bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chemical Functionalization Meets Enhanced Electrical Conductivity in Iron Oxide Nanoparticles
Authors: Singh Neha , Pritam Anurag , Fransson Jonas , Mondal Prakash Chandra 
Published: January 2025

AbstractAn excellent combination of either oxides or metallic nanoparticles (NPs) and functional π‐electron rich conjugated molecules can originate a variety of intriguing phenomena convenient for technological applications. Functional π‐conjugated aromatic molecules can hold the potential to control the size, shape, morphology, and optoelectronic properties of nanoparticles through the formation of covalent interfaces. Interfacial charge transfer at the nanoparticles−molecules interfaces plays vital roles in modulating photophysical and electrical conductivity properties, which found enormous applications in catalysis, electrical, and magnetism. This work illustrates iron oxide nanoparticles (Fe3O4 NPs) capped with in situ generated aryl radicals for tuning electrical properties. Organic molecules with different functional groups are covalently attached to the surface of Fe3O4 NPs through radical formation. An electrical insulating pristine Fe3O4 NPs turns into semiconductor behavior upon aryl radical functionalization, which is due to the synergistic and efficient intermolecular charge transfer between Fe3O4 NPs of mixed valence metal ions (Fe2+, a d6 electronic system, and Fe3+, a d5 electronic system) and π‐electron rich aromatic molecules (donor–acceptor interactions). A theoretical framework strongly supports the experimental findings. These findings on tuning the electrical conductivity of nanoparticles using a small molecule can provide a promising avenue for a wide range of electronic applications.
Incorporating Bone‐Derived ECM into Macroporous Microribbon Scaffolds Accelerates Bone Regeneration
Authors: Villicana Cassandra , Su Ni , Yang Andrew , Tong Xinming , Lee Hung Pang , Ayushman Manish , Lee Jeehee , Tai Michelle , Kim Tayne , Yang Fan 
Published: February 2025

AbstractTissue‐derived extracellular matrix (tdECM) hydrogels serve as effective scaffolds for tissue regeneration by promoting a regenerative immune response. While most tdECM hydrogels are nanoporous and tailored for soft tissue, macroporosity is crucial for bone regeneration. Yet, there's a shortage of macroporous ECM‐based hydrogels for this purpose. The study aims to address this gap by developing a co‐spinning technique to integrate bone‐derived ECM (bECM) into gelatin‐based, macroporous microribbon (µRB) scaffolds. The effect of varying doses of bECM on scaffold properties was characterized. In vitro studies revealed 15% bECM as optimal for promoting MSC osteogenesis and macrophage (Mφ) polarization. When implanted in a mouse critical‐sized cranial bone defect model, 15% bECM with tricalcium phosphate (TCP) microparticles significantly accelerated bone regeneration and vascularization, filling over 55% of the void by week 2. Increasing bECM to 25% enhanced mesenchymal stem cell (MSC) recruitment and decreased M1 Mφ polarization but reduced overall bone formation and vascularization. The findings demonstrate co‐spun gelatin/bECM hydrogels as promising macroporous scaffolds for robust endogenous bone regeneration, without the need for exogenous cells or growth factors. While this study focused on bone regeneration, this platform holds the potential for incorporating various tdECM into macroporous scaffolds for diverse tissue regeneration applications.
Metal‐Free, Selective Ortho‐Deuteration of N‐Heterocyclic Oxides
Authors: Montoli Arianna , Dimasi Alessandro , Citarella Andrea , Ronchi Paolo , Passarella Daniele , Fasano Valerio 
Published: February 2025

AbstractReplacing hydrogen with deuterium raises the activation energy for C−D bond cleavage. This approach has gained attention in drug design, especially to protect the ortho‐position of pyridines, which are susceptible to enzymatic oxidation. Until now, direct hydrogen isotope exchange has been largely restricted to the use of reactive organolithium reagents or metal‐catalysed deuteration methods. In this work, we present a metal‐free, selective ortho‐deuteration of N‐heterocycles starting from their N‐oxides, proceeding at room temperature in just 5 minutes. This method achieves high deuterium incorporation across a broad range of N‐heterocycles, including bioactive compounds. Experimental and computational studies have elucidated the mechanism of the reaction, showing that regioselectivity is driven by a successful increase in acidity at the ortho‐position, enabling deprotonation by the in‐situ generated dimsyl anion.
Lactylation of HDAC1 Confers Resistance to Ferroptosis in Colorectal Cancer
Authors: Yang Zhou , Su Wei , Zhang Qinglin , Niu Lili , Feng Baijie , Zhang Yu , Huang Feng , He Jiaxin , Zhou Qinyao , Zhou Xin , Ma Longjun , Zhou Jingwan , Wang Yuanrong , Xiong Wenjing , Xiang Jun , Hu Zhilin , Zhan Qiang , Yao Bing 
Published: January 2025

AbstractColorectal cancer (CRC) is highly resistant to ferroptosis, which hinders the application of anti‐ferroptosis therapy. Through drug screening, it is found that histone deacetylase inhibitor (HDACi) significantly sensitized CRC to ferroptosis. The combination of HDACi and ferroptosis inducers synergically suppresses CRC growth both in vivo and in vitro. Mechanically, HDACi reduces ferroptosis suppressor protein (FSP1) by promoting its mRNA degradation. Specifically, it is confirmed that HDACi specifically targets HDAC1 and promotes the H3K27ac modification of fat mass‐ and obesity‐associated gene (FTO) and AlkB Homolog 5, RNA Demethylase (ALKBH5), which results in significant activation of FTO and ALKBH5. The activation of FTO and ALKBH5 reduces N6‐methyladenosine (m6A) modification on FSP1 mRNA, leading to its degradation. Crucially, lactylation of HDAC1K412 is essential for ferroptosis regulation. Both Vorinostat (SAHA) and Trichostatin A (TSA) notably diminish HDAC1K412 lactylation in comparison to other HDAC1 inhibitors, exhibiting a consistent trend of increasing susceptibility to ferroptosis. In conclusion, the research reveals that HDACi decreases HDAC1K412 lactylation to sensitize CRC to ferroptosis and that the combination of HDACi and ferroptosis inducers can be a promising therapeutic strategy for CRC.
On‐Demand Sintering of Gold Nanoparticles via Controlled Removal of o‐Nitrobenzyl Thiol Ligands Under Record‐Low Power for Conductive Patterns
Authors: Im Jisun , Heaton Charles , Putri Nur R. E. , Liu Changxu , Usuba Junichi , Butler Kevin , Fay Michael , Han Grace G. D. , Hooshmand Helia , Thompson Adam , Wildman Ricky , Hague Richard , Turyanska Lyudmila , Tuck Christopher 
Published: January 2025

AbstractMetal nanoparticles‐based nanoinks have shown potential for fabricating metallic components essential to the realization of innovative 3D‐printed electronic devices. However, fabricating metallic patterns on flexible, heat‐sensitive substrates remains challenging due to high temperature and high energy sources, such as intense pulsed light (IPL), involved in the sintering process. Here an efficient sintering method is presented using ultralow power UV by leveraging the photocleavable ligand, o‐nitrobenzyl thiol (NT), – functionalized gold nanoparticles (AuNPs). The controlled removal of NT ligands upon UV irradiation enhances light absorption by reducing the filling factor of voids in the printed layer, increasing the layer temperature, and facilitating further ligand desorption. This positive feedback mechanism accelerates nanoparticle sintering at several orders of magnitude lower energy than IPL, achieving an electrical conductivity of 7.0 × 106 S m−1. This nanoink promises the parallel printing of multimaterial components through ultralow power photonic sintering for fabricating multifunctional 3D‐printed electronic devices.
Homospermidine synthase evolution and the origin(s) of pyrrolizidine alkaloids in Apocynaceae
Authors: Smith Chelsea R. , Kaltenegger Elisabeth , Teisher Jordan , Moore Abigail J. , Straub Shannon C. K. , Livshultz Tatyana 
Published: January 2025

AbstractPremiseEnzymes that are encoded by paralogous genes and produce identical specialized metabolites in distantly related plant lineages are strong evidence of parallel phenotypic evolution. Inference of phenotypic homology for metabolites produced by orthologous genes is less straightforward, since orthologs may be recruited in parallel into novel pathways. In prior research on pyrrolizidine alkaloids (PAs), specialized metabolites of Apocynaceae, the evolution of homospermidine synthase (HSS), an enzyme of PA biosynthesis, was reconstructed and a single origin of PAs inferred because HSS enzymes of all known PA‐producing Apocynaceae species are orthologous and descended from an ancestral enzyme with the motif (VXXXD) of an optimized HSS.MethodsWe increased sampling, tested the effect of amino acid motif on HSS function, revisited motif evolution, and tested for selection to infer evolution of HSS function and its correlation with phenotype.ResultsSome evidence supports a single origin of PAs: an IXXXD HSS‐like gene, similar in function to VXXXD HSS, evolved in the shared ancestor of all PA‐producing species; loss of HSS function occurred multiple times via pseudogenization and perhaps via evolution of an IXXXN motif. Other evidence indicates multiple origins: the VXXXD motif, highly correlated with the PA phenotype, evolved two or four times independently; the ancestral IXXXD gene was not under positive selection, while some VXXXD genes were; and substitutions at sites experiencing positive selection occurred on multiple branches in the HSS‐like gene tree.ConclusionsThe complexity of the genotype‐function‐phenotype map confounds the inference of PA homology from HSS‐like gene evolution in Apocynaceae.
A ZnO‐based Catalytic System for the Synthesis of Hydrogen Peroxide from Air
Authors: Wang Lan , Fang Chunyao , Xu Boran , Yu Yunlong , Liu Youmei , Fu Xianbiao , Cao Ang , Sun Qiangqiang , Zhou Shaobing 
Published: February 2025

AbstractHydrogen peroxide (H2O2) has a wide range of applications as an eco‐friendly and sustainable oxidant. However, the clean, efficient and convenient synthesis of this compound remains challenging. This work demonstrates a rationally designed electron‐self‐supplied catalytic system capable of generating H2O2 from water and atmospheric oxygen without extra energy input. This catalytic system is made of a ZnO coating containing oxygen vacancies and a Zn substrate. The ZnO catalyst layer obtains electrons from the Zn substrate to synthesize H2O2. The H2O2 concentration produced by this catalytic system is up to 17.9 mM without any secondary processing. This remarkably high concentration is attributed to the formation of a liquid film on the hydrophilic ZnO surface that promotes the oxygen reduction reaction by accelerating the transfer of oxygen from the ambient air to the catalyst surface. By integrating with atmospheric fog collection, this system can continuously collect H2O2 directly from the air.
Chemistry as a Catalyst for Transforming the Health and Wealth of South Africa
Authors: Veale Clinton G. L. , Woodland John G. , Wicht Kathryn J. , Chibale Kelly 
Published: January 2025

AbstractSouth Africa's rich natural resources remain a key driver of its chemical industrialisation but are tainted and constrained by its complex colonial history. Thirty years since the advent of democracy in South Africa, deep sociopolitical inequalities are amplified by an intolerable infectious disease burden amongst disadvantaged communities. In that respect, South Africa shares challenges with many other nations in the Global South; there are limited opportunities for the economic development and growth needed to uplift all strata of society. This Viewpoint examines the role of the chemical sciences in South Africa's unique history and the current state of its academic and industrial sectors, with a focus on the intersection of chemistry, healthcare and biomedical research. We argue that the opportunities offered through chemistry research and development, including local manufacturing, should be exploited and that scientific advancements should be tailored to and integrated with the socioeconomic realities of South Africa for an effective and multidisciplinary approach to improving healthcare outcomes. This Viewpoint aims to inspire a renewed focus on the pivotal role of chemical scientists and their broader societal contributions to combating the country's infectious disease burden and shaping a healthier future for South Africa.
Photoacids and Photobases: Applications in Functional Dynamic Systems
Authors: Yucknovsky Anna , Amdursky Nadav 
Published: January 2025

AbstractBrønsted photoacids and photobases are a unique class of molecules that undergo a major change in their pKa values between their ground and excited states, resulting in donating or accepting a proton, respectively, but only after light excitation. This property of photoacids/photobases makes them an attractive tool for light‐gating various dynamic processes. Here, we review the use of this property to manipulate functional dynamic systems with light. We discuss how a proton transfer event that can happen upon light excitation from a photoacid to a chemical moiety of a certain system or, vice versa, from the system to a photobase, can result in a shift in the equilibrium of the system, resulting in some dynamicity. We detail various systems, including self‐assembly processes of nanostructures, self‐propulsion of droplets, catalysis for hydrogen evolution or CO2 capturing, nanotechnological devices based on enzymatic processes, and changes in proton‐conducting ionophores and materials. We detail the basic guidelines for using Brønsted photoacids and photobases in a desired system and conclude with the current technological gaps in further using these molecules.
A Remarkable ParaCEST Activity Shown by a Co(II) Complex of Bis‐Dipicolinamideacetamide With One Inner Sphere Water Molecule
Authors: Rath Soumyadarshi , Kumar Panda Suvam , Chattapadhya Anupriya , Goswami Chandan , Kumar Singh Akhilesh 
Published: February 2025

AbstractReaction of the BDPAA (N,N‐dimethyl pyridine‐based tri(carboxamide)) with iron tetrafluoroborate, cobalt chloride and nickel triflate separately in methanol/acetonitrile affords the complex, [Fe(BDPAA)(H2O)](BF4)2, [Co(BDPAA)(H2O)]Cl2 and [Ni(BDPAA)(H2O)](CF3SO3)2, respectively. The solid‐state structural analysis of cobalt and nickel complexes of bis‐dipicolinamideacetamide (BDPAA) ligand and the solution state paraCEST studies of all three complexes are presented. Among these complexes, only Co(II)‐BDPAA complex exhibits remarkable paraCEST activity due to exchangeable carboxamide NH2 protons, whereas the corresponding Fe complex shows very little CEST effect and Ni complex did not show CEST activity at all. Single crystal X‐ray analysis of [Co(BDPAA)(H2O)]Cl2 indicates that the Co(II) ion exhibits a seven‐coordination with N3O2 from the ligand and one inner sphere water molecule, leading to a distorted pentagonal bipyramidal (pbp) geometry. Presaturation of the picolinamide protons of the Co complex, 73 ppm distant from the bulk water signal by 25 μT pulse at 37 °C leads to an 18 % decrease in intensity of 1H NMR signals due to CEST effect. The Co‐BDPAA complex shows the best CEST effect at pH around 7.4‐7.6. The measured proton exchange rate constant (kex) values for the CEST peaks at 20 and 73 ppm were approximately 3.66×103 s−1 and 3.74×103 s−1, respectively.
Electrolyte Strategies at Extreme Temperatures for Aqueous Zinc Batteries
Authors: Liu Xingtai , Yao Jia , Xia Chao , Wang Xiaofang , Lv Lin , Zhang Jun , Wan Houzhao , Wang Hao 
Published: February 2025

AbstractThe state of aqueous zinc batteries at extreme temperature environment is an important parameter for their widespread application. However, low ionic conductivity and sluggish ionic diffusion at low temperature, and aggravated untoward reactions in the interface of electrode‐electrolyte at high temperature, seriously limit the practical application of zinc‐ion batteries. Currently, numerous zinc‐ion batteries capable of operating within a broad temperature range have been proposed. Herein, the reason of the performance decline at extreme temperature is discussed from the perspective of thermodynamics and dynamics. Then, from the additives/co‐solvents, high concentration salts, hydrogels and other aspects, the main strategies of electrolyte are introduced in detail. Finally, the possible directions to further improve the high and low temperature performance of zinc‐ion batteries are proposed. It is hoped that this review will be helpful to the design and manufacture of wide temperature zinc‐ion battery electrolyte and provide reference for the application of rechargeable zinc‐ion battery in extreme environment.
A Comparison of Medium Probability Versus High Probability Instructions to Increase Cooperation in the Context of the High Probability Instructional Sequence
Authors: Wilder David A. , Sheppard Christina , Izquierdo Franchesca , Flynn Kira 
Published: February 2025

ABSTRACTThe high‐probability instructional sequence has been shown to be effective to increase cooperation with low‐probability requests. However, for some individuals, it may be difficult to identify high‐probability instructions, and some high‐probability instructions may become less likely to evoke cooperation over time. Thus, under some circumstances medium probability instructions, or instructions which may be less likely to evoke cooperation than high‐probability instructions, may be a useful temporary alternative to increase cooperation. In the current study, we compared medium probability instructions to high probability instructions to increase cooperation among three children with autism spectrum disorder. The results showed that for two participants, the medium probability instructions improved cooperation as much as the high‐probability instructions. For a third participant, the medium probability instructions improved cooperation over baseline, but not to the level observed with the high‐probability instructions. Results are discussed in terms of the mechanisms responsible for the effects of instructional sequences.
Employing Diaryl Pyrrolone Fluorescence With Ninhydrin and Phenylacetaldehyde for Sensitive Determination of Alendronate Sodium in Bulk and Pharmaceutical Tablets: Evaluation of Method Greenness
Authors: Derayea Sayed M. , Mohammed Fatma F. 
Published: January 2025

ABSTRACTAlendronate sodium (ALN) is used to treat osteoporosis in men and women who experienced menopause. A new, sensitive, environmentally friendly, selective, and reasonably priced spectrofluorimetric technique was devised for ALN determination utilizing the reaction of the drug with ninhydrin and phenylacetaldehyde in the presence of Teorell–Stenhagen buffer (pH 7). The interaction yielded a highly luminescent diaryl pyrrolone product with strong emission at 464 nm following excitation at 390 nm. Optimization of various method parameters was performed, and a calibration curve was constructed. Linear regression statistical analysis shows a highly strong correlation (r = 0.9995). The method could determine ALN in the linear concentration range of 0.5–4.0 μg mL−1. Adopting ICH guidelines criteria, method validation was done, and the results confirmed the acceptable accuracy and precision. The LOD and LOQ values were computed as 0.13 and 0.41 μg mL−1, respectively. Application of the method for the analysis of oral tablets containing ALN alone or combined with vitamin D3 was successfully performed with no interferences from vitamin D3 or other coformulated excipients, proving excellent selectivity. Moreover, the method was evaluated for environmental greenness via three different tools confirming its acceptable greenness. Hence, the method can be successfully utilized in quality control laboratories.
Signals vs. Reality: Consumer Responses to Green Claims in Quick Commerce
Authors: Choubey Vardhan , Joshi Prasad , Chakraborty Debarun , Khare Apoorv , Appolloni Andrea 
Published: January 2025

ABSTRACTThe strengthened supply chain has made delivery fast to consumers. However, quick deliveries compromise sustainability by emitting carbon and impacting environment by rapid shipping practices. In this context, the study aimed to examine consumer perceptions of the green claims made by quick commerce companies. A model was built using signalling theory, elaboration likelihood model (ELM), agenda‐setting theory (AST) and cognitive load theory (CLT). A longitudinal study was conducted across two phases using a self‐administered questionnaire for data collection. Data were collected from 512 respondents in Phase 1 and 478 respondents in Phase 2. Initially, the study examined how signals sent to consumers affect credibility, complexity and visibility regarding green claims. It was found that signals were positively influencing credibility (CRD), visibility (VIS) and complexity (COX). Next, the study explored the relationship between these three factors and consumer responses to green claims (RCR). Results indicated that COX, VIS and CRD were positively influencing RCR. Finally, the study examined the moderating role of environmental actions taken by companies (EBC). It was found that consumers are also changing and getting more educated about green claims and greenwash. It was observed that companies' environmental actions moderated credibility and complexity, which positively influenced consumer response towards green claims during Phase 1. However, such influences were not moderated by environmental actions during Phase 2. The consumers were aware and were not affected by some actions claiming companies' green practices. Visibility was moderated during both phases by company action. Thus, if companies can show through signals that they are engaged in green practices, consumers will accept it. However, in the long run, even visibility will require fact‐checks.