bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rational Design of PDI‐Based Linear Conjugated Polymers for Highly Effective and Long‐Term Photocatalytic Oxygen Evolution
Authors: Liu Di , Yang Xuan , Chen Peiyan , Zhang Xinling , Chen GaoYuan , Guo Qiwei , Hou Huan , Li Yi 
Published: March 2023

AbstractConstructed through relatively weak noncovalent forces, the stability of organic supramolecular materials has shown to be a challenge. Herein, the designing of a linear conjugated polymer is proposed through creating a chain polymer connected via bridging covalent bonds in one direction and retainingπ‐stacked aromatic columns in its orthogonal direction. Specifically, three analogs of linear conjugated polymers through tuning the aromatic core and its covalently linked moiety (bridging group) within the building block monomer are prepared. Cooperatively supported by strongπ–πstacking interactions from the extended aromatic core of perylene and favorable dipole–dipole interactions from the bridging group, the as‐expected high crystallinity, wide light absorption, and increased stability are successfully achieved for Oxamide‐PDI (perylene diimide) through ordered molecular arrangement, and present a remarkable full‐spectrum oxygen evolution rate of 5110.25 µmol g−1 h−1without any cocatalyst. Notably, experimental and theoretical studies reveal that large internal dipole moments within Oxamide‐PDI together with its ordered crystalline structure enable a robust built‐in electric field for efficient charge carrier migration and separation. Moreover, density functional theory (DFT) calculations also reveal oxidative sites located at carbon atoms next to imide bonds and inner bay positions based on proven spatially separated photogenerated electrons and holes, thus resulting in highly efficient water photolysis into oxygen.
Engineering Fano‐Resonant Hybrid Metastructures with Ultra‐High Sensing Performances
Authors: Lio Giuseppe Emanuele , Ferraro Antonio , Kowerdziej Rafał , Govorov Alexander O. , Wang Zhiming , Caputo Roberto 
Published: March 2023

AbstractMetamaterials‐based sensors are of primary interest in physics, materials science, medicine, and biophysics thanks to their ability to detect very tiny amount of molecules spread into a medium. Here, a metastructure utilizing the epsilon near zero (εNZ) and Fano–Rabi physics is engineered to design a system with ultra‐high sensitivity. So far, a dedicated study of such systems has been missing. In this work, the authors report the results of their efforts to fill the gap by considering a metasurface, designed as a periodical array of rings with a cross in their center, placed on top of a silver (Ag) and zinc oxide (ZnO) epsilon near‐zero optical nanocavity (εNZ‐ONC) metamaterial. The accurate selection of the metasurface parameters allows the design of a sensor exhibiting an extremely high sensitivity of about 16 000 and 21 000 nm RIU−1 depending on incoming polarization. This work paves the way for the development of novel groundbreaking devices for biomedical and environmental application based on plasmonic and photonic design principles.
Fluorescence Filter Nanoarchitectonics with Polydiacetylene‐Based Supramolecular Chiral Gel for Generating Tunable Circularly Polarized Luminescence
Authors: Zhai Donghua , Jiang Jian , Yuan Chenhuan , Wang Decai , Jiang Yuqian , Liu Minghua 
Published: March 2023

AbstractCircularly polarized luminescence (CPL) can be generated from chiral luminescent materials. It can also be achieved from achiral emissive dyes by selectively filtering their fluorescence with chiroptical active materials. In this work, a novel polydiacetylene‐based supramolecular chiral gel is fabricated as a handedness‐selective fluorescence filter for generating CPL. The gelator consists of a diacetylene alkyl chain and a chiral histidine (His) head group (HisDA). It can self‐assemble into nanoribbon and turn into the blue phase, purple phase and red phase polydiacetylene‐His (HisPDA) upon photopolymerization. The resulting L/D‐HisPDA gels show variable circular dichroism (CD) with the change in color. Furthermore, multiple CPL signals are achieved after fluorescence excited with achiral dyes D1–D3 passing through HisPDA gel. The intensity of CPL increases gradually in both D1 and D3 dye systems along with the change of the HisPDA gel from blue phase to red phase, while the CPL signal is inverted for the D2 dye system. The handedness of the CPL signal is opposite to the CD signal of HisPDA gel in all the cases, demonstrating that CPL is originated through a handedness‐selective fluorescence adsorption mechanism. This study offers a new strategy for obtaining tunable CPL via adjustable chiral fluorescence filters.
Syntheses and Photophysical Properties of Pnictogen‐ and Chalcogen‐Containing Diheteroanthracenes
Authors: Fujii Toshiki , Urushizaki Aya , Imoto Hiroaki , Naka Kensuke 
Published: March 2023

AbstractHerein, we synthesized pnictogen (P, As, Sb)‐ and chalcogen (O, S)‐containing diheteroanthracene derivatives with 8π‐electron systems. As opposed to the pnictogen atoms, the chalcogen atoms significantly affected the conformations of the diheteroanthracenes. In addition, the S‐containing compounds exhibited relatively large Stokes shifts owing to significant structural relaxations compared with those of the O‐containing compounds. Computational calculations revealed that the bent conformations of the S‐containing compounds in their ground states planarized upon photoexcitation.
A Traceless Chiral Shift Reagent Based on Nonbonding Interactions with Single‐Handed Helical Poly(quinoxaline‐2,3‐diyl)
Authors: Fujie Takaya , Yamamoto Takeshi , Suginome Michinori 
Published: March 2023

AbstractA single‐handed poly(quinoxaline‐2,3‐diyl) (PQX) has been found to serve as a new type of chiral shift reagent (CSR) for determining the enantiomeric ratio by NMR spectroscopy. Even though there is no specific binding site in the PQX, its nonbonding interaction with chiral analytes leads to a significant shift of the NMR chemical shift, allowing quantification of the enantiomeric ratio. The new type of CSR has the advantages of a wide scope of analytes including ethers, haloalkanes, and alkanes, easy tunability of the degree of chemical shifts by measurement temperature, and erasability of proton signals of CSR because of the short spin‐spin (T2) relaxation of the macromolecular scaffold.
Methylierung nicht‐aktivierter Alkene mit modifizierten Methyltransferasen zur Diversifizierung von Terpenoiden
Authors: Aberle Benjamin , Kowalczyk Daniel , Massini Simon , Egler‐Kemmerer Alexander‐N. , Gergel Sebastian , Hammer Stephan C. , Hauer Bernhard 
Published: March 2023

AbstractTerpenoide sind aus Isopren‐Bausteinen aufgebaut und haben zahlreiche biologische Funktionen. Eine selektive Modifizierung ihres Kohlenstoffgerüsts hat das Potenzial die biologischen Aktivitäten zu verändern oder zu optimieren. Die Synthese von Terpenoiden mit einem nicht‐natürlichen Kohlenstoffgerüst ist jedoch aufgrund der Komplexität dieser Moleküle oft ein schwieriges Unterfangen. In dieser Arbeit berichten wir über die Identifizierung und das Engineering von (S)‐Adenosyl‐l‐Methionin‐abhängigen Sterol‐Methyltransferasen für die selektive C‐Methylierung von linearen Terpenoiden. Das entwickelte Enzym katalysiert die selektive Methylierung von nicht‐aktivierten Alkenen in Mono‐, Sesqui‐ und Diterpenoiden zur Herstellung von C11‐, C16‐ und C21‐Derivaten. Die präparative Umsetzung und Isolation der Produkte zeigt, dass dieser Biokatalysator die Bildung von C−C‐Bindungen mit hoher Chemo‐ und Regioselektivität durchführt. Die Methylierung des Alkens erfolgt höchstwahrscheinlich über ein Carbokation‐Zwischenprodukt und eine regioselektive Deprotonierung. Diese Methode eröffnet neue Wege zur Modifizierung des Kohlenstoffgerüsts von Alkenen im Allgemeinen und Terpenoiden im Besonderen.
Triphenylamine‐Derived Solid‐State Emissive Carbon Dots for Multicolor High‐Efficiency Electroluminescent Light‐Emitting Diodes
Authors: Zhao Biao , Ma Huanyu , Jia Haoran , Zheng Mengyun , Xu Kunxiang , Yu Runnan , Qu Songnan , Tan Zhan'ao 
Published: March 2023

AbstractTwo kinds of triphenylamine‐derived solid‐state emissive carbon dots (CDs) with orange and yellow color are facilely synthesized through solvothermal treatment, taking advantage of the nonplanar structure and good carrier mobility of triphenylamine unit. Theoretical calculations show that the triphenylamine structure could greatly inhibit the direct π–π stacking of aromatic skeletons and enhance the fluorescence properties of CDs in aggregation state. By adopting the CDs as single emissive layer, high‐performance orange‐color and green‐color electroluminescent light‐emitting diodes (LEDs) are successfully fabricated, with maximum brightness of 9450/4236 cd m−2, high current efficiency of 1.57/2.34 cd A−1 and low turn‐on voltage of 3.1/3.6 eV are respectively achieved. Significantly, white‐color LED device is further prepared. This work provides a universal platform for the construction of novel solid‐state emissive CDs with significant applications in photoelectric device.
Manipulating Electric Double Layer Adsorption for Stable Solid‐Electrolyte Interphase in 2.3 Ah Zn‐Pouch Cells
Authors: Wang Yu , Liang Bochun , Zhu Jiaxiong , Li Geng , Li Qing , Ye Ruquan , Fan Jun , Zhi Chunyi 
Published: March 2023

AbstractConstructing a reliable solid‐electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn0) electrodes. Contrary to conventional “bulk solvation” mechanism, we found the SEI structure is dominated by electric double layer (EDL) adsorption. We manipulate the EDL adsorption and Zn2+ solvation with ether additives (i.e. 15‐crown‐5, 12‐crown‐4, and triglyme). The 12‐crown‐4 with medium adsorption on EDL leads to a layer‐structured SEI with inner inorganic ZnFx/ZnSx and outer organic C−O−C components. This structure endows SEI with high rigidness and strong toughness enabling the 100 cm2 Zn||Zn pouch cell to exhibit a cumulative capacity of 4250 mAh cm−2 at areal‐capacity of 10 mAh cm−2. More importantly, a 2.3 Ah Zn||Zn0.25V2O5⋅n H2O pouch cell delivers a recorded energy density of 104 Wh Lcell−1 and runs for >70 days under the harsh conditions of low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8 g Ah−1), and high‐areal‐capacity (≈13 mAh cm−2).
CuNi Nanoalloys with Tunable Composition and Oxygen Defects for the Enhancement of the Oxygen Evolution Reaction**
Authors: Gioria Esteban , Li Shuang , Mazheika Aliaksei , Naumann d'Alnoncourt Raoul , Thomas Arne , Rosowski Frank 
Published: March 2023

AbstractColloidal synthesis is an excellent tool for the study of cooperative effects in nanoalloys. In this work, bimetallic CuNi nanoparticles of defined size and composition are fully characterized and tested for the oxygen evolution reaction. Copper addition to nickel leads to modifications in the structural and electronic properties, showing a higher concentration of surface oxygen defects and formation of active Ni3+ sites under reaction conditions. The ratio OV/OL between oxygen vacancies and lattice oxygen shows a clear correlation with the overpotential, being an excellent descriptor of the electrocatalytic activity. This is attributed to modifications in the crystalline structure, leading to lattice strain and grain size effects. Bimetallic Cu50Ni50NP showed the lowest overpotential (318 mV vs RHE), low Tafel slope (63.9 mV dec−1), and excellent stability. This work unravels the relative concentration between oxygen defects and lattice oxygen (OV/OL) as an excellent descriptor of the catalytic activity of bimetallic precatalysts.
Methylation of Unactivated Alkenes with Engineered Methyltransferases To Generate Non‐natural Terpenoids
Authors: Aberle Benjamin , Kowalczyk Daniel , Massini Simon , Egler‐Kemmerer Alexander‐N. , Gergel Sebastian , Hammer Stephan C. , Hauer Bernhard 
Published: March 2023

AbstractTerpenoids are built from isoprene building blocks and have numerous biological functions. Selective late‐stage modification of their carbon scaffold has the potential to optimize or transform their biological activities. However, the synthesis of terpenoids with a non‐natural carbon scaffold is often a challenging endeavor because of the complexity of these molecules. Herein we report the identification and engineering of (S)‐adenosyl‐l‐methionine‐dependent sterol methyltransferases for selective C‐methylation of linear terpenoids. The engineered enzyme catalyzes selective methylation of unactivated alkenes in mono‐, sesqui‐ and diterpenoids to produce C11, C16 and C21 derivatives. Preparative conversion and product isolation reveals that this biocatalyst performs C−C bond formation with high chemo‐ and regioselectivity. The alkene methylation most likely proceeds via a carbocation intermediate and regioselective deprotonation. This method opens new avenues for modifying the carbon scaffold of alkenes in general and terpenoids in particular.
A New Series of D1‐A‐D2‐type ESIPT‐TICT‐AIE Active Orange‐to‐red Emissive Unsymmetrical Azines: Their All‐throughout Mechanochemical Synthesis and Exploration of Photophysical Properties
Authors: Bhosle Akhil A. , Banerjee Mainak , Hiremath Sharanabasava D. , Bhasikuttan Achikanath C. , Chatterjee Amrita 
Published: March 2023

AbstractAzines are interesting compounds exhibiting aggregation‐induced‐emission (AIE) and twisted‐intramolecular‐charge‐transfer (TICT) properties that have exciting prospects in chemosensing and bioimaging applications. They commonly have symmetrical structures and there is no report on red‐emissive unsymmetrical azines. Herein, we report a novel class of orange‐to‐red emissive hydroxybenzothiazole(HBT)‐based unsymmetrical azines (BTDPA) with triple photophysical characteristics of ESIPT‐TICT‐AIE. The dyes were synthesized by an all‐throughout mechanochemical route in a sustainable way. They displayed D1‐A‐D2 character and fluoresce strongly both in organic solvents due to ESIPT and in the solid state by AIE via TICT. The incorporation of different electron‐withdrawing groups (EWGs) and electron‐donating groups (EDGs) at either HBT or diphenyl‐methylene moiety resulted in tunable fluorescence properties. The red‐emissive character was achieved by keeping EDG both at HBT (−OMe) and the diphenyl‐methylene moiety (−NMe2) (λem 680 nm). The dyes exhibited good quantum yields, large Stoke shifts (upto 293 nm) and were utilized in nitroaromatics and Cu2+ sensing.
Ferritin in cancer therapy: A pleiotropic tumoraffin nanocage‐based transport
Authors: Deng Guodong , Li Yang , Liang Ning , Hu Pingping , Zhang Yan , Qiao Lili , Zhang Yingying , Xie Jian , Luo Hui , Wang Fei , Chen Fangjie , Liu Fengjun , Xu Deguo , Zhang Jiandong 
Published: March 2023

AbstractBackgroundFerritin, a ubiquitously distributed iron storage protein, can specifically target tumor cells through transferrin receptor 1. Due to its rearrangeable nanocage structure, ferritin can be loaded with anticancer drugs. Combined with amino acid modifications on the outer‐ and/or inner‐spaces of the nanocage, ferritins can be further coupled with antigens, antibodies, and nucleotide sequences. Since ferritin is naturally presented in the human body, when used in vivo, ferritin exhibits good biocompatibility, and no immunogenic response occurs. These makes ferritin an ideal nanocarrier which shows broad application prospects in cancer therapy.MethodsIn this study, to find articles, a search was made in PubMed with the keywords ferritin, drug delivery, drug delivery, and cancer treatment.ResultsAccording to the investigation, some studies suggest that ferritin can be loaded with drugs and targeted for delivery to tumor tissue. Therefore, ferritin nanocarriers loaded with drugs can be used in chemotherapy, photodynamic therapy (PDT), photothermal therapy (PTT) and immunotherapy. Importantly, the specific targeting of ferritin nanocarriers to tumor cells increases the effectiveness of related therapies and reduces side effects.ConclusionsWe conclude in this paper that the superior properties of ferritin nanocarriers as an emerging drug delivery system make them a promising cancer treatment strategy. In the future, it is worth conducting clinical trials to further investigate the safety and efficacy of ferritin nanocarriers in patients.
Transcriptomic data in tumor‐adjacent normal tissues harbor prognostic information on multiple cancer types
Authors: Oh Euiyoung , Lee Hyunju 
Published: March 2023

AbstractBackgroundIn identifying prognostic markers in cancer, the roles of tumor‐adjacent normal tissues are often confined to drawing expression differences between tumor and normal tissues rather than being treated as the main targets of investigations. Thus, differential expression analysis between tumors and adjacent normal tissues is performed prior to prognostic analysis in previous studies. However, recent studies have suggested that the prognostic relevance of differentially expressed genes (DEGs) is insignificant for some cancers, contradicting conventional approachesMethodsThis study investigated the prognostic efficacy of transcriptomic data from tumors and adjacent normal tissues using The Cancer Genome Atlas dataset. Prognostic analysis using Cox regression models and survival prediction using machine‐learning models and feature selection methods were employed.ResultsThe results revealed that for kidney, liver, and head and neck cancer, adjacent normal tissues harbored higher proportions of prognostic genes and exhibited better survival prediction performance than tumor tissues and DEGs in machine‐learning models. Furthermore, the application of a distance correlation‐based feature selection method to kidney and liver cancer using external datasets revealed that the selected genes for adjacent normal tissues exhibited higher prediction performance than those for tumor tissues. The study results suggest that the expression levels of genes in adjacent normal tissues are potential prognostic markers. The source code of this study is available athttps://github.com/DMCB‐GIST/Survival_Normal.
Minimizing Product Inhibition in DNA Self‐Replication: Insights for Prebiotic Replication from the Role of the Enzyme in Lesion‐Induced DNA Amplification**
Authors: Park Hansol , Parshotam Shyam , Hales Sarah C. , Mittermaier Anthony K. , Gibbs Julianne M. 
Published: March 2023

AbstractSelf‐replication of nucleic acids in the absence of enzymes represents an important and poorly understood step in the origin of life as such reported systems are strongly hindered by product inhibition. Studying one of the few successful examples of enzymatic DNA self‐replication based on a simple ligation chain reaction, lesion‐induced DNA amplification (LIDA), can shed light on how this fundamental process may have originally evolved. To identify the unknown factors that lead LIDA to overcome product inhibition we have employed isothermal titration calorimetry and global fitting of time‐dependent ligation data to characterize the individual steps of the amplification process. We find that incorporating the abasic lesion into one of the four primers substantially decreases the stability difference between the product and intermediate complexes compared with complexes without the abasic group. In the presence of T4 DNA ligase this stability gap is further reduced by two orders of magnitude revealing that the ligase also helps overcome product inhibition. Kinetic simulations reveal that the intermediate complex stability and the magnitude of the ligation rate constant significantly impact the rate of self‐replication, suggesting that catalysts that both facilitate ligation and stabilize the intermediate complex might be a route to efficient nonenzymatic replication.
Boronic Acid Assisted Self‐Assembly of Functional RNAs
Authors: Lelièvre‐Büttner Amandine , Schnarr Theodor , Debiais Mégane , Smietana Michael , Müller Sabine 
Published: March 2023

AbstractBoronate esters formed by reaction of an oligonucleotide carrying a 5′‐boronic acid moiety with the 3′‐terminalcis‐diol of another have been shown previously to assist assembly of fragmented DNAzymes. Here we demonstrate that boronate esters replacing the natural phosphodiester linkage at selected sites of two functional RNAs, the hairpin ribozyme and the Mango aptamer, allow assembly of functional structures. The hairpin ribozyme, a small naturally occurring RNA that supports the reversible cleavage of appropriate RNA substrates, is very sensitive to fragmentation. Splitting the ribozyme at four different sites led to a significant decrease or even loss of cleavage and ligation activity. Ribozymes assembled from fragments capable of boronate ester formation showed restoration of cleavage activity in some but not all cases, dependent on the split site. Ligation proved to be more challenging, no supportive effect of the boronate ester was observed. Split variants of the Mango aptamer also showed a dramatic loss of functionality, which however, was restored when 5′‐boronic acid modified fragments were used for assembly. These studies show for the first time that boronate esters as internucleoside linkages can act as surrogates of natural phosphodiesters in functional RNA molecules.
Sweetened Alkylated Verdazyls Effectively Kill Cancer Cells under Light Irradiation
Authors: Votkina Darya E. , Abramov Alexander A. , Kovalskaya Ekaterina S. , Plotnikov Evgenii V. , Postnikov Pavel S. , Stepanova Elena V. , Petunin Pavel V. 
Published: March 2023

AbstractThe development of novel photo‐dynamic therapy (PDT) agents enabling to treat the oxygen‐deficient tumors is the emerging tasks for the modern medicinal chemistry. Herein, we describe the design and preparation of water‐soluble agents for PDT which generate active radical species upon light irradiation. Two conjugates of carbohydrates with 1,2,4,6‐substituted‐1,4‐dihydro‐1,2,4,5‐tetrazin‐3(2H)‐ones (AlkVZs) demonstrated high oxygen‐independent cytotoxicity on PC‐3 and Jurkat cancer cells under light irradiation combining with low toxicity in the dark. The efficacy of prepared compounds was estimated using MTT and Alamar Blue tests as well as microscopic dead/live colored images and flow cytometry. The analysis of obtained results reveals the influence of sugar moiety on the activity of AlkVZs. We believe that obtained compounds have high potency as platform for design of new agents for photo‐dynamic therapy.
Conjugates of 1,3‐ and 1,2‐Acylglycerols with Stigmasterol: Synthesis, NMR Characterization, and Impact on Lipid Bilayers
Authors: Gładkowski Witold , Chojnacka Anna , Włoch Aleksandra , Pruchnik Hanna , Grudniewska Aleksandra , Dunal Anna , Dudek Anita , Maciejewska Gabriela , Rudzińska Magdalena 
Published: March 2023

AbstractThe main aim of research was synthesis and spectroscopic characterization of new conjugates in which stigmasterol was linked via carbonate or succinyl linker with 1,3‐ and 1,2‐acylglycerols of palmitic and oleic acid. Acylglycerols containing stigmasterol residue at internal position have been synthesized from 2‐benzyloxypropane‐1,3‐diol or dihydroxyacetone. Their asymmetric counterparts containing stigmasterol residue attached to sn‐3 position have been obtained from (S)‐solketal. Eight synthesized conjugates were used to create the liposomes as nanocarriers of phytosterols to increase their stability and protect them from degradation during thermal‐oxidative treatments. Fluorimetric and ATR‐FTIR methods were used to determine the impact of synthesized conjugates on the physicochemical properties of the lipid bilayer. The results indicate that conjugates with palmitic acid are better candidates for use as the potential stigmasterol nanocarriers compared to those with oleic acid because they increase the stiffness of the lipid bilayer and temperature of the main phase transition. The obtained results are the first step in designing of stigmasterol‐enriched liposomal carriers with higher thermo‐oxidative stability for their potential use in the food industry.