bluuebunny/crossref_metadata_2025 huggingface dataset:
Aqueous Electrolyte With Weak Hydrogen Bonds for Four‐Electron Zinc–Iodine Battery Operates in a Wide Temperature Range
Authors: Liu Tingting , Lei Chengjun , Wang Huijian , Li Jinye , Jiang Pengjie , He Xin , Liang Xiao
Published: June 2024

In the pursuit of high‐performance energy storage systems, four‐electron zinc–iodine aqueous batteries (4eZIBs) with successive I−/I2/I+ redox couples are appealing for their potential to deliver high energy density and resource abundance. However, susceptibility of positive valence I+ to hydrolysis and instability of Zn plating/stripping in conventional aqueous electrolyte pose significant challenges. In response, polyethylene glycol (PEG 200) is introduced as co‐solvent in 2 m ZnCl2 aqueous solution to design a wide temperature electrolyte. Through a comprehensive investigation combining spectroscopic characterizations and theoretical simulations, it is elucidated that PEG disrupts the intrinsic strong H‐bonds of water by global weak PEG–H2O interaction, which strengthens the O─H covalent bond of water and intensifies the coordination with Zn2+. This synergistic effect substantially reduces water activity to restrain the I+ hydrolysis, facilitating I−/I2/I+ redox kinetics, mitigating I3− formation and smoothening Zn deposition. The 4eZIBs in the optimized hybrid electrolyte not only deliver superior cyclability with a low fading rate of 0.0009% per cycle over 20 000 cycles and a close‐to‐unit coulombic efficiency but also exhibit stable performance in a wide temperature range from 40 °C to −40 °C. This study offers valuable insights into the rational design of electrolytes for 4eZIBs.
A Thioether‐Bridging Surface Modification of Polymeric Microspheres Offers Nonbiological Protein A‐Mimetic Affinity for IgG
Authors: Kishida Takanori
Published: June 2024

Surface modification of polymeric materials to control their interaction with proteins has been studied extensively, leading to widespread bio‐applications. However, the development of nonbiological, smart polymer surfaces, mimicking the recognition ability of biomolecules, remains a challenge. The present study presents a thioether‐bridging surface modification of polymeric microspheres as a new approach for mimicking protein A affinity for immunoglobulin G (IgG). The bridge‐modified surface is created through an epoxide linking reaction of porous polymeric microspheres with potassium thioacetate in a 2:1 molar ratio, acting as a protein A ligand, which is essential for industrial IgG purification. This surface exhibits buffer responsiveness and selective high‐affinity binding to the IgG Fc region. Remarkably, a comparison among the binding behaviors of a series of thioether‐modified microspheres indicates that bridging structures composed of β,β′‐dihydroxysulfide play a predominant role in IgG recognition. This straightforward approach can lead to the development of economical and practical nonbiological alternatives to protein A‐conjugated materials, providing solutions for various applications such as biosensors and site‐specific reagents utilizing the affinity of the IgG Fc region. The improved understanding of protein interactions at bridged/non‐bridged interfaces can be valuable in various applications such as implant materials and biomaterials.
High‐Resolution Printing‐Based Vertical Interconnects for Flexible Hybrid Electronics
Authors: Ma Sihang , Dahiya Abhishek Singh , Christou Adamos , Zumeit Ayoub , Dahiya Ravinder
Published: June 2024

Flexible hybrid electronics (FHE) is an emerging area that combines printed electronics and ultra‐thin chip (UTC) technology to deliver high performance needed in applications such as wearables, robotics, and internet‐of‐things etc. The integration of UTCs on flexible substrates and the access to devices on them requires high resolution interconnects, which is a challenging task as thermal and mechanical mismatches do not allow conventional bonding methods to work. To address this challenge, the resource‐efficient, area‐efficient, and low‐cost printing routes for obtaining vertical interconnection accesses (VIAs) are demonstrated here. It is demonstrated how high‐resolution printers (electrohydrodynamic and extrusion‐based direct‐ink writing printers) can be used for patterning of high‐resolution, freeform, vertical conductive structures. To access the transistors on UTCs, the VIAs, obtained using conventional photolithography and plasma etching steps, are filled with conductive silver nanoparticle‐based ink/paste using high‐resolution printers. Comprehensive studies are performed to compare and benchmark in terms of: i) the printing speed and throughput of the printers, ii) the electrical performance of vertically connected transistors in UTCs, and iii) the electrical performance stability of FHE system (interconnects and UTCs) under mechanical bending conditions. This in‐depth study shows the potential use of printing technologies for development of high‐density 3D integrated FHE systems.
Catalytic Transfer Vinylation of Alcohols
Authors: Opačak Saša , Tin Sergey
Published: June 2024

This review focuses on summarising the studies on transition metal catalysed transfer vinylation of alcohols using vinyl ethers and vinyl acetate as vinylating agents. Mercury, palladium, iridium and gold catalysts are discussed herein. Selected examples from publications and patents are given for the purpose of analysing functional group tolerance towards the methodology. In addition, mechanistic pathways are described.
In Situ Triflation‐Tandem Cross‐Coupling Enables Synthesis and Photophysical Studies of Indenones and Benzofulvenes
Authors: Mondal Sourav , Biswas Krishna , Ganesh Venkataraman
Published: June 2024

Indan‐1,3‐diones stand as versatile precursors to a plethora of complex molecules with wide applications; however, their direct cross‐coupling methodologies remain largely unexplored. Herein, we unveil an in situ triflation‐tandem cross‐coupling strategy to synthesize a diverse variety of indenones and benzofulvenes from indan‐1,3‐diones. The successful synthesis of a neolignan natural product and the key intermediate of Indatraline (antidepressant) showcased the synthetic utility of the methodology. The strategy enabled tuning the electronic characteristics of indenones and benzofulvenes, modulating the HOMO‐LUMO gaps. The photophysical properties of these molecules were studied, and the experimental results were compared with the predictions obtained from the DFT studies.
Fabrication of S‐Scheme GDY‐CuI/ZnWO4 Photocatalyst to Promote Electron Transfer for Enhanced Photocatalytic H2 Evolution
Authors: Wang Kai , Wang Miao , Xie Haiyan , Li Songling , Kong Xu , Jin Zhiliang
Published: June 2024

The exceptional performance of graphdiyne (GDY) in photocatalysis for hydrogen evolution attracts much attention, but the narrow band gap of GDY complicates the effective realization of the dissociation between photogenerated charges and photogenerated holes. In this study, GDY‐CuI is synthesized by cross‐coupling method, and the wide bandgap ZnWO4 is introduced into it by low‐temperature mixing, which effectively constructed the GDY‐CuI/ZW‐50 double S‐scheme heterojunction. The optimized GDY‐CuI/ZW‐50 catalyst photocatalytic hydrogen evolution performance reached 308.61 µmol after 5 h of visible light irradiation, which is 12.86 and 6.56 times than that of GDY‐CuI and ZnWO4, respectively. The improved efficiency of hydrogen evolution is attributed to the formation of a double S‐scheme heterojunction between GDY, CuI, and ZnWO4 and an internal electric field, which promotes charge transfer, reduces the complexation rate of photogenerated electrons, and enhances the redox capacity of photogenerated charges. A combination of photoelectrochemical analysis, in situ X‐ray photoelectron spectroscopy (In situ XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) results revealed the electron transfer mechanism. This work will provide new ideas for the design and preparation of GDY‐based photocatalysts.
Molybdenum Disulfide Memristors for Next Generation Memory and Neuromorphic Computing: Progress and Prospects
Authors: Wells R. A. , Robertson A. W.
Published: June 2024

In the last 15 years memristors have been investigated as devices for high‐density, low‐power, non‐volatile, resistive random access memory (ReRAM) beyond Moore's law. They also show potential in neuromorphic logic architectures to overcome the Von–Neumann bottleneck of classical circuitry facilitating better hardware for artificial intelligence (AI) and artificial neural network (ANN) systems. Molybdenum disulfide (MoS2) has emerged as a promising material for memristor devices of monolayer thickness due to its direct bandgap, high carrier mobility and environmental stability. In this review, recent progress in the development of MoS2 memristors the current understanding of the mechanisms behind their function are examined. The remaining obstacles to a commercially viable device principle and how these may be surmounted in light of the rapid progress that has already been made are also discussed.
Photochemical Oxidation of Substrate Water Analogs and Halides by Photosystem II
Authors: Shin Jieun , Kanyo Jean , Debus Richard J. , Brudvig Gary W.
Published: June 2024

Photosystem II (PSII) is a multi‐subunit protein‐pigment complex with diverse redox‐active cofactors, which enabled the biological availability of O2 on Earth. The substrate specificity and the underlying redox chemistry of the Mn4CaO5 catalytic center are investigated using alternate substrates such as small molecules (ammonia and methanol) and halides (Cl‐, Br‐, I‐) instead of the natural substrate water. Changes in the kinetic profiles of steady‐state O2 evolution and of dichlorophenolindophenol (DCIP) photochemical reduction by PSII as well as the detection of modified sites by proteomic analysis implied the possibility of alternate substrate photooxidation. Of particular interest is the role of two chlorides bound close to the putative water channels in the native system. The mutation of D2‐K317 to alanine is believed to impair the binding of a catalytically relevant chloride, eliminating the chloride requirement for water oxidation catalysis. The efficiency of small molecule photooxidation by the OEC is enhanced by the mutated D2‐K317A PSII complex without the competition from chloride. These results provide insight into the role of bound chloride in native PSII as a filter for enhancing the selectivity of water oxidation. The design principles for PSII may be extended to new strategies for developing highly selective catalysts.
Have agricultural and applied economists lost sight of the land‐grant mission? A textual analysis of Presidential Addresses and Invited Papers from 1919–2022
Authors: Wilson Norbert L. W. , Hochhaus Natalie
Published: June 2024

Agricultural and applied economists have maintained a public discourse at the Agricultural and Applied Economics Association (AAEA) meetings and subsequently published papers discussing the mission of land‐grant institutions and the role of AAEA members in that mission. With a content analysis of 4001 Invited Papers and Presidential Speeches, we find agricultural and applied economists questioned their profession's purpose and role within the land‐grant system. The reflective questions still apply to land‐grant institutions and the agricultural and applied economics profession. We argue that AAEA members are crucial in addressing the food and agricultural challenges connected to society's deepest needs today and into the future.
Is nutrition‐sensitive fish farming a panacea for Africa's increasing malnutrition burden? The case of Sierra Leone
Authors: Okeke‐Ogbuafor Nwamaka , Gray Tim , Sankoh Salieu , Bangura Abigail Abibatu , Stead Selina , Rajah Edward
Published: June 2024

Fish is vital for reducing hunger and malnutrition. However, the combined impact of climate change and overfishing is increasing the hunger and malnutrition burden on the African continent and its population of over 200 million people who depend on marine capture fishing and related activities for survival. Fish farming was introduced to alleviate these problems, and our study assessed the extent to which current fish farming activities in the least developed countries (LDCs) like Sierra Leone provide sufficient micro‐ and macro‐nutrients for local communities. The present study which is based on data from 300 survey questionnaires and 77 semi‐structured interviews administered in three communities in Sierra Leone, and from two expert judgments which investigated the nutritional impact of fish farming activities in Sierra Leone, revealed that (1) there is a range of sub‐standard fish farming activities from sampled farms; (2) that these activities could diminish the nutritional quality of farmed fish; and (3) that coastal communities were suspicious of eating or investing in fish farming. To alleviate Africa's increasing malnutrition, burden, our research highlights the need for investment in nutrition‐sensitive fish farming – a refocus from an emphasis on increasing production and income. The nutritional quality of farmed fish is a more basic consideration than the quantity of production for securing a healthy and economically viable fish farming sector for LDCs like Sierra Leone.
A Bayesian optimization approach for data‐driven mixed‐integer nonlinear programming problems
Authors: Morlet‐Espinosa Javier , Flores‐Tlacuahuac Antonio
Published: June 2024

The optimization of process systems within the field of Chemical Engineering often confronts uncertainties that can exert significant influences on the performance and dependability of the obtained solutions. This research endeavors to investigate the application of Bayesian optimization in the realm of constrained mixed integer nonlinear problems. A comparative analysis was conducted, exploring different surrogate models, and evaluating diverse kernel functions and acquisition functions. Furthermore, a sampling strategy was devised to assess the enhancement achieved by the acquisition function. The findings of this article reveal the superior performance of sparse Gaussian processes in conjunction with computationally inexpensive acquisition functions, thereby highlighting their suitability for addressing mixed integer nonlinear programming problems characterized by noisy functions and stochastic behavior. Consequently, this article presents a computationally efficient approach to effectively tackle the challenges associated with data‐driven mixed integer nonlinear programming problems within the domain of Process System Engineering.
Insect herbivory on woody broadleaf seedlings along a subtropical elevational gradient supports the resource concentration hypothesis
Authors: Wang Xiaoran , Chen Lin , Zhang Hongwei , Liu Pengcheng , Shang Xiaofan , Wang Fang , Zhang Zhaochen , Zhao Jingchao , Sun Mufan , Chen Junhong , Zhang Jian
Published: June 2024

Premise

Theories of plant–herbivore interactions hold that seedlings are more vulnerable to herbivory in warmer and more stable climates at lower elevations. Hypotheses of plant apparency, resource concentration, and resource availability have been proposed to explain variability in leaf herbivory. However, seasonal differences in the effects of these hypotheses on leaf herbivory on seedlings remain unclear.

Methods

We evaluated the three herbivory hypotheses by comparing the percentage and frequency of leaf herbivory in understory broadleaf seedlings in a subtropical forest in May (spring) and October (autumn) along an elevational gradient (290–1370 m a.s.l.). In total, we measured 2890 leaves across 696 seedlings belonging to 95 species and used beta regressions to test the effects of plant apparency (e.g., leaf area, seedling height), resource concentration (e.g., plant species diversity), and resource availability (e.g., canopy openness, soil available N and P) on leaf herbivory.

Results

Seedlings exhibited unimodal patterns of leaf herbivory along elevation, with drivers of leaf herbivory varying by the month. Variation in the frequency of leaf herbivory was best explained by the resource concentration hypothesis (e.g., plant species diversity) in both months, and herbivory was lower on seedlings in sites with higher plant diversity. Plant apparency hypothesis (e.g., leaf area, seedling height) was weakly supported only in spring, and the evidence for resource availability hypothesis (e.g., canopy openness, soil nutrients) was mixed.

Conclusions

This study supports the resource concentration hypothesis and reveals the importance of seasonal difference on understanding leaf herbivory patterns and the drivers of plant diversity in subtropical forests.
Effects of particle size and particle concentration of poly (ethylene‐co‐methacrylic acid) on properties of epoxy resin
Authors: Nascimento Allana , Trappe Volker , Pavasaryte Lina , Melo José , Barbosa Ana Paula Cysne
Published: June 2024

Self‐healing polymers have been developed to improve durability and reduce costs associated with maintenance during service. The addition of thermoplastics to thermosets to produce mendable polymers appears as a promising self‐healing technique. In this study, poly (ethylene‐co‐methacrylic acid) (EMAA) was added to epoxy resin and the effects of EMAA addition on epoxy properties were evaluated. Specimens with two different contents of thermoplastic and particles sizes were manufactured. A two‐level full factorial experimental design was used to evaluate the effect of particle size and particle content on properties of epoxy modified with addition of EMAA. Tensile tests and dynamic mechanical analysis (DMA) were used and the evaluated responses were tensile strength, modulus of elasticity, and glass transition temperature (Tg). X‐ray computed tomography (XCT) was used to investigate particle size and concentration after manufacturing. It was found that the particle concentration has greater effects on stress–strain behavior of epoxy while Tg was not significantly affected by neither of the analyzed entrance variables.
Irreversible temperature indicator based cellulose membranes conjugated with leuco‐dye pigment
Authors: Carvalho Margarida , Tavares Ana. P. M. , Marques Maria A. , Alves Joaquim J. , Figueira Joana , Morais Maria , Pinto Joana V. , Moreira Felismina T. C.
Published: June 2024

This research focuses on the development of thermochromic membranes made of cellulose acetate (CA) for temperature monitoring of sensitive food products. Two dual TC membranes developed for the control of different temperature ranges were formulated using a three‐component system: a leuco‐dye membrane (crystal violet lactone, CVL) integrated with an acidic membrane containing the color developer (salicylic acid) and the acidic solvent with different melting points (decanoic acid, DA, or methacrylic acid, MA). The CVL membrane, together with the DA membrane, showed an irreversible color change when exposed to 35°C, which was facilitated by the melting of DA. The CVL membrane also underwent an irreversible color change when exposed to 15°C together with the MA membrane. The membranes were characterized in detail using scanning electron microscopy. The evaluation of color changes, reproducibility, specificity, and stability ensured the practical suitability of these membranes. Overall, this innovative approach has proven to be a reproducible, sustainable, cost‐effective method to produce irreversible colorimetric temperature sensors. These sensors have significant potential for applications in the food and pharmaceutical industries and offer a promising way to improve product safety and quality.
Cyclotriphosphazene: A Versatile Building Block for Diverse Functional Materials
Authors: Lee Johnathan Joo Cheng , Chua Ming Hui , Wang Suxi , Qu Zhengyao , Zhu Qiang , Xu Jianwei
Published: June 2024

Cyclotriphosphazene (CP) is a cyclic inorganic compound with the chemical formula N3P3. This unique molecule consists of a six‐membered ring composed of alternating nitrogen and phosphorus atoms, each bonded to two chlorine atoms. CP exhibits remarkable versatility and significance in the realm of materials chemistry due to its easy functionalization via facile nucleophilic substitution reactions in mild conditions as well as intriguing properties of resultant final CP‐based molecules or polymers. CP has been served as an important building block for numerous functional materials. This review provides a general and broad overview of the synthesis of CP‐based small molecules through nucleophilic substitution of hexachlorocyclotriphosphazene (HCCP), and their applications, including flame retardants, liquid crystals (LC), chemosensors, electronics, biomedical materials, and lubricants, have been summarized and discussed. It would be expected that this review would offer a timely summary of various CP‐based materials and hence give an insight into further exploration of CP‐based molecules in the future.
Zur Berechnung von Trägern mit nachgiebigem Verbund
Authors: Konrad Albert
Published: June 2024

Zur Behandlung von Trägern, die aus beliebig vielen Einzelteilen mit abschnittsweise konstanten Querschnitten und nachgiebigen Verbindungsmitteln bestehen, werden die erforderlichen linearen Differenzialgleichungen erster und zweiter Ordnung hergeleitet und fundamental gelöst. Dies ermöglicht die Ermittlung sämtlicher Zustandsgrößen der Träger für beliebige Lagerungen und Belastungen.
Combining descriptive and predictive modeling to systematically design depth filtration‐based harvest processes for biologics
Authors: Liu Peter , Hartmann Michael , Shankaran Ajay , Li Hong , Welsh John
Published: June 2024

Advances in upstream production of biologics–particularly intensified fed‐batch processes beyond 10% cell solids–have severely strained harvest operations, especially depth filtration. Bioreactors containing high amounts of cell debris (more than 40% particles <10 µm in diameter) are increasingly common and drive the need for more robust depth filtration processes, while accelerated timelines emphasize the need for predictive tools to accelerate development. Both needs are constrained by the current limited mechanistic understanding of the harvest filter‐feedstream system. Historically, process development relied on screening scale‐down depth filter devices and conditions to define throughput before fouling, indicated by increasing differential pressure and/or particle breakthrough (measured via turbidity). This approach is straightforward, but resource‐intensive, and its results are inherently limited by the variability of the feedstream. Semi‐empirical models have been developed from first principles to describe various mechanisms of filter fouling, that is, pore constriction, pore blocking, and/or surface deposit. Fitting these models to experimental data can assist in identifying the dominant fouling mechanism. Still, this approach sees limited application to guide process development, as it is descriptive, not predictive. To address this gap, we developed a hybrid modeling approach. Leveraging historical bench scale filtration process data, we built a partial least squares regression model to predict particle breakthrough from filter and feedstream attributes, and leveraged the model to demonstrate prediction of filter performance a priori. The fouling models are used to interpret and provide physical meaning to these computational models. This hybrid approach–combining the mechanistic insights of fouling models and the predictive capability of computational models–was used to establish a robust platform strategy for depth filtration of Chinese hamster ovary cell cultures. As new data continues to teach the computational models, in silico tools will become an essential part of harvest process development by enabling prospective experimental design, reducing total experimental load, and accelerating development under strict timelines.
Recent Developments in the Biosynthesis of Aziridines
Authors: Maurer Sabina J. , Petrarca de Albuquerque Joao L. , McCallum Monica E.
Published: June 2024

Only 0.016 % of all known natural products contain an aziridine ring, but this unique structural feature imparts high reactivity and cytotoxicity to the compounds in which it is found. Until 2021, no naturally occurring aziridine‐forming enzymes had been identified. Since 2021, the biosynthetic enzymes for ~10 % of known aziridine containing natural products have been identified and characterized. This article describes the recent advances in our understanding of enzyme‐catalyzed aziridine formation in the context of historical methods for aziridine formation through synthetic chemistry.
Marijuana rescheduling: What do the experts say
Authors: Knopf Alison
Published: June 2024

Parents are rightly concerned about the increased use of high potency cannabis, which has been linked in several research reports to first episode psychosis. Consider the word “first” — psychosis can be a lifelong chronic condition.
An unusual presentation of severe obstructive sleep apnea with nocturnal seizure‐like movements: A case report
Authors: Rahimi Negin , Amirifard Hamed , Jameie Melika
Published: June 2024

Key Clinical Message

This study suggests that severe obstructive sleep apnea can present as sleep‐related epileptic or non‐epileptic seizures. A detailed history and physical examination, along with polysomnography and video electroencephalography findings can lead to the correct diagnosis.

Obstructive sleep apnea (OSA) is defined by recurrent episodes of the upper airway complete or partial collapse while sleeping. The obstructive episodes result in gradual suffocation that increases breathing attempts till the person is awakened. The main manifestations are excessive daytime sleepiness, snoring, observed episodes of stopped breathing, and abrupt awakenings accompanied by gasping or choking. Nevertheless, there are very few reports of patients with OSA, manifesting other symptoms such as seizure‐like movements. Differentiating OSA with nocturnal seizures could be challenging due to their overlapping features. A 53‐year‐old man presented to the clinic, experiencing seizure‐like involuntary movements during nocturnal sleep for the past 2 years with a frequency of 2–3 times per night. Neurologic examinations were normal. Further evaluation with polysomnography revealed impaired arousal followed by seizure‐like movements during sleep. Video electroencephalography (EEG) did not show any epileptiform discharges, ruling out the nocturnal seizure diagnosis. The patient was diagnosed with OSA. Subsequently, continuous positive airway pressure (CPAP) treatment resolved all symptoms.
Exploring the use of telepractice Dohsa‐hou to adults with intellectual disabilities
Authors: Yamazaki Masayoshi , Takahashi Shinichiro , Tanaka Junichi , Takahashi Makoto
Published: June 2024

Key Clinical Message

This study presents the application of an authentic Japanese bodywork approach Dohsa‐hou to adults with intellectual disabilities who live in a care facility. Amid the COVID‐19 pandemic, such people remained disconnected from their families and friends, for which reason many of them experience anxiety, stress and inability to enjoy leisure activities. Given the lockdown circumstances, we decided to use for the first time in the field telepractice to provide Dohsa‐hou. The results showed that participants experienced a gradual positive mood change and also expressed a desire to continue the sessions. Considering this, although further research is still needed, we assume that telepractice Dohsa‐hou might be a viable substitute for the face‐to‐face sessions.
MOF‐derived Ni‐WxC/carbon catalysts: Application to cellulose conversion into glycols
Authors: Boulos Joseph , Goc Firat , Marinova Maya , Perret Noémie , Rataboul Franck , Royer Sébastien , Dhainaut Jérémy
Published: June 2024

In this work, a series of Ni‐WxC/carbon materials have been prepared from a MOF precursor, DUT‐8(Ni), following different tungsten deposition routes. After pyrolysis, nickel‐tungsten alloys and tungsten carbide phases over nitrogen‐doped carbons were obtained. These materials were applied to cellulose hydrogenolysis, where molar yields of up to 46 % in ethylene glycol (EG) and 9 % in propylene glycol (PG) were obtained at 245 °C after 1 hour of reaction time. The best performing catalyst demonstrated promising stability, as the EG yield remained constant over 3 recycling tests and very little nanoparticles sintering was observed.
Hybrid Ethylcellulose Polymeric Films: Ag(I)‐Based Components and Curcumin as Reinforcing Ingredients for Enhanced Food Packaging Properties
Authors: Crispini Alessandra , Aiello Iolinda , Godbert Nicolas , La Deda Massimo , di Maio Giuseppe , Tagarelli Antonio , Elliani Rosangela , De Rose Renata , Scarpelli Francesca
Published: June 2024

Bio‐active ethylcellulose (EC) polymeric films have been obtained by incorporating curcumin (curc) and Ag(I)‐based compounds, known for their antioxidant and antimicrobial activity, respectively, within the polymeric matrix. The recently reported Ag(I) coordination polymer, in both its structural forms (α‐[(bpy)Ag(OTf)]∞ and β‐{[(bpy)Ag][OTf]}∞), and the [(bpy)Ag(OTf)]∞‐curc polymeric co‐crystal (bpy=2,2′‐bipyridine; OTf=trifluoromethanesulfonate) have been selected as Ag(I) species. The hybrid composite films have been prepared through the simple solvent casting method and characterized through Powder X‐Ray Diffraction (PXRD), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), UV‐vis spectroscopy. The deep investigation of the film samples highlighted the non‐inert behaviour of EC towards these specific active ingredients. Antimicrobial tests showed that EC films embedding the Ag(I)‐based compounds present good antimicrobial performance, in particular against Staphylococcus aureus, used as a model of Gram‐positive bacteria. In addition, Silver migration tests, performed on the Ag(I)‐incorporating EC films, evidenced low values of silver release particularly in the case of the EC films incorporating [(bpy)Ag(OTf)]∞‐curc.
A Photoredox Thiol‐yne Reaction for the Synthesis of Vinyl Sulfide‐Based Coumarins and its Effect on Fluorescence Properties
Authors: Toubia Isabelle , Puteaux Chloé , Weronika Swiderska Karolina , Hubert‐Roux Marie , Renard Pierre‐Yves , Sabot Cyrille
Published: June 2024

Coumarins still remain one of the most widely explored fluorescent dyes, with a broad spectrum of applications spanning various fields, such as molecular imaging, bioorganic chemistry, materials chemistry, or medical sciences. Their fluorescence is strongly based on a push‐pull mechanism involving an electron‐donating group (EDG), mainly located at the C7 or C8 positions of the dye core. Unfortunately, up to now, these positions have been very limited to hydroxyl or amino groups. In this study, we present in detail the synthesis of the first series of coumarins bearing a vinyl sulfide as the EDG at the C7 position. These derivatives were prepared by thiol‐yne reaction, promoted by ruthenium‐ or porphyrin‐based photoredox catalysis, enabling rapid late‐stage diversification. We also functionalized coumarins with short peptides, and BSA protein as a proof‐of‐concept study, in a single‐step process. This strategy, capable of proceeding under aqueous conditions, overcomes the protection/deprotection steps usually required by traditional methods, which also use strong bases and organic solvents. Moreover, the photophysical properties such as absorption and emission of obtained coumarins (for 3‐CF3, 3‐benzothiazole, 6–8‐difluoro derivatives), predominantly exhibited large Stokes shifts (up to 204 nm) and maintained intramolecular charge transfer (ICT) characteristics.
Development of Fluorenyl‐Based Copolyimines with Adjustable Mechanical Properties, Recyclability and Friction Resistance
Authors: Wang Haiyue , Huang Qirui , Liu Cai , Hong Wei , Li Jianing , Ma Juanjuan , Yu Ping , Wang Chunyu , Yan Xuzhou
Published: June 2024

Dynamic polyimines are a class of fascinating dynamic polymers with recyclability and reparability owing to their reversible Schiff‐base reactions. However, balancing the dynamic properties and mechanical strength of dynamic polyimines presents a major challenge due to the dissociative and associative nature of the imine bonds. Herein, we introduced bulky fluorene groups and polyether amine into the skeleton of polyimine networks to achieve a tradeoff in comprehensive properties. The resulting dynamic polyimines with fluorene groups (Cardo‐DPIs) were successfully synthesized by combining the rigid diamine 9,9‐bis(4‐aminophenyl)fluorene and the flexible polyether amine, demonstrating a high tensile strength of 64.7 MPa. Additionally, Cardo‐DPIs films with more content of rigid fluorene groups exhibited higher water resistance, glass transition temperature and wear‐resisting ability. Moreover, the Cardo‐DPIs films not only efficiently underwent thermal reshaping, but also exhibited excellent self‐healing capabilities and chemical degradation in acidic solutions. Furthermore, the resulting films can achieve fully closed‐loop recovery by free amine solution for 2 h at room temperature. This study broadens the scope of dynamic polyimine materials and promotes the balanced development of their functional and mechanical properties.
Highly Active and Selective Fe‐MOF/2D‐Montmorillonite Photocatalyst via in‐situ Preparation for Hydroxylation of Benzene to Phenol
Authors: Xu Xuetong , Jia Xu , Liu Cong , Qiao Jiaolong , Wang Fuying , Zhang Liuxue , Yang Dan , Zhang Yuan , Wang Xiulian
Published: June 2024

The photocatalytic hydroxylation of benzene to phenol is an important reaction for the synthesis of fine chemicals and pharmaceuticals. However, the development of efficient and selective photocatalysts for this reaction remains a challenge. Here, a highly active and selective Fe‐MOF/2D‐montmorillonite (Fe‐MOF/MMT) photocatalyst was prepared via an in‐situ method for the hydroxylation of benzene to phenol under the visible light irradiation. The Fe‐MOF/MMT composite exhibited excellent photocatalytic performance, with phenol yield of 30.3 % and benzene selectivity of 96.5 % within 4 hours. The high activity and selectivity of the Fe‐MOF/MMT photocatalyst were attributed to the synergistic effect between the Fe‐MOF and MMT, as well as the unique 2D structure of MMT, which facilitated charge separation and transfer. The Fe‐MOF/MMT composite also showed good stability and re‐used without significant decrease of activity. This study demonstrated that the potential of Fe‐MOF/MMT as a highly efficient and selective photocatalyst for the hydroxylation of benzene to phenol and provided an insight into the design of advanced photocatalysts for sustainable chemical synthesis.
Implications for the Hydrogenation of Propyne and Propene with Parahydrogen due to the in situ Transformation of Rh2C to Rh0/C
Authors: Pokochueva Ekaterina V. , Kountoupi Evgenia , Janák Marcel , Kuznetsov Denis A. , Prosvirin Igor P. , Müller Christoph R. , Fedorov Alexey , Koptyug Igor V.
Published: June 2024

NMR spectroscopy studies using parahydrogen‐induced polarization have previously established the existence of the pairwise hydrogen addition route in the hydrogenation of unsaturated hydrocarbons over heterogeneous catalysts, including those based on rhodium (Rh0). This pathway requires the incorporation of both hydrogen atoms from one hydrogen molecule to the same product molecule. However, the underlying mechanism for such pairwise hydrogen addition must be better understood. The involvement of carbon, either in the form of carbonaceous deposits on the surface of a catalyst or as a metal carbide phase, is known to modify catalytic properties significantly and thus could also affect the pairwise hydrogen addition route. Here, we explored carbon's role by studying the hydrogenation of propene and propyne with parahydrogen on a Rh2C catalyst and comparing the results with those for a Rh0/C catalyst obtained from Rh2C via H2 pretreatment. While the catalysts Rh2C and Rh0/C differ notably in the rate of conversion of parahydrogen to normal hydrogen as well as in terms of hydrogenation activity, our findings suggest that the carbide phase does not play a significant role in the pairwise H2 addition route on rhodium catalysts.
Unlocking the Charge‐Storage Potential of a Phenanthraquinone‐based Two‐Dimensional Covalent Organic Framework (2D COF)
Authors: Günther Tyran , Hedbom Daniel , Åhlén Michelle , Yoshino Haruka , Miyasaka Hitoshi , Kasai Hitoshi , Oka Kouki , Emanuelsson Rikard
Published: June 2024

The high surface area, open pore‐structure and atomic‐level organization inherent in many covalent organic frameworks (COFs) make them an attractive polymer platform for developing functional materials. Herein, a chemically robust 2D COF (TpOMe‐DAPQ COF) containing phenanthraquinone moieties was prepared by condensing 2,4,6‐trimethoxy‐1,3,5‐benzenetricarbaldehyde (TpOMe) and 2,7‐diamino‐9,10‐phenanthraquinone (DAPQ) using the convenient mechanochemical method. The poor charge‐storage capacity of the pristine TpOMe‐DAPQ COF was substantially improved by first investigating its redox‐site accessibility (RSA) using different conductivity‐enhancement methods, and then optimizing the amount of EDOT needed to perform an in‐situ polymerization. The resulting composite (0.4EDOT@TpOMe‐DAPQ) was characterized and its enhanced charge‐storage capabilities enabled it to be used as an anode material in an aqueous Mn beaker‐cell battery capable of delivering 0.76 V. This work outlines the rational design approach used to develop a functional charge‐storage material utilizing a COF‐based polymerization platform.
Diindeno‐Fused Corannulene‐Extended Tetrathiafulvalenes
Authors: Pedersen Viktor Bliksted Roug , Jasti Ramesh , Nielsen Mogens Brøndsted
Published: June 2024

Two regioisomeric extended tetrathiafulvalenes (TTFs) incorporating diindeno‐fused corannulene spacers were synthesized from suitable dione precursors using Horner‐Wadsworth‐Emmons olefination reactions. Both compounds are strong chromophores with a longest‐wavelength absorption that exhibited some degree of charge‐transfer character as inferred from solvatochromic behaviors and frontier orbital calculations. The compounds underwent two reversible one‐electron oxidations and a quasi‐reversible third oxidation during cyclic voltammetry conditions. The mono‐ and dications had characteristic NIR absorptions and both were EPR active. The dications with potential diradicaloid characters underwent reactions when generated in bulk.
Irresponsible to others but responsible to me: Testing employees' responses to external corporate social irresponsibility and internal corporate social responsibility
Authors: Yue Cen April , Song Baobao , Tao Weiting , Kang Minjeong
Published: June 2024

Drawing upon deonance theory and expectancy violation theory, we investigate how employees react when their companies engage in corporate social irresponsibility (CSiR) that harms external stakeholders who are not employees themselves. Furthermore, we introduce the concept of perceived internal corporate social responsibility (CSR), which refers to employees' perceptions of how organizational actions and policies benefit them personally. We developed a conceptual model that illustrates the joint influence of external CSiR and internal CSR on employees' perceptual, relational, and behavioral outcomes. An online survey with 417 full‐time US employees revealed that employees tend to evaluate unethical corporate practices holistically, in the context of other factors, such as the company's moral character and internal CSR, rather than based on external immorality. Our study contributes to a deeper understanding of employee reactions to both CSR and CSiR, emphasizing the importance of organizations evaluating the broader ramifications of their unethical actions.
Plasma EBV quantification is associated with the efficacy of immune checkpoint blockade and disease monitoring in patients with primary pulmonary lymphoepithelioma‐like carcinoma
Authors: Zhong Yu‐Min , Chen Ji , Jiang Jie , Zhou Wen‐Bin , Gao Ling‐Ling , Zhang Shui‐Lian , Yan Wen‐Qing , Chen Yu , Zhang Dong‐Kun , Lu Dan‐Xia , Lv Zhi‐Yi , Xie Zhi , Huang Ying , Guo Wei‐Bang , Wang Bin‐Chao , Yang Jin‐Ji , Yang Xue‐Ning , Wu Yi‐Long , Zhang Xu‐Chao
Published: June 2024

Objectives

Primary pulmonary lymphoepithelioma‐like carcinoma (PLELC) is a subtype of lung carcinoma associated with the Epstein–Barr virus (EBV). The clinical predictive biomarkers of immune checkpoint blockade (ICB) in PLELC require further investigation.

Methods

We prospectively analysed EBV levels in the blood and immune tumor biomarkers of 31 patients with ICB‐treated PLELC. Viral EBNA‐1 and BamHI‐W DNA fragments in the plasma were quantified in parallel using quantitative polymerase chain reaction.

Results

Progression‐free survival (PFS) was significantly longer in EBNA‐1 high or BamHI‐W high groups. A longer PFS was also observed in patients with both high plasma EBNA‐1 or BamHI‐W and PD‐L1 ≥ 1%. Intriguingly, the tumor mutational burden was inversely correlated with EBNA‐1 and BamHI‐W. Plasma EBV load was negatively associated with intratumoral CD8+ immune cell infiltration. Dynamic changes in plasma EBV DNA level were in accordance with the changes in tumor volume. An increase in EBV DNA levels during treatment indicated molecular progression that preceded the imaging progression by several months.

Conclusions

Plasma EBV DNA could be a useful and easy‐to‐use biomarker for predicting the clinical activity of ICB in PLELC and could serve to monitor disease progression earlier than computed tomography imaging.
Impact of food additives on neurodevelopmental processes in zebrafish (Danio rerio): Exploring circadian clock genes and dopamine system
Authors: Christy L. Divya , Vignesh K. , Nellore Jayshree , Tippabathani Jayakrishna
Published: June 2024

Assessing the impact of food additives on neurodevelopmental processes extends beyond traditional acute toxicity evaluations to address subtler, long‐term effects. This study investigates the impact of common food additives (tartrazine, sunset yellow, sodium benzoate, and aspartame) on neurodevelopment in zebrafish embryos, observed from 18 hours postfertilization (hpf) to 91 days postfertilization (dpf). Results show reduced 96 hpf locomotor activity after aspartame exposure, with elevated additives correlating with decreased heart rates and induced neurodegenerative phenotypes, including bent tails and abnormal pigmentation. Although locomotor activity decreases at 7 days postexposure, a gradual recovery is observed. Transcriptome analysis indicates alterations in clock genes (Cry2 and Per2) and dopamine‐related genes (NURR1 and tyrosine hydroxylase) in zebrafish larvae. Dietary additive exposure during embryonic development impacts clock genes, influencing dopamine activity and resulting in neurobehavioral changes. This study underscores potential risks associated with dietary additive exposure during critical developmental stages, warranting reconsideration of consumption guidelines, especially for expectant mothers. Observed neurodevelopmental toxicity, even below recommended levels, emphasizes the importance of safeguarding neurodevelopmental health in early life. Our findings contribute to understanding the neurotoxic effects of dietary additives, emphasizing the necessity of protecting neurodevelopment during vulnerable periods. This study is the first to demonstrate a direct correlation between food additives and the dysregulation of key circadian rhythm and dopaminergic genes in zebrafish, providing new insights into the neurodevelopmental impacts of dietary additives. These findings pave the way for further research into the molecular mechanisms and potential implications for human health.
Collective wetting transitions of submerged gas‐entrapping microtextured surfaces
Authors: Arunachalam Sankara , Mishra Himanshu
Published: June 2024

Numerous natural and industrial processes entail the spontaneous entrapment of gas/air as rough/patterned surfaces are submerged under water. As the wetting transitions ensue, the gas diffuses into the water leading to the fully water‐filled state. However, the standard models for wetting do not account for the microtexture's topography on collective wetting transitions. In other words, it is not clear whether the lifetime of n cavities arranged in a one‐dimensional (I‐D) line or a two‐dimensional (II‐D) (circular or square) lattice would be the same or not as a single 0‐D cavity. In response, we tracked the time‐dependent fates of gas pockets trapped in I‐D and II‐D lattices and compared them with wetting transitions in commensurate 0‐D cavities. Interestingly, the collective wetting transitions in the I‐D and the II‐D arrays had a directionality such that the gas from the outermost cavities was lost the first, while the innermost got filled by water the last. In essence, microtexture's spatial organization afforded shielding to the loss of the gas from the innermost cavities, which we probed as a function of the microtexture's pitch, surface density, dimensionality, and hydrostatic pressure. These findings advance our knowledge of wetting transitions in microtextures and inspiring surface textures to protect electronic devices against liquid ingression.
The influence of cosmetic treatments in the uptake of in vitro cocaine contamination in hair
Authors: Dombroski Alexandra , Betancourt Marialejandra Faure , Alvarado Alexis , St. Fleur Patricia , Pomales Argeliz , Concheiro‐Guisan Marta , Pego Ana Miguel Fonseca
Published: June 2024

Hair analysis is a powerful tool to assess drug use, yet the challenge of external contamination complicates its interpretation. Understanding the influence of cosmetic hair treatments is pivotal as their presence may affect this phenomenon. This study investigated the effects of four cosmetic treatments (bleach, henna, gel, and dry shampoo) on the external in vitro contamination of cocaine and its primary metabolite, benzoylecgonine (BE). Hair samples were divided into four groups: A‐hair treated with cosmetics then contaminated; B‐hair contaminated then subjected to cosmetic treatment; and C‐hair solely contaminated (control group). Negative hair samples (n = 24) were immersed in a cocaine and BE aqueous solution of 1 μg/mL for 24 h. All hair samples were analyzed by a LC–MSMS procedure successfully validated according to ANSI/ASB Standard 036 guidelines (limit of quantification at 10 pg/mg). Henna in Group A (n = 13) resulted in the most substantial reduction for cocaine (92%), while bleach in Group B (n = 15) showed an 80% decrease. For BE, Group A henna (n = 13) exhibited a 50% reduction, and Group B bleach (n = 15) demonstrated a 71% decrease, all compared to Group C (n = 24). The study found no significant differences concerning hair color (black (n = 3), brown (n = 10), red (n = 5) and blond (n = 6)) or shape (straight (n = 6), wavy (n = 16), curly (n = 1), and coily (n = 1)). All analysis were performed in triplicate with variations below 20%. These findings emphasize that cosmetic treatments do affect cocaine/BE concentrations in hair when exposed to external contamination, highlighting the importance of considering an individual's cosmetic history prior to interpretation.