bluuebunny/crossref_metadata_2025 huggingface dataset:
DETECTION OF PNEUMONIA FROM X-RAY IMAGES USING DEEP LEARNING TECHNIQUES
Authors: BAKIR Halit , OKTAY Semih , TABARU Emre
Published: April 2023

X-ray images is one of the most common utilities used by health care specialists for detecting healthy problems in patients’ chest. In this work, deep learning techniques have been adopted for diagnosing and detecting of lung diseases. First, an experimental study has been conducted for selecting the best artificial neural network ANN model that can be used for lung X-Ray image classification. The obtained best model has been used for classifying the lung X-Ray images into three classes (Multi class classification) namely bacterial pneumonia, viral pneumonia, and healthy lung. After that, three well-known CNN architectures, namely ResNet, Inception, and MobileNet have been adopted and used as a feature extractor for the selected best ANN model. Moreover, the above-mentioned ANN model (both with and without the features extraction phase) has been used for classifying the lung X-Ray images as healthy and pneumonia lungs (Binary classification). As a result of the study, the proposed ANN model with ResNet feature extraction phase gave the highest classification accuracy rate of 81.67% when multi-class classification has been conducted on the lung X-Ray dataset. On the other hand, the proposed ANN model with MobileNet feature extraction phase gave the highest accuracy rate of 95.67% when a binary classification has been conducted on the X-Ray image dataset.
THE EFFECT OF LEVOTHYROXINE TREATMENT ON MATERNAL AND PERINATAL OUTCOMES IN PREGNANT WOMEN WITH SUBCLINICAL HYPOTHYROIDISM: A 5-YEAR RETROSPECTIVE STUDY AT A TERTIARY CARE HOSPITAL IN TURKEY
Authors: ERBIYIK Halil İbrahim , PALALIOGLU Rabia Merve
Published: April 2023

Subclinical hypothyroidism is characterized by elevated thyroid stimulating hormone (TSH) levels with normal free thyroxine (fT4) levels. The aim of this study was to compare obstetric and neonatal outcomes in pregnant women with and without treatment for subclinical hypothyroidism. In this study, maternal and perinatal outcomes were evaluated in a total of 270 pregnant women who were diagnosed with subclinical hypothyroidism as a result of screening performed in three trimesters of pregnancy between 2015 and 2020 and followed up in our clinic, 149 of whom received levothyroxine treatment and 121 of whom did not receive treatment. Further, different cutoff values for TSH were compared. The rates of neonatal intensive care unit (NICU) requirement were not different according to the levothyroxine use status of the patients (p=0.73, p>0.05). Miscarriage rates did not differ according to levothyroxine use (p=0,87, p>0,05). TSH, T4 and antithyroid peroxidase levels did not differ according to the maternal use of levothyroxine (p>0,05). Birth weight, gestational week at birth, 1- and 5-minute APGAR scores, neonatal TSH and T4 levels did not differ according to the maternal use of levothyroxine (p>0,05). Among the adverse maternal and perinatal outcomes, the need for NICU admission and the rates of placental abruption, fetal distress, preterm premature rupture of membranes, preeclampsia, preterm labor, and small for gestational age were not significantly different among the TSH cutoff groups (p>0,05). The rate of premature rupture of membranes was higher in the group with TSH levels ≥2.5 mIU/L (p=0.04). Choosing 2.5 mIU/L as the cutoff value for TSH levels allows early diagnosis of subclinical hypothyroidism with a higher rate in pregnant Turkish women and proactive therapeutic management. Our study provides limited evidence for the success of levothyroxine therapy for adverse obstetric and neonatal outcomes.
ANALYZING THE CRITICAL SUCCESS FACTORS IN THE ONLINE-GAME DEVELOPMENT: A FRAMEWORK PROPOSAL USING THE DELPHI-TOPSIS METHOD
Authors: Linares Barbero Manuela , GALLEGO PEREIRA MARIA DOLORES , BUENO AVILA SALVADOR
Published: April 2023

The online-game industry has increased exponentially in the last years, boosted by the global pandemic crisis, and it´s expected to continue growing. Moreover, specialized software (game engines) is used to develop online-games. This fast growth of both, online-game industry and game engines, shows the convenience for a better understanding of online-games´ development. Thus, this paper aims to define a critical success factors (CSF) framework in developing online-games, and it combines the Delphi and TOPSIS methodology. Concretely, its application follows. First, CSF were recognized from the literature. Second, they were verified by contacting software developers of the game engine Unity using Delphi methodology. Then, a numerical example of the TOPSIS methodology is shown. This method allowed to generate a framework of 21 critical factors, grouped in 3 dimensions: (1) Game content design, (2) Value added and (3) Game motivation. The results revealed that competition is the most important factor in the Social motivation construct. Also, Mission and tasks, and User interface are the most important factors in the Game content design dimension. Definitely, this framework provides a tool for decision making in the online-game development process.

Keywords: TOPSIS, Delphi, online-games, video-games, game engine, critical factors, web software
Use of Active Surveillance vs Definitive Treatment Among Men With Low- and Favorable Intermediate–Risk Prostate Cancer in the US Between 2010 and 2018
Authors: Al Hussein Al Awamlh Bashir , Barocas Daniel A. , Zhu Alec , Tosoian Jeffrey J. , Ponsky Lee , Negoita Serban , Shoag Jonathan E.
Published: April 2023

This cross-sectional study of data from the Surveillance, Epidemiology and End Results database assesses temporal trends in the use of active surveillance and watchful waiting vs definitive treatment in men with low- and favorable intermediate–risk prostate cancer in the US between 2010 and 2018.
Frequency of Use and Outcomes of Colonoscopy in Individuals Older Than 75 Years
Authors: El Halabi Jessica , Burke Carol A. , Hariri Essa , Rizk Maged , Macaron Carole , McMichael John , Rothberg Michael B.
Published: April 2023

Importance

The benefits from colorectal cancer (CRC) screening may take 10 to 15 years to accrue. Therefore, screening is recommended for older adults who are in good health.

Objective

To determine the number of screening colonoscopies done in patients older than 75 years with a life expectancy of fewer than 10 years, diagnostic yield, and associated adverse events within 10 days and 30 days of the procedure.

Design

This cross-sectional study with a nested cohort between January 2009 and January 2022 in an integrated health system assessed asymptomatic patients older than 75 years who underwent screening colonoscopy in the outpatient setting. Reports with incomplete data, any indication other than screening, patients who had a colonoscopy within the previous 5 years, and patients with a personal history of inflammatory bowel disease or CRC were excluded.

Exposures

Life expectancy based on a prediction model from previous literature.

Main Outcomes and Measures

The primary outcome was the percentage of screened patients who had limited (<10 years) life expectancy. Other outcomes included colonoscopy findings and adverse events that developed within 10 days and 30 days of the procedure.

Results

A total of 7067 patients older than 75 years were included. The median (IQR) age was 78 (77-79) years, 3967 (56%) were women, and 5431 (77%) were White with an average of 2 comorbidities (taken from a select group of comorbidities). The proportion of colonoscopies performed on patients with a life expectancy of fewer than 10 years aged 76 to 80 years was 30% in both sexes and increased with age—82% of men and 61% of women aged 81 to 85 years (71% total), and 100% of patients beyond the age of 85 years. Adverse events requiring hospitalizations were common at 10 days (13.58 per 1000) and increased with age, particularly among patients older than 85 years. The detection of advanced neoplasia varied from 5.4% among patients aged 76 to 80 years to 6.2% in those aged 81 to 85 years and 9.5% among patients older than 85 years (P = .02). Of the total population, 15 patients (0.2%) had invasive adenocarcinoma; among patients with a life expectancy of fewer than 10 years, 1 of 9 was treated, whereas 4 of 6 patients with a life expectancy of greater than or equal to 10 years were treated.

Conclusions and Relevance

In this cross-sectional study with a nested cohort, most screening colonoscopies performed in patients older than 75 years were in patients with limited life expectancy and associated with increased risk of complications. Colorectal cancer was exceedingly rare.
Inorganic Filler Enhanced Formation of Stable Inorganic‐Rich Solid Electrolyte Interphase for High Performance Lithium Metal Batteries
Authors: Guo Chi , Du Kang , Tao Runming , Guo Yaqing , Yao Shuhao , Wang Jianxing , Wang Deyu , Liang Jiyuan , Lu Shih‐Yuan
Published: April 2023

Lithium metal (LM) is a promising anode material for next generation lithium ion based electrochemical energy storage devices. Critical issues of unstable solid electrolyte interphases (SEIs) and dendrite growth however still impede its practical applications. Herein, a composite gel polymer electrolyte (GPE), formed through in situ polymerization of pentaerythritol tetraacrylate with fumed silica fillers, is developed to achieve high performance lithium metal batteries (LMBs). As evidenced theoretically and experimentally, the presence of SiO2not only accelerates Li+transport but also regulates Li+solvation sheath structures, thus facilitating fast kinetics and formation of stable LiF‐rich interphase and achieving uniform Li depositions to suppress Li dendrite growth. The composite GPE‐based Li||Cu half‐cells and Li||Li symmetrical cells display high Coulombic efficiency (CE) of 90.3% after 450 cycles and maintain stability over 960 h at 3 mA cm−2and 3 mAh cm−2, respectively. In addition, Li||LiFePO4full‐cells with a LM anode of limited Li supply of 4 mAh cm−2achieve capacity retention of 68.5% after 700 cycles at 0.5 C (1 C = 170 mA g−1). Especially, when further applied in anode‐free LMBs, the carbon cloth||LiFePO4full‐cell exhibits excellent cycling stability with an average CE of 99.94% and capacity retention of 90.3% at the 160th cycle at 0.5 C.
Organogels versus Hydrogels: Advantages, Challenges, and Applications
Authors: Kuzina Mariia A. , Kartsev Dmitrii D. , Stratonovich Alexander V. , Levkin Pavel A.
Published: April 2023

Organogels are an important class of gels, and are comparable to hydrogels owing to their properties as liquid‐infused soft materials. Despite the extensive choice of liquid media and compatible networks that can provide a broader range of properties, relatively few studies are reported in this area. This review presents the applicability of organogels concerning their choice of components, unique properties, and applications. Their distinctive features compared to other gels are discussed, including multi‐stimuli responses, affinity to a broad range of substances, thermal and environmental stability, electronic and ionic conductivity, and actuation. The active role of solvents is highlighted in the versatility of organogel properties. To differentiate between organogels and other gels, these are classified as gels filled with different organic liquids, including highly polar organic solvents and binary solvent systems. Most promising applications of organogels as sophisticated multifunctional materials are discussed in light of their unique features.
An Iminostilbene Functionalized Benzimidazoline for Enhanced n‐Type Solution Doping of Semiconducting Polymers for Organic Thermoelectrics
Authors: Rossi Pietro , Pallini Francesca , Coco Giulia , Mattiello Sara , Tan Wen Liang , Mezzomo Lorenzo , Cassinelli Marco , Lanzani Guglielmo , McNeill Christopher R. , Beverina Luca , Caironi Mario
Published: April 2023

Doped organic semiconductors play a central role in the development of several innovative optoelectronic and energy harvesting applications. Currently, the realization of thermoelectric generators, which require both hole‐ and electron‐transporting materials with high electrical conductivity, is strongly hindered by the scarce availability of stable solution‐processable n‐dopants and their limited efficiency. Herein, the synthesis of 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzimidazol‐2‐yl)‐dibenzazepine (IStBI), a novel derivative belonging to the well‐known family of the benzimidazoline compounds, is presented. The functionalization with the planarized and rigid iminostilbene substituent allows, without significantly affecting the compound electronic structure, an efficient intercalation of the dopant molecules inside the ordered regions of thin films of the benchmark n‐type polymer poly(N,N′‐bis‐2‐octyldodecylnaphthalene‐1,4,5,8‐bis‐dicarboximide‐2,6‐diyl‐alt‐5,5′‐2,2′‐bithiophene) P(NDI2OD‐T2). Consequently, a maximum electrical conductivity of (1.14 ± 0.13) × 10−2 S cm−1 is recorded, exceeding by one order of magnitude what previously achieved upon solution doping of the reference P(NDI2OD‐T2) with benzimidazoline derivatives. The thermoelectric power factor is also simultaneously increased. The findings confirm that tailoring of the dopant chemical structure to improve structural interactions with the host semiconductors can be employed as a successful strategy to achieve more effective n‐doping, helping to close the performance gap with p‐type materials.
Highly Sensitive and Color Adaptable Polyurethane‐Based Strain Sensors with Embedded Silver Nanowires
Authors: Liu Yuemei , Lyu Pei , Hu Jun , Tang Wenyang , Huang Ya , Wang Baoshun , Xu Weilin , Liu Xin , Zhang Rufan
Published: April 2023

Wearable strain sensors are expected to meet the requirements of high sensitivity, facile fabrication, and high aesthetics to realize practical applications. However, reported sensitive strain sensors fail to exhibit multicolor due to high light absorption. Herein, a flexible strain sensor with high sensitivity and color‐exhibition ability is fabricated by half‐embedding silver nanowires (AgNWs) into dyeable thermoplastic polyurethane (TPU) films through thermal annealing. A sheet resistance of 11.5 Ω sq−1 and a transmittance above 79.9% at 550 nm is obtained for intact AgNWs/TPU films. A gauge factor of 34 797 is achieved at a tensile strain of 9%, indicating the high sensitivity for monitoring tiny movement changes. Besides, the high transparency allows color exhibition after dying. The multicolor AgNWs/TPU films are further rolled into rod‐shaped yarns and weaved with commercial yarns to form wearable colorful electronics.
Femtosecond Laser Fabrication of Microchannels in Transparent Hard Materials
Authors: Lu Yue , Li Yun‐Fei , Wang Gong , Yu Yu , Bai Zhenxu , Wang Yulei , Lu ZhiWei
Published: April 2023

The excellent characteristics of transparent hard materials such as high hardness, high transparency, corrosion resistance, and high temperature resistance enable their applications in microfluidic substrates even in harsh environments. Microchannels are important parts in microfluidic systems, and the preparation of microchannel structures in transparent hard materials deserves further in‐depth study. The traditional processing method is contact processing with large thermal influence and low processing efficiency, so it is impossible to obtain complex microchannels with high quality and high aspect ratio. The femtosecond laser processing is a non‐contact processing approach with no thermal damage, high processing accuracy, and easy to form complex microchannels, making it the best choice for processing microchannels in transparent hard materials. This work reviews the recent advances in femtosecond laser processing of transparent hard materials to form microchannel structures, focusing on the reaction mechanism, processing methods, and the obtained microchannel structures, including surface microchannels, 2D microchannels, and 3D microchannels. Furthermore, the application of microchannel structure in microfluidic field, including optical inspection and biochemical reaction, is also described.
In Vitro Study on AI‐PRS Enabled Precision Cocktail Drugs Design for Treating Human Colorectal Carcinoma
Authors: Yang Hsin‐Yu , Goudar Venkanagouda S. , Hung Yi‐Chi , Ouyang Chih‐Hsuan , Rashid Masturah Bte Mohd Abdul , Juo Liang‐Yi , Wu Jen‐Kuei , Cheng Ya‐Wen , Wei Po‐Li , Tzeng Huey‐En , Jiang Jeng‐Kai , Chow Edward Kai‐Hua , Yang Chih‐Yung , Ho Chih‐Ming , Yen Yun , Tseng Fan‐Gang
Published: April 2023

Colorectal cancer (CRC) is currently the third most common cancer in the world. Due to the development of treatment resistance, the efficacy of current chemotherapeutic agents against CRC has reached a plateau. Drug activity depends on the entire physiological response; therefore, drug‐dose parameters cannot be designed efficiently by using conventional prediction‐based methodologies. In this work, the AI‐PRS (artificial intelligence‐based phenotypic response surface) platform is successfully applied to find optimal drug‐dose combinations in vitro from a pool of ten approved drugs. The AI‐PRS platform optimizes effective drug‐dose combinations without reference to molecular pathways or drug interaction data. With the aid of AI‐PRS platform, efficient one, two, three, and four drug‐dose combinations from in vitro studies are found. Of hundreds of combinations, regorafenib (R)/gemcitabine (G)/cetuximab (C)/5‐fluorouracil (U) drug‐dose combination exhibits the best activity on four CRC cell lines, two circulating tumor cells (CTCs), and one patient derived xenografts (PDX) cell lines. The three‐drug combination of R/G/U shows the highest toxicity (70%) in the PDX cell line. Four‐drug combination of R/G/C/U displays the best toxicity (80%) in in vitro cultured CTCs. The findings from the present derived cells reveal the prospective validation of the AI‐PRS platform, which may help identify customized and highly efficient drug‐dose combinations for future CRC treatment.
DOPA Residues Endow Collagen with Radical Scavenging Capacity**
Authors: Kurth Markus , Barayeu Uladzimir , Gharibi Hassan , Kuzhelev Andrei , Riedmiller Kai , Zilke Jennifer , Noack Kasimir , Denysenkov Vasyl , Kappl Reinhard , Prisner Thomas F. , Zubarev Roman A. , Dick Tobias P. , Gräter Frauke
Published: April 2023

Here we uncover collagen, the main structural protein of all connective tissues, as a redox‐active material. We identify dihydroxyphenylalanine (DOPA) residues, post‐translational oxidation products of tyrosine residues, to be common in collagen derived from different connective tissues. We observe that these DOPA residues endow collagen with substantial radical scavenging capacity. When reducing radicals, DOPA residues work as redox relay: they convert to the quinone and generate hydrogen peroxide. In this dual function, DOPA outcompetes its amino acid precursors and ascorbic acid. Our results establish DOPA residues as redox‐active side chains of collagens, probably protecting connective tissues against radicals formed under mechanical stress and/or inflammation.
Synergy of Cu/C3N4 Interface and Cu Nanoparticles Dual Catalytic Regions in Electrolysis of CO to Acetic Acid
Authors: Yan Xupeng , Zhang Menglu , Chen Yizhen , Wu Yahui , Wu Ruizhi , Wan Qiang , Liu Chunxiao , Zheng Tingting , Feng Rongjuan , Zhang Jing , Chen Chunjun , Xia Chuan , Zhu Qinggong , Sun Xiaofu , Qian Qingli , Han Buxing
Published: April 2023

Electrochemical reduction reaction of carbon monoxide (CORR) offers a promising way to manufacture acetic acid directly from gaseous CO and water at mild condition. Herein, we discovered that the graphitic carbon nitride (g‐C3N4) supported Cu nanoparticles (Cu−CN) with the appropriate size showed a high acetate faradaic efficiency of 62.8 % with a partial current density of 188 mA cm−2 in CORR. In situ experimental and density functional theory calculation studies revealed that the Cu/C3N4 interface and metallic Cu surface synergistically promoted CORR into acetic acid. The generation of pivotal intermediate −*CHO is advantage around the Cu/C3N4 interface and migrated *CHO facilitates acetic acid generation on metallic Cu surface with promoted *CHO coverage. Moreover, continuous production of acetic acid aqueous solution was achieved in a porous solid electrolyte reactor, indicating the great potential of Cu−CN catalyst in the industrial application.
High‐Current Capable and Non‐Flammable Protic Organic Electrolyte for Rechargeable Zn Batteries
Authors: Raza Bareera , Zhang Yu , Chen Jiahang , Shamraiz Umair , Zhang Yang , Naveed Ahmad , Wang Jiulin
Published: April 2023

Rechargeable Zinc batteries (RZBs) are considered a potent competitor for next‐generation electrochemical devices, due to their multiple advantages. Nevertheless, traditional aqueous electrolytes may cause serious hazards to long‐term battery cycling through fast capacity fading and poor Coulombic efficiency (CE), which happens due to complex reaction kinetics in aqueous systems. Herein, we proposed the novel adoption of the protic amide solvent, N‐methyl formamide (NMF) as a Zinc battery electrolyte, which possesses a high dielectric constant and high flash point to promote fast kinetics and battery safety simultaneously. Dendrite‐free and granular Zn deposition in Zn‐NMF electrolyte assures ultra‐long lifespan of 2000 h at 2.0 mA cm−2/2.0 mAh cm−2, high CE of 99.57 %, wide electrochemical window (≈3.43 V vs. Zn2+/Zn), and outstanding durability up to 10.0 mAh cm−2. This work sheds light on the efficient performance of the protic non‐aqueous electrolyte, which will open new opportunities to promote safe and energy‐dense RZBs.
Zinc(II) complexation strategy for ultra‐sensitive fluorimetric estimation of molnupiravir: Applications and greenness evaluation
Authors: Salman Baher I. , Hara Mohammed A. , El Deeb Sami , Ibrahim Adel E. , Saraya Roshdy E. , Ali Marwa F. B.
Published: April 2023

The endemicity of the pandemic coronavirus disease 2019 (COVID‐19) infection proved to be transitional only. Spikes are forming again in 2023, and high expectations are returning for reinfections and viral mutations. Molnupiravir (MOL) has been approved as an oral antiviral drug for the treatment of the COVID‐19 causative virion. Therefore, the development of an ultrasensitive, instantaneous, and cost‐effective method for the quantification of MOL in real plasma samples and formulated dosage form are mandatory. The proposed approach is based on the synthesis of a MOL metal‐chelation product. MOL as a ligand was chelated with 1.0 mM zinc(II) in an acetate buffer (pH 5.3). After illumination at 340 nm, the intensity of the MOL fluorescence measured at 386 nm was increased by about 10‐fold. The linearity range was found to be from 60.0 to 800.0 ng mL−1 with limit of quantitation (LOQ) of 28.6 ng mL−1. Two methods were utilized for measuring the greenness of the proposed method (Green Analytical Procedure Index [GAPI] and analytical greenness metric [AGREE] methods), with results equal to 0.8. The binding stoichiometry of MOL with the zinc(II) ion was found to be 2:1. All the experimental parameters were optimized and validated using International Conference on Harmonization (ICH) and United States Food and Drug Administration (US‐FDA) recommendations. Furthermore, the fluorescent probes were successfully utilized in real human plasma with high percentages of recovery (95.6%–97.1%) without any matrix interferences. The mechanism of fluorescent complex formation was confirmed using 1H NMR in the presence and absence of Zn(II). The method was further utilized for testing content uniformity of MOL in its marketed capsule dosage forms.
Coordination Dynamics of Iron is a Key Player in the Catalysis of Non‐heme Enzymes
Authors: Zhang Jinyan , Wu Peng , Zhang Xuan , Wang Binju
Published: April 2023

Mononuclear nonheme iron enzymes catalyze a large variety of oxidative transformations responsible for various biosynthesis and metabolism processes. Unlike their P450 counterparts, non‐heme enzymes generally possess flexible and variable coordination architecture, which can endow rich reactivity for non‐heme enzymes. This Concept highlights that the coordination dynamics of iron can be a key player in controlling the activity and selectivity of non‐heme enzymes. In ergothioneine synthase EgtB, the coordination switch of the sulfoxide radical species enables the efficient and selective C−S coupling reaction. In iron(II)‐ and 2‐oxoglutarate‐dependent (Fe/2OG) oxygenases, the conformational flip of ferryl‐oxo intermediate can be extensively involved in selective oxidation reactions. Especially, the five‐coordinate ferryl‐oxo species may allow the substrate coordination via O or N atom, which may facilitate the C−O or C−N coupling reactions via stabilizing the transition states and inhibiting the unwanted hydroxylation reactions.
Activity Regulation of Fenton/Fenton‐like Reactions in Single‐Atom Catalysis
Authors: Liang Xiao , Wang Dingsheng
Published: April 2023

On the one hand, Fenton‐like reactions are common side reactions in electrocatalytic oxygen reduction reaction (ORR). The generated reactive oxygen species (ROS) could damage the active sites of single‐atom catalysts (SACs), thereby affecting the stability of the catalysts. On the other hand, the Fenton‐like reaction could generate radicals with strong oxidative properties, which could be used in the degradation of pollutants and tumor therapy. In this review, we summarize strategies to limit the occurrence of Fenton‐like reactions and improve the stability of SACs. In addition, the promotion of Fenton‐like reactivity of SACs and its application in related fields are also concluded.
Plasma‐catalytic Ammonia Synthesis via Eley‐Rideal Reactions: A Kinetic Analysis
Authors: Rouwenhorstm Kevin H. R. , Lefferts Leon
Published: April 2023

The reaction mechanism of plasma‐catalytic ammonia synthesis is not fully understood. MgO supported Ru, Co, Pt, Pd, Cu and Ag catalysts are tested in a DBD plasma at temperature between room temperature and 500 °C and plasma power between 3.8 W and 6.4 W. The resulting ammonia production in the presence of a plasma and a catalyst can be distinguished into (1) temperature‐independent plasma‐based ammonia synthesis, and (2) temperature‐dependent plasma‐catalytic ammonia synthesis. Turn‐over‐frequencies (TOF) are calculated based on the rate of the second pathway and chemisorption data, measuring the number of active sites. Underestimation of TOFs caused by ammonia decomposition was minimized by using exclusively observations at low ammonia concentration. The kinetic results suggest that the Eley‐Rideal reaction between N radicals from the plasma with chemisorbed H atoms is the rate‐determining step for plasma‐catalytic ammonia synthesis on Ru/MgO, Co/MgO, Pt/MgO, Pd/MgO, and Cu/MgO, with apparent activation barriers in the range 18–24 kJ mol−1. In contrast, the apparent activation barrier on Ag/MgO is significant higher at 30 kJ mol−1, suggesting a shift in rate determining step. The low H coverage on Ag may induce a shift to a Langmuir‐Hinshelwood pathway, via adsorption of N radicals on the metal surface.
Redox Convergent Synthesis and Reactivity of a Cobalt(III)‐Pentasulfido Compound
Authors: Atta Sayan , Majumdar Amit
Published: April 2023

A new mononuclear cobalt(III)‐pentasulfido compound, [(L)Co(S5)] (3) has been synthesized by using a convergent redox reaction between elemental sulfur and two new cobalt(II)‐thiolato compounds, [(L)Co(SR)] (R=Ph, 2 a; 2,6‐Me2‐C6H4, 2 b), which in turn were synthesized from a dimeric cobalt(II) complex, [(L)2Co2]2+ (1). Compound 3 features a low‐spin, diamagnetic, Co(III) center with a coordinated pentasulfido (S52−) chain and has no precedence in the literature. Compound 3 is highly stable towards reduction with a potential of −1.36 V (vs. Cp2Fe+/Cp2Fe) and gives back 1 upon chemical/electrochemical reduction. Reaction of 3 with phosphines yields back 1 and phosphine sulfides, while protonation of the coordinated S52− chain in 3 leads to the formation of 1, elemental sulfur and H2S. Finally, transfer of the coordinated S52− chain in 3 to selected organic compounds, such as MeI, PhCH2Br and PhCOCl, for the generation of organopolysulfido compounds has been demonstrated.
Mechanisms of the Reaction of Elemental Sulfur and Polysulfides with Cyanide and Phosphines**
Authors: Sharma Jyoti , Champagne Pier Alexandre
Published: April 2023

The reactions of elemental sulfur (S8) and polysulfides with nucleophiles are relevant to organic synthesis, materials science and biochemistry, but the mechanisms by which they operate are still unknown due to the inherent thermodynamic and kinetic instability of polysulfide intermediates. Using Density Functional Theory (DFT) calculations at the ωB97X‐D/aug‐cc‐pV(T+d)Z/SMD(MeCN) // ωB97X‐D/aug‐cc‐pVDZ/SMD(MeCN) level of theory, we studied the mechanisms behind the reaction of elemental sulfur and polysulfides with cyanide and phosphines, which quantitatively generate the monosulfide products thiocyanate and phosphine sulfides, respectively. All plausible pathways including nucleophilic decomposition, unimolecular decomposition, scrambling reactions, and attack on thiosulfoxides, have been considered to provide the first comprehensive mechanistic picture for this class of reactions. Overall, intramolecular cyclization is identified as the most favorable decomposition pathway for long polysulfides. For short polysulfides, a mixture of unimolecular decomposition, nucleophilic attack, and scrambling pathways can be expected.
BAr2‐Bridged Azafulvene Dimers with Tunable Energy Levels for Photostable Near‐Infrared Dyes
Authors: Tan Tiancheng , Nakamura Tomoya , Murdey Richard , Hu Shuaifeng , Truong Minh Anh , Wakamiya Atsushi
Published: April 2023

Organic dyes with strong absorption in the near‐infrared (NIR) region are potentially useful in medical applications, such as tumor imaging and photothermal therapy. In this work, new NIR dyes combining BAr2‐bridged azafulvene dimer acceptors with diarylaminothienyl donors in a donor–acceptor–donor configuration were synthesized. Surprisingly, it was found that in these molecules the BAr2‐bridged azafulvene acceptor adopts a 5‐membered, rather than 6‐membered ring structure. The influence of the aryl substituents on the HOMO and LUMO energy levels of the dye compounds was assessed from electrochemical and optical measurements. Strong electron‐withdrawing fluorinated substituents (Ar=C6F5, 3,5‐(CF3)2C6H3) lowered the HOMO energy while preserving the small HOMO–LUMO energy gap, resulting in promising NIR dye molecules that combine strong absorption bands centered around 900 nm with good photostability.
Real‐Time Optimization Using Machine Learning Models Applied to the 4,4′‐Diphenylmethane Diisocyanate Production Process
Authors: Ehlhardt Jens , Ahmad Afaq , Wolf Inga , Engell Sebastian
Published: April 2023

In this work, the optimal time‐varying allocation of steam in a large‐scale industrial isocyanate production process is addressed. This is a problem that falls into the category of real‐time optimization (RTO). The application of RTO in practice faces two problems: First the available rigorous process models may not be suitable for use in real‐time connected to the process. Second, there is always a mismatch between the predictions of the model and the behavior of the real plant. We address the first problem by training a neural net model as a surrogate to data generated by a rigorous simulation model so that the model is simple to implement and short execution times result. The second problem is tackled by adapting the optimization problem based on measured data such that convergence to the optimal operating conditions for the real plant is achieved.
Numerical simulations and validation of gas–solid flows in a fluidized‐bed roaster based on the CFD‐DPM model
Authors: Ma Xue‐Yi , Wang De‐Xi , Liu Bo , Dong Hui , Zhao Liang
Published: April 2023

In view of the complex gas–solid flow characteristics in a fluidized‐bed roaster, the discrete phase model (DPM) provided by ANSYS software was used to numerically analyze the model using a coupled algorithm. The asymmetric flow phenomenon in the transition section at the top of the furnace was found to be unfavourable to the gas–solid flow, and an inverted U‐shaped furnace structure was proposed to optimize the transition section at the top of the furnace. A large cold experimental setup was built to verify the model. The results showed that the air velocity is mainly in the axial upward direction; under the action of the gas, the solid particles and the air velocity are basically in the same direction. The main furnace and subfurnace connection section changes the movement of the gas–solid mixture, and its unreasonable structure leads to the asymmetric flow phenomenon of the gas–solid fluid at the top of the furnace. Compared with the previous furnace structure, the uniformity of gas–solid flow in the optimized ‘inverted U‐shaped’ structure has been significantly improved. The cold experimental results are in good agreement with the numerical simulation results, which verifies the accuracy of the proposed model.
Modelling of polymerization kinetics and molar mass development in the nitroxide‐mediated polymerization (NMP) of styrene in supercritical carbon dioxide using the PC‐SAFT equation of state
Authors: López‐Domínguez Porfirio , Ríos‐López Marlene , Rivera‐Peláez Jesús Eduardo , Barragán‐Aroche José Fernando , Vivaldo‐Lima Eduardo
Published: April 2023

A mathematical model for polymerization kinetics and molar mass development in the nitroxide‐mediated polymerization (NMP) of vinyl monomers in supercritical carbon dioxide (scCO2) has been developed. The method of moments is used for molar mass development. The perturbed‐chain statistical associating fluid theory (PC‐SAFT) equation of state is used to estimate the number of stable phases present at equilibrium in the reaction mixture, critical number average chain length at which polymer particles are formed, and monomer concentration in each phase. Pure and binary PC‐SAFT interaction parameters are estimated from liquid–liquid equilibrium (LLE) and liquid–vapour equilibrium (LVE) experimental data at 60 to 129°C. The effect of pressure on monomer conversion and molar mass development in the polymerization of styrene (Sty) using benzoyl peroxide (BPO) and 2,2,6,6‐Tetramethylpiperidinyl‐1‐oxyl (TEMPO) at 120°C and 300–500 bar is studied. It was observed that increasing pressure increases polymerization rate without significantly affecting molar mass development.
Experimental estimation of the settling velocity and drag coefficient of the hollow cylindrical particles settling in non‐Newtonian fluids in an annular channel
Authors: Mohammad Hussain , Munshi Basudeb
Published: April 2023

The drag coefficient data of particles settling in an annular channel is very much essential for designing different solid–fluid handling equipment, such as the fluidized bed. Experimental settling velocity, wall factor, and drag coefficient data of the hollow‐cylinder particle are presented. Carboxymethyl cellulose solution has been used as the working fluid with a flow index of 0.64 ≤ n ≤ 0.91 and a consistency index of 0.31 ≤ K ≤ 1.81. The experimental results covered a wide diameter ratio range (0.14 ≤ deq/L ≤ 0.46), hollow cylinder inner to outer diameter ratio (0.2 ≤ di/do ≤0.8), and Reynolds number (0.05 ≤ Re ≤ 51 and 0.09 ≤ Re∞ ≤ 55). deq, di, and do are the equivalent inner and outer diameters of the particle, L is the annular gap, and Re and Re∞ are the Reynolds numbers in the presence and absence of the wall effect, respectively. The wall factor decreased, and the drag coefficient increased with deq/L and di/do ratios. The above parameters declined with the Reynolds number. The hollow cylinder experienced a lesser wall effect than the spherical particles settling in a non‐annular channel. In some cases, the wall factor of the hollow cylinder is found to be equal to the spherical particles settling in an annular channel. The developed correlations have successfully predicted the drag coefficients of the hollow cylinder.
Electrochemical Energy Storage in Nitrogen/Metal‐doped Carbon Aerogels Derived from Polyurea‐crosslinked Alginate Aerogels
Authors: Samartzis Nikolaos , Athanasiou Michail , Raptopoulos Grigorios , Paraskevopoulou Patrina , Ioannides Theophilos
Published: April 2023

Porous carbons obtained from pyrolysis of biomass have been proved to be a great choice for energy storage applications, owing to the endless supply of precursors ‐ hence low cost, and of course due to the significant advantages of carbon aerogels such as high specific surface area, good conductivity, and light weight. Most reports on energy storage devices that use carbon aerogels either employ energy intensive processes, such as freeze‐drying, or rely on activation protocols. Therefore, it is significant to establish cost‐effective and eco‐friendly protocols, which will boost the competitiveness of such materials. Herein, we present a thorough electrochemical characterization, and we demonstrate the performance of some nitrogen/metal co‐doped alginate‐derived carbon aerogels in aqueous supercapacitors. Those carbon aerogels were synthesized by pyrolysis of polyurea‐crosslinked alginate aerogels and exhibited excellent energy/power density as well as cycling stability, in comparison to analogous materials reported in the literature.
Enzyme‐Free Nucleic Acid Circuits for Fold‐Change Detection
Authors: Wang Likun , Zhao Jiayan , Xiong Xiewei , Li Li , Zhu Tong , Pei Hao
Published: April 2023

Fold‐change detection is widespread in sensory systems of various organisms. Dynamic DNA nanotechnology provides an important toolbox for reproducing structures and responses of cellular circuits. In this work, we construct an enzyme‐free nucleic acid circuit based on the incoherent feed‐forward loop using toehold‐mediated DNA strand displacement reactions and explore its dynamic behaviors. The mathematical model based on ordinary differential equations is used to evaluate the parameter regime required for fold‐change detection. After selecting appropriate parameters, the constructed synthetic circuit exhibits approximate fold‐change detection for multiple rounds of inputs with different initial concentrations. This work is anticipated to shed new light on the design of DNA dynamic circuits in the enzyme‐free environment.
An Aggregation‐Induced Emission‐Based Fluorescence Turn‐On Probe for Efficient Detection of HS− in Water, Wine, and Living Cells
Authors: Meng Yanan , Yao Xinya , Zhong Keli , Li Yang , Tang Lijun
Published: April 2023

Hydrogen sulfide (H2S), as one of the important endogenous biological regulators, plays a critical role in mediating a wide range of physiological processes. The development of rapid, sensitive, and reliable detection techniques for H2S would be highly appealing. In this paper, a new type of AIE‐based fluorescence turn‐on probe TPA‐M for the detection of H2S has been constructed, involved the rapid release of AIE‐based fluorophore TPA‐CHO with a remarkable fluorescence turn‐on phenomenon in THF/H2O (2/8, v/v, HEPES=20 μM, pH=7.3) medium, exhibiting the attractive advantages such as high sensitivity with the detection limit as low as 1.92×10−3 ppm, excellent selectivity over other anion analytes and biothiols, significant anti‐interference ability and fast response time (within 10 min). What's more, the practical application evaluation indicated that the probe TPA‐M could be efficiently employed in imaging exogenously added H2S in living MCF‐7 cells and detecting H2S in actual water and wine samples.
Decarboxylative Mannich Reactions with N‐Alkyl Imines
Authors: Pinaud Marine , Vaïtilingom Leïla , Gnanalingam Gayathiri , Xavier Tania , Le Gall Erwan , Presset Marc
Published: April 2023

The use ofN‐alkyl imines in decarboxylative Mannich reaction with substituted malonic acids half oxyesters (SMAHOs) has been developed to afford a direct access to secondary β2,3‐aminoesters. The transformation occurs under very practical conditions (DABCO as a catalyst in bulk toluene and open to air) and can be performed with a broad range of each substrate in yields of 36 to 97 %. Importantly, the reaction was found to require the use of acidic additives in combination with the organocatalyst to limit the competitive olefination reaction.
Cover Image
Authors: Wang Lifu , Gong Enpu , Yang Zhenyuan , Guan Changqing , Zhang Yongli , Huang Wentao
Published: April 2023

The cover image of the colonial rugose coral Fomichevella is based on the Research Article Controlling of the Late Palaeozoic glaciation on reef evolution: A case study of a late Kasimovian coral reef in southern Guizhou, South China by Lifu Wang et al., https://doi.org/10.1002/gj.4685.

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“I felt imprisoned”: A qualitative exploration of controlling behaviors in adolescent and emerging adult dating relationships
Authors: De Sousa Deziray , Paradis Alison , Fernet Mylène , Couture Stéphanie , Fortin Andréanne
Published: April 2023

Introduction

First dating relationships can elicit intense emotions that youth may attempt to alleviate by using control tactics that negatively impact the quality of their relationship and their partner's well‐being. Despite the breadth of research on dating violence, studies examining control tactics in youth relationships are limited. The current qualitative study documented control tactics from the perspective of youth who are currently in dating relationships.

Method

Individual semistructured interviews were conducted with 39 participants aged 15–22 years old to gather information regarding conflict management strategies used in their dating relationships. The participants were recruited from high schools and junior colleges across the province of Quebec, Canada.

Results

Direct content analysis revealed three categories of control tactics, including, isolation, domination, and emotional manipulation. These findings highlight the importance of further examining control dynamics in adolescent and emerging adult dating relationships to improve dating violence prevention programs.

Conclusions

Educational programs can help prevent control from escalating to more direct forms of violence by supporting youth in identifying unhealthy relationship dynamics and providing them with tools to either safely end the relationship or communicate their concerns with their partner.
Micro‐nano porous structured tantalum‐coated dental implants promote osteogenic activity in vitro and enhance osseointegration in vivo
Authors: Cui Jiantong , Zhang Shaoqing , Huang Meng , Mu Xiaodan , Hei Junhao , Yau Vicky , He Huixia
Published: April 2023

Due to its excellent biocompatibility and corrosion resistance, tantalum demonstrates versatility as an implant material. However, limited studies investigated the role of tantalum coated titanium‐based dental implants. This study aimed to investigate the potential application of micro‐nano porous structured tantalum coating on the surface of titanium dental implant. In the present study, micro‐nano porous structured tantalum coating was prepared by vacuum plasma spraying (VPS) under selected optimum parameters, various characteristics of tantalum coating (Ta/Ti), including the morphology, potential, constituent, and hydrophilia, were investigated in comparison with its respective control groups, sandblasted titanium (Ti) and titanium coating (Ti/Ti). The adhesion, proliferation, and osteogenic differentiation ability of rat bone marrow mesenchymal cells (BMSCs) on different materials were assessed in vitro. Then the osseointegration capacity of Ti, Ti/Ti, Ta/Ti, and Straumann implants in canine mandible was evaluated with micro‐CT, histological sections, and energy dispersive X‐ray spectroscopy. These results demonstrated that micro‐nanostructured, uneven, and granular tantalum coating was successfully prepared on titanium substrate by VPS with pore size ranging from 50 nm to 5 μm and thickness ranging from 80 to 100 μm. Tantalum coating revealed the highest surface potential, best hydrophilia, and most protein adsorption among Ta/Ti, Ti/Ti, and Ti. Furthermore, Ta/Ti surfaces significantly promoted the adhesion, proliferation, and osteogenic differentiation of BMSCs. In vivo, Ta/Ti implants displayed positive osseointegration capability associated with increased bone mineral density and formation of new bone around implants without tantalum particles released. Together, these findings indicate that tantalum‐coated titanium dental implants may serve as a new type of dental implant.
The combined effect of Raspberry Ketone with Resveratrol against oxidative stress and steatohepatitis in rats: Pharmacokinetic and pharmacodynamic studies
Authors: Verma Saurabh , Goand Umesh K. , Rathaur Shivam , Garg Richa , Katekar Roshan , Gayen Jiaur R.
Published: April 2023

Raspberry Ketone (RK) and Resveratrol (RSV) are natural phenolic antioxidants and anti‐inflammatory agents. However, its combined pharmacokinetic and pharmacodynamics potentials are not reported. The study aims to assess the combined effect of RK with RSV to protect rats from carbon‐tetrachloride (CCl4) induced oxidative stress and NASH. The toxicant CCl4 was employed at a concentration of 1 mL/kg as a 1:1 (v/v) mixture with olive oil twice weekly for 6 weeks to induce liver toxicity. Animal treatment was followed for 2 weeks. Silymarin was used as a standard control drug to compare the hepatoprotective effect of RK and RSV. Hepatic histology, oxidative stress, MMP, reduced glutathione (GSH), plasma levels of SGOT, SGPT, and lipid profile (total cholesterol and triglycerides) were measured. Anti‐inflammation genes (IL‐10), and fibrotic genes (TGF‐β) were also examined in liver tissue. Oral administration of combined RK with RSV (50 + 50 mg/kg for 2 weeks) showed significantly more hepatoprotection by significantly decreasing elevated plasma markers and lipid profile than alone RK and RSV (100 mg/kg daily for 2 weeks). It also significantly alleviated the hepatic lipid peroxidation, restoring the activities of GSH levels in the liver. RT‐PCR and Immunoblotting studies confirmed that significantly upregulation of anti‐inflammation genes and protein expression (MMP‐9) ameliorated the disease. Pharmacokinetic studies confirmed more synergistic stability in simulated gastric‐intestinal fluids (FaSSGF, FaSSIF) and rat liver microsomes (CYP‐450, NADPH oxidation & glucuronidation. Moreover, coadministration of drugs augmented the relative bioavailability, Vd/F (L/Kg), and MRT0‐∞(h), which leads to more efficacy. This pharmacokinetic and pharmacodynamic reveals a new adjuvant therapy for the treatment of steatohepatitis.
Chlorogenic acid protective effects on paraquat‐induced pulmonary oxidative damage and fibrosis in rats
Authors: Larki‐Harchegani Amir , Fayazbakhsh Fatemeh , Nourian Alireza , Nili‐Ahmadabadi Amir
Published: April 2023

Paraquat (PQ) is a widely used herbicide that can cause severe oxidative and fibrotic injuries in lung tissue. Due to the antioxidant and anti‐inflammatory properties of chlorogenic acid (CGA), the present study investigated its effects on PQ‐induced pulmonary toxicity. To this end, 30 male rats were randomly categorized into five groups of six. Initially, the first and third groups were treated intraperitoneally (IP) with normal saline and CGA (80 mg/kg) for 28 consecutive days, respectively. The second, fourth, and fifth groups were treated with normal saline and 20 and 80 mg/kg of CGA for 28 consecutive days, respectively, and received a single dose of PQ (IP, 20 mg/kg) on Day 7. Then, the animals were anesthetized with ketamine and xylazine, and lung tissue samples were collected for biochemical and histological examinations. The results showed that PQ significantly increased hydroxyproline (HP) and lipid peroxidation (LPO) and decreased the lung tissue antioxidant capacity. In addition, myeloperoxidase (MPO) activity increased significantly, while glutathione peroxidase (GPx), catalase (CAT), and superoxide dismutase (SOD) activity declined substantially. The administration of therapeutic doses of CGA could prevent the oxidative, fibrotic, and inflammatory effects of PQ‐induced lung toxicity, and these changes were consistent with histological observations. In conclusion, CGA may improve the antioxidant defense of lung tissue and prevent the spread of inflammation and the development of PQ‐induced fibrotic injuries by enhancing antioxidant enzymes and preventing inflammatory cell infiltration.