23,408 results
Search Results
2. Photo‐Controllable Ultralong Room‐Temperature Phosphorescence: State of the Art.
- Author
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Nie, Fei and Yan, Dongpeng
- Subjects
PHOTOCHROMIC materials ,PHOSPHORESCENCE ,ELECTRONIC paper ,INORGANIC polymers ,DIARYLETHENE ,SMALL molecules ,OPTOELECTRONICS ,MOIETIES (Chemistry) - Abstract
In this concept, we showcase the upsurge in the studies of dynamic ultralong room‐temperature phosphorescence (RTP) materials containing inorganic and/or organic components as versatile photo‐responsive platforms. The goal is to provide a comprehensive analysis of photo‐controllable RTP, and meanwhile delve into the underlying RTP properties of various classes of photochromic materials including metal‐organic complexes, organic‐inorganic co‐crystals, purely organic small molecules and organic polymers. In particular, the design principles governing the integration of the photochromic and RTP moieties within a single material system, and the tuning of dynamic RTP in response to light are emphasized. As such, this concept sheds light on the challenges and opportunities of using these tunable RTP materials for potential applications in optoelectronics, particularly highlighting their use of reversible information encryption, erasable light printing and rewritable smart paper. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
3. Cd/Cd(OH)2 Nanosheets Enhancing the Electrocatalytic Activity of CO2 Reduction to CO.
- Author
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Jia, Xiaoyan, Qi, Kongsheng, Yang, Jie, Fan, Zixi, Hua, Zhixin, Wan, Xiaoqi, Zhao, Yuhua, Mao, Yidan, and Yang, Dexin
- Subjects
NANOSTRUCTURED materials ,ELECTROLYTIC reduction ,GREENHOUSE effect ,CARBON dioxide ,CARBON paper ,ENERGY shortages ,ELECTRIC charge - Abstract
Electric‐driven conversion of carbon dioxide (CO2) to carbon monoxide (CO) under mild reaction conditions offers a promising approach to mitigate the greenhouse effect and the energy crisis. Surface engineering is believed to be one of the prospective methods for enhancing the electrocatalytic activity of CO2 reduction. Herein, hydroxyl (OH) groups were successfully introduced to cadmium nanosheets to form cadmium and cadmium hydroxide nanocomposites (i. e. Cd/Cd(OH)2 nanosheets) via a facile two‐step method. The as‐prepared Cd/Cd(OH)2/CP (CP indicates carbon paper) electrode displays excellent electrocatalytic activity for CO2 reduction to produce CO. The Faradaic efficiency of CO reaches 98.3 % and the current density achieves 23.8 mA cm−2 at −2.0 V vs. Ag/Ag+ in a CO2‐saturated 30 wt% 1‐butyl‐3‐methylimidazole hexafluorophosphate ([Bmim]PF6)‐65 wt% acetonitrile (CH3CN)‐5 wt% water (H2O) electrolyte. And the CO partial current density can reach up to 71.6 mA cm−2 with the CO Faradaic efficiency of more than 85 % at −2.3 V vs. Ag/Ag+, which stands out against Cd/CP, Cd(OH)2/CP, and Cd/CdO/CP electrodes. The excellent electrocatalytic performance of the Cd/Cd(OH)2/CP electrode can be attributed to its unique structural properties, suitable OH groups, perfect interaction with electrolyte, abundant active sites and fast electron transfer rate. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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4. Room Temperature Hydroxyl Group‐Assisted Preparation of Hydrophobicity‐Adjustable Metal‐Organic Framework UiO‐66 Composites: Towards Continuous Oil Collection and Emulsion Separation.
- Author
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Xiang, Wenlong, Liu, Huiwen, Zhu, Jiabin, Gong, Hongyang, and Cao, Qizheng
- Subjects
METAL-organic frameworks ,SUPERHYDROPHOBIC surfaces ,EMULSIONS ,PETROLEUM ,CONTACT angle ,FILTER paper - Abstract
Developing a straightforward and effective hydrophobic modification for metal−organic frameworks (MOFs) under mild conditions is meaningful for MOF applications. Here, a post‐synthetic modification approach assisted with metal hydroxyl groups at room temperature is reported to induce hydrophobicity in the hydrophilic UiO‐66. The bonding between Zr−OH in UiO‐66 and n‐tetradecylphosphonic acid (TDPA) is the vital force for the modifier TDPA. Superhydrophobic and superoleophilic composites were constructed for efficient oil‐water separation by coating TDPA‐modified UiO‐66 (P‐UiO‐66) on commercial melamine sponges (MS) and filter papers (FP) with water contact angles of 153.2° and 155.6°, respectively. The P‐UiO‐66/MS composite could quickly and selectively absorb oily liquids up to 43 times its weight from water. The P‐UiO‐66/MS achieved continuous oil collection with high separation efficiencies (≥99.4 %). In addition, P‐UiO‐66/FP and P‐UiO‐66/MS showed high separation efficiencies for water‐in‐oil emulsions (≥98.5 %) and oil‐in‐water emulsions, respectively, with high resistance to low/high temperatures and acid/base conditions. The metal hydroxyl group‐assisted post‐synthetic modification strategy offers a facile and broad way to prepare hydrophobic MOFs for promising applications in environmental fields. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
5. Disulphide Cross‐Linked Ultrashort Peptide Hydrogelator for Water Remediation.
- Author
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Kanti Das, Basab, Samanta, Raju, Ahmed, Sahnawaz, and Pramanik, Bapan
- Subjects
PEPTIDES ,AMINO acid sequence ,WATER pollution ,BUFFER solutions ,FILTER paper - Abstract
A single amino acid in a peptide sequence can play an important role to tune the self‐assembly and hydrogelation behaviour. Here, a C‐terminal cysteine‐containing ultrashort peptide hydrogelator forms hydrogel through non‐covalent and covalent interactions. Interestingly, the hydrogel is insoluble in water and buffer solutions at different pH values (1‐13) and is thixotropic and injectable. In recent years, removing dyes from contaminated water has become a significant concern because of the shortage of freshwater resources. Therefore, the adsorption of dyes through a reliable, straightforward, nontoxic, cheap, and environmentally friendly adsorbent has become a popular topic. Hence, the hydrogelator was exploited to remove organic dyes from wastewater, harnessing its applicability in the gel phase and solid supports (filter paper and cotton). [ABSTRACT FROM AUTHOR]
- Published
- 2023
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6. Fenton‐Like Reaction: Recent Advances and New Trends.
- Author
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Xiao, Jiaying, Guo, Sufang, Wang, Dong, and An, Qi
- Subjects
HABER-Weiss reaction ,HYDROGEN peroxide ,SOIL degradation ,IRON ions ,OIL spills ,SOIL pollution - Abstract
The Fenton reaction refers to the reaction in which ferrous ions (Fe2+) produce hydroxyl radicals and other reactive oxidizing substances by decomposing hydrogen peroxide (H2O2). This paper reviews the mechanism, application system, and materials employed in the Fenton reaction including conventional homogeneous and non‐homogeneous Fenton reactions as well as photo‐, electrically‐, ultrasonically‐, and piezoelectrically‐triggered Fenton reactions, and summarizes the applications in the degradation of soil oil pollutions, landfill leachate, textile wastewater, and antibiotics from a practical point of view. The mineralization paths of typical pollutant are elucidated with relevant case studies. The paper concludes with a summary and outlook of the further development of Fenton‐like reactions. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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7. Electrochemically Assisted Cycloaddition of Carbon Dioxide to Styrene Oxide on Copper/Carbon Hybrid Electrodes: Active Species and Reaction Mechanism.
- Author
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Li, Wenze, Qi, Ke, Lu, Xingyu, Qi, Yujie, Zhang, Jialong, Zhang, Bingsen, and Qi, Wei
- Subjects
STYRENE oxide ,CARBON dioxide ,RING formation (Chemistry) ,CARBON electrodes ,CARBON paper ,SURFACE charges - Abstract
A novel electrochemically assisted cycloaddition process is proposed, in which highly efficient coupling of CO2 with styrene oxide (SO) can be achieved to form styrene carbonate (SC) as a high‐value‐added product. A series of Cu catalysts with different morphologies and chemical states were fabricated on carbon paper (CP) by using in‐situ electrodeposition, and the sample with nano‐dendrimer structure was found to exhibit a relatively high activity of 74.8 % SC yield with 92.7 % SO conversion under gentle reaction conditions, thus showing its potential for practical applications. The relatively high electrochemically active surface area and charge transfer ability of dendrimer‐like Cu benefited the electrochemical reaction. In particular, the Cu2+ species that were formed in situ during the reaction played a vital role in enhancing the activity and selectivity of the proposed Cu/CP hybrid catalyst. Cu2+ atoms served as active sites that can not only electrochemically activate CO2 but also facilitate the ring opening of SO. Mechanistic analysis suggested that the reaction followed electrochemical and liquid‐phase heterogeneous paths, which provide a new green and sustainable route for efficient utilization of CO2 resources for fine chemical electrosynthesis. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
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8. Secret Paper with Vinegar as an Invisible Security Ink and Fire as a Decryption Key for Information Protection.
- Author
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Chen, Fei‐Fei, Zhu, Ying‐Jie, Zhang, Qiang‐Qiang, Yang, Ri‐Long, Qin, Dong‐Dong, and Xiong, Zhi‐Chao
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VINEGAR ,CELLULOSE fibers ,CRYPTOGRAPHY ,DATA warehousing ,INK ,NANOWIRE devices ,QUANTUM information science - Abstract
Security inks based on photoluminescent materials are mostly investigated for security applications, such as information encryption and decryption, anti‐counterfeiting, and data storage. Although they are invisible to the naked eye under ambient light, they can be detected under ultraviolet or near‐infrared light. Herein, a new kind of secret paper made from network‐structured ultralong hydroxyapatite nanowires and cellulose fibers has been developed. White vinegar, a common cooking ingredient, is used as an invisible security ink. Covert information on the secret paper written with white vinegar is totally invisible under natural light, but it can be decrypted and clearly read after exposure to fire; the response time to fire is short (<10 s). The ways of writing on the secret paper are diverse by using various pens loaded with white vinegar. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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9. Luminescent Organic‐Inorganic Hybrid Metal Halides: An Emerging Class of Stimuli‐Responsive Materials.
- Author
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Wang, Zeping and Huang, Xiaoying
- Subjects
METAL halides ,ELECTRONIC paper ,ORGANIC conductors ,ORGANOMETALLIC compounds - Abstract
Luminescent organic‐inorganic metal halides (OIMHs) are well known as a new materials family in recent years. Novel materials and applications of luminescent OIMHs have been explored by changing either the organic component or the metal halide species. Thereinto, the stimuli‐responsive (SR) phenomena in OIMHs have drawn much attention recently, for not only their attractive application potential but also the helpfulness in understanding the stability of OIMHs to the external environment. Herein, the luminescent OIMHs that are sensitive to external stimuli including contact, pressure, mechanical grinding, light, heat, and gas molecules, are reviewed, with an emphasis on analyses of the structural change during the SR process. The applications of SR luminescent OIMHs in widespread fields, including gas sensing, information encryption, and rewritable luminescent paper are summarized. Finally, the challenges that deserve to be further explored in this research field are discussed, which provides certain guidance for the future study of SR luminescent OIMHs. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
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10. Metalloporphyrin‐Based Metal–Organic Frameworks on Flexible Carbon Paper for Electrocatalytic Nitrite Oxidation.
- Author
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Pila, Taweesak, Chirawatkul, Prae, Piyakeeratikul, Panchanit, Somjit, Vetiga, Sawangphruk, Montree, and Kongpatpanich, Kanokwan
- Subjects
METALLOPORPHYRINS ,X-ray absorption near edge structure ,METAL-organic frameworks ,CARBON paper ,CARBON films ,X-ray photoelectron spectroscopy - Abstract
Deposition of redox‐active metal–organic frameworks (MOFs) as thin films on conductive substrates is of great importance to improve their electrochemical performance and durability. In this work, a series of metalloporphyrinic MOF crystals was successfully deposited as thin films on carbon fiber paper (CFP) substrates, which is an alternative to rigid glass substrates. The specific dimensions of the obtained films could be adjusted easily by simple cutting. Metalloporphyrinic MOFs on CFP with different active metal species have been employed for electrochemical conversion of the carcinogenic nitrite into the less toxic nitrate. The MOFs on CFP exhibit remarkable improvement in terms of the electrocatalytic performance and reusability compared with the electrodes prepared from MOF powder. The contribution from metal species of the porphyrin units and reaction mechanisms was elucidated based on the findings from X‐ray photoelectron spectroscopy (XPS) and in situ X‐ray absorption near edge structure (XANES) measured during the electrochemical reaction. By integrating the redox‐active property of metalloporphyrinic MOFs and high conductivity of CFP, MOF thin films on CFP provided a significant improvement of electrocatalytic performance to detoxify the carcinogenic nitrite with good stability. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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11. Building Polyoxometalate "Nano‐Walls" on 3D Porous Carbon Paper: A Solar Steam Generation System for Water Purification.
- Author
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De, Qingcuomu and Xu, Xinxin
- Subjects
CARBON paper ,WATER purification ,SALINE water conversion ,SOLAR thermal energy ,SOLAR energy conversion ,MARITIME shipping ,WATER efficiency - Abstract
As promising fresh‐water purification devices, solar steam generation systems have attracted significant attention recently. However, in practice, the approach often suffers from a poor solar energy conversion efficiency and a low water production rate due to poor material selection and inefficient microscopic structure design. Here, we fabricate an efficient solar steam generation system by "building" polyoxometalate "nano‐walls" on rice paper‐derived three‐dimensional porous carbon paper. In this solar steam generation system, the height of the vertically aligned CoP4Mo6 "nano‐walls" range from 100 to 150 nm with thicknesses about 15 to 25 nm. Under 1 sun irradiation (1 sun = 1 kW m−2), the surface temperature increases from 29 to 50 °C in a short time with a solar thermal conversion efficiency achieving 92.8 %. The stability and durability of this solar steam generation system, which withstands fifteen cycle continuous tests, also offer good prospects. Its attractive solar energy conversion performance originates from the intense sunlight absorption and high conversion ability of the CoP4Mo6 "nano‐walls", as well as extremely promising heat localization and water transportation properties of the three‐dimensional porous carbon paper. This solar steam generation system, which has produced some inspiring results, is employed for seawater desalination and for purification of water polluted with organic dyes. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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12. Emergent Properties in Chemistry ‐ Relating Molecular Properties to Bulk Behavior.
- Author
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Sieroka, Norman, Lossau, Tammo, and Neudecker, Tim
- Subjects
QUANTUM phase transitions ,CHEMICAL properties - Abstract
Certain properties of an object only emerge when a sufficient number of those objects are present in a definite arrangement. For example, one or two water molecules cannot said to be in a liquid state, but a drop of water can be. This concept of emergence has been studied extensively, but only occasionally discussed explicitly in the context of chemistry. In this paper, we aim to show the fruitfulness of the concept of emergence for chemical inquiry by considering four case studies of emergent chemical properties, i. e., the liquidity and freezing of water, structural properties of crystals, thermodynamical phase transitions and quantum mechanical phenomena. We show that some of these properties emerge gradually, some at discrete points, and some should be taken to emerge only when the number of constituents tends to infinity. We argue that studying the way in which chemical properties emerge presents a useful avenue for research that promises greater insight into the nature of those properties. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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13. Palladium‐Catalyzed Enantioselective [4+2] Cycloaddition of 4‐Vinylbenzodioxinones with Barbiturate‐Derived Alkenes: Con‐struction of Chiral Spirobarbiturate−Chromanes.
- Author
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Tang, Yi, Huang, Mingxia, Ding, Siyuan, Liu, Xinyao, Huyang, Xiaochun, Wang, Bo, and Guo, Hongchao
- Subjects
ALKENES ,RING formation (Chemistry) ,PALLADIUM ,CATALYSIS - Abstract
In this paper, Pd‐catalyzed [4+2] decarboxylative cycloaddition of 4‐vinylbenzodioxinones with barbiturate‐derived alkenes has been developed, leading to various spirobarbiturate−chromane derivatives in high yields with excellent diastereo‐ and enantioselectivities. The scale‐up reaction and further derivation of the product were demonstrated. A plausible reaction mechanism was also proposed. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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14. Recent Advances of Flexible MXene and its Composites for Supercapacitors.
- Author
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Jiang, Shiben, Lu, Linghong, and Song, Yan
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ELECTRIC conductivity ,SURFACE chemistry - Abstract
MXenes have unique properties such as high electrical conductivity, excellent mechanical properties, rich surface chemistry, and convenient processability. These characteristics make them ideal for producing flexible materials with tunable microstructures. This paper reviews the laboratory research progress of flexible MXene and its composite materials for supercapacitors. And introduces the general synthesis method of MXene, as well as the preparation and properties of flexible MXene. By analyzing the current research status, the electrochemical reaction mechanism of MXene was explained from the perspectives of electrolyte and surface terminating groups. This review particularly emphasizes the composite methods of freestanding flexible MXene composite materials. The review points out that the biggest problem with flexible MXene electrodes is severe self‐stacking, which reduces the number of chemically active sites, weakens ion accessibility, and ultimately lowers electrochemical performance. Therefore, it is necessary to composite MXene with other electrode materials and design a good microstructure. This review affirms the enormous potential of flexible MXene and its composite materials in the field of supercapacitors. In addition, the challenges and possible improvements faced by MXene based materials in practical applications were also discussed. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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15. Synthesis of [1]Benzothieno[3,2‐b][1]benzothiophenes through Iodine‐Mediated Sulfur Insertion Reaction.
- Author
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Ito, Kazuki, Nakamura, Kohei, and Yoshida, Kazuhiro
- Subjects
ORGANIC field-effect transistors ,SULFUR ,THIOPHENES - Abstract
[1]Benzothieno[3,2‐b][1]benzothiophenes (BTBTs) are important molecules that have been extensively studied as high‐performance organic field‐effect transistors (OFETs). Therefore, it is important to develop a simple synthetic method for these molecules. In this paper, a synthetic method to obtain the BTBTs from 2‐arylbenzo[b]thiophenes and elemental sulfur, in which two C−S bonds are formed at once, is described. In this method, molecular iodine plays a very important role as an additive. The role of iodine is discussed in the presumed reaction pathways. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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16. Versatile Polymerization‐Induced Emission Polymers from Barbier Polymerization of Cinnamic Esters with Tunable Emission.
- Author
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Sun, Xiao‐Li, Chen, Yu‐Jiao, Cai, Hua‐Wen, Gu, Xi‐Yao, Li, De‐Shan, Wu, Liang‐Tao, and Wan, Wen‐Ming
- Subjects
HYDROXYCINNAMIC acids ,ESTERS ,POLYMERIZATION ,POLYMERS ,CHEMICAL structure ,EXPLOSIVES - Abstract
Cinnamic ester is a common and abundant chemical substance, which can be extracted from natural plants. Compared with traditional esters, cinnamic ester contains α,β‐unsaturated carbonyl structure with multiple reactive sites, resulting in more abundant reactivities and chemical structures. Here, a versatile polymerization‐induced emission (PIE) is successfully demonstrated through Barbier polymerization of cinnamic ester. Attributed to its abundant reactivities of α,β‐unsaturated carbonyl structure, Barbier polymerization of cinnamic esters with different organodihalides gives polyalcohol and polyketone via 1,2‐addition and 1,4‐addition, respectively, which is also confirmed by small molecular model reactions. Meanwhile, these organodihalides dependant polyalcohol and polyketone exhibit different non‐traditional intrinsic luminescence (NTIL) from aggregation‐induced emission (AIE) type to aggregation‐caused quenching (ACQ) type, where novel PIE luminogens (PIEgens) are revealed. Further potential applications in explosive detection are carried out, where it achieves TNT detection sensitivity at ppm level in solution and ng level on the test paper. This work therefore expands the structure and functionality libraries of monomer, polymer and NTIL, which might cause inspirations to different fields including polymer chemistry, NTIL, AIE and PIE. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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17. Plasma Technology for Advanced Electrochemical Energy Storage.
- Author
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Liang, Xinqi, Liu, Ping, Qiu, Zhong, Shen, Shenghui, Cao, Feng, Zhang, Yongqi, Chen, Minghua, He, Xinping, Xia, Yang, Wang, Chen, Wan, Wangjun, Zhang, Jun, Huang, Hui, Gan, Yongping, Xia, Xinhui, and Zhang, Wenkui
- Subjects
LITHIUM-air batteries ,ENERGY storage ,LITHIUM sulfur batteries ,CARBON offsetting ,RADICALS (Chemistry) ,LITHIUM-ion batteries - Abstract
"Carbon Peak and Carbon Neutrality" is an important strategic goal for the sustainable development of human society. Typically, a key means to achieve these goals is through electrochemical energy storage technologies and materials. In this context, the rational synthesis and modification of battery materials through new technologies play critical roles. Plasma technology, based on the principles of free radical chemistry, is considered a promising alternative for the construction of advanced battery materials due to its inherent advantages such as superior versatility, high reactivity, excellent conformal properties, low consumption and environmental friendliness. In this perspective paper, we discuss the working principle of plasma and its applied research on battery materials based on plasma conversion, deposition, etching, doping, etc. Furthermore, the new application directions of multiphase plasma associated with solid, liquid and gas sources are proposed and their application examples for batteries (e. g. lithium‐ion batteries, lithium‐sulfur batteries, zinc‐air batteries) are given. Finally, the current challenges and future development trends of plasma technology are briefly summarized to provide guidance for the next generation of energy technologies. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
18. Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials.
- Author
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Chen, Xu‐Yong, Cao, Li‐Hui, Bai, Xiang‐Tian, and Cao, Xiao‐Jie
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IONIC structure ,GAS absorption & adsorption ,HYDROGEN as fuel ,CRYSTAL structure ,SEPARATION of gases - Abstract
Hydrogen‐bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π–π stacking, highly interpenetrated networks, charge‐assisted, ligand‐bond‐assisted, molecular weaving, and covalent cross‐linking. Charge‐assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge‐assisted ionic HOFs, and introduces the different building block construction modes of charge‐assisted ionic HOFs. Highlight the applications of charge‐assisted ionic HOFs in gas adsorption and separation, proton conduction, biological applications, etc., and prospects for the diverse design of charge‐assisted ionic HOFs structures and multifunctional applications. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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19. Controlling Cyclic Dienamine Reactivity in Radical tert‐Alkylation for Molecular Diversity to Synthesize Multicyclic Compounds Possessing a Quaternary Carbon.
- Author
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Kusano, Shinjiro and Nishikata, Takashi
- Subjects
RADICALS (Chemistry) ,ORGANIC synthesis ,ALKYL compounds ,CARBON ,ALKYLATION ,ENAMINES - Abstract
Synthesis of diverse sterically congested molecules from a single important intermediate is one of the ideal synthetic strategies in organic synthesis. In this paper, we found that γ‐oxoalkyl substituted cyclohexenone derivatives (OAC) possessing a quaternary carbon are a useful key intermediate to derive both congested fused [5,6] rings and spirocycles. For this purpose, we have established an efficient synthetic method to obtain OAC by tertiary alkylation of β‐methylcyclohexenone derivatives using α‐bromocarbonyl compounds as a tertiary alkyl source. The key to the success of this reaction is controlling the reactivity of the dienamine intermediate. While there have been many reports on enamine reactions, dienamine reactions have not been well studied. Herein, we report controlling reactivity of dienamines and molecular diversification from OAC. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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20. One‐Step Photochemical Preparation of CdS/Poly(MMA‐co‐MAA) Composite with Enhanced Photocatalytic Activity.
- Author
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Huang, Zhenxun, Ma, Qingrong, and Sun, Fengqiang
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PHOTOCATALYSTS ,METHYL methacrylate ,METHACRYLIC acid ,ENVIRONMENTAL chemistry ,PHOTODEGRADATION ,SILVER phosphates - Abstract
This paper presents a one‐step photochemical method for the preparation of CdS/Poly(MMA‐co‐MAA) composite photocatalyst, based on the concept of simultaneous photocatalytic polymerization of organic monomers during UV‐light induced formation of CdS. The preparation is carried out in an aqueous solution of Na2S2O3, CdSO4, methyl methacrylate (MMA) and methacrylic acid (MAA), under a UV lamp. The continuously formed CdS particles with photocatalytic activity act the role of initiator to directly initiate the copolymerization of MMA and MAA, resulting in the in situ formation of the composite and full contact of the CdS particles with the oxygen‐containing groups in the polymer. Taking the photocatalytic degradation of methylene blue as a case study, the composite exhibited significantly higher activity under simulated solar light compared to the pure CdS. By analysis on various data, the enhanced photocatalytic activity is attributed to the enhanced visible light absorption, and especially the high electron‐hole separation efficiency caused by the electrostatic interaction between photogenerated holes and carbonyl oxygen atoms with negatively charged features. Furthermore, the composite displays excellent sunlight activity and recyclability, suggesting its potential for practical applications. Such a one‐step construction strategy relying only on photo‐energy is green, low‐cost and promising in obtaining high‐performance semiconductor/polymer composite photocatalysts. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
21. Celebrating Maurizio Prato's Passion, Talent and Imagination.
- Author
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Bianco, Alberto, Bonchio, Marcella, Bonifazi, Davide, Da Ros, Tatiana, Maggini, Michele, Mateo‐Alonso, Aurelio, and Tecilla, Paolo
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YLIDES ,NANOSCIENCE ,MATERIALS science ,PHOTOINDUCED electron transfer ,EDUCATORS ,ORGANIC reaction mechanisms ,CHLOROPLASTS ,ORGANIC chemistry - Abstract
This article introduces a special collection of papers dedicated to Maurizio Prato, a renowned scientist in the field of carbon nanostructures and molecular nanoscience. The collection showcases Prato's team's achievements in integrating complex frontier research with groundbreaking advancements in these fields. Prato's work focuses on designing and synthesizing carbon nanostructures for applications in regenerative medicine and solar energy research. The article highlights Prato's scientific journey, his contributions to sustainable materials, and his impact on shaping functional nano-interfaces through precision chemistry. The Prato lab has made significant contributions to nanotechnology, particularly in the area of functionalized carbon nanotubes (f-CNT). Their research has shown that f-CNT are more biocompatible and easily cleared from the body compared to nonfunctionalized CNT. The lab has applied this knowledge to develop solutions for challenging problems such as healing spinal cord injuries and using water as a solar fuel. Their work in regenerative medicine has shown promising results in repairing severe and irreversible nervous system lesions, while their research in energy conversion has explored the use of f-CNT for solar energy conversion. Maurizio Prato, the leader of the lab, has fostered an interdisciplinary and collaborative environment, encouraging his team to explore diverse research avenues and promoting intellectual freedom. His mentorship and open-mindedness have been instrumental in the lab's success. [Extracted from the article]
- Published
- 2024
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22. Pd‐Catalysed Direct Arylation of Distyrylbenzene: Strong Dual‐state Fluorescence and Electrochromism.
- Author
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Nipate, Atul B. and Rao, M. Rajeswara
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FLUORESCENCE yield ,ELECTROCHROMIC effect ,ARYLATION ,FLUORESCENCE ,ARYL group ,CARBAZOLE ,TRIPHENYLAMINE - Abstract
Distyrylbenzenes (DSBs) are well‐known for their strong multicolour fluorescence. Fluorescence tuning of DSB via further functionalization/arylation, on the other hand, is uncommon. This paper reports a Pd‐catalysed direct arylation approach for introducing different aryl groups onto fluorobenzene‐containing DSB moiety (7) in high yields (67–72 %). The versatile methodology allows the substitution of neutral [tolyl (1)], electron‐deficient [p‐formyl benzene (2), p‐acetyl benzene (3), p‐nitrobenzene (4)] and electron‐rich [carbazole (5), triphenylamine (6)] aryl groups. The electron‐deficient aryls render mono‐substitution, while the electron‐rich counterparts promote di‐substitution. The compounds (1–6) show blue, green, and yellow fluorescence in both the solution and solid states; the fluorescence quantum yields reach >98 % and the peak maxima span from 425 to 560 nm. The mono‐carbazole DSB (5) exhibit white light emission (WLM) in polar solvents (acetone, DMF, CH3CN, DMSO and NMP) with very high fluorescence quantum yields (φf) of 60–80 %. For WLM, such high efficiency (φf) is somewhat uncommon. Moreover, visible‐to‐NIR reversible electrochromism is demonstrated by the TPA‐integrated DSB (6). The colour of 6 changes from pristine light yellow to orange, and the absorption maxima shifts from 372 to 1500 nm when a positive potential of 1.0 V vs Ag/Ag+ is applied. Moreover, the system shows high colouration efficiency in the NIR region with fast switching speeds for colouration and decolouration as fast as 0.98 s and 1.05 s. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
23. Nucleophilic Substitution at Phosphorus Centres – Old and Recent Studies and a Final Solution of Mechanistic and Related Stereochemical Problems.
- Author
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Mikołajczyk, Marian
- Subjects
NUCLEOPHILIC substitution reactions ,PHOSPHORUS compounds ,PHOSPHORUS ,CYCLIC compounds ,STEREOCHEMISTRY ,PHOSPHORUS in water ,SUBSTITUTION reactions - Abstract
Among many problems of a fundamental value in the heteroatom chemistry the mechanism and stereochemistry of the nucleophilic substitution reaction at the phosphorus and other heteroatom centres have attracted great attention of phosphorus chemists already in the middle of the last century. This review, which does not have a comprehensive character, summarizes the selected original contributions aimed at solution of the mechanism of SN2−P reaction and its relationship with stereochemistry. The breakthrough in these studies was the Westheimer's concept and his rules which is presented at the beginning of this article. Next, a series of papers is presented where the stereochemistry of the substitution at phosphorus was investigated in cyclic five‐, four‐ and six‐membered ring phosphorus compound. The majority of these reactions have been found to occur with retention of the P‐configuration. In the third part of this account, the selected examples of substitution reactions at phosphorus in acyclic compounds are discussed. As the results of all the investigations discussed did not allow to undoubtedly ascribe the mechanism (SN2 or A−E) to the investigated reactions, in the last part the SN‐P reactions are presented, the mechanism of which has been established by combination of the stereochemical and DFT‐studies. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
24. Dansylated Nitrile N‐Oxide as the Fluorescent Dye Clickable to Unsaturated Bonds without Catalyst.
- Author
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Oku, Yuki, Nakajima, Noriyuki, Hamada, Masahiro, and Koyama, Yasuhito
- Subjects
FLUORESCENT dyes ,THREE-dimensional printing ,NITRILE oxides ,FLUORESCENCE spectroscopy ,NITRILE derivatives ,POLYMER blends ,MOLECULAR spectra - Abstract
Fluorescent polymeric materials have been exploited in the fields of aesthetical purposes, biomedical engineering, and three‐dimensional printing applications. While the fluorescent materials are prepared by the polymerization of fluorescent monomer or the blending a fluorescent dye with common polymer, the covalent immobilization of fluorescent dye onto common polymers is not the practical technique. In this paper, dansylated nitrile N‐oxide (Dansyl‐NO) has been designed and synthesized to be a stable nitrile N‐oxide as the derivative of 2‐hydroxy‐1‐naphthaldehyde. While Dansyl‐NO shows good reactivity to an alkene and an alkyne to give fluorescent Dansyl‐Ene and Dansyl‐Yne, respectively, it hardly reacts to a nitrile. The results indicate that Dansyl‐NO serves as a fluorescent dye clickable to alkenes and alkynes. To know the effects of solvent on the fluorescent properties, the UV‐vis and fluorescence spectra of Dansyl‐Ene are measured in three solvents. Dansyl‐Ene shows fluorescent solvatochromism, which appears to be red‐shifted along with the increase in solvent polarity. Poly(styrene‐co‐butadiene) directly reacts with Dansyl‐NO to give fluorescent modified SB. The emission spectrum of modified SB is blue‐shifted compared with that of Dansyl‐Ene. The blue‐shift could be possibly attributed to the presence of less polar polymer skeleton around the dansyl moieties of modified SB. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
25. Porous Anionic Co(II) Metal‐Organic Framework, with a High Density of Amino Groups, as a Superior Luminescent Sensor for Turn‐on Al(III) Detection.
- Author
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Chand, Santanu, Verma, Gaurav, Pal, Arun, Pal, Shyam Chand, Ma, Shengqian, and Das, Madhab C.
- Subjects
AMINO group ,METAL-organic frameworks ,DETECTORS ,FREE groups ,FILTER paper ,ION channels - Abstract
Accumulation of high concentrations of Al(III) in body has a direct impact on health and therefore, the trace detection of Al(III) has been a matter for substantial concern. An anionic metal organic framework ({[Me2NH2]0.5[Co(DATRz)0.5(NH2BDC)] ⋅ xG}n; 1; HDATRz=3,5‐diamino‐1,2,4‐triazole, H2NH2‐BDC=2‐amino‐1,4‐benzenedicarboxylic acid, G=guest molecule) composed of two types of secondary building units (SBU) and channels of varying sizes was synthesized by employing a rational design mixed ligand synthesis approach. Free −NH2 groups on both the ligands are immobilized onto the pore surface of the MOF which acts as a superior luminescent sensor for turn‐on Al(III) detection. Furthermore, the large channels could allow the counter‐ions to pass through and get exchanged to selectively detect Al(III) in presence of other seventeen metal ions with magnificent luminescence enhancement. The observed limit of detection is as low as 17.5 ppb, which is the lowest among the MOF‐based sensors achieved so far. To make this detection approach simple, portable and economic, we demonstrate MOF filter paper test for real time naked eye observation. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
26. Sustainable and Robust Graphene Cellulose Paper Decorated with Lithiophilic Au Nanoparticles to Enable Dendrite‐free and High‐Power Lithium Metal Anode.
- Author
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Diao, Wan‐Yue, Xie, Dan, Li, Yan‐Fei, Jiang, Ru, Tao, Fang‐Yu, Sun, Hai‐Zhu, Wu, Xing‐Long, Zhang, Xiao‐Ying, and Zhang, Jing‐Ping
- Subjects
GOLD nanoparticles ,CELLULOSE ,METALS ,LITHIUM cell electrodes ,GRAPHENE ,CELLULOSE nanocrystals ,HYDROGEN evolution reactions ,GRAPHITE oxide - Abstract
Lithium metal anodes (LMAs) with high energy density have recently captured increasing attention for development of next‐generation batteries. However, practical viability of LMAs is hindered by the uncontrolled Li dendrite growth and infinite dimension change. Even though constructing 3D conductive skeleton has been regarded as a reliable strategy to prepare stable and low volume stress LMAs, engineering the renewable and lithiophilic conductive scaffold is still a challenge. Herein, a robust conductive scaffold derived from renewable cellulose paper, which is coated with reduced graphene oxide and decorated with lithiophilic Au nanoparticles, is engineered for LMAs. The graphene cellulose fibres with high surface area can reduce the local current density, while the well‐dispersed Au nanoparticles can serve as lithiophilic nanoseeds to lower the nucleation overpotential of Li plating. The coupled relationship can guarantee uniform Li nucleation and unique spherical Li growth into 3D carbon matrix. Moreover, the natural cellulose paper possesses outstanding mechanical strength to tolerate the volume stress. In virtue of the modulated deposition behaviour and near‐zero volume change, the hybrid LMAs can achieve reversible Li plating/stripping even at an ultrahigh current density of 10 mA cm−2 as evidenced by high Coulombic efficiency (97.2 % after 60 cycles) and ultralong lifespan (1000 cycles) together with ultralow overpotential (25 mV). Therefore, this strategy sheds light on a scalable approach to multiscale design versatile Li host, promising highly stable Li metal batteries to be feasible and practical. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
27. Enhanced Energy Density of Coaxial Fiber Asymmetric Supercapacitor Based on MoS2@Fe2O3/Carbon Nanotube Paper and Ni(OH)2@NiCo2O4/Carbon Nanotube Fiber Electrodes.
- Author
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He, Hang, Yang, Xijia, Wang, Liying, Zhang, Xueyu, Li, Xuesong, and Lü, Wei
- Subjects
SUPERCAPACITOR electrodes ,ENERGY density ,ENERGY storage equipment ,ENERGY storage ,FIBERS ,POWER density - Abstract
Fiber supercapacitors are promising energy storage devices for potential application in wearable and miniaturized portable electronics, which currently suffer from difficulties in achieving high capacitance and energy density synchronously owing to the limited specific surface area of the electrode materials and material incompatibility between the two electrodes. Herein, a strategy is developed for the manufacture of coaxial asymmetric fiber supercapacitors by wrapping a core of PVA‐KOH gel electrolyte‐coated Ni(OH)2@NiCo2O4/CNT fibers with MoS2@Fe2O3/CNT paper. The as‐prepared coaxial fiber asymmetric supercapacitors exhibit a specific capacitance of 373 mF cm−2 (at a current density of 2 mA cm−2) and energy density of 0.13 mW h cm−2 (at a power density of 3.2 mW cm−2), and also show good rate capability, long cycle life, and excellent flexibility. This work provides the possibility for the practical application of fiber supercapacitors in wearable and portable energy storage equipment. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
28. Structural Self‐Assembly and Applications of Metal–Organic Molecular Containers with Flexible Backbones.
- Author
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Yang, Lu, Huang, Xiaoxue, Wang, Suna, Zhang, Daopeng, and Zhou, Zhen
- Subjects
FLEXIBLE packaging ,SUPRAMOLECULAR chemistry ,MOLECULAR recognition ,CHEMICAL properties ,FUNCTIONAL groups ,SPINE - Abstract
Supramolecular chemistry has become an interdisciplinary discipline of chemistry, physics, and biology. As a huge subunit of supramolecular compounds, the functional metal–organic supramolecular systems with well‐defined cavities which are able to accommodate size‐suitable guests via benign host‐guest behavior, have been known as "metal–organic molecular containers" (MOMCs) and attracted much attentions for their rich chemical properties and wide potential applications in molecular recognition, catalysis, bio‐medical and other fields. In particular, the MOMCs with flexible backbones exhibit a unique feature both in the aspect of structural construction and applications, due to the free rotation and self‐adaptively of the specific functional groups in the skeletons. In this paper, we review several selected examples of the coordination‐driven metal–organic supramolecular systems from the aspects of self‐assembly construction to the various applications. The self‐assembly strategies, especially the different choice of organic ligands with flexible backbones during the construction, leading to quite diverse configurations compared to the rigid ligands, have been also discussed to show a different perspective of metal–organic system construction. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
29. A New Kind of Fireproof, Flexible, Inorganic, Nanocomposite Paper and Its Application to the Protection Layer in Flame-Retardant Fiber-Optic Cables.
- Author
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Dong, Li ‐ Ying and Zhu, Ying ‐ Jie
- Subjects
NANOCOMPOSITE materials ,FIREPROOFING agents ,FIBER optic cables ,BIOCOMPATIBILITY ,TENSILE strength - Abstract
An innovative method for making a new kind of highly flexible, fireproof, inorganic, nanocomposite paper made from glass fibers (GFs) coated with network-structured hydroxyapatite ultralong nanowires (NS-HANWs) is reported. The NS-HANW/GF paper is fireproof, high-temperature resistant, highly flexible, highly exquisite, and smooth, which is comparable to high-quality advanced coated paper. The most incredible characteristic of the NS-HANW/GF paper is its incombustibility. The as-prepared NS-HANW/GF paper, with the addition of optimized inorganic additives, has high mechanical properties (tensile strength ≈16 MPa) and the tensile strength is nearly 15 times that of GF paper. In addition, the NS-HANW/GF paper exhibits a high biocompatibility, owing to the coating effect of NS-HANWs on GFs. Thermal analysis indicates that the NS-HANW/GF paper has high thermal stability at high temperatures up to 1000 °C. Competitive to conventional insulation materials, the NS-HANW/GF paper exhibits a low thermal conductivity and excellent heat insulation performance. Experiments show that the NS-HANW/GF paper is promising for application in the protection layer of fire-retardant fiber-optic cable. The NS-HANW/GF paper can also be used as printing, copying, or writing paper; nonflammable China paper; fire-retardant wallpaper; specialty fireproof paper; and so on. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
30. Covalent Organic Frameworks as Electrode Materials for Alkali Metal‐ion Batteries.
- Author
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Cui, Shuzhen, Miao, Wenxing, Peng, Hui, Ma, Guofu, Lei, Ziqiang, Zhu, Lei, and Xu, Yuxi
- Subjects
CARBON-based materials ,ALKALIES ,POROSITY ,ELECTRODES ,COVALENT bonds ,CONJUGATED polymers - Abstract
Covalent organic frameworks (COFs) are a class of porous crystalline polymeric materials constructed by linking organic small molecules through covalent bonds. COFs have the advantages of strong covalent bond network, adjustable pore structure, large specific surface area and excellent thermal stability, and have broad application prospects in various fields. Based on these advantages, rational COFs design strategies such as the introduction of active sites, construction of conjugated structures, and carbon material composite, etc. can effectively improve the conductivity and stability of the electrode materials in the field of batteries. This paper introduces the latest research results of high‐performance COFs electrode materials in alkali metal‐ion batteries (LIBs, SIBs, PIBs and LSBs) and other advanced batteries. The current challenges and future design directions of COFs‐based electrode are discussed. It provides useful insights for the design of novel COFs structures and the development of high‐performance alkali metal‐ion batteries. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
31. "Bubble‐Diode" Breathable Electrodes for Fast Gas Transport.
- Author
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He, Yi and Tan, Peng
- Abstract
Bubbles arising from wild gas evolution commonly exist in electrochemical systems, particularly in water electrolysis and rechargeable aqueous batteries (e. g. Zn‐air batteries). Substantial energy dissipation occurs due to the obstruction of active sites and ion‐conducting pathways by evolving bubbles. Efforts are made to elucidate effective strategies for fast gas transport, most of which focus on minimizing bubble size and facilitating their timely detachment through complex techniques such as constructing super‐hydrophilic nano‐structure electrodes, flowing electrolytes, and ultrasonic oscillation. Recently, an innovative, facile, and highly efficient method utilizing a breathable electrode design to promote gaseous molecules to the external environment emerges as a promising approach since it avoids remarkable bubble accumulation while remaining free of additional accessories. This paper highlights the origin and evolution of this promising design. Starting with introducing the basic concept of traditional breathable electrodes based on hydrophobic polymer networks and discussing the current progress made in underlying mechanisms, a detailed description of the advanced design inspired by a "bubble‐diode" concept with superior breathability follows. This Concept aims to contribute to a deep understanding of this technology and paves the way for further advancements in this renewable energy era. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
32. Scaffold Editing of Cubanes into Homocubanes, Homocuneanes via Cuneanes.
- Author
-
Takebe, Hiyori and Matsubara, Seijiro
- Subjects
CUBANES ,ISOMERIZATION ,BIOISOSTERES ,EDITING ,CATALYSTS - Abstract
The selective synthesis of cage‐type hydrocarbons through the editing of the highly symmetric molecule cubane can be anticipated as one of the efficient approaches. In this paper, we identify a catalyst that facilitates the efficient scaffold isomerization of cubanes into homocubanes. This approach, which involves the direct synthesis of homocubanol esters, is promising as a novel method for the synthesis of phenoxy bioisosteres. Additionally, we observed that the isomerization of 1,4‐bis(acyloxymethl)cubane results in the generation of both D2‐ and C2‐symmetrical bishomocubanes. The same catalyst was also applied to the isomerization of acyloxymethylcuneanes, producing homocuneanol esters. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
33. Colloidal and Thermal Stability of Three‐Component Hybrid Materials Containing Clay Mineral, Polysaccharide and Surfactant.
- Author
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Godek, Ewelina, Maciołek, Urszula, Kosińska‐Pezda, Małgorzata, Byczyński, Łukasz, Nowicka, Aldona, and Grządka, Elżbieta
- Subjects
HYBRID materials ,COLLOIDAL stability ,POLYSACCHARIDES ,CLAY minerals ,ALGINIC acid ,HALLOYSITE ,CELLULOSE fibers - Abstract
The paper presents the colloidal and thermal stability of the three‐component hybrid materials containing halloysite, polysaccharides (alginic acid, cationic cellulose and hydroxyethyl cellulose) and Tritons. TX‐100, TX‐165 and TX‐405 were used as non‐ionic surfactants. Stability and other properties of the hybrid materials were tested by the following methods: UV–Vis, TGA (thermogravimetric analysis) and DSC (differential scanning calorimetry), CHN (elemental analysis), SEM‐EDX (scanning electron microscopy with energy dispersive X‐ray spectroscopy) and tensiometry. According to the results with the increasing polymer concentration the colloidal stability of the tested systems also increases. Moreover, the addition of the surfactants causes the increase of polysaccharide adsorption but the colloidal stability of the tested systems decreases due to large weights of formed aggregates. As follows from the thermal analysis, the comparison of the TG/DTG‐DSC curves obtained for the investigated polymers confirms that their thermal decomposition courses have some common features. The obtained results have the application potential in the formation of the materials for the pollutants removal from water and sewages. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
34. Direct Lithium Extraction Using Intercalation Materials.
- Author
-
Wang, Jing and Koenig, Gary M.
- Subjects
CHEMICAL processes ,SUSTAINABLE development ,ELECTRIC vehicles ,ELECTRIC vehicle batteries ,LITHIUM ,CHEMICAL purification - Abstract
Worldwide lithium demand has surged in recent years due to increased production of Li‐ion batteries for electric vehicles and stationary storage. Li supply and production will need to increase such that the transition towards increased electrification in the energy sector does not become cost prohibitive. Many countries have taken policy steps such as listing Li as a critical mineral. Current commercial Li mining is mostly from dedicated mine sources, including ores, clays, and brines. The conventional ways to extract Li+ from those resources are through chemical processing and includes steps of calcination, leaching, precipitation, and purification. The environmental and economic sustainability of conventional Li processing has recently received increased scrutiny. Routes such as direct Li+ extraction may provide advantages relative to conventional Li+ extraction technologies, and one possible route to direct Li+ extraction includes leveraging intercalation materials. Intercalation material processing has recently demonstrated high selectivity towards Li+ as opposed to other cations. Reviews and reports of direct Li+ extraction with intercalation materials are limited, even as this technology has started to show promise in smaller‐scale demonstrations. This paper will review selective Li+ extraction via intercalation materials, including both electrochemical and chemical methods to drive Li+ in and out, and efforts to characterize the Li+ insertion/deinsertion processes. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
35. Elucidating the Electronic Nature of Rh‐based Paddlewheel Catalysts from 103Rh NMR Chemical Shifts: Insights from Quantum Mechanical Calculations.
- Author
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Gui, Xin, Sorbelli, Diego, Caló, Fabio P., Leutzsch, Markus, Patzer, Michael, Fürstner, Alois, Bistoni, Giovanni, and Auer, Alexander A.
- Subjects
RHODIUM catalysts ,NUCLEAR magnetic resonance spectroscopy ,CATALYST structure ,LIGANDS ,CATALYSTS ,ELECTRONIC structure - Abstract
The tremendous importance of dirhodium paddlewheel complexes for asymmetric catalysis is largely the result of an empirical optimization of the chiral ligand sphere about the bimetallic core. It was only recently that a H(C)Rh triple resonance 103Rh NMR experiment provided the long‐awaited opportunity to examine – with previously inconceivable accuracy – how variation of the ligands impacts on the electronic structure of such catalysts. The recorded effects are dramatic: formal replacement of only one out of eight O‐atoms surrounding the metal centers in a dirhodium tetracarboxylate by an N‐atom results in a shielding of the corresponding Rh‐site of no less than 1000 ppm. The current paper provides the theoretical framework that allows this and related experimental observations made with a set of 19 representative rhodium complexes to be interpreted. In line with symmetry considerations, it is shown that the shielding tensor responds only to the donor ability of the equatorial ligands along the perpendicular principal axis. Axial ligands, in contrast, have no direct effect on shielding but may come into play via the electronic cis ${cis}$ ‐effect that they exert onto the neighboring equatorial sites. On top of these fundamental interactions, charge redistribution within the core as well as the electronic trans ${trans}$ ‐effect of ligands of different donor strengths is reflected in the recorded 103Rh NMR shifts. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
36. Easy to Use DFT Approach for Computational pKa Determination of Carboxylic Acids.
- Author
-
Pezzola, Silvia, Venanzi, Mariano, Galloni, Pierluca, Conte, Valeria, and Sabuzi, Federica
- Subjects
CYANO group ,ACETIC acid ,GROUP 15 elements ,CARBOXYLIC acids ,SOLVATION ,FUNCTIONALS - Abstract
In pKa computational determination, the challenge in exploring and fostering new methodologies and approaches goes in parallel with the amelioration of computational performances. In this paper a "ready to use methodology" has been compared to other strategies, such as the re‐shaping in solvation cavity (Bondi radius re‐shaping), wanting to assess its reliability in predicting the pKa of a broad list of carboxylic acids. Thus, the functionals B3LYP and CAM‐B3LYP have been selected, using SMD as continuum solvation model. Exploiting our previous results, two water molecules were made explicit on the reaction centre. Data show that our model (CAM‐B3LYP/2H2O) is capable to accurately predict pKa, leading to mean absolute error (MAE) values lower than 0.5. Noteworthy, good results were achieved in computing the pKa of substituents bearing nitro and cyano groups. Focusing on B3LYP, eventually remarkable outputs were obtained only when Bondi correction was applied to the complex with two water molecules. Hence, massive outcomes were obtained in foreseeing the trichloro and trifluoro acetic acid pKa. These findings demonstrated that no complex level of theory nor external factor is required to accurately predict carboxylic acids pKa, with MAE well below 0.5 units. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
37. Modifying the Catalytic Activity of Lipopeptide Assemblies with Nucleobases.
- Author
-
Vela‐Gallego, Sonia, Lewandowski, Bartosz, Möhler, Jasper, Puente, Alonso, Gil‐Cantero, David, Wennemers, Helma, and de la Escosura, Andrés
- Subjects
CATALYTIC activity ,BASE pairs ,PEPTIDES ,FATTY acids ,MOIETIES (Chemistry) - Abstract
Biohybrid catalysts that operate in aqueous media are intriguing for systems chemistry. In this paper, we investigate whether control over the self‐assembly of biohybrid catalysts can tune their properties. As a model, we use the catalytic activity of functional hybrid molecules consisting of a catalytic H‐dPro‐Pro‐Glu tripeptide, derivatized with fatty acid and nucleobase moieties. This combination of simple biological components merged the catalytic properties of the peptide with the self‐assembly of the lipid, and the structural ordering of the nucleobases. The biomolecule hybrids self‐assemble in aqueous media into fibrillar assemblies and catalyze the reaction between butanal and nitrostyrene. The interactions between the nucleobases enhanced the order of the supramolecular structures and affected their catalytic activity and stereoselectivity. The results point to the significant control and ordering that nucleobases can provide in the self‐assembly of biologically inspired supramolecular catalysts. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
38. Mo2C/Reduced Graphene Oxide Composites with Enhanced Electrocatalytic Activity and Biocompatibility for Microbial Fuel Cells.
- Author
-
Guo, Wenxian, Chen, Meiqiong, Liu, Xiaoqing, Cheng, Faliang, and Lu, Xihong
- Subjects
MICROBIAL fuel cells ,GRAPHENE oxide ,CORPORATE bonds ,CARBON paper ,BIOCOMPATIBILITY ,CHARGE exchange - Abstract
A simple, cost‐effective strategy was developed to effectively improve the electron transfer efficiency as well as the power output of microbial fuel cells (MFCs) by decorating the commercial carbon paper (CP) anode with an advanced Mo2C/reduced graphene oxide (Mo2C/RGO) composite. Benefiting from the synergistic effects of the superior electrocatalytic activity of Mo2C, the high surface area, and prominent conductivity of RGO, the MFC equipped with this Mo2C/RGO composite yielded a remarkable output power density of 1747±37.6 mW m−2, which was considerably higher than that of CP‐MFC (926.8±6.3 mW m−2). Importantly, the composite also facilitated the formation of 3D hybrid biofilm and could effectively improve the bacteria–electrode interaction. These features resulted in an enhanced coulombic efficiency up 13.2 %, nearly one order of magnitude higher than that of the CP (1.2 %). [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
39. Single‐Step Synthesis of NiI from NiII with H2.
- Author
-
Takahashi, Chiaki, Yatabe, Takeshi, Nakai, Hidetaka, and Ogo, Seiji
- Subjects
ATOMIC hydrogen ,HYDROGEN atom ,CHARGE exchange ,IRON-nickel alloys ,HYDROGENASE ,CHEMISTS - Abstract
Chemists have long sought to regulate the reactivity of H2, to yield hydride ions, hydrogen atoms, or electrons on demand. One source of inspiration for achieving this control is [NiFe]hydrogenase ([NiFe]H2ase), which reacts with H2 to form various hydrogen active species such as NiIII hydride species, NiII hydride species, and NiI low‐valent species. Chemists have attempted to synthesize these hydrogen active species not only as models for the active species of [NiFe]H2ase, but also as electron transfer catalysts. However, the synthesis of NiI complex directly from H2 has not been reported. This paper reports the first example of a single‐step synthesis of a NiI complex, via reaction of a NiII complex with H2, stable for over 3 months at room temperature and we further demonstrate a reductive coupling of acridinium ions as part of a reaction cycle. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
40. Stimuli‐Responsive Properties on a Bisbenzofuropyrazine Core: Mechanochromism and Concentration‐Controlled Vapochromism.
- Author
-
Nakamura, Shotaro, Okubo, Kohei, Nishii, Yuji, Hirano, Koji, Tohnai, Norimitsu, and Miura, Masahiro
- Subjects
OPTICAL properties ,ORGANIC solvents ,CRYSTAL structure - Abstract
Stimulus‐responsive organic materials with luminescence switching properties have attracted considerable attention for their practical applications in sensing, security, and display devices. In this paper, bent‐type bisbenzofuropyrazine derivatives, Bent‐H and Bent‐sBu, with good solubilities were synthesized, and their physical and optical properties were investigated in detail. Bent‐H gave three crystalline polymorphs, and they showed different luminescence properties depending on their crystal packing structures. In addition, Bent‐H exhibited mechanochromic luminescence in spite of its rigid skeleton. Bent‐sBu exhibited unique concentration‐dependent vapochromic luminescence. Ground Bent‐sBu was converted to blue‐emissive, green‐emissive, and green‐emissive high‐viscosity solution states at low, moderate, and high concentrations of CHCl3 vapor, respectively. This finding represents a concentration‐dependent multi‐phase transition with an organic solvent, which is of potent interest for application in sensing systems. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
41. Chiral TPE Foldamers in Macrocycles: Aggregation Enhanced Emission and Circularly Polarized Luminescence.
- Author
-
Wang, Yuxiang, Cui, Liwen, Wang, Yiran, Li, Fei, Li, Yunzhi, and Meng, Qi
- Subjects
CHIRALITY of nuclear particles ,FLUORESCENCE yield ,LUMINESCENCE ,MOIETIES (Chemistry) - Abstract
Chiral macrocycles with circularly polarized luminescence (CPL) have attracted increasing attention due to the rigid structure, symmetrical chiral geometry and large luminescence dissymmetry factors (glum). However, most chiral macrocycles are more emissive in solutions but have weakened fluorescence quantum yields (ΦF) in aggregates, limiting their further application. In this paper, chiral macrocycle R/S‐PhTPE was synthesized by combining chiral macrocycle architectonics with Z‐o‐phenyltetraphenylethylene (PhTPE) foldamer. Enhanced solution state emission and characteristic aggregation enhanced emission (AEE) effect can be observed for R/S‐PhTPE due to the folded PhTPE conformation. Macrocycle immobilization and folded conformation endow PhTPE moiety with stable helical conformation. Most importantly, R/S‐PhTPE exhibits opposite CPL signals compared with common chiral TPEs, demonstrating the evident impact of folded conformation. This work reports the first and deep insights into the chiroptical properties of chiral PhTPE foldamers, and will provide a new strategy to tune ΦF and CPL signals of AIE active chiral macrocycles. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
42. The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide.
- Author
-
Cunha, Ana V., Havenith, Remco W. A., Van Alsenoy, Christian, and Blockhuys, Frank
- Subjects
KETONES ,VALENCE bonds ,DENSITY functional theory ,STATE bonds ,CHEMICAL bond lengths - Abstract
The surprising differences between the experimental solid‐state and calculated gas‐phase structures of 5‐oxo‐1,3,2,4‐dithiadiazole (Roesky's ketone, 1) and 1‐oxo‐1,2,4,3,5‐trithiadiazole (Roesky's sulfoxide, 2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations' considerable overestimations of the C−S and S−S bond lengths in 1 and 2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of 1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C−S bond with considerable double‐bond character – an effect which does not exist for the isolated molecule – explaining the much shorter bond in the solid state. For 2, a similar conclusion can be drawn for the S−S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main‐group systems remains a contributing factor. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
43. Highly Luminescent Dual Mode Polymeric Nanofiber‐Based Flexible Mat for White Security Paper and Encrypted Nanotaggant Applications.
- Author
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Gangwar, Amit Kumar, Gupta, Ashish, Kedawat, Garima, Kumar, Pawan, Singh, Bhanu Pratap, Singh, Nidhi, Srivastava, Avanish K., Dhakate, Sanjay R., and Gupta, Bipin Kumar
- Subjects
LUMINESCENCE ,NANOFIBERS ,NANORODS ,ELECTROSPINNING ,NANOFABRICS ,POLYVINYL alcohol - Abstract
Abstract: Increasing counterfeiting of important data, currency, stamp papers, branded products etc., has become a major security threat which could lead to serious damage to the global economy. Consequences of such damage are compelling for researchers to develop new high‐end security features to address full‐proof solutions. Herein, we report a dual mode flexible highly luminescent white security paper and nanotaggants composed of nanophosphors incorporated in polymer matrix to form a nanofiber‐based mat for anti‐counterfeiting applications. The dual mode nanofibers are fabricated by electrospinning technique by admixing the composite of NaYF
4 :Eu3+ @NaYF4 :Yb3+ , Er3+ nanophosphors in the polyvinyl alcohol solution. This flexible polymer mat derived from nanofibers appears white in daylight, while emitting strong red (NaYF4 :Eu3+ ) and green (NaYF4 :Yb3+ , Er3+ ) colors at excitation wavelengths of 254 nm and 980 nm, respectively. These luminescent nanofibers can also be encrypted as a new class of nanotaggants to protect confidential documents. These obtained results suggest that highly luminescent dual mode polymeric nanofiber‐based flexible white security paper and nanotaggants could offer next‐generation high‐end unique security features against counterfeiting. [ABSTRACT FROM AUTHOR]- Published
- 2018
- Full Text
- View/download PDF
44. Distance versus Capillary Flow Dynamics‐Based Detection Methods on a Microfluidic Paper‐Based Analytical Device (μPAD).
- Author
-
Chung, Soo, Jennings, Christian M., and Yoon, Jeong‐Yeol
- Subjects
CAPILLARY flow ,MICROFLUIDICS ,POINT-of-care testing ,CHEMICAL detectors ,DISTANCES - Abstract
In recent years, there has been high interest in paper‐based microfluidic sensors or microfluidic paper‐based analytical devices (μPADs) towards low‐cost, portable, and easy‐to‐use sensing for chemical and biological targets. μPAD allows spontaneous liquid flow without any external or internal pumping, as well as an innate filtration capability. Although both optical (colorimetric and fluorescent) and electrochemical detection have been demonstrated on μPADs, several limitations still remain, such as the need for additional equipment, vulnerability to ambient lighting perturbation, and inferior sensitivity. Herein, alternative detection methods on μPADs are reviewed to resolve these issues, including relatively well studied distance‐based measurements and the newer capillary flow dynamics‐based method. Detection principles, assay performance, strengths, and weaknesses are explained for these methods, along with their potential future applications towards point‐of‐care medical diagnostics and other field‐based applications. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
45. A Multiaddressable Dyad with Switchable Cyan/Magenta/Yellow Colors for Full‐Color Rewritable Paper.
- Author
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Qin, Tianyou, Han, Jiaqi, Geng, Yue, Ju, Le, Sheng, Lan, and Zhang, Sean Xiao‐An
- Subjects
SOLID state chemistry ,MOLECULAR switches ,PIGMENTS ,SUBSTRATES (Materials science) ,DISPERSION (Chemistry) - Abstract
Abstract: Reversible multicolor displays on solid media created from single‐molecule pigments are a long‐awaited goal. Herein, a new and simple molecular dyad, which can undergo switchable cyan (C), magenta (M), and yellow (Y) color changes in both solution and the solid state upon exposure to light, water/acid, and nucleophiles, has been designed and synthesized. The stimuli used herein can be applied independent of each other, which is beneficial for color changes without mutual interference. For comparison, mixtures of the two molecular switching motifs that form the basis of the dyad were also studied. The dyad greatly outperforms the corresponding mixed system with respect to reversible color switching on the paper substrate. Its potential for full‐color rewritable paper with excellent reversibility has been demonstrated. Legible multicolor prints, that is, high color contrast and resolution, good dispersion, and excellent reversibility, were achieved by using common water‐jet and light‐based printers. This work provides a very promising approach for the further development of full‐color switchable molecules, materials, and displays. [ABSTRACT FROM AUTHOR]
- Published
- 2018
- Full Text
- View/download PDF
46. Thioxanthylium Cations: Highly Reversible Hydrochromic Mate‐rials with Tunable Color and Moisture Sensitivity.
- Author
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Chua, Ming Hui, Soo, Xiang Yun Debbie, Goh, Wei Peng, Png, Zhuang Mao, Zhu, Qiang, and Xu, Jianwei
- Subjects
MOISTURE ,CATIONS ,TRIFLUOROACETIC acid ,COLOR ,HUMIDITY - Abstract
Hydrochromic materials, which change color in response to moisture, are highly sought‐after due to some unique applications such as moisture detection, humidity monitoring, anti‐counterfeiting, and sweat‐pore mapping. We herein report a new thioxanthene‐9‐ols/thioxanthylium cations hydrochromic system. The hydrochromic thioxanthylium cations can be generated/regenerated by exposing a chemically stable thioxanthene‐9‐ol to trifluoroacetic acid (TFA). The intensely colored thioxanthylium cations can be chemically reverted to the colorless thioxanthene‐9‐ol. Interestingly, the conversion between thioxanthene‐9‐ol and its cation species was found to be highly reversible in most cases (up to 50 activation‐deactivation cycles). The color and moisture‐sensitivity of thioxanthylium cations were also validated to be tunable via functionalization of the thioxanthene core with different aliphatic and aromatic groups at its 9 or 2,7‐positions. Finally, paper probes were prepared using solution‐immersion and inkjet‐printing techniques to demonstrate the system's potential applications in humidity sensing and anti‐counterfeiting [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
47. Chalcogen Bonding (ChB) as a Robust Supramolecular Recognition Motif of Benzisothiazolinone Antibacterials.
- Author
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Pizzi, Andrea, Daolio, Andrea, Beccaria, Roberta, Demitri, Nicola, Viani, Fiorenza, and Resnati, Giuseppe
- Subjects
ANTIFOULING paint ,BINDING sites ,GRAM-negative bacteria ,ANTIBACTERIAL agents ,CHEMICAL reactions ,COVALENT bonds - Abstract
1,2‐benzisothiazol‐3(2H)‐one derivatives are highly active against a broad spectrum of fungi as well as Gram positive and Gram negative bacteria. For this reason they are extensively used, for example, as additives in detergents, leather products, paper coatings, and antifouling paintings. In this paper experimental findings are reported proving that the sulfur atom of benzisothiazolinones have a remarkable tendency to form short and directional chalcogen bondings on the extension of the covalent N−S bond and, to a lesser extent, of the C−S bond. Analyses of the Cambridge Structural Database confirm the interaction as a primary recognition motif of these systems. The electrophilicity of sulfur is crucial in the chemical reactions initiating the cascade of events resulting in the biopharmacological activities of benzisothiazolinones. The reported results suggest that the electrophility of sulfur may play a role also at earlier stages than the reactive ones, namely it may pin the compounds at the active site of target enzymes via chalcogen bondings that preorganize the system in the conformation required for the bonds formation/cleavage determining the biopharmacological activity [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
48. Light‐Controlled Chemoenzymatic Immobilization of Proteins towards Engineering of Bioactive Papers.
- Author
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Hilberg, Valentina, Avrutina, Olga, Ebenig, Aileen, Yanakieva, Desislava, Meckel, Tobias, Biesalski, Markus, and Kolmar, Harald
- Subjects
RING formation (Chemistry) ,ENCAPSULATION (Catalysis) ,PERICYCLIC reactions ,CHEMICAL reactions ,SORTASES - Abstract
Efficient and reliable methods for the generation of bioactive papers are of growing interest in relation to point‐of‐care testing devices that do not require extensive analytical equipment. Herein, we report the immobilization of functional proteins on paper fibers using a modular chemoenzymatic approach. The synthetic strategy relies on a combination of highly efficient spatially controllable photo‐triggered cycloaddition followed by site‐specific sortase A‐catalyzed transamidation. This site‐directed and regiospecific method has allowed unidirectional and covalent immobilization of several proteins displaying different functional properties, with ramifications for application in paper‐based diagnostics. Protein‐functionalized paper: A modular approach to covalent protein immobilization on paper fibers is reported, which relies on a set of highly efficient pericyclic reactions in combination with site‐specific enzymatic coupling. Following initial derivatization of a cellulosic surface (see figure), light‐triggered covalent anchoring of an enzyme recognition site ensures enzyme‐promoted ligation of desired proteins with preservation of their function. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
49. An Effective Osteogenesis Porous CaP/Collagen Interface Compatible with Various Substrates Fabricated by Controlled Mineralization in a Delicately Adjustable Organic Matrix.
- Author
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Ma, Zequn, Li, Weiyang, Zhang, Yihe, Shi, Rui, Zhang, Yi, Zhang, Jingshuang, Li, Xiangming, Lu, Limei, and An, Qi
- Subjects
BONE growth ,COLLAGEN ,BIOMIMETIC materials ,MINERALIZATION ,TISSUE engineering ,METAL mesh ,FILTER paper ,MELANOGENESIS - Abstract
Increasing bone formation on the surfaces of implants such as screws, plates, or shims holds great significance for clinical medicine. However, osteogenesis implant coatings that mimic natural bone in terms of both their components and structural features are still lacking. Here we report the biomimetic interface of calcium phosphate (CaP) in a collagen matrix fabricated by controlled mineralization that presents biomimetic porous features. The porous CaP/collagen interface, with a thickness of about 1 μm, significantly enhances osteogenesis, as verified at both the gene and protein levels as well as by in vivo experiments. Taking advantage of the generality of the method, the biomimetic interface was prepared on a variety of substrates, including conductive substrates, 3D metal meshes, plastic or elastic substrates, and even on filter papers. The adjustability and generality of the method have enabled new characterization tests to be developed during experiments on cells and thus should greatly facilitate clinical medicine and tissue engineering. [ABSTRACT FROM AUTHOR]
- Published
- 2019
- Full Text
- View/download PDF
50. Surface Modification Functionalized Carbon Dots.
- Author
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Wang, Haolin, Ai, Lin, Song, Ziqi, Nie, Mingjun, Xiao, Jiping, Li, Guoping, and Lu, Siyu
- Subjects
SYNTHETIC products ,NATURAL products ,CARBON ,ORGANIC products ,ORGANIC compounds - Abstract
Carbon dots (CDs) smaller than 10 nm constitute a new type of fluorescent carbon‐based nanomaterial. They have attracted much attention owing to their unique structures and excellent photoelectric properties. Primitive CDs usually comprise carbon and oxygen and are synthesized in one step from various natural products or synthetic organic compounds, usually via microwave or hydrothermal methods. However, the uniformity of surface functional groups often make CDs lack the diversity of active sites required for specific applications. Therefore, the functionalization of CDs by specific groups is a powerful strategy for improving their photophysical and photochemical properties. This paper reviews surface modification strategies to overcome these shortcomings. Functionalizing CDs using covalent or non‐covalent modification can give them unique properties and broaden their applicability. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
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