bluuebunny/crossref_metadata_2025 huggingface dataset:
TADF Regulation by Tuning Keto‐Energy Levels, ISC/RISC Equilibrium in Coordination Polymers with Excited State Intramolecular Proton Transfer (ESIPT)
Authors: Fu Peng‐Yan , Yi Shao‐Zhe , Wang Zhong‐Hao , Huang Yan‐Ting , Fan Ya‐Nan , Pan Mei
Published: February 2024

Thermally activated delayed fluorescence (TADF) and long persistent luminescence (LPL) are emerging photophysical hotspots, which involve the singlet/triplet excited states and two‐way energy transfer processes between them via intersystem crossing (ISC) or reverse intersystem crossing (RISC). Herein, a new tactic is reported for the regulation of keto‐energy levels and ISC/RISC equilibrium via the introduction of electron‐withdrawing fluorine in a series of excited state intramolecular proton transfer (ESIPT) ligands and corresponding Cd(II) coordination polymers. Among them, the fluorine p‐substituted to the hydroxy group along the nodal plane on the phenol site improves the thermodynamic stability of the keto‐isomers of the ligand, thereby lowering the keto‐energy level and promoting the ESIPT process effectively. Uniquely, the lower‐energy keto excited state makes the ISC/RISC equilibrium shift to the direction of RISC progress, and thus arousing efficient TADF in the constructed coordination polymer. A comprehensive transient photophysical and theoretical study verifies the greatly promoted RISC progress, rather than suppressed ISC is aroused in the p‐substituted system, suggesting a clear‐cut strategy in the design of coordination polymers with good TADF performance.
Water regime and fertilizer‐phosphorus source effects on greenhouse gas emissions from rice
Authors: Della Lunga Diego , Brye Kris R. , Roberts Trenton L. , Brye Jonathan , Evans‐White Michelle , Lessner Daniel J. , Henry Christopher G.
Published: February 2024

Greenhouse gas (GHG) emissions from rice (Oryza sativa) systems have been correlated to water management practice, but to date, no study has directly evaluated three main GHGs (i.e., methane [CH4], nitrous oxide [N2O], and carbon dioxide [CO2]) under flood‐ and furrow‐irrigated conditions at the same time as affected by various fertilizer‐phosphorus (P) sources, in particular the reportedly slow‐release struvite‐P source. Therefore, the objective of this study was to evaluate the effect of water regime (flooded and furrow‐irrigated) and fertilizer‐P source (diammonium phosphate, chemically precipitated struvite, electrochemically precipitated struvite [ECST], triple superphosphate, and an unamended control) on GHG emissions and two‐ and three‐gas global warming potentials (GWP* and GWP, respectively) in the greenhouse. Methane emissions were 10 times greater (p < 0.05) under flooded (29.4 kg CH4 ha−1 season−1) than under furrow‐irrigated conditions (2.9 kg CH4 ha−1 season−1), and four times lower (p < 0.05) with ECST (3.4 kg CH4 ha−1 season−1) than other fertilizer‐P sources, while CO2 emissions were three times greater (p < 0.05) under furrow‐irrigated (23,428 kg CO2 ha−1 season−1) than under flooded (8290 kg CO2 ha−1 season−1) conditions. The GWP* under furrow‐irrigated conditions was almost 40% lower (p < 0.05) than under flooded conditions. Although N2O emissions were unaffected by fertilizer‐P source, the N2O contribution to GWP* was more than 80% under furrow‐irrigated conditions. Flood‐ and furrow‐irrigated water regimes require diversified approaches in GHG mitigation, where the best management for ECST needs to be more fully evaluated.
Cotton cultivar response to potassium fertilizer under irrigated and dryland conditions
Authors: Davis Savana , Gajula Praveen , Dodds Darrin , Krutz Jason , Gore Jeff , Varco Jac , Raper Tyson , Dhillon Jagmandeep
Published: February 2024

Cotton (Gossypium hirsutum L.) cultivars vary in their response to environmental factors. Recently, interest in cotton cultivars' response to varying potassium (K) fertilizer application rates and irrigation has increased. As such, the effect of cotton varieties (early and mid‐maturing), K fertilizer application rates, and irrigation on cotton growth, development, and yield were investigated in Starkville, MS, on two soil mapping units (SMUs): a Leeper silty clay loam (LSCL) and a Marietta fine sandy loam (MFSL). Cotton plant height was positively correlated with SMU, especially LSCL, reaching 60–110 cm on average, in both irrigated and rainfed conditions. Cotton lint yield, fiber quality, and leaf K concentration responded to K and irrigation, and these responses were SMU specific. Particularly, in LSCL, the early‐maturing cultivar, DP 1518 B2XF, responded to K application rate in a positive linear manner in terms of lint yield under both irrigated and rainfed conditions, whereas mid‐maturing DP 1646 B2XF did not. Moreover, lint yield in irrigated MFSL soil increased with K application rate, whereas no responses were observed in rainfed conditions. These data suggest that irrigation, SMU, and cultivar combination could have an impact on K response of cotton and should be considered when making fertility recommendations or decisions.
Age barriers in allogeneic hematopoietic cell transplantation: Raising the silver curtain
Authors: Munshi Pashna N. , McCurdy Shannon R.
Published: February 2024

Allogeneic hematopoietic cell transplantation (HCT) is no longer exclusively for the young. With an aging population, development of non‐intensive remission‐inducing strategies for hematologic malignancies, and novel graft‐versus‐host disease‐prevention platforms, an older population of patients is pursuing HCT. The evolving population of HCT recipients requires an overhaul in the way we risk‐stratify and optimize patients prior to HCT. Here, we review the history and current state of HCT for older adults and propose an assessment and intervention flow to bridge the gaps in today's clinical guidelines.
On‐Surface Synthesis of Silole and Disila‐Cyclooctene Derivatives
Authors: Sun Kewei , Kurki Lauri , Silveira Orlando J. , Nishiuchi Tomohiko , Kubo Takashi , Foster Adam S. , Kawai Shigeki
Published: February 2024

The incorporation of Si atoms into organic compounds significantly increases a variety of functionality, facilitating further applications. Recently, on‐surface synthesis was introduced into organosilicon chemistry as 1,4‐disilabenzene bridged nanostructures were obtained via coupling between silicon atoms and brominated phenyl groups at the ortho position on Au(111). Here, we demonstrate a high generality of this strategy via syntheses of silole derivatives and nanoribbon structures with eight‐membered sila‐cyclic rings from dibrominated molecules at the bay and peri positions on Au(111), respectively. Their structures and electronic properties were investigated by a combination of scanning tunneling microscopy/spectroscopy and density functional theory calculations. This work demonstrates a great potential to deal with heavy group 14 elements in on‐surface silicon chemistry.
Binding FSI− to Construct a Self‐Healing SEI Film for Li‐Metal Batteries by In situ Crosslinking Vinyl Ionic Liquid
Authors: Qin Yinping , Wang Hefeng , Zhou Jingjing , Li Ruyi , Jiang Chun , Wan Yi , Wang Xiaoyi , Chen Zhenlian , Wang Xiaolei , Liu Yang , Guo Bingkun , Wang Deyu
Published: February 2024

The solid electrolyte interphase (SEI) membrane on the Li metal anode tends to breakdown and undergo reconstruction during operation, causing Li metal batteries to experience accelerated decay. Notably, an SEI membrane with self‐healing characteristics can help considerably in stabilizing the Li‐electrolyte interface; however, uniformly fixing the repairing agent onto the anode remains a challenging task. By leveraging the noteworthy film‐forming attributes of bis(fluorosulfonyl)imide (FSI−) anions and the photopolymerization property of the vinyl group, the ionic liquid 1‐vinyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (VMI‐FSI) was crosslinked with polyethylene oxide (PEO) in this study to form a self‐healing film fixing FSI− groups as the repairing agent. When they encounter lithium metal, the FSI− groups are chemically decomposed into LiF & Li3N, which assist forming SEI membrane on lithium sheet and repairing SEI membrane in the cracks lacerated by lithium dendrite. Furthermore, the FSI− anions exchanged from film are electrochemically decomposed to generate inorganic salts to strengthen the SEI membrane. Benefiting from the self‐healing behavior of the film, Li/LiCoO2 cells with the loading of 16.3 mg cm−2 exhibit the initial discharge capacities of 183.0 mAh ⋅ g−1 and are stably operated for 500 cycles with the retention rates of 81.4 % and the average coulombic efficiency of 99.97 %, operated between 3.0–4.5 V vs. Li+/Li. This study presents a new design approach for self‐healing Li metal anodes and durable lithium metal battery.
Förster Resonance Energy Transfer: Stimulus‐Responsive Purely Organic Room Temperature Phosphorescence through Dynamic B−N bond
Authors: Tu Liangjing , Chen Yi , Song Xiaojuan , Jiang Wanqing , Xie Yujun , Li Zhen
Published: February 2024

Recently, stimulus‐responsive organic materials with room‐temperature phosphorescence (RTP) properties have attracted significant attention owing to their potential applications in chemical sensing, anticounterfeiting, and displays. However, molecular design currently lacks systematicity and effectiveness. Herein, we report a capture‐release strategy for the construction of reversible RTP via B/N Lewis pairs. Specifically, the RTP of the Lewis acid of 7‐bromo‐5,9‐dioxa‐13b‐boranaphtho[3,2,1‐de]anthracene (BrBA) can be deactivated through capturing by the Lewis base, N,N‐diphenyl‐4‐(pyridin‐4‐yl)aniline (TPAPy), and reactivated by dissociation of B−N bonds to release BrBA. Reversible RTP is attributed to the exceptional self‐assembly capability of BrBA, whereas the tunable RTP colors are derived from distinct Förster resonance energy transfer (FRET) processes. The potential applications of RTP materials in information storage and anti‐counterfeiting were also experimentally validated. The capture‐release approach proposed in this study offers an effective strategy for designing stimulus‐responsive materials.
Mixed‐Linker Strategy for the Construction of Sulfone‐Containing D–A–A Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Production
Authors: Shu Chang , Yang Xiaoju , Liu Lunjie , Hu Xunliang , Sun Ruixue , Yang Xuan , Cooper Andrew I. , Tan Bien , Wang Xiaoyan
Published: February 2024

The solar‐driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h−1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment.
Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks
Authors: Su Alice Y. , Apostol Petru , Wang Jiande , Vlad Alexandru , Dincă Mircea
Published: February 2024

Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3‐TAT)2 (TAT=triazatruxene; R=H, Et, n‐Bu, n‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3‐TAT)2 to Ni3(HIBu3‐TAT)2. Partial exfoliation of Ni3(HIBu3‐TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.
Effect of dispersants on the hydroxyapatite‐filled natural rubber biocomposites with enhanced functional properties
Authors: Sowińska‐Baranowska Anna , Maciejewska Magdalena
Published: February 2024

The aim of this work was application of the hydroxyapatite (HAP) in various amounts by weight as a filler of natural rubber (NR) biocomposites. Innovatively, silanes, that is, (3‐aminopropyl)‐triethoxysilane (APTES) and bis[3‐(triethoxysilyl)propyl] tetrasulfide (TESPTS), surfactant, that is, cetyltrimethylammonium bromide (CTAB), and alkylimidazolium ionic liquids (ILs) with halide anions, that is, 1‐butyl‐3‐methylimidazolium chloride (BmiCl) and 1‐decyl‐3‐methylimidazolium bromide (DmiBr), were used to improve the dispersion of the HAP and curatives particles in the rubber matrix, and consequently the curing characteristics and properties of NR biocomposites. The influence of HAP and dispersants on the crosslink density, tensile properties, thermal stability, resistance to thermo‐oxidative aging, and ability to damp vibration of vulcanizates were investigated. It has been proven, that HAP can be efficiently used as a filler of NR biocomposites alternatively to commercial inactive or active fillers, for example, chalk, talc, or silica. The optimal HAP content is 30 phr. HAP did not detrimentally affect the curing characteristics of NR composites, crosslink density, and damping properties of the vulcanizates, while significantly raised their tensile strength, thermal stability, and resistance to thermo‐oxidative aging. Most importantly, CTAB and ILs considerably improved the dispersion of HAP and curatives particles in the NR matrix and consequently lowered the vulcanization temperature by approximately 25°C and enhanced by approximately 50% the crosslink density and tensile strength of the NR biocomposites.
Insights into the tiger stripe phenomenon of polypropylene and its blend in injection molding with a rapid heat exchange mold
Authors: Luo Guojun , Ou Xianglin , Peng Li , Wang Lin , Song Wenbo , Liu Qiang , Huang Xianbo , Niu Yanhua , Li Guangxian
Published: February 2024

To examine the formation of tiger stripes (TS) phenomenon on the surface of the injection molding parts, a home‐made injection mold with a rapid heat exchange system and in situ measurement of pressure and temperature was designed and manufactured. Based on this special mold, the TS diagrams as a function of mold temperature and injection pressure for isotactic polypropylene (iPP) and its blend with a type of polyolefin elastomer (iPP/POE) were explored for the first time. It is found that there exists a critical mold temperature and a critical injection pressure for the TS appearance or disappearance in both systems. The critical temperatures of TS disappearance for iPP and iPP/POE are ~50 and ~ 120°C, respectively. As evidenced by the correlation between melt pressure drop and TS appearance, the wall slip mechanism is regarded as the main cause of TS formation. Compared with the critical shear stress of wall slip (σw) in totally molten PP, the lower σw value in this study further indicates that the wall slip could be facilitated by the crystallization of iPP during injection. Combined with white light interferometer, micro‐area x‐ray diffraction nanoindentation and scanning electron microscopy, it is demonstrated that the cloudy and glossy region of TS in pure iPP system could be distinguished by surface crystallinity. In the blend system, however, the rubber phase orientation as a dominant factor contributes to the glossiness of TS.
Primary Antioxidant Power and Mpro SARS‐CoV‐2 Non‐Covalent Inhibition Capabilities of Miquelianin
Authors: Spiegel Maciej , Prejanò Mario , Russo Nino , Marino Tiziana
Published: February 2024

The antioxidant power of quercetin‐3‐O‐glucuronide (miquelianin) has been studied, at the density functional level of theory, in both lipid‐like and aqueous environments. In the aqueous phase, the computed pKa equilibria allowed the identification of the neutral and charged species present in solution that can react with the ⋅OOH radical. The Hydrogen Atom Transfer (HAT), Single Electron Transfer (SET) and Radical Adduct Formation (RAF) mechanisms were considered, and the individual, total and fraction corrected rate constants were obtained. Potential non‐covalent inhibition of Mpro from SARS‐CoV‐2 by miquelianin has been also evaluated.
Disturbance observer‐based control for cable‐driven parallel robots with external disturbance using deep reinforcement learning
Authors: Lu Yanqi , Yao Weiran , Wu Chengwei , Li Xiaolei , Sun Guanghui
Published: February 2024

In cable‐driven parallel robots (CDPRs) practical applications, external disturbances inevitably influence the actuator performance, leading to low positioning accuracy of end‐effector (EE), and even system crashes. This paper addresses a disturbance observer‐based control scheme using deep reinforcement learning (RL) to suppress the effect of external disturbances. A controller via the non‐singular terminal sliding mode (NTSM) is proposed to enhance the system robustness. The estimation of the disturbance is investigated, and the deep RL is employed to enhance the model‐based disturbance observer, namely, the RLDO, and a corresponding controller via NTSM (RLDO‐NTSMC) is proposed. Simulations and experimental results validate that the RLDO effectively improves the estimation accuracy, and the RLDO‐NTSMC significantly increases the control accuracy of CDPRs. The root mean square errors of the EE's positioning errors controlled by the RLDO‐NTSMC decreased by over 93% compared with the classical augmented proportional–derivative (APD) controller.
Challenges and prospects in energetic application of Pithecellobium dulce (Roxb.) Benth as a bioenergy tree
Authors: Aleman‐Ramirez Jose Luis , Okoye Patrick U. , Torres‐Arellano Soleyda , Sebastian Pathiyamattom J.
Published: February 2024

A report on the Pithecellobium dulce tree is provided in this review. The main characteristics of the tree, its chemical composition, traditional applications and future application in the bioenergy area are addressed. Pithecellobium dulce is a leguminous tree characterized by being fast growing, nitrogen fixing and largely available. In addition, it is distinguished by growing in different types of soils from acid to alkaline and with little water. This review could serve as a scientific basis to promote and carry out new research work focused on individual and comprehensive use for various bioenergetic processes, from the different parts that make up the P. dulce tree such as its leaves, pods, branches, flowers, fruit and seeds. Among the bioenergetic processes that could be developed are the production of bioethanol, biodiesel, biogas, heterogeneous catalysts, biochar, activated carbon and nanoparticles, among other applications.
Performance of 4,5‐diphenyl‐1H‐imidazole derived highly selective ‘Turn‐Off’ fluorescent chemosensor for iron(III) ions detection and biological applications
Authors: Rajendran Praveena , Murugaperumal Parvathavarthini , Nallathambi Sengottuvelan , Perdih Franc , Ayyanar Siva , Chellappan Selvaraju
Published: February 2024

Two fluorescent chemosensors, denoted as chemosensor 1 and chemosensor 2, were synthesized and subjected to comprehensive characterization using various techniques. The characterization techniques employed were Fourier‐transform infrared (FTIR), proton (1H)‐ and carbon‐13 (13C)‐nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization (ESI) mass spectrometry, and single crystal X‐ray diffraction analysis. Chemosensor 1 is composed of a 1H‐imidazole core with specific substituents, including a 4‐(2‐(4,5‐c‐2‐yl)naphthalene‐3‐yloxy)butoxy)naphthalene‐1‐yl moiety. However, chemosensor 2 features a 1H‐imidazole core with distinct substituents, such as 4‐methyl‐2‐(4,5‐diphenyl‐1H‐imidazole‐2‐yl)phenoxy)butoxy)‐5‐methylphenyl. Chemosensor 1 crystallizes in the monoclinic space group C2/c. Both chemosensors 1 and 2 exhibit a discernible fluorescence quenching response selectively toward iron(III) ion (Fe3+) at 435 and 390 nm, respectively, in dimethylformamide (DMF) solutions, distinguishing them from other tested cations. This fluorescence quenching is attributed to the established mechanism of chelation quenched fluorescence (CHQF). The binding constants for the formation of the 1 + Fe3+ and 2 + Fe3+ complexes were determined using the modified Benesi–Hildebrand equation, yielding values of approximately 2.2 × 103 and 1.3 × 104 M−1, respectively. The calculated average fluorescence lifetimes for 1 and 1 + Fe3+ were 2.51 and 1.17 ns, respectively, while for 2 and 2 + Fe3+, the lifetimes were 1.13 and 0.63 ns, respectively. Additionally, the applicability of chemosensors 1 and 2 in detecting Fe3+ in live cells was demonstrated, with negligible observed cell toxicity.
Inhibitory Effects of Endemic Thyme's Thymol‐Carvacrol Chemotype Essential Oil on Aspergillus Species with Free Radical Scavenging Properties
Authors: Mirahmadi Seyed Fazel , Shayganfar Alireza
Published: February 2024

There is a burgeoning focus on utilizing the antifungal and antioxidant properties of essential oils derived from various plants as a modern and natural approach to combat the growth of fungi that contaminate food. In this study, we used essential oils extracted from Thymus daenensis Celak. subsp. daenensis to address three mycotoxin‐producing species of Aspergillus, specifically A. flavus, A. parasiticus, and A. niger, all of which are recognized contaminants of food and agricultural products. Concurrently, the antioxidant properties of the essential oils were evaluated, revealing their noteworthy role in the antifungal activity. Essential oils were derived from T. daenensis subsp. daenensis was observed to have a significant inhibitory effect on all three species of Aspergillus, as evidenced by the minimum inhibitory concentration (MIC) ranging from 575 to 707 ppm and the half‐maximal inhibitory concentration (IC50) ranging from 237 to 280 ppm. These results confirm the strong antifungal activity of the essential oils. Furthermore, the essential oil exhibited free radical scavenging activity, resulting in an EC50 value of 37.1 μg/ml. In summary, T. daenensis subsp. daenensis essential oil demonstrated a competitive advantage over other similar plants and synthetic antibiotics. This indicates the promising potential of this essential oil as a natural antifungal agent to control Aspergillus growth and mycotoxin contamination. It offers an alternative or complementary approach to conventional antifungal agents and could be a valuable addition to the arsenal of natural remedies to address fungal contamination in food and agricultural products.
Ether Bond Cleavage of a Phenylcoumaran β‐5 Lignin Model Compound and Polymeric Lignin Catalysed by a LigE‐type Etherase from Agrobacterium sp.
Authors: Rashid Goran M. M. , Rivière Guillaume N. , Cottyn‐Boitte Betty , Majira Amel , Cézard Laurent , Sodré Victoria , Lam Richard , Fairbairn Julia A. , Baumberger Stéphanie , Bugg Timothy D. H.
Published: February 2024

A LigE‐type beta‐etherase enzyme from lignin‐degrading Agrobacterium sp. has been identified, which assists degradation of polymeric lignins. Testing against lignin dimer model compounds revealed that it does not catalyse the previously reported reaction of Sphingobium SYK‐6 LigE, but instead shows activity for a β‐5 phenylcoumaran lignin dimer. The reaction products did not contain glutathione, indicating a catalytic role for reduced glutathione in this enzyme. Three reaction products were identified: the major product was a cis‐stilbene arising from C−C fragmentation involving loss of formaldehyde; two minor products were an alkene arising from elimination of glutathione, and an oxidised ketone, proposed to arise from reaction of an intermediate with molecular oxygen. Testing of the recombinant enzyme against a soda lignin revealed the formation of new signals by two‐dimensional NMR analysis, whose chemical shifts are consistent with the formation of a stilbene unit in polymeric lignin.
Toward Rational Design of Nickel Catalysts for Thermocatalytic Decomposition of Methane for Carbon Dioxide‐Free Hydrogen and Value‐Added Carbon Co‐Product: A Review
Authors: Weber Robert S. , Xu Mengze , Lopez‐Ruiz Juan A. , Jiang Changle , Hu Jianli , Dagle Robert A.
Published: February 2024

Thermocatalytic decomposition of methane provides opportunities for hydrogen (H2) production with no emission of carbon dioxide. However, high‐value carbon products need to be produced for economic deployment of thermocatalytic decomposition and to achieve a minimum H2 selling price below the U.S, Department of Energy target of $ 1/kg H2. In this review, we re‐evaluate data on catalyst development reported in the literature and propose correlations between catalyst characteristics, catalytic stability, and properties of carbon co‐products. In the first part of the review, growth mechanisms for carbon nanotubes using state‐of‐the‐art chemical vapor deposition are reviewed to catalog the effects of catalyst characteristics, the influence of carbon sources, interactions between metal particles and supports, and metal particle sizes on carbon growth. In the second part, representative developments in mono‐, bi‐, and tri‐metallic nickel catalysts are highlighted. We present kinetic analysis of reactions catalyzed by mono‐metallic nickel catalysts, which generates a correlation between metal particle size and catalyst stability. Rational design of Ni‐based catalysts for TCD of methane requires attention to the size of the metal particle and effective normalization of the reaction rates. Further attention to the distribution of the metal particle sizes may help identify catalyst properties that contribute longevity and selectivity to processes that use them. While it is tempting to focus on the highest valued carbon products (e. g., CNTs and CFs), analysis of the markets for other carbon products suggests that a more flexible approach may generate comparable returns without the risk associated with specialization.
Electrochemical Impedance Spectroscopy of Li‐S Batteries: Effect of Atomic Vanadium‐ and Cobalt‐Modified Ketjen Black‐Sulfur Cathode, Sulfur Loading, and Electrolyte‐to‐Sulfur Ratio
Authors: Fazal Hira , Eroglu Damla , Kilic Aysegul , Ali Nazakat , Yan Changyu , Zai Jiantao , Qian Xuefeng
Published: February 2024

The polysulfide shuttle mechanism and insulating characteristics of sulfur and discharge products are the two major drawbacks of Li−S batteries. These increase internal cell resistances, resulting in low battery performance and life. In this study, we investigate the effect of cathode material on the cell resistances by preparing two different cathodes: by encapsulating sulfur (S) with pure Ketjen black (KBS) and with atomic vanadium and cobalt‐modified Ketjen black (VCKBS). In addition to the cathode material, the influence of crucial cell design parameters, namely electrolyte‐to‐sulfur (E/S) ratio and sulfur loading, on the cell resistances and battery performance is also compared. Electrochemical impedance spectroscopy (EIS) is applied to determine the individual cell resistances, whereas a system‐level performance model is used to estimate the system‐level specific energies and energy densities. The comparison of the cathodes shows that VCKBS significantly improves both cell‐ and system‐level performances, which are attributed to a significant decrease in cell resistances. The cells with higher sulfur loadings and lower E/S ratios show poorer performance for both cathodes. On the other hand, an E/S ratio of 6 mg L−1 can result in high cell‐ and system‐level performances for the VCKBS cathode.
A 30‐year overview of sodium‐ion batteries
Authors: Gao Yun , Zhang Hang , Peng Jian , Li Lin , Xiao Yao , Li Li , Liu Yang , Qiao Yun , Chou Shu‐Lei
Published: February 2024

Sodium‐ion batteries (NIBs) have emerged as a promising alternative to commercial lithium‐ion batteries (LIBs) due to the similar properties of the Li and Na elements as well as the abundance and accessibility of Na resources. Most of the current research has been focused on the half‐cell system (using Na metal as the counter electrode) to evaluate the performance of the cathode/anode/electrolyte. The relationship between the performance achieved in half cells and that obtained in full cells, however, has been neglected in much of this research. Additionally, the trade‐off in the relationship between electrochemical performance and cost needs to be given more consideration. Therefore, systematic and comprehensive insights into the research status and key issues for the full‐cell system need to be gained to advance its commercialization. Consequently, this review evaluates the recent progress based on various cathodes and highlights the most significant challenges for full cells. Several strategies have also been proposed to enhance the electrochemical performance of NIBs, including designing electrode materials, optimizing electrolytes, sodium compensation, and so forth. Finally, perspectives and outlooks are provided to guide future research on sodium‐ion full cells.
Experimental methods in chemical engineering: X‐ray fluorescence—XRF
Authors: González Mario Ferreiro , Saadatkhah Nooshin , Patience Gregory S.
Published: February 2024

X‐ray fluorescence (XRF) is a non‐destructive spectrometric technique to detect elements with an atomic number from 11 (sodium) and beyond 92 (uranium). When X‐rays or gamma rays eject tightly bound inner core electrons, an electron from an outer shell will fill the empty orbital and fluoresce. Every element has a characteristic fluorescence, which depends on the element and the electrons in the orbitals that are ejected and those that fill the orbital. With the characteristic energy of the fluorescence, we determine elemental composition and concentration when adequately calibrated. Typical run times range from a second to a few minutes with an sensitivity to as low as (ppm). XRF guns are portable devices that produce qualitative data while libraries loaded to laboratory instruments are capable of producing quantitative data. A broad range of scientists and engineers apply XRF in research—140 of the 250 scientific categories in the Web of Science (WoS) cite XRF analyses. Of the 10,000 articles indexed in WoS since 2018, chemical engineering ranks fifth with the most articles. The focus of the research in this category includes adsorption and waste water, combustion and pyrolysis, catalysis and zeolites, and nanoparticles and oxidation.
Synthesis of MFe2O4 (M=Ni, Co) Nanoparticles by a Bicontinuous Microemulsion Method for the Oxygen Evolution Reaction
Authors: Sultan Faiz , González Sepúlveda Guillermo E. , Medina Dora I. , Videa Marcelo , Sánchez‐Domínguez Margarita , Cholula‐Díaz Jorge L.
Published: February 2024

Developing efficient and low‐cost electrocatalysts for the oxygen evolution reaction (OER) is crucial for sustainable hydrogen production through water splitting. In this study, CoFe2O4 and NiFe2O4 nanoparticles as electrocatalysts were prepared via an inexpensive method involving the use of bicontinuous microemulsions as nanoreactors. The crystalline structure, morphology, and elemental composition of the electrocatalysts were characterized by XRD, Raman spectroscopy, TEM, and EDS elemental mapping. The electronic structure and textural properties were examined using XPS and the nitrogen adsorption‐desorption method. The OER measurements were carried out in a standard three‐electrode system. CoFe2O4 demonstrated relatively higher OER catalytic activity than NiFe2O4 in 1 M KOH solution, with a smaller overpotential of 410 mV to achieve a current density of 10 mA cm−2 and a smaller Tafel slope of 80 mV dec−1. In contrast, NiFe2O4 offered a higher overpotential of 450 mV to reach the same current density. The superior performance of CoFe2O4 is ascribed to higher ECSA, better conductivity, and lower charge transfer resistance. However, both electrocatalysts showed stability up to more than three hours of continuous performance.
Synergizing edge computing and blockchain for cyber‐physical systems
Authors: Thakur Payal , Sehgal Vivek Kumar
Published: February 2024

As a foundational technology for managing decentralized systems like smart grids and healthcare systems, blockchain is attracting a lot of interest. However, owing to excessive resource requirements and low scalability with frequent‐intensive transactions, its use in resource‐constrained mobile devices is restricted. To let mobile devices offload processing tasks to cloud resources, edge computing can be used. For scalability and secure transactions, the integration with edge computing guarantees consistent access, distributed computing, and non‐compromised storage. To accomplish effective integration, critical challenges such as reliability, adaptability, and resource planning must be resolved. Despite these efforts, further study is still needed to address issues with confidentiality, flexibility, and reliability to develop a workable, secure decentralized data storage system. This study utilizes edge computing to build an Internet of Things (IoT) architecture that satisfies the safety and scalability necessary criteria for integration along with the integration of peer‐to‐peer and blockchain technologies. Already‐existing blockchain and related technologies have also been investigated to suggest solutions that address issues like secrecy, reliability, and scalability in order to successfully incorporate blockchain in IoT systems. Our experimental findings indicate that achieving low rates of stale blocks and promoting decentralization requires a meticulous selection of block sizes and generation intervals. It is essential to maintain block creation intervals as short as practically possible, and utilizing blocks with a size below 1 MB is advisable.
MAGIC‐DR: An interpretable machine‐learning guided approach for acute myeloid leukemia measurable residual disease analysis
Authors: Shopsowitz Kevin , Lofroth Jack , Chan Geoffrey , Kim Jubin , Rana Makhan , Brinkman Ryan , Weng Andrew , Medvedev Nadia , Wang Xuehai
Published: February 2024

Multiparameter flow cytometry is widely used for acute myeloid leukemia minimal residual disease testing (AML MRD) but is time consuming and demands substantial expertise. Machine learning offers potential advancements in accuracy and efficiency, but has yet to be widely adopted for this application. To explore this, we trained single cell XGBoost classifiers from 98 diagnostic AML cell populations and 30 MRD negative samples. Performance was assessed by cross‐validation. Predictions were integrated with UMAP as a heatmap parameter for an augmented/interactive AML MRD analysis framework, which was benchmarked against traditional MRD analysis for 25 test cases. The results showed that XGBoost achieved a median AUC of 0.97, effectively distinguishing diverse AML cell populations from normal cells. When integrated with UMAP, the classifiers highlighted MRD populations against the background of normal events. Our pipeline, MAGIC‐DR, incorporated classifier predictions and UMAP into flow cytometry standard (FCS) files. This enabled a human‐in‐the‐loop machine learning guided MRD workflow. Validation against conventional analysis for 25 MRD samples showed 100% concordance in myeloid blast detection, with MAGIC‐DR also identifying several immature monocytic populations not readily found by conventional analysis. In conclusion, Integrating a supervised classifier with unsupervised dimension reduction offers a robust method for AML MRD analysis that can be seamlessly integrated into conventional workflows. Our approach can support and augment human analysis by highlighting abnormal populations that can be gated on for quantification and further assessment. This has the potential to speed up MRD analysis, and potentially improve detection sensitivity for certain AML immunophenotypes.
Fine‐needle aspiration diagnosis of secondary malignant tumors of the thyroid gland: A single‐institution experience of 17 cases
Authors: Zhang Wei , Lei Jianyuan , Chen Jie , Li Wensheng
Published: February 2024

Background

Fine‐needle aspiration (FNA) is the most commonly used preoperative pathological diagnostic tool for thyroid tumors. Secondary malignant tumors of the thyroid gland account for less than 3% of all thyroid malignancies. The aim of this study was to investigate the types and cytopathological features of secondary thyroid tumors, evaluate diagnostic pitfalls in FNA.

Methods

Cases of secondary thyroid tumors diagnosed in the Department of Pathology of Shaanxi Provincial People's Hospital were collected, and their clinical data, cytologic features, immunohistochemical results, and histopathological diagnoses were summarized.

Results

The study included 17 cases (8 males and 9 females) with a mean age of 60.4 ± 9.4 years (range, 45–83 years). Six cases had a known history of primary malignancy prior to FNA aspiration diagnosis. The most common organs of origin were the lungs (5 cases, 3 adenocarcinoma, and 2 small‐cell carcinoma) and esophagus (5 cases, 3 squamous‐cell carcinoma, 1 adenocarcinoma, and 1 small‐cell carcinoma). The next most common was squamous‐cell carcinoma of the larynx (3 cases), and gastric tumor (2 cases), including 1 lymphoma and 1 adenocarcinoma. Cell blocks and immunohistochemistry were performed in 12 of these cases. Comparison of the impact of positive history and IHC availability on the accuracy of pathologic diagnosis showed that both were statistically significant.

Conclusion

FNA is an effective means of diagnosing secondary malignancies of the thyroid, in which knowledge of the patient's history of malignancy is essential, and the use of cell blocks and immunohistochemistry helps to clarify the pathological diagnosis.
Rapid Fabrication of Electrodes for Symmetrical Solid Oxide Cells by Extreme Heat Treatment
Authors: Fan Weiwei , Sun Zhu , Wang Manxi , Li Manxian , Chen Yuming
Published: February 2024

Symmetrical solid oxide cells (SSOCs) are very useful for energy generation and conversion. To fabricate the electrode of SSOC, it is very time‐consuming to use the conventional approach. In this work, we design and develop a novel method, extreme heat treatment (EHT), to rapidly fabricate electrodes for SSOC. We show that by using the EHT method, the electrode can be fabricated in seconds (the fastest method to date), benefiting from enhanced reaction kinetics. The EHT‐fabricated electrode presents a porous structure and good adhesion with the electrolyte. In contrast, tens of hours are needed to prepare the electrode by the conventional approach, and the prepared electrode exhibits a dense structure with a larger particle size due to the lengthy treatment. The EHT‐fabricated electrode shows desirable electrochemical performance. Moreover, we show that the electrocatalytic activity of the perovskite electrode can be tuned by the vigorous approach of fast exsolution, deriving from the increased active sites for enhancing the electrochemical reactions. At 900 °C, a promising peak power density of 966 mW cm−2 is reached. Our work exploits a new territory to fabricate and develop advanced electrodes for SSOCs in a rapid and high‐throughput manner.
Blood perfusion status is important in the prognosis of ventricular aneurysm complicated by ventricular septal rupture
Authors: Huang Siyuan , Zhang Shicheng , Song Yangwu , Feng Wei
Published: February 2024

Aims

Due to its low incidence, poor prognosis, and high mortality in the acute phase, the long‐term prognosis of the left ventricular aneurysm (LVA) complicated by ventricular septal rupture (VSR) has received little attention. This study focus on the long‐term prognosis of patients with LVA complicated by relatively stable VSR.

Methods and results

Over a decade of retrospection, 68 patients with both LVA and VSR were compared with 136 patients with LVA alone after propensity score matching. Patients with both LVA and VSR were further divided into two groups depending on whether pre‐operative intra‐aortic balloon pump (IABP) was used (23 pre‐operative IABP vs. 45 non‐pre‐operative IABP). The primary endpoint was defined as major adverse cardiovascular and cerebrovascular events, a composite endpoint including mortality, myocardial infarction, revascularization, stroke, and heart failure. Patients with both LVA and VSR were generally in a worse condition upon admission compared with those with LVA alone [percentage of patients in New York Heart Association IV: 42.6% (29/68) vs. 11.0% (15/136), P < 0.001]. Both pre‐operative and post‐operative IABP use rates were significantly higher in patients with both LVA and VSR than in patients with LVA alone [pre‐operative IABP use rates: 33.8% (23/68) vs. 0.74% (1/136), P < 0.001 and post‐operative IABP use rates: 33.8% (23/68) vs. 10.3% (14/136), P < 0.001]. No significant difference was observed in the primary endpoint between patients with both LVA and VSR and those with LVA alone (log‐rank test, P = 0.63, median follow‐up time 63 months). We further investigated the effect of pre‐operative IABP on the long‐term prognosis of patients with both LVA and VSR. Patients who applied pre‐operative IABP had a worse long‐term prognosis than those who did not (log‐rank test, P = 0.0011).

Conclusions

The long‐term prognosis of LVA combined with VSR was not inferior than LVA alone after surgery, but poor blood perfusion status was associated with a worse prognosis.
‘Dutch’ according to children and mothers: Nationality stereotypes and citizenship representation
Authors: de Bruijn Ymke , Yang Yiran , Mesman Judi
Published: February 2024

This research examines the endorsement of the nationality stereotype Dutch = White among children and associations with citizenship representations of their mothers (Study 1). Additionally, Study 2 explores how mothers include the concept of Dutch citizenship in the upbringing of their children. Study 1 shows that children (n = 197, 57% girls, 7–13 years old) from different ethnic‐racial backgrounds (White Dutch, Turkish‐Dutch, Black Dutch, Chinese‐Dutch) all endorsed the nationality stereotype and did so to a similar extent. Most mothers rated civic citizenship as more important than ethnic citizenship, but maternal citizenship representations were unrelated to child nationality stereotype. Study 2 shows that mothers often do not actively and consciously include the topic of Dutch citizenship in their upbringing, but might confirm the nationality stereotype in more implicit ways. Future studies are needed to examine how to work towards a more inclusive view of nationality among children in the Dutch context.
Performance evaluation and development of FE modeling for passive greenhouse solar dryer for potato chips drying
Authors: Kumar Lalan , Prakash Om , Ahmad Asim , Das Biplab , Brar L. S.
Published: February 2024

Food losses and hunger around the world are majorly attributed to the lack of diverse food processing technologies and standardized methods. Solar energy is a potential solution for drying agricultural products, but traditional solar drying methods are not yet widely used. This study developed a finite element model using COMSOL Multiphysics to assess the performance of a passive greenhouse dryer for drying food products. The proposed model was used to simulate the drying of potato slices, and the results showed that the dryer was able to reduce the moisture content of the potato slices from 1 to 0.005 in 3 h. The drying efficiency was 20.52%, the relative humidity inside the drying chamber was 25.2%, and the energy and exergy efficiencies were 63.46% and 94.01%, respectively. Overall, the results of this study suggest that the passive greenhouse dryer is a suitable drying method for potato chips. The model developed in this study can be used to further optimize the design of the dryer and to evaluate its performance for other food products.
Cobalt chromite nanoparticle effects on kapok diesel emulsion performance and emission characteristics at various injection pressures
Authors: Anbarasan B. , Muralidharan K. , Sakthi Rajan C. , Rajkumar T.
Published: February 2024

Alternative fuels derived from vegetable oil have great potential as diesel fuel replacements in the transportation and manufacturing sectors. The aim of this study is to use cobalt chromite nanoparticles as a fuel additive with biodiesel in engine and to experimentally investigate the influence of injection pressure on combustion parameters. As an addition, cobalt chromite nanoparticles are used with biodiesel made from kapok oil, which is blended with mineral diesel at a ratio of 20:80. The engine is operated at various injection pressures (200–260 bar) and with an 80 ppm nanoparticle concentration. The results have shown that the increased injection pressure caused by the use of nanoparticles enhances engine combustion properties, such as the peak pressure and the rate of heat release. The main purpose of this research was to investigate the effects of a CoCr2O4 + KME20 mix on a CI engine, with the hope of improving engine performance characteristics. This investigation examines the effects of varying test fuel injection pressures. The increased injection pressure of CoCr2O4 + KME20 resulted in better performance and combustion. The 240‐bar IP was shown to be superior to lower IPs because of its greater penetration length and more uniform formation. The IP rating of 240 bar represented a significant improvement over competing products with respect to emission controls. In addition to reducing our reliance on fossil fuels, this also prevents harmful chemicals from being released into the air.
Assessing the types of policy networks in policymaking: Empirical evidence from administrative reform in Italy
Authors: Capano Giliberto , Erittu Eleonora , Francisci Giulio , Natalini Alessandro
Published: February 2024

Policy networks can propose solutions (policy communities, and epistemic communities), defend specific instruments (instrument constituencies), and programmatically prioritize change or stability (programmatic groups). This paper focuses on two specific networks that have been present in 30 years of administrative reform in Italy, and it empirically assesses what type of network they are according to their origins, developments over time, membership and motivations to stay together, and role in the policymaking. This comparison, while improving the current understanding of the networking taking place in the Italian administrative reform, shows that if policy networks are very relevant in the policy process, it is analytically more fruitful and empirically more reliable to assess their characteristics empirically, rather than to assume their existence in advance (and make hypotheses on this basis) or to use the concept in a purely metaphorical manner.