bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nonlinear model predictive control for mode‐switching operation of reversible solid oxide cell systems
Authors: Li Mingrui , Allan Douglas A. , Dinh San , Bhattacharyya Debangsu , Dabadghao Vibhav , Giridhar Nishant , Zitney Stephen E. , Biegler Lorenz T. 
Published: August 2024

AbstractSolid oxide cells (SOCs) are a promising dual‐mode technology for the production of hydrogen through high‐temperature water electrolysis, and the generation of power through a fuel cell reaction that consumes hydrogen. Switching between these two modes as the price of electricity fluctuates requires reversible SOC operation and accurate tracking of hydrogen and power production set points. Moreover, a well‐functioning control system is important to avoid cell degradation during mode‐switching operation. In this article, we apply nonlinear model predictive control (NMPC) to an SOC module and supporting equipment and compare NMPC performance to classical proportional‐integral (PI) control strategies, while switching between the modes of hydrogen and power production. While both control methods provide similar performance across various metrics during mode switching, NMPC demonstrates a significant advantage in reducing cell thermal gradients and curvatures (mixed spatial‐temporal partial derivatives), thereby helping to mitigate long‐term degradation.
Shielding effect‐engineered single‐crystalline Ti‐rich nanosized aggregated TS‐1 for 1‐hexene epoxidation
Authors: Zong Ze , Deng Xuliang , Lin Dong , Xu Yang , He Qiuming , Ma Zhe , Chen De , Yang Chaohe , Feng Xiang 
Published: August 2024

AbstractTitanosilicate with H2O2 stands out as a highly consequential oxidized catalytic system, prized for its user‐friendly operation, mild conditions, and eco‐friendly attributes. However, a synthesis strategy for large surface area titanosilicalites approaching the theoretical lowest Si/Ti ratio without extra‐framework Ti species remains an ongoing challenge. In this study, we successfully synthesized single‐crystalline Ti‐rich nanosized aggregated TS‐1 by shielding effect with a Si/Ti polymer. This polymer demonstrated effectiveness in restraining TiO2 species by regulating the proximity of Si/Ti species in Ti‐Diol‐Si polymers. The polymer not only facilitated the synthesis of single‐crystalline Ti‐rich TS‐1 but also exploited the chain length of PEG, functioning as a shielding cage by hydrogen bonds, to synthesize nanosized aggregated TS‐1 (TS‐1‐PEG400). This TS‐1‐PEG400 exhibited superior conversion (~60%), selectivity (~90%), and stability in 1‐hexene epoxidation. This study not only establishes a synthesis pathway for Ti‐rich TS‐1 but also holds the potential to enhance related industrial oxidation reactions involving titanosilicates and H2O2.
Thermodynamic implications of size, hydrophilicity, and fluorine content on perfluoroalkyl adsorption in NU‐1000
Authors: Johnson Phillip I. , Gregory Garrett N. , Bukowski Brandon C. 
Published: August 2024

AbstractThe molecular mechanisms that drive adsorption are critical for engineering new adsorbents to capture environmental contaminants, such as perfluoroalkyl substances (PFAS). Metal–organic frameworks (MOFs) have been shown to adsorb some classes of PFAS, yet a fundamental understanding of how PFAS identity and water competition affect adsorption capacity is unknown. Here, grand canonical Monte Carlo simulations of perfluoroalkanoic acids (PFAAs) adsorption in the MOF NU‐1000 were performed with coadsorbed water and varying carbon chain length sizes to interrogate how PFAS structure affects adsorption capacity. We found that larger PFAAs adsorb favorably into NU‐1000 than shorter chain PFAAs due to the formation of pore‐filling aggregates that stabilize anionic adsorption to the node. Due to their size and hydrophilicity, shorter chains tend to limit interactions with the adsorbent. These insights offer directions for developing novel materials that promote aggregate formation to capture and retain a wider set of PFAS from aqueous solutions.
π‐Extended 4,5‐Fused Bis‐Fluorene: Highly Open‐Shell Compounds and their Cationic Tetrathiafulvalene Derivatives
Authors: Lirette Frédéric , Bliksted Roug Pedersen Viktor , Gagnon Félix , Brøndsted Nielsen Mogens , Fernández Israel , Morin Jean‐François 
Published: August 2024

AbstractThe synthesis of diradical organic compounds has garnered significant attention due to their thermally accessible spin inversion and optoelectronic properties. Yet, preparing such stable structures with high open‐shell behavior remains challenging. Herein, we report the synthesis and properties of four π‐extended, fused fluorene derivatives with high diradical character, taking advantage of a molecular design where the closed‐shell does not include any Clar sextet, comparatively to a maximum of 5 in the corresponding open‐shell state. This led to an unusual open‐shell triplet ground state with an outstanding singlet‐triplet energy difference (ΔEST) of ca. 19 kcal/mol, one of the highest values reported to date for an all‐carbon conjugated scaffold. Incorporation of dithiafulvene units at each end of the molecule (at the five‐membered rings) furnishes extended tetrathiafulvalenes (TTFs) undergoing reversible oxidations to the radical cation and diradical dication. The various pro‐aromatic structures presented herein show highly localized spin density and a limited conjugation due to the confined π‐electrons in the aromatic cycles, as supported by 1H NMR, UV/Visible, EPR spectroscopy and DFT calculations.
Piper chaba Stem Extract Assisted Facile Synthesis of Zinc Oxide Nanoparticles for Photocatalytic and Antimicrobial Applications
Authors: Pervin Shova , Saha Prianka , Rahman S. M. Mahbubur , Ullah Md. Wali , Ahmmad Bashir , Mahiuddin Md. 
Published: August 2024

ABSTRACTThe versatile application of metal‐based nanoparticles has led to a recent rise in interest in the low‐cost and eco‐friendly green chemistry‐based development of metal oxide nanoparticles. This work focuses on the photocatalytic and antibacterial uses of the zinc oxide nanoparticles (ZnONPs) that were produced based on a green approach employing stem extract of Piper chaba. The formation of ZnONPs was preliminary validated by the appearance of an absorption band at 373 nm and a stretching band due to ZnO at 480 cm−1 in UV–Vis and FTIR spectrum, respectively. The crystalline nature of ZnONPs with a hexagonal wurtzite phase and an average crystallite size of 25 nm was validated by XRD analysis. ZnONPs' crystalline nature was further supported by TEM, which further showed that they were mostly cubic in form and had an average length of 30 nm. Synthesized ZnONPs demonstrated significant antibacterial activity against Salmonella typhi, Vibrio cholerae, Escherichia coli, and Staphylococcus aureus and lucrative photocatalytic activity with the rate constant value of 0.0273 min−1 towards the degradation of methylene blue under sunlight exposure. Therefore, a facile, affordable, and ecologically sustainable method like this might be used for the large‐scale synthesis of ZnONPs.
Ligand‐Boosted Copper Catalysis for Air‐Tolerant Methoxylation of (Hetero)aryl Halides With Sodium Methoxide
Authors: Xu Ke , Wu Shigang , Zou Gang 
Published: August 2024

ABSTRACTAn air‐tolerant, simple yet highly efficient copper‐catalyzed methoxylation of (hetero)aryl bromides and some activated chlorides has been developed by using copper(II) chloride/2,2‐bipyridine as catalyst precursor. A wide range of (hetero)aryl bromides and electron‐deficient chlorides could be efficiently methoxylated in good to excellent yields at 1‐mol% catalyst loading albeit showing a functional group compatibility dependent on the electronic properties of aryl ring. Applications of the practical protocol have been demonstrated in multigram synthesis of 3,4,5‐trimethoxytoluene.
Enhancing durable electrical conductivity in multi‐walled carbon nanotubes‐epoxy composites via laser repetition rate nanojoining for flexible electronics
Authors: Barayavuga Theogene , Jianlei Cui , wei Fengqi , Mei Huanhuan , Rahman Mostafizur , Wang Zhijun , Mei Xuesong 
Published: August 2024

AbstractWith the development of nanotechnology, laser matter interaction has become intriguing for many applications, including the manufacturing of flexible electronics to improve interface behaviors. Employing high laser repetition rate nanojoining transfer patterning, this study ensures the robust and consistent stability of electrical properties of MWCNTs. This procedure meticulously eliminates contaminants from the interface between flexible PET substrates and carbon nanotube‐containing epoxy, significantly influencing the degree of alteration in composite material and interface behaviors. By increasing the laser repetition rate from the original sample to the sample irradiated by a laser with a repetition rate of 80 kHz, the defect concentration in carbon nanotubes decreases from 0.448 × 106/nm2 to 0.39376 × 106/nm2, respectively. The relationship between defect concentration and electrical conductivity in semiconductor carbon nanotubes under laser irradiation is multifaceted and context‐dependent. Optimizing the laser repetition rate is crucial in defining the kind and density of semiconductor carbon nanotubes. This study found an electrical conductivity of 3.6799 × 10−4 S/m at a laser repetition rate of 80 kHz. Laser ablation nanojoining with a high laser repetition rate is poised to become a key recycling method for plastic materials in future industries. When MWCNTs are used in processing new materials, this method not only enhances the electrical and mechanical properties of recycled plastics but also creates high‐performance composites with added value. Additionally, the quick nature of this process helps minimize toxicity in material processing by reducing exposure time and the need for harmful chemicals. These composites exhibit superior properties suitable for advanced applications such as flexible electronics, sensors, and nanocomposite materials, contributing to both sustainability and economic value in various industrial sectors.
Naphthalene Diimide and Bis‐Heteroleptic Ru(II) Complex‐Based Hybrid Molecule with 3‐in‐1 Functionalities
Authors: Rashid Ambreen , Mondal Sahidul , Musha Islam Abu Saleh , Mondal Subal , Ghosh Pradyut 
Published: August 2024

AbstractMultipurpose applications of a newly developed homobimetallic Ru(II) complex, Ru‐NDI[PF6]4, which incorporates 1,10‐phenanthroline and triazole‐pyridine ligands and linked via a (−CH2−)3 spacer to the reputed anion‐π interacting NDI system, are described. Solution‐state studies of the bimetallic complex, including EPR, PL, UV‐vis, and NMR experiments, reveal two sequential one‐electron transfers to the NDI unit, generating NDI⋅− and NDI2− in the presence of F− selectively. This process inhibits the primary electron transfer from Ru(II) to the NDI unit, thereby allowing the 3MLCT‐based emission of the complex to be recovered, resulting in a corresponding ten‐fold increase in luminescence intensity. DFT and TD‐DFT computational studies further elucidate the experimentally observed absorption spectra of the complex. Secondly, CT‐DNA binding studies with the complex are performed using various spectroscopic analyses such as UV‐vis, PL, and CD. Comparative DNA binding studies employing EB and molecular docking reveal that the binding with CT‐DNA occurs through both intercalative and groove binding modalities. Thirdly, the photocatalytic activities of the complex towards C−C, C−N, and C−O bond formation in organic cross‐coupling reactions, including the amidation of α‐keto acids to amines and the oxidation of alcohol to aldehydes, are also demonstrated.
Foam Ti Supported Pd Catalysts for the Selective Hydrogenation of Nitroaromatics
Authors: Yang Di , Li Weijie , Deng Xin , Chai Yuchao , Wu Guangjun , Li Landong 
Published: August 2024

AbstractThe selective hydrogenation of nitroaromatics plays an essential role in the chemical industry for the synthesis of anilines and their derivatives, which are known as crucial fine chemicals and pharmaceuticals. In this study, we demonstrate the preparation of Pd/Ti monolith catalyst containing well‐isolated metallic Pd sites on Ti substrate through a simple impregnation method, showing remarkable catalytic properties in the selective hydrogenation of nitroaromatics containing various functional groups. Kinetic analyses reveal an apparent activation energy of 61 kJ/mol and the kinetic isotope effect (KH2/KD2) of ~1.7 in the hydrogenation of 3‐chloronitrobenzene over Pd/Ti‐200 ppm catalyst, indicating the facile dissociation of dihydrogen and the subsequent efficient hydrogenation. The Pd/Ti‐200 ppm catalyst also demonstrates good stability and recyclability, maintaining its performance over multiple cycles. This simple but innovative approach not only enhances the efficiency of Pd catalysts in the selective hydrogenation of nitroaromatics but also offers significant potential for industrial applications in aniline production.
Evaluation of NAD+ precursors for improved metabolism and productivity of antibody‐producing CHO cell
Authors: Han Hye‐Jin , Kim Hagyeong , Yu Hyun Gyu , Park Jong Uk , Bae Joo Hee , Lee Ji Hwan , Hong Jong Kwang , Baik Jong Youn 
Published: August 2024

AbstractIn the previous study, the culture medium was treated with nicotinamide adenine dinucleotide (NAD+) under the hypothesis that NAD+ regeneration is a major factor causing excessive lactate accumulation in Chinese hamster ovary (CHO) cells. The NAD+ treatment improved metabolism by not only reducing the Warburg effect but also enhancing oxidative phosphorylation, leading to enhanced antibody production. Building on this, four NAD+ precursors – nicotinamide mononucleotide (NMN), nicotinic acid (NA), nicotinamide riboside (NR), and nicotinamide (NAM) – were tested to elevate intracellular NAD+ levels more economically. First, the ability of CHO cells to utilize both the salvage and Preiss‐Handler pathways for NAD+ biosynthesis was verified, and then the effect of NAD+ precursors on CHO cell cultures was evaluated. These precursors increased intracellular NAD+ levels by up to 70.6% compared to the non‐treated group. Culture analysis confirmed that all the precursors induced metabolic changes and that NMN, NA, and NR improved productivity akin to NAD+ treatment, with comparable integral viable cell density. Despite the positive effects such as the increase in the specific productivity and changes in cellular glucose metabolism, none of the precursors surpassed direct NAD+ treatment in antibody titer, presumably due to the reduction in nucleoside availability, as evidenced by the decrease in ATP levels in the NAD+ precursor‐treated groups. These results underscore the complexity of cellular metabolism as well as the necessity for further investigation to optimize NAD+ precursor treatment strategies, potentially with the supplementation of nucleoside precursors. Our findings suggest a feasible approach for improving CHO cell culture performances by using NAD+ precursors as medium and feed components for the biopharmaceutical production.
WNT5A is a putative epi‐driver of prostate cancer metastasis to the bone
Authors: Wilkinson Emma J. , Raspin Kelsie , Malley Roslyn C. , Donovan Shaun , Nott Louise M. , Holloway Adele F. , Dickinson Joanne L. 
Published: August 2024

AbstractBackgroundCurrent diagnostic tools are unable to distinguish low‐grade indolent prostate cancer (PrCa) from that with a propensity to become metastatic and/or lethal. Recent evidence suggests that reprogramming of the transcriptome may drive the metastatic phenotype, and that this reprogramming is controlled, at least in part, by epigenetic changes to the DNA of cancer cells, including methylation. These changes, referred to as ‘epigenetic drivers,’ have previously been associated with cancer cell survival.MethodsHere, using Illumina Methylation EPIC array data of paired primary PrCa and metastatic bone samples, we identified WNT5A as a putative epi‐driver of PrCa metastasis to the bone, which was further validated in vitro.ResultsSignificantly higher WNT5A methylation was observed in primary PrCa samples and 22Rv1 cells compared to metastatic bone samples and PC‐3 cells. This higher methylation was associated with significantly lower WNT5A gene expression.ConclusionGiven the limited effective therapies available for metastatic cancer sufferers, particularly those whose disease has metastasised to the bone, WNT5A presents as a potential putative target for therapy.
Migrated toothpick causing a hepatic abscess with portal vein thrombosis: A case report and review of literature
Authors: Joueidi Faisal , Alzahrani Ali A. , Altaweel Abdulaziz A. , Alwhaibi Omar , Elgohary Ahmed , Bin Saad Khalid O. 
Published: August 2024

Key Clinical MessageAccidental foreign body ingestion is the most common hidden cause of abdominal pain. A high index of suspicion should be implemented in patients with unresolved abdominal pain. Here we reported a 54‐year‐old patient with vague abdominal pain who had a successful laparoscopic removal of a toothpick.AbstractToothpicks and fish bones are considered one of the most common accidentally ingested foreign bodies. Fortunately, most patients are asymptomatic. About 80%–90% of ingested foreign bodies pass through the gut spontaneously within a week. We present a case of a 54‐year‐old female with chronic epigastric pain and fever found to have a foreign body (toothpick) that penetrated the stomach and migrated to the liver causing liver abscess with portal vein thrombosis. The patient was managed with laparoscopic removal of the foreign body with an uneventful postoperative course.
Surgical and oncologic approach to leiomyosarcoma of the inferior vena cava: A case report
Authors: Maniso Feleke Hailmariam , Woldegeorgis Mathewos Assefa , Bedada Hawi Furgassa 
Published: August 2024

Key Clinical MessageLMS of IVC needs a multidisciplinary approach. Surgical excision with free margin is the cornerstone of management. Upon case‐by‐case selection, adjuvant chemotherapy may play a role in better oncologic outcome.AbstractLeiomyosarcoma (LMS) of the inferior vena cava (IVC) is a rare form of mesenchymal origin malignancy with less than 400 cases reported to date. Surgery is the mainstay of management but it requires vast experience in vascular and visceral surgery to attain a free tumor margin. Subsequent adjuvant treatment with chemotherapy and radiation remains as an area of gray zone. We report the case of a 61‐year‐old man with an 8‐month history of abdominal pain. Upon physical examination, an ill‐defined mass over the right side of the lower abdomen and bilateral lower extremity edema were detected. Abdominal ultrasound with Doppler revealed a right‐side retroperitoneal mass invading the IVC with extensive venous thrombosis for which anticoagulation was initiated. Computed Tomography of the abdomen revealed a huge heterogeneously enhancing mass involving the whole length of the infrarenal IVC obstructing the IVC lumen with collateral veins draining through the paralumbar veins and inferior epigastric veins bilaterally. With a top differential of primary IVC LMS, a midline longitudinal laparotomy was performed with an intraoperative finding of a tumor arising from the infra‐renal IVC which was excised. Gore‐Tex graft was used to reconstruct the IVC. There was an injury to the right common iliac artery and it was repaired by end‐to‐end anastomosis. Histopathology confirmed a high‐grade LMS of the IVC and surgical margin status was unknown. He was given adjuvant Chemotherapy consisting of Doxorubicin and Dacarbazine. He has been on follow‐up at the Oncology side with a good performance status.
The use of negative pressure therapy for the treatment of gunshot wounds in a limited resource setting in eastern part of the Democratic Republic of Congo: Case series
Authors: Munguakonkwa Paul Budema , de Dieu Namegabe Tumsifu Jean , Murhula Gauthier Bahizire , Kuhigwa Georges Toha , Cikomola Fabrice Gulimwentuga , Kabesha Théophile Barwamire , Kibendelwa Zacharie Tsongo , Mukuku Olivier , Okitotsho Stanis Wembonyama 
Published: August 2024

Key Clinical MessageThe use of negative pressure therapy in the management of gunshot wound have a favorable outcome, NPT is easy to build, accelerates wound budding, reduces patient's stay in hospital and its low cost. It showed reassuring results in the management of wound with soft tissue lost, comparatively to other dressing.AbstractWounds due to gunshot injuries are common in east of Republic Democratic of Congo and its management should be well known by surgeons and other health practitioners. Reconstruction is possible with simple surgeries using skin grafts and negative pressure therapy (NPT). In this study, we present our results of wounds treatment after gunshot injury with a simple non‐surgical procedure using NPT. We present four patients with soft tissue losses caused by gunshot injury. These patients underwent an average of four to eight sessions of vacuum dressing, the length of hospital stay was decrease and soft tissue losses were reconstructed using at the end skin grafts.
Ammonia Synthesis Rate Over a Wide Operating Range: From Experiments to Validated Kinetic Models
Authors: Nadiri Solmaz , Attari Moghaddam Alireza , Folke Jan , Ruland Holger , Shu Bo , Fernandes Ravi , Schlögl Robert , Krewer Ulrike 
Published: August 2024

AbstractWith the increasing demand for flexible operation of ammonia production, the feasibility of using reaction kinetic models to predict the performance of a Haber Bosch reactor in a wide operating range must be evaluated. This study compares the feasibility of a lumped Temkin rate expression with a more complex lumped microkinetic model in predicting turnover rates across diverse temperatures and feed compositions. Evaluation and validation were carried out through ammonia synthesis experiments on a magnetite‐based industrial catalyst at temperatures ranging from 548 K to 773 K and H2 : N2 ratios between 4 : 1 to 1 : 1 at 90 bar. While excellent agreement between model predictions and experiments was observed at 648 K, significant discrepancies emerged at 548 K. These findings are valuable for both state‐of‐the‐art ammonia synthesis reactors and green ammonia plants utilizing electrolysis‐derived hydrogen, where flexible operating conditions are paramount. Moreover, integrating site density as a function of temperature and the partial pressure of H2 into the lumped microkinetic model marks a notable advancement, promising enhanced precision in addressing varied operating conditions.
In Situ Transformation of Hybrid Bismuth Halide into Rhombohedral Bismuth for Electrochemical CO2 Reduction to Formate
Authors: Tian Bao‐Qiang , Hou Juan‐Juan , Wang Ting , Gao Yang , Zhang Junming , Lu Wenbo , Jia Jianfeng 
Published: August 2024

AbstractBi‐based electrocatalysts have attracted high attention due to their high selectivity for formate, low cost, and high biocompatibility. Surface modification with halides can adjust the surface charge distribution of metal catalysts, thereby regulating the binding force of the intermediate. Organic‐inorganic hybrid bismuth halides provide an alternative, especially low dimensional structures. Herein, zero‐dimensional hybrid bismuth halides containing Bi4I16 units (denoted as Bi4I16) was recommended as pre‐catalyst due to the Bi ⋅ ⋅ ⋅ Bi spacing in Bi4I16 is 4.760 Å, nearly equaling to the Bi ⋅ ⋅ ⋅ Bi spacing in rhombohedral Bi (4.750 Å). The equal spacing may be more beneficial for the electricity‐driven in situ conversion and rearrangement of Bi atoms in the catalytic process. As a contrast, zero‐dimensional bismuth halide containing Bi2I9 units (denoted as Bi2I9) with shorter Bi ⋅ ⋅ ⋅ Bi spacing (4.2415 Å) was prepared. The working electrode prepared by Bi4I16 ink was measured for CO2RR, and the partial formate current density can reach 8.2 mA cm−2 at −1.1 V vs RHE. The Bi4I16 catalyst delivers a maximum Faradaic Efficiency (FE, ~80 %) for formate at −0.86 V vs RHE and maintain a FE higher than 78.5 % after 16 h.