bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of high‐intensity ultrasound, cooling rate, and storage temperature on physical properties and oil binding capacity in fully hydrogenated palm‐kernel lipid matrices
Authors: Marsh Melissa Abigail , Anjum Nabila , Maleky Farnaz , Martini Silvana
Published: October 2024

The ability of a fat crystal network to entrap liquid oil is known as oil binding capacity (OBC) and is an imperative property in semi‐solid fats for use in confectionary, bakery, and snack products. Understanding the factors that increase the OBC of fats is crucial for developing fat‐based foods that are more resistant to unwanted oil migration. In this study, fully hydrogenated palm‐kernel based (FHPKO) lipid matrices were crystallized under different processing conditions to generate samples with a wide range of physical properties and OBC. Three dilutions were created by combining FHPKO with soybean oil (SBO)—75% FHPKO (containing 25% SBO), 50% FHPKO (50% SBO), and 20% FHPKO (80% SBO) and were crystallized at 33, 30, and 22°C; respectively. All the samples were crystallized using fast (FCR; 4.6°C/min) and slow (SCR; 0.1°C/min) cooling rates, as well as with (w) and without (wo) high‐intensity ultrasound (HIU; 20 kHz). These processing conditions resulted in four different sets of samples—FCR wo HIU, FCR w HIU, SCR wo HIU, SCR w HIU. Immediately after processing, the sample's hardness, solid fat content (SFC), viscoelasticity (G′, G″, δ), microstructure, melting behavior (Tpeak, enthalpy), and OBC using a centrifuge method (labeled OBCc) were analyzed. Samples were then stored at 22 and 5°C for 48 h and the aforementioned properties were measured again as well as OBC using a filter paper method (labeled OBCp). Results show that both OBCc and OBCp were positively correlated with the sample's SFC (rs = 0.912, p < 0.001; rs = 0.777, p < 0.001), storage moduli (G′) (rs = 0.674, p < 0.001; rs = 0.526, p = 0.017), hardness (rs = 0.793, p < 0.001; rs = 0.812, p < 0.001), enthalpy (rs = 0.842, p < 0.001; rs = 0.812, p < 0.001), and the number of crystals (rs = 0.655, p < 0.001; rs = 0.728, p < 0.001); respectively. While no correlation between OBCp and the sample's peak melting temperature and microstructure was recorded, a negative association between the sample's peak melting temperature (rs = −0.782, p < 0.001), phase angle (δ) (rs = −0.801, p < 0.001), and crystal diameter (rs = −0.470, p = 0.004) was documented for OBCc. These results suggest oil binding capacity of palm‐kernel based crystallized fats can be increased by formulating harder fats that are elastic, contain more crystals, and have higher SFC and enthalpy. Additionally, the FCR with HIU processing conditions was the most effective in increasing the OBC.
Low‐valent Main‐group Catalysis under Ambient Conditions using a Germylene Cation**
Authors: Kumar Hemant , Mahawar Pritam , Dua Purva , Singh Vivek Kumar , Shukla Pratima , Joshi Prakash Chandra , Rajaraman Gopalan , Nagendran Selvarajan
Published: October 2024

Catalysis using low‐valent main‐group compounds is usually done under inert conditions; no example of such catalysis has been doable entirely in ambient conditions until now. This aspect is addressed in this work through an air‐ and water‐stable germylene cation [DPMGe][(OH)B(C6F5)3] (2) (DPM=dipyrromethene); it efficiently catalyzes aldehyde and ketone hydrosilylations under ambient conditions. Detailed theoretical studies reveal that compound 2’s stability is bolstered by the interaction between the anion and germanium's frontier orbitals. However, the detachment of the anion (in the solution) alters the capability of compound 2 to render exceptional catalytic efficiency. Compound 2 was synthesized under ambient conditions by the equimolar reaction of DPMGeOH (1) with B(C6F5)3.
Chlorine conversion impact on activated carbon block filters: Water quality and nitrification risk in chloraminated water
Authors: Jakpa Horace , Alfredo Katherine
Published: October 2024

The effectiveness of a periodic free chlorine conversion period (FClP) as a nitrification mitigation measure has been scrutinized in chloraminated distribution systems, and knowledge about the response of activated carbon block (ACB) point‐of‐use (POU) filters to this practice is unknown. In this study, three similar filters were monitored bracketing three successive FClPs in the laboratory, aimed at studying the response of ACB POU filters to FClP and the occurrence of nitrification. Results indicate that stagnating filters fostered biofilm growth and increased nitrite concentration (2.5 mg/L‐N) above the EPA maximum contaminant level (MCL). Despite FClP being effective at mitigating nitrification and reducing nitrite concentration far below EPA MCL, this was only temporary. Filters that were microbially seeded before an FClP event re‐nitrified immediately after chloramination resumed. Successive FClPs induced a microbial community change and failed at controlling nitrification, resulting in elevated nitrite and microbial exposure.
Artificial intelligence‐based dynamic capabilities and circular supply chain: Analyzing the potential indirect effect of frugal innovation in retailing firms
Authors: AL‐khatib Ayman wael , Ramayah Thurasamy
Published: October 2024

Academics and practitioners are increasingly interested in the role of the circular supply chains in maximizing resource use and improving sustainable performance. However, the shift from linear to circular supply chains is still at an early stage and still needs more research. The current study seeks to test the direct effects of artificial intelligence‐based dynamic capabilities on frugal innovation and circular supply chains in a group of retail firms operating in Jordan. The current paper also aims to test the potential indirect effect of frugal innovation. To achieve these objectives, a research framework was developed that explains hypothesized relationships between the previous constructs and was tested empirically through a sample of 212 respondents from the top administrative level in these firms. The casual and quantitative approach was employed to test the hypothetical relationships, and the partial least squares‐structural equation modelling (PLS‐SEM) approach was employed as a tool to analyze the data. The empirical results reported through data analysis showed acceptance of all hypothesized relationships that were hypothesized in this study, as there was a positive effect of both artificial intelligence‐based dynamic capabilities and frugal innovation on circular supply chains. In addition, the mediation was statistically significant, as frugal innovation mediated the relationship between artificial intelligence‐based dynamic capabilities and circular supply chains. This study had a set of interesting contributions at the theoretical and the managerial contributions, as this paper is the first work in the body of the literature that explores these innovative relationships. The current paper also contributed to developing recommendations that would improve sustainable performance in the retail sector by enhancing its dynamic capabilities based on artificial intelligence tools, which leads to strengthening circular supply chains.
Does waste disclosure waste?
Authors: Bai Min , Qin Yafeng , Dasgupta Avijit
Published: October 2024

This study investigates the motivations behind firms disclosing their waste production. Analyzing data from S&P 500 companies spanning from 2010 to 2018, we explore the influence of board characteristics on this corporate decision. Our findings reveal that firms with a higher proportion of female directors or independent directors, the establishment of a sustainability committee, and external verification of their sustainability reports are more inclined to disclose their waste production. Further examination demonstrates variations in these trends across firms with distinct characteristics. In particular, the impact of female directors proves especially significant for larger, younger firms with higher leverage, a greater number of employees, or firms compliant with the Global Reporting Initiative (GRI). Conversely, the presence of a sustainability committee appears to have a more pronounced impact on smaller, younger, and less profitable firms that do not comply with GRI standards.
Usnic Acid Derivatives as Multi‐Target Anti‐Alzheimer's Disease Agents: Design, Synthesis, X‐Ray Single Crystal Structure of Zn(II) Complex and Biological Activities
Authors: Zhao Lihua , Li Bingbing , Zheng Lin
Published: October 2024

Alzheimer's disease (AD) is multifactorial, which makes the design of multi‐target‐directed ligands an attractive strategy for the development of anti‐AD drugs. In order to enhance the anti‐AD effects and reduce the toxicity, two usnic acid (UA) derivatives (1–2) were designed, synthesized and fully characterized by introducing dimethylamine Schiff base moiety into the toxic “triketone” portion. Ellman's method and molecular docking were used to test the cholinesterase inhibitory activities. Antioxidant activities were studied with Fenton reaction, cyclic voltammetry and C. elegans. The results showed that compared with UA, 1–2 had stronger anti‐cholinesterase activities and similar antioxidant activities. Notably, solvent evaporation of 2 and ZnCl2 formed a single crystal, which was revealed to be a Zn(II) complex with UA and tertiary amine as mixed ligands by X‐ray diffraction. The hydrolysis of 2 was thus furtherly studied by HPLC. Furthermore, the crystal structure supported the replacement of toxic “triketone” moiety in the chelation process, playing a detoxifying role and at the same time regulating metal homeostasis. In silico prediction also showed low hepatotoxicity and acceptable drug‐likeness of 1–2. Overall, this work provided useful insights into multi‐target anti‐AD candidates with the natural product UA as the lead compound.
Novel Insecticidal Benzo[4,5]imidazo[1,2‐b]pyrazole Derivatives Idenatified Through Ring‐Closure Scaffold Hopping on Fipronil
Authors: Zhou Cong , Li Guanglong , Wang Sihui , Li Zhong , Qian Xuhong , Cheng Jiagao
Published: October 2024

A series of innovative benzo[4,5]imidazo[1,2‐b]pyrazole scaffold containing compounds were rationally designed through a ring‐closure scaffold hopping strategy and synthetized with an intermediate derivatization approach. Physicochemical properties analysis indicated the potential pesticide‐likeness of the target compounds. The optimal target compound A14 showed relatively good insecticidal activity against P. xylostella, with an LC50 value of 37.58 mg/L, and demonstrated lower acute fish toxicity compared to fipronil. Docking binding mode analysis demonstrated that compound A14 bound to GABAR through a H‐bond between the amide group and the residue of 6’Thr. The differences in binding modes between benzo[4,5]imidazo[1,2‐b]pyrazole target compounds and fipronil may be a key factor for the reduced insecticidal activities. The elucidated binding mode and SAR profile lay a foundation for the further structural optimization of insecticidal benzo[4,5]imidazo[1,2‐b]pyrazole derivatives.
Assessment of Artemisia Campestris L. Leaf Extract Effects on Polycystic Ovarian Syndrome in Rats, Antioxidant and α‐Amylase Inhibition Activities
Authors: Cherfi Inasse , Mahboub Nasma , Toumi Ikram , Eddine Laouini Salah , Gamal Hasan Gamil , Bouafia Abderrhmane , Alharthi Fahad , Bin Emran Talha
Published: October 2024

Polycystic Ovarian Syndrome (PCOS) is characterized by metabolic and reproductive dysfunction, often associated with elevated oxidative stress markers in the bloodstream. This study examines the potential antioxidant properties and α‐amylase inhibitory activity of Artemisia campestris leaves extract (Artemisia campestris L) and its effects on rats with induced PCOS. Estradiol valerate was administered to ten mature Wistar rats to induce PCOS, while a control group consisted of five mature Wistar rats. Following a 16‐day induction period, the rats were categorized into three groups: a control group, a PCOS group, and an experimental group receiving 200 mg/kg body weight of A. campestris L. extract orally for 15 days. Serum levels of follicle‐stimulating hormone (FSH) and luteinizing hormone (LH) were measured using the ELISA technique. The group treated with A. campestris L. extract exhibited significantly reduced LH levels compared to the PCOS group. Histomorphometric analysis indicated notable changes in follicle counts and the thickness of the theca layer. These findings suggest a significant alleviation of PCOS symptoms, potentially linked to the effects of A. campestris L. on oxidative stress pathways. Furthermore, aqueous extracts of A. campestris L. displayed potent in vitro inhibition of α‐amylase, with an IC50 value of 2.418 μg/mL.
Supramolecular Conductive Hydrogels for Tissue Engineering Applications
Authors: Bhavsar Aashwini , Pati Falguni , Chakraborty Priyadarshi
Published: October 2024

Owing to their unique attributes, including reversibility, specificity, directionality, and tunability, supramolecular biomaterials have evolved as an excellent alternative to conventional biomaterials like polymers, ceramics, and metals. Supramolecular hydrogels, in particular, have garnered significant interest because their fibrous architecture, high water content, and interconnected 3D network resemble the extracellular matrix to some extent. Consequently, supramolecular hydrogels have been used to develop biomaterials for tissue engineering. Supramolecular conductive hydrogels combine the advantages of supramolecular soft materials with the electrical properties of metals, making them highly relevant for electrogenic tissue engineering. Given the versatile applications of these hydrogels, it is essential to periodically review high‐quality research in this area. In this review, we focus on recent advances in supramolecular conductive hydrogels, particularly their applications in tissue engineering. We discuss the conductive components of these hydrogels and highlight notable reports on their use in cardiac, skin, and neural tissue engineering. Additionally, we outline potential future developments in this field.
Evaluation of Potency and Specificity of Cryptophycin‐Loaded Antibody‐Drug Conjugates
Authors: Bitsch Peter , Dessin Cedric , Bitsch Sebastian , Voss Jona , Becker Janine , Sharma Panna , Biyani Neha , Kochat Harry , Sewald Norbert , Kolmar Harald
Published: October 2024

An enhanced variant of the antimitotic toxin cryptophycin was conjugated to the anti‐Her2 monoclonal antibody (mAb) Trastuzumab upon Michael addition. Either antibodies with freed hinge‐region cysteines or THIOMAB formats with engineered cysteines in the mAbs light chain were added to a maleimide derivative of cryptophycin. These Antibody‐Drug Conjugates (ADCs) showed retained binding to Her2 positive tumor cells and highly efficient cell killing in double‐digit pM range on high Her2‐expressing SK‐BR‐3 cells. Two ADCs (DAR 6, DAR 3) showed superior cell killing of the cell lines JIMT‐1 and RT112 with medium receptor expression level in comparison with a DAR 6 MMAE ADC serving as reference. The observed cell cytotoxicity is target‐dependent since no impact on cell viability was observed for low Her2‐expressing MDA‐MB468 cells. Particularly the DAR 3 ADC in THIOMAB format exhibiting desirable biophysical properties and high potency emerged as a promising candidate for further in vivo investigations.
Correlating Heterogeneities in Support Fragmentation to Polymer Morphology in Metallocene‐Based Propylene Polymerization Catalysis
Authors: Dorresteijn Joren M. , Valadian Roozbeh , Ji Yuntao , Zanoni Silvia , Bossers Koen W. , Nikolopoulos Nikolaos , Cirriez Virginie , Welle Alexandre , Curulla‐Ferré Daniel , Vogt Eelco T.C. , Meirer Florian , Weckhuysen Bert M.
Published: October 2024

In the field of olefin polymerization catalysis, metallocenes are heterogenized with methylaluminoxane onto silica supports to yield active catalysts. During olefin polymerization, these silica supports act as a framework to control the fragmentation stage, thereby influencing the final polymer product and preventing reactor fouling and fines formation. This study investigates the influence of different silica supports induced on the final polymer product. To study a broad range of silica supports from an industrial silica database, we utilize a hierarchical clustering method to cluster the supports based on their physical properties. From the clustering method, five supports representing the clusters and an industrial benchmark were analyzed at different polymerization stages using focused ion beam–scanning electron microscopy (FIB–SEM) and microcomputed tomography (microCT). This combined FIB‐SEM/microCT methodology revealed differences in both fragmentation behavior and polymer morphologies based on structural features, including macropores, mesopores, spray‐dried shells, spray‐dried spheres, and denser shells. The heterogeneity and ideal fragmentation behavior was further assessed by calculating the replication factor of each support, indicating that silica materials containing macropores and spray‐dried shells have an almost ideal replication phenomenon. This multiscale analysis revealed new understanding of catalyst fragmentation for different supports. This understanding could in the future be further developed by the addition of more supports or additional analysis of the supports to the industrial database.
Balanced Rh+‐Rh0 Sites over Rh Clusters Enhance Heterogeneous Hydroformylation of Aldehyde
Authors: Yang Qi , Zheng Ying , Feng Yi , Ding Jie , Li Maoshuai , Huang Shouying , Wang Mei‐Yan , Ma Xinbin
Published: October 2024

Controlling the metal geometric and electronic structure is of significance in developing efficient catalysts for heterogeneous hydroformylation. This study examines the structural sizes of Rh and Rh+‐Rh0 distribution to construct a highly active catalyst for formaldehyde hydroformylation. The active sites for hydroformylation require several Rhn atoms, while single‐atom Rh can solely catalyze hydrogenation. The highest activity was achieved on Rh nanoclusters (0.95 nm), giving a TOF of 191 h−1 and selectivity of 82% for glycolaldehyde formation. The tunability of the electronic properties of Rh nanoclusters and the synergistic interaction between Rh+ and Rh0 are essential for enhanced activity. Pseudo‐in situ FT‐IR analysis elucidated that formaldehyde adsorbed on Rh nanocluster prefers to produce glycolaldehyde via hydroformylation, while formaldehyde adsorbed on isolated Rhδ+ sites tends to form methanol via hydrogenation. This study provides a new insight into the design of heterogeneous catalysts and guidance for understanding the reaction mechanism for aldehydes/olefins hydroformylation.
Step Towards Enzymatic Bioelectrorefinery: Design of a Ligninolytic Hybrid Air‐Breathing Biocathode
Authors: Mishyn Vladyslav , Floret Juliette , Chabbert Brigitte , Aguié‐Béghin Véronique , Crônier David , Carducci Nunzio Giorgio G. , Hickey David P. , Abdellaoui Sofiene
Published: October 2024

Lignins, abundant aromatic biopolymers and one of the major components of lignocellulosic biomass, remain the most underutilized renewable bioresources of aromatics and hydrocarbons on the Earth. Numerous physical and chemical processes have been developed for lignin valorization; however, they generally suffer from environmentally unfriendly, harsh conditions and lack reaction specificity. On the other hand, milder methods involving biocatalysts exist but are impeded by many limitations, such as cofactor regeneration, deleterious enzyme–lignin interactions, and low stability. In this work, we attempt to eliminate the constrains encountered in enzyme‐based lignin valorization processes through the development of a novel electrochemically assisted bioprocess. This “all‐in‐one” biocathode incorporates a hybrid electrocatalytic interface combining a hydrogen peroxide‐generating passive air‐breathing gas diffusion electrode with an immobilized hydrogen peroxide‐consuming lignin peroxidase on a single surface and catalyzing the depolymerization of lignins. The ligninolytic potential of this bioelectrochemical device is demonstrated using both lignin models (veratryl alcohol and veratrylglycerol β‐guaiacyl ether) and a technical lignin at room temperature in aqueous media with the reaction efficiency of 14.9% per hour.
Recent Advances in the Development of Targeted Activation Strategies for Organoboron Prodrugs
Authors: Liu Moyi , Zou Taotao
Published: October 2024

Elevated levels of reactive oxygen species (ROS) are a hallmark of varieties of diseases such as cancer, inflammation, and neurodegenerative disorders. Inspired by the discrepancy of ROS concentrations between pathological tissues and the normal counterparts, an increasing number of ROS‐responsive theragnostic prodrugs are developed in past years, with particularly high proportions of organoboron‐based prodrugs that can respond to H2O2. Unfortunately, increasing studies have demonstrated that the intrinsic ROS (H2O2) levels in most pathological tissue are only slightly higher than normal tissues and are not adequate to activate organoboron prodrugs; in contrast, several organoboron compounds have been clinically approved in which boronic acid acts as electrophilic warhead. To this end, developing more robust and universal approaches for boronic acid‐prodrug activation becomes highly attractive. In this context, we discuss the recently reported activation strategies for boron‐caged prodrugs with a particular focus on their design principles and activation mechanisms. The perspectives on the future directions for this important research area are discussed as well.
(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals
Authors: Scharnhölz Moritz , Gamboa Carballo Jose Juan , Trapp Nils , Verel Rene , Coburger Peter , Grützmacher Hansjörg
Published: October 2024

Dehalogenation of (PBr)2C2(PPh3)2 with potassium graphite, KC8, leads to Cs‐P4C4(PPh3)4, which can be viewed as a PPh3 adduct of a Cs‐symmetric P4C4 cage. An isolable intermediate was found and in combination with DFT calculations, the structure of a S4‐symmetric P4C4(PPh3)4 cage is proposed for this species. That a 1,3‐diphosphete type Ph3P→P2C2←PPh3 heterocycle is a short‐lived intermediate in the dehalogenation reaction is indicated by trapping experiments which allowed to isolate and fully characterize the [Fe(CO)4] complexes [Fe(CO)4(κ‐P−P2C2{PPh3}2] and [(Fe(CO)4)2(μ2‐κ‐P−P2C2{PPh3}2]. The conversion of S4‐P4C4(PPh3)4 to Cs‐P4C4(PPh3)4 prompted a (re)investigation of the isomerization of various P4X4 species (X=S, NH, NMe; CH2), which shows that these proceed on Minimum Energy Reaction Pathways (MERPs) with two transition states embracing one intermediate. In contrast, the isomerization S4‐P4C4(PR3)4 to Cs‐P4C4(PR3)4 is a one‐step process.
Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M2Ru3 (M=Fe, Ru)
Authors: Liu Xiao‐Lin , Li Yi , Wang Hao , Yang Yu‐Ying , Liu Han , Wu Xin‐Tao , Sheng Tian‐Lu
Published: October 2024

In this work, we report the design and synthesis of two chain‐like pentanuclear cyanido‐bridged complexes trans‐[Ru(bpy)2(μ‐CN)2][cis‐Ru(bpy)2(μ‐NC)M(dppe)Cp*]2[PF6]4 (M=Fe, 14+; M=Ru, 24+) and the electronic communication properties of their oxidized products 1m+ (m=6, 7, 8) and 2n+ (n=5, 6, 7, 8). The single‐crystal X‐ray diffraction analysis of 1m+ (m=4, 6, 7) and 24+ show that 14+ and 24+ possess a Z‐type array structure, 17+ is a U‐type one, and 16+ exhibits both the types. The investigations indicate that both 1 and 2 show an extraordinarily strong electronic interaction between the two side Ru across the central NC−Ru−CN, leading to the formation of a fully delocalized cyanidometal Ru−Ru−Ru bridge for both three‐electron oxidized states 17+ and 27+. Moreover, it should be noted that in 1 there exists no electronic interaction between the two terminal Fe ions. Upon substitution of Fe by Ru, however, 2 exhibits an electronic interaction between the two terminal metal ions across the trinuclear cyanidometal CN−Ru−NC−Ru−CN−Ru−NC bridge which is up to 20 Å.
Revisiting Butafulvene Formation by Thermal Dimerization of Fluorene‐Based Dialkynes ‐ Effects of Aromatic Substituents
Authors: Schuldt Moritz P. , Maximenko Tatjana , Rominger Frank , Mastalerz Michael
Published: October 2024

Butafulvenes, together with pentafulvenes and [3]radialenes, form a series of constitutional benzene isomers in which aromaticity changes significantly and can be strongly substituent dependent. Butafulvene, as a member of this series, is frequently proposed to be antiaromatic. Based on butafulvenes Hopf, Zimmerman and coworkers first time described, derivatives thereof were synthesized and the effects of substituents on both the stability of the intermediate isobenzenes and on their optoelectronic and (anti)aromatic properties are discussed.
Regio‐, Site‐ and Stereo‐Selective Aziridination of Conjugated Dienes Enabled by Palladium/Copper/Iodide/Oxygen Cooperation
Authors: Meng Jingjie , Wang Junwei , Zhang Jingang , Yang Zehua , Wu Zhengxing , Zhang Wanbin
Published: October 2024

Vinylaziridines are important building blocks in organic chemistry, especially in the synthesis of nitrogen‐containing heterocycles. The direct and efficient transfer of an appropriate nitrogen source to readily accessible conjugated dienes is a notable methodology. The Pd‐catalyzed oxidative 1,2‐difunctionalization of conjugated dienes through a π‐allyl‐palladium species should be an ideal method for the selective synthesis of vinylaziridines. However, this method faces the challenge of regioselectivity, often resulting in 1,4‐difunctionalization instead. In this study, we developed a Pd‐catalyzed aerobic 1,2‐difunctionalization of conjugated dienes via a π‐allyl‐palladium species to achieve regio‐, site‐ and stereo‐selective aziridination under the synergistic effects of PdII, CuI, I−, and O2. The π‐allyl palladium species formed in the system undergoes an unusual iodination process, leading to the formation of an allyl iodide intermediate. Subsequently, the vinylaziridine is obtained through intramolecular SN2′ substitution of the allyl iodide.
A Combined Experimental and Computational Exploration of Heteroleptic cis‐Pd2L2L’2 Coordination Cages through Geometric Complementarity
Authors: Tarzia Andrew , Shan Wentao , Posligua Victor , Cox Cameron J. T. , Male Louise , Egleston Benjamin D. , Greenaway Rebecca L. , Jelfs Kim E. , Lewis James E. M.
Published: October 2024

Heteroleptic (mixed‐ligand) coordination cages are of interest as host systems with more structurally and functionally complex cavities than homoleptic architectures. The design of heteroleptic cages, however, is far from trivial. In this work, we experimentally probed the self‐assembly of Pd(II) ions with binary ligand combinations in a combinatorial fashion to search for new cis‐Pd2L2L’2 heteroleptic cages. A hierarchy of computational analyses was then applied to these systems with the aim of elucidating key factors for rationalising self‐assembly outcomes. Simple and inexpensive geometric analyses were shown to be effective in identifying complementary ligand pairs. Preliminary results demonstrated the viability of relatively rapid semi‐empirical calculations for predicting the topology of thermodynamically favoured assemblies with rigid ligands, whilst more flexible systems proved challenging. Stemming from this, key challenges were identified for future work developing effective computational forecasting tools for self‐assembled metallo‐supramolecular systems.
In Situ Construction of Perovskite Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ/CoRu Nanoparticles with Co–N–C Composite Enabling Efficient Bifunctional Electrocatalyst for Zinc‐Air Batteries
Authors: Wei Jialu , Wang Jingyu , Zhang Wei , Mao Yuezhen , Sun Chunwen
Published: October 2024

Bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential components of rechargeable zinc‐air batteries. In this study, we synthesized a Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ (PBMCRO) perovskite composite with in situ exsolved CoRu nanoparticles and Co–N–C, functioning as an efficient bifunctional electrocatalyst for zinc‐air batteries. The in situ exsolution of CoRu nanoparticles from the perovskite oxide was facilitated by the reducing action of 2‐methylimidazole (2‐MIM). Concurrently, Co–N–C was used to decorate PBMCRO, forming a novel bifunctional composite electrode of Co–N–C–PBMCRO. The incorporation of CoRu nanoparticles introduces a significant number of electrochemically active oxygen vacancies in the perovskite matrix, enhancing ORR and OER performance. Additionally, the Co–N–C synergistically improves electrochemical activity while preserving the structural stability of the perovskite oxide. The prepared Co–N–C–PBMCRO catalyst demonstrates significantly enhanced bifunctional performance compared to the undecorated pristine perovskite Pr0.5Ba0.5MnO3−δ (PBMO). The zinc‐air battery with Co–N–C–PBMCRO catalyst achieve a peak power density of approximately 90 mW/cm2 and exhibit remarkable cycling stability for 788 h. This study presents a novel and effective strategy to enhance the catalytic performance of perovskite‐based air electrodes for rechargeable metal‐air batteries.
Responsive Chirality: Tailoring Supramolecular Assemblies with External Stimuli as Future Platforms for Electronic/Spintronic Materials
Authors: Kataria Meenal , Seki Shu
Published: October 2024

Supramolecular chirality is the major branch of supramolecular chemistry, which not only plays important roles in biological processes but also in synthetically designed aggregated systems. To understand the complex processing of biological systems, the only way is to design supramolecular chiral ensembles that mimic natural biomolecules such as Deoxyribonucleic acid (DNA), Ribonucleic acid (RNA), amino acids, etc. In addition, chiral systems and self‐assemblies as molecular motifs with breaking spatial inversion symmetry have been regarded as key substances in electronics and spintronics as well as in fundamental chemistry and physics. Here, in this review, our major concern is understanding modulation in spatial arrangements and packing modes under the impact of any external stimuli, which results in tailoring the handedness of resulted supramolecular chiral superstructures. We, in this review, highlighted the role of external stimuli such as solvent, chemical additives, photo exposure, etc. in altering the supramolecular chirality for their future utility as “active switches” in optoelectronic and spintronic devices and applications.
Luminescent Radical Polymers
Authors: Zhang Ziteng , Zhang Jianyu , Zhi Sun Jing , Zhang Haoke , Zhang Xinghong , Zhong Tang Ben
Published: October 2024

Organic radicals are gaining significant interest in luminescent materials due to their unique properties, which present unprecedented opportunities for innovation across various fields, from display technology to biomedical applications. However, addressing challenges related to stability and low fluorescence efficiency is crucial to unlocking their full potential for practical applications. Polymerization has emerged as an effective strategy to enhance intra‐ and interchain through‐space interactions, enabling the creation of stable luminescent radicals with excellent processing and multifunctional properties. This concept emphasizes the strategic use of polymerization in designing and synthesizing stable main‐chain and side‐chain radical polymers. This approach not only broadens the scope of stable radicals but also improves their luminescence properties as photofunctional materials.
In Situ Self‐Assembly of Antibody‐Rhamnose Complex as a Pre‐Targeting Strategy for Enhanced Cancer Immunotherapy
Authors: Hong Haofei , Zhou Kun , Lin Han , Li Yanchun , Wu Zhimeng
Published: October 2024

Enhancing the Fc effector functions of monoclonal antibodies (mAbs) is a proven strategy for improving cancer immunotherapy. In this study, we present a novel pre‐targeting approach that integrates host‐guest chemistry with an antibody‐recruiting concept to create mAbs with superior effector functions. Using rituximab (RTX), a clinically approved anti‐CD20 mAb, as our model, we modified RTX by conjugating it with adamantane (Ada) derivatives and various polyethylene glycol (PEG) linkers to produce RTX‐Ada conjugates. These conjugates effectively formed RTX‐rhamnose (Rha) complexes in situ through self‐assembly, driven by host‐guest interactions with Rha‐modified β‐cyclodextrin. This mechanism successfully redirected endogenous anti‐Rha antibodies to target cells, enhancing the availability of Fc domains for improved effector functions, including complement‐dependent cytotoxicity (CDC). A structure‐activity relationship study indicated that the potency of these in situ complexes was significantly influenced by the length of the PEG linker used; shorter PEG linkers correlated with higher CDC activity. Given the variability in endogenous antibody levels among individuals, this strategy presents a flexible and promising platform for enhancing the efficacy of mAb‐based cancer immunotherapy.
Late‐Stage Functionalization Using a Popular Titrating Agent: Aryl‐Chlorides and ‐Fluorides Activation by the Diphenylacetic Acid Dianion
Authors: Cerveri Alessandro , Russo Giulia , Sparascio Sara , Merli Daniele , Maggi Raimondo , Della Ca' Nicola , Lanzi Matteo , Maestri Giovanni
Published: October 2024

Aryl‐chlorides and ‐fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar−X bonds. The generation of aryl radicals via activation of strong Ar−X bonds is possible through the irradiation of tailor‐made organic anions, which become reductants stronger than lithium metal. We report that the combination of visible light with the cheap diphenylacetic acid dianion is an even better tool, showing excellent activity across a variety of complex substrates and providing opportunities for late‐stage drug modification. Ar−X bonds are chemoselectively activated in the presence of more easily reducible functions, such as Alk‐Cl ones and carbonyl groups. These results pave the way to original synthetic strategies that would be otherwise considered impossible.
Investigation of Muscarinic Acetylcholine Receptor M3 Activation in Atomistic Detail: A Chemist's Viewpoint
Authors: Drabek Matthäus , Emmerich Rolf , Djulic Nuri , Bünemann Moritz , Schlitzer Martin , Kolb Peter
Published: October 2024

We analyzed the precise ligand:receptor interactions required for activation of the muscarinic acetylcholine receptor M3, a prototypical G protein‐coupled receptor and potential diabetes target. Starting from literature‐known compounds and docking solutions, ligands were tailored for the modulation of this receptor's activation. Several aspects of the structure‐activity relationship of agonists were investigated in atomistic detail, in order to delineate how the receptor can be activated via the orthosteric site. Such exquisitely precise knowledge is instrumental for designing potent and effiacious ligands. We put this strategy into practice and acquired or synthesized and measured a diverse set of 55 ligands ranging from small fragment‐like amines coordinating D3.32 to bigger molecules extending towards helices 5 and 6 with diphenyl moieties. In the course of these investigations, we showed that the polarizability of the amine nitrogen and the rigidity and size of the moieties in the space delimited by helices 5 and 6 are the two key elements distinguishing potent and efficacious ligands from those that are not. The resulting data set will be highly useful in drug design and molecular machine learning alike.
Facile Fabrication of LaFeO3 Supported Pd Nanoparticles as Highly Effective Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reaction
Authors: Sun Ying , Yin Juanjuan , Wang Ying , Zhang Ping , Ma Lingjuan , Li Jisen
Published: October 2024

Supported Pd catalysts have been widely studied due to their enormous potential as candidates for heterogeneous Suzuki–Miyaura coupling reactions. However, the sintering and low activity of active sites still remain challenges. A vesicle‐shaped LaFeO3‐supported Pd catalyst (I−Pd/LaFeO3) was successfully fabricated using the impregnation method and tested for the Suzuki–Miyaura coupling reaction. Compared to P−Pd/LaFeO3 prepared with photo‐deposition and Pd/Al2O3 prepared with impregnation, the I−Pd/LaFeO3 catalyst exhibits significantly higher catalytic activity, stability, and reusability. The chemical composition and electron states of different Pd‐based catalysts were well studied based on various characterizations and the results indicated that the excellent performance of I−Pd/LaFeO3 can be attributed to its unique nanostructure and the strong interactions between LaFeO3 and palladium nanoparticles. The impregnation method and the choice of the LaFeO3 support show a great influence on the electronic properties of Pd species, their reducibility, and, consequently, their reaction behavior. This unique LaFeO3 supported Pd catalyst provided an environmentally friendly heterogeneous method for the Suzuki–Miyaura coupling reaction.
Improving QoS in cloud resources scheduling using dynamic clustering algorithm and SM‐CDC scheduling model
Authors: Varmeziar Tayebeh , Shiri Mohamad Ebrahim , Rahmani Parisa
Published: October 2024

Quality of Service (QoS) regulates and controls network resources by setting priorities for specific data types. Many clustering algorithms are used to cluster cloud workloads, most of which are static. However, the lack of dynamic algorithms is seen in the face of huge databases that are real‐time and according to the existing clustering conditions. Additionally, fair allocation of tasks on servers and efficient resource utilization pose challenges. In this research, two solutions are proposed to improve the quality of service: the first solution uses the chameleon dynamic algorithm, a method to improve service quality. The chameleon algorithm has been able to show significant performance due to its high accuracy in detecting the smallest distance between clusters. This dynamic algorithm outperforms static algorithms with classification accuracy and response speed, which are the most important parameters of service quality. The second part of the proposed solution is to use the Scheduling Model using Cloud Data Centers (SM‐CDC) system to select the best service provider based on the clustering done in the previous step. A SM‐CDC technique is developed to handle cloud storage center tasks that are stored in electronic devices. According to the comparison with existing scheduling policies, SM‐CDC offered 36% decrease on response time, 50% reduction on cost of resources, and 40% improvement on QoS Satisfaction.
A Review on Network Covert Channel Construction and Attack Detection
Authors: Khadse Mrinal Ashish , Dakhane Dhananjay Manohar
Published: October 2024

A covert network channel is a communication channel in which the message is secretly transmitted to the recipient. Sometimes, covert network channels are vulnerable to multiple attacks. Therefore, the message must be properly secure. In most cases, the covert channel is used to ensure data protection and allow users to freely access the Internet. In this paper, several recent studies are reviewed on covert network channels and examine the existing works from 2015 to 2024. This review article also discusses the undetectability and reliability of different types of covert network channels. Furthermore, a detailed description of the covert network channel's ability to hide in containers is provided. Existing research on covert network channels explains a few techniques for detecting attacks in secret data communication. However, several machine learning and deep learning techniques have been discussed in this article. Additionally, this article describes the accuracy of detection through an overview of current technologies. In addition, various countermeasures to prevent attacks in covert channels are also discussed in detail. However, in this case, the bandwidth limitations, data set limitations, and covert channel capacity are clearly defined, which will help future researchers build covert network channels and detect attacks. Finally, this work considers the challenges faced by covert network channels and the future scope of application.
High‐Performance Organic Field‐Effect Transistors and Inverters with Good Flexibility and Low Operating Voltage
Authors: Yang Fukang , Liu Shining , Li Congling , Lv Aifeng
Published: October 2024

Organic field‐effect transistors (OFETs) with good flexibility and low operating voltage, are of great meaning for the low power stretchable and wearable electronic devices. The operating voltage and flexibility are easily affected by the dielectric layers in the OFETs. Bilayer dielectrics comprising both high‐ and low‐permittivity (k) insulating polymers, have been reported. The flexible bilayer dielectrics can combine the advantages of both insulating polymers, which are high charge carriers from low‐k polymers and low operating voltage from high‐k polymers. However, the effect of film thicknesses in the bilayer dielectrics on the OFET performance is seldom investigated. Here, bilayer dielectrics comprising high‐k polyvinyl alcohol (PVA) and low‐k polymethylmethacrylate (PMMA) were fabricated. And PVA/PMMA bilayers with three different PVA film thicknesses are carefully investigated. The 300 nm PVA/100 nm PMMA bilayer dielectric makes the pentacene OFETs show the highest hole mobility of 1.24 cm2 V−1s−1 and the corresponding inverters give a high voltage gain of 40 and a noise margin of 2.3 V (77 % of 1/2 VDD) at low operating voltage of 6 V. Both the pentacene transistors and the inverters still work properly under bending radium of 5.85 mm, proving the good prospects of the PVA/PMMA bilayer dielectric in practical applications.
Graphene Oxide and its Composites: Advanced Membranes for Selective Water Permeation
Authors: Lee Byeongho , Kim Choonsoo
Published: October 2024

Graphene oxide (GO) membranes have gained significant attention as a promising material for separation by selective permeation processes due to their advantageous structural and chemical properties, including high water permeability, chemical resistance, and mechanical strength. In this study, we explore the potential applications of GO membranes in pervaporation to separate liquid mixtures. The layered structure and hydrophilic nature of GO membrane facilitate rapid and selective water transport through angstrom‐scale interlayer spacings, resulting in superior performance over conventional polymeric and inorganic membranes. The unique mass transport mechanisms – slip flow and molecular alignment – enable GO membranes to selectively permeate water over organic solvents. For chemical dehydration, GO membranes are the most potential candidates. Furthermore, advancements in composite GO membranes and cross‐linking techniques that improve their stability and separation performance are discussed. This study highlights the advantages of GO membranes and their potential to replace or complement existing technologies, by emphasizing their role in advancing membrane‐based separation and promoting environmental sustainability. Future research is expected to optimize the fabrication techniques for GO membranes and expand their application scope.
Post‐CCSD(T) Thermochemistry of Chlorine Fluorides as a Challenging Test Case for Evaluating Density Functional Theory and Composite Ab Initio Methods
Authors: Karton Amir , Haasler Matthias , Kaupp Martin
Published: October 2024

Quantum chemistry plays a key role in exploring the chemical properties of highly reactive chlorine polyfluoride compounds (ClFn). Here, we investigate the thermochemical properties of ClFn species (n=2–6) by means of high‐level thermochemical procedures approximating the CCSDT(Q) and CCSDTQ5 energies at the complete basis set limit. We consider total atomization energies (TAEs), Cl−F bond dissociation energies (BDEs), F2 elimination energies (F2 elim.), ionization potentials (IPs), and electron affinities (EAs). The TAEs have significant contributions from post‐CCSD(T) correlation effects. The higher‐order triple excitations, CCSDT−CCSD(T), are negative and amount to −0.338 (ClF2), −0.727 (ClF3), −0.903 (ClF4), −1.335 (ClF5), and −1.946 (ClF6) kcal/mol. However, the contributions from quadruple (and, where available, also quintuple) excitations are much larger and positive and amount to +1.335 (ClF2), +1.387 (ClF3), +2.367 (ClF4), +2.399 (ClF5), and +3.432 (ClF6) kcal/mol. Thus, the contributions from post‐CCSD(T) excitations exceed the threshold of chemical accuracy in nearly all cases. Due to their increasing hyper‐valency and multireference character, the ClFn series provides an interesting and challenging test case for both density functional theory and low‐level composite ab initio procedures. Here, we highlight the limitations in achieving overall chemical accuracy across all DFT and most composite ab initio procedures.
Triel Bonds with Methyl Groups as Electron Donors. A Pentacoordinate Carbon Atom
Authors: Wang Xin , Cheng Yuwei , Li Qingzhong , Scheiner Steve
Published: October 2024

The triel bond (TrB) formed between Be(CH3)2/Mg(CH3)2 and TrX3 (Tr=B, Al, and Ga; X=H, F, Cl, Br, and I) is investigated via the MP2/aug‐cc‐pVTZ(PP) quantum chemical protocol. The C atoms of the methyl groups in M(CH3)2 are characterized by a negative electrostatic potential and act as an electron donor in a triel bond with the π‐hole above the Tr atom of planar TrX3. The interaction energy spans a wide range between −2 and −69 kcal/mol. Mg(CH3)2 forms a stronger TrB than does Be(CH3)2, which comports with the more negative electrostatic potential on its methyl groups. Some of the complexes involving Mg display a high degree of transfer of the methyl group from Mg to Tr, which is accompanied by an inversion of the bridging methyl and a sizable pyramidalization of the TrX3 unit. The geometries of these complexes have the properties of the long sought pentacoordinate C which has eluded identification and characterization in the past.
Lattice Strain Regulated by Hetero/Homo Atom Interface Merging on NiMo Nanocluster for High‐Performance Hydrogen Production
Authors: Xie Yulu , Liu Baiqiang , Mo Feifan , Qin Xiaochen , Shu Hang , Deng Renchao , Ye Tingfang , Meng Meng , Li Puhai , Hu Yu‐wen , Li Yuquan , Liu Wei , Yang Hao
Published: October 2024

Lattice strain engineering represents a cutting‐edge approach capable of delivering enhanced performance across various applications. The lattice strain can affect the performance of electrochemical catalysts by changing the binding energy between the surface‐active sites and intermediates. In this work, lattice strain is regulated through a homo/heterogeneous atomic interface merging. The strong lattice strain and electronic interactions between Ni and Mo facilitated the reaction kinetic of HER. The prepared NiMo@SSM exhibits excellent HER catalytic performance with 70 mV overpotential at the current density of 10 mA cm−2 and long‐term stability. The method of controlling lattice strain through hetero/homo atom interface merging provides a new strategy for designing high‐performance alkaline HER electrocatalysts.