bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thermally Stable P‐Chiral Supramolecular Phosphines, their Self‐Assembly and Implication in Rh‐Catalyzed Asymmetric Hydrogenation
Authors: Chandanshive Amol C. , Gonnade Rajesh G. , Chikkali Samir H. 
Published: June 2024

AbstractP‐chiral supramolecular phosphine ligands are crucial for asymmetric transformations, but their synthesis is tedious. We report a one‐step synthesis of thermally stable P‐chiral supramolecular phosphines and their performance in the asymmetric hydrogenation of functionalized alkenes. A rational designing and synthesis of (R, R)‐QuinoxP* ligated palladium complex (Pd‐2) in excellent yield is reported. This Pd‐2 catalyzed a direct P−C coupling of 2,3‐dihydro‐1‐H‐phosphindole (A1)/1,2,3,4‐tetrahydrophosphindoline (A2) with 1‐(3‐iodophenyl)urea (B1)/2‐iodo /6‐hydroxy pyridine (B2) and,produced corresponding ligands L1–L3. The P−C coupling between A1 and B2 produced 6‐(2,3‐dihydro‐1H‐phosphindol‐1‐yl)pyridine‐2(1H)‐one (L2) with an excellent enantiomeric excess of up to 99 %. L2 was found to be remarkably stable even at 150 °C and did not oxidize/hydrolyze for at least 24 hours in open air. Such thermal stability and an impediment to oxidation are unprecedented. L2 self‐assembled and produced L2−C1 (Pt), L2−C2(Pd), and L2−C3(Rh) assemblies. The utility of the self‐assembled P‐chiral ligand was demonstrated in the Rh‐catalyzed asymmetric hydrogenation (AH) of functionalized olefins. The L2−C3 catalyzed AH of functionalized alkenes and delivered chiral products with excellent enantioselectivity of >99 %. A small library of 16 substrates was subjected to AH using L2−C3 to produce chiral compounds with excellent conversion and ee.
Rational Design of Highly Selective Sialyllactose‐Imprinted Nanogels
Authors: Contardi Cecilia , Mavliutova Liliia , Serra Massimo , Rubes Davide , Dorati Rossella , Vistoli Giulio , Macorano Alessio , Sellergren Börje , De Lorenzi Ersilia 
Published: June 2024

AbstractWe describe a facile method to prepare water‐compatible molecularly imprinted polymer nanogels (MIP NGs) as synthetic antibodies against target glycans. Three different phenylboronic acid (PBA) derivatives were explored as monomers for the synthesis of MIP NGs targeting either α2,6‐ or α2,3‐sialyllactose, taken as oversimplified models of cancer‐related sT and sTn antigens. Starting from commercially available 3‐acrylamidophenylboronic acid, also its 2‐substituted isomer and the 5‐acrylamido‐2‐hydroxymethyl cyclic PBA monoester derivative were initially evaluated by NMR studies. Then, a small library of MIP NGs imprinted with the α2,6‐linked template was synthesized and tested by mobility shift Affinity Capillary Electrophoresis (msACE), to rapidly assess an affinity ranking. Finally, the best monomer 2‐acrylamido PBA was selected for the synthesis of polymers targeting both sialyllactoses. The resulting MIP NGs display an affinity constant≈106 M−1 and selectivity towards imprinted glycans. This general procedure could be applied to any non‐modified carbohydrate template possessing a reducing end.
Targeted Endoperoxides Delivering Singlet Oxygen to Cancer Cell Mitochondria: Exploration of the Therapeutic Potential
Authors: Liu Ziang , Wang Lei , Sun Rensong , Wu Hao , Wang Yang , Zhang Shengli , Li Guangzhe , Shao Kun , Akkaya Engin U. 
Published: June 2024

AbstractThe clinical practice of photodynamic therapy of cancer (PDT) is mostly limited to superficial types of cancer. The major reason behind this limited applicability is the need for light in the photogeneration of ROS, and in particular singlet oxygen. In order to circumvent this major roadblock, we designed and synthesized naphthalene‐derived endoperoxides with mitochondria targeting triphenylphosphonium moieties. Here, we show that these compounds release singlet oxygen by thermal cycloreversion, and initiate cell death with IC50<10 μM in cancer cell cultures. The mouse 4T1 breast tumor model study, where the endoperoxide compound was introduced intraperitoneally, also showed highly promising results, with negligible systemic toxicity. Targeted delivery of singlet oxygen to cancer cell mitochondria could be the breakthrough needed to transform Photodynamic Therapy into a broadly applicable methodology for cancer treatment by keeping the central tenet and discarding problematic dependencies on oxygen or external light.
Electronic and Molecular Structures of a Series of Nickel Bis‐1,1‐Dithiolates
Authors: Macleod Cailean I. , Keramidas Odysseas D. , Miras Haralampos N. , Sproules Stephen 
Published: June 2024

AbstractA series of homoleptic Ni bis‐1,1‐dithiolates, [Ni(S2C2RR′)2]2− (R=CN, R′=CN, CO2Et, CONH2, Ph, Ph‐4‐Cl, Ph‐4‐OMe, Ph‐4‐NO2, Ph‐3‐CF3, Ph‐4‐CF3, Ph‐4‐CN; R=NO2, R′=H; R=R′=CO2Et) have been synthesized from the reaction of the alkali metal salt of the ligand and nickel chloride, and isolated as tetraphenylphosphonium or tetrabutylammonium salts. The complexes were characterized by X‐ray crystallography, high‐resolution mass spectrometry, and infrared (IR), nuclear magnetic resonance (NMR) and electronic absorption spectroscopies. The molecular structures show a rigidly square planar Ni(II) center linking two four‐membered chelate rings whose dimensions are constant across the series. The electronic effect of the ligand substituent is revealed in the 13C NMR and electronic spectra, and corroborated by density functional calculations. Electron withdrawing groups deshield the low‐field CS2 resonance, and the signature charge transfer band in the visible region is red‐shifted. These observables have been accurately reproduced computationally, and revealed the Ni contribution to the ground state diminishes with decreasing electron withdrawing capacity of the ligand substituent. In contrast to 1,2‐dithiolates, the redox inactivity afforded by 1,1‐dithiolates stems from the smaller chelate ring and substantially reduced sulfur content that is key to stabilizing the radical form.
Carborane Conjugates with Ibuprofen, Fenoprofen and Flurbiprofen: Synthesis, Characterization, COX Inhibition Potential and In Vitro Activity
Authors: Sonam Sonam , Jelača Sanja , Laube Markus , Schädlich Jonas , Pietzsch Jens , Maksimović‐Ivanić Danijela , Mijatović Sanja , Kaluđerović Goran N. , Hey‐Hawkins Evamarie 
Published: June 2024

AbstractThe most effective anticancer drugs currently entail substantial and formidable side effects, and resistance of tumors to chemotherapeutic agents is a further challenge. Thus, the search for new anticancer drugs as well as novel therapeutic methods is still extremely important. Non‐steroidal anti‐inflammatory drugs (NSAIDs) can inhibit COX (cyclooxygenase), overexpressed in some tumors. Carboranes are emerging as promising pharmacophores. We have therefore combined both moieties in a single molecule to design drugs with a dual mode of action and enhanced effectiveness. The NSAIDs ibuprofen, flurbiprofen, and fenoprofen were connected with 1,2‐dicarba‐closo‐dodecaborane(12) via methylene, ethylene or propylene spacers. Three sets of carborane‐NSAID conjugates were synthesized and analyzed through multinuclear (1H, 11B, and 13C) NMR spectroscopy. Conjugates with methylene spacers exhibited the most potent COX inhibition potential, particularly conjugates with flurbiprofen and fenoprofen, displaying higher selectivity towards COX‐1. Furthermore, conjugates with methylene and ethylene spacers were more efficient in suppressing the growth of human cancer cell lines than their propylene counterparts. The carborane‐flurbiprofen conjugate with an ethylene spacer was the most efficient and selective toward the COX‐2‐negative cell line HCT116. Its mode of action was basically cytostatic with minor contribution of apoptotic cell death and dominance of cells trapped in the division process.
A variational construction of Hamiltonian stationary surfaces with isolated Schoen–Wolfson conical singularities
Authors: Gaia Filippo , Orriols Gerard , Rivière Tristan 
Published: June 2024

AbstractWe construct using variational methods Hamiltonian stationary surfaces with isolated Schoen–Wolfson conical singularities. We obtain these surfaces through a convergence process reminiscent to the Ginzburg–Landau asymptotic analysis in the strongly repulsive regime introduced by Bethuel, Brezis and Hélein. We describe in particular how the prescription of Schoen–Wolfson conical singularities is related to optimal Wente constants.
FLOLSTM: Fuzzy logic‐driven optimized LSTM for improved malicious traffic detection in hypervisor environments
Authors: Kumar Anumukonda Naga Seshu , Yadav Rajesh Kumar , Raghava Nallanthighal Srinivasa 
Published: June 2024

SummaryIn the ever‐evolving realm of cloud computing, the challenge of intrusion detection has grown increasingly intricate and vital. With the proliferation of cyber‐attacks and the widespread use of virtualized environments, there is a pressing need for network security solutions that are not only innovative and robust but also easily comprehensible. These solutions must possess the ability to effectively detect malicious activities, provide visibility into network operations, adapt to changing requirements, and promptly alert stakeholders to any suspicious behavior. In this study, we introduce a groundbreaking approach known as fuzzy logic‐driven optimized long short‐term memory (LSTM)—FLOLSTM, specifically designed for hypervisor‐based environments. By integrating fuzzy logic with an optimized LSTM neural network, FLOLSTM aims to significantly enhance the detection of attack traffic within hypervisor networks by combining the interpretability and uncertainty management capabilities of fuzzy logic with the temporal pattern recognition prowess of LSTM. The research methodology involves meticulous data collection from hypervisor monitors, followed by rigorous cleaning and preprocessing to enhance data reliability. Subsequently, the preprocessed data is input into the FLOLSTM classifier to identify malicious activities. Furthermore, the performance of the LSTM is fine‐tuned using the waterwheel plant optimization (WPO) algorithm. Experimental evaluations compare the efficiency of the proposed FLOLSTM with existing techniques across various metrics including accuracy, recall, precision, F‐measure, specificity, false‐positive rate (FPR), and false‐negative rate (FNR). Overall, the FLOLSTM model represents a significant advancement in intrusion detection for cloud environments, offering a potent blend of interpretability, accuracy, and efficiency. Its superior performance underscores its capacity to enhance network security and effectively mitigate cyber threats in dynamic and virtualized settings, thereby making a substantial impact on the field of cyber security.
Tailoring Light‐Harvesting in Zn‐Porphyrin and Carbon Fullerene based Donor‐Acceptor Complex through Ethynyl‐Extended Donor π‐Conjugation
Authors: Ahmed Raka , Manna Arun K. 
Published: June 2024

AbstractOrganic photovoltaic efficiency though currently limited for practical applications, can be improved by means of various molecular‐level modifications. Herein the role of extended donor
‐conjugation through ethynyl‐bridged meso‐phenyl/pyridyl on the photoinduced charge‐transfer kinetics is studied in noncovalently bound Zn‐Porphyrin and carbon‐fullerene based donor‐acceptor complex using time‐dependent optimally tuned range‐separated hybrid combined with the kinetic rate theory in polar solvent. Noncovalent dispersive interaction is identified to primarily govern the complex stability. Ethynyl‐extended
‐conjugation results in red‐shifted donor‐localized Q‐band with substantially increased dipole oscillator strength and smaller exciton binding energy, suggesting greater light‐harvesting efficiency. However, the low‐lying charge‐transfer state below to the Q‐band is relatively less affected by the ethynyl‐extended
‐conjugation, yielding reduced driving forces for the charge‐transfer. Detailed kinetics analysis reveals similar order of charge‐transfer rate constants (~1012 s−1) for all donor‐acceptor composites studied. Importantly, enhanced light‐absorption, smaller exciton binding energy and similar charge‐transfer rates together with reduced charge‐recombination make these complexes suitable for efficient photoinduced charge‐separation. These findings will be helpful to molecularly design the advanced organic donor‐acceptor blends for energy efficient photovoltaic applications.
The Facile and Controllable Synthesis of Ultrafine Sn Nanocrystals Loaded on Carbon Black for High‐Performance Lithium Storage
Authors: Zhao Ying , Li Gaofu , Kong Xianglong , Zhao Xudong , Liu Liu , Wang Sihao , Li Guoling , Zhang Milin , Liu Zhiliang , Yang Piaoping 
Published: June 2024

AbstractSn and C nanocomposites are ideal anode materials for high‐energy and high‐power density lithium ion batteries. However, their facile and controllable synthesis for practical applications is still a critical challenge. In this work, a facile one‐step method is developed to controllably synthesize ultrafine Sn nanocrystals (< 5 nm) loaded on carbon black (Sn@C) through Na reducing SnCl4 by mechanical milling. Different from traditional up‐down mechanical milling method, this method utilizes mechanical milling to trigger bottom‐up reduction reaction of SnCl4. The in‐situ formed Sn nanocrystals directly grow on carbon black, which results in the homogeneous composite and the size control of Sn nanocrystals. The obtained Sn@C electrode is revealed to possesses large lithium diffusion coefficient, low lithiation energy barrier and stable electrochemical property during cycle, thus showing excellent lithium storage performance with a high reversible capacity (942 mAh g−1 at a current density of 100 mA g−1), distinguished rate ability (480 mAh g−1 at 8000 mA g−1) and superb cycling performance (730 mAh g−1 at 1000 mA g−1 even after 1000 cycles).
Si Single‐Atom Sites Anchored Carbon Anode Achieving the Zero‐Strain Feature and Superior Li+ Storage Performance
Authors: Liu Jieqian , Wang Fei , Mao Jian 
Published: June 2024

AbstractOvercoming the significant volume strain in silicon‐based anodes has been the focus of research for decades. The strain/stress in silicon‐based anodes is inversely proportional to their size. In this study, we design atomic Si sites to achieve the ultimate size effect, which indeed exhibits a zero‐strain feature. Compared with conventional silicon‐based anodes with alloying addition reactions, the lithium‐ion storage mechanism of atomic Si sites is solid‐solution reactions, which brings about the zero‐strain feature. Additionally, the ligand structure of atomic Si sites remains constant during cycling. This zero‐strain feature results in excellent cycling stability. Furthermore, the exposed atomic Si sites enhance the electrochemical reaction kinetics, leading to outstanding rate performance. Moreover, the anode inherits the advantages of silicon‐based anodes, including a low working voltage (~0.21 V) and high specific capacity (~2300 mAh g−1 or ~1203 mAh cm−3). This work establishes a novel pathway for designing low/zero‐strain anodes.
Graphdiyne‐Induced CoN/CoS2 Heterojunction: Boosting Efficiency for Bifunctional Oxygen Electrochemistry in Zinc‐Air Batteries
Authors: Cui Min , Yuan Yanan , Wu Yue , Che Zhongmei , Li Peixuan , Yang Xiaochen , Chen Yuqi , Hu Wei , Wang Jingui , Wang Shuai , Guo Yingshu , Wu Zexing 
Published: June 2024

AbstractThe performance of zinc‐air battery is constrained by the sluggish rate of oxygen electrode reaction, particularly under high current discharge conditions where the kinetic process of the oxygen reduction reaction (ORR) decelerates significantly. To address this challenge, we present a novel phase transition strategy that facilitates the creation of a heteroatom‐doped heterointerface (CoN/CoS2). The meticulously engineered CoN/CoS2/NC electrocatalyst displays a superior ORR half‐wave potential of 0.87 V and an OER overpotential of 320 mV at 10 mA cm−2. Experimental and computational analysis confirm that the CoN/CoS2 heterostructure optimizes local charge distribution, accelerates electron transfer, and tunes active sites for enhanced catalysis. Notably, this heterojunction improves stability by resisting corrosion and degradation under harsh alkaline conditions, thus demonstrating superior performance and longevity in a custom‐made liquid zinc‐air battery. This research provides valuable practical and theoretical foundations for designing efficient heterointerfaces in electrocatalysis applications.
Modes of governance for sustainability transitions: Conceptual definitions
Authors: Massuga Flavia , Doliveira Sérgio Luis Dias , Kuasoski Marli , Mangoni Simone Soares 
Published: June 2024

AbstractThe unsustainability of production and consumption patterns and the socio‐technical systems in the energy, mobility, water, and solid waste sectors highlights the need for sustainability transitions. However, the transition management perspective indicates that these transformations cannot be managed in the traditional hierarchical sense. Therefore, new modes of governance are required to deal with the complexity and nature of sustainability issues. This study seeks to elucidate these matters by bringing the literature on sustainability transitions, transition management, and governance modes closer to each other, generating a better understanding of governance in transitions. In addition to the theoretical discussion on the linked concepts, this study also contributes by presenting and characterizing five modes of governance that can facilitate the paths to transformation. They are participatory, collaborative, multilevel, smart, and network governance. These modes of governance differ according to the actors involved and the nature of their interactions and encompass different political processes, institutional structures, and policy content. The assumption is that the modes of governance addressed, which distance themselves from conventional approaches based on top‐down control, can favor transition initiatives that promote transformative processes toward a more resilient and sustainable society. However, the inherent embeddedness of the public service is recognized, which requires transitions in governance itself through institutional adaptations and changes in the role of actors and public officials.
Magnetocaloric Analysis of Novel Polycrystalline Sm0.5Sr0.4Nd0.1Mn1‐xTixO3(0≤x≤0.2) that Correlates Structural and Magnetic Properties
Authors: Raman Rajesh , I. B. Shameem Banu , Sankar Raman , Moovendran Kalimuthu 
Published: June 2024

AbstractThis article summarizes the impact of the Ti ion at the Mn site of polycrystalline Sm0.5Sr0.4Nd0.1MnO3 samples, exploring the correlation between the structural, microstructural, magnetic, and magnetocaloric properties through the solid‐state route. The Rietveld refinement pattern divulges that all samples are crystallized predominantly in the orthorhombic phase with the Pnma space group. Temperature‐dependent magnetic studies of Sm0.5Sr0.4Nd0.1Mn1‐xTixO3 (x=0, 0.1, 0.2) expose phase separation phenomena in the field cooling curve, where the first peak at 42 K corresponds to the antiferromagnetic charge ordering or spin orientation of spontaneous magnetization, and the second peak at 87 K, 75.91 K, and 74.28 K corresponds to the paramagnetic to ferromagnetic transition. The maximum magnetic entropy changes (ΔSM) at T=110 K are discerned to be 2.5 J Kg−1 K−1, 1.65 J Kg−1 K−1, and 1.31 J Kg−1 K−1, respectively. Normalization of ΔS values in Sm0.5Sr0.4Nd0.1Mn1‐xTixO3 (x=0, 0.1, 0.2) does not overlap the universal behavior at magnetic fields (1T ‐ 7T), confirming the existence of field‐induced second‐order magnetic transitions. The relative cooling power (RCP) values are found to be 777.96 J Kg−1, 255.28 J Kg−1, and 190.58 J Kg−1 respectively. Further, the enhancement of the working span temperature and the broadening of specific heat capacity peaks in Sm0.5Sr0.4Nd0.1Mn1‐xTixO3 (x=0.1, 0.2) samples make these materials a promising candidate to serve as operating substances in magnetic refrigeration.
Perceived general similarity and relationship satisfaction: The role of attributional confidence
Authors: Lee Ting Hin , Ng Ting Kin 
Published: June 2024

AbstractEven though many studies have examined the link between individuals' perceived general similarity to their romantic partners and their own relationship satisfaction, there are not many studies focusing on the impact of perceived general similarity reported by the partner. The present work uncovers the potential mediating roles of one's and the partner's attributional confidence in the effects of one's and the partner's perceived general similarity on relationship satisfaction. To investigate the mechanisms, two studies were conducted at individual and dyadic levels. A total of 395 individuals (51.4% female) aged 17–67 (M = 22.06, SD = 4.68) in unmarried opposite‐gender relationships were recruited in Study 1 and 227 unmarried opposite‐gender couples were employed in Study 2. Across two studies, the indirect effect of perceived general similarity on relationship satisfaction via attributional confidence was significant. In particular, the actor effects of perceived general similarity on relationship satisfaction were mediated by the actor effects of attributional confidence. Moreover, the partner effects of perceived general similarity on relationship satisfaction were mediated by partner attributional confidence (i.e., one's partner's perceived general similarity on one's relationship satisfaction via one's partner's attributional confidence). The present findings shed light on the mechanisms through which perceived general similarity fosters relationship satisfaction among opposite‐gender relationships.