bluuebunny/crossref_metadata_2025_split huggingface dataset:
One‐Step Process for the Regiodivergent Double Hydrocyanation of 1,3‐Butadiene
Authors: Long Jinguo , Wang Ting , Zhong Hongyu , Jiao Mingdong , Morandi Bill , He Lin , Cheng Gui‐Juan , Fang Xianjie 
Published: December 2024

AbstractIn industry, the two important nitrile starting materials, adiponitrile and 2‐methylglutaronitrile, are primarily manufactured through the well‐known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel‐catalyzed divergent, one‐step double hydrocyanation of 1,3‐butadiene to produce either adiponitrile or 2‐methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity‐determining step. Organometallic studies confirm the formation of well‐defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel‐catalyzed synthesis of adiponitrile and 2‐methylglutaronitrile from butadiene, and it also represents a high‐level of catalyst‐controlled regioselectivity via the fine‐tuning of ligand pocket geometry.
Decoding regulatory programs underlying placode and dermal condensate cell fate commitment during hair follicle induction via single‐cell multi‐omics analysis
Authors: Li Fang , Li Minghao , Zhang Tongtong , Sui Menghua , Khatib Hasan , Wang Xin 
Published: December 2024

AbstractUnderstanding differences in chromatin state and changes in gene regulatory landscape of placode (Pc) and dermal condensate are crucial for decoding hair follicle (HF) morphogenesis programs. To identify cell‐type‐specific chromatin accessibility patterns in the developing HF, we integrated chromatin accessibility and transcriptome profiles at single‐cell resolution during the murine HF induction stage. We applied unbiased analyses to identify seven major HF cell types and reclustered dermal (Der) and epithelium (Epi) subtypes to trace their cell fate specification. Our analysis showed that gene regulation in Der and Epi lineages is largely determined by cis‐regulatory elements that direct gene expression in response to specific developmental cues. The chromatin accessibility of Twist2, Enpp2, Dkk1, and Sox2 varied from fibroblasts (Fb) to pre‐DC lineage, while that of Edar, Lhx2, and Wnt10b varied from Epi to Pc lineage. Cell‐type‐specific enrichment of transcription factor binding motifs implicated Twist2 and Nfatc4 as key regulators in Fb to pre‐DC fate specification, and Fos, Bach1, and Klf1 in Epi to Pc niche fate specification. Additionally, alignment of cell‐type‐specific peaks to super‐enhancer databases identified key regulatory elements in both lineages. We identified and validated the critical cis‐regulatory elements in pre‐DC and Pc fate specifications through embryonic dorsal skin culture in vitro, suggesting that these elements may regulate critical genes essential for HF induction. Overall, our results provide a foundation for a comprehensive analysis of gene regulatory programs that initiate HF development, offering insights into the molecular mechanism of HF morphogenesis and clinical treatments of alopecia by skin grafts.
Photothermal Miniemulsion Polymerization by Amphiphilic Gold Nanoclusters
Authors: Yang Ning , Kang Yuetong , Liu Jiaren , Wang Jiaxi , Zan Yonghui , Zhao Xuan , Wang Xiaoyu , Li Lidong 
Published: December 2024

AbstractGold nanoclusters (AuNCs), which are approximately 2 nm in size, exhibit distinctive photophysical and catalytic properties, but their performance is often compromised by environmental factors. To mitigate these challenges, attempts have been made to incorporate AuNCs into polymer matrices to enhance their stability. Miniemulsion polymerization has proven to be an effective method for fabricating organic‐inorganic composites. Here, we present a facile photothermal‐assisted method for miniemulsion polymerization utilizing AuNCs, which serve as co‐stabilizers of the emulsion and photothermal conversion agents. By grafting tryptamine onto hydrophilic AuNCs, the amphiphilic AuNCs were spontaneously adsorbed at the styrene/water interfaces, resulting in stable nanoemulsions. Taking advantage of the photothermal properties of surface‐bounded AuNCs, rapid polymerization of styrene within the nanoemulsion was successfully initiated by external laser irradiation. The prepared nanocomposites inherited the photothermal activity of AuNCs and exhibited good photothermal stability and repeatability. This approach not only facilitates remote control of chemical reactions, but also optimizes the distribution of AuNCs within the final polymer matrix, thereby enabling the efficient synthesis of nanocomposites while exploiting the unique photofunctionality of AuNCs.
Single‐Atom Based Metal‐Organic Frameworks for Efficient C−S Cross‐Coupling
Authors: Sai Kumar Gobbilla , Kumar Deepak , Thakur Aditya , Gupta Mukul , Kumar Velpula Praveen , Lo Rabindranath , Jayaramulu Kolleboyina 
Published: December 2024

AbstractSingle‐atom‐based Metal‐Organic Frameworks (MOFs) hold great promising candidates for heterogeneous catalysis, demonstrating outstanding catalytic activity and exceptional product selectivity. This is attributed to their optimal atom utilization, high surface energy, and the presence of unsaturated coordination environments. Here in, we have developed a nickel single‐atom catalyst (SAC) featuring Ni single atoms covalently attached to defect‐engineered Zr‐oxide clusters within the stable UiO‐66 (Universitetet i Oslo) framework, synthesized via a straightforward solution impregnation method (denoted as UiO‐66/Ni now onwards). The resulting UiO‐66/Ni catalyst, with a uniform distribution of nickel single atoms, exhibits remarkable stability and demonstrates exceptional performance in C−S coupling reactions of various aryl thiols and aryl halides, yielding desired products with outstanding catalytic activity and selectivity, regardless of electron‐donating or withdrawing substituents at room temperature and maintains robust stability even after six cycles. Advanced density functional theory calculations have been exploited to clarify the mechanism of C−S cross‐coupling for examining the influence of substituents on the aromatic ring of aryl thiols through free energy profiles. The collaborative action of nickel single atoms and the defects of UiO‐66 during the oxidative addition and reductive elimination steps facilitated the formation of energetically favorable C−S cross‐coupling products. This study offers valuable insights for the development of enhanced single atom‐based hybrid catalytic systems for heterogeneous coupling reactions.
Broadband Excited YAlO3:Cr3+, Er3+ Phosphors for Enhancing the Spectral Response of GaSb Solar Cell
Authors: Tawalare P. K. , Nafdey R. A. , Tumram Priya V. , Krupadam R. J. , Moharil S. V. 
Published: December 2024

ABSTRACTWe report Er3+ emission in YAlO3 host, sensitized by Cr3+. The excitation bands of Cr3+ at 416 and 555 nm are broad and effectively cover the region 400–600 nm. The phosphor can be useful for converting 400–600 nm radiations to infrared (IR) light around 1521 nm. This property can be useful for enhancing the spectral response of some solar cells such as GaSb to wavelengths below 600 nm down to 400 nm for which the photovoltaic conversion is poor.
Anatomical etiology of bunny lines based on cadaveric dissection and ultrasonographic evaluation
Authors: Ahn Haeryun , Hu Hyewon , Kim Soo‐Bin , Lee Ji‐Hyun , Choi You‐Jin , Hu Kyung‐Seok , Shah‐Desai Sabrina , Abe Shinichi , Kim Hee‐Jin 
Published: December 2024

AbstractBunny lines are vertical and diagonal wrinkles attributed to contractions of the nasalis muscle. Common management involves botulinum toxin (BoNT) injections into wrinkles immediately below the nasal bridge. Here, we investigated the anatomical structures underneath bunny lines and their relationships with adjacent muscular structures. The area between the medial canthus and nasal dorsum was examined by ultrasonography in 13 adult volunteers (mean age, 29.4 years) and dissected in 39 cadavers. The findings consistently showed a non‐muscular area (bunny triangle) between the borders of the procerus, nasalis, orbicularis oculi (OOc), and levator labii superioris alaeque nasi (LLSAN) muscles. The size and shape of the bunny triangle vary according to the width of the procerus and nasalis muscles. The muscles neighboring the bunny lines affect the thinning of the thin skin between the medial canthus and nasal dorsum. Our results indicate that conventional BoNT injection into bunny line wrinkles is likely to target connective tissue rather than a muscle, potentially producing suboptimal results. Therefore, the BoNT injection points probably need to target the borders of the procerus, nasalis, OOc, and LLSAN muscles to be most efficient.
Norcrohalane A, an Unusual C15nor‐Halimane‐Type Diterpenoid from Croton crassifolius
Authors: Tang Qing , Tang Yu‐Jun , Wu Tian‐Yuan , Zheng Wei‐Xuan , Zhu Hui‐Hui , Situ Qian‐Yi , Ou Hui‐Lin , Li Can‐Jie , Zhang Yu‐Bo , Wang Guo‐Cai 
Published: December 2024

ABSTRACTAn unusual C15 nor‐halimane‐type diterpenoid, norcrohalane A (1), a new nor‐lasserane‐type sesquiterpenoid, norcrolasane A (2), along with four known compounds (3–6) were isolated from the roots of Croton crassifolius. Compound 1 represents the first example of a C15 nor‐halimane‐type diterpenoid, which features a rare 6/6/6 tricyclic ring system, and the A ring is aromatic. Compound 2 is a rare nor‐lasserane‐type sesquiterpenoid. Their structures and absolute configurations were established by a combination of mass spectrometry, nuclear magnetic resonance, electronic circular dichroism calculation, and single‐crystal X‐ray diffraction analyses. The anti‐neuroinflammatory activities of 1–6 were evaluated for their inhibitory effects on nitric oxide (NO) production in lipopolysaccharide‐induced BV2 cells, and compounds 1 and 2 showed moderate inhibition on NO production with IC50 values of 26.82 ± 0.61 and 17.35 ± 0.78 µM, respectively.
Experimental Spin State Determination of Iron(II) Complexes by Hirshfeld Atom Refinement
Authors: Brüx Daniel , Ebel Ben , Pelzer Niklas , Kalf Irmgard , Kleemiss Florian 
Published: December 2024

AbstractIn this study, we present the first experimental determination of the spin state of transition metal complexes by using Hirshfeld Atom Refinement. For the demonstration, the two iron(II) complexes, (NH4)2Fe(SO4)2 ⋅ 6 H2O and lFe(pic)3jCl2 ⋅ EtOH were investigated. The method involves the refinement using wavefunctions of different spin multiplicity and comparison against experimental diffraction data by means of refinement indicators and residual electron density. Our results show a clear distinction between high‐spin and low‐spin configurations, even for compounds with spin‐crossover behavior. The presented work demonstrates the potential of Hirshfeld Atom Refinement for the experimental determination of spin states in transition metal complexes.
Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide
Authors: Ogasahara Riku , Mae Miyu , Matsuura Keisuke , Yoshimura Sota , Ishimoto Takayoshi , Udagawa Taro , Harada Kazuo , Fujioka Hiroyoshi , Kamiya Mako , Asada Rio , Uchiyama Hiromasa , Tozuka Yuichi , Akai Shuji , Sawama Yoshinari 
Published: December 2024

AbstractDeuterated molecules are of growing interest because of the specific characteristics of deuterium, such as stronger C−D bonds being stronger than C−H bonds. Polyethylene glycols (PEGs) are widely utilized in scientific fields (e. g., drug discovery and material sciences) as linkers and for the improvement of various properties (solubility in water, stability, etc.) of mother compounds. Therefore, deuterated PEGs can be used as novel tools for drug discovery. Although the H/D exchange reaction (deuteration) is a powerful and straightforward method to produce deuterated compounds, the deuteration of PEGs bearing many unactivated C(sp3)−H bonds has not been developed. Herein, we report the photocatalytic deuteration of multiple sites of PEGs using tetra‐n‐butylammonium decatungstate (TBADT) and D2O as an inexpensive deuterium source. This deuteration can be adapted to PEG derivatives bearing various substituents ((hetero)aryl, benzoyl, alkyl, etc.). The deuteration efficiencies of the α‐oxy C(sp3)−H bonds at the terminal positions of the PEGs were strongly influenced by the substituents. These reactivities were elucidated by density functional theory calculations of the reaction barriers towards the formation of radical intermediates, induced by the excited state of TBADT and the PEG substrate. In addition, the applicability of deuterated PEGs to internal standard experiments and Raman spectroscopy was demonstrated.
MOF Derived Cobalt Ferrite Cubic Rod‐Like Materials for Highly Efficient Electrochemical Simultaneous Detection of Multiple Heavy Metal Ions
Authors: Guo Jieli , Ye Mengli , Xing Xiujing , Lv Yaokang , Xiong Wei , Li Hao 
Published: December 2024

AbstractA series of CoFe2O4 materials derived from metal‐organic framework were successfully constructed by the solvent‐thermal method. The morphology of a typical sample CoFe2O4‐1 was mostly in the form of a cubic rod‐like structure with a size distribution of 3.2±0.2 μm, while a small amount of the structure presented hexagonal shape with uniform size dispersion. The XPS characterization results confirmed that the CoFe2O4‐1 material contained Co3+ (Co2+/Co3+=0.98), and the redox reaction between Co2+ and Fe3+ produced more Fe2+ (Fe2+/Fe3+=1.63), leading to the production of more OV on the surface of the CoFe2O4‐1 material (OV%=0.34), thereby facilitating the efficient adsorption of the efficient adsorption of heavy metal ions (HMIs). CoFe2O4‐1/GCE as a typical electrode presented excellent performance for the detection of multiple HMIs. The results should be attributed to the good electrical conductivity and large electrochemically active surface area of CoFe2O4‐1/GCE, accelerating the transport of ions and charges in the system. Interestingly, there are interaction mechanisms between the HMIs when performing simultaneous detection, suggesting the detection of target ions can be facilitated by adding additional ions. This study provides new research insights for the development of highly sensitive electrochemical sensors for real‐time environmental monitoring.
Elucidating the High Affinity Copper(II) Complexation by the Iron Chelator Deferasirox Provides Therapeutic and Toxicity Insight
Authors: Orta Rivera Aixa M. , Landrau Correa Luis A. , Schiavone‐Chamorro Selene L. , Rankins Moriana , Pérez Otero Mariela V. , Benjamín‐Rivera Josué A. , Vega Aponte José A. , Ebenki Valerie B. , Vargas Figueroa Adriana I. , Astashkin Andrei V. , Fernández‐Vega Lauren , Tinoco Arthur D. 
Published: December 2024

AbstractTinoco A‐Team Deferasirox (Def), an orally administered iron‐chelating drug, has drawn significant interest in repurposing for anticancer application due to the elevated Fe demand by cancer cells. But there are also concerns about its severe off target health effects. Herein Cu(II) binding is studied as a potential off target interaction. The aqueous solution stability and speciation of the ternary complex Cu(Def)(pyridine) was studied by UV‐Vis and EPR spectroscopy, ESI‐mass spectrometry, and cyclic voltammetry under physiologically relevant conditions. The complex is observed to be a redox active, mononuclear Cu(II) complex in square planar geometry. UV‐Vis spectroscopy demonstrates that at pH 7.4 the complex is quite stable (ϵ337nm=10,820 M−1 cm−1) with a log K=16.65±0.1. Cu scavenging from the Cu transporters ceruloplasmin and albumin was also studied. Def does not inhibit ceruloplasmin activity but forms a ternary Cu(II) complex at the bovine serum albumin ATCUN site. Cu(Def)(py) displays potent but nonselective cytotoxicity against A549 cancer and MRC‐5 noncancer lung cells but the potency of the ternary protein complex was more moderate. This work elucidates potential Def toxicity from Cu complexation in the body but also cytotoxic synergy between the metal and chelator that informs on new drug design directions.
The Competition Between Cation‐Anion and Cation‐Triglyme Interaction in Solvate Ionic Liquids Probed by Far Infrared Spectroscopy and Molecular Dynamics Simulations
Authors: Kristin Philipp Jule , Fumino Koichi , Appelhagen Andreas , Paschek Dietmar , Ludwig Ralf 
Published: December 2024

AbstractGlyme‐based electrolyte solutions provide new concepts for developing suitable lithium‐ion batteries. The so‐called solvate ionic liquids (SILs) are promising electrolytes. They are most efficient in equimolar mixtures of lithium bis(trifluoromethanesulfonyl)imide ([Li][NTf2]) and glyme, wherein the [Li]+ cation is supposedly fully solvated by glyme molecules. Here, we performed far (FIR) and mid (MIR) infrared spectroscopy for probing the solvation and local structures around the [Li]+ ions. In particular, we studied the competition between the triglyme molecule (G3) and the salt anions for the coordination to the lithium cations with increasing [Li][NTf2] concentration. The formation of nano structures in the [Li][NTf2]:G3 mixtures is discussed in terms of contact (CIP) and solvent‐separated (SIP) ion pairs in solution. At low salt concentrations, the [Li]+ cations are solvated by two triglyme molecules resulting in SIPs only. With increasing salt concentration, [Li]+ is predominantly solvated by one triglyme molecule as [Li(triglyme)1]+ but still remains in contact to one of the four oxygen atoms of the [NTf2]− anion. Molecular dynamics (MD) simulations provide a molecular picture of the [Li][NTf2]:G3 mixtures that supports the conclusions drawn from the experimental findings.
Unraveling Phenanthrenoid Dimerization in Juncus acutus: A DFT‐guided Exploration of Radical‐Coupling Reaction Mechanisms
Authors: Coppola Federico , Cimino Paola , Rega Nadia , Zuppolini Simona , Di Fabio Giovanni , Zarrelli Armando 
Published: December 2024

Juncus acutus is a plant found near ponds and brackish marshes, producing secondary metabolites like phenanthrenoid dimers with antibacterial, antioxidant, and anti‐inflammatory activities. Despite this, little is known about the detailed mechanisms behind their dimerization reactions. In this study, we used Density Functional Theory to explore the reaction mechanisms of phenanthrene and dihydrophenanthrene species in radical coupling, both in gas‐phase and solution. The dimerization reactions, initiated by the OH radical, result in the formation of two phenanthrenoid dimers (homodimer and heterodimer). The OH radical abstracts a hydrogen atom from the hydroxyl group, leading to the formation of radicals and water. Our analysis of electronic spin density highlighted the preferred reactive sites that drive regioselective dimer formation. Furthermore, the study identifies a triplet π‐π stacked intermediate preceding the diketone formation on the singlet potential energy surface, revealing a two‐state reactivity mechanism. The diketone dimers are then converted via a water‐mediated keto‐enol tautomerization into their dienolic forms, completing the reaction pathway. This work offers insights into the complex dimerization processes of phenanthrenoids in nature, using computational methods to shed light on poorly understood molecular mechanisms in plant organisms.
Reactions of Unsymmetric Chiral Dialdehydes with Lysine: Regio‐ and Enantioselective Macrocyclization and Fluorescent Sensing
Authors: Mao Yifan , Li Yichen , Davis Stephanie , Pu Lin 
Published: December 2024

AbstractThree BINOL‐based unsymmetric chiral dialdehydes, (S)‐4, (S)‐5, and (S)‐6, each containing a salicylaldehyde moiety and an ortho‐, meta‐ or para‐substituted benzaldehyde unit, are synthesized and used to react with the enantiomers of an unsymmetric chiral diamine, lysine. These reactions represent the first examples of regioselective as well as enantioselective reactions of an unsymmetric chiral dialdehyde with an unsymmetric chiral diamine to generate unsymmetric chiral macrocycles. The addition of Zn2+ can further enhance the selectivity for the macrocycle formation. Compounds (S)‐4 and (S)‐5 are found to exhibit chemoselective and enantioselective fluorescent recognition of lysine in the presence of Zn2+.
Recent Development of DNA‐based Biohybrid Systems Driven by Light
Authors: Pastorel Zachary , Zanzi Juliette , Canac Yves , Baslé Olivier , Smietana Michael 
Published: December 2024

AbstractPhotochemistry has provided a powerful alternative to generate reactive intermediates under mild reaction conditions and photobiocatalysis is currently widely applied in organic synthesis. While enzyme‐based photocatalysis has attracted a lot of attention, light‐driven DNA‐based biohybrid systems are also increasingly being applied to a large variety of applications from molecular imaging to enantioselective catalysis, and other fields such as DNA‐encoded libraries (DELs). This review gives insights into these research fields by classifying the existing light‐driven DNA‐based biohybrid systems developed to date.
Preparation and Physicochemical Properties of Inorganic Solidified Foam for Forest Fire
Authors: You Bo , Zeng Lei , Shi Yu , Yang Ming , Gao Ke , Gong Zhe , Xu Meifeng 
Published: December 2024

ABSTRACTTo optimize the performance of inorganic solidified foam and apply it effectively in forest fire fighting, three different ionic surfactants were combined with four viscosity‐increasing foam stabilizers. Then, the ratio of inorganic solidified foam was changed to investigate the effects of four factors, namely, water–binder ratio, quick‐setting agent dosing, fly ash dosing, and foam dosing, on the foaming multiple and stability of the inorganic solidified foam. Finally, the fluidity and adhesion ability of the inorganic solidified foam were tested with different quick‐setting agent dosages and foam dosages, and the optimal working condition range of the inorganic solidified foam was determined based on the test results. The results showed that when SDS:APG = 7:1, the foaming multiples of the foam were higher and it could reach 52.5 times when the surfactant content in the solution was 1.2 wt%; among the four viscosity‐increasing stabilizers, the stabilizing effect of xanthan gum was the best. The inorganic solidified foam exhibits an extended foaming time when utilizing a water–binder ratio of 0.45 and a fly ash dosage of 0.5. To ensure optimal mobility and a specific adhesion thickness, it is recommended to maintain a foam dosage of 6 V or higher, with mobility falling within the 11–13 range. The preferred ratio for creating inorganic solidified foam involves a water–binder ratio of 0.45, a 0.6 wt% dosage of accelerating agent, a 0.5 fly ash content, and a foam mixing of 7 V.