bluuebunny/crossref_metadata_2025 huggingface dataset:
Benzenehexol‐Based 2D Conjugated Metal–Organic Frameworks with Kagome Lattice Exhibiting a Metallic State
Authors: Wang Zhiyong , St. Petkov Petko , Zhang Jianjun , Liang Baokun , Revuelta Sergio , Xiao Ke , Tiwari Kajal , Guo Quanquan , Li Zichao , Zhang Jichao , Qi Haoyuan , Zhou Shengqiang , Kaiser Ute , Heine Thomas , Cánovas Enrique , Parkin Stuart S. P. , Feng Xinliang , Dong Renhao
Published: April 2024

2D conjugated metal–organic frameworks (2D c‐MOFs) are emerging as unique electroactive materials for electronics and spintronics. The structural design and discovery of Kagome‐type 2D c‐MOFs exhibiting a metallic state are of paramount significance, yet remain rarely explored. Here, the solution synthesis of benzenehexol‐based 2D c‐MOFs based is presented on the tetrahydroxy‐1,4‐quinone (THQ) ligand. This study shows that controlling the pH of the reaction system to ≈7.5 yields an energetically favorable nonporous Cu3(C6O6) with a Kagome lattice, while at a pH of ≈10, the known porous Cu3(C6O6)2 with a honeycomb lattice is obtained. The crystal structures of both Cu3(C6O6)2 and Cu3(C6O6) are resolved with near‐atomic precision (resolution, 1.8 Å) using an imaging technique. Unlike the p‐type semiconducting behavior of Cu3(C6O6)2, theoretical studies identify Cu3(C6O6) as a metal due to its unique structural topology. The metallic state of Cu3(C6O6) is experimentally validated by terahertz time‐domain spectroscopy (THz‐TDS), which shows an increase in conductivity upon cooling. Scattering‐type scanning near‐field optical microscopy (s‐SNOM) measurements further support these findings by revealing an increase in normalized reflectivity with decreasing temperature. This work provides a new avenue for tailoring the structural topology of 2D c‐MOFs to attain the Kagome lattice and metallic state.
Two‐Step Perovskite Solar Cells with > 25% Efficiency: Unveiling the Hidden Bottom Surface of Perovskite Layer
Authors: Wang Fei , Wang Taomiao , Sun Yonggui , Liang Xiao , Yang Guo , Li Qiannan , Li Yongjun , Zhou Xianfang , Zhu Quanyao , Ng Annie , Lin Haoran , Yuan Mingjian , Shi Yumeng , Wu Tom , Hu Hanlin
Published: April 2024

While significant efforts in surface engineering have been devoted to the conversion process of lead iodide (PbI2) into perovskite and top surface engineering of perovskite layer with remarkable progress, the exploration of residual PbI2 clusters and the hidden bottom surface on perovskite layer have been limited. In this work, a new strategy involving 1‐butyl‐3‐methylimidazolium acetate (BMIMAc) ionic liquid (IL) additives is developed and it is found that both the cations and the anions in ILs can interact with the perovskite components, thereby regulating the crystallization process and diminishing the residue PbI2 clusters as well as filling vacancies. The introduction of BMIMAc ILs induces the formation of a uniform porous PbI2 film, facilitating better penetration of the second‐step organic salt and fostering a more extensive interaction between PbI2 and the organic salt. Surprisingly, the oversized residual PbI2 clusters at the bottom surface of the perovskite layer completely diminish. In addition, advanced depth analysis techniques including depth‐resolved grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and bottom thinning technology are employed for a comprehensive understanding of the reduction in residual PbI2. Leveraging effective PbI2 management and regulation of the perovskite crystallization process, the champion devices achieve a power conversion efficiency (PCE) of 25.06% with long‐term stability.
A Rhombic 2D Conjugated Metal–Organic Framework as Cathode for High‐Performance Sodium‐Ion Battery
Authors: Qi Meiling , Cheng Linqi , Wang Heng‐Guo , Cui Fengchao , Yang Qingyuan , Chen Long
Published: April 2024

2D conjugated metal–organic frameworks (2D c‐MOFs) have garnered significant attention as promising electroactive materials for energy storage. However, their further applications are hindered by low capacity, limited cycling life, and underutilization of the active sites. Herein, Cu‐TBA (TBA = octahydroxyltetrabenzoanthracene) with large conjugation units (narrow energy gap) and a unique rhombus topology is introduced as the cathode material for sodium‐ion batteries (SIBs). Notably, Cu‐TBA with a rhombus topology exhibits a high specific surface area (613 m2 g−1) and metallic band structure. Additionally, Cu‐TBA outperforms its hexagonal counterpart, Cu‐HHTP (HHTP = 2,3,6,7,10,11‐hexahydroxyltriphenylene), demonstrating superior reversible capacity (153.6 mAh g−1 at 50 mA g−1) and outstanding cyclability with minimal capacity decay even after 3000 cycles at 1 A g−1. This work elucidates a new strategy to enhance the electrochemical performance of 2D c‐MOFs cathode materials by narrowing the energy gap of organic linkers, effectively expanding the utilization of 2D c‐MOFs for SIBs.
Elucidation of Spatial Cooperativity in Chemo‐Immunotherapy by a Sequential Dual‐pH‐Responsive Drug Delivery System
Authors: Wang Shihao , Liu Lifeng , Tian Limin , Xu Pengcheng , Li Shixuan , Hu Lixin , Xia Yanming , Ding Yang , Wang Jian , Li Suxin
Published: April 2024

Combining immune checkpoint blockade with chemotherapy through nanotechnology is promising in terms of safety and efficacy. However, the distinct subcellular distribution of each ingredient's action site makes it challenging to acquire an optimal synergism. Herein, a dual‐pH responsive hybrid polymeric micelle system, HNP(αPDL16.9, Dox5.3), is constructed as a proof‐of‐concept for the spatial cooperativity in chemo‐immunotherapy. HNP retains the inherent pH‐transition of each polymer, with stepwise disassembly under discrete pH thresholds. Within weakly acidic extracellular tumor environment, αPDL1 is first released to block the checkpoint on cell membranes. The remaining intact Doxorubicin‐loaded micelle NP(Dox)5.3 displays significant tropism toward tumor cells and releases Dox upon lysosomal pH for efficient tumor immunogenic cell death without immune toxicity. This sequential‐released pattern boosts DC activation and primes CD8+ T cells, leading to enhanced therapeutic performance than single agent or an inverse‐ordered combination in multiple murine tumor models. Using HNP, the indispensable role of conventional type 1 DC (cDC1) is identified in chemo‐immunotherapy. A co‐signature of cDC1 and CD8 correlates with cancer patient survival after neoadjuvant Pembrolizumab plus chemotherapy in clinic. This study highlights spatial cooperativity of chemo‐ and immuno‐agents in immunoregulation and provides insights into the rational design of drug combination for future nanotherapeutics development.
Metal–Drug Coordination Nanoparticles and Hydrogels for Enhanced Delivery
Authors: Wong Ka‐Ying , Nie Zhenyu , Wong Man‐Sau , Wang Yang , Liu Juewen
Published: April 2024

Drug delivery is a key component of nanomedicine, and conventional delivery relies on the adsorption or encapsulation of drug molecules to a nanomaterial. Many delivery vehicles contain metal ions, such as metal–organic frameworks, metal oxides, transition metal dichalcogenides, MXene, and noble metal nanoparticles. These materials have a high metal content and pose potential long‐term toxicity concerns leading to difficulties for clinical approval. In this review, recent developments are summarized in the use of drug molecules as ligands for metal coordination forming various nanomaterials and soft materials. In these cases, the drug‐to‐metal ratio is much higher than conventional adsorption‐based strategies. The drug molecules are divided into small‐molecule drugs, nucleic acids, and proteins. The formed hybrid materials mainly include nanoparticles and hydrogels, upon which targeting ligands can be grafted to improve efficacy and further decrease toxicity. The application of these materials for addressing cancer, viral infection, bacterial infection inflammatory bowel disease, and bone diseases is reviewed. In the end, some future directions are discussed from fundamental research, materials science, and medicine.
Formation of Highly Tunable Periodic Plasmonic Structures on Gold Films Using Direct Laser Writing
Authors: Vilkevičius Kernius , Tsibidis George D. , Selskis Algirdas , Stratakis Emmanuel , Stankevičius Evaldas
Published: April 2024

Direct laser writing method is a promising technique for the large‐scale and cost‐effective fabrication of periodic nanostructure arrays exciting hybrid lattice plasmons. This type of electromagnetic mode manifests a narrow and deep resonance peak with a high dispersion whose precise controllability is crucial for practical applications in photonic devices. Here, the formation of differently shaped gold nanostructures using the direct laser writing method on Au layers of different thicknesses is presented. The resonance peak is demonstrated to be highly dependent on the shape of the structures in the array, thus its position in the spectra, as well as the quality, can be additionally modulated by changing the morphology. The shape of the structure and the resonance itself pertain not only on the laser pulse energy but also on the grating period. This overlapping effect occurring at distances smaller than the diameter of the focused laser beam is studied in detail. By taking advantage of the highly controllable plasmonic resonance, the fabricated gratings open up new opportunities for applications in sensing.
Tumor Biomechanics Alters Metastatic Dissemination of Triple Negative Breast Cancer via Rewiring Fatty Acid Metabolism
Authors: Filipe Elysse C. , Velayuthar Sipiththa , Philp Ashleigh , Nobis Max , Latham Sharissa L. , Parker Amelia L. , Murphy Kendelle J. , Wyllie Kaitlin , Major Gretel S. , Contreras Osvaldo , Mok Ellie T. Y. , Enriquez Ronaldo F. , McGowan Suzanne , Feher Kristen , Quek Lake‐Ee , Hancock Sarah E. , Yam Michelle , Tran Emmi , Setargew Yordanos F. I. , Skhinas Joanna N. , Chitty Jessica L. , Phimmachanh Monica , Han Jeremy Z. R. , Cadell Antonia L. , Papanicolaou Michael , Mahmodi Hadi , Kiedik Beata , Junankar Simon , Ross Samuel E. , Lam Natasha , Coulson Rhiannon , Yang Jessica , Zaratzian Anaiis , Da Silva Andrew M. , Tayao Michael , Chin Ian L. , Cazet Aurélie , Kansara Maya , Segara Davendra , Parker Andrew , Hoy Andrew J. , Harvey Richard P. , Bogdanovic Ozren , Timpson Paul , Croucher David R. , Lim Elgene , Swarbrick Alexander , Holst Jeff , Turner Nigel , Choi Yu Suk , Kabakova Irina V. , Philp Andrew , Cox Thomas R.
Published: April 2024

In recent decades, the role of tumor biomechanics on cancer cell behavior at the primary site has been increasingly appreciated. However, the effect of primary tumor biomechanics on the latter stages of the metastatic cascade, such as metastatic seeding of secondary sites and outgrowth remains underappreciated. This work sought to address this in the context of triple negative breast cancer (TNBC), a cancer type known to aggressively disseminate at all stages of disease progression. Using mechanically tuneable model systems, mimicking the range of stiffness's typically found within breast tumors, it is found that, contrary to expectations, cancer cells exposed to softer microenvironments are more able to colonize secondary tissues. It is shown that heightened cell survival is driven by enhanced metabolism of fatty acids within TNBC cells exposed to softer microenvironments. It is demonstrated that uncoupling cellular mechanosensing through integrin β1 blocking antibody effectively causes stiff primed TNBC cells to behave like their soft counterparts, both in vitro and in vivo. This work is the first to show that softer tumor microenvironments may be contributing to changes in disease outcome by imprinting on TNBC cells a greater metabolic flexibility and conferring discrete cell survival advantages.
Spermidine‐Functionalized Injectable Hydrogel Reduces Inflammation and Enhances Healing of Acute and Diabetic Wounds In Situ
Authors: Wu Qianqian , Yang Runjiao , Fan Wenxuan , Wang Li , Zhan Jing , Cao Tingting , Liu Qiming , Piao Xianshu , Zhong Yinghui , Zhao Wenxian , Zhang Shuhan , Yu Jiaao , Liang Song , Roberts Thomas M. , Wang Bingdi , Liu Zhenning
Published: April 2024

The inflammatory response is a key factor affecting tissue regeneration. Inspired by the immunomodulatory role of spermidine, an injectable double network hydrogel functionalized with spermidine (DN‐SPD) is developed, where the first and second networks are formed by dynamic imine bonds and non‐dynamic photo‐crosslinked bonds respectively. The single network hydrogel before photo‐crosslinking exhibits excellent injectability and thus can be printed and photo‐crosslinked in situ to form double network hydrogels. DN‐SPD hydrogel has demonstrated desirable mechanical properties and tissue adhesion. More importantly, an “operando” comparison of hydrogels loaded with spermidine or diethylenetriamine (DETA), a sham molecule resembling spermidine, has shown similar physical properties, but quite different biological functions. Specifically, the outcomes of 3 sets of in vivo animal experiments demonstrate that DN‐SPD hydrogel can not only reduce inflammation caused by implanted exogenous biomaterials and reactive oxygen species but also promote the polarization of macrophages toward regenerative M2 phenotype, in comparison with DN‐DETA hydrogel. Moreover, the immunoregulation by spermidine can also translate into faster and more natural healing of both acute wounds and diabetic wounds. Hence, the local administration of spermidine affords a simple but elegant approach to attenuate foreign body reactions induced by exogenous biomaterials to treat chronic refractory wounds.
Human MHC Class II and Invariant Chain Knock‐in Mice Mimic Rheumatoid Arthritis with Allele Restriction in Immune Response and Arthritis Association
Authors: Romero‐Castillo Laura , Li Taotao , Do Nhu‐Nguyen , Sareila Outi , Xu Bingze , Hennings Viktoria , Xu Zhongwei , Svensson Carolin , Oliveira‐Coelho Ana , Sener Zeynep , Urbonaviciute Vilma , Ekwall Olov , Burkhardt Harald , Holmdahl Rikard
Published: April 2024

Transgenic mice expressing human major histocompatibility complex class II (MHCII) risk alleles are widely used in autoimmune disease research, but limitations arise due to non‐physiologic expression. To address this, physiologically relevant mouse models are established via knock‐in technology to explore the role of MHCII in diseases like rheumatoid arthritis. The gene sequences encoding the ectodomains are replaced with the human DRB1*04:01 and 04:02 alleles, DRA, and CD74 (invariant chain) in C57BL/6N mice. The collagen type II (Col2a1) gene is modified to mimic human COL2. Importantly, DRB1*04:01 knock‐in mice display physiologic expression of human MHCII also on thymic epithelial cells, in contrast to DRB1*04:01 transgenic mice. Humanization of the invariant chain enhances MHCII expression on thymic epithelial cells, increases mature B cell numbers in spleen, and improves antigen presentation. To validate its functionality, the collagen‐induced arthritis (CIA) model is used, where DRB1*04:01 expression led to a higher susceptibility to arthritis, as compared with mice expressing DRB1*04:02. In addition, the humanized T cell epitope on COL2 allows autoreactive T cell‐mediated arthritis development. In conclusion, the humanized knock‐in mouse faithfully expresses MHCII, confirming the DRB1*04:01 alleles role in rheumatoid arthritis and being also useful for studying MHCII‐associated diseases.
Swing Origami‐Structure‐Based Triboelectric Nanogenerator for Harvesting Blue Energy toward Marine Environmental Applications
Authors: Liu Weilong , Wang Xiutong , Yang Lihui , Wang Youqiang , Xu Hui , Sun Yanan , Nan Youbo , Sun Congtao , Zhou Hui , Huang Yanliang
Published: April 2024

The appearance of triboelectric nanogenerators (TENG) provides a promising energy technology for harvesting abundant water wave energy. Here, the design and fabrication of a swinging origami‐structured TENG (SO‐TENG) tailored specifically for water wave energy harvesting are presented. The design incorporates an oscillating structure weighted at the bottom, inducing reciprocating motion propelled by the inertia of passing water waves. This reciprocating motion efficiently converts mechanical into electrical energy through the origami structure. By employing origami as the monomer structure, the surface contact area between friction layers is enhanced, thereby optimizing output performance. the swinging structure, combined with the placement of heavy objects, enhances the folding and contact of the origami, allowing it to operate effectively in low‐frequency water wave environments. This configuration exhibits robust power generation capabilities, making it suitable for powering small electronic devices in water wave environments. Furthermore, when applied to metal corrosion protection, the SO‐TENG demonstrates notable efficacy. Compared to exposed Q235 carbon steel, Q235 carbon steel protected by SO‐TENG exhibits a significant reduction in open‐circuit potential drop, approximately 155 mV, indicative of superior anti‐corrosion properties. It lays a solid foundation for water wave energy collection and self‐powered metal corrosion protection in marine environments.
Managing risk in commodity processing using formula pricing contracts: An application to ethanol
Authors: Bullock David W. , Wilson William W.
Published: April 2024

As is the case with many commodity processors, manufacturers of ethanol face considerable margin risk from a wide range of input and output prices and the interrelation of these risks with the technical operational efficiency of the plant. Buyers of ethanol desire greater budget certainty for future ethanol purchases. An approach to pricing that has found considerable use in the livestock, dairy, and milling industries is the use of component‐based formula pricing. This study constructs a Monte Carlo simulation model of a typical South Dakota ethanol plant that uses a formula contract to fix components of the ethanol price. The simulation results indicate that the contract has considerable margin risk management benefits for the ethanol producer. The buyer also achieves marginal risk management benefits but with greater budget certainty as the components are fixed. Additional observations of interest to the industry are drawn from the sensitivity results of the simulations. [EconLit Citations: Q13, G17].
Ultrabright NIR AIEgen nanoparticles‐enhanced lateral flow immunoassay platform for accurate diagnostics of complex samples
Authors: Shu Jia , Li Yujian , Cai Huan , Fu Qing , Li Chunyang , Yuan Jianbo , Zhao Yan , Liu Changjin , Wu Haiping , Ling Doudou , Liu Zhangluxi , Su Guannan , Cao Qingfeng , Huang Xiaolin , Chen Rui , Yang Peizeng
Published: April 2024

Accurate and sensitive near‐infrared (NIR) luminescent lateral flow immunoassay (LFIA) has attracted considerable attention in the field of point‐of‐care testing (POCT). However, the detection accuracy and sensitivity are often compromised by the low fluorescence quantum efficiency (<10%) of the NIR fluorescent probe. Herein, ultrabright NIR AIEgen nanoparticles (PS@AIE830NPs) composed of polystyrene (PS) nanoparticles and NIR aggregation‐induced emission luminogen (AIEgen) with the maximum emission at 830 nm (AIE830) is reported, and its potential to promote an accurate and sensitive detection of complex samples by LFIA is described. The relative quantum yield (QY) of the PS@AIE830NPs was 14.76%, which was superior to that of the polymer embedding method and indocyanine green (ICG)‐based NIR nanoparticles. The PS@AIE830NPs immunolabeled‐LFIA combined with laboratory‐built NIR‐LFIA portable quantitative instruments (detected light range > 800 nm) completely eliminated background interference and allowed highly accurate and sensitive detection without any pre‐treatment steps. The limits of detection (LODs) for aflatoxin B1 (AFB1) in soy sauce, alpha hemolysin (Hla) of Staphylococcus aureus biomarker in joint fluid, and C‐reactive protein (CRP) in human haemolysed samples were 0.01 ng mL−1, 0.02 µg mL−1, and 0.156 mg L−1, respectively, commensurating with those of the corresponding gold standard assays and covering the detection range of interests. It is anticipated that the ultrabright NIR AIEgen nanoparticles will serve as a universally applicable signal probe for NIR‐LFIA diagnostics, promising to expand the range of applications for quantitative detection of complex samples.
Novel Alu insertion in the ZEB2 gene causing Mowat‐Wilson syndrome
Authors: Barington Maria , Bak Mads , Kjartansdóttir Kristín Rós , Hansen Thomas van Overeem , Birkedal Ulf , Østergaard Elsebet , Hove Hanne Buciek
Published: April 2024

Alu elements are short, interspersed elements located throughout the genome, playing a role in human diversity, and occasionally causing genetic diseases. Here, we report a novel Alu insertion causing Mowat‐Wilson syndrome, a rare neurodevelopmental disorder, in an 8‐year‐old boy displaying the typical clinical features for Mowat‐Wilson syndrome. The variant was not initially detected in genome sequencing data, but through deep phenotyping, which pointed to only one plausible candidate gene, manual inspection of genome sequencing alignment data enabled us to identify a de novo heterozygous Alu insertion in exon 8 of the ZEB2 gene. Nanopore long‐read sequencing confirmed the Alu insertion, leading to the formation of a premature stop codon and likely haploinsufficiency of ZEB2. This underscores the importance of deep phenotyping and mobile element insertion analysis in uncovering genetic causes of monogenic disorders as these elements might be overlooked in standard next‐generation sequencing protocols.
“Why did I choose genetics?”: A survey of current and recent medical genetics and genomics residents provides insight into recruitment efforts
Authors: Hayek Jennifer Cassady , Blitzer Miriam G. , Robin Nathaniel H.
Published: April 2024

There is a shortage of clinical geneticists, even with concerted recruitment efforts. Previously, no data had been collected about why young career geneticists chose this specialty. To investigate this question, we carried out a survey of current and recent medical genetics and genomics residents. The goal of this survey was to understand their reasons for pursuing medical genetics and genomics as a specialty. Results demonstrate that, for most, interest in genetics begins in medical school and was largely influenced by mentorship. This suggests that placing greater focus on introducing medical genetics as a clinical specialty and fostering robust mentorship of students in preclinical years may increase recruitment into medical genetics residencies.
Neuropathologic changes at age 90+ related to sleep duration 19 to 40 years earlier: The 90+ Study
Authors: Melikyan Zarui A. , Kawas Claudia H. , Paganini‐Hill Annlia , Jiang Luohua , Bukhari Syed , Montine Thomas J. , Mander Bryce A. , Corrada María M.
Published: April 2024

INTRODUCTION

We investigated the association between sleep duration and neuropathologic changes 19 to 40 years later in oldest‐old (age 90+) participants of The 90+ Study.

METHODS

Participants self‐reported sleep duration and underwent neuropathologic evaluation. We categorized sleep duration as < 7, 7 to 8 = reference, > 8 hours and dichotomized neuropathologic changes as present/absent. We estimated odds ratio (OR) and 95% confidence intervals (CI) using logistic regression.

RESULTS

In 264 participants, mean age at sleep self‐report was 69 years, mean age at autopsy was 98 years, and mean interval between sleep self‐report and autopsy was 29 years (range: 19–40). Those reporting > 8 hours of sleep had lower likelihood of limbic‐predominant age‐related TDP‐43 encephalopathy neuropathologic change (LATE‐NC) inclusions (OR = 0.18; CI = 0.04–0.82) and amyloid beta deposits (OR = 0.34; 95% CI = 0.12–0.94).

DISCUSSION

Long self‐reported sleep is associated with lower odds of neurodegenerative neuropathologic changes 19 to 40 years later in the oldest‐old, suggesting a potential role of sleep in accumulation of dementia‐related neuropathologies.

Highlights

Association of self‐reported sleep with non‐Alzheimer's disease neuropathologic changes has not been explored.

Whether sleep duration is related to dementia neuropathologic changes decades later is unclear.

Long self‐reported sleep is associated with lower odds of Alzheimer's disease neuropathologic change 19 to 40 years later in the oldest‐old.

Long self‐reported sleep is associated with lower odds of limbic‐predominant age‐related TDP‐43 encephalopathy neuropathologic change 19 to 40 years later in the oldest‐old.
In Situ Formation of Platinum‐Carbon Catalysts in Propane Dehydrogenation
Authors: Nerl Hannah C. , Plodinec Milivoj , Götsch Thomas , Skorupska Katarzyna , Schlögl Robert , Jones Travis E. , Lunkenbein Thomas
Published: April 2024

The catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt−C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride‐type Pt−C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.
Organic Donor–Acceptor Thermally Activated Delayed Fluorescence Photocatalysts in the Photoinduced Dehalogenation of Aryl Halides
Authors: Bryden Megan Amy , Crovini Ettore , Comerford Thomas , Studer Armido , Zysman‐Colman Eli
Published: April 2024

We report a family of donor‐acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC‐TRZ, that are strongly photoreducing. Both Eox and thus E*ox could be tuned via substitution of the DMAC donor with a Hammett series of p‐substituted phenyl moieties while Ered remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to Ered=−2.72 V could be dehalogenated at low PC loading (1 mol %) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.
Large Libraries of Structurally Diverse Macrocycles Suitable for Membrane Permeation
Authors: Nielsen Alexander L. , Bognar Zsolt , Mothukuri Ganesh K. , Zarda Anne , Schüttel Mischa , Merz Manuel L. , Ji Xinjian , Will Edward J. , Chinellato Monica , Bartling Christian R. O. , Strømgaard Kristian , Cendron Laura , Angelini Alessandro , Heinis Christian
Published: April 2024

Macrocycles offer an attractive format for drug development due to their good binding properties and potential to cross cell membranes. To efficiently identify macrocyclic ligands for new targets, methods for the synthesis and screening of large combinatorial libraries of small cyclic peptides were developed, many of them using thiol groups for efficient peptide macrocyclization. However, a weakness of these libraries is that invariant thiol‐containing building blocks such as cysteine are used, resulting in a region that does not contribute to library diversity but increases molecule size. Herein, we synthesized a series of structurally diverse thiol‐containing elements and used them for the combinatorial synthesis of a 2,688‐member library of small, structurally diverse peptidic macrocycles with unprecedented skeletal complexity. We then used this library to discover potent thrombin and plasma kallikrein inhibitors, some also demonstrating favorable membrane permeability. X‐ray structure analysis of macrocycle‐target complexes showed that the size and shape of the newly developed thiol elements are key for binding. The strategy and library format presented in this work significantly enhance structural diversity by allowing combinatorial modifications to a previously invariant region of peptide macrocycles, which may be broadly applied in the development of membrane permeable therapeutics.
A H2O2 Self‐Charging Zinc Battery with Ultrafast Power Generation and Storage
Authors: Zhang Yan , Hu Yang , Wang Huimin , Tian Jinlei , Niu Zhiqiang
Published: April 2024

Self‐charging power systems are considered as promising alternatives for off‐grid energy devices to provide sustained electricity supply. However, the conventional self‐charging systems are severely restricted by the energy availability and time‐consuming charging process as well as insufficient capacity. Herein, we developed an ultrafast H2O2 self‐charging aqueous Zn/NaFeFe(CN)6 battery, which simultaneously integrates the H2O2 power generation and energy storage into a battery configuration. In such battery, the chemical energy conversion of H2O2 can generate electrical energy to self‐charge the battery to 1.7 V through the redox reaction between H2O2 and NaFeFe(CN)6 cathode. The thermodynamically and kinetically favorable redox reaction contributes to the ultrafast H2O2 self‐charging rate and the extremely short self‐charging time within 60 seconds. Moreover, the rapid H2O2 power generation can promptly compensate the energy consumption of battery to provide continuous electricity supply. Impressively, this self‐charging battery shows excellent scalability of device architecture and can be designed to a H2O2 single‐flow battery of 7.06 Ah to extend the long‐term energy supply. This work not only provides a route to design self‐charging batteries with fast charging rate and high capacity, but also pushes forward the development of self‐charging power systems for advanced large‐scale energy storage applications.
PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event
Authors: Hanania Nicole , Eghbarieh Nadim , Masarwa Ahmad
Published: April 2024

While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation of C−C and C‐heteroatom bonds, their potential as energy‐transfer reactive groups has remained unexplored. Yet, this potential holds the key to generating elusive polyborylated biradical species, which can be captured by olefins, thereby leading to the construction of new highly‐borylated scaffolds. Herein, we report a designed energy‐transfer strategy for photosensitized [2+2]‐cycloadditions of poly‐borylated alkenes with various olefins enabling the regioselective synthesis of diverse poly‐borylated cyclobutane motifs, including the 1,1‐di‐, 1,1,2‐tri‐, and 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong to a family that presently lacks efficient synthetic pathways. Interestingly, when α‐methylstyrene was used, the reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into the outcome of 1,5‐hydrogen atom transfer process. In addition, the polyborylated cyclobutanes are then demonstrated to be useful in selective oxidation processes resulting in the formation of cyclobutanones and γ‐lactones.
A promising perspective through potential antimicrobial, anti‐cancer, and antiviral activity against SARS‐CoV‐2 of silver(I) complexes: Synthesis, characterization, density functional theory calculations, and in‐silico molecular docking studies
Authors: Elhusseiny Amel F. , Sherif Naglaa M. , Soliman Saied M. , Ali Ali Eldissouky , Elsayed Eman Hassan
Published: April 2024

This study tends to accomplish the sustainable development goal, which calls for all healthy lives. Antibiotic resistance, cancer, and severe acute respiratory syndrome coronavirus all showed high death rates in recent years. Our approach is to make better medications available to fight these feared health issues. In this context, three silver(I) complexes (1–3) based on the antibiotic gemifloxacin (HGMF) were synthesized and thoroughly examined using analytical, spectral, and thermal methods. The density functional theory suggested that complex 1 has a bent coordination environment while 2 and 3 have a distorted trigonal planar geometry. The optimal donor and acceptor centers were determined by the natural‐bond orbital analysis. Interaction of complexes with calf‐thymus DNA has been investigated and their binding constants were ordered as 3 > 2 > 1. The antimicrobial activity against 10 pathogenic microorganisms demonstrated that complex 3 exhibited superior activity compared with standard antibiotics. Testing against mammalian cell lines, liver carcinoma, breast carcinoma, and colon carcinoma revealed that complex 3 showed remarkable cell growth inhibition activity with IC50 values ranging from 3.0 to 9.3 μg/mL. Studies of Molecular docking against SARS‐CoV‐2 main protease Mpro (ID: 6 WTT) proved a powerful type of interaction at the active site. Complex 3 exhibits a potent inhibition effect with a total binding energy of −12.58 kcal/mol compared with the reference ligand inhibitor K36 suggesting its ability to block viral protease. This study presents promising bioactive candidates that have a practical impact on various medicinal fields.
Preparation and application of the water‐based acrylic self‐polishing resin: Good storage stability, good film‐forming matrix of marine antifouling coatings
Authors: Liu Yuhua , Liu Wenyan , Wei Shuqing , Yue Yuhao , Dong Lei , Yu Liangmin , He Guangling
Published: April 2024

In order to reduce the release of volatile organic compounds (VOCs), it is of great practical significance to develop water‐based self‐polishing antifouling coatings instead of traditional acrylic self‐polishing antifouling coatings. However, when preparing film forming matrix resin emulsions for water‐based antifouling coatings, the use of emulsifiers in large amounts causes film‐forming defects and poor adhesion. Herein, soap‐free emulsion polymerization is utilized to prepare resin emulsions by copolymerization of hydrophilic monomers, lipophilic monomers and polymerizable hydrophilic ionic monomers. The hydrophilic structure can give the water‐based polymer self‐emulsification function to maintain the stability of the emulsion and can promote the fusion between the latex particles by forming hydrogen bonds and coordination bonds, and its connection with the pigments and fillers in the coating can also promote the excellent film formation of the coating. The experimental results show that the water‐based self‐polishing antifouling resin emulsion has good storage stability and compatibility with the pigments and fillers. The coatings formulated using this emulsion as the film‐forming matrix firmly adhered to substrates and displayed satisfactory antifouling performance even after being exposed to a real sea environment for 18 months. This study presents a simple approach for the development of water‐based resin emulsion with good storage stability and good water‐based self‐polishing marine antifouling coatings.
From PID to ADRC and back: Expressing error‐based active disturbance rejection control schemes as standard industrial 1DOF and 2DOF controllers
Authors: Stankovic Momir , Ting He , Madonski Rafal
Published: April 2024

In this paper, we uncover a new connection between standard proportional‐integral (PI), proportional‐integral‐derivative (PID) controllers and active disturbance rejection control (ADRC), from which we establish formal conditions of equivalence between the two control schemes. Using the equivalence, we devise a step‐by‐step procedure of transitioning from PI/PID to error‐based ADRC. We also show how to go from one degree‐of‐freedom (1DOF) to two degree‐of‐freedom (2DOF) ADRC while retaining a standard 2DOF PI/PID structure. Both procedures facilitate expressing error‐based ADRC schemes as standard industrial 1DOF and 2DOF controllers. This allows the designed controller to have the desired characteristic of ADRC (i.e., strong robustness against internal and external uncertainties) while still being expressed in a form that is familiar to industrial practitioners, where PI/PID structures are still the workhorse of modern control systems. The paper's results ensure backward compatibility of future ADRC‐based solutions and foster the adoption of active disturbance rejection‐based methods in industrial practice as a viable alternative to standard controllers. To further support the findings, a set of tests is conducted in time and frequency domain.
Understanding the Effects of Bi Modification on the Properties of Ni‐Rich Cathodes
Authors: Meng Zifei , Hou Jiahui , Thanwisai Panya , Fu Jinzhao , Yao Zeyi , Zheng Yadong , Jin Wenting , Wang Zexin , Yang Zhenzhen , Ma Xiaotu , Wang Yan
Published: April 2024

With the skyrocketing market demands for energy storage, lithium ions batteries (LIB) with higher energy density are urgently needed. Cathodes play a critical role in determining the energy density of LIB, and the most popular one is Ni‐rich cathode due to its high capacity. However, due to the fast structural degradation, Ni‐rich cathode materials should be further modified to achieve higher stability. Herein, we introduce bismuth ions in LiNi0.83Co0.11Mn0.06O2 cathodes by adding Bi2O3 during sintering to optimize the specific capacity and cycle stability. By adding 0.1 % mol Bi, the Li+ diffusion and structural stability are effectively optimized, leading to improved electrochemical performances. The modified sample delivers much higher specific capacity (222.9 mAhg−1, 0.05 C) than unmodified sample (204 mAhg−1, 0.05 C). Meanwhile, the specific capacity of optimized sample after 100 cycles at 0.33 C is 27.75 mAhg−1 higher than that of unmodified sample. Therefore, this work demonstrates that Bi modification can be regarded as a possible solution to optimizing the electrochemical performance of Ni‐rich cathodes.
Effect of biochar structure on the selective adsorption of heavy components in bio‐oil
Authors: Zhu Haonan , Yan Shanshan , Wu Yansheng , Xu Hao , Chen Haoran , Zhang Hong , Guo Xin , Hu Xun , Zhang Shu , Gao Wenran
Published: April 2024

In this study, biochars with different structures were prepared through HNO3 oxidation and secondary pyrolysis to study the relationship between the structure of biochar and its selectivity for the adsorption of light and heavy aromatics in bio‐oil. The results showed that the adsorption rates of biochar with different structures ranged from 2.90 to 4.00 g bio‐oil per g biochar. The influence of pore structure was dominant, followed by the influence of O‐containing functional groups and the degree of graphitization. The higher the adsorption capacity of biochar for bio‐oil, the smaller the concentrations of the light aromatic model compounds in the absorbed bio‐oil (ABO). Among the five light aromatics, biochar has the best adsorption selectivity for dihydroxybiphenyl and the worst for eugenol and propyl phenol. This is attributed to the diphenyl ring structure of dihydroxybiphenyl, which makes it more susceptible to adsorption, and other light model compounds only have one benzene ring. In summary, biochar demonstrates better adsorption selectivity for heavy aromatics than light aromatics. The more developed the pore structure is, the more enriched O‐containing functional groups are, and the higher the graphitization degree of biochar is, the better the selective adsorption of aromatic compounds in bio‐oil.
The invisible support of community schools in a highly unequal education system: Exploring the experiences of minority pupils and teachers
Authors: Coudenys Blansefloer , Dekeyser Graziela , Agirdag Orhan , Clycq Noel
Published: April 2024

This study contributes to the research on ethnic educational inequality, by deepening the current understanding of education initiatives organised by the ethnic‐cultural minoritised communities most affected by these inequalities. A univariate analysis was performed on data from an original survey conducted in Flanders, in which 816 teachers and 3037 pupils from 60 primary schools were asked about, among other things, their experience with and their perceptions of these educational initiatives. The results of this analysis show that these community‐based education initiatives are widely attended by ethnic minority youth, but also that teachers in mainstream schools are rarely informed or even aware of the existence of these initiatives, or the important role they play in their pupils' lives. The broader social and scientific implications are discussed in this paper, as little to no similar larger‐scale research exists that maps the relationship between these community‐based education initiatives and mainstream educational institutions.
Online preconcentration and determination of five alkaloids in Yangxinshi tablet by large‐volume sample stacking and micelle to solvent stacking in cyclodextrin‐modified electrokinetic chromatography
Authors: Zhou Rui , Liu Wenping , Li Jin , Du Kunze , He Jun , Yao Yaqi , Chang Yanxu
Published: April 2024

The two‐step preconcentration technique consisting of large‐volume sample stacking (LVSS) and micelle to solvent stacking (MSS) in cyclodextrin‐modified electrokinetic chromatography (CDEKC) was developed for the analysis of five cationic alkaloids in complex Chinese herbal prescriptions. Relevant parameters affecting separation and stacking performance were optimized separately. Under the optimal LVSS–MSS–CDEKC conditions, less analysis time and organic solvent were required, and the enhancement factors of analytes ranged from 12 to 15 compared with the normal CDEKC separation mode. Further, all validation results demonstrated good applicability and multiple alkaloids (epiberberine, dehydrocorydaline, jatrorrhizine, coptisine and berberine) in Yangxinshi tablet (YXST) have been simultaneously determined. This approach presents powerful potential for the determination of multiple components in complex preparations of Chinese medicine.
EL Greco Platform: A novel Python programming learning platform that uses a real robot
Authors: Rousouliotis Minas , Vasileiou Marios , Manos Nikolaos , Kavallieratou Ergina
Published: April 2024

This paper introduces the El Greco Platform, a Python programming platform for distance learning that employs an educational robot. This website allows prospective learners to remotely control Greco, a social humanoid robot designed to be cost‐effective, simple to construct, and appropriate for use in education. El Greco is capable of performing multiple tasks, including combined movements. These Robot capabilities can be programmed using either Python code or the Blockly library, which adds an editor to an application that visualizes coding concepts as interlocking blocks. Programming a robot appears to be a significantly more effective and creative method for students to learn a programming language. This educational tool was designed primarily for use by students and allows anyone to learn Python while controlling a robot for free. El Greco Platform features gamification elements that increase the enjoyment and engagement of the learning experience while reinforcing the concepts taught. The survey results on students aged 13–18 revealed that the El Greco Platform captivated the study participants and positively affected their attitudes toward programming and robotics. In addition, it significantly impacted their comprehension of programming and motivated them to seek additional opportunities to expand their knowledge of robotics and programming.
Industrial Distillation Fractions of Garlic Essential Oil, Design, Synthesis, and Antifungal Activity Evaluation of Aliphatic Substituted Trisulfide Derivatives
Authors: Chen Yao , Wang Hui , Wang Haiyang , Gao Jie , Huang Yamin , Zhang Yu , Lv Xianhai
Published: April 2024

Garlic oil has a wide range of biological activities, and its broad‐spectrum activity against phytopathogenic fungi still has the potential to be explored. In this study, enzymatic treatment of garlic resulted in an increase of approximately 50 % in the yield of essential oil, a feasible GC‐MS analytical program for garlic oil was provided. Vacuum fractionation of the volatile oil and determination of its inhibitory activity against 10 fungi demonstrated that garlic oil has good antifungal activity. The antifungal activity levels were ranked as diallyl trisulfide (S‐3)>diallyl disulfide (S‐2)>diallyl monosulfide (S‐1), with an EC50 value of S‐3 against Botrytis cinerea reached 8.16 mg/L. Following the structural modification of compound S‐3, a series of derivatives, including compounds S‐4~7, were synthesized and screened for their antifungal activity. The findings unequivocally demonstrated that the compound dimethyl trisulfide (S‐4) exhibited exceptional antifungal activity. The EC50 of S‐4 against Sclerotinia sclerotiorum reached 6.83 mg/L. SEM, In vivo experiments, and changes in mycelial nucleic acids, soluble proteins and soluble sugar leakage further confirmed its antifungal activity. The study indicated that the trisulfide bond structure was the key to good antifungal activity, which can be developed into a new type of green plant‐derived fungicide for plant protection.
Functions of HP1 in preventing chromosomal instability
Authors: Ding Zexian , Peng Lei , Zeng Jinghua , Yuan Kejia , Tang Yan , Yi Qi
Published: April 2024

Chromosomal instability (CIN), caused by errors in the segregation of chromosomes during mitosis, is a hallmark of many types of cancer. The fidelity of chromosome segregation is governed by a sophisticated cellular signaling network, one crucial orchestrator of which is Heterochromatin protein 1 (HP1). HP1 dynamically localizes to distinct sites at various stages of mitosis, where it regulates key mitotic events ranging from chromosome–microtubule attachment to sister chromatid cohesion to cytokinesis. Our evolving comprehension of HP1's multifaceted role has positioned it as a central protein in the orchestration of mitotic processes.
Effects of pea flour substitution and sodium metabisulfite on physical and sensory properties of pancake formulations
Authors: Paladugula Moorti P. , Smith Brennan M. , Ardoin Ryan P. , Morris Craig F. , Kiszonas Alecia M.
Published: April 2024

Background and Objectives

Pulse flours are gaining popularity in baked goods, but their use is limited due to strong flavors. This study analyzed the addition of pea flour to pancakes, with and without sodium metabisulfite (SMB), to assess their impact on pancake quality and reduce off‐flavors.

Findings

Because pancake formulations were standardized based on batter viscosity, only at 20% pea flour incorporation did changes to pancake physical quality occur. Adding pea flour to pancakes impacted sensory aspects such as cooked pea flavor, nutty flavor, and pea odor. In combination with SMB, pea flour can be added up to 5% without imparting significant cooked pea flavor to pancakes. SMB also reduced pea odor in pancakes with 1%–5% pea flour.

Conclusions

Pea flour can be added to pancakes without significantly affecting physical quality, as long as the batter viscosity is optimized. SMB can have a positive effect on limiting off‐flavors in pancakes containing pea flour. This research provides valuable insights into the effects of substituting pea flour in soft wheat batter‐based bake systems.

Significance and Novelty

Pancakes with up to 20% pea flour had similar physical characteristics to wheat pancakes. Pea flavors were detectible at 5% inclusion, and SMB reduced off‐flavor perception at low pea flour inclusion rates.