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Menthol Oxidation to Menthone: An Important Chemical Transformation
Mariana Falcão Lopes Princisval Carlos and Marcus Vinicius Nora de Souza
General Chemistry    2023, 9 (3-4): 230002-230002.   DOI: 10.21127/yaoyigc20230002
Abstract652)      PDF (1941KB)(424)       Save
Oxidation is a key transformation in chemistry being involved in a wide range of processes. In natural products, this reaction plays a critical role in the biosynthesis of several classes from different sources. In this context, the oxidation of menthol to menthone is an important reaction with a variety of applications in several fields, such as natural products, organic synthesis, and medicinal chemistry. Considering this, the present article aims to review different methodologies and oxidation reagents capable of performing this transformation, including the green chemistry process.
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Hydrogen Spillover in Electrochemical Hydrogen Evolution Reaction
Ziyao Chen, Huai Qin Fu, Mengyang Dong, Yu Zou, Porun Liu, Huijun Zhao
General Chemistry    2022, 8 (3-4): 220007-220007.   DOI: 10.21127/yaoyigc20220007
Abstract499)      PDF (769KB)(549)       Save
The dissociative chemisorption and energetically driven migration of atomic hydrogen on heterogenous electrocatalysts, i.e., hydrogen spillovers, which occur during electrochemical turnovers, have been intensively investigated recently on high-performance electrocatalysts for hydrogen evolution reaction. The elucidation of the hydrogen spillover not only reshapes the mechanistic understanding of the catalytic landscape but also aids in formulating efficient reaction pathways for catalyst designs. This perspective hence concisely summarizes the status of research on the hydrogen spillover effect in recent years, as well as the experimental methods to characterize the hydrogen spillover process and presents a prospect for future research direction.
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Steric Hindrance Functionalized Porphyrins as Charge Trapping Elements for Organic Field Effect Transistor Memory
Meng Xie, Linyi Bian, Hao Chong, Zhewei Zhang, Guangyi Liu, and Linghai Xie
General Chemistry    2022, 8 (3-4): 220006-220006.   DOI: 10.21127/yaoyigc20220006
Abstract442)      PDF (1162KB)(169)       Save
Two novel fluorenyl-porphyrins 2Flu-TPP and 4Flu-TPP serving as charge trapping elements are designed and synthesized through BF 3.Et 2O catalyzed Friedel-Crafts reaction. With steric hindrance building blocks of fluorene units, 2Flu-TPP and 4Flu-TPP present highly nonplanar 3-dimensional structure, which could effectively inhibit molecular packing and intermolecular arrangement of porphyrins. As charge trapping elements, porphyrin groups provide the hole trapping sites, while fluorene units act as a hole blocking group to reduce the formation of leakage current paths. The pentacene-based organic field effect transistor memory devices based on 2Flu-TPP and 4Flu-TPP show memory windows of 48.93 and 49.20 V, respectively. The 2Flu-TPP device shows reliable endurance property with a large ON/OFF current ratio (1.1×10 7) and good charge retention time (2.41×10 5 after 2×10 3 s). This study suggests that porphyrin based steric hindrance small molecular elements have great promise for high-performance organic field effect transistor memory.
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Halogen Bonding Promotes Purely Organic Room-Temperature Phosphorescence
Kuo Liu, Bao-Yi Ren and Fu-Shun Liang
General Chemistry    2022, 8 (3-4): 220005-220005.   DOI: 10.21127/yaoyigc20220005
Abstract287)      PDF (919KB)(206)       Save
Purely organic room-temperature phosphorescence (RTP) materials are promising candidates for high-tech applications. Herein, we highlight new development that promotes RTP emission of organic small molecules, high phosphorescent efficiency and long lifetime, via inter/intro-molecular halogen bonding.
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The Eternal Quest for Practical Low Bandgap Polymers
Seth C. Rasmussen, Spencer J. Gilman, Wyatt D. Wilcox
General Chemistry    2023, 9 (1-2): 220010-220010.   DOI: 10.21127/yaoyigc20220010
Abstract255)      PDF (756KB)(214)       Save
The bandgap ( Eg) of conjugated materials effects a variety of critical properties such that efforts to control the bandgap have become a basic tenet in the design of conjugated polymers. One goal of such efforts is to minimize the Eg with the goal of producing technologically useful low bandgap ( Eg < 1.5 eV) polymers. This perspective will introduce the two primary approaches to low Eg polymers ( i.e., quinoidal systems and donor-acceptor frameworks) and discuss important new directions for both design principles.
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Colloidal Carbon Quantum Dots for Anticounterfeiting
Yuanyuan Han, Yuanming Zhang and Haiguang Zhao
General Chemistry    2023, 9 (3-4): 220014-220014.   DOI: 10.21127/yaoyigc20220014
Abstract236)      PDF (2441KB)(206)       Save
More attentions have been paid for developing anti-counterfeiting technologies to fight the endless emergence of fake and inferior products. Compared with inorganic quantum dots, colloidal carbon dots (C-dots) are emerging fluorescent nanomaterials, which have been used for various types of optical and electrical applications, because they have composition-dependent optical properties, including high quantum yield, tunable absorption/emission spectra and good chemical-/photo-stability. In this minireview, we summarized and updated the most recent research works for the use of colloidal C-dots for optical anticounterfeiting applications. We focus on the fluorescent, persistent luminescence and phosphorescent C-dots. In the end, we enclosed this minireview with our owner perspectives on the challenges of C-dots based anticounterfeiting.
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Advancements in Perovskite Solar Cells: Interface and Additive Engineering Innovations
Haokun Jiang, Mingzhe Zhu, Zhongmin Zhou
General Chemistry    2024, 10 (1-2): 230004-230004.   DOI: 10.21127/yaoyigc20230004
Abstract235)      PDF (1630KB)(168)       Save
In the photovoltaic field, perovskite solar cells (PSCs) are gaining momentum due to the implementation of interface and additive engineering as viable approaches to advance commercialization. Our review begins with an outline of the latest progress in PSCs, followed by essential background information. The primary focus is on recent studies of small molecules and ionic liquids employed in interface and additive engineering to enhance device stability and performance. Ferrocenyl-bis-thio- phene-2-carboxylate (FcTc 2) and 3,4-bis(4-bromophenyl)-cyclobut-3-ene-1,2-dione (BED) belong to interface engineering, while 3-ethylbenzo[ b]thiophene-1,1-dioxide (PSAD), 1-bromo-4-(methylsulfinyl) benzene (BMMS), 1-(4-bromophenyl)-6,7-diphenylimidazo indolizine (PDPII) and 9-bromo-6,7-diphenyl- pyrido[2,1- a]isoquinolin-5-ium hexafluoro-phosphate (DPPIQ +PF 6 -), utilized in our previous research, are part of additive engineering. These studies centered around the potential interactions between additives and perovskites and the mechanisms these compounds minimize or passivate defects. Our aim with this review is to shed light on these findings and inspire continued theoretical and experimental investigations.
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On the Ground State Structures of Bimetallic Ni mCu n ( m + n ≤ 6) Clusters and Their Reactivity toward O 2
Heriberto Cruz-Martínez, Eduardo A. Ortiz-Vázquez, Hugo Rojas-Chávez, Patrizia Calaminici
General Chemistry    2023, 9 (1-2): 220012-220012.   DOI: 10.21127/yaoyigc20220012
Abstract231)      PDF (981KB)(178)       Save
Extensive auxiliary density functional theory (ADFT) computations were performed to study the most stable structures, stabilities and chemical reactivity toward O 2 of bimetallic Ni mCu n ( m + n ≤ 6) clusters. The shape of the most stable structures changes as the number of Ni and Cu atoms of the system under study increases with a consequent change of the energy, magnetic and reactivity properties. All obtained minimum-energy structures for these bimetallic systems composed with three and four atoms possess triangular and rhombic structures, respectively. According to our computations, the most stable structures for Ni 4Cu, Ni 3Cu 2, and Ni 2Cu 3 clusters are trigonal-bipyramidal, while, for the NiCu 4 cluster, two structures were identified as the most stable (with planar and trigonal-bipyramidal structures, respectively). The most stable structure for the Ni 5Cu cluster is octahedral, while for the Ni 4Cu 2, Ni 3Cu 3, Ni 2Cu 4, and NiCu 5 clusters, an incomplete pentagonal bipyramid was found as the ground-state structure. For all cluster sizes, as the number of Cu atoms in the system increases, the magnetic moment per atom tended to decrease. The O 2 adsorption on bimetallic Ni mCu n ( m + n = 6) clusters is more favored when O 2 binds by a bridge-type bond. Moreover, our computations indicate that O 2 is preferentially adsorbed on the Ni atoms of bimetallic Ni mCu n ( m + n = 6) clusters.
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Chemical Sensing Technology towards Global Public Safety (I): Fluorescent Probes for Detection of Phosgene
Ruilong Sheng
General Chemistry    2023, 9 (3-4): 220011-220011.   DOI: 10.21127/yaoyigc20220011
Abstract224)      PDF (605KB)(180)       Save
Phosgene, an important chemical warfare agent (CWA), has received great attention in the field of counterterrorism and public safety monitoring. Developing new sensing methods/tools for efficient detection of phosgene is an urgent challenge to be solved. For chemists, it is pivotal to create fast, low cost, portable, selective, sensitive, as well as visualizable chemical sensors/probes for real-time phosgene detection. This article reviewed and discussed current trend and statement of phosgene-specific fluorescent probes, providing concise “fast glance” and systematic “big picture” to the related researchers and public safety engineers. Moreover, the outlook in this field was also stated.
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Recent Advances on Metal-Free Quantum Dots as Green Photocatalysts for Photoinduced Atom Transfer Radical Polymerization
Tengbao Li, Songli Ma, Li Zhou
General Chemistry    2024, 10 (1-2): 230006-230006.   DOI: 10.21127/yaoyigc20230006
Abstract212)      PDF (3229KB)(139)       Save
Visible-light mediated photoinduced reversible deactivation radical polymerization (RDRP) is a promising method for producing well-defined polymers; however, it typically requires metal-containing catalysts, which can be toxic and limit practical applications. Therefore, developing new RDRP techniques is crucial. One promising approach is visible-light mediated photoinduced atom transfer radical polymerization (photoATRP), which utilizes metal-free photocatalysts and eco-friendly light to catalyze polymerization. PhotoATRP offers more precise control over polymerization kinetics and can be performed in diverse solvents, including water, enhancing versatility and enabling the production of polymers with well-defined structures, low molecular weight distribution indexes, and controllable relative molecular weights. This minireview outlines recent advances on photoATRP using metal-free quantum dots (QDs) as photocatalysts. The research progress and influence factors for QDs-based photoATRP, as well as the mechanistic insights into the process, were discussed. Finally, we address the challenges and opportunities facing QDs-based photoATRP.
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Comparative Analysis of AquaSun Sol-Gel Coating and Commercial Antifouling Paint in Protecting Shipbuilding Steel in Port Seawaters
Rosaria Ciriminna, Salvatore Vacante, Antonino Scurria, Gabriella Di Carlo, Mario Pagliaro, Annamaria Visco
General Chemistry    2023, 9 (1-2): 230001-230001.   DOI: 10.21127/yaoyigc20230001
Abstract211)      PDF (500KB)(155)    PDF(mobile) (500KB)(5)    Save
The results of the first tests aimed to assess antifouling activity of new AquaSun sol-gel paint coated on shipbuilding steel immersed in highly polluted port seawaters, compared to a state-of-the-art self-polishing commercial silyl acrylate antifouling topcoat containing high amounts of cuprous oxide and copper pyrithione, are promising.
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Synthesis of Regioselective Carbohydrates Building Blocks by Heterogeneous Engineered Biocatalysts
Jose M. Palomo
General Chemistry    2022, 8 (3-4): 220009-220009.   DOI: 10.21127/yaoyigc20220009
Abstract194)      PDF (924KB)(138)       Save
Regioselective synthesis of carbohydrate building blocks by the application of biocatalytic approaches represents a convenient and sustainable way for the production of pharmaceuticals. The enormous potential of enzymes for the transformation of synthetic chemicals with high regioselectivity is on increasing awareness. This perspective focuses on showing some of the advances on the use of lipases engineering as immobilized catalyst for regioselective deprotection processes for potential industrial production glycoderivatives building blocks.
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Enhanced Lithium Storage Performance of Al-Doped V 2O 5 Nanowire Cathode Materials
Wenhan Xu, Ting Zhou, Jingcheng Ji, Yanwei Li, Shangwang Le
General Chemistry    2024, 10 (1-2): 230005-230005.   DOI: 10.21127/yaoyigc20230005
Abstract169)      PDF (2840KB)(108)       Save
One-dimensional (1D) Al-doped V 2O 5 nanowires were synthesized by a hydrothermal method and subsequent heat treatment process. The microstructure, surface morphology, and electrochemical performance of the as-prepared 1D Al-doped V 2O 5 nanowires were analyzed by XRD, XPS, SEM, CV, EIS, and galvanostatic discharge/charge tests. The results show that Al 3+ doping can effectively increase the V 4+ concentration in V 2O 5 material and prevent the agglomeration of V 2O 5 nanowires. When used as a cathode material for lithium-ion batteries (LIBs), the Al-doped V 2O 5 sample exhibits much-enhanced cycling performance, improved high-rate capability, higher electrochemical reaction reversibility, and lower electrochemical reaction resistance than the pure V 2O 5 sample (without Al 3+ doping).
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Synthesis, DMF Sensing and Proton Conduction of a Two-Dimensional Metal-Organic Framework
Datang Chen, Weiming Liao, Jun He
General Chemistry    2023, 9 (1-2): 230003-230003.   DOI: 10.21127/yaoyigc20230003
Abstract169)      PDF (791KB)(135)       Save
A two-dimensional layered metal-organic framework, [Eu(C 26H 15NO 4)Cl] n (EuCDDB), was synthesized by the reaction of EuCl 3·6H 2O and 4,4'-(9 H-carbazole-3,6-diyl)dibenzoic acid (H 2CDDB) through one-pot solvothermal process, and characterized by several technologies of single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared spectrum. The crystal structure reveals that hydrogen bonding interaction happens between NH groups and coordinated chloride ions from the adjacent coordination layers, meanwhile, well-opened one-dimensional channel allows the accommodation of water molecules. These characteristics endow EuCDDB with a considerable proton conductivity of 3.70 × 10 -6 S cm -1 under 90 °C and relative humidity of 90%. In addition, EuCDDB also exhibits turn-on luminescent sensing on DMF molecules by enhanced Eu 3+ red emission resulting from efficient ligand-to-metal energy transfer process.
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On Carbon “Replacing” the Core in Classical Semiconductor Core/ZnS Quantum Dots
Weixiong Liang, Kirkland Sheriff, Buta Singh, Haijun Qian, Simran Dumra, Jordan Collins, Subhadra Yerra, Liju Yang, Ya-Ping Sun
General Chemistry    2024, 10 (1-2): 240001-240001.   DOI: 10.21127/yaoyigc20240001
Abstract148)      PDF (1497KB)(115)       Save
Among best known semiconductor quantum dots (QDs) are CdSe/ZnS core/shell nanostructures, whose much enhanced photoexcited state properties over those of uncapped CdSe nanoparticles are rationalized in the literature such that “the ZnS capping with a higher bandgap than CdSe passivates the core crystallite removing the surface traps”. In this work, the method commonly employed in the ZnS capping of CdSe for CdSe/ZnS QDs was applied to the same capping of small carbon nanoparticles (CNPs) for CNP/ZnS core/shell nanostructures, which are conceptually and configuration-wise equivalent to the replacement of the semiconductor (CdSe) core with CNP in the classical core/shell QDs. The fluorescence emission properties of CNP/ZnS core/shell nanostructures were found to be similar to those of organic functionalized CNPs in classically defined carbon dots (CDots), both dramatically enhanced from those of “naked” CNPs in solvent dispersions. Mechanistic implications of the findings are discussed.
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Contents: Gen. Chem. 1-2/2023
General Chemistry    2023, 9 (1-2): 0-0.  
Abstract86)      PDF (483KB)(28)       Save
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Contents: Gen. Chem. 3-4/2022
General Chemistry    2022, 8 (3-4): 0-0.  
Abstract80)      PDF (336KB)(25)       Save
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Contents: Gen. Chem. 3-4/2023
General Chemistry    2023, 9 (3-4): 0-0.  
Abstract58)      PDF (526KB)(33)       Save
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Contents: Gen. Chem. 1-2/2024
General Chemistry    2024, 10 (1-2): 0-0.  
Abstract39)      PDF (874KB)(19)       Save
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