few species are unique in producing massive lignotubers that develop from repeated fires; however, within the CFP, the majority of species in this subgenus do not resprout and are obligate seeders. Two have disjunct subspecies that are facultative seeders or obligate seeders.

Conclusions

Previously, speciation in this genus was contended to have occurred in the late Miocene within the CFP. The syndrome of obligate seeding is most strongly represented in this region, and we hypothesize that evolution of this syndrome was a response to increased predictability of fire driven by the Mediterranean climate and the long interval between fires.
Stationarity of the Special Relationship Between the Geographical Distribution of Body Size and Day Length in Japanese Adolescents: Spatial and Temporal Analysis Using a GTWR Model
Authors: Yokoya Masana , Higuchi Yukito
Published: November 2024

Objectives

Northern Japanese children tend to have larger physiques; however, the underlying cause remains unknown. Previous geographical correlation analyses revealed an unusual trend; effective day length was negatively correlated with height and positively correlated with weight (adjusted for height). This paradoxical relationship suggests a thyroid hormone‐like effect and possible photoperiodic response. This study aimed to determine whether this phenomenon remains consistent over time and across different regions of Japan.

Methods

We used geographically and temporally weighted regression (GTWR) to examine whether the relationship between height and effective day length, which differs from the relationship between weight and effective day length, varies by location and time. GTWR models each observation point separately, allowing for spatial and temporal variations. The analysis included the average height and weight data of children and adolescents by prefecture from 1989 to 2019, along with effective day length considering illuminance above 5000 lx derived from the agrometeorological grid square data.

Results

Height was used as the dependent variable, whereas weight and effective day length were used as independent variables. For height estimation, the coefficients of weight and effective day length were consistently positive and negative, respectively, although the regression coefficients showed minor geographical and temporal variations.

Conclusion

The opposite correlation between height and effective day length and that between weight and effective day length were consistent. This suggests that the phenomenon is more likely driven by environmental factors than by economic or genetic influences.
Expanding the Molecular and Clinical Phenotype of Patients With De Novo Variants in KIF5C: A Six Patient Case Series
Authors: Gracie Sara , Deshpande Prasannakumar , Hollos Patrik , De Dios Karl , Martin Donna M. , Pritchard Amanda B. , Scott Schwoerer Jessica A. , Behrmann Meghan R. , Seaver Laurie H. , Brown Kathleen , Fernandez Raymond J. , Larson Austin , Coffey Eleanor
Published: November 2024

Heterozygous de novo loss of function variants in the motor domain of KIF5C are associated with a neurodevelopmental disorder characterized by infantile‐onset epilepsy, frontal cortical dysplasia, and developmental delays including motor and speech impairments. Previously, only three missense variants in KIF5C were known to be pathogenic. We identified an additional six patients with significant developmental delays with heterozygous de novo variants in the KIF5C gene (Glu237Val, Thr93Ile, Thr93Asn, Ser90del, Lys92Arg, and Glu237Lys), of which four variants have not been reported before. Functional assessment was performed on fluorescently‐tagged KIF5C variants expressed in isolated hippocampal neurons. The pathogenic de novo variants displayed significantly reduced motor function compared to the wild‐type KIF5C. We conclude that the pathogenic de novo variants presented have decreased motor domain activity and that is likely to be the etiology of the patients' symptoms given the gene's constraint in the population. By adding these patients to the seven patients previously reported, we are able to expand the phenotypic spectrum associated with pathogenic KIF5C variants. Evaluation of the neurodevelopmental phenotype of additional individuals with loss of function variants in KIF5C is indicated to further characterize the spectrum of associated phenotypes.
Isotopic evidence of diet breadth hunter‐gatherers changes during the Holocene in the Central Pampean Dunefields (Argentina, South America)
Authors: Scheifler Nahuel A. , Messineo Pablo G. , Bocherens Hervé , Politis Gustavo G.
Published: November 2024

Objectives

Based on the analysis of stable carbon and nitrogen isotopes of bone collagen, stable carbon isotopes of bone apatite and an extensive AMS dating series (~10,000–299 years cal BP), the human paleodiets of 34 individuals from the Central Pampean Dunefields (Argentina, South America) are evaluated.

Materials and Methods

These data are interpreted from the isotopic ecology of animals with archaeofaunal evidence of consumption and isotopic models of human diet. Multivariate carbon and nitrogen stable isotope model and Bayesian stable isotope ellipses were used to interpret human diets.

Results

Analysis of isotopic values indicates intake of enriched lipids and/or carbohydrates in relation to the proteins consumed throughout the Holocene. The isotopic values of Middle Holocene humans in relation to the values of exploited resources point out that individuals obtained protein mainly from guanaco. Subsequently, there was an increase in the human breadth diet during the Late Holocene, with a greater relevance of small prey of high trophic levels and vegetables. This contrasts with zooarchaeological information indicating generalist human diets during the Middle Holocene and specialized human diets in guanaco during the Late Holocene.

Conclusions

It is proposed that during the Middle Holocene arid period, the combination of low human population density and high residential mobility in wide foraging ranges allowed the guanaco to be the main source of protein. During the Late Holocene humid period, there was an increase in human population density and a decrease in residential mobility, which caused greater pressure on foraging territories and increased dietary breadth.
Hong‐Ou‐Mandel Interference on a Lattice: Symmetries and Interactions
Authors: Njoya Mforifoum Mama Kabir , Buchleitner Andreas , Dufour Gabriel
Published: November 2024

The Hong‐Ou‐Mandel interference of two identical particles evolving on a 1D tight‐binding lattice where a potential barrier plays the role of a beam splitter is described. Careful consideration of the symmetries underlying the two‐particle interference effect allows to reformulate the problem in terms of ordinary wave interference in a Michelson interferometer. This approach is easily generalized to the case where the particles interact, and we compare the resulting analytical predictions for the bunching probability to numerical simulations of the two‐particle dynamics.
Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes
Authors: Wei Zhong , Jing Xu , Zhao Song , Yang Yang , Duan Chunying
Published: November 2024

An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking the off‐on‐off selectivity in the semi‐hydrogenation of alkynes. Water serves as a critical regulator, modulating the catalyst states, reaction rates, and endpoints. The choice of solvent system influences the activity of host–guest binding and the reaction types of homogeneous and heterogeneous catalysis, effectively modifying the reaction steps involved in the Z→E isomerization during the semi‐hydrogenation of alkynes. Kinetic and inhibition experiments indicate that the catalyst mimics the binding and activation characteristics of enzymes towards substrates, enabling selective transformations within the confined enzyme‐mimicking environment. The utility of this switchable cage‐confined catalysis has been demonstrated in the synthesis and modification of complex biologically active molecules with controllable E/Z selectivity. This work sheds light on the design and control of artificial supramolecular counterparts of enzymes, offering fundamental insights into the factors influencing the activity and catalytic selectivity of biological macromolecules.
Surface Coordination Chemistry of Graphitic Carbon Nitride from Ag Molecular Probes
Authors: Amanullah Sk , Cao Weicheng , Brack Enzo , Plodinec Milivoj , Copéret Christophe
Published: November 2024

Graphitic carbon nitride (g‐C3N4) has gained significant attention for its catalytic properties, especially in the development of Single Atom Catalysts (SACs). However, the surface chemistry underlying the formation of these isolated metal sites remains poorly understood. In this study we employ Surface OrganoMetallic Chemistry (SOMC) together with advanced microscopic and spectroscopic techniques for an in‐depth analysis of functionalized g‐C3N4 materials, where tailored organosilver probe molecules are used to monitor surface processes and characterize resulting surface species. A multi‐technique approach – including high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM), X‐ray absorption spectroscopy (XAS), and multinuclear solid‐state Nuclear Magnetic Resonance spectroscopy (ssNMR), coupled with density functional theory (DFT) calculations – identifies three primary surface species in Ag‐functionalized g‐C3N4: bis‐NHC‐Ag+, dispersed Ag+ sites, and physisorbed molecular precursor. These findings highlight a dynamic grafting process and provide insights into the surface coordination chemistry of functionalized g‐C3N4 materials.
Synthesis and Characterization of Lithium Pyrocarbonate (Li2[C2O5]) and Lithium Hydrogen Pyrocarbonate (Li[HC2O5])
Authors: Spahr Dominik , Bayarjargal Lkhamsuren , Bykov Maxim , Brüning Lukas , Jurzick Pascal L. , Milman Victor , Giordano Nico , Mezouar Mohamed , Winkler Björn
Published: November 2024

The anhydrous pyrocarbonate and the first hydrogen pyrocarbonate Li[HC2O5] have been synthesized in a laser‐heated diamond anvil cell at moderate pressures (
 GPa). The structures of the two compounds have been obtained from single crystal X‐ray diffraction data. Raman spectroscopy and DFT calculations have been employed to further characterize their structure‐property relations. The present results significantly enlarge the group of inorganic pyrocarbonates by the discovery of the hydrogenated pyrocarbonate anion Li[HC2O5]−. In the structure of Li[HC2O5] there is a symmetric O−H−O arrangement at high pressures, which converts to a conventional O−H
O hydrogen bond upon pressure release.
Biomimetic Elastic Single‐Atom Protrusions Enhance Ammonia Electrosynthesis
Authors: Sun Yuntong , Huang Yin , Yao Fanglei , Tian Meng , Wang Jin , Fan Wenjun , Zhu Junwu , Lee Jong‐Min
Published: November 2024

Electrocatalytic nitrogen (N2) reduction reaction (eNRR) is a promising route for sustainable ammonia (NH3) generation, but the eNRR efficiency is dramatically impeded by sluggish reaction kinetics. Herein, inspired by the dynamic extension‐contraction of sea anemone tentacles in response to environmental changes, we propose a biomimetic elastic Mo single‐atom protrusion on vanadium oxide support (pSA Mo/VOH) electrocatalyst featuring a symmetry‐breaking Mo site and an elastic Mo−O4 pyramid for efficient eNRR. In situ spectroscopy and theoretical calculations reveal that the protruding Mo‐induced symmetry‐breaking structure optimizes the d‐electron filling of Mo, enhancing the back‐donation to the π* antibonding orbital, effectively polarizing the N≡N bond and reducing the barrier from *N2 to *N2H. Notably, the elastic Mo−O4 pyramidal structure of pSA Mo provides a dynamic Mo−O microenvironment during continuous eNRR processes. This optimizes the electronic structure of the Mo sites based on different reaction intermediates, enhancing the adsorption of various N intermediates and maintaining low barriers throughout the six‐step hydrogenation process. Consequently, the elastic pSA Mo/VOH exhibits an excellent NH3 yield rate of 50.71±1.12 μg h−1 mg−1 and a Faradaic efficiency of 35.38±1.03 %, outperforming most electrocatalysts.
Comediating Adsorption and Electron Transfer via Dual‐Active Site Catalyst Construction for Improving the Treatment of Extraction Wastewater
Authors: Wu Meirong , Li Jiexiang , Sun Wei , Yang Yue
Published: November 2024

Solvent extraction is widely applied, while extraction wastewater treatment remains a huge challenge because of the stability of extractants. Heterogeneous Fenton‐like catalysis is a promising method, but the short half‐life of hydroxyl radicals (⋅OH) generated by hydrogen peroxide (H2O2) activation results in unsatisfactory ⋅OH utilization and organics removal. Herein, an efficient strategy for treating extraction wastewater based on comediating adsorption and electron transfer by fluorine and nitrogen co‐doped carbon (FNC) catalyst with dual‐active site was developed. Specially, N sites adsorb organics and F sites activate H2O2, shortening the migration distance of ⋅OH. Theoretical calculation and di(2‐ethylhexyl) phosphoric acid (D2EHPA) extraction wastewater degradation experiment showed that F site with electron acquisition can transfer electrons provided by electron‐rich D2EHPA enriched at N sites to H2O2, facilitating the continuous generation of ⋅OH through lowering the energy barrier for H2O2 activation. As a result, 96.49 % D2EHPA in simulated wastewater and 90.26 % total organic carbon in real extraction wastewater were removed. Moreover, FNC catalyst exhibited excellent reusability and ionic adaptability, and can be extended to the removal of various extractants. The proposed dual‐active site catalyst provides an effective strategy for Fenton‐like reaction to treat refractory extraction wastewater, promoting sustainable development of solvent extraction industry.
Copper‐Catalyzed Simultaneous Dehydrogenation and Enantioselective Allylic Oxidation of Alkanes Using Chiral Heterogeneous Ligands to Produce Allylic Esters and Theoretical Investigation of the Mechanism
Authors: Majidian Shiva , Rashid Hersh I. , Naghdi Yunes , Irani Mehdi , Samadi Saadi
Published: November 2024

A new asymmetric method for preparing chiral allylic esters from various unactivated alkanes through simultaneous dehydrogenation and enantioselective allylic oxidation in the presence of chiral heterogeneous oxazoline–based ligands is reported for the first time. For this purpose, chiral amino oxazoline ligands, synthesized from chiral amino alcohols and cyanogen bromide, were immobilized on modified MCM‐41 mesoporous silica. These chiral heterogeneous ligands were then characterized using Fourier‐transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and Brunauer–Emmett–Teller and Barrett–Joyner–Halenda techniques. Finally, copper complexes of these ligands were employed in the synthesis of chiral allylic esters, achieving the best result with a 90% yield and 77% enantiomeric excess. Evaluation of the recyclability of the chiral heterogeneous catalysts revealed that they can be reused three times without a noticeable reduction in the results. In addition, the mechanism of formation of the chiral allylic esters was investigated using a density functional theory method.
Crystal Structures and Biological Profiles of Novel Tridentate Schiff Bases Nickel (II) Complexes
Authors: Özbağcı Duygu İnci , Erdağı Sevinç İlkar , Aydın İpek , Aydın Rahmiye , Arı Ferda , Zorlu Yunus
Published: November 2024

Novel bioactive ternary nickel (II) complexes, [Ni(5BrSal‐Phe)(phen)] (1) and [Ni(5BrSal‐Tyr)(phen)] (2) (5BrSal‐Tyr: Schiff base derived from 5‐bromosalicylaldehyde and L‐tyrosine, 5BrSal‐Phe: Schiff base derived from 5‐bromosalicylaldehyde and L‐phenylalanine, phen: 1,10‐phenanthroline), have been synthesized and characterized by electronic absorption spectroscopy, CHN, FTIR, ESI‐MS and X‐ray crystallography techniques. Interaction of the complexes with biomolecules (calf thymus DNA (CT‐DNA) and bovine serum albumin (BSA)) has been investigated by electronic absorption and fluorescence spectroscopy. The results show that the complexes can bind to CT‐DNA via a minor groove binding mode. Moreover, the fluorescence quenching mechanism between the complexes and BSA is a static quenching process. The antiproliferative activities of the complexes against breast cancer cells (MCF‐7 and MDA‐MB‐231) and healthy breast epithelial cells (MCF‐10A) were investigated. The complex 2 was found to have promising antiproliferative activity in selected cell line, with lower IC50 values than cisplatin. Molecular docking studies suggest that the complexes may serve as potential chemotherapeutic agents. These complexes have been observed to interact with various targets within cells, including the epidermal growth factor receptor (EGFR), bovine serum albumin (BSA), and B‐DNA. Analyses indicate that these interactions are supported not only by conventional hydrogen bonds but also van der Waals forces and π‐π interactions. Additionally, determining binding constants and regions enhances our understanding of how the complexes interact with target molecules. The results emphasize the importance of the complexes in cancer therapy by highlighting the necessity of understanding their molecular‐level interactions with targets.
Enhancing the Light‐Driven Photocatalytic Degradation Activity of ZnO Nanoparticles With the Synergistic Incorporation of Er and Tb Elements
Authors: Slimani Y. , Mohamed M. J. S. , Sivakumar R. , Gondal M. A. , Vignesh R. , Thakur A. , Baykal A. , Nawaz M. , Almessiere M. A.
Published: November 2024

The existence of organic pollutants in aqueous media has become a vital issue and a critical threat to human health, where organic toxic dyes represent the major contaminants in wastewater. Over the past few years, photocatalytic techniques have garnered a lot of interest in dye removal from wastewater. In this study, a series of ErxTbxZn1 − 2xO nanophotocatalysts (where x = 0.00, 0.01, 0.03, and 0.05) were synthesized and coded as ZET0, ZET1, ZET2, and ZET3 NPs (nanoparticles). The chemical and physical characteristics of the NPs were investigated using Fourier‐transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy‐dispersive X‐ray (EDX) spectroscopy, and ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS) techniques. Further examination by performing photocatalytic experiments, ZET1 NPs demonstrated effective Rhodamine B (RhB) dye degradation within 60 min. It was found that the kinetic rate constant values were 0.008, 0.097, 0.050, and 0.040 min−1 for ZET0, ZET1, ZET2, and ZET3 NPs, respectively. Aside from their remarkable photocatalytic degradation efficiency, these ZET1 photocatalysts are highly stable even after five consecutive cycles. In addition, the active species test revealed that the primary oxidation species involved in the photocatalytic process are holes (h+) and hydroxyl radicals (•OH), and a possible photocatalytic mechanism for degrading RhB by ZET1 photocatalysts was tentatively proposed. The enhancement of the photocatalytic degradation efficiency is due to the low recombination rate of photogenerated charge carriers, as well as a strong synergistic impact of Tb, Er, and ZnO components. Thus, the current study could offer a versatile strategy for the design of new and effective nano photocatalysts for wastewater purification in the future.
Utilization of poly(methacrylic acid)‐rice straw graft copolymers for Pb2+ ions removal from wastewater: Synthesis, characterization, and adsorption studies
Authors: Mostafa Khaled , Saleh Basma , El‐Sanabary Azza A.
Published: November 2024

Rice straw bio waste was converted into a high‐performance adsorbent for Pb2+ ions removal by grafting it with methacrylic acid using microwave irradiation. For this purpose, six levels of poly(MAA)‐rice straw graft copolymers having different graft yields % with increasing order and designated as (PMAARSGC‐I to PMAARSGC‐VI) were prepared and characterized using FTIR, SEM, XRD, TGA, zeta potential and BET analysis. Different factors affecting the Pb2+ removal expressed as adsorption capacity such as pH, extent of grafting, treatment time, and lead ions concentrations were studied in detail. Various kinetics models (pseudo‐first‐order, pseudo‐second‐order, Elovich, and intraparticle diffusion), isothermal (Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich) and thermodynamic studies have been applied. The results demonstrated that (a) FT‐IR, SEM, XRD, TGA, zeta potential, and BET analysis confirmed the formation of carboxyl groups onto the graft copolymer, (b) the adsorption capacity increased with increasing the Pb2+ concentration and extent of grafting within the range studied; pH from 1 to 6; and the adsorption time up to 60 min then leveled off afterward, (c) maximum adsorption capacity of poly(MAA)‐rice straw graft copolymer was found to be 118 mg/g at pH 6, 200 mg/L lead ions concentration, adsorption time, 60 min, and 0.1 g adsorbent, (d) the kinetic and isothermal studies revealed that the privilege of Elovich model and pseudo‐second‐order rate equation as well the Langmuir model with more R2 value. The calculated thermodynamic parameters indicated that the adsorption process was achievable, spontaneous, and exothermic at 298–318 K. Finally, the preliminary adsorption mechanism representing the interaction between the adsorbent and adsorbate has been projected.
Synergistic effects of tertiary amine and imidazole accelerators on epoxy resin curing
Authors: Liu Shuangyi , Liu Zhaojun , Jiang Dong , Zong Ran , Zhong Aosheng , Shentu Baoqing
Published: November 2024

Abstarct

In order to improve the curing rate, this study investigated the influence of various accelerators and their combinations on the curing behavior of epoxy resins. differential scanning calorimetry (DSC) was used to analyze the curing behavior of various accelerators in diglycidyl ether of the bisphenol A epoxy resin and the methyl hexahydrophthalic anhydride curing system, and activation energies were calculated using the Kissinger and Ozawa models. The results indicated a self‐catalytic characteristic in the curing process and showed that the activation energies for tris(dimethylaminomethyl)phenol (DMP‐30) and 1‐cyano‐2‐ethyl‐4‐methylimidazole (2E4MZ‐CN) were significantly lower compared to N,N‐dimethylbenzylamine, demonstrating higher curing reactivity. Furthermore, a novel strategy combining tertiary amine accelerator (DMP‐30) and imidazole accelerator (2E4MZ‐CN) was proposed and the activation energy variations with the degree of cure were analyzed employing the KAS method. When the mass ratio of DMP‐30 to 2E4MZ‐CN was 1:3, the activation energy was 59.08 kJ/mol, approximately 12% lower than using a single accelerator, which indicated the synergistic effects of the accelerators. Finally, the mechanism of synergistic effect of tertiary amine and imidazole accelerators on epoxy resin curing were proposed.
3D printing molding of UV‐curing liquid silicone rubber by UV follow curing
Authors: Liu Bing , Ma Baoji
Published: November 2024

Silicone rubber is renowned for its excellent mechanical properties and high biocompatibility. 3D printing enables the realization of more complex structures and the development of more flexible and diverse functions, providing more opportunities and a more comprehensive range of applications in aerospace, biomedical, flexible wearable, soft robotics, and other fields. However, silicone rubber is often hindered by poor rheology and low curing efficiency, which significantly affects the forming performance of the parts. Therefore, this study introduces a UV‐follow curing method for direct ink writing (UFC‐DIW) utilizing UV‐curable silicone rubber. First, a kind of liquid silicone rubber (UV‐LSR) capable of rapid curing under UV light was synthesized, both its curing kinetics and rheological behavior were thoroughly investigated. Then, UV‐LSR inks with lower shear stress were printed using the UFC‐DIW method. A comparative analysis was conducted between the overall structure produced via UFC‐DIW and parts molded through postprinting integral curing methods. The results show that while parts cured postprinting exhibit deformation correlated with printing height, those fabricated using UFC‐DIW maintain structural integrity without deformation. It demonstrates that the UFC‐DIW method can effectively improve the formability of the parts.
Tunable Circularly Polarized Luminescence Enabled by Photo‐induced Phase Transition in a Blue‐phase Liquid Crystal with a Wide Room‐temperature Window
Authors: Kang Wenxin , Meng Xianyu , Ren Tianqi , Guo Jinbao
Published: November 2024

Chiral luminescent liquid crystal (LC) materials with switchable circularly polarized luminescence (CPL) signals have received extensive attention, in which the use of light stimulation to achieve different CPL states is of great significance. However, there are very few reports on the generation and regulation of CPL signals enabled by blue phase LC (BPLC). Herein, achieving CPL signal inversion based on the phase transition induced by light/temperature stimulation in a BPLC system with a wide room‐temperature window is reported. A binaphthalene azo‐based chiral photoswitch (S)‐switch 3 with high helical twisted power (HTP) and large HTP variation is synthesized, and a BP system with a wide room temperature range is further fabricated by doping (S)‐switch 3 and a fluorescence molecule into a bulk LC. By regulating the doping amount of (S)‐switch 3, a phase transition from BP to cholesteric (Ch) phase at room temperature is observed upon 365 nm UV light irradiation or during cooling process, and the polarization inversion of CPL signal is correspondingly found due to the different CPL generation mechanisms of BPLC and CLC. This study provides a new strategy for the flexible regulation of CPL signals in a BPLC system.
High‐Performance Supercapacitor Electrodes Based on Porosity‐Controllable Carbon Paper by Centrifugal Spinning
Authors: Ji Boshi , Wu Zhiyu , Hu Jun , Huang Chen , Lyu Pei , Pan Heng , Ren Jie , Shang Bin , Liu Xin
Published: November 2024

Carbon paper is widely utilized in supercapacitors primarily for its notable attributes, including high specific surface area, commendable electrical conductivity, and excellent chemical stability. Then investigate the effect of carbon paper with different porosities as supercapacitor substrates on the electrochemical performance of electrodes. Meanwhile, tungsten oxide is grown on the surface of carbon paper using the hydrothermal method to test the electrochemical performance of the composite electrode. The prepared carbon paper and oxygen‐deficient tungsten oxide (WOx) composite electrode (CP@WOx) exhibit an area‐specific capacitance of 915.8 mF/cm2 at a current density of 5 mA/cm2. In addition, the electrode exhibits good cycling stability. After 20,000 cycles, the capacitance remains 104.1 % of the original capacity at 50 mA/cm2 current density. Solid‐state symmetric supercapacitors assembled using CP@WOx electrode exhibit excellent performance in terms of surface energy density of 6.25 μWh/cm2 (at a power density of 0.6 mW/cm2) and maintain 100.4 % of their original capacity after 7000 charge/discharge cycles. Relying on the higher productivity advantage of centrifugal spinning technology over electrostatic spinning technology and other preparation processes, this study develops a new way of thinking for the large‐scale production of composite electrode materials, which has more considerable potential for large‐scale development.
Unleashing viral mimicry: A combinatorial strategy to enhance the efficacy of PARP7 inhibitors
Authors: Manetsch Patrick , Hottiger Michael O.
Published: November 2024

Cancer cells exploit mechanisms to evade immune detection triggered by aberrant self‐nucleic acids (NA). PARP7, a key player in this immune evasion strategy, has emerged as a potential target for cancer therapy. PARP7 inhibitors reactivate NA sensing, resulting in type I interferon (IFN) signaling, programmed cell death, anti‐tumor immunity, and tumor regression. Cancer cells with elevated IFN‐stimulated gene (ISG) scores, representing a viral mimicry‐primed state, are particularly sensitive to PARP7 inhibition. This review focuses on the endogenous sources of NA in cancer and the potential to exploit elevated aberrant self‐NA in cancer therapy. We describe strategies to increase cytoplamic NA levels, including targeting epigenetic control, DNA damage response, and mitochondrial function. We also discuss targeting RNA processing pathways, such as splicing and RNA editing, to enhance the immunostimulatory potential of existing NA. Combining PARP7 inhibitors with NA elevating strategies may improve cancer immunotherapy, especially for tumors with high ISG scores.
Spectral Investigation of Enhanced Orange Emission in Eu3+ Activated LaPO4 Nanophosphors Through Codoping With Na+ and Bi3+ Ions
Authors: Aswathy R Chandran , Linju Ann Jacob , Issac Paul , Gijo Jose , Prijil Mathew , S Sisira
Published: November 2024

Lanthanum phosphate is a well‐known potential host for rare earth activators for phosphor‐converted white LED application. Na+ and Bi3+ codoped Eu3+ activated LaPO4 nanophosphor is successfully synthesized using citrate‐based hydrothermal method at ambient condition and confirmed by XRD, EDS and XPS analysis. The excitation spectra of the sample exhibit sharp f‐f characteristics peak of Eu3+ at 393 nm that is found to be the most dominant. The comparative photoluminescence studies of La1‐xPO4:xEu3+(x = 0.10), La1‐x‐y PO4:xEu3+, yNa+(x = 0.10, y = 0.05), and La1‐x‐y‐zPO4:xEu3+, yNa+, zBi3+ (x = 0.10, y = z = 0.05) reveal a progressive enhancement of the orange emission from Eu3+ as Na+ and (Na+, Bi3+) ions are incorporated into the LaPO4 matrix. The dominance of 5D0‐7F1 magnetic dipole transition contributing a major part of orange luminescence of the nanophosphors and the symmetric site occupancy of Eu3+ was justified from the observed trend of in the Judd–Ofelt intensity parameters. The CIE studies confirm the improvement in color purity of emission from 32.5% to 90.6% due to the presence of Na+ and Bi3+ions.
Method development and validation of an analytical quality by design ultrafast liquid chromatographic method for the determination of bedaquiline from pharmaceutical bulk and nanoemulsions
Authors: Ajayi Taiwo Oreoluwa , Poka Madan Sai , Witika Bwalya Angel
Published: November 2024

Bedaquiline (BDQ) is a drug used to treat multidrug‐resistant tuberculosis (MDR‐TB). It exhibits exposure‐dependent efficacy in eliminating Mycobacterium tuberculosis (Mtb). An easy, efficient and precise reverse‐phase ultrafast liquid chromatography (RP‐UFLC) method was developed to validate the free base of the antitubercular medication BDQ. BDQ was separated using a 10:90 v/v mobile phase of ammonium acetate buffer solution (pH = 5.4) and high‐performance liquid chromatography–grade methanol, with a flow rate of 1.5 mL/min and a UV detection wavelength of 226 nm. By using the Box–Behnken design (BBD) and response surface methodology (RSM), the method was optimised by varying critical analytical attributes (CAA) and critical performance attributes (CPAs) namely ammonium acetate fraction (%), flow rate (ml/min), buffer system molarity (M) and pH. BDQ was eluted at 7.5 min utilising isocratic elution. The method was linear in the concentration range of 0.5–300 μg/mL with limit of detection values of 0.039 μg/mL and limit of quantification of 0.12 μg/mL. The results indicate that this validated method can be used as an alternative method for assay of BDQ.