bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stereospecific 3‐Aza‐Cope Rearrangement Interrupted Asymmetric Allylic Substitution‐Isomerization
Authors: Zhuang Hong‐Feng , Gu Jun , Ye Zhiwen , He Ying 
Published: October 2024

AbstractTransition‐metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well‐established. However, the asymmetric allylic arylation of acyclic internal alkenes with aryl nucleophiles remains challenging and underdeveloped. Herein we report a stereospecific 3‐aza‐Cope rearrangement interrupted asymmetric allylic substitution‐isomerization (Int‐AASI) that enables asymmetric allylic arylation. By means of this stepwise strategy, both enantioenriched allylic arylation products and axially chiral alkenes could be readily obtained in high enantioselectivities. Experimental studies support a mechanism involving a cascade of asymmetric allylic amination, stereospecific 3‐aza‐Cope rearrangement and alkene isomerization. Density functional theory studies detailed the reasons of achieving the high chemoselectivity, regioselectivity, stereoselectivity and stereospecificity, respectively.
Modulating the Anticancer Activity of Square‐Planar Platinum (II) Complex by Its Chelated Diphosphine
Authors: Li Ying , Hou Zhenguo , Xiao Zhiyin , Lu Chunxin , Jin Jing , He Yi , Jin Jia , Suntharalingam Kogularamanan 
Published: October 2024

ABSTRACTThis work reports the preparations and anticancer activities of a set of platinum (II) complexes. Two types of bidentate ligands, azadiphosphine (PNP) and diphosphine (PP), were applied to afford different kinds of platinum centers, the homoleptic complexes, [Pt (PNP)2]2+ (1 and 2) and [Pt (PP)2]2+ (4), and the hybrid complex, [Pt (PNP)(PP)]2+ (3). All these complexes are characterized by various analytical techniques, and their structures were validated using single‐crystal X‐ray diffraction analysis. Notably, the stability of the complexes 1–4 is differentiated both in phosphate‐buffered saline (PBS) and in the culture media (RPMI‐1640), relative to the type of coordinated diphosphine ligands, specifically, the more PNP ligands, the less stability. The bite angles of P‐Pt‐P bonds in 1–4 would be reliant on their stability, so that complexes 1 and 2 with small bite angles tend to be labile. A mechanistic understanding on the decomposition of 2 is proposed with the aid of mass analysis. As a result, their anticancer activities should be also associated with their stability so that the chelated ligands, with more PNP ligands, lead to more cytotoxicity. Mechanistically, the poisonous platinum (II) derivatives of complex 2 should interact with the nucleus DNA, whereas the intact complex 4 is not traceable, confirming from a γ‐H2AX‐related immunofluorescence staining kit. Additionally, complex 2 exhibits severe toxicity toward several cancer cells as well as a normal cell. Furthermore, complex 2 has inhibited the formation and viability of three‐dimensional T24 mammospheres, reminding it of a promising candidate for anticancer treatments. Overall, the present work provides a way for the systematic investigation to elucidate how a bidentate diphosphine ligand modulates the stability and the anticancer activities of the corresponding square‐planner platinum (II) complex.
Preparation of internally‐plasticized poly(vinyl chloride) by grafting hyperbranched cardanol epoxy polyglycerol
Authors: You Zeyu , Nie Xiaoan , Yu Min , Fu Renli , Chen Jie 
Published: October 2024

AbstractA novel epoxy plasticizer (HCEP) with a hyperbranched polyglycerol structure was synthesized using reduced glycerol and cashew phenol as raw materials. Then it was grafted onto poly(vinyl chloride) (PVC) through click reaction to form self‐plasticized PVC. The structure of the product was characterized with various methods. The effects of the degree of internal plasticizer substitution on the properties of PVC were tested through dynamic mechanical, mechanical property, and thermogravimetric analyses. The amorphous dendritic structure of HCEP effectively enhances the free volume of grafted PVC, leading to a reduction in the glass transition temperature and a significant enhancement in flexibility at room temperature. The maximum elongation at break is 289.89%. The grafting of plasticizers onto PVC avoids the leaching of plasticizers during usage, providing a viable solution for reducing reliance on phthalate‐based plasticizers.
Diffusion of Responsibility for Actions With Advice
Authors: Cooper Dylan A. 
Published: October 2024

ABSTRACTDiffusion of responsibility is typically defined as the effect by which people feel less responsible for outcomes of their actions when they act as a member of a group than when they act individually. The research reported here extends the concept of diffusion of responsibility to contexts in which the actor has received advice. Responsibility when using advice and when acting contrary to advice are compared to each other, as well as to responsibility when acting alone or as part of a group. To provide a more complete picture, this research consolidates disparate concepts from previous work on diffusion of responsibility, including felt, judged, and anticipated responsibility assessments; distributive and case‐based models of responsibility; and positive and negative outcomes. Across three experiments, using advice conveyed less responsibility than either acting alone or acting contrary to advice, with greater use of advice further reducing responsibility. The magnitude of diffusion was influenced by the task outcome valence in ways consistent with self‐serving bias when acting alone and other‐serving bias when using advice. Diffusion was greater with distributive than case‐based responsibility models. The results were generally consistent across felt, judged, and anticipated responsibility, as well as with choice and judgment tasks. Implications and future research possibilities are discussed.
Quantitative Susceptibility Mapping Values Quantification in Deep Gray Matter Structures for Relapsing‐Remitting Multiple Sclerosis: A Systematic Review and Meta‐Analysis
Authors: Mohammadi Sana , Ghaderi Sadegh , Fatehi Farzad 
Published: October 2024

ABSTRACTBackground/ObjectivesThis systematic review and meta‐analysis aimed to investigate the role of magnetic susceptibility (χ) in deep gray matter (DGM) structures, including the putamen (PUT), globus pallidus (GP), caudate nucleus (CN), and thalamus, in the most common types of multiple sclerosis (MS) and relapsing‐remitting MS (RRMS), using quantitative susceptibility mapping (QSM).MethodsThe literature was systematically reviewed up to November 2023, adhering to PRISMA guidelines. This study was conducted using a random‐effects model to calculate the standardized mean difference (SMD) in QSM values between patients with RRMS and healthy controls (HCs). Publication bias and risk of bias were also assessed.ResultsNine studies involving 1074 RRMS patients with RRMS and 640 HCs were included in the meta‐analysis. The results showed significantly higher QSM (χ) values in the PUT (SMD = 0.40, 95% confidence interval [CI] = 0.22–0.59, p = .000), GP (SMD = 0.60, 95% CI = 0.50–0.70, p = .00), and CN (SMD = 0.40, 95% CI = 0.15–0.66, p = .005) of RRMS patients compared to HCs. However, there were no significant differences in the QSM values in the thalamus between patients with RRMS and HCs (SMD = −0.33, 95% CI −0.67–0.01, p = .026). Age‐ and sex‐based subgroup analysis demonstrated that younger patients (< 40 years) in the PUT, GP, and CN groups and larger male populations (> 25%) in the PUT and GP groups had more significant χ. Interestingly, thalamic QSM values were found to decrease in RRMS patients over 40 years of age and in higher male populations. Sex‐based subgroup analysis indicated higher iron levels in the PUT and GP of RRMS patients regardless of sex. QSM values were higher in certain brain regions (PUT, GP, and CN) during the early stages (disease duration < 9.6 years) of RRMS, but lower in the thalamus during the later stages (disease duration > 9.6 years) than HCs.Discussion/ConclusionQSM may serve as a biomarker for understanding χ value alterations such as iron dysregulation and its contribution to neurodegeneration in RRMS, especially in the basal ganglia nuclei including PUT, GP, and CN.
Serinc2 Drives the Progression of Cervical Cancer Through Regulating Myc Pathway
Authors: Wang Xiaoping , Jiang Chen , Li Qing 
Published: October 2024

ABSTRACTBackgroundAs one of the most common malignancies, cervical cancer (CC) seriously affects women's health. This study aimed to investigate the biological function of Serinc2 in CC.MethodsSerinc2 expression was surveyed utilizing immunohistochemistry, western blot, and qRT‐PCR. CC cell viability, invasion, proliferation, migration, and apoptosis, were detected via CCK‐8, Transwell assay, colony formation, wound healing assay, and flow cytometry. Glucose consumption, lactate production, and ATP levels were determined by the corresponding kit. The protein expression of c‐Myc, PDK1, HK2, PFKP, LDHA, Snail, Vimentin, N‐cadherin, and E‐cadherin was detected via western blot. The interaction between the promoter of PFKP and Myc was confirmed through luciferase reporter assay and Chip assay. In vivo, to evaluate the function of Serinc2 on tumor growth, a xenograft mouse model was used.ResultsIn CC tissues and cells, Serinc2 was upregulated. In CC cells, knockdown of Serinc2 suppressed cell invasion, proliferation, migration, decreased the expression of Snail, Vimentin, N‐cadherin, HK2, PFKP, LDHA, and PDK1, increased E‐cadherin expression, reduced glucose consumption and the production of lactate and ATP, and induced cell apoptosis; Serinc2 overexpression led to the opposite results. Mechanically, Serinc2 promoted Myc expression, and Myc induced PFKP expression. Furthermore, overexpressed Myc abolished the inhibitive influences of Serinc2 knockdown on the malignant behaviors of CC cells. Additionally, knockdown of Serinc2 inhibited tumor growth and reduced the protein expression of c‐Myc, PFKP, LDHA, and PDK1 in vivo.ConclusionsKnockdown of Serinc2 inhibited the malignant progression of CC, which was achieved via Myc pathway. Our study provides novel insight into CC pathogenesis.
Involvement of Cholinergic and Cyclooxygenase Pathways in the Diuretic Effects of Rosmarinic Acid
Authors: Felício Macarini Anelise , Bolda Mariano Luísa Nathalia , de Cássia Vilhena da Silva Rita , Corrêa Rogério , de Souza Priscila 
Published: October 2024

AbstractRosmarinic acid (RA) is a natural antioxidant known for its diverse biological activities. Although its diuretic activity has been previously established, the mode of action remained unclear. To investigate this, we examined the diuretic activity of RA alone and in combination with hydrochlorothiazide (HCTZ), amiloride (AML), atropine (ATR), and indomethacin (INDO) to see if any of these drugs could interfere with RA's activity in an 8 hour acute diuresis animal model. We observed that RA increases urine excretion and may have a synergistic effect in the HCTZ+RA group, with a potassium‐sparing capacity. In the AML+RA group, we also noted increased urine excretion while sodium and potassium excretion decreased. ATR and INDO prevented RA from increasing urine excretion, suggesting a potential interaction with muscarinic receptors or a role in promoting prostaglandin production. Additionally, molecular docking analysis indicated possible interactions with key receptors involved in increased diuresis or free‐electrolyte water excretion.
Synthesis and characterization of hybrid gold‐coated cereal particles from sorghum bran flour and wheat bran flour
Authors: Norton Amie E. , Kim Min Jung , Peiris Kamaranga H. S. , Cox Sarah , Tilley Michael , Smolensky Dmitriy , Bean Scott R. 
Published: October 2024

AbstractBackground and ObjectivesThis study investigated the effect of using different phenolic‐containing grain brans on nanoparticle properties.FindingsThis study successfully synthesized nanoparticles from bran flour isolated from three different sources: sorghum (Sumac and Burgundy) and hard red winter wheat (cv. 1863). The phenolic contents of the three brans were measured as 33.40, 4.98, and 1.59 mg GAE/g, respectively. NPs synthesized from the bran flour had phenolic content measuring 6.41 (sorghum‐Sumac bran), 5.31 (sorghum‐Burgundy bran), and 1.15 mg GAE/g (wheat bran). Adding gold to the NPs decreased phenolic content in all three cases: 2.50 (sorghum‐Sumac bran), 1.80 (sorghum‐Burgundy bran), and 0.30 (wheat‐bran) mg GAE/g. Thus, the synthesis had an impact on the phenolic content. The sizes of the particles were measured using dynamic light scattering: 159 (sorghum‐Sumac), 78 (sorghum‐Burgundy), and 117 (wheat) nm, respectively. After gold was added, the sizes of the particles changed to 113 (sorghum‐Sumac), 115 (sorghum‐Burgundy), and 94 (wheat) nm, respectively.ConclusionsCereal bran is an eco‐friendly source of biopolymers for producing nanoparticles. With its high phenolic content, sorghum bran is ideal for making nanoparticles with various applications. Wheat and sorghum bran is a mill by‐product that can be used to synthesize nanoparticles, increasing the value of these agricultural products.Novelty and SignificanceA method was established to develop gold nanoparticles from grain bran. These methods can be used to develop value‐added products across many different applications.
The Role of NiSe2 Nanosheets in Boosting the Photocatalytic H2 Generation of Ultrafine ZnCdS Nanoparticles Under Visible Light
Authors: He Gang , Zeng Qingru , Luo Wei , Liu Yimin , Wei Yuezhou , Zeng Deqian 
Published: October 2024

AbstractThe exploration for a suitable cocatalyst to substitute noble metals is crucial to establishing an efficient photocatalytic system. In this study, a facile solution‐based approach is employed to integrate sheetlike NiSe2 nanostructure as a cocatalyst onto ultrafine ZnCdS nanoparticles, with the objective of enhancing photocatalytic H2 production. Notably, the optimized 3% NiSe2/ZnCdS photocatalyst exhibits a remarkable enhancement in photocatalytic H2 evolution rate, achieving 7779 µmol g−1 h−1, representing an 8.3‐fold increase compared to ZnCdS. Furthermore, the NiSe2/ZnCdS demonstrate exceptional stability during cycling tests. The impressive photocatalytic performance can be ascribed to the presence of NiSe2 nanosheets, which facilitate photoinduced electron transfer and offer active sites for the H2 evolution reaction. In addition, a comprehensive analysis of experimental data and density functional theory (DFT) calculations elucidates a plausible mechanism for the enhanced photocatalytic performance. This study provides valuable insights into the development of noble‐metal‐free ZnCdS‐based photocatalysts, a promising candidate for efficient solar‐to‐H2 energy conversion due to their growing prominence in the field.
Recent Advances in Electronic Structure Modifications of Layered Double Hydroxide (LDH) for the Water Splitting Application
Authors: Gaur Ashish , Sharma Jatin , Lim Dong‐Ha , Lee Hae In , Han HyukSu 
Published: October 2024

AbstractElectrocatalytic water splitting is a feasible method for large‐scale hydrogen production. Recently, layered double hydroxides (LDH) have been identified as a possible candidate for accelerating the water splitting process. Nevertheless, certain structural alterations are necessary for immaculate LDH because of their weak electrocatalytic activity. These structural changes alter the local reaction environment by modulating the electronic structure of the metal center present in the LDH. This electronic structure tailoring is accomplished by a variety of processes, including heteroatom doping, single atom inclusion, cationic defect, oxygen vacancy creation, and heterostructure formation. Recently, there has been an uptick of advancement in this field, and it is necessary to summarize these developments. This review provides a concise summary of the current reports on the electronic structure manipulation of layered double hydroxide. The review begins by examining the local environmental changes of LDH resulting from the insertion of single atoms. Subsequently, we explore the charge transfer that occurs at the interface between LDH and other transition metal heterostructures. In addition, we explored the impact on the metal center near the vacancies on the basal plane of LDH. Finally, we presented a future perspective and guidance for advancing this field in electrocatalysis.
Composite Separators with Very High Garnet Content for Solid‐State Batteries
Authors: Vattappara Kevin , Finsterbusch Martin , Fattakhova‐Rohlfing Dina , Kvasha Andriy 
Published: October 2024

AbstractLithium‐metal solid‐state batteries are attractive as next generation of Li‐ion batteries due to higher safety and potentially higher energy density. To improve processability, solid‐composite separators combine advantages of inorganic and polymer separators in hybrid structure. We report a systematic approach to fabricate composite separators with high content (90–95 wt %) of ceramic Li‐ion conducting Li6.45Al0.05La3Zr1.6Ta0.4O12 (LLZO) powder embedded in a polyethylene oxide (PEO)‐LiTFSI (20 : 1) matrix and understand factors affecting their properties and performance. Separators with good mechanical flexibility and excellent thermal stability were obtained, by optimizing materials and processing parameters. It was found that PEO molecular weight strongly influences the microstructure and electrochemical properties of the separators. In optimized separator with 90 wt % of LLZO and PEO with Mw 300,000 g/mol, a total ionic conductivity of 1.4×10−5 S/cm at 60 °C was achieved. The ceramic‐rich separator showed excellent long‐term cycling stability for more than 460 cycles (1000 h) at 0.1 mA/cm2 in Li/Li symmetrical cells and achieved a critical current density of 0.25 mA/cm2. The separators also enabled initial discharge capacities of more than 160 mAh/g in full cells with Li metal anode and composite solid‐state LiNi0.6Co0.2Mn0.2O2 cathode, although rapid capacity fade was observed after 10 cycles in fully solid‐state configuration.
Performance Effects of Different Shutdown Methods on Three Electrode Materials for Electromethanogenesis
Authors: Rohbohm Nils , Lang Maren , Erben Johannes , Gemeinhardt Kurt , Patel Nitant , Ilic Ivan K. , Hafenbradl Doris , Rodrigo Quejigo Jose , Angenent Largus T. 
Published: October 2024

AbstractIndustrial applications of microbial electrochemical systems will require regular maintenance shutdowns, involving inspections and component replacements to extend the lifespan of the system. Here, we examined the impact of such shutdowns on the performance of three electrode materials (i. e., platinized titanium, graphite, and nickel) as cathodes in a microbial electrochemical system that would be used for electromethanogenesis in power‐to‐gas applications. We focused on methane (CH4) production from hydrogen (H2) and carbon dioxide (CO2) using Methanothermobacter thermautotrophicus. We showed that the platinized titanium cathode resulted in high volumetric CH4 production rates and Coulombic efficiencies. Using a graphite cathode would be more cost‐effective than using the platinized titanium cathode in microbial electrochemical systems, but showed an inferior performance. The microbial electrochemical system with the nickel cathode showed improvements compared to the graphite cathode. Additionally, this system with a nickel cathode demonstrated the fastest recovery during a shutdown experiment compared to the other two cathodes. Fluctuations in pH and nickel concentrations in the catholyte during power interruptions affected CH4 production recovery in the system with the nickel cathode. This research enhances understanding of the integration of biological and electrochemical processes in microbial electrochemical systems, providing insights into electrode selection and operating strategies for effective and sustainable CH4 production.
Metal–Salen‐Incorporated conjugated microporous polymers as robust artificial leaves for solar‐driven reduction of atmospheric CO2 with H2O
Authors: Wu Wei , Dong Zhaocen , Chen Mantao , Li Waner , Liao An , Liu Qing , Zhang Yachao , Zhou Zhixin , Zeng Chao , Gong Xuezhong , Dai Chunhui 
Published: October 2024

AbstractExploration of efficient and stable photocatalysts to mimic natural leaves for the conversion of atmospheric CO2 into hydrocarbons utilizing solar light is very important but remains a major challenge. Herein, we report the design of four novel metal–salen‐incorporated conjugated microporous polymers as robust artificial leaves for photoreduction of atmospheric CO2 with gaseous water. Owing to the rich nitrogen and oxygen moieties in the polymeric frameworks, they show a maximum CO2 adsorption capacity of 46.1 cm3 g−1 and adsorption selectivity for CO2/N2 of up to 82 at 273 K. Under air atmosphere and simulated solar light (100 mW cm−2), TEPT‐Zn shows an excellent CO yield of 304.96 μmol h−1 g−1 with a selectivity of approximately 100%, which represents one of the best results in terms of organic photocatalysts for gas‐phase CO2 photoreduction so far. Furthermore, only small degradation in the CO yield is observed even after 120‐h continuous illumination. More importantly, a good CO yield of 152.52 μmol g−1 was achieved by directly exposing the photocatalytic reaction of TEPT‐Zn in an outdoor environment for 3 h (25–28°C, 52.3 ± 7.9 mW cm−2). This work provides an avenue for the continued development of advanced polymers toward gas‐phase photoconversion of CO2 from air.
Cleavage of a Peroxide Bond via a Dual Attack by Functional Mimics of Glutathione Peroxidase
Authors: Kumar Rai Rakesh , Islam Amirul , Shankar Pati Rudra , Roy Gouriprasanna 
Published: October 2024

AbstractNonmetal‐containing peroxidase enzymes, including glutathione peroxidase (GPx), and peroxiredoxins, control cellular redox levels by catalyzing the reduction of H2O2. The remarkably higher reactivity of GPx enzyme as compared to the fully dissociated synthetic selenolate/thiolate molecule is probably due to the dual‐attack on the peroxide bond (HO1−O2H) by the enzyme; The first one is a nucleophilic attack of the selenolate/thiolate moiety to O1 atom and the second attack at the O2 atom of the peroxide bond by the acidic “parked proton” from Trp or His residue present at the enzyme's active site, leading to the facile cleavage of O−O bond. Herein, we report two synthetic compounds (1 and 2), having a selenolate (Se−) and a proton donor (imidazolium or −COOH group) moieties, which showed excellent GPx‐like activity via dual‐attack on the peroxide bond. The combined effect of selenolate moiety that donates electrons to the antibonding (σ*) orbital of O1−O2 bond and the imidazolium or carboxylic acid moiety at the side chain that forms a strong H‐bonding with the O2 atom facilitates O−O bond cleavage of H2O2 more efficiently. 1 and 2 exhibit remarkable ability in protecting Cu(I)‐complex [TpmCu(CH3CN)]+ (9) against H2O2 by acting as a sacrificial antioxidant, thereby preventing metal‐mediated ROS production.
Diels‐Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes
Authors: Jester Fabian , Kaczun Tobias , Maier Steffen , Meiners Paul , Weigold Svenja , Rominger Frank , Dreuw Andreas , Freudenberg Jan , Bunz Uwe H. F. 
Published: October 2024

AbstractWe investigated the Diels‐Alder reaction of 6,13‐bis(triisopropylsilylethynyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off‐center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring. Epoxynaphthalene adducts of 1 as well as its anthracene and tetracene congeners were deoxygenated, easily furnishing triarenobarrelenes with TIPS‐ethynyl substituents at the bridgeheads, attractive building blocks for porous solids and higher acene‐based trimers.