bluuebunny/crossref_metadata_2025 huggingface dataset:
Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64 % Efficiency All Polymer Solar Cells
Authors: Deng Min , Xu Xiaopeng , Qiu Wuke , Duan Yuwei , Li Ruipeng , Yu Liyang , Peng Qiang
Published: June 2024

All‐polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (PDs) and polymer acceptors (PAs) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three PAs, namely PBTPICm‐BDD, PBTPICγ‐BDD and PBTPICF‐BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y‐typed non‐fullerene small molecular acceptors (NF‐SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the PD being interspersed into the acceptor material, which improve the solubility between the PD and PA. The PBTPICγ‐BDD and PBTPICF‐BDD displayed better miscibility with PBQx‐TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50 % and 17.17 % were achieved for PBQx‐TCl : PBTPICγ‐BDD and PBQx‐TCl : PBTPICF‐BDD devices, respectively. With the addition of PYFT‐o as the third component into PBQx‐TCl : PBTPICγ‐BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64 % was realized finally.
Optical Monitoring of Supramolecular Interactions in Polymers
Authors: Kiebala Derek J. , Dodero Andrea , Weder Christoph , Schrettl Stephen
Published: June 2024

Many stimuli‐responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self‐healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure–property relationships of these materials, direct correlations between molecular‐level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen‐bonding ureido‐4‐pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross‐linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross‐linker content, processing history, and applied stimuli. We demonstrate that the stimuli‐induced dissociation of hydrogen‐bonding linkages strongly depends on the initial cross‐link density, which also dictates whether the force‐induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.
Metastable Supramolecular Assembly of Simple Monomers Enabled by Confinement: Towards Aqueous Phase Room Temperature Phosphorescence
Authors: Wang Ruixing , Ma Da , Kong Xianggui , Peng Feifei , Cao Xiaoqing , Zhao Yufei , Lu Chao , Shi Wenying
Published: June 2024

The application of supramolecular assembly (SA) with room temperature phosphorescence (RTP) in aqueous phase has the potential to revolutionize numerous fields. However, using simple molecules with crystalline RTP to construct SA with aqueous phase RTP is hardly possible from the standpoint of forces. The reason lies in that the transition from crystal to SA involves a structure transformation from highly stable to more dynamic state, leading to increased non‐radiative deactivation pathways and silent RTP signal. Here, with the benefit of the confinement from the layered double hydroxide (LDH), various simple molecules (benzene derivatives) can successfully form metastable SA with aqueous phase RTP. The maximum of RTP lifetime and efficiency can reach 654.87 ms and 5.02 %, respectively. Mechanistic studies reveal the LDH energy trap can strengthen the intermolecular interaction, providing the prerequisite for the existence of metastable SA and appearance of aqueous phase RTP. The universality of this strategy will usher exploration into other multifunctional monomer, facilitating the development of SAs with aqueous phase RTP.
Multiple Stabilization Effects of Benzylhydrazine on Scalable Perovskite Precursor Inks for Improved Perovskite Solar Cell Production
Authors: Reinecke Sean B. , Yeddu Vishal , Zhang Dongyang , Barr Chris , Wulff Jeremy E. , Dayneko Sergey V. , Kokaba Mohammad Reza , Saidaminov Makhsud I.
Published: June 2024

Perovskite precursor inks suffer various forms of degradation, such as iodide anion oxidation and organic cation breakdown, hindering reliable perovskite solar cell manufacturing. Here we report that benzylhydrazine hydrochloride (BHC) not only retards the buildup of iodine as previously reported but also prevents the breakdown of organic cations. Through investigating BHC and iodine chemical reactions, we elucidate protonation and dehydration mechanisms, converting BHC to harmless volatile compounds, thus preserving perovskite film crystallization and solar cell performance. This inhibition effect lasts nearly a month with minimal BHC, contrasting control inks without BHC where organic cations fully react in less than a week. This enhanced understanding, from additive stabilization to end products, promises improved perovskite solar cell production reliability.
Enantioselective Allylboration of Acetylene: A Versatile Tool for the Stereodivergent Synthesis of Natural Products
Authors: Álvarez‐Constantino Andrés M. , Chaves‐Pouso Andrea , Fañanás‐Mastral Martín
Published: June 2024

Efficient catalytic methods that allow the use of simple and abundant chemical feedstocks for the preparation of synthetically versatile compounds are central to modern synthetic chemistry. Acetylene is a basic feedstock with a remarkable production over one million tons per year, although it is underutilized in the stereoselective synthesis of fine chemicals. Here we report a facile catalytic multicomponent reaction that allows for the enantio‐ and diastereoselective allylboration of acetylene gas. This process is catalyzed by a chiral copper catalyst, operates without specialized equipment or pressurization, and provides chiral skipped dienes bearing stereodefined and orthogonally functionalized olefins with excellent levels of chemo‐, regio‐, enantio‐ and diastereoselectivity. The combined stereochemical features and orthogonal functionalization make the products privileged structural scaffolds to access the complete set of stereoisomers of the chiral skipped diene core through simple enantio‐ and diastereodivergent pathways. The utility of the method is demonstrated with the enantioselective synthesis of three bioactive natural skipped diene products, namely (+)‐Nyasol, (+)‐Hinokiresinol and Phorbasin C, and other related synthetically relevant chiral molecules.
Efficient Silver(I)‐Containing I–Motif DNA Hybrid Catalyst for Enantioselective Diels–Alder Reactions
Authors: Dong Xingchen , Qiu Ziyang , Wang Zixiao , Li Jiaqi , Qin Weijun , Dang Jingshuang , Zhou Wenqin , Jia Guoqing , Chen Yashao , Wang Changhao
Published: June 2024

The inherent chiral structures of DNA serve as attractive scaffolds to construct DNA hybrid catalysts for valuable enantioselective transformations. Duplex and G‐quadruplex DNA‐based enantioselective catalysis has made great progress, yet novel design strategies of DNA hybrid catalysts are highly demanding and atomistic analysis of active centers is still challenging. DNA i‐motif structures could be finely tuned by different cytosine‐cytosine base pairs, providing a new platform to design DNA catalysts. Herein, we found that a human telomeric i‐motif DNA containing cytosine‐silver(I)‐cytosine (C‐Ag+‐C) base pairs interacting with Cu(II) ions (i‐motif DNA(Ag+)/Cu2+) could catalyze Diels–Alder reactions with full conversions and up to 95 % enantiomeric excess. As characterized by various physicochemical techniques, the presence of Ag+ is proved to replace the protons in hemiprotonated cytosine‐cytosine (C : C+) base pairs and stabilize the DNA i‐motif to allow the acceptance of Cu(II) ions. The i‐motif DNA(Ag+)/Cu2+ catalyst shows about 8‐fold rate acceleration compared with DNA and Cu2+. Based on DNA mutation experiments, thermodynamic studies and density function theory calculations, the catalytic center of Cu(II) ion is proposed to be located in a specific loop region via binding to one nitrogen‐7 atom of an unpaired adenine and two phosphate‐oxygen atoms from nearby deoxythymidine monophosphate and deoxyadenosine monophosphate, respectively.
Remarkable Second Harmonic Generation Response in (C5H6NO)+(CH3SO3)−: Unraveling the Role of Hydrogen Bond in Thermal Driven Nonlinear Optical Switch
Authors: Zhang Zi‐Peng , Liu Xin , Wang Rui‐Xi , Zhao Shuang , He Wen‐Jie , Chen Hong‐Yu , Deng Xue‐Bin , Wu Li‐Ming , Zhou Zhengyang , Chen Ling
Published: June 2024

Heat‐activated second harmonic generation (SHG) switching materials are gaining interest for their ability to switch between SHG on and off states, offering potential in optoelectronic applications. The novel nonlinear optical (NLO) switch, (C5H6NO)+(CH3SO3)− (4‐hydroxypyridinium methylsulfonate, 4HPMS), is a near‐room‐temperature thermal driven material with a strong SHG response (3.3 × KDP), making it one of the most potent heat‐stimulated NLO switches. It offers excellent contrast of 13 and a high laser‐induced damage threshold (2.5 × KDP), with reversibility > 5 cycles. At 73 °C, 4HPMS transitions from the noncentrosymmetric Pna21 room temperature phase (RTP) to the centrosymmetric P21/c phase, caused by the rotation of the (C5H6NO)+ and (CH3SO3)− due to partially thermal breaking of intermolecular hydrogen bonds. The reverse phase change exhibits a large 50 °C thermal hysteresis. Density functional theory (DFT) calculations show that (C5H6NO)+ primarily dictates both the SHG coefficient (dij) and birefringence (▵n(Zeiss) = 0.216 vs ▵n(cal.) = 0.202 at 546 nm; Δn(Immersion) = 0.210 vs ▵n(cal.) = 0.198 at 589.3 nm), while the band gap (Eg) is influenced synergistically by (C5H6NO)+ and (CH3SO3)−. Additionally, 4HPMS‐RTP also exhibits mechanochromism upon grinding as well as an aggregation‐enhanced emission in a mixture of acetone and water.
Using MXene as a Chemically Induced Initiator to Construct High‐Performance Cathodes for Aqueous Zinc‐Ion Batteries
Authors: Chen Jie , Liu Yanpeng , Xiao Baoquan , Huang Juanjuan , Chen Hongwei , Zhu Kun , Zhang Junkai , Cao Guozhong , He Guanjie , Ma Jing , Peng Shanglong
Published: June 2024

MXene usually exhibits weak pseudo‐capacitance behavior in aqueous zinc‐ion batteries, which cannot provide sufficient reversible capacity, resulting in the decline of overall capacity when used as the cathode materials. Taking inspiration from polymer electrolyte engineering, we have conceptualized an in situ induced growth strategy based on MXene materials. Herein, 5.25 % MXene was introduced into the nucleation and growth process of vanadium oxide (HVO), providing the heterogeneous nucleation site and serving as an initiator to regulate the morphology and structural of vanadium oxide (T‐HVO). The resulted materials can significantly improve the capacity and rate performance of zinc‐ion batteries. The growth mechanism of T‐HVO was demonstrated by both characterizations and DFT simulations, and the improved performance was systematically investigated through a series of in situ experiments related to dynamic analysis steps. Finally, the evaluation and comparison of various defect introduction strategies revealed the efficient, safety, and high production output characteristics of the in situ induced growth strategy. This work proposes the concept of in situ induced growth strategy and discloses the induced chemical mechanism of MXene materials, which will aid the understanding, development, and application of cathode in aqueous zinc‐ion batteries.
Ultrasonic weldability of thick and heavier nonwoven fabrics
Authors: Kara Sukran
Published: June 2024

Nonwovens have wide application areas due to their advantageous properties like low cost, high production efficiency, and tuneable properties. They are mostly used for disposable products. Combining bicomponent fiber spinning with hydroentanglement method is one of the innovative methods to obtain nonwovens for durable applications. On the other hand, ultrasonic welding is an alternative assembling method for disposable products made of low weight nonwovens. In this study, the ultrasonic weldability of relatively heavier weight and thicker nonwoven fabrics made of polyester: polyamide bicomponent microfilaments were examined in order to combine the advantages of nonwovens and ultrasonic welding. Relatively higher thickness and weight, and also fiber composition of the nonwoven fabrics were compelling effects of the study that drove the motivation. Overall 60 samples were produced using five nonwoven fabrics with varying unit masses and 12 selected ultrasonic welding types. Seam strength and strain assessments were supported with stereomicroscope and visual inspections in evaluating the welds. Results showed that despite having thick seam lines up to 1.6 mm, successful welded seams could be obtained. Depending on the welding parameters, seam lines of some samples exhibited waviness, color changes, and deformations but these situations did not drastically affect the seam strength of samples.
Combined effect of montmorillonite Cloisite 30B and graphene nanoplatelets on high‐density polyethylene matrix under high strain rate dynamic compression
Authors: Grison Vagner , Romanzini Daiane , Dias Rafael R. , Pereira Iaci M. , Zattera Ademir J. , Piazza Diego
Published: June 2024

Laminated polymer composites are widely used in ballistic barriers where polyethylene can be applied. The mechanical properties of polymers can be improved with the addition of nanofillers. Therefore, this work evaluates the effect of the combination of montmorillonite Cloisite 30B (OMt) and graphene (Gr) on the dynamics compression properties obtained from a split‐Hopkinson pressure bar (SHPB) test for nanostructured maleinized high‐density polyethylene (HDPE). The nanofillers are incorporated into the polymeric matrix in its molten state, and their dispersion is evaluated through x‐ray diffraction and transmission electron microscopy analyses. Thermal analysis, including differential scanning calorimetry and thermogravimetric analysis are performed. Additionally, the viscoelastic behavior of the materials is studied from the results of storage and loss modulus obtained by dynamic‐mechanical analysis. Under the SHPB test conditions, it is possible to evaluate the material stress–strain curve, identifying its yield point, compressive strength, and deformations to calculate the elastic stiffness and toughness of the material. The nanocomposite with 3% OMt and 0.75% Gr (wt.%) shows the highest average compressive strength and toughness values. Furthermore, this sample shows similar Tpeak temperature, improved crystallinity index, storage, and loss modulus, with similar glass transition temperature compared to the HDPE sample.
Gender‐inclusive financial and demographic literacy: Monetizing the gender mortality gap
Authors: Apicella Giovanna , De Giorgi Enrico , Di Lorenzo Emilia , Sibillo Marilena
Published: June 2024

Longevity crucially affects demand for pensions, insurance products and annuities. Consistent empirical evidence shows that women have historically experienced lower mortality rates than men. In this article, we study a measure of the gender gap in mortality rates, we call “Gender Gap Ratio”, across a wide range of ages and for four countries: France, Italy, Sweden, and USA. We show the stylized facts that characterize the trend of the Gender Gap Ratio, both in its historical evolution and future projection. Focusing on an example temporary life annuity contract, we give a monetary consistency to the Gender Gap Ratio. We show evidence that a Gender Gap Ratio that ranges between 1.5 and 2.5, depending on age, translates into a significant reduction of up to 23% in the benefits from a temporary life annuity contract for women with respect to men, against the same amount invested in the life annuity. The empirical evidence discussed in this article documents the crucial importance of working toward a more widespread demographic literacy, for example, a range of tools and strategies to raise longevity consciousness among individuals and policy‐makers, in the framework of gender equality policies.
Die Digitalisierung der Prüfung des Standsicherheitsnachweises
Authors: Achenbach Marcus , Weber Beatrix , Rivas Paul
Published: June 2024

Die Einführung des digitalen Bauantragsverfahrens ermöglicht, die Prüfung des Standsicherheitsnachweises vollständig papierlos durchzuführen. Dadurch können sowohl statische Berechnung als auch Konstruktionspläne medienbruchfrei geprüft werden, weshalb eine Beschleunigung des Verfahrens erwartet werden kann. Der Übergang von Papier zu PDF stellt einen deutlichen Fortschritt für die beteiligten Parteien dar, kann aber hinsichtlich des Grads der Digitalisierung nur ein Anfang sein. Der größtmögliche Grad der Digitalisierung wird durch die Verwendung von BIM (BIM: Building Information Modeling) in Verbindung mit den notwendigen Datenumgebungen (CDE) erreicht. Da der Einsatz von BIM bei Planung, Errichtung und Betrieb von Gebäuden erhebliche Vorteile bietet, ist die weitere Verbreitung absehbar bzw. wird von der Bundes‐ und den Landesregierungen die Anwendung teilweise bereits vorgeschrieben. Auswirkungen auf die Prüfung und Genehmigung von Bauwerken sind daher zu erwarten. In diesem Aufsatz wird untersucht, wie digitalisierte Prüfprozesse gestaltet werden können. Die Prozesse werden vorgestellt und hinsichtlich des Reifegrads der Digitalisierung bewertet.
Comparative investigation of tellurium‐doped transition metal nanoparticles (Zn, Sn, Mn): Unveiling their superior photocatalytic and antibacterial activity
Authors: Umar Misbah , Ajaz Humayun , Javed Mohsin , Bahadur Ali , Iqbal Shahid , Mahmood Sajid , Sarwar Afifa , Alotaibi Khalid M. , Alshalwi Matar
Published: June 2024

In this study, tellurium‐doped and undoped metal oxide nanoparticles (NPs) (ZnO, Mn3O4, SnO2) are compared, and a practical method for their synthesis is presented. Nanocomposites were created using the coprecipitation process, and comparisons between the three material categories under study were made using a range of characterization methods. The produced materials were subjected to structural, morphological, elemental composition, and functional group analyses using XRD, FESEM in combination with EDS, and FTIR. The optical characteristics in terms of cutoff wavelength were evaluated using UV–visible spectroscopy. Catalyzing the breakdown of methylene blue (MB) dye, the isolated nanocomposites demonstrated very consistent behavior when utilized as catalysts. Regarding both doped and undoped ZnO NPs, the maximum percentage of degradation was found to be 98% when exposed to solar Escherichia coli and Staphylococcus aureus, which stand for gram‐positive and gram‐negative bacteria, respectively, and were chosen as model strains for both groups using the disk diffusion technique in the context of in vitro antibacterial testing. Doped and undoped ZnO NPs exhibited greater antibacterial efficacy, with significant inhibition zones measuring 31.5 and 37.8 mm, compared with other metal oxide NPs.
Chemiluminescence data modeling using parallel factor analysis for the simple and sensitive determination of diphenoxylate in human plasma and tablets
Authors: Koohsarian Maryam , Mokhtari Ali , Hooshmand Shabnam
Published: June 2024

In this study, a chemiluminescence (CL) method was developed to determine diphenoxylate in tablets and human plasma. This is the first CL method proposed to determine diphenoxylate. Creating three‐dimensional data caused the parallel factor analysis algorithm (PARAFAC) to be used for the first time in CL methods. The method is based on the fact that diphenoxylate enhances the weak CL produced in the reaction of Ru(phen)32+ and acidic Ce(IV), and the concentration of Ce(IV) solution has a different effect on the CL response of diphenoxylate and the blank plasma. The calibration curve was linear from 4.0 × 10−8 to 1.6 × 10−6 mol L−1 (R2 = 0.9954), and the detection limit was 1.3 × 10−8 mol L−1 (S/N = 3). The sampling rate was about 30 samples per hour, and the % RSD for 10 repeated measurements of 4 × 10−7 mol L−1 diphenoxylate was 5.4%. The interference effects of some ions, amino acids, and common additives were also investigated. The CL method was successfully used to determine diphenoxylate in tablets, and the results were statistically confirmed by the reference method. The proposed CL method and the PARAFAC algorithm were successfully used to determine the concentration of diphenoxylate in human blood plasma samples.
Chromogenic fusion proteins as alternative textiles dyes
Authors: Watkins Tyson , Moffitt Kaylee , Speight Robert E. , Navone Laura
Published: June 2024

The widespread adoption of fast fashion has led to a significant waste problem associated with discarded textiles. Using proteins to color textiles can serve as a sustainable alternative to chemical dyes as well as reduce the demand for new raw materials. Here, we explore the use of chromogenic fusion proteins, consisting of a chromoprotein and a carbohydrate‐binding module (CBM), as coloring agents for cellulose‐based textiles such as cotton. We examined the color properties of chromoproteins AeBlue, SpisPink and Ultramarine alone and fused to CBM under various conditions. AeBlue, SpisPink and Ultramarine exhibited visible color between pH 4‐9 and temperatures ranging from 4 to 45℃. Fusing CBM Clos from Clostridium thermocellum and CBM Ch2 from Trichoderma reesei to the chromoproteins had no effect on the chromoprotein color properties. Furthermore, binding assays showed that chromoprotein fusions did not affect binding of CBMs to cellulosic materials. Cotton samples bound with Ultramarine‐Clos exhibited visible purple color that faded progressively over time as the samples dried. Applying 10% 8000 polyethylene glycol to cotton samples markedly preserved the color over extended periods. Overall, this work highlights the potential of chromoprotein‐CBM fusions for textile dying which could be applied as a color maintenance technology or for reversible coloring of textiles for events or work wear, contributing to sustainable practices and introducing new creative opportunities for the industry.
Upper end of the central canal of the human spinal cord: Quantitative anatomical study and 3D modeling
Authors: Lefevre Etienne , Quang Megane Le , Chotard Guillaume , Knafo Steven , Mengelle Pierre , Taupin Yanis , Liguoro Dominique , Jecko Vincent , Vignes Jean‐Rodolphe , Roblot Paul
Published: June 2024

The upper end of the central canal of the human spinal cord has been repeatedly implicated in the pathogenesis of various diseases, yet its precise normal position in the medulla oblongata and upper cervical spinal cord remains unclear. The purpose of this study is to describe the anatomy of the upper end of the central canal with quantitative measurements and a three‐dimensional (3D) model. Seven formalin‐embalmed human brainstems were included, and the central canal was identified in serial axial histological sections using epithelial membrane antigen antibody staining. Measurements included the distances between the central canal (CC) and the anterior medullary fissure (AMF) and the posterior medullary sulcus (PMS). The surface and perimeter of the CC and the spinal cord were calculated, and its anterior–posterior and maximum lateral lengths were measured for 3D modeling. The upper end of the CC was identified in six specimens, extending from the apertura canalis centralis (ACC) to its final position in the cervical cord. Positioned on the midline, it reaches its final location approximately 15 mm below the obex. No specimen showed canal dilatation, focal stenosis, or evidence of syringomyelia. At 21 mm under the ACC in the cervical cord, the median distance from the CC to the AMF was 3.14 (2.54–3.15) mm and from the CC to the PMS was 5.19 (4.52–5.43) mm, with a progressive shift from the posterior limit to the anterior third of the cervical spinal cord. The median area of the CC was consistently less than 0.1 mm2. The upper end of the CC originates at the ACC, in the posterior part of the MO, and reaches its normal position in the anterior third of the cervical spinal cord less than 2 cm below the obex. Establishing the normal position of the upper end of this canal is crucial for understanding its possible involvement in cranio‐cervical junction pathologies.
A novel method to manage a dislodged self‐expanding transcatheter aortic valve
Authors: Qureshi Waqas , Walker Jennifer , Mina George , Kakouros Nikolaos
Published: June 2024

Despite advancements in technology, operator experience, and procedural planning, transcatheter aortic valve replacement (TAVR) procedures are complex, and complications remain inevitable. Valve embolization may prove to be fatal and conventional rescue techniques are dependent on the anatomy of the aorta. We describe a case of postimplant embolization of a self‐expanding valve during valve‐in‐valve application where the valve could not be stabilized due to the anatomy of the aorta and a novel technique was utilized to stabilize the valve in the aortic arch using a wire fixed to the left axillary artery.
Percutaneous intervention of a giant native coronary artery aneurysm using self‐expanding stents
Authors: Chaturvedi Abhishek , Haberman Dan , Waksman Ron , Bernardo Nelson L.
Published: June 2024

In the absence of standardized management guidelines, coronary artery aneurysms (CAAs) present therapeutic challenges. Percutaneous coronary intervention (PCI) is rarely explored, especially in giant aneurysms with persistent angina, where surgery might be presumed as a preferred option. We describe the technical aspects and feasibility of PCI using Gore Viabahn expanded polytetrafluoroethylene (ePTFE)‐covered nitinol self‐expanding stents in a 66‐year‐old woman with a complex medical history and an enlarging, symptomatic right coronary artery aneurysm. The case was complicated by endoleak after the first stent, but intravascular ultrasound guidance enabled the precise deployment of additional stents, resulting in the successful exclusion of the aneurysm. This case demonstrates steps to successful CAA PCI with Gore Viabahn ePTFE‐covered nitinol self‐expanding stents and emphasizes that in unsuitable surgical candidates, PCI might be a potential alternative for symptomatic CAAs.
Immune checkpoint inhibitor‐induced myasthenia gravis, myocarditis, and myositis: A case report
Authors: Basnet Arjun , Sharma Nava Raj , Gautam Sudarshan , Lamichhane Saral , Kansakar Sajog , Tiwari Kripa , Pokhrel Madalasa , Singh Sehajpreet
Published: June 2024

Key Clinical Message

Immune checkpoint inhibitors can rarely lead to occurrence of myositis, myocarditis, and myasthenia gravis (MG). Early recognition and multidisciplinary management are crucial for optimal outcomes. Vigilance for overlapping toxicities is essential in patients receiving combination immunotherapy.

The use of immune checkpoint inhibitors (ICIs) has revolutionized cancer treatment, but it is associated with immune‐related adverse events (IRAEs) affecting various organ systems. The simultaneous occurrence of MG, myocarditis, and myositis highlights the complex nature of IRAEs. Early recognition and comprehensive multidisciplinary management are crucial for optimal patient outcomes. We present a unique case report of a 76‐year‐old male patient with advanced melanoma who developed concurrent myositis, myocarditis, and MG while receiving combination immunotherapy with Nivolumab and Ipilimumab. This case underscores the significance of recognizing and addressing the “Terrible Triad” of IRAEs in patients receiving ICIs. Healthcare providers should maintain a high index of suspicion for overlapping toxicities and promptly initiate appropriate interventions.
Root canal therapy used in conjunction with follow‐ups for the nonsurgical handling of an enormous periapical lesion of endodontic origin: Clinical case record
Authors: Rao Nitin R. , Mujeeb Abdul , Kottur Aishwarya A. , Mathur Ankita , Snigdha Niher Tabassum Siddiqua , Karobari Mohmed Isaqali
Published: June 2024

Key Clinical Message

The main objective of root canal therapy is to locate all the canals, cleaning, and shaping, and obturation to obtain fluid tight seal and to heal the periapical lesion if present.

The proper cleaning, shaping, and disinfection of the pulp chambers, as well as the filling of the canals, are critical to the efficacy of treatment with root canals. The success of an endodontically treated tooth is dependent on the accuracy of the diagnosis, disinfection, cleaning and shaping, obturation, and finally, the prosthetic rehabilitation management. Root canal therapy should provide a hermatic as well as fluid impenetrable seal which prevents the progression of periapical infection. There are two ways to treat such lesions: surgical and nonsurgical methods. If the root canal is cleaned, shaped, and sealed properly and adequately without the use of a surgical procedure, these lesions will recover during nonsurgical root canal therapy. This case series focuses primarily on the nonsurgical treatment of an enormous periapical lesion and provides evidence that these lesions respond well without surgery.
Accurate Control on the Nucleophilic Addition of H2O to Internal Alkynes: An Ag catalyzed Regiospecific Hydration Strategy
Authors: Wang Shiyang , Xia Zongxiang , Sheng Jie , Cui Jiaxue , Yao Tong , Liu Yu , Liu Chunhui , Liu Zuyong , Tao Jie , Wu Yuanqi
Published: June 2024

In the absence of directing auxiliaries, catalytic addition of nucleophiles to unactivated alkynes with accurate control of regioselectivity remains an ongoing challenge in organic chemistry. Herein, we realized a Ag‐catalysed regiospecific hydration process of unactivated alkynes. Computational investigations offered insights into the origin of the regiochemical outcome. The practicability and efficacy of the protocol was exemplified by its simple reaction conditions without incorporation of acidic additives, as well as the tolerance of a wide range of alkynes equipped with various functional groups, leading to the ketone products in up to 98 % yield. Direct modification of bioactive organic molecules and gram‐scale experiments further showcased the application potential of the strategy. The catalyst control principles are expected to advance efforts towards the development of general site‐selective addition of nucleophile to unsaturated substrates, removing the requirement for neighboring activating groups.
Insight into the Better Collaboration of NiO and MnOx in NiMn2O4 Spinel for Enhanced the Catalytic Oxidation Performance of Toluene
Authors: Zhang Haohong , Xin Yaqin , Deng Yang , An Xia , Liu Xuezhen , Wu Xu
Published: June 2024

NiMn oxides with different ratios (NixMnyOz) as well as spinel‐type NiMn2O4 oxides were synthesized and utilized in the catalytic oxidation of toluene. The results indicate that NiMn2Ox synthesized by the oxygen‐only roasting method exhibits superior catalytic activity due to the appropriate metal valence distribution. The catalytic activity is strongly related with the crystalline phase structures, NiMn2O4 spinel oxides catalyst shows the best low‐temperature performance with 90 % conversion (T90) at 230 °C. Characterization results reveal that the superb catalytic performance of NiMn2O4 spinel oxide is mainly profit by the larger surface area, more abundant surface fugacious oxygen, stronger toluene adsorption capacity than that of the other NixMnyOz catalysts, which in favor of the speedy conversion of benzoic acid, improving the toluene catalytic performance. This finding provides a novel design strategy of NiMn composite oxides for synthesis of high‐efficiency performance toluene catalysts.
Generation of Reactive Oxygen Species on MIL‐100(Fe)/TiO2 Driven by Mild Natural Light
Authors: Yu Chengzhuo , Xu Jin , Wang Yarui , Wang Silong , Xiong Li , Geng Fanglan , Shang Zesen , Wu Huasheng , Lv Jitao , Zhao Lixia , Wang Yawei
Published: June 2024

Reactive oxygen species (ROS), as one kind of the most highly oxidizing oxidants, are difficult to generate and utilize in the natural light conditions, since many materials require external strong stimuli for ROS release to be effective as pollutant degradation or biocide. In this work, we surprisingly found the ROS generation on MIL‐100(Fe)/TiO2 driven by mild natural light. Then ROS generation patterns and mechanism was revealed by chemiluminescence (CL) and density functional theory (DFT). Meanwhile, rhodamine B (RhB) can also be removed by MIL‐100(Fe)/TiO2 under natural light, which further evidence the ROS generation under the natural light. This work provides a new direction for spontaneously generating ROS releasing without external strong stimuli and has the broad potential applications in the field of pollutant degradation or antimicrobials under natural conditions.
LDHs and their Derivatives for Electrochemical Energy Storage and Conversion Systems: Design, Insights and Applications
Authors: Liu Jianyi , Zheng Kaitian , Hua Yingxi , Peng Lipei , Meng Xiangjun , Zhang Chi , Su Rui , Tao Xinyue , Hu Hongzhou , Guo Yugao , Xu Chunjian
Published: June 2024

Electrochemical energy storage and conversion systems (EESCSs), including batteries, supercapacitors, fuel cells, and water electrolysis technologies, enabling the direct conversion between chemical and electrical energies. They are key to the flexible storage and utilization of renewable energy and play an important role in future energy technologies. The physical and chemical properties of electrode materials significantly influence the performance of EESCSs, necessitating the development of materials with both high cost‐effectiveness and superior electrochemical storage and catalytic capabilities. Layered double hydroxides (LDHs), due to their unique properties as high surface area, evenly distributed active sites, and tunable compositions, makes themselves and the derivatives have become focal points in the EESCSs. This review summarizes recent advances of LDH and their derivates for diverse EESCSs applications, aims to elucidate the modification strategies of LDH materials and provide valuable insights for exploring LDH‐derived materials in various electrochemical devices, offering interdisciplinary perspectives for the rational design of LDH‐based materials.
Silver‐Catalyzed Olefination of Aryl Aldehydes Using Propiolates
Authors: Manwar Rina Raju , Balamurugan Rengarajan
Published: June 2024

Olefination of aldehydes is one of the fundamental reactions in organic synthesis. The commonly used Wittig olefination reaction however uses stoichiometric quantities reagents under basic conditions resulting in stoichiometric amounts of byproducts. Known catalytic alternate to the Wittig reaction requires stoichiometric amounts of silane reducing agents and high temperature. Herein, we report a base‐free olefination of aryl aldehydes using propiolates as a surrogate for the Witting reagent under silver catalysis. Trimethyl orthoformate, in the presence of a silver catalyst adds to the alkynoate to form the nucleophilic silver allenolate which reacts with the reactive oxocarbenium ion formed from aldehyde under the reaction conditions. Subsequently, decarbonylation occurs to form the olefin. Trans olefin is formed exclusively from simple aryl aldehydes and cinnamaldehydes. Such a silver allenolate is conceptually novel and has not been explored so far.
Novel methodology to couple decline curve analysis with CFD reservoir simulations for complex shale gas reservoirs
Authors: Khadri Syed Oubee , Al‐Marri Mohammed J. , Nasser Mustafa , Sadooni Fadhil , Shirif Ezeddin , Hussein Ibnelwaleed A.
Published: June 2024

Shale reservoirs are highly complex and are difficult to study using conventional reservoir simulation tools. This study introduces a novel methodology for estimating production from complex shale gas reservoirs by coupling decline curve analysis (DCA) with computational fluid dynamics (CFD) simulations. The proposed method uses exponential DCA to analyze production data from a dual porosity–permeability shale gas transport model. These complexities include fracture characteristics, geomechanical properties, nanopore confinement effects, and multiple flow mechanisms contributing to the total production performance. The shale gas transport model is validated through historical production data from Marcellus shale. The new methodology also tests fracture characteristics. It shows that increased porosity and permeability will increase the recoverable reserves but will have varying effects on the decline rate. The paper demonstrates the advantages of the proposed methodology over conventional reservoir simulation tools. It provides insights into the factors affecting shale gas production performance through the inclusion of the complexities of an unconventional shale gas reservoir. The paper provides a proof of concept on the particular reservoir of which the field data is provided—Barnett and Marcellus Shale.
QSKCG: Quantum‐based secure key communication and key generation scheme for outsourced data in cloud
Authors: Adouth Vamshi , Rajagopal Eswari
Published: June 2024

In the era of digital proliferation, individuals opt for cloud servers to store their data due to the diverse advantages they offer. However, entrusting data to cloud servers relinquishes users' control, potentially compromising data confidentiality and integrity. Traditional auditing methods designed to ensure data integrity in cloud servers typically depend on Trusted Third Party Auditors. Yet, many of these existing auditing approaches grapple with intricate certificate management and key escrow issues. Furthermore, the imminent threat of powerful quantum computers poses a risk of swiftly compromising these methods in polynomial time. To overcome these challenges, this paper introduces a Quantum‐based Secure Key Communication and Key Generation Scheme QSKCG for Outsourced Data in the Cloud. Leveraging Elliptic Curve Cryptography, the BB84 secure communication protocol, certificateless signature, and blockchain network, the proposed scheme is demonstrated through security analysis, affirming its robustness and high efficiency. Additionally, performance analysis underscores the practicality of the proposed scheme in achieving post‐quantum security in cloud storage.
Fuzzy logic‐based computation offloading technique in fog computing
Authors: Soni Dinesh , Kumar Neetesh
Published: June 2024

The fog computing environment expands the capabilities of cloud computing by moving computing, storage, and networking services closer to IoT devices. These resource‐constrained IoT devices often face challenges like high task failure rates and extended execution latency due to data traffic congestion. Distributing IoT services through task offloading across different layers of computing paradigms enhances QoS (Quality of Service) parameters. This endeavor aims to allocate custom workflow‐based real‐time tasks or jobs for processing across various cloud/fog/edge layers, optimizing QoS factors like makespan, energy consumption, and cost. In the fog computing environment, challenges arise due to uncertainties related to job execution locations and the ability to predict future user requirements. Fuzzy logic offers low‐complexity solutions for handling unpredictable and rapidly changing conditions. This paper proposes a hybrid fog‐cloud‐based computing architecture and an intelligent fuzzy logic‐based computation offloading approach. This approach effectively allocates workloads among edge, fog, and cloud layers, resulting in improvements in makespan time (7.51%), energy consumption (4.63%), and cost (13.60%). The proposed method selects suitable processing units or compute nodes for job execution, utilizing heterogeneous resources. Simulation results demonstrate that the proposed methodology outperforms current state‐of‐the‐art algorithms.
GPU parallel processing to enable extensive criticality analysis in state estimation
Authors: Nishio Ayres , Do Coutto Filho Milton B. , Stachinni de Souza Julio C. , Clua Esteban W. G.
Published: June 2024

Power system monitoring relies on the reliability of state estimation (SE) results. SE plays a dominant role in data debugging if sufficient data is available. Criticality analysis (CA) integrates SE as a module in which measurements—taken one‐by‐one or in groups (tuples) of minimal cardinality—are designated crucial. The combinatorial nature of extensive CA (not restricted to identifying low‐cardinality critical tuples) characterizes its computational complexity and imposes challenging limits to go beyond. In simple terms, these limits are established by the number of measurements to be combined, the cardinality of tuples, and the computing time required to check the criticality condition. This paper proposes an innovative computational solution to expand CA limits found to date in the literature. A framework with multi‐threads designed cleverly on a graphics processing unit (GPU) parallel processing environment is built. The conceived architecture favors evaluating massive measurement combinations of diverse cardinality in extensive CA. Numerical results reveal significant speed‐ups with the proposed approach, contrasting with those reported in research efforts published so far.
Mesoporous Metal Sponges Produced by Explosive Decomposition
Authors: Cortie Michael B. , Supansomboon Supitcha , Dowd Annette , Arnold Matthew D.
Published: June 2024

The formation of mesoporous gold sponges by explosive decomposition of ‘knallgold’ (also known as ‘fulminating’ gold) is studied. Proof‐of‐principle experiments are conducted and then the phenomena are further investigated using ‘toy physics’ molecular dynamics simulations. The simulations invoked various ratios of a volatile Lennard–Jones element G and a noble metal element N. In both experiment and simulation the morphology of the resulting sponge is found to depend on the stoichiometry of the starting material. As the mole fraction of G (χG) is increased from 0.5 to close to 1.0 in the simulations, the morphology of the sponges changes from closed to open, with a corresponding increase in the average mean curvature from 0 to +0.12 inverse Lennard–Jones length (L) units. The average Gaussian curvature of the simulated sponges is always negative, with the minimum value of 0.05 L−2 being found for χG≈0.65. In broad agreement with experiment, sponge formation in the simulations is bounded by stoichiometry; no sponges form if χG is <0.52, for χG between 0.52 and 0.70 the sponge is characterized by vermicular cavities whereas classic bicontinuous fibrous sponges form for 0.70<χG<0.85 and, finally, discrete particles result if χG>0.85.
Spotlight on Zinc: Exploring the Visible Light Responsiveness of Zinc Complexes
Authors: Wada Yoshimasa , Sunada Yusuke
Published: June 2024

Group 12 element zinc(II)‐based d10 complexes have long been known for their inherent colorlessness, which has limited their applications in visible light‐driven photophysical and photochemical applications, despite the attractiveness of inexpensive and low‐toxicity zinc metal. Based on precedents with nickel(0) and copper(I) complexes, which also adopt the d10 electronic configuration, achieving a visible light response from zinc(II) complexes seems feasible; however, investigations and proactive design strategies specifically tailored to zinc remain lacking. In this context, the present invited concept paper highlights zinc‘s potential for visible light responsiveness and evaluates how molecular designs can achieve this capability. After delineating the differences between zinc and other d10 metal centers, we review recent developments in zinc complexes that exhibit visible light absorption and compare these complexes with previously reported colorless complexes to identify key distinctions. This study provides critical insights into the molecular design guidelines that are pivotal for harnessing the emerging potential of zinc for visible light responses.
Comprehensive Evaluation of OATP‐ and BCRP‐Mediated Drug–Drug Interactions of Methotrexate Using Physiologically‐Based Pharmacokinetic Modeling
Authors: Hwang Sejung , Lee Yujin , Jang Yeonseo , Cho Joo‐Youn , Yoon Seonghae , Chung Jae‐Yong
Published: June 2024

Methotrexate (MTX) is an antifolate agent widely used for treating conditions such as rheumatoid arthritis and hematologic cancer. This study aimed to quantitatively interpret the drug–drug interactions (DDIs) of MTX mediated by drug transporters using physiologically‐based pharmacokinetic (PBPK) modeling. An open‐label, randomized, 4‐treatment, 6‐sequence, 4‐period crossover study was conducted to investigate the effects of rifampicin (RFP), an inhibitor of organic anionic transporting peptides (OATP) 1B1/3, and febuxostat (FBX), an inhibitor of breast cancer resistance protein (BCRP), on the pharmacokinetics of MTX in healthy volunteers. PBPK models of MTX, RFP, and FBX were developed based on in vitro and in vivo data, and the performance of the simulation results for final PBPK models was validated in a clinical study. In the clinical study, when MTX was co‐administered with RFP or FBX, systemic exposure of MTX increased by 33% and 17%, respectively, compared with that when MTX was administered alone. When MTX was co‐administered with RFP and FBX, systemic exposure increased by 52% compared with that when MTX was administered alone. The final PBPK model showed a good prediction performance for the observed clinical data. The PBPK model of MTX was well developed in this study and can be used as a potential mechanistic model to predict and evaluate drug transporter‐mediated DDIs of MTX with other drugs.
Critical Factors Affecting the Selective Transformation of 5‐Hydroxymethylfurfural to 3‐Hydroxymethylcyclopentanone Over Ni Catalysts
Authors: Morales María V. , Conesa José M. , Campos‐Castellanos Eduardo , Guerrero‐Ruiz Antonio , Rodríguez‐Ramos Inmaculada
Published: June 2024

The ring‐rearrangement of 5‐hydroxymethylfurfural (HMF) to 3‐hydroxymethylcyclopentanone (HCPN) was investigated over Ni catalysts supported on different carbon supports and metallic oxides with different structure and acid‐base properties. Their catalytic performance was tested in a batch stirred reactor in aqueous solution at 180 °C and 30 bar of H2. Under these conditions, the HMF hydrogenation proceeds through three possible competitive routes: (i) a non‐water path leading to the total hydrogenation product, 2,5‐di‐hydroxymethyl‐tetrahydrofuran (DHMTHF), and two parallel acid‐catalyzed water‐mediated routes responsible for (ii) ring‐opening and (iii) ring‐rearrangement reaction products. All catalyst systems primarily produced HCPN, but reaction rates and product distribution were influenced by several variables, some of them intensely analyzed in this work. The most proper conditions resulted to be the presence of the medium/strong Lewis's acidity of a Ni/ZrO2 catalyst (initial TOF=5.99 min−1 and 73 % HCPN selectivity) or the Brønsted acidity originated by an oxidized high surface area graphite, Ni/HSAG‐ox (initial TOF=5.92 min−1 and 87 % HCPN selectivity). However, too high density of acidic sites on the catalyst support (Ni/Al2O3) and sulfur impurities from the HMF feedstock led to catalyst deactivation by coke deposition and Ni poisoning, respectively.