bluuebunny/crossref_metadata_2025_split huggingface dataset:
Regenerating Chemotherapeutics through Copper‐Based Nanomedicine: Disrupting Protein Homeostasis for Enhanced Tumor Therapy
Authors: Wu Xubo , Wu Qinghe , Hou Mengfei , Jiang Yifei , Li Meng , Jia Guoping , Yang Huizhen , Zhang Chunfu 
Published: July 2024

AbstractThe bis‐(diethyldithiocarbamate)‐copper (CuET), the disulfiram (DSF)‐Cu complex, has exhibited noteworthy anti‐tumor property. However, its efficacy is compromised due to the inadequate oxidative conditions and the limitation of bioavailable copper. Because CuET can inactivate valosin‐containing protein (VCP), a bioinformatic pan‐cancer analysis of VCP is first conducted in this study to identify CuET as a promising anticancer drug for diverse cancer types. Then, based on the drug action mechanism, a nanocomposite of CuET and copper oxide (CuO) is designed and fabricated utilizing bovine serum albumin (BSA) as the template (denoted as CuET‐CuO@BSA, CCB). CCB manifests peroxidase (POD)‐mimicking activity to oxidize the tumor endogenous H2O2 to generate reactive oxygen species (ROS), enhancing the chemotherapy effect of CuET. Furthermore, the cupric ions released after enzymatic reaction can regenerate CuET, which markedly perturbs intracellular protein homeostasis and induces apoptosis of tumor cells. Meanwhile, CCB triggers cuproptosis by inducing the aggregation of lipoylated proteins. The multifaceted action of CCB effectively inhibits tumor progression. Therefore, this study presents an innovative CuET therapeutic strategy that creates an oxidative microenvironment in situ and simultaneously self‐supply copper source for CuET regeneration through the combination of CuO nanozyme with CuET, which holds promise for application of CuET for effective tumor therapy.
Exploring the Possibility of Thermally Assisted Creation and Annihilation of Anti‐Frenkel Defects in a Multiferroic Oxide for Tuning Interfacial Ferroelectricity
Authors: Yeo Youngki , Kim Jihun , Suh Jeonghun , Jang Jinhyuk , Kang Kyungrok , Schoenherr Peggy , Kim Kwang‐Tak , Kim Yong‐Jin , Kim Kee Hoon , Ulrich Clemens , Seidel Jan , Choi Si‐Young , Yang Chan‐Ho 
Published: July 2024

AbstractLattice defects such as oxygen vacancies, interstitials, and their complexes are present in crystalline oxide materials. In particular, anti‐Frenkel defects, which refer to charge‐neutral anion vacancy‐interstitial pairs, are strongly coupled with ferroelectric and dielectric properties as electric dipoles. However, in order to observe their macroscopic manifestation, delicate defect controls are required to the extent that electronic and ionic charges are almost completely suppressed. Here, the thermal cycle dependence of dielectric and piezoelectric properties is scrutinized in the strain‐driven morphotropic phase boundaries of multiferroic La‐substituted BiFeO3 thin films. Electrochemical impedance spectroscopy provides the Warburg feature that is considered evidence of the ionic origin. The observations are discussed based on anti‐Frenkel defects that are created or annihilated reversibly by thermal cycles through high‐temperature structural phase transition temperature or magnetic Néel temperature. The defect dipoles are spontaneously aligned by the flexoelectric effect in the phase boundaries inducing a metastable interfacial ferroelectric phase. The findings offer useful insight into defect dipoles.
Bunte Salts for Electrochemical Deuteroalkylthiolation of Heteroarenes
Authors: Lu Ruhan , Tao Qisheng , Qian Qing , Li Bo , Zhang Yuhuan , Gao Yongyuan 
Published: July 2024

AbstractThis study presents a strategy for the electrochemical deuteroalkylthiolation of heteroarenes, using Bunte salt as a deuterium‐alkylthio source. This reaction occurs in an undivided cell without the need for catalysts, oxidants, or electrolytes, yielding a variety of deuteroalkylthiolated heteroarenes.
Advances in α‐Hydroxylation of β‐Dicarbonyl Compounds
Authors: Peng Shuai , Su Fangyao , Yin Shuting , Sun Baoguo , Tian Hongyu , Liang Sen 
Published: July 2024

AbstractThe α‐hydroxy‐β‐dicarbonyl motif is essential in many biologically active compounds, sparking significant interest in their synthesis. This review comprehensively examines the advancements in the α‐hydroxylation of β‐dicarbonyl compounds, systematically categorizing the methods based on the types of oxidants employed and highlighting advances in asymmetric α‐hydroxylation. It evaluates the substrate scope, advantages, and disadvantages of each approach, summarizing the possible intermediates involved and the types of reaction mechanisms.
Cathode Modification of Sodium‐Ion Batteries for Improved energy Density: A Review
Authors: Wan Xiaoyuan , Li Yanlin , Chen Shenghua , Duan Wenyuan , Lei Wanying 
Published: July 2024

AbstractIn recent years, with the large‐scale commercial application of lithium‐ion batteries, the shortage of lithium resource reserves and the rising price limit its development. The sodium‐ion batteries as a new type of secondary chemical power supply, with ample resources, high safety, as well as great electrochemical performance, are expected to form complementary with Lithium‐ion batteries in the domain of extensive electrochemical energy storage and low‐velocity electric vehicles. However, due to its low energy density, it remains challenging to develop high‐performance sodium‐ion batteries. As is well‐known, the cathode material is the essential factor affecting the performance of sodium‐ion batteries. In order to solve these questions, cathode modification of sodium‐ion batteries aroused wide concern for improving the electrochemical performance. Here, the authors first discuss the challenges of sodium‐ion batteries, and review the energy storage mechanism and the causes of the low energy density. Then, recent studies on cathode modification are summarized based on the mainstream cathode materials in sodium‐ion batteries including sodium‐based transition‐metal oxides, polyanionic compounds, and Prussian blue analogues. Finally, the prospects of sodium‐ion batteries are proposed, which provides promising strategies for the development and practical application of cathode materials in the future.
MEN1 Deficiency‐Driven Activation of the β‐Catenin‐MGMT Axis Promotes Pancreatic Neuroendocrine Tumor Growth and Confers Temozolomide Resistance
Authors: Xu Junfeng , Lou Xin , Wang Fei , Zhang Wuhu , Xu Xiaowu , Ye Zeng , Zhuo Qifeng , Wang Yan , Jing Desheng , Fan Guixiong , Chen Xuemin , Zhang Yue , Zhou Chenjie , Chen Jie , Qin Yi , Yu Xianjun , Ji Shunrong 
Published: July 2024

AbstractO6‐methylguanine DNA methyltransferase (MGMT) removes alkyl adducts from the guanine O6 position (O6‐MG) and repairs DNA damage. High MGMT expression results in poor response to temozolomide (TMZ). However, the biological importance of MGMT and the mechanism underlying its high expression in pancreatic neuroendocrine tumors (PanNETs) remain elusive. Here, it is found that MGMT expression is highly elevated in PanNET tissues compared with paired normal tissues and negatively associated with progression‐free survival (PFS) time in patients with PanNETs. Knocking out MGMT inhibits cancer cell growth in vitro and in vivo. Ectopic MEN1 expression suppresses MGMT transcription in a manner that depends on β‐Catenin nuclear export and degradation. The Leucine 267 residue of MEN1 is crucial for regulating β‐Catenin‐MGMT axis activation and chemosensitivity to TMZ. Interference with β‐Catenin re‐sensitizes tumor cells to TMZ and significantly reduces the cytotoxic effects of high‐dose TMZ treatment, and MGMT overexpression counteracts the effects of β‐Catenin deficiency. This study reveals the biological importance of MGMT and a new mechanism by which MEN1 deficiency regulates its expression, thus providing a potential combinational strategy for treating patients with TMZ‐resistant PanNETs.
Nitrogen Bicoupled Carbon Bonding for Electrocatalysis of CO2 and Nitrobenzene via Engineering Hydroxyl Assisted Cobalt Single Atom
Authors: Zheng Jingui , Xu Shaohan , Sun Lingzhi , Pan Xun , Xie Qihao , Li Lina , Cai Junzhuo , Zhao Guohua 
Published: July 2024

AbstractThe coupling of CO2 and nitrogen‐containing species nitrobenzene has become an appealing and sustainable strategy for synthesizing high‐valuable organic nitrides. However, how to realize the nitrogen bicoupled carbon bonding (C─N─C) between two CO2 and nitrobenzene has been an insurmountable challenge. Hydroxyl‐assisted cobalt single atom (CoN2O2‐(OH)2) is engineered to achieve C─N─C bonding for N, N‐dimethylaniline synthesis. The CO2 is adsorbed through hydroxyl groups, that can be reduced and C─N coupling with nitrobenzene reduction intermediate on nearby Co site, and the vacant hydroxyl group continues to adsorb next CO2, which is sequentially coupled with an intermediate of C─N coupling, achieving C─N─C bonding for synthesis N, N‐dimethylaniline. Herein, first, C─N─C bonding is achieved for green synthesis of N, N‐dimethylaniline via electrocatalytic reduction of nitrobenzene and CO2 in an aqueous phase, with a yield of 505.2 µmol L−1 h−1 on CoN2O2‐(OH)2. In situ characterizations and DFT calculations together demonstrated that the key of C─N─C bonding is that *PhNCH3 intermediate of C─N bonding continues to couple with *CO achieving C─N─C bonding to generate *PhNCOCH3 for N, N‐dimethylaniline synthesis with a much lower free energy is far easier to take place on CoN2O2‐(OH)2. This work provides inspiring new insight into the green synthesis of long‐chain organic nitrides.
Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO2 Photoreduction Performance
Authors: Tailor Naveen Kumar , Singh Shreya , Singh Nikhil , Nayak Pabitra Kumar , Saini Saurabh K. , Das Srimanta , Venkanna Guguloth , Senanayak Satyaprasad P , Kumar Mahesh , Ghosh Dibyajyoti , Tripathi Komal , Pant Kamal Kishore , Satapathi Soumitra 
Published: July 2024

AbstractDouble perovskite have attracted substantial attention as prospective materials for applications in optoelectronics and photocatalysis. Significant efforts are devoted to modulating the properties of double perovskites to improve their performance. One promising approach involves substituting silver (Ag) with copper (Cu), which offers favorable electronic characteristics. Despite promising theoretical predictions, the experimental synthesis of copper‐based double perovskites has presented notable challenges. Here, the challenges of Cu incorporation in double perovskites and the subsequent – impact of Cu on the photocatalytic activity of halide perovskites toward CO2 reduction are explored. Combining detailed computational thermodynamic studies, it is found that Cu does not form the traditional double perovskite structure that is Cs2CuBiCl6; it stays as an interstitial dopant in its pristine Cs3Bi2Cl9 structure. The Cu‐Cs3Bi2Cl9 are found to exhibit enhanced CO2 photoreduction activity than the pristine Cs3Bi2Cl9. Further, transient absorption results show that Cu dopants enhance the carrier generation because of introduced sub‐bandgap states, and it is found that carrier decay lifetime is elevated in Cu‐Cs3Bi2Cl9, which can enhance the participation of carriers in CO2 photoreduction. The study explores the challenges and opportunities of copper doping in halide perovskites, offering the potential for developing efficient CO2 reduction photocatalysts.
Longer‐term surveillance imaging and endoscopy critical for majority of patients in detection of sinonasal malignancy recurrence
Authors: Kwiecien Catherine , Workman Alan D. , Wilensky Jadyn , Lerner David K. , Rathi Vinay K. , Douglas Jennifer E. , Kohanski Michael A. , Kuan Edward C. , Palmer James N. , Adappa Nithin D. 
Published: July 2024

AbstractBackgroundSinonasal malignancy surveillance paradigms are often based on Head and Neck National Comprehensive Cancer Network guidelines, which do not recommend standard surveillance imaging beyond 6 months without concerning symptomatology or physical examination findings.MethodsThis was a retrospective analysis of all patients who underwent resection of sinonasal malignancy at a tertiary care center over a 20‐year period from 2000 to 2020, with an ensuing surveillance period demonstrating recurrence.ResultsFifty‐two patients with sinonasal malignancy recurrence were included, with an average time to recurrence of 30.9 months and a follow‐up period of over 60 months. Recurrence was diagnosed by routine imaging or endoscopy in asymptomatic patients in a majority (60%) of cases, while the remaining minority of diagnoses followed new symptomatology. Asymptomatic recurrence was associated with perineural spread of tumor at initial resection (p = 0.025), but not with age (p = 0.85) or stage at diagnosis (p = 0.68). Expectedly, positron emission tomography/computed tomography (CT) more often detected regional or distant recurrence, while structural imaging (CT/magnetic resonance imaging) demonstrated more frequent detection of recurrence in those with perineural spread of tumor (p = 0.01).ConclusionsOur findings support high rates of asymptomatic recurrence in sinonasal malignancy, with the majority of recurrences diagnosed by routine endoscopy or imaging. Tailored and extended surveillance guidelines are necessary relative to those utilized for other head and neck mucosal cancers, and are especially appropriate when features such as perineural spread are present.
Diagnostic criteria for eosinophilic chronic rhinosinusitis: Comparative analysis and novel scoring system
Authors: Lee Jae Yoon , Kim Do Hyun , Kim Sung Won , Im Yeon Hee , Park Chan Soon , Kim Dong Hyun , Alkhars Zainab , Kim Soo Whan 
Published: July 2024

AbstractBackgroundAccurate identification of eosinophilic chronic rhinosinusitis is essentialg because its treatment and prognosis substantially differ from other subtypes.MethodsThis retrospective observational study included 640 patients who underwent endoscopic sinus surgery for chronic rhinosinusitis in a single tertiary center from January 2021 to December 2022. Receiver operating characteristic curves were generated to compare accuracy, sensitivity, specificity of the novel scoring system, and previous diagnostic criteria (Japanese Epidemiological Survey of Refractory Eosinophilic Chronic Rhinosinusitis, European Forum for Research and Education in Allergy and Airway Diseases, European Position Paper on Rhinosinusitis and Nasal Polyps, and Sakuma et al.) for predicting eosinophilic chronic rhinosinusitis (ECRS) by tissue eosinophil count ≥70 per high power field.ResultsPatients were randomly divided into estimation (n = 430) and validation (n = 210) groups. The area under the receiver operating characteristic curve for the novel score was 0.753 (95% confidence interval [CI], 0.670–0.835) in the estimation group, 0.729 (0.629–0.830) in the validation group, and 0.661 (0.584–0.738) in the 20‐fold cross‐validation with the entire dataset.ConclusionsWe propose a novel scoring system that incorporates three key parameters: “novel score = blood eosinophil (%) + total Lund–Mackay score of anterior ethmoid sinuses + 2 if nasal polyp present” greater than 7 can be reliably used for diagnosing ECRS. This system can facilitate decision‐making processes regarding the administration of oral steroids and biologics targeting type 2 inflammation prior to surgical intervention.
Reasons for undergoing amyloid imaging among diverse enrollees in the A4 study
Authors: Magana‐Ramirez Christina M. , Irizarry‐Martinez Gimarie , Gillen Daniel L. , Grill Joshua D. 
Published: July 2024

AbstractINTRODUCTIONUnderstanding attitudes toward participation among diverse preclinical Alzheimer's disease (AD) trial participants could yield insights to instruct future recruitment.METHODSUsing data from the Anti‐Amyloid Treatment in Asymptomatic AD (A4) Study, we examined differences among mutually exclusive racial and ethnic groups in views and perceptions of amyloid imaging (VPAI), a measure of motivations to undergo amyloid biomarker testing in the setting of preclinical AD. We used linear regression to quantify differences at baseline.RESULTSCompared to non‐Hispanic or Latino (NH) White participants, Hispanic or Latino (3.52 points, 95% confidence interval [CI]: [2.61, 4.42]); NH Asian (2.97 points, 95% CI: [1.71, 4.22]); and NH Black participants (2.79 points, 95% CI: [1.96, 3.63]) participants demonstrated higher levels of endorsement of the VPAI items at baseline.DISCUSSIONDifferences may exist among participants from differing ethnic and racial groups in motivations to undergo biomarker testing in the setting of a preclinical AD trial.Highlights
Representative samples in AD clinical trials are vital to result in generalizability.
We assessed motivations to undergo amyloid imaging in a preclinical AD trial.
Racial and ethnic minority groups showed higher endorsement of VPAI items.
Differences were driven by perceived risk, plan/prepare, and curiosity domains.
Few observations among racial and ethnic groups changed after biomarker disclosure.
Predicting continuous amyloid PET values with CSF tau phosphorylation occupancies
Authors: Wisch Julie K. , Gordon Brian A. , Barthélemy Nicolas R. , Horie Kanta , Henson Rachel L. , He Yingxin , Flores Shaney , Benzinger Tammie L. S. , Morris John C. , Bateman Randall J. , Ances Beau M. , Schindler Suzanne E. 
Published: July 2024

AbstractINTRODUCTIONCerebrospinal fluid (CSF) tau phosphorylation at multiple sites is associated with cortical amyloid and other pathologic changes in Alzheimer's disease. These relationships can be non‐linear. We used an artificial neural network to assess the ability of 10 different CSF tau phosphorylation sites to predict continuous amyloid positron emission tomography (PET) values.METHODSCSF tau phosphorylation occupancies at 10 sites (including pT181/T181, pT217/T217, pT231/T231 and pT205/T205) were measured by mass spectrometry in 346 individuals (57 cognitively impaired, 289 cognitively unimpaired). We generated synthetic amyloid PET scans using biomarkers and evaluated their performance.RESULTSConcentration of CSF pT217/T217 had low predictive error (average error: 13%), but also a low predictive range (ceiling 63 Centiloids). CSF pT231/T231 has slightly higher error (average error: 19%) but predicted through a greater range (87 Centiloids).DISCUSSIONTradeoffs exist in biomarker selection. Some phosphorylation sites offer greater concordance with amyloid PET at lower levels, while others perform better over a greater range.Highlights
Novel pTau isoforms can predict cortical amyloid burden.
pT217/T217 accurately predicts cortical amyloid burden in low‐amyloid individuals.
Traditional CSF biomarkers correspond with higher levels of amyloid.
A Modular Dual‐Catalytic Aryl‐Chlorination of Alkenes
Authors: Li Bo , Bunescu Ala , Drazen Daniel , Rolph Katherine , Michalland Jean , Gaunt Matthew J. 
Published: July 2024

AbstractAlkyl chlorides are a class of versatile building blocks widely used to generate C(sp3)‐rich scaffolds through transformation such as nucleophilic substitution, radical addition reactions and metal‐catalyzed cross‐coupling processes. Despite their utility in the synthesis of high‐value functional molecules, distinct methods for the preparation of alkyl chlorides are underrepresented. Here, we report a visible‐light‐mediated dual catalysis strategy for the modular synthesis of highly functionalized and structurally diverse arylated chloroalkanes via the coupling of diaryliodonium salts, alkenes and potassium chloride. A distinctive aspect of this transformation is a ligand‐design‐driven approach for the development of a copper(II)‐based atom‐transfer catalyst that enables the aryl‐chlorination of electron‐poor alkenes, complementing its iron(III)‐based counterpart that accommodates non‐activated aliphatic alkenes and styrene derivatives. The complementarity of the two dual catalytic systems allows the efficient aryl‐chlorination of alkenes bearing different stereo‐electronic properties and a broad range of functional groups, maximizing the structural diversity of the 1‐aryl, 2‐chloroalkane products.
Enzymmaschinerie für bakteriellen Glucosidmetabolismus über einen konservierten nicht‐hydrolytischen Abbauweg
Authors: Kastner Klara , Bitter Johannes , Pfeiffer Martin , Grininger Christoph , Oberdorfer Gustav , Pavkov‐Keller Tea , Weber Hansjörg , Nidetzky Bernd 
Published: July 2024

AbstractFlexible Substrataufnahme aus Nährstoffreservoirs ist für Mikroorganismen entscheidend, um sich in kompetitiven natürlichen Umgebungen durchzusetzen. Zur Aufnahme von Glucose aus verschiedenen Glucosid‐ und Disaccharid‐Substraten haben viele frei‐ und symbiotisch lebende Bakterien, neben der Hydrolyse, einen nicht‐hydrolytischen Stoffwechselweg entwickelt. Dieser besteht aus vier biochemischen Schritten und wird von einem distinkten Genlocus (glycoside utilization locus, GUL) codiert. Mechanistisch integriert der Stoffwechselweg die Oxidation und Reduktion am Glucosyl/Glucose‐C3 mit der eliminativen Spaltung der glycosidischen Bindung und der Addition von Wasser an das Eliminationsprodukt in zwei aufeinanderfolgenden, von Lyasen katalysierten Reaktionen. In dieser Studie zeigen wir, basierend auf der Untersuchung von Enzymen des Pflanzenpathogens Agrobacterium tumefaciens, ein konserviertes Aktivitätszentrum in beiden Lyasen, welches um ein zentrales Mn2+ Metallion angeordnet ist. Weiters identifizieren wir die strukturellen Voraussetzungen für die spezifische Katalyse der 3‐Ketoglucosid Eliminierung zu 2‐Hydroxy‐3‐ketoglycal und der Hydratisierung des Glycal zu 3‐Ketoglucose. Die Erweiterung unserer Suche nach GUL‐codierten putativen Lyasen auf das menschliche darmkommensale Bakterium Bacteroides thetaiotaomicron führte uns zur Entdeckung eines Ca2+‐koordinierten Aktivitätszentrums in einem Glycosidase‐ähnlichen Protein. Das Enzym katalysiert die eliminative Spaltung von 3‐Ketoglucosiden entgegengesetzter (α) anomerer Konfiguration im Vergleich zu den von der A. tumefaciens Lyase präferierten Substraten (β). Strukturelle und biochemische Vergleiche zeigen die molekular‐mechanistische Basis der Stereokomplementarität der beiden 3‐Ketoglucosid Lyasen. Unsere Ergebnisse identifizieren ein grundlegendes Set von GUL‐codierten Lyasen für den Glucosidmetabolismus und erlauben es, der Gendiversität von GULs in der Domäne von Bakterien physiologische Bedeutung zuzuschreiben.
Facilitating Formate Selectivity via Optimizing eg* Band Broadening in NiMn Hydroxides for Ethylene Glycol Electro‐Oxidation
Authors: Wang Zhen , Li Junhua , Zhang Qi , Wu Chao , Meng Haoyan , Tang Ying , Zou Anqi , Zhang Yiming , Ma Rui , Lv Xiang , Yu Zhigen , Xi Shibo , Xue Junmin , Wang Xiaopeng , Wu Jiagang 
Published: July 2024

AbstractEthylene glycol electro‐oxidation reaction (EGOR) on nickel‐based hydroxides (Ni(OH)2) represents a promising strategy for generating value‐added chemicals, i.e. formate and glycolate, and coupling water‐electrolytic hydrogen production. The high product selectivity was one of the most significant area of polyols electro‐oxidation process. Yet, developing Ni(OH)2‐based EGOR electrocatalyst with highly selective product remains a challenge due to the unclear cognition about the EGOR mechanism. Herein, Mn‐doped Ni(OH)2 catalysts were utilized to investigate the EGOR mechanism. Experimental and calculation results reveal that the electronic states of eg* band play an important role in the catalytic performance and the product selectivity for EGOR. Broadening the eg* band could effectively enhance the adsorption capacity of glyoxal intermediates. On the other hand, this enhanced adsorption could lead to reduced side reactions associated with glycolate formation, simultaneously promoting the cleavage of C−C bonds. Consequently, the selectivity for formate was notably augmented by these enhancements. This work offers new insights into the regulation of catalyst electronic states for improving polyol electrocatalytic activity and product selectivity.