bluuebunny/crossref_metadata_2025 huggingface dataset:
Reversible Glass‐Crystal Transition in a New Type of 2D Metal Halide Perovskites
Authors: Wang Wei , Liu Cheng‐Dong , Fan Chang‐Chun , Zhang Wen
Published: June 2024

Crystalline metal halide perovskites (MHPs) have ushered in remarkable advancements across diverse fields, including materials, electronics, and photonics. While the advantages of crystallinity are well‐established, the ability to transition to a glassy state with unique properties presents unprecedented opportunities to expand the structure‐property relationship and broaden the application scope for 2D MHPs. Up until now, the exploration of amorphous analogs for MHPs is confined to high‐pressure conditions, limiting in‐depth studies and practical applications. In this context, a new type of 2D MHPs is synthesized by incorporating halogen substituted organic cations, resulting in a remarkable combination of low melting temperature and inhibited crystallization. This new type of 2D MHPs can be effectively melt‐quenched into a glassy state except for (DMIEA)3Pb2I7 (DMIEA = N, N‐dimethyl iodoethylammonium) counterpart. Analysis of the crystallization activation energy for (DMIPA)4Pb3I10 (DMIPA = N, N‐dimethyl iodopropylammonium) reveals a low crystallization activation energy of 60.7 ± 4.0 kJ mol−1, which indicates a fast glass‐crystal transition. The type of atypical 2D MHP showcases facile and reversible switching between glassy and crystalline states and opens up novel possibilities for applications, such as nonvolatile memory, optical communication, and neuromorphic computing.
Simultaneously Improving Stretchability and Efficiency of Flexible Organic Solar Cells by Incorporating a Copolymer Interlayer in Active Layer
Authors: Zhang Dongling , Wu Yue , Yan Cenqi , Cheng Pei , Zhang Guangye , Yang Hang , Cui Chaohua
Published: June 2024

Mechanical stretchability is a vital criterion for the wearable application of organic solar cells (OSCs), while the excessive rigidity of fused‐ring small molecular acceptors make the photovoltaic film hard to meet the stretchable requirements. Herein, an effective strategy is developed to construct an intrinsically stretchable active layer by inserting copolymer PM6‐b‐PYSe as an interlayer between layer‐by‐layer processed D18 and BTP‐eC9. The copolymer interlayer shunts the penetration of BTP‐eC9 and facilitates an appropriate phase separation, favoring the enhanced crack onset strain of 17.69% compared to the D18/BTP‐eC9 film (9.67%). Combining with the optimal energy levels, prolonged carrier lifetime, and suppressed bimolecular recombination aroused by the incorporation of PM6‐b‐PYSe, the D18/PM6‐b‐PYSe/BTP‐eC9‐based OSC yields an encouraging efficiency of 17.97%. In particular, the device demonstrates excellent mechanical property, which can retain over 80% after 4000 bending cycles. This work provides an effective strategy to simultaneously enhance the intrinsic mechanical stretchability and photovoltaic performance of flexible OSCs.
Action Programmed Nanoantibiotics with pH‐Induced Collapse and Negative‐Charged‐Surface‐Induced Deformation against Antibiotic‐Resistant Bacterial Peritonitis
Authors: Zhang Xiao , Liu Penghui , Zhang Ran , Zheng Wenhong , Qin Di , Liu Yinghang , Wang Xin , Sun Tongyi , Gao Yuanyuan , Li Li‐Li
Published: June 2024

The incorporation of well‐designed antibiotic nanocarriers, along with an antibiotic adjuvant effect, in combination with various antibiotics, offers an opportunity to combat drug‐resistant strains. However, precise control over morphology and encapsulated payload release can significantly impact their antibacterial efficacy and synergistic effects when used alongside antibiotics. Here, this study focuses on developing lipopeptide‐based nanoantibiotics, which demonstrate an antibiotic adjuvant effect by inducing pH‐induced collapse and negative‐charged‐surface‐induced deformation. This enhances the disruption of the bacterial outer membrane and facilitates drug penetration, effectively boosting the antimicrobial activity against drug‐resistant strains. The modulation regulations of the lipopeptide nanocarriers with modular design are governed by the authors. The nanoantibiotics, made from lipopeptide and ciprofloxacin (Cip), have a drug loading efficiency of over 80%. The combination with Cip results in a significantly low fractional inhibitory concentration index of 0.375 and a remarkable reduction in the minimum inhibitory concentration of Cip against multidrug‐resistant (MDR) Escherichia coli (clinical isolated strains) by up to 32‐fold. The survival rate of MDR E. coli peritonitis treated with nanoantibiotics is significantly higher, reaching over 87%, compared to only 25% for Cip and no survival for the control group. Meanwhile, the nanoantibiotic shows no obvious toxicity to major organs.
Engineering Mesoscale T Cell Receptor Clustering by Plug‐and‐Play Nanotools
Authors: Sánchez M. Florencia , Faria Sevi , Frühschulz Stefan , Werkmann Lars , Winter Christian , Karimian Tina , Lanzerstorfer Peter , Plochberger Birgit , Weghuber Julian , Tampé Robert
Published: June 2024

T cell receptor (TCR) clustering and formation of an immune synapse are crucial for TCR signaling. However, limited information is available about these dynamic assemblies and their connection to transmembrane signaling. In this work, TCR clustering is controlled via plug‐and‐play nanotools based on an engineered irreversible conjugation pair and a peptide‐loaded major histocompatibility complex (pMHC) molecule to compare receptor assembly in a ligand (pMHC)‐induced or ligand‐independent manner. A streptavidin‐binding peptide displayed in both tools enabled their anchoring in streptavidin‐pre‐structured matrices. Strikingly, pMHC‐induced clustering in the confined regions exhibit higher density and dynamics than the ligand‐free approach, indicating that the size and architecture of the pMHC ligand influences TCR assembly. This approach enables the control of membrane receptor clustering with high specificity and provides the possibility to explore different modalities of receptor activation.
Highly‐Aligned All‐Fiber Actuator with Asymmetric Photothermal‐Humidity Response and Autonomous Perceptivity
Authors: Zhang Yufan , Zhou Xinran , Liu Luyun , Wang Shuang , Zhang Yue , Wu Mengjie , Lu Zeren , Ming Zechang , Tao Jin , Xiong Jiaqing
Published: June 2024

Soft robots adapt to complex environments for autonomous locomotion, manipulation, and perception are attractive for robot‐environment interactions. Strategies to reconcile environment‐triggered actuation and self‐powered sensing responses to different stimuli remain challenging. By tuning the in situ vapor phase solvent exchange effect in continuous electrospinning, an asymmetric highly‐aligned all‐fiber membrane (HAFM) with a hierarchical “grape‐like” nanosphere‐assembled microfiber structure (specific surface area of 13.6 m2 g−1) and excellent mechanical toughness (tensile stress of 5.5 MPa, and fracture toughness of 798 KJ m−3) is developed, which shows efficient asymmetric actuation to both photothermal and humidity stimuli. The HAFM consists of a metal‐organic framework (MOF)‐enhanced moisture‐responsive layer and an MXene‐improved photothermal‐responsive layer, which achieves substantial actuation with a bending curvature up to ≈7.23 cm−1 and a fast response of 0.60 cm−1 s−1. By tailoring the fiber alignment and bi‐layer thickness ratio, different types of micromanipulators, automatic walking robots, and plant robots with programmable structures are demonstrated, which are realized for self‐powered information perception of material type, object moisture, and temperature by integrating the autonomous triboelectric effect induced by photothermal‐moisture actuation. This work presents fiber materials with programable hierarchical asymmetries and inspires a common strategy for self‐powered organism‐interface robots to interact with complex environments.
Intramolecular Buchner Reaction: Experimental and Theoretical Comparison of the Effect of the Carbene Substituent on the Chemoselectivity
Authors: Tuyen Phung Bich , Medini Amira , Maldivi Pascale , Poisson Jean‐François , Bessières Bernard , Darses Benjamin
Published: June 2024

The intramolecular Buchner reaction is a powerful transformation able to dearomatize benzenic rings. However, the competitive C−H insertion of the carbene moiety into benzylic positions still remains a limitation, and the reasons governing this uncomplete chemoselectivity are poorly understood. The carbene substitution, in particular, has been observed to influence the selectivity strongly, though the currently proposed explanation relying on the electrophilicity of the metallocarbene hardly describes some experimental results reported in the literature. In this article, we present our experimental observations of intramolecular rhodium‐catalyzed Buchner reactions, combined with DFT calculations on selected carbene substituents, to propose a complementary explanation for the observed chemoselectivity modification.
Boosting Solar Water Splitting Performance of Cu3BiS3‐Based Photocathode via Ag Doping Strategy
Authors: Hu Yucheng , Shi Zhentao , Ren Xiaoliang , Cao Yuxi , Xiao Guohong , Huang Dingwang , Jiang Feng
Published: June 2024

A photovoltaic wittichenite semiconductor of Cu3BiS3, due to its optimal bandgap, high light absorption coefficient, and various advantages of low cost and environmental‐friendliness, has been considered a competitive candidate for solar absorber materials of photocathode for photoelectrochemical water splitting. However, the presence of various deleterious defects in the Cu3BiS3 lattice and its high conduction band minimum are detrimental factors that restrict further enhancements in the conversion efficiency of Cu3BiS3‐based photocathode. Herein, a one‐step solution‐based Ag element doping strategy is proposed to improve the crystalline quality of Cu3BiS3 films, which includes enlarging the grain size and reducing the intergranular gaps. Additionally, the Ag‐doped Cu3BiS3 layer can form a more favorable band alignment with the buffer layer. Ultimately, the fabricated composite Cu3BiS3‐based photocathode doped with 3% Ag delivers a remarkable photocurrent density of 13.6 mA cm−2 under 0 VRHE, an applied bias photon‐to‐current efficiency of 2.85%, and long‐term stability exceeding 12 h. Furthermore, with the assistance of a BiVO4 photoanode, the tandem cell also achieves an unbiased solar‐to‐hydrogen efficiency of 2.64%, with no significant decline observed within 20 h.
Tillage and crop sequences for organic Cirsium arvense management in the Northern Great Plains
Authors: Larson Christian D. , Hettinger Kara , Carr Patrick M. , Miller Perry R. , Volkman McKenna , Chichinsky Daniel , Seipel Tim
Published: June 2024

The perennial rhizomatous weed Cirsium arvense (L.) Scop. is difficult to manage on semiarid organic farms. Our objective was to quantify the impact of eight 4‐year crop sequences crossed with standard‐ and reduced‐tillage on C. arvense occurrence (presence/absence), stem density, and aboveground biomass at two semiarid sites in Montana. The sequences represented a range of crop competition from high (multiple years of perennial forage [alfalfa, Medicago sativa L.]) to low (2 years of continuous fallow), with intermediate sequences consisting of different annual species. Final‐year spring wheat (Triticum aestivum L. emend. Thell.) was planted in all sequences to determine impacts on subsequent cash crop production. Through time, alfalfa and double fallow sequences reduced C. arvense density and biomass where it was established, although its invasion into new areas increased in the double fallow. Final‐year C. arvense occurrence and stem density were lower in the alfalfa sequence compared with six and four annual crop sequences, respectively (p < 0.05). Final year C. arvense biomass was higher at one site than the other, although not in the double fallow sequence. Wheat grain yields differed in response to crop sequences at the two sites: at one site, grain yield was lowest in the alfalfa sequence, especially when standard‐tillage was used, while yields were highest in the alfalfa and double fallow sequences at the other site. Using perennial forages in semiarid organic systems can be effective for managing C. arvense, but subsequent cash crop yield may be depressed.
Multi‐synergistic chemotherapeutic drug assemblies to activate colorectal cancer immunotherapy by modulating the multilevel immunosuppressive characteristics
Authors: Zheng Rongrong , Huang Chuyu , Zhou Hangyu , Zhao Lixin , Li Qiuyuan , Chen Guangmiao , Zhao Linping , Li Shiying
Published: June 2024

The life‐threatening colorectal cancer exhibits multilevel immunosuppressive characteristics, including low immunogenicity, abnormal cellular metabolism, and acidic immunosuppressive microenvironment. In this work, multi‐synergistic chemotherapeutic drug assemblies are fabricated to activate colorectal cancer immunotherapy by modulating the multilevel immunosuppressive characteristics. Without any drug excipients, the glycolysis inhibitor of lonidamine (LON), indoleamine 2,3‐dioxygenase 1 (IDO‐1) inhibitor of NLG919 (NLG), and the photosensitizer of chlorine e6 could self‐assemble into drug assemblies (LNC) with uniform nano‐size distribution and increased drug stability. Moreover, LNC could also promote cellular uptake and enhance drug penetration to enable efficient drug co‐delivery. Especially, the photodynamic therapy (PDT) of LNC could disrupt tumor cells to release tumor‐associated antigens, thus efficiently suppressing primary tumor growth and improving tumor immunogenicity. Meanwhile, LNC could also reduce the activity of IDO‐1 and attenuate the glycolysis metabolism, thereby reversing the multilevel immunosuppressive characteristics to promote T cell activation. Benefiting from the multi‐synergistic effects, LNC efficiently eradicates the primary tumor growth and also activates systemic antitumor immunity for metastatic tumor inhibition. Such a simple formulation but a multi‐synergistic strategy may accelerate the development of translational nanomedicine for colorectal cancer immunotherapy by using small molecular drug combinations.
Challenge accepted: Evolutionary lineages versus taxonomic classification of North American shrub willows (Salix)
Authors: Marinček Pia , Léveillé‐Bourret Étienne , Heiduk Ferris , Leong Jing , Bailleul Stéphane M. , Volf Martin , Wagner Natascha D.
Published: June 2024

Premise

The huge diversity of Salix subgenus Chamaetia/Vetrix clade in North America and the lack of phylogenetic resolution within this clade has presented a difficult but fascinating challenge for taxonomists to resolve. Here we tested the existing taxonomic classification with molecular tools.

Methods

In this study, 132 samples representing 46 species from 22 described sections of shrub willows from the United States and Canada were analyzed and combined with 67 samples from Eurasia. The ploidy levels of the samples were determined using flow cytometry and nQuire. Sequences were produced using a RAD sequencing approach and subsequently analyzed with ipyrad, then used for phylogenetic reconstructions (RAxML, SplitsTree), dating analyses (BEAST, SNAPPER), and character evolution analyses of 14 selected morphological traits (Mesquite).

Results

The RAD sequencing approach allowed the production of a well‐resolved phylogeny of shrub willows. The resulting tree showed an exclusively North American (NA) clade in sister position to a Eurasian clade, which included some North American endemics. The NA clade began to diversify in the Miocene. Polyploid species appeared in each observed clade. Character evolution analyses revealed that adaptive traits such as habit and adaxial nectaries evolved multiple times independently.

Conclusions

The diversity in shrub willows was shaped by an evolutionary radiation in North America. Most species were monophyletic, but the existing sectional classification could not be supported by molecular data. Nevertheless, monophyletic lineages share several morphological characters, which might be useful in the revision of the taxonomic classification of shrub willows.
Metal‐Catalyzed Coupling of N‐Tosylhydrazones with Compounds Containing C−H/Heteroatom‐H Bonds
Authors: Akanksha  , Singh Ajaya K. , Asthana Anupama , Ravi Rangnath , Kishor Jha Abadh
Published: June 2024

The present review covers various advances in the field of metal‐catalyzed coupling of N‐tosylhydrazones with compounds containing C−H/heteroatom‐H bonds, including transition metal catalysts i. e., Pd, Rh, Cu, Ag, Ni and Co and resulting alkylated, alkenylated, alkynylated, allenylated, annulated and many other products. A metal carbene migratory insertion process play a key role in carbon‐carbon single bond (C−C) and carbon‐carbon double bond (C=C) formation and undergoes variety of cascade reactions to synthesize a wide scope of pharmaceutically and medicinally valuable scaffoldings.
Enantioselective Construction of Tetrahydroindole Skeletons by Rh‐Catalyzed [2+2+2] Cycloaddition of Homopropargyl Enamides with Alkynes
Authors: Yamashiro Kairi , Fujii Kohei , Sato Yu , Masutomi Koji , Shimotsukue Ryota , Nagashima Yuki , Tanaka Ken
Published: June 2024

We have developed the Rh‐catalyzed enantioselective [2+2+2] cycloaddition of homopropargyl enamides (tosylamide‐tethered 1,6‐enynes) with alkynes to construct tetrahydroindole skeletons found in natural alkaloids and pharmaceuticals. This cycloaddition proceeds at room temperature in high yields and regio‐ and enantioselectivity with a broad substrate scope. The preparative scale reaction followed by substituent conversion on the nitrogen atom and the diastereoselective [4+2] cycloaddition with singlet O2 affords hexahydroindole‐diols bearing three stereogenic centers and variable substituents on the nitrogen. Mechanistic studies have revealed that the substituents of the enynes change the ratio of intramolecular and intermolecular rhodacycle formation when using terminal alkynes, varying the ee values of the cycloadducts.
Bilateral Unsymmetrical Disulfurating Reagent Design for Polysulfide Construction
Authors: Yu Qing , Zhang XiangJin , Jiang Xuefeng
Published: June 2024

Polysulfides are significant compounds in life science, pharmaceutical science, and materials science. Therefore, polysulfide construction is in great demand. The controllable sequential installation of groups on both ends of a S−S motif faces an enormous challenge owing to the reversible nature of the covalent S−S bond. A library was established with two divergent mask groups for bilateral unsymmetrical disulfurating reagents (R1O−SS−SO2R2). Sequential coupling with preferential activation of the S−SO2 bond (37.6 kcal/mol) and controllable activation of the S−O bond (54.8 kcal/mol) in the presence of the S−S bond (62.0 kcal/mol) enabled successive reactions at each end of the S−S motif to afford unsymmetrical disulfides and trisulfides, even for the cross‐linkage of natural products, pharmaceuticals, peptides, and a protein (bovine serum albumin).
Exploring Macroscopic Dipoles of Designed Cyclic Peptide Ordered Assemblies to Harvest Piezoelectric Properties
Authors: Mahapatra Souvik Panda , Pahan Saikat , Chatterjee Abhijit , Roy Souvik , Puneeth Kumar D. R. , Gopi Hosahudya N.
Published: June 2024

Crystalline materials exhibiting non‐centrosymmetry and possessing substantial surface dipole moments play a critical role in piezoelectricity. Designing biocompatible self‐assembled materials with these attributes is particularly challenging when compared to inorganic materials and ceramics. In this study, we elucidate the crystal conformations of novel cyclic peptides that exhibit self‐assembly into tubular structures characterized by unidirectional hydrogen bonding and piezoelectric properties. Unlike cyclic peptides derived from alternating L‐ and D‐amino acids, those derived from new δ‐amino acids demonstrate the formation of self‐assembled tubes with unidirectional hydrogen bonds. Further, the tightly packed tubular assemblies and higher macrodipole moments result in superior piezoelectric coefficients compared to peptides with lower macrodipole moments. Our findings underscore the potential for designing cyclic peptides with unidirectional hydrogen bonds, thereby paving the way for their application in design of biocompatible piezo‐ and ferroelectric materials.
Molecular dynamics study of cross‐linking degrees effect on the aging resistance of epoxy asphalt: Insights from oxygen diffusion
Authors: Chen Fei , Min Zhaohui , Li Mingyue , Huang Wei , Wang Qichang
Published: June 2024

To interpret the diffusion behavior of oxygen in epoxy asphalt with different cross‐linking degrees, epoxy asphalt‐oxygen diffusion layer models were constructed. The effect of temperature on oxygen diffusion and the number of oxygen molecules penetrating the epoxy asphalt was quantitatively analyzed. Fick's second law was used to determine the oxygen diffusion coefficient. The Mean square displacement (MSD) was extracted to analyze the effect of cross‐linking degree on the molecular motion of the base asphalt. The results show that as the cross‐linking degree increases, the number of oxygen in the epoxy asphalt decreases, accompanied by a reduction in the oxygen diffusion coefficient. Temperature significantly affects the rate of oxygen diffusion, with higher temperatures leading to greater diffusion depths over the same simulation time. The oxygen diffusion coefficient of epoxy asphalt ranges from 4.60 × 10−11 to 2.20 × 10−10 m2/s at temperatures of 298–373 K. The epoxy system markedly restricts the movement of base asphalt molecules, with saturate being most affected by cross‐linking degree and asphaltene the least. A high cross‐linking network impedes the asphalt‐oxygen contact oxidation, enhancing epoxy asphalt's anti‐aging capacity. These findings provide support for optimizing epoxy asphalt formulations and guiding the development of anti‐oxidant epoxy asphalt.
Discovery of 2‐phenylquinazolines as potent Mycobacterium avium efflux pump inhibitors able to synergize with clarithromycin against clinical isolate
Authors: Cernicchi Giada , Rampacci Elisa , Massari Serena , Manfroni Giuseppe , Barreca Maria Letizia , Tabarrini Oriana , Cecchetti Violetta , Felicetti Tommaso , Di Luca Mariagrazia , Poma Noemi Violeta , Tavanti Arianna , Passamonti Fabrizio , Rindi Laura , Sabatini Stefano
Published: June 2024

Nontuberculous mycobacteria (NTM), which include the Mycobacterium avium complex, are classified as difficult‐to‐treat pathogens due to their ability to quickly develop drug resistance against the most common antibiotics used to treat NTM infections. The overexpression of efflux pumps (EPs) was demonstrated to be a key mechanism of clarithromycin (CLA) resistance in NTM. Therefore, in this work, 24 compounds from an in‐house library, characterized by chemical diversity, were tested as potential NTM EP inhibitors (EPIs) against Mycobacterium smegmatis mc2 155 and M. avium clinical isolates. Based on the acquired results, 12 novel analogs of the best derivatives 1b and 7b were designed and synthesized to improve the NTM EP inhibition activity. Among the second set of compounds, 13b emerged as the most potent NTM EPI. At a concentration of 4 µg/mL, it reduced the CLA minimum inhibitory concentration by 16‐fold against the clinical isolate M. avium 2373 overexpressing EPs as primary mechanism of CLA resistance.
Design, Green Synthesis and in silico Studies of New Substituted Naphtho[1,2‐e][1,3]Oxazines as Potential Acetylcholinesterase Inhibitors
Authors: Pouramiri Behjat , Abbasi Maryam , Hadadianpour Elahe
Published: June 2024

Alzheimer's disease (AD) is a prevalent neurodegenerative condition characterized by progressive cognitive decline and memory impairment resulting from the degeneration and death of brain neurons. Acetylcholinesterase (AChE) inhibitors as the primary pharmacotherapy for numerous neurodegenerative conditions, leveraging their capacity to modulate acetylcholine levels crucial for cognitive function. Recently, oxazine and its derivatives have brought worthy synthetic interest due to their extensive biological activities including, anti‐acetylcholinesterase, anti‐oxidant, anti‐pyretic, anti‐tubercular, anti‐convulsant, anti‐microbial, anti‐malarial, and anti‐cancer activities. In this study, a series of novel naphtho[1,2‐e][1,3]oxazine derivatives has been designed and synthesized with potential of acetylcholinesterase (AChE) inhibition. The target products have been prepared by a one‐pot and three‐component condensation reaction of 2‐naphthol, various aromatic aldehydes, and arylmethanimine in the presence of 3‐methyl‐1‐sulfonic acid imidazolium chloride ([Msim]Cl) as an effective and recyclable ionic liquid catalyst under microwave irradiation solvent‐free condition. The chemical structures of all resulting products were confirmed by spectroscopic methods (IR, 1H‐NMR, 13C NMR) as well as elemental analysis. The molecular docking studies has also been performed to investigate the synthetic compounds in the the AChE active site gorge. The results showed that all these derivatives interact with the enzymes with high affinity in binding pocket. The MM‐GBSA studies were performed for all synthesized derivatives and among them, compound 3‐(4‐Chlorophenyl)‐1‐phenyl‐2,3‐dihydro‐1H‐naphtho[1,2‐e][1,3]oxazine 5f, showed the lowest the binding free energy (−48.04 kcal mol−1). In general, oxazine derivatives could be proposed as the strong AChE inhibitors.
Unexpected massive bleeding during the modified LeFort III advancement surgery for Crouzon syndrome: A case report
Authors: Modarresi Zahra Sadat , Hajiani Narges , Bakhtiari Zeinab , Mohammadi Farnoush
Published: June 2024

Key Clinical Message

Vigilant monitoring for postoperative complications, including bleeding and dysrhythmia, is crucial in patients with craniosynostosis syndromes like Crouzon syndrome undergoing craniofacial surgery, with a thorough evaluation, including coagulation tests, assisting in diagnosing underlying conditions such as von Willebrand disease subtype 1 to inform appropriate management strategies.

Crouzon syndrome is a rare genetic disorder affecting craniofacial structures. Its etiology is the premature fusion of cranial sutures. The LeFort III advancement surgery is a commonly used approach to correct malformations related to midface hypoplasia. Complications following surgical treatment of craniosynostosis and craniofacial syndromes can include both intracranial and extracranial problems. Reporting of this syndrome and the surgery complications, in addition to consideration of other differential diagnoses, can help improve the treatment plan and surgery outcomes. The aim of the article is to report a 14‐year‐old female with Crouzon syndrome who underwent the modified LeFort III osteotomy and developed unexpected massive bleeding during the surgery. Post‐surgery, she experienced complications including dysrhythmia, hypothermia, and cyanosis. Treatment included fluid therapy, blood transfusions, and antibiotic therapy for suspected septic shock. Differential diagnosis was disseminated intravascular coagulation but was ruled out. Post‐discharge, coagulation tests suggested von Willebrand disease subtype 1 as the diagnosis. Excessive bleeding during surgery for craniosynostosis syndromes is a significant and concerning issue in the surgical management of Crouzon syndrome. For patients with von Willebrand disease who are candidates for elective surgeries, von Willebrand factor concentrates or recombinant von Willebrand factor can be used.
Recent Development of Transition Metal‐based Amorphous Electrocatalysts for Water Splitting
Authors: Lu Bowen , Gao Haohao , Hua Zile
Published: June 2024

Electrochemical water splitting, including the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is a promising hydrogen production technology. However, in practice, the high overpotentials and sluggish reaction kinetics associated with the anode OER process are the major obstacles to the smooth progress of electrocatalytic water splitting. Amorphous electrocatalysts, a crucial family of functional materials, exhibit unexpected performance due to their special short‐range ordered and long‐range disordered atom arrangement, abundant defect sites and adjustable composition. To date, while numerous recent publications showcase promising results for transition metal‐based amorphous electrocatalysts, including amorphous metal phosphide and metal hydroxide electrocatalysts with remarkable HER and OER properties respectively, the utilization of single‐function HER or OER catalysts tends to augment system complexity for water electrolysis, thereby escalating the cost of hydrogen production. In this regard, amorphous HER/OER bifunctional electrocatalysts are desired. In this review, we summarize the recent development on transition metal‐based amorphous catalysts for electrochemical water splitting. The design strategies for constructing HER/OER bifunctional transition‐metal‐based amorphous electrocatalysts are highlighted here, also including the exploration of relationship between catalyst structures and their remarkably improved performance. Finally, the possibilities of amorphous bifunctional catalysts for practical industrial applications are evaluated and future research direction are suggested.
Visible‐Light‐Driven Heterocyclic Fluoroalkylation Via Electron Donor−Acceptor Complexes
Authors: Li Yufei , Xie Kaili , Yang Shimin , Dai Peng , Guo Jianbo , Gu Yucheng , Xia Qing , Zhang Weihua
Published: June 2024

Heterocyclic fluoroalkylation is initiated through a photochemical reaction involving an electron donor–acceptor complex. The reaction proceeds smoothly without requiring a photocatalyst, transition metal catalyst or additional oxidant. Through extensive experiments, we optimised the heterocyclic fluoroalkylation method and confirmed its versatility and effectiveness on various substrates. The process synthesises fluoroalkylated quinoxalinones and indolones with high efficiency and was successfully extended to gram‐scale applications, highlighting its practical utility. Detailed mechanistic analyses, supported by density functional theory calculations elucidated the role of the electron donor–acceptor complexes and deciphered the distinct radical chain reaction mechanism inherent in the halogen‐atom transfer pathway. Given the importance of fluoroalkyl groups in pharmaceuticals, this simple and efficient method promises substantial applications in medicinal chemistry and materials science.
Influence of Ammonia and Different Promoters on the Iron‐Based Fischer‐Tropsch Synthesis
Authors: Einemann Madita , Neumann Fabian , Roessner Frank
Published: June 2024

The material properties of precipitated iron promoted with either K, Mn, Pt, Ru, Zn, respectively, and their catalytic performance in the Fischer‐Tropsch synthesis were evaluated. A special attention was paid to the influence of ammonia on the reaction. Different spectroscopic methods e. g. XPS and XANES revealed the structure of both iron and the corresponding promoter. Conclusions were also drawn for the activated (reduced) catalysts. Applying temperature programmed reduction and XRD, the presence of iron nitrides through ammonia treatment was discovered. In the presence of ammonia under the Fischer‐Tropsch reaction conditions the formation of amines was detected. The highest yield of amines was observed for the manganese promoted catalyst. The investigation of hydrogen activating and not activating promoters in combination with iron, made it possible to hypothesise about the mechanism of the incorporation of ammonia into hydrocarbons under Fischer‐Tropsch reaction conditions.
Thiolated Cyanines Appended to Partially Pegylated Gold Nanoparticles for Fluorescence Quenching of Two‐Channel Photothermal Inks
Authors: Pallavicini Piersandro , Colombi Chiara , Baccini Caterina , Gatti Beatrice , D'Alfonso Laura , Dacarro Giacomo , Cattani Silvia , Diaz Fernandez Yuri A. , Doveri Lavinia , Milanese Chiara , Secchi Andrea
Published: June 2024

Following a new approach, we prepared a nanoink with two separate photothermally responsive absorption bands. One is the localized surface plasmon resonance (LSPR) absorption of gold nanoparticles (AuNP, d=17 nm), the second is the absorption band of two cyanine (Cy) dyes, Cy7‐C6 or Cy7‐C11, grafted to the AuNP surface through thiolated bridges of different lengths: the close proximity to the Au surface induces full quenching of the Cy fluorescence, resulting in thermal relaxation on irradiation. Attempts to full coat AuNP with the lipophilic Cy7‐C6 and Cy7‐C11 lead to precipitation from aqueous solutions. We thus prepared AuNP with partial pegylation (30, 50, or 70 %), using a long chain thiol‐terminated PEG bearing a ‐COOH function. Addition until saturation of either Cy7‐C6 or Cy7‐C11 to the partially pegylated AuNP gave the AuNP@Cy/PEGX% hybrids (X=30, 50, 70) that are stable in water and in the water/alcohol mixtures used to prepare the nanoinks. Further overcoating of AuNP@Cy7‐C6/PEG50 % with PAH (polyallylamine hydrochloride) avoids LSPR hybridization in the dry nanoink printouts, that present two separate bands. When irradiated with laser sources near their absorption maxima, the printouts of the AuNP@Cy7‐C6/PEG50 %@PAH nanoink respond on two channels, giving different temperature increases depending on the irradiation wavelengths. This enhances the potentiality of use of these nanoinks for photothermal anticounterfait printouts, making more difficult to reproduce the correct ΔT vs λirradiation output.
Elucidating Heavy‐Atom‐Tunneling Kinetics in the Cope Rearrangement of Semibullvalene
Authors: Angiolari Federica , Mandelli Giacomo , Huppert Simon , Aieta Chiara , Spezia Riccardo
Published: June 2024

In this work, we characterize the temperature dependence of kinetic properties in heavy atom tunneling reactions by means of molecular dynamics simulations, including nuclear quantum effects (NQEs) via Path Integral theory. To this end, we consider the prototypical Cope rearrangement of semibullvalene. The reaction was studied in the 25–300 K temperature range observing that the inclusion of NQEs modifies the temperature behavior of both free energy barriers and dynamical recrossing factors with respect to classical dynamics. Notably, while in classical simulations the activation free energy shows a very weak temperature dependence, it becomes strongly dependent on temperature when NQEs are included. This temperature behavior shows a transition from a regime where the quantum effects are limited and can mainly be traced back to zero point energy, to a low temperature regime where tunneling plays a dominant role. In this regime, the free energy curve tunnels below the potential energy barrier along the reaction coordinate, allowing much faster reaction rates. Finally, the temperature dependence of the rate constants obtained from molecular dynamics simulations was compared with available experimental data and with semi‐classical transition state theory calculations, showing comparable behaviors and similar transition temperatures from thermal to (deep) tunneling regime.
Improving the Photodynamic Activity of Water‐Soluble Porphyrin–Polysaccharide Complexes by Folic Acid Modification
Authors: Nishimura Kotaro , Kono Nanami , Oshige Ayano , Takahashi Haruko , Yamana Keita , Kawasaki Riku , Ikeda Atsushi
Published: June 2024

Studies have shown that folate receptors are highly expressed in various cancer cells. Here, we synthesized folic acid‐conjugated pullulan (FAPL) as a solubilizing agent to improve the photodynamic activity of porphyrin derivative–polysaccharide complexes. The porphyrin derivative–FAPL complex exhibited long‐term stability in an aqueous solution, attributed to the folic acid modification. Furthermore, in vitro and in vivo experiments highlighted the enhanced photodynamic activity of the porphyrin derivative–FAPL complex toward 4T1 breast‐cancer cells, compared with the activities of the porphyrin derivative–pullulan complex and Photofrin. This enhanced activity is attributed to the improvement of intracellular uptake by the folate receptor.
N‐Doped Carbon Coated Bimetallic CoFe2O4 Nanomembranes as An Enhanced Negative Electrode for Asymmetric Supercapacitors
Authors: Li Ruizhi , Li Weiqun , Li Yuhua , Zhu Shengyuan , Ba Xin , Zhou Yingke
Published: June 2024

In‐suit nitrogen‐doped carbon layer coated on CoFe2O4 nanomembrane (NC−CoFe2O4) directly grown on carbon cloth was successfully fabricated. The electrochemical performance was conveniently manipulated by regulating the molar ration of Co2+ : Fe3+ (molar ration=1 : 2, CoFe2O4 nanomembrane, 2.9 F cm−2). Nitrogen‐doped (N‐doped) carbon coating strategy on CoFe2O4 nanomembrane (NC−CoFe2O4) via annealing of polypyrrole (PPy) was presented and NC−CoFe2O4 nanomembranes displayed a prominent capacitance of 12.1 F cm−2 (2563.8 F g−1) at 5 mA cm−2. More important, the composite demonstrated more stable microstructure and showed long‐term cycling stability (16.0 % decrease after 7000 cycles), which was significantly better than the unmodified CoFe2O4 (55.8 % decrease after 1000 cycles). To verify the practicability of the materials, an aqueous asymmetric supercapacitor has been fabricated using NC−CoFe2O4 composite anode and MnO2/CNTs cathode, and the device has a remarkable wide operating voltage range of 1.9 V. In addition, the assembled device has an exceptional specific capacity of 1.3 F cm−2 at 10 mA cm−2, high energy density (43.3 Wh kg−1 at a power density of 642.9 W kg−1), and also with a good capacity retention rate of 84.9 % after 1000 cycles.
Ramie Degumming Waste‐Derived Nitrogen and Molybdenum Dual‐Doped Porous Carbon for High‐Performance Lithium–Sulfur Batteries
Authors: Yang Zhehan , Ruan Qingling , Chen Tiezhu , Ren Xiaolei , Lin Juan , Gu Xingxing
Published: June 2024

The high energy density and low cost of sulfur make lithium–sulfur batteries one of the most promising candidates for the next generation of energy storage. Nevertheless, the application is still hampered by the shuttle effect of soluble lithium polysulfides (LiPSs) intermediates and slow redox kinetics, resulting in irreversible loss of the active material, severe self‐discharge and poor cycle stability of the electrode. Therefore, in this work, a novel Mo,N co‐doped porous carbon (Mo,N−C) was successfully synthesized by simply calcining a mixture of ramie degumming waste with cost‐effective molybdenum salt, and then employed as the LiPSs anchor. Due to the conductive carbon matrix, abundant porous structures as well as the doping Mo and N heteroatoms, the sluggish redox kinetic of the cathode has been significantly improved and the shuttle phenomenon of LiPSs has been effectively inhibited, consequently, the as‐prepared Mo,N−C/S‐0.4 composite cathode could demonstrate a good initial capacity of 1379.2 mAh g−1 at 0.2 C, and the reversible capacity could remain at 997.5 mAh g−1 after 100 cycles. Even at a high discharge rate of 1.0 C, the capacity could remain at 700.2 mAh g−1 after 400 cycles. This work provides a new avenue for utilizing waste biomass in clean energy storage.
Edge computing collaborative offloading strategy for space‐air‐ground integrated networks
Authors: Xiang Biqun , Zhong Bo , Wang Anhua , Mao Wuping , Liu Liang
Published: June 2024

Due to geographical factors, it is impossible to build large‐scale communication network infrastructure in remote areas, which leads to poor network communication quality in these areas and a series of delay‐sensitive tasks cannot be timely processed and responded. Aiming at the problem of limited coverage in remote areas, the space‐air‐ground integrated networks (SAGIN) combined with mobile edge computing (MEC) can provide low latency and high reliability transmission for offloading delay‐sensitive tasks for users in remote areas. Considering the strong limitation of satellite resources in the space‐ground integrated network and insufficient energy of local user equipment, firstly, a satellite‐UAV cluster‐ground three‐layer edge computing network architecture is proposed in this paper. Under the condition that the delay requirements of various ground tasks are met, the task offloading problem is transformed into a Stackelberg game between ground user equipment and edge servers. In addition, it is proved that the existence of Nash equilibrium in non‐cooperative game between ground user equipment by using potential game. Finally, a Nash equilibrium iterative offloading algorithm based on Stackelberg game (NEIO‐SG) is proposed to find the optimal offloading strategy for tasks to minimize the system offloading cost and the optimal forwarding percentage strategy for offloading tasks to maximize the utility function of the edge server. Simulation results show that compared to other baseline algorithms, NEIO‐SG reduces the total system latency during task offloading by about 13 and the energy consumption of the edge server by about 35.
Halogen Bonding to the π‐Systems of Polycyclic Aromatics
Authors: Amonov Akhtam , Scheiner Steve
Published: June 2024

The propensity of the π‐electron system lying above a polycyclic aromatic system to engage in a halogen bond is examined by DFT calculations. Prototype Lewis acid CF3I is placed above the planes of benzene, naphthalene, anthracene, phenanthrene, naphthacene, chrysene, triphenyl, pyrene, and coronene. The I atom positions itself some 3.3–3.4 Å above the polycyclic plane, and the associated interaction energy is about 4 kcal/mol. This quantity is a little smaller for benzene, but is roughly equal for the larger polycyclics. The energy only oscillates a little as the Lewis acid slides across the face of the polycyclic, preferring regions of higher π‐electron density over minima of the electrostatic potential. The binding is dominated by dispersion which contributes half of the total interaction energy.
Pharmacokinetics, Pharmacodynamics, and Safety of Vadadustat in Healthy Volunteers and Patients with Chronic Kidney Disease
Authors: Navarro‐Gonzales Pamela , Ganz Tomas , Pergola Pablo E. , Zuk Anna , Dykstra Kevin
Published: June 2024

Vadadustat is an oral hypoxia‐inducible factor prolyl hydroxylase inhibitor for treating anemia in chronic kidney disease (CKD). Single ascending dose (SAD) and multiple ascending dose (MAD) studies assessed pharmacokinetics (PK), pharmacodynamics (PD), and safety of vadadustat in healthy volunteers. A single‐dose, open‐label study was conducted in patients with CKD stages 3 and 4 not on dialysis. In the SAD study, 48 healthy adult men (n = 8/cohort) received single doses of vadadustat (80–1,200 mg) or placebo. In the MAD study, 34 healthy adult men (n = 8–9/cohort) received daily vadadustat (500–900 mg) or placebo for 10 days. In the single‐dose CKD study, 22 male and female patients with CKD (stage 3: n = 10; stage 4: n = 12) received single doses of vadadustat (500 mg). PK parameters included plasma vadadustat; PD biomarkers were measured, including erythropoietin (EPO) levels, reticulocytes, and others. Plasma vadadustat peaked 3–4 hours after single or multiple dosing in healthy volunteers, with a mean t
1/2 of approximately 4.5 hours. In patients with CKD, plasma vadadustat peaked at 5–6 hours, with a mean t
1/2 of 7.2 (stage 3) and 8.5 (stage 4) hours. Vadadustat AUC∞ and C
max increased dose proportionally in SAD and MAD trials. In all trials, EPO concentrations increased in a dose‐related manner and returned approximately to baseline by 24 hours. Adverse events were mild and considered not study drug related. The PK and PD results of these studies were utilized for further clinical development of vadadustat for treatment of anemia in CKD patients.
Insight into Spectral Properties and Solvatochromic Behavior of [b]‐Fused BODIPYs: Experimental and Computational Study
Authors: Ksenofontova Ksenia V. , Shagurin Artyom Yu. , Molchanov Evgeniy E. , Ksenofontov Alexander A. , Sbytov Dmitrii A. , Kalyamanova Yana E. , Danilova Elena A. , Marfin Yuriy S.
Published: June 2024

Two π‐extended derivatives of boron‐dipyrromethene (BODIPY) – unsymmetrical benzo[b]‐fused BODIPY 1 and symmetrical naptho[b]‐fused BODIPY 2 – were synthesized. Spectroscopic and photophysical properties of the synthesized fluorescent dyes were investigated in various organic media. Both BODIPY 1 and BODIPY 2 distinguished by bathochromically shifted absorption and emission bands compared to their non‐fused derivatives, while possessing green (526–543 nm) and red (664–708 nm) absorbance and fluorescence, respectively. Spectral characteristics of the investigated fluorescent dyes were found to be weakly depended on solvent polarizability in case of BODIPY 1 and greatly influenced by both solvent polarizability and dipolarity in case of BODIPY 2. Quantum chemical calculations were used to clarify the relationships between geometry/electronic structure and spectral properties/solvatochromic behavior of BODIPY 1 and BODIPY 2.
Applications of Surface Plasmon Resonance (SPR) to the Study of Diverse Protein‐Ligand Interactions
Authors: Burris Dana M. , Gillespie Samuel W. , Campbell Emma Joy , Ice S. Nick , Yadav Vikas , Picking William D. , Lorson Christian L. , Singh Kamal
Published: June 2024

Functional characterization of enzymes/proteins requires determination of the binding affinity of small molecules or other biomolecules with the target proteins. Several available techniques, such as proteomics and drug discovery strategies, require a precise and high‐throughput assay for rapid and reliable screening of potential candidates for further testing. Surface plasmon resonance (SPR), a well‐established label‐free technique, directly measures biomolecular affinities. SPR assays require immobilization of one interacting component (ligand) on a conductive metal (mostly gold or silver) and a continuous flow of solution containing potential binding partner (analyte) across the surface. The SPR phenomenon occurs when polarized light excites the electrons at the interface of the metal and the dielectric medium to generate electromagnetic waves that propagate parallel to the surface. Changes in the refractive index due to interaction between the ligand and analyte are measured by detecting the reflected light, providing real‐time data on kinetics and specificity. A prominent use of SPR is identifying compounds in crude plant extracts that bind to specific molecules. Procedures that utilize SPR are becoming increasingly applicable outside the laboratory setting, and SPR imaging and localized SPR (LSPR) are cheaper and more portable alternative for in situ detection of plant or mammalian pathogens and drug discovery studies. LSPR, in particular, has the advantage of direct attachment to test tissues in live‐plant studies. Here, we describe three protocols utilizing SPR‐based assays for precise analysis of protein‐ligand interactions. © 2024 Wiley Periodicals LLC.

This article was corrected on 06 July 2024. See the end of the full text for details.

Basic Protocol 1: SPR comparison of binding affinities of viral reverse transcriptase polymorphisms

Basic Protocol 2: SPR screening of crude plant extract for protein‐binding agents

Basic Protocol 3: Localized SPR–based antigen detection using antibody‐conjugated gold nanoparticles