bluuebunny/crossref_metadata_2025 huggingface dataset:
Engineering Triple‐Phase Boundary in Pt Catalyst Layers for Proton Exchange Membrane Fuel Cells
Authors: Li Yi , Wu Zirui , Wang Cheng , Yu Xiwen , Gao Wanguo , Wang Bing , Wu Congping , Yao Yingfang , Yang Juan , Zou Zhigang
Published: January 2024

Engineering triple‐phase boundaries in low Pt‐loaded catalyst layers is highly desired yet challenging due to the poor Pt utilization caused by inhomogeneous Nafion ionomer coverage over catalyst nanoparticles and high mass transport resistance near catalyst surface. Herein, an effective Pt catalyst/support design strategy by using urea to modify the carbon supports is reported, in which the balance between nitrogen doping and Pt nanoparticle deposition can be well achieved without sacrificing catalyst performance. The nitrogen‐modified carbon with the positively charged surface can electrostatically attract with ionomer with negative charges in a catalyst ink. Meanwhile, ionomer can be preserved into a solid catalyst layer, forming a desirable ionomer/catalyst interface with improved dry proton accessibility and lowered oxygen transport resistance. Consequently, this interface leads to striking performance improvement in the kinetic and mass transport regions in the membrane electrode assembly level, with the current density of 1.11 A cm−2 at 0.65 V under 50% RH and 85 °C operating conditions, reaching 2.8 times this value compared with the one without modification.
Impact of Viscosity on Human Hepatoma Spheroids in Soft Core–Shell Microcapsules
Authors: Peng Xuan , Janićijević Željko , Lemm Sandy , Hauser Sandra , Knobel Michael , Pietzsch Jens , Bachmann Michael , Baraban Larysa
Published: January 2024

The extracellular environment regulates the structures and functions of cells, from the molecular to the tissue level. However, the underlying mechanisms influencing the organization and adaptation of cancer in three‐dimensional (3D) environments are not yet fully understood. In this study, the influence of the viscosity of the environment is investigated on the mechanical adaptability of human hepatoma cell (HepG2) spheroids in vitro, using 3D microcapsule reactors formed with droplet‐based microfluidics. To mimic the environment with different mechanical properties, HepG2 cells are encapsulated in alginate core–shell reservoirs (i.e., microcapsules) with different core viscosities tuned by incorporating carboxymethylcellulose. The significant changes in cell and spheroid distribution, proliferation, and cytoskeleton are observed and quantified. Importantly, changes in the expression and distribution of F‐actin and keratin 8 indicate the relation between spheroid stiffness and viscosity of the surrounding medium. The increase of F‐actin levels in the viscous medium can indicate an enhanced ability of tumor cells to traverse dense tissue. These results demonstrate the ability of cancer cells to dynamically adapt to the changes in extracellular viscosity, which is an important physical cue regulating tumor development, and thus of relevance in cancer biology.
A Novel N‐Type Molecular Dopant With a Closed‐Shell Electronic Structure Applicable to the Vacuum‐Deposition Process
Authors: Matsuo Takaya , Kawabata Kohsuke , Takimiya Kazuo
Published: January 2024

Rational design, synthesis, and characterization of a new efficient versatile n‐type dopant with a closed‐shell electronic structure are described. By employing the tetraphenyl–dipyranylidene (DP0) framework with two 7π‐electron systems modified with N,N‐dimethylamino groups as the strong electron‐donating substituent, 2,2′,6,6′‐tetrakis[4‐(dimethylamino)phenyl]‐4,4′‐dipyranylidene (DP7), a closed‐shell molecule with an extremely high‐lying energy level of the highest occupied molecular orbital, close to 4.0 eV below the vacuum level, is successfully developed. Thanks to its thermal stability, DP7 is applicable to vacuum deposition, which allows utilization of DP7 in bulk doping for the development of n‐type organic thermoelectric materials and contact doping for reducing contact resistance in n‐type organic field‐effect transistors. As vacuum‐deposition processable n‐type dopants are very limited, DP7 stands out as a useful n‐type dopant, particularly for the latter purpose.
Rational Modified Organic Functional Charge‐Transfer Complexes toward Optical/Photothermal Behavior Tuning through Decay Pathway Regulation
Authors: Xiang Wenxin , Sun Hua , Zhang Jiacheng , Wang Shuai , Pan Chen , Yao Lei , Ma Shuang , Li Wenju , Dan Wenyan , Zhang Jing
Published: January 2024

Doping has been proven to be a good way to regulate the optical and electrical properties of the active elements including both inorganic and organic materials. In this paper, the study demonstrates a bipolar doping strategy for an intrinsic charge‐transfer binary‐complex through the use of p‐ and n‐type dopants, which incorporate toward highly‐ordered ternary complexes. Benefitting from the good lattice matching and energy level tuning, the supramolecular system with a large doping concentration range (0 ≤ x ≤ 50% or 40%) assembles into the original crystal lattice and exhibits tunable luminescence or quenching phenomena even at very low ratio. The 7h‐benzo[c]carbazole (BCZ) dopped cocrystals show yellow–green to red emission due to the Förster resonance energy transfer (FRET); while only 5% 7,7,8,8‐tetracyanoquinodimethane (TCNQ) dopant can bring superior photothermal (PT) behavior with a high PT conversion efficiency up to 75.3%, owing to the efficient non‐radiative decay way contribution. It is believed that the strong π–π interactions and free rotation of −C(C≡N)2 promote this decay way transition. This work on the charge‐transfer complex doping system suggests the great potential in optical, photothermal imaging, and therapy applications as well as information memory and photo sensing.
Defect Engineering of Nanocrystal‐In‐Glass Composites for Ultrashort Optical Pulse Monitoring
Authors: Lin Quanhua , Lin Xianqiu , Feng Xu , Yang Wangming , Tan Jiajia , Qiu Wenjie , Yao Shunchun , Chen Zhifeng , Qiu Jianrong , Zhou Shifeng
Published: January 2024

The rational control of intrinsic defects in materials can significantly enhance their scientific and technological potentials, but it remains a long‐standing challenge in nanocrystal‐in‐glass composites (NGCs). Herein, a defect engineering strategy mediated by the mixed alkali effect is proposed and experimentally demonstrated for NGCs. Interestingly, the hybridization of large alkali ions can effectively increase the barrier of Li+ migration and reduce the Li‐related defects in LiNbO3 NGC. As a result, a novel LiNbO3 NGC with greatly reduced Li‐related defects, high crystallinity of over 60%, and excellent optical transmission are successfully fabricated. This unique NGC configuration facilitates efficient transverse second harmonic generation (TSHG) in a broad wavelength region. Based on the above effects, a standard TSHG device is fabricated and implemented to monitor ultrashort optical pulses with duration in the order of ≈10−13 s over a broad wavelength region, down to 780 nm. The proposed strategy not only provides a new idea for defect engineering in materials science but also has great significance for boosting the practical applications of NGCs in ultrashort optical pulse monitoring.
Realizing Efficient Deep Blue Light‐Emitting Diodes and Single Component White Light‐Emitting Diodes with Low Efficiency Roll‐Offs from Anthracene‐Based Organic Emitters
Authors: Feng Zijun , Cheng Zhuang , Su Zihan , Wan Liang , Ge Shuyuan , Liu Hanxuan , Ma Xiaobo , Liu Futong , Lu Ping
Published: January 2024

Purely organic emitters that can efficiently utilize triplet excitons are highly desired for organic light‐emitting diodes (OLEDs). Hot exciton channel has emerged as a competitive strategy for the efficient harvest of triplet exciton to improve the OLEDs performance and suppress efficiency roll‐off in devices. Here, two deep blue emitters, OPACN and SPACN are designed and synthesized, employing diphenylanthracene (PAnP) unit as central core, sp3 hybridized O and S atom as conjugation blocker, and electron‐withdrawing cyano group as intramolecular charge transfer (ICT) introducer. Especially, OPACN presents bluer emission with electroluminescence (EL) peak at 436 nm, CIE coordinates of (0.16, 0.10), and a maximum external quantum efficiency (EQE) of 8.7%, while SPACN shows an EL peak at 444 nm, CIE coordinates of (0.17, 0.12) and a maximum EQE of 9.0%. Furthermore, the single‐component white organic light‐emitting diode (WOLED) based on OPACN exhibits dual emission from monomer and excimer with EQE of 5.4%. And even the luminance increases to 1000–10 000 cd m−2, the EQE still remains as high as 5.2% and 4.4%, respectively, showing very low efficiency roll‐offs. These results demonstrate an alternative approach for designing high‐performance deep blue OLEDs and WOLEDs based on single component.
Tensile Stress‐Activated and Exosome‐Transferred YAP/TAZ‐Notch Circuit Specifies Type H Endothelial Cell for Segmental Bone Regeneration
Authors: Wang Feng , Li Shanyu , Kong Lingchi , Feng Kai , Zuo Rongtai , Zhang Hanzhe , Yu Yifan , Zhang Kunqi , Cao Yuting , Chai Yimin , Kang Qinglin , Xu Jia
Published: January 2024

The Ilizarov technique has been continuously innovated to utilize tensile stress (TS) for inducing a bone development‐like regenerative process, aiming to achieve skeletal elongation and reconstruction. However, it remains uncertain whether this distraction osteogenesis (DO) process induced by TS involves the pivotal coupling of angiogenesis and osteogenesis mediated by type H endothelial cells (THECs). In this study, it is demonstrated that the Ilizarov technique induces the formation of a metaphysis‐like architecture composed of THECs, leading to segmental bone regeneration during the DO process. Mechanistically, cell‐matrix interactions‐mediated activation of yes‐associated protein (YAP)/transcriptional co‐activator with PDZ‐binding motif (TAZ) transcriptionally upregulates the expression of Notch1 and Delta‐like ligand 4, which act as direct positive regulators of THECs phenotype, in bone marrow endothelial cells (BMECs) upon TS stimulation. Simultaneously, the Notch intracellular domain enhances YAP/TAZ activity by transcriptionally upregulating YAP expression and stabilizing TAZ protein, thus establishing the YAP/TAZ‐Notch circuit. Additionally, TS‐stimulated BMECs secrete exosomes enriched with vital molecules in this positive feedback pathway, which can be utilized to promote segmental bone defect healing, mimicking the therapeutic effects of Ilizarov technique. The findings advance the understanding of TS‐induced segmental bone regeneration and establish the foundation for innovative biological therapeutic strategies aimed at activating THECs.
Tuning Stoichiometry for Enhanced Spin‐Charge Interconversion in Transition Metal Oxides
Authors: Chen Hetian , Jiang Dingsong , Zhang Qinghua , Liang Yuhan , Liu Jingchun , Tang Aihua , Chai Yahong , Yu Pu , Nan Tianxiang , Yi Di
Published: January 2024

Interconversion of spin and charge current provides a key route for low‐power spin memory and logic devices. Recent advances have revealed efficient spin‐charge interconversion in 4d and 5d transition metal oxides. However, the strategies to tune the conversion efficiency, essential for the generation and detection of spin‐current, are limited to engineering the crystalline structure of oxides. Here, a simple and broadly applicable approach by tuning the cation stoichiometry is reported. In the model system of 5d perovskite SrIrO3, it is shown that a significant Ir cation deficiency is induced by controlling the oxygen partial pressure during deposition. This off‐stoichiometry leads to an enhancement of the spin‐to‐charge conversion efficiency by around three times, accompanied by an increase of electrical resistivity at room temperature. Furthermore, a significant increase of inverse spin Hall voltage is observed by implementing the Ir‐deficient SrIr1‐xO3, highlighting the promising role of atomic defects in developing oxides for sensitive spin‐current detection. This work opens a new pathway to engineer the spin‐charge interconversion efficiency in oxides and offers new opportunities to integrate complex oxides in energy‐efficient spintronic devices.
Rapid cycle deliberate practice to improve airway skills and performance of trainees in a pediatric emergency department
Authors: Edmunds Katherine J. , Shah Ashish , Geis Gary L. , Kerrey Benjamin T. , Klein Gina , DeBra Rebecca , Zhang Yin , Ahaus Karen , Boyd Stephanie , Thomas Phillip , Dean Preston
Published: January 2024

Objective

The study objective was to determine the effect of a rapid cycle deliberate practice (RCDP) program on simulated and actual airway skills by pediatric emergency medicine (PEM) fellows.

Methods

We designed and implemented a 12‐month RCDP airway skills curriculum for PEM fellows at an academic pediatric institution. The curriculum was designed using airway training literature, RCDP principals, and internal quality assurance airway video review program. Simulation training scenarios increased in complexity throughout the curriculum. PEM fellows participated in monthly sessions. Two PEM faculty facilitated the sessions, utilizing a step‐by‐step objective structured clinical evaluation (OSCE)‐style tool for each scenario. Data were collected for all four levels of the Kirkpatrick Model of Training Evaluation—participant response (reaction, pre–post session survey), skills performance in the simulation setting (learning, pre–post OSCE), skills performance for actual patients (behavior, video review), and patient outcomes (results, video review).

Results

During the study period (August 2021 to June 2022), 13 PEM fellows participated in 112 sessions (mean nine sessions per fellow). PEM fellows reported improved comfort in all domains of airway management, including intubation performance. Participant OSCE scores improved posttraining (pretraining median score for trainees 57 [IQR 57–59], posttraining median 61 [IQR 61–62], p = 0.0005). Over the 12 months, PEM fellows performed 45 intubation attempts in the pediatric emergency department (median patient age 4 years [IQR 1–9 years]). Compared to a 5‐year historical cohort, participants had higher first‐pass success (87% vs. 71%, p = 0.028) and shorter attempt duration (22 s vs. 29 s, p = 0.018). There was no significant difference in the frequency of oxyhemoglobin desaturation in the training period versus the historical period (7% vs. 15%, p = 0.231).

Conclusions

At multiple levels of educational outcomes, including participant behavior and patient outcomes, an RCDP program was associated with improved airway skills and performance of PEM fellows.
Stellate ganglion block for treating post‐COVID‐19 parosmia
Authors: Naimi Bita R. , Garvey Emily , Chandna Megha , Duffy Alexander , Hunter Stephanie R. , Mandloi Shreya , Kahn Chase , Farquhar Douglas , D'Souza Glen , Rabinowitz Mindy , Rosen Marc , Toskala Elina , Roedl Johannes B. , Zoga Adam , Nyquist Gurston , Rosen David
Published: January 2024

Background

Post‐COVID parosmia may be due to dysautonomia and sympathetic hyperresponsiveness, which can be attenuated by stellate ganglion block (SGB). This study evaluates SGB as a treatment for post‐COVID olfactory dysfunction (OD).

Methods

Retrospective case series with prospective data of patients with post‐COVID OD undergoing unilateral (UL) or bilateral (BL) SGB. Patients completed Brief Smell Identification Tests (BSIT) (12 points maximum) and post‐procedure surveys including parosmia severity scores on a scale of 1 (absent) to 10 (severe). Scores were compared from before treatment (pre‐SGB) to after first (SGB1) or second (SGB2) treatments in overall, UL, and BL cohorts.

Results

Forty‐seven patients with post‐COVID OD underwent SGB, including 23 UL and 24 BL. Twenty patients completed pre‐ and post‐SGB BSITs (eight UL and 12 BL). Twenty‐eight patients completed postprocedure surveys (11 UL and 17 BL). There were no differences in BSIT scores from pre‐SGB to post‐SGB1 or post‐SGB2 for the overall (p = 0.098), UL (p = 0.168), or BL (p = 0.230) cohorts. Parosmia severity for the overall cohort improved from pre‐SGB (8.82 ± 1.28) to post‐SGB1 (6.79 ± 2.38) and post‐SGB2 (5.41 ± 2.35), with significant differences from pre‐SGB to post‐SGB1 (p < 0.001) and pre‐SGB to post‐SGB2 (p < 0.001), but not post‐SGB1 to post‐SGB2 (p = 0.130). Number of parosmia triggers decreased for overall (p = 0.002), UL (p = 0.030) and BL (p = 0.024) cohorts. Quality of life (QOL) improved for all cohorts regarding food enjoyment, meal preparation, and socialization (p < 0.05).

Conclusion

SGB may improve subjective parosmia and QOL for patients with post‐COVID OD, however it may not affect odor identification. Further placebo‐controlled studies are warranted.
Enhanced Charge Carrier Dynamics on Sb2Se3 Photocathodes for Efficient Photoelectrochemical Nitrate Reduction to Ammonia
Authors: Ren Shijie , Gao Rui‐Ting , Nguyen Nhat Truong , Wang Lei
Published: January 2024

Ammonia (NH3) is recognized as a transportable carrier for renewable energy fuels. Photoelectrochemical nitrate reduction reaction (PEC NO3RR) offers a sustainable solution for nitrate‐rich wastewater treatment by directly converting solar energy to ammonia. In this study, we demonstrate the highly selective PEC ammonia production from NO3RR by constructing a CoCu/TiO2/Sb2Se3 photocathode. The constructed CoCu/TiO2/Sb2Se3 photocathode achieves an ammonia Faraday efficiency (FE) of 88.01 % at −0.2 VRHE and an ammonia yield as high as 15.91 μmol h−1 cm−2 at −0.3 VRHE with an excellent onset potential of 0.43 VRHE. Dynamics experiments and theoretical calculations have demonstrated that the CoCu/TiO2/Sb2Se3 photocathode possesses high light absorption capacity, excellent carrier transfer capability, and high charge separation and transfer efficiencies. The photocathode can effectively adsorb the reactant NO3− and intermediate, and the CoCu co‐catalyst increases the maximum Gibbs free energy difference between NO3RR and HER. Meanwhile, the Co species enhances the spin density of Cu, and increases the density of states near the Fermi level in pdos, which results in a high PEC NO3RR activity on CoCu/TiO2/Sb2Se3. This work provides a new avenue for the feasibility of efficient PEC ammonia synthesis from nitrate‐rich wastewater.
Divergent Synthesis of Multi‐Substituted Aminotetralins via [4+2] Annulation of Aldimines with Alkenes by Rare‐Earth‐Catalyzed Benzylic C(sp3)−H Activation
Authors: Cong Xuefeng , Zhuo Qingde , Hao Na , Mishra Aniket , Nishiura Masayoshi , Hou Zhaomin
Published: January 2024

The search for efficient and selective methods for the divergent synthesis of multi‐substituted aminotetralins is of much interest and importance. We report herein for the first time the diastereoselective [4+2] annulation of 2‐methyl aromatic aldimines with alkenes via benzylic C(sp3)−H activation by half‐sandwich rare‐earth catalysts, which constitutes an efficient route for the divergent synthesis of both trans and cis diastereoisomers of multi‐substituted 1‐aminotetralin derivatives from readily accessible aldimines and alkenes. The use of a scandium catalyst bearing a sterically demanding cyclopentadienyl ligand such as C5Me4SiMe3 or C5Me5 exclusively afforded the trans‐selective annulation products in the reaction of aldimines with styrenes and aliphatic alkenes. In contrast, the analogous yttrium catalyst, whose metal ion size is larger than that of scandium, yielded the cis‐selective annulation products. This protocol features 100 % atom‐efficiency, excellent diastereoselectivity, broad substrate scope, and good functional group compatibility. The reaction mechanisms have been elucidated by kinetic isotope effect (KIE) experiments and the isolation and transformations of some key reaction intermediates.
Stress Dissipation Driven by Multi‐Interface Built‐In Electric Fields and Desert‐Rose‐Like Structure for Ultrafast and Superior Long‐Term Sodium Ion Storage
Authors: Li Jinhang , Yu Huiying , Zhao Yingying , Zhu Kai , Zhu Chunling , Ren Jing , Chou Shulei , Chen Yujin
Published: January 2024

The kinetics and durability of conversion‐based anodes greatly depend on the intrinsic stress regulating ability of the electrode materials, which has been significantly neglected. Herein, a stress dissipation strategy driven by multi‐interface built‐in electric fields (BEFs) and architected structure, is innovatively proposed to design ultrafast and long‐term sodium ion storage anodes. Binary Mo/Fe sulfide heterostructured nanorods with multi‐interface BEFs and staggered cantilever configuration are fabricated to prove our concept. Multi‐physics simulations and experimental results confirm that the inner stress in multiple directions can be dissipated by the multi‐interface BEFs at the micro‐scale, and by the staggered cantilever structure at the macro‐scale, respectively. As a result, our designed heterostructured nanorods anode exhibits superb rate capability (332.8 mAh g−1 at 10.0 A g−1) and durable cyclic stability over 900 cycles at 5.0 A g−1, outperforming other metal chalcogenides. This proposed stress dissipation strategy offers a new insight for developing stable structures for conversion‐based anodes.
Anion‐Counterion Strategy toward Organic Cocrystal Engineering for Near‐Infrared Photothermal Conversion and Solar‐Driven Water Evaporation
Authors: Zhang Meng‐Meng , Chen Shun‐Li , Bao An‐Ran , Chen Yanqi , Liang Hui , Ji Shaomin , Chen Jiecheng , Ye Bowei , Yang Qingwei , Liu Yuli , Li Jiayu , Chen Wenbin , Huang Xinda , Ni Shaofei , Dang Li , Li Ming‐De
Published: January 2024

An anion‐counterion strategy is proposed to construct organic mono‐radical charge‐transfer cocrystals for near‐infrared photothermal conversion and solar‐driven water evaporation. Ionic compounds with halogen anions as the counterions serve as electron donors, providing the necessary electrons for efficient charge transfer with unchanged skeleton atoms and structures as well as the broad red‐shifted absorption (200–2000 nm) and unprecedented photothermal conversion efficiency (~90.5 %@808 nm) for the cocrystals. Based on these cocrystals, an excellent solar‐driven interfacial water evaporation rate up to 6.1±1.1 kg ⋅ m−2 ⋅ h−1 under 1 sun is recorded due to the comprehensive evaporation effect from the cocrystal loading in polyurethane foams and chimney addition, such performance is superior to the reported results on charge‐transfer cocrystals or other materials for solar‐driven interfacial evaporation. This prototype exhibits the great potential of cocrystals prepared by the one‐step mechanochemistry method in practical large‐scale seawater desalination applications.
Dye‐Sensitized Photocatalysis: Hydrogen Evolution and Alcohol‐to‐Aldehyde Oxidation without Sacrifical Electron Donor
Authors: Romito Deborah , Govind Chinju , Nikolaou Vasilis , Fernández‐Terán Ricardo J. , Stoumpidi Aspasia , Agapaki Eleni , Charalambidis Georgios , Diring Stéphane , Vauthey Eric , Coutsolelos Athanassios G. , Odobel Fabrice
Published: January 2024

There is a growing interest in developing dye‐sensitized photocatalytic systems (DSPs) to produce molecular hydrogen (H2) as alternative energy source. To improve the sustainability of this technology, we replaced the sacrificial electron donor (SED), typically an expensive and polluting chemical, with an alcohol oxidation catalyst. This study demonstrates the first

dye‐sensitized system using a diketopyrrolopyrrole dye covalently linked to 2,2,6,6‐tetramethyl‐1‐piperidine‐N‐oxyl (TEMPO) based catalyst for simultaneous H2 evolution and alcohol‐to‐aldehyde transformation operating in water with visible irradiation.
Sulfonylurea receptor 2 (SUR2), intricate sensors for intracellular Mg‐nucleotides
Authors: Hou Tianyi , Chen Lei
Published: January 2024

SUR2, similar to SUR1, is a regulatory subunit of the ATP‐sensitive potassium channel (KATP), which plays a key role in numerous important physiological processes and is implicated in various diseases. Recent structural studies have revealed that, like SUR1, SUR2 can undergo ligand‐dependent dynamic conformational changes, transitioning between an inhibitory inward‐facing conformation and an activating occluded conformation. In addition, SUR2 possesses a unique inhibitory Regulatory helix (R helix) that is absent in SUR1. The binding of the activating Mg‐ADP to NBD2 of SUR2 competes with the inhibitory Mg‐ATP, thereby promoting the release of the R helix and initiating the activation process. Moreover, the signal generated by Mg‐ADP binding to NBD2 might be directly transmitted to the TMD of SUR2, prior to NBD dimerization. Furthermore, the C‐terminal 42 residues (C42) of SUR2 might allosterically regulate the kinetics of Mg‐nucleotide binding on NBD2. These distinctive properties render SUR2 intricate sensors for intracellular Mg‐nucleotides.
Antioxidant, anti‐inflammatory and epigenetic potential of curcumin in Alzheimer's disease
Authors: Abdul‐Rahman Toufik , Awuah Wireko Andrew , Mikhailova Tatiana , Kalmanovich Jacob , Mehta Aashna , Ng Jyi Cheng , Coghlan Megan Ariel , Zivcevska Marija , Tedeschi Alexander J. , de Oliveira Emerson Costa , Kumar Akinchita , Cantu‐Herrera Emiliano , Lyndin Mykola , Sikora Kateryna , Alexiou Athanasios , Bilgrami Anwar L. , Al‐Ghamdi Khalid Mohammed , Perveen Asma , Papadakis Marios , Ashraf Ghulam Md
Published: January 2024

Alzheimer's disease (AD) constitutes a multifactorial neurodegenerative pathology characterized by cognitive deterioration, personality alterations, and behavioral shifts. The ongoing brain impairment process poses significant challenges for therapeutic interventions due to activating multiple neurotoxic pathways. Current pharmacological interventions have shown limited efficacy and are associated with significant side effects. Approaches focusing on the early interference with disease pathways, before activation of broad neurotoxic processes, could be promising to slow down symptomatic progression of the disease. Curcumin—an integral component of traditional medicine in numerous cultures worldwide—has garnered interest as a promising AD treatment. Current research indicates that curcumin may exhibit therapeutic potential in neurodegenerative pathologies, attributed to its potent anti‐inflammatory and antioxidant properties. Additionally, curcumin and its derivatives have demonstrated an ability to modulate cellular pathways via epigenetic mechanisms. This article aims to raise awareness of the neuroprotective properties of curcuminoids that could provide therapeutic benefits in AD. The paper provides a comprehensive overview of the neuroprotective efficacy of curcumin against signaling pathways that could be involved in AD and summarizes recent evidence of the biological efficiency of curcumins in vivo.
(Benz)imidazo[1,2‐a]quinolinium Salts: Access via Unprecedented Regiospecific non‐AAIPEX Strategy and Study of Their Tunable Properties
Authors: Bauri Somnath , Ramachandran Arya , Rit Arnab
Published: January 2024

An unprecedented non‐AAIPEX protocol has been developed to access diverse monosubstituted cationic polycyclic heteroaromatic compounds (cPHACs) from the readily available azolium salts and phenacyl bromides via Ru(II)‐catalyzed tandem annulation cum aromatization. This atom‐economic protocol executes a range of intermediate steps e. g. double C−H activation, nucleophilic addition, annulation, and dehydration cum aromatization in one‐pot manner under the generation of H2O as the sole byproduct. Moreover, the systematic tunability of photo‐physical and electrochemical properties of these new class of cPHACs can be authenticated from the DFT calculated frontier molecular orbital energies that might be beneficial for their potential applications in optoelectronics and DNA intercalation.
Pd‐Catalysed Direct Arylation of Distyrylbenzene: Strong Dual‐state Fluorescence and Electrochromism
Authors: Nipate Atul B. , Rao M. Rajeswara
Published: January 2024

Distyrylbenzenes (DSBs) are well‐known for their strong multicolour fluorescence. Fluorescence tuning of DSB via further functionalization/arylation, on the other hand, is uncommon. This paper reports a Pd‐catalysed direct arylation approach for introducing different aryl groups onto fluorobenzene‐containing DSB moiety (7) in high yields (67–72 %). The versatile methodology allows the substitution of neutral [tolyl (1)], electron‐deficient [p‐formyl benzene (2), p‐acetyl benzene (3), p‐nitrobenzene (4)] and electron‐rich [carbazole (5), triphenylamine (6)] aryl groups. The electron‐deficient aryls render mono‐substitution, while the electron‐rich counterparts promote di‐substitution. The compounds (1–6) show blue, green, and yellow fluorescence in both the solution and solid states; the fluorescence quantum yields reach >98 % and the peak maxima span from 425 to 560 nm. The mono‐carbazole DSB (5) exhibit white light emission (WLM) in polar solvents (acetone, DMF, CH3CN, DMSO and NMP) with very high fluorescence quantum yields (φf) of 60–80 %. For WLM, such high efficiency (φf) is somewhat uncommon. Moreover, visible‐to‐NIR reversible electrochromism is demonstrated by the TPA‐integrated DSB (6). The colour of 6 changes from pristine light yellow to orange, and the absorption maxima shifts from 372 to 1500 nm when a positive potential of 1.0 V vs Ag/Ag+ is applied. Moreover, the system shows high colouration efficiency in the NIR region with fast switching speeds for colouration and decolouration as fast as 0.98 s and 1.05 s.
Greener Approach Towards Synthesis of Palladium‐Decorated Graphene Derivatives for Hydrogen Adsorption
Authors: Głowniak Sylwia , Szczęśniak Barbara , Choma Jerzy , Jaroniec Mietek
Published: January 2024

A simple, green, and relatively fast procedure was used to prepare palladium decorated graphene‐based materials. A parent graphene‐like material with a high specific surface area of up to 384 m2/g and a total pore volume of 0.42 cm3/g was prepared via a fast, solvent‐free ball milling of graphite powder only. Post‐synthetic modification of this graphene‐like material was performed via a simplified method using palladium chloride and a small amount of a non‐harsh reducing agent – formic acid. Palladium decoration (2.1 wt%) allowed obtaining a few times higher hydrogen adsorption (0.42 wt% at 30 °C and 40 bar) compared to that on bare graphene‐based materials. Palladium‐decorated graphene materials are promising for hydrogen storage and their usage in this application represents an alternative for conventional fossil fuels. The proposed synthesis and post‐modification strategies are in line with green synthesis strategies.
Application of Exciton Coupling for Characterization of Nanographene Edge
Authors: Sekiya Ryo , Haino Takeharu
Published: January 2024

The structural characterization of nonstoichiometric nanographene (NG)‐organic hybrid materials is usually difficult. The number of substituents on the edge and their arrangements are frequently questioned but are difficult to answer. Since the number of functional groups is closely related to the distance between the nearest neighbors (dISD), the extraction of dISD from spectroscopic data could provide important information on their structural characterization. We show that exciton coupling, which is a theoretical prediction of the absolute structures of discrete molecules, is a possible candidate to address this issue. The comparison of the calculated CD spectra of the chiral chromophores extracted from the model NG edge with the observed edge spectra indicated a dISD of ca. 8 Å; this corresponded to substitution on every other armchair edge. Furthermore, an up‐up‐down‐down alternate orientation was found to be a possible edge structure. Although the procedure was limited to NGs carrying chiral substituents, our method could facilitate the detailed structural characterization of NG‐organic hybrid materials.
Amino Acid Polymerization on Silica Surfaces
Authors: Samrout Ola El , Berlier Gloria , Lambert Jean‐François
Published: January 2024

The polymerization of unactivated amino acids (AAs) is an important topic because of its applications in various fields including industrial medicinal chemistry and prebiotic chemistry. Silica as a promoter for this reaction, is of great interest owing to its large abundance and low cost. The amide/peptide bond synthesis on silica has been largely demonstrated but suffers from a lack of knowledge regarding its reaction mechanism, the key parameters, and surface features that influence AA adsorption and reactivity, the selectivity of the reaction product, the role of water in the reaction, etc. The present review addresses these problems by summarizing experimental and modeling results from the literature and attempts to rationalize some apparent divergences in published results. After briefly presenting the main types of silica surface sites and other relevant macroscopic features, we discuss the different deposition procedures of AAs, whose importance is often neglected. We address the possible AA adsorption mechanisms including covalent grafting and H‐bonding and show that they are highly dependent on silanol types and density. We then consider how the adsorption mechanisms determine the occurrence and outcome of AA condensation (formation of cyclic dimers or of long linear chains), and outline some recent results that suggest significant polymerization selectivity in systems containing several AAs, as well as the formation of specific elements of secondary structure in the growing polypeptide chains.
Why a complete medical exam is necessary prior to diagnosing ADHD
Authors: Knopf Alison
Published: January 2024

A recent literature review highlights the need to investigate a patient's medical issues before diagnosing, and treating, attention‐deficit hyperactivity disorder (ADHD). According to the review which looked at studies conducted over the past 20 years, several medical conditions can be misdiagnosed as ADHD. These conditions may have a similar presentation to ADHD, especially in regard to inattentive symptoms. Some examples are absence seizure disorder, diabetes, thyroid dysfunction, sleep deprivation, post‐concussion states, inflammatory bowel disease, iron deficiency states and anemia, and disordered breathing.
Graphene Oxide‐Arginine Composites: Efficient Dual Function Materials for Integrated CO2 Capture and Conversion
Authors: Mantovani Sebastiano , Pintus Angela , Kovtun Alessandro , Gondolini Angela , Casadio Simone , Sanson Alessandra , Marforio Tainah D. , Calvaresi Matteo , Rancan Marzio , Armelao Lidia , Bertuzzi Giulio , Melucci Manuela , Bandini Marco
Published: January 2024

The “on‐demand” capture and utilization of CO2 is effectively realized with a readily accessible dual function organic composite. The covalent and controlled derivatization of graphene oxide (GO) surface with naturally occurring arginine led to a “smart” material capable of capturing (chemisorption) CO2 from high‐purity flue‐gas as well as low‐concentration streams (i. e. direct air capture) and concomitant chemical activation toward the incorporation into cyclic carbonates. The overall integrated CO2 capture and conversion (ICCC) strategy has been fully elucidated mechanistically via dedicated computational, spectroscopic and thermal analyses.
Arm‐current sensorless model predictive control for grid‐interfacing modular multilevel converter with reduced switching frequency
Authors: Sharma Ankita , Chilipi Rajasekharareddy , Praveen Kumar Kunisetti V.
Published: January 2024

Model predictive control (MPC) emerges as an attractive alternative for the control of modular multilevel converters (MMCs) owing to its superior dynamic performance and ease of implementation. Nevertheless, conventional MPC's performance could be further improved by reducing dependence on weighting factors, switching frequency, and computational burden. To achieve these objectives, an arm‐current sensorless MPC is developed for a grid‐interfacing MMC in this article. The MPC is integrated with an arm‐current sensorless reduced switching frequency voltage balance algorithm that requires only
switching vectors (where
number of submodules per arm) to optimize the cost function. This method does not require knowledge of arm‐current direction to decide the charging and discharging state of the submodule capacitors. The developed control not only reduces the switching frequency of devices but also eliminates the need to sense the arm currents. As a result, it reduces the system's cost, complexity, computational burden, switching losses and provides a more reliable control method for MMCs with superior dynamic performance. Further, the effect of parameter mismatch on the developed MPC's dynamic performance and stability is studied. The developed MPC's effectiveness is validated through both simulation and experimental results and also compared with existing methods under different conditions.
Faculty retirement — Maintaining identity and purpose
Authors: Freebairn‐Smith Laura
Published: January 2024

In an article for The Chronicle of Higher Education (“A Professor's Last Crucial Decision: When to Retire”), Deborah K. Fitzgerald wrote:
Consider the reflections of a recently retired academic leader, Part 2
Authors: Hodges Dawn Z.
Published: January 2024

Last month you met Joe Alexander, a former colleague of mine who recently retired. We haven’t worked together since 1981, so I had a lot to learn about his career. I enjoyed hearing about his success.
Prepare for undergrad student‐workers to bring more labor unions to campus
Authors: Caldwell Trevor R.
Published: January 2024

The confluence of increased interest in unionization among undergraduate workers and a recent National Labor Review Board decision that made it far easier for unions to be recognized may mean more unions on campus in the very near future.
Fewer young men are enrolling in college
Authors: Sutton Halley
Published: January 2024

Men are responsible for a majority of the enrollment declines at colleges and universities — particularly at four‐year institutions. That finding comes from a recently released report by the Pew Research Center, which found that men's enrollment at colleges and universities has been declining over the past decade, with recent numbers down 1.2 million from its peak in 2011. Only 0.2 million fewer women are enrolled in college than peak 2011 numbers.
A Practical, Scalable Synthesis of 1,18‐Octadecanedioic acid‐Paclitaxel (ODDA‐PTX)
Authors: Rositano Vincenzo , Gambini Andrea , Allegrini Pietro , Bernardi Anna , Senaldi Luca
Published: January 2024

Paclitaxel is one of the most important chemotherapy agents and it has shown activity against a variety of human cancers. In the past years several derivatives and formulations have been developed to improve its activity and reduce its toxicity. Recently, 1,18‐Octadecanedioic acid‐Paclitaxel (ODDA‐PTX), obtained by conjugation of paclitaxel with a long‐chain diacid, has emerged as a promising paclitaxel prodrug, with high efficacy and low toxicity. A novel strategy for its synthesis has been developed and is herein described. The approach is based on the mono‐allyl protection of octadecanedioic acid (ODDA) and on the Pd‐catalyzed removal of the allyl ester after coupling with paclitaxel. This strategy is superior to previously reported procedures in that it affords the ODDA‐PTX product with much higher purity, avoids chromatographic purifications and can be practically scaled‐up for the industrial production of ODDA‐PTX.
Copper‐Mediated Cross‐Dehydrogenative Coupling Reaction of Pyrrole and Indole Derivatives with Thiols
Authors: Ma Wenbo , Xu Yue , Gu Qilin , Zheng Tao , Gu Linghui
Published: January 2024

A copper‐mediated C(sp2)−H thiolation of pyrrole and indole derivatives with commercially available thiols utilizing a removable monodentate directing group is described. This protocol tolerated a broad range of functional groups and provided the thiolated products in 40 %–97 % yields. Furthermore, the synthetic utility of this protocol was demonstrated by the late‐stage functionalization of bioactive tryptophan peptide. Preliminary mechanistic studies indicated that a Cu(II)/Cu(III) reaction model is most likely to be involved in this C−H thiolation.
Utilizing Density Functional Theory and SCAPS Simulations for Modeling High‐Performance MASnI3‐Based Perovskite Solar Cells
Authors: Shah Masood , Ahmad Ibrar , Hayat Khizar , Munawar Muhammad , Mushtaq Muhammad , Ahmad Waqar , Shah Abdullah , Karim Shah Said
Published: January 2024

This study uses computational analysis to comprehensively investigate lead‐free organic–inorganic CH3NH3SnI3 (MASnI3)‐based perovskite solar cells (PSCs). The optoelectronic properties of MASnI3 are investigated using density functional theory with first‐principles calculations, highlighting its potential for photovoltaic applications. Key findings include the determination of a crucial bandgap (0.97 eV), identification of the onset of photon absorption at energies exceeding 2 eV, and characterization of material properties, such as the absorption and extinction coefficients, reflectivity, and refractive index. Device optimization through simulations explores parameters such as layer thickness, defect density, and different charge transport layers, resulting in a remarkable enhancement in the power conversion efficiency to 16.72%. Additionally, this study focuses on the influence of the working temperature, series resistance (R
s), and shunt resistance (R
sh) on the photovoltaic device performance. Hence, a high photovoltaic efficiency in MASnI3‐based PSCs can be achieved by carefully optimizing the device performance parameters and effectively managing the defect densities.
Deep oxidative desulfurization of real fuels by a new nanocomposite based on mono Cd(II)‐substituted Keggin‐type silicotungstate, cobalt ferrite and polyaniline as an efficient nanocatalyst
Authors: Khalafi Nasrin , Rezvani Mohammad Ali , Jafarian Vahab , Ardeshiri Hadi Hassani , Mohammadi Mohammad , Akhoondi Amir Hossein
Published: January 2024

To obtain clean fuel, synthesis and characterization of a novel nanocomposite based on mono CdII‐substituted silicotungstate (K3SiW11CdO39), cobalt ferrite (CoFe2O4), and polyaniline (PAN) was presented for the first time. K3SiW11CdO39@CoFe2O4@PAN was identified by FT‐IR, XRD, SEM, and EDX techniques. The outcomes of the characterizations have shown that K3SiW11CdO39 and CoFe2O4 are uniformly dispersed on the PAN surface. The K3SiW11CdO39@CoFe2O4@PAN was employed as a heterogeneous catalyst in the extractive coupled oxidative desulfurization (ECOD) of both real gasoline and dibenzothiophene (DBT) as a thiophenic model fuel. Under relatively mild reaction conditions, the catalytic performance of the as‐prepared nanocatalyst in the ECOD procedure was studied by incorporating acetic acid/hydrogen proxied as an oxidant system at a volume ratio of 1:2. Based on the results, the K3SiW11CdO39@CoFe2O4@PAN nanocatalyst demonstrated effectiveness of up to 95% with 0.1 g at 35°C under optimal operating conditions in the ECOD process. Additionally, the synthesized nanocatalyst exhibited the ability to undergo five consecutive runs in the ECOD process without any discernible reduction in its activity.
Comparative analysis of cloud resources forecasting using deep learning techniques based on VM workload traces
Authors: Kollu Praveen Kumar , Janjanam Tejaswini Sambrajyam , Siram Kavya Sharmila
Published: January 2024

The major cost of running a cloud is power consumption. Under‐utilization of resources that are kept idly on, over‐allocation of resources, and so on, are a few reasons for excessive power utilization by the data centers. So, to optimize the power consumption, future resource usage of virtual machines (VM) can be forecasted using their trace logs. Based on this prediction, excessively allocated VM resources can be freed thereby reducing the number of physical machines as well as the carbon footprint. In this work, we present a comparative study of some deep learning techniques such as multilayer perceptron (MLP), autoregressive neural network (ARNN), convolutional neural network (CNN), long short‐term memory (LSTM) network in forecasting the CPU, memory usage of many VMs. The GWA‐T‐12 Bitbrains data center dataset consisting of 1250 VMs' workload traces is used in this work. The main goal is to avoid underload/overload in VMs which occurs sometimes while trying to optimize resource allocation. We achieved a maximum of 98% accuracy in future resource requirement forecasting. Among all models, MLP attained the highest accuracy.
An evaluation of the inflation forecasting performance of the European Central Bank, the Federal Reserve, and the Bank of England
Authors: Argiri Eleni , Hall Stephen G. , Momtsia Angeliki , Papadopoulou Daphne Marina , Skotida Ifigeneia , Tavlas George S. , Wang Yongli
Published: January 2024

We provide an overview of the formulation of the forecasts of the European Central Bank, the Federal Reserve, and the Bank of England. We also provide statistical assessments of the performance of the forecasting process of those central banks. We find that the inflation forecasts have, by‐and‐large, been unbiased and efficient at the very short‐term forecast horizon. The performance deteriorates over longer horizons. This latter finding could be attributable, inter alia, to the approach applied in the integration in the forecasting process of the assumptions on the future market‐implied interest rate path.
Ethyl acetate fraction of oregano seed protects non‐alcoholic fatty liver in high‐fat diet‐induced obese mice through modulation of Srebp‐1c
Authors: Lee Hyun‐Jong , Bae Ji‐Yun , Park Kye Won , Kim Mi‐Ja
Published: January 2024

Oregano (Origanum vulgare) seed is used as spices and is known to have anti‐inflammatory, antibacterial, and antioxidant effects. The anti‐fatty liver effects of oregano seed ethyl acetate (OSEA) were evaluated in high‐fat diet (HFD)‐induced obese mice. OSEA was orally administered with HFD for 10 weeks. The body weight, aspartate aminotransferase, alanine aminotransferase, cholesterol, triglyceride, and low‐density lipoprotein levels in the HFD with 100 mg/kg of OSEA significantly decreased by approximately 1.21‐, 1.44‐, 2.12‐, 1.12‐, 1.05, and 1.59 times, respectively, while high‐density lipoprotein levels increased by approximately 1.05 times compared to those in the HFD group (p < .05). In addition, the distribution of liver fat in the HFD with 100 mg/kg OSEA (OSEA 100) group decreased significantly (p < .05). Therefore, OSEA supplementation can ameliorate fatty liver disease and reduce the accumulation of triglycerides in adipose tissue. The expression of genes involved in liver fat accumulation, such as sterol regulatory element‐binding protein‐1c (Srebp‐1c), fatty acid synthase (Fas), stearoyl‐CoA desaturase‐1 (Scd1), and acetyl‐CoA carboxylase 1 (Acc1), significantly decreased in OSEA 100 by approximately 2.6‐, 1.74‐, 1.89‐, and 1.56‐times, respectively (p < .05). Therefore, OSEA may modify obesity and liver fat accumulation by regulating the expression of genes involved in lipid metabolism.