bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of CTA and DNAN Using Flow Chemistry
Authors: Mittal Ankit Kumar , Prakash Gaurav , Pathak Pramod , Maiti Debabrata 
Published: August 2022

AbstractThis paper describes a flow chemistry approach for synthesising two high‐energy molecules, cyanuric triazide (CTA) and 2,4‐dinitroanisole (DNAN), and scaling them up to multi‐gram scale using an automated flow reactor system. The flow chemistry approach offers high degree of safety and easy to scale compared to conventional syntheses. The development of two processes: a. CTA via azidation of cyanuric chloride; b. DNAN via methoxylation of 2,4‐dinitrichlorobenzene (2,4‐DNCB) on an automated commercially available flow reactor system is described. High yield (>95%) was achieved in both the processes. Very short reaction times (30 seconds) were applied. The process parameters were optimized using the automated flow chemistry system. The optimized process was scaled to multi gram scale (>30 g/hr). The method can be considered fit for the safe production of CTA and DNAN at multi gram scale in laboratory.
Highly Active and Efficient Cu@SiO2 Catalyst: Enabled Nucleophilic and Electrophilic Activation of Active Methylene Compounds
Authors: Naikwadi Dhanaji R. , Bankar Balasaheb D. , Kachgunde Hanuman G. , Biradar Ankush V. 
Published: August 2022

AbstractThe utility of copper is strikingly afforded due to the variable oxidation state being widely used in various organic reactions. The copper‐catalyzed C−C bond formation with active methylene compounds are a straightforward approach with widespread uses in synthetic organic chemistry. A significantly lower amount of Cu‐supported SiO2 catalyst was synthesized through sol‐gel method. The microscopy analysis reveals the formation of spherical morphology and the uniform distribution of Cu nanoparticles of 2.5 nm size. Furthermore, copper was found in Cu+2 state by XPS analysis. The NH3‐TPD analysis estimated the 0.092 mmol/g acidic sites. The synthesized multifunctional catalyst was used for gabapentin intermediates through a series of active methylene compounds through tandem organic reactions. The catalyst gave excellent conversion (99%) and selectivity (99%) of the desired product. The catalyst was found to be highly stable and recycled for six cycles without losing any activity and selectivity to the reaction product.
[Ph4P]+[Cu(CF2H)2]−: A Powerful Difluoromethylating Reagent Inspired by Mechanistic Investigation
Authors: Zhao Haiwei , Leng Xuebing B. , Zhang Wei , Shen Qilong 
Published: August 2022

AbstractThe quest of the active species in copper‐mediated difluoromethylation of aryl halides led to the discovery of a powerful difluoromethylating reagent [Ph4P]+[Cu(CF2H)2]−2. Complex2was able to difluoromethylate a variety of electrophiles including electron‐deficient and electron‐rich aryl iodides, heteroaryl iodides, activated heteroaryl bromides, chloride and aryl bromides with a directing group, as well as other electrophiles such as alkenyl iodide, benzyl bromides, allyl bromides, alkyl iodide, allyl carbonates and acid chloride. In addition, in the presence of an oxidant, complex2reacted with various lithiumnbutyl arylboronic acid pinacol esters, alkyne and heteroarene. Moreover, complex2could transmetalate the difluoromethyl reagent to other metals such as [Ph4P]+[CuCl2]−and [(DPPF)PdCl2].
Quanteninterferenz in gemischtvalenten Komplexen: Modifikation elektronischer Kopplung durch Substituenteneffekte
Authors: Harrison Daniel P. , Grotjahn Robin , Naher Masnun , Ghazvini Seyed M. B. H. , Mazzucato Daniel M. , Korb Marcus , Moggach Stephen A. , Lambert Colin , Kaupp Martin , Low Paul J. 
Published: August 2022

AbstractIn 2‐ und 5‐Position einer Phenylenbrücke eines schwach koppelnden gemischtvalenten [{Cp*(dppe)RuC≡C}2(μ‐1,3‐C6H4)]+ Komplexes hat ein OMe‐Substituent nur geringen Einfluss auf dessen Elektronenstruktur. In 4‐Position hingegen erhöht dieser die elektronische Delokalisation im Grundzustand sowie die Intensität des IVCT‐Überganges. Schwingungsfrequenzen und TDDFT‐Berechnungen (LH20t‐D3(BJ), def2‐SVP, COSMO (CH2Cl2)) an ([{Cp*(dppe)RuC≡C}2(μ‐1,3‐C6H3‐n‐OMe)]+ (n = 2, 4, 5) Modellen zeigen eine exzellente Übereinstimmung mit experimentellen Ergebnissen. Die stärkere Kopplung im Grundzustand geht auf eine veränderte Zusammensetzung des β‐HOSO zurück, verursacht durch den 4‐OMe Substituenten und dessen ortho‐ oder para‐Stellung zu jedem der Metallfragmente. Die Intensität des IVCT‐Überganges erhöht sich mit stärkerer β‐HOSO‐ und β‐LUSO‐Überlappung. Die relativen Phasen von β‐HOSO und β‐LUSO im 4‐OMe‐substituierten Komplex sind in Einklang mit den Vorhersagen über konstruktive Quanteninterferenz, basierend auf molekularen Schaltkreisregeln.
Electron‐Deficient Benzo[de]isoquinolino[1,8‐gh]quinoline Diamide π‐Electron Systems
Authors: Yu Craig P. , Yamamoto Akito , Kumagai Shohei , Takeya Jun , Okamoto Toshihiro 
Published: August 2022

AbstractSynthetically versatile electron‐deficient π‐electron systems are urgently needed for organic electronics, yet their design and synthesis are challenging due to the low reactivity from large electron affinities. In this work, we report a benzo[de]isoquinolino[1,8‐gh]quinoline diamide (BQQDA) π‐electron system. The electron‐rich condensed amide as opposed to the generally‐employed imide provides a suitable electronic feature for chemical versatility to tailor the BQQDA π‐electron system for various electronic applications. We demonstrate an effective synthetic method to furnish the target BQQDA parent structure, and highly selective functionalization can be performed on bay positions of the π‐skeleton. In addition, thionation of BQQDA can be accomplished under mild conditions. Fine‐tuning of fundamental properties and supramolecular packing motifs are achieved via chemical modifications, and the cyanated BQQDA organic semiconductor demonstrates a high air‐stable electron‐carrier mobility.
Synthesis of Atropisomeric Hydrazides by One‐Pot Sequential Enantio‐ and Diastereoselective Catalysis
Authors: Portolani Chiara , Centonze Giovanni , Luciani Sara , Pellegrini Andrea , Righi Paolo , Mazzanti Andrea , Ciogli Alessia , Sorato Andrea , Bencivenni Giorgio 
Published: August 2022

AbstractThe first catalytic enantioselective and diastereoselective synthesis of atropisomeric hydrazides was achieved using a sequential catalysis protocol. This strategy is based on a one‐pot sequence of two organocatalytic cycles featuring the enamine amination of branched aldehydes followed by nitrogen alkylation under phase‐transfer conditions. The resulting axially chiral hydrazides were obtained directly from commercially available reagents in high yields and with good stereocontrol. The permutation of organocatalysts allowed easy access to all stereoisomers, enabling a stereodivergent approach to enantioenriched atropisomeric hydrazides.
Quantum Interference in Mixed‐Valence Complexes: Tuning Electronic Coupling Through Substituent Effects
Authors: Harrison Daniel P. , Grotjahn Robin , Naher Masnun , Ghazvini Seyed M. B. H. , Mazzucato Daniel M. , Korb Marcus , Moggach Stephen A. , Lambert Colin , Kaupp Martin , Low Paul J. 
Published: August 2022

AbstractWhilst 2‐ or 5‐OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuC≡C}2(μ‐1,3‐C6H4)]+ have little influence on the electronic structure of this weakly coupled mixed‐valence complex, a 4‐OMe substituent enhances ground state electron delocalization, and increases the intensity of the IVCT transition. Vibrational frequency and TDDFT calculations (LH20t‐D3(BJ), def2‐SVP, COSMO (CH2Cl2)) on ([{Cp*(dppe)RuC≡C}2(μ‐1,3‐C6H3‐n‐OMe)]+ (n=2, 4, 5) models are in excellent agreement with the experimental results. The stronger ground state coupling is attributed to the change in composition of the β‐HOSO brought about by the 4‐OMe group, which is ortho or para to each of the metal fragments. The intensity of the IVCT transition increases with the greater overlap of the β‐HOSO and β‐LUSO, whilst the relative phases of the β‐HOSO and β‐LUSO in the 4‐OMe substituted complex are consistent with predictions of constructive quantum interference from molecular circuit rules.
Development of high‐performance partially biobased thermoset polyester using renewable building blocks from isosorbide, 1,3‐propanediol, and fumaric acid
Authors: Hofmann Mateus , Garrido Mário , Machado Marina , Correia João R , Bordado João C 
Published: August 2022

AbstractResearch on biobased thermoset resins has been overlooked when compared with the rapid progress on biobased thermoplastics. The objective of this work was to develop unsaturated polyester prepolymers based on building blocks derived from renewable raw materials, namely, biobased isosorbide, 1,3‐propanediol, and fumaric acid, with petroleum‐derived phthalic anhydride. The prepolymers developed herein behaved as low‐molecular weight macromolecules (oligoesters), with Mn varying between 1.2 and 1.5 kDa, but achieved a high bio‐content of up to 87.1 wt%. The prepolymers were incorporated into reactive diluents comprising a blend of 2‐hydroxyethyl methacrylate and styrene, formulated to be eco‐friendlier and less toxic than typical styrene‐only incorporation approach, thus resulting in resins with viscosities between 750 and 950 cP. These resins are suitable for use in various fiber‐reinforced polymer production techniques, such as manual lamination, vacuum infusion, and pultrusion, having the benefit of presenting over 50 wt% of bio‐content in some formulations. Moreover, the crosslinked polyester resins (thermosets) exhibit comparable mechanical and thermomechanical behavior to their petrochemical‐based counterparts, with modulus of elasticity and tensile strength of up to 3.9 GPa and 62.1 MPa, respectively, and glass transition temperatures of up to 106°C, making them greener alternatives for high‐performance structural applications.
The added value and differentiation among ESG investment strategies in stock markets
Authors: Meira Erick , Cunha Felipe Arias Fogliano de Souza , Orsato Renato J. , Miralles‐Quirós María Mar , Miralles‐Quirós José Luis 
Published: August 2022

AbstractEnvironmental, social, and governance (ESG) investment strategies have garnered increasing attention in stock markets worldwide. The number of related funds and their money inflow, for instance, have more than doubled over the past 3 years. Yet, one fundamental question remains unanswered in the specialized literature: has there been any added value and statistical differentiation among ESG strategies in stock markets? We contribute to this discussion by assessing a range of ESG investment strategies across the globe. Daily closing prices of ESG best practices indices are collected for the period between 2011 and 2021, along with proxies for the market portfolio and the risk‐free rate. Empirical assessments are then conducted using classic and modern portfolio metrics as well as nonparametric tests. The results indicate a considerable degree of differentiation of the governance factor in every region studied, while the environmental and social agendas have remained considerably intertwined, with their theoretical portfolios showing similar risk–return profiles and high levels of correlation. The relative performance of ESG factors across regions has also varied considerably, with most developed economies prioritizing the environmental and social agenda for investments, and the governance factor providing better risk‐adjusted returns in emerging markets and in the Unites States. Implications and an agenda for future research are further discussed.
Bias reported by family caregivers in support received when assisting patients with cancer‐related decision‐making
Authors: Dionne‐Odom J. Nicholas , Ornstein Katherine A. , Azuero Andres , Harrell Erin R. , Gazaway Shena , Watts Kristen Allen , Ejem Deborah , Bechthold Avery C. , Lee Kyungmi , Puga Frank , Miller‐Sonet Ellen , Williams Grant R. , Kent Erin E. 
Published: August 2022

AbstractBackgroundFamily caregivers play an increasing role in cancer treatment decision‐making. We examined bias reported by family caregivers in the support they and their patient received from their healthcare team when making these decisions, including associations with distress.MethodsAnalysis of 2021 national survey data of family caregivers of patients with cancer (N = 2703). Bias experienced in decision support was assessed with the item: “Have you felt that the support you and the person with cancer have received for making cancer‐related decisions by your doctor or healthcare team has been negatively affected by any of the following?” Check‐all‐that‐apply response options included: age, race, language, education, political affiliation, body weight, insurance type or lack of insurance, income, religion, sexual orientation, and gender/sex. Chi‐square and regression analyses assessed associations between bias and caregiver distress (GAD‐2, PHQ‐2).ResultsOf 2703 caregiver respondents, 47.4% (n = 1281) reported experiencing ≥1 bias(es) when receiving decision support for making cancer‐related decisions. Bias was more prevalent among younger caregivers, males, transwomen/men or gender non‐conforming caregivers, racial/ethnic minorities, and those providing care over a longer time period. The odds of having high anxiety (GAD‐2 scores ≥ 3) were 2.1 times higher for caregivers experiencing one type of bias (adjusted OR, 2.1; 95% CI, 1.6–2.8) and 4.2 times higher for caregivers experiencing ≥2 biases (adjusted OR, 4.2; 95% CI, 3.4–5.3) compared to none. Similar results were found for high depression scores (PHQ‐2 scores ≥ 3).ConclusionsNearly half of caregivers involved in their care recipients' cancer‐related decisions report bias in decision support received from the healthcare team. Experiencing bias was strongly associated with high psychological distress.
Synthesis of Interconnected Hollow Carbon Nanospheres with Controllable In Situ N‐Doping Level for Supercapacitors
Authors: Zhang Hu , Liu Yongchuan , Lin Changxin , Zhang Yining 
Published: August 2022

AbstractNitrogen‐doped hollow carbon spheres (HCSs) are regarded as ideal supercapacitors electrode materials due to their excellent electrochemical properties. However, studies of nitrogen doping at different levels based on precise structure control are rarely reported so far. Herein, we controllably prepared hollow carbon nanospheres with carbon walls connected by a hard template method and used the difference in the number of nitrogen‐containing functional groups in the precursor to control the nitrogen doping amount of carbon nanospheres. Interestingly, with the N‐doped content increasing, the specific capacitance of supercapacitors shows accordingly upward tendency by the better electrode interface environment. Compared to the control group (lower amount nitrogen‐doping), the highest N‐contained HCSs (NIHCSs‐2) shows the best electrochemical performance (256 F g−1) in supercapacitors. The excellent electrochemical behaviour of NIHCSs‐2 demonstrates that hollow carbon nanospheres with high nitrogen content have great potential in electrochemical energy storage device applications.
Surface chemistry engineering of layered oxide cathodes for sodium‐ion batteries
Authors: Li Jiayang , Hu Haiyan , Wang Jiazhao , Xiao Yao 
Published: August 2022

AbstractSodium‐ion batteries (SIBs) have attracted extensive attention to be applied in large‐scale energy storage due to their low cost and abundant storage resources. Among cathode materials for SIBs, layered oxide cathodes are considered one of the most promising candidates for practical application owing to their high theoretical capacities, simple synthesis routes, and environmental friendliness. However, poor air stability, complicated interfacial reaction, and irreversible phase translation of layered oxide cathodes pose problems for the long‐term cycle as well as rate performance. In this review, the recent achievements and progress in surface engineering chemistry strategies to improve the electrochemical performance of SIBs have been summarized including mechanical mixing, in‐situ coating methods, and designing unique interfacial structures. Moreover, inspired by previous studies, we propose an innovative concept of interface conversion reaction with bulk penetration doping integration, which is expected to deal with both interfacial and intrinsic issues synchronously through heat treatment. It could not only eliminate residual sodium compounds on the surface and improve air stability but also suppress the dissolution and the migration of transition metal and the phase transformation. The insights that came up in this review can be considered as a guide for surface engineering on layered oxide cathode for SIBs.
Image tampering detection in image forensics using earthworm‐rider optimization
Authors: Cristin Rajan , Premnath Sasi Padma , Ananth John Patrick 
Published: August 2022

SummaryThis article introduces a novel earthworm‐rider optimization algorithm (EW‐ROA), by integrating the earthworm algorithm in the rider optimization algorithm for the detection of the tampered regions optimally. Initially, the individual binary maps are generated using the image blocks of the input image are fed to five forensic tools, and then they are concatenated into a single binary map. The features are extracted from the binary map moreover they are feed to classifier for the detection of the tampered image via the deep belief neural network, which is trained using the proposed earthworm‐rider optimization algorithm. The proposed system attains a highest accuracy of 0.9402, sensitivity of 0.98, and specificity of 0.98 that shows the superiority of the proposed system in effective tampering detection.
A compact highly isolated two‐ and four‐port ultrawideband Multiple Input and Multiple Output antenna with Wireless LAN and X‐band notch characteristics based on Defected Ground Structure
Authors: Kumar Praveen , Ali Tanweer , Pai Manohara M. M. 
Published: August 2022

SummaryA novel two‐ and four‐port antenna structure are proposed to achieve improved isolation and operate in the ultrawideband (UWB) frequency range. The projected designs comprise a hybrid circular and rectangular embedded UWB antenna with a partial ground plane. The alteration of the radiating and ground planes modifies the current flow and aids in realizing a broader bandwidth. The dual‐band notches are created on UWB using slot and stubs. The U‐shape slot on the feedline neutralizes the current flow at 5.2 GHz, and a pair of symmetrical H‐shape stubs across the feedline couples the current flow from the feedline to stubs at 7.4 GHz frequency, and negligible current reaches the radiator. The dual‐band notch UWB antenna is reproduced to create two‐port and four‐port MIMO antennas with a less than quarter wavelength spacing. Using a deficient ground structure, better isolation between the interelements is achieved. The projected two‐ and four‐port design has overall physical geometry of 0.2λ × 0.4λ × 0.02λ and 0.5λ × 0.4λ × 0.02λ and provides a measured impedance bandwidth between 3.3–12.8 and 3.1–12 GHz, respectively. The distinctive feature of both antenna designs is incorporating simple and effective defective ground structures as decoupling structures in the ground plane to generate better than 25 dB isolation across the operational spectrum. The current between the interelement is suppressed via the ground plane, leading to mutual coupling reduction. In addition, complete MIMO diversity parameters and time‐domain characteristics are explored, and the findings show that the proposed designs are appropriate for wireless applications.
Versatile use of Carmofur: A comprehensive review of its chemistry and pharmacology
Authors: Islam Mohammad Mohiminul , Mirza Shama P. 
Published: August 2022

AbstractCarmofur, 1‐hexylcarbamoyl‐5‐fluorouracil (HCFU) is an antineoplastic drug, which has been in clinics in Japan since 1981 for the treatment of colorectal cancer. Subsequently, it was also introduced in China, Korea, and Finland. Besides colorectal cancer, it has also shown antitumor activity in other cancers such as breast, head and neck, pancreatic, gastrointestinal, and solid brain tumors. A prodrug of 5‐fluorouracil (5‐FU), carmofur has shown better gastrointestinal stability and superior antiproliferative activity compared to its active counterpart 5‐FU. Recently, carmofur has gained attention as an acid ceramidase inhibitor and as a potential lead compound against several noncancerous diseases such as coronavirus disease 2019, Krabbe disease, acute lung injury, Parkinson's disease, dementia, childhood ependymoma etc. Carmofur has also been reported to have antifungal, and antimicrobial properties. Nevertheless, no comprehensive review is available on this drug. Herein, we summarized the chemistry, pharmacokinetics, and pharmacology of carmofur based on the literature published between January 1976 and March 2022 as identified from PubMed and Google Scholar search engines.
Construction of 3,3'‐Bicarbazoles and Indolocarbazoles by Using Visible Light
Authors: El Ain María Alexia , Puiatti Marcelo , Budén María Eugenia 
Published: August 2022

AbstractA synthetic and mechanistic study of novel iterative double cyclization intramolecular SRN1 reactions from diarylamines bearing two aryl halide moieties was carried out. This cyclization affords symmetric and unsymmetric 3,3'‐bicarbazoles and indolocarbazoles compounds in regular to very good yields. The synthetic strategy employed for their preparation was a Buchwald‐Hartwig arylation of anilines followed by an intramolecular SRN1 reaction, in the presence of base and visible light, at room temperature. The mechanism is non‐trivial and it was studied using spectroscopy and computational calculations, employing the DFT method, with B3LYP and M06‐2X functionals and 6‐31+G*, def2SVP and def2TZVP as bases and radicals are proposed as intermediates.
Pyrazine Alkylation with Aldehydes and Haloalkanes Using N,N’‐Bis(trimethylsilyl)‐1,4‐dihydropyrazine Derivatives
Authors: Tsurugi Hayato , Matsuno Minami , Kawakami Tomomi , Mashima Kazushi 
Published: August 2022

AbstractN,N’‐Bis(trimethylsilyl)‐1,4‐dihydropyrazines are useful starting materials for synthesizing alkylpyrazines upon combination with aldehydes and tetra(n‐butyl)ammonium fluoride. Various aryl, heteroaryl, and alkyl aldehydes are utilized as sources of the alkyl substituents; reactions with electron‐rich aldehydes afford the corresponding alkylpyrazines in good yields. The overall reaction sequence was clarified by DFT calculations; in this reaction, activation of the N‐trimethylsilyl moiety by fluoride, forming the electron‐rich silicate intermediate Int‐1, is the key step for the subsequent C−C bond formation with aldehydes, and the following 1,3‐proton transfer from Int‐3 to Int‐4 is the rate‐determining step. In addition, treatment of N,N’‐bis(trimethylsilyl)‐2,5‐dimethyl‐1,4‐dihydropyrazines (1 a) with electron‐deficient alkyl halides under fluoride‐free conditions affords the corresponding alkylated pyrazines.