Mghaib Al Shahrani, Mabrook S. Amer, Ahmad A. Alsaleh, Prabhakarn Arunachalam and Abdullah M. Al-Mayouf
The fabrication of earth-abundant electrocatalysts capable of facilitating hydrogen evolution reactions (HER) is essential for creating sustainable hydrogen fuel by water splitting. Here, we present a one-pot hydrothermal approach for producing aluminum and phosphorus co-doped NiS/Ni3S2/WS2 heterostructure hybrid frameworks on nickel foam. The optimal Al and Al, P/NiWS-b@NF catalyst exhibits high HER activity with overpotentials of 139 and 227 mV at current densities of 10 and 50 mA cm−2, respectively, thanks to the synergistic effect of the various constituents of the catalyst. What is more, it also exhibits a promising Tafel slope of 124 mV dec−1 and is electrocatalytically durable for 10 hours in 0.5 M H2SO4 solution. The high HER activity of Al, P/NiWS-b@NF could be explained by the large number of active sites of the hierarchical heterostructure and electron effects produced by the combination of interfacial and aluminum and phosphorus doping.
制备能够促进氢进化反应(HER)的富土电催化剂对于通过水分裂产生可持续氢燃料至关重要。在此,我们介绍了一种在泡沫镍上制备铝磷共掺杂 NiS/Ni3S2/WS2 异质结构杂化框架的单锅水热法。由于催化剂中各种成分的协同作用,最佳的铝和铝磷/NiWS-b@NF 催化剂表现出很高的 HER 活性,在电流密度为 10 mA cm-2 和 50 mA cm-2 时,过电位分别为 139 mV 和 227 mV。此外,它还表现出 124 mV dec-1 的良好塔菲尔斜率,并且在 0.5 M H2SO4 溶液中具有 10 小时的电催化持久性。Al、P/NiWS-b@NF 的高 HER 活性可归因于分层异质结构的大量活性位点以及界面掺杂和铝磷掺杂结合产生的电子效应。
{"title":"Al, P-co-doping and interface engineering synergistically boost the electrocatalytic performance of WS2/Ni3S2/NiS nanosheet heterostructure for efficient hydrogen evolution reaction†","authors":"Mghaib Al Shahrani, Mabrook S. Amer, Ahmad A. Alsaleh, Prabhakarn Arunachalam and Abdullah M. Al-Mayouf","doi":"10.1039/D4RA05868B","DOIUrl":"https://doi.org/10.1039/D4RA05868B","url":null,"abstract":"<p >The fabrication of earth-abundant electrocatalysts capable of facilitating hydrogen evolution reactions (HER) is essential for creating sustainable hydrogen fuel by water splitting. Here, we present a one-pot hydrothermal approach for producing aluminum and phosphorus co-doped NiS/Ni<small><sub>3</sub></small>S<small><sub>2</sub></small>/WS<small><sub>2</sub></small> heterostructure hybrid frameworks on nickel foam. The optimal Al and Al, P/NiWS-b@NF catalyst exhibits high HER activity with overpotentials of 139 and 227 mV at current densities of 10 and 50 mA cm<small><sup>−2</sup></small>, respectively, thanks to the synergistic effect of the various constituents of the catalyst. What is more, it also exhibits a promising Tafel slope of 124 mV dec<small><sup>−1</sup></small> and is electrocatalytically durable for 10 hours in 0.5 M H<small><sub>2</sub></small>SO<small><sub>4</sub></small> solution. The high HER activity of Al, P/NiWS-b@NF could be explained by the large number of active sites of the hierarchical heterostructure and electron effects produced by the combination of interfacial and aluminum and phosphorus doping.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra05868b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rehana A. Khan, Vishnu A. Adole, Thansing B. Pawar and Bapu S. Jagdale
This study explores a novel and eco-friendly synthesis of 22 derivatives of 2-aryl/heteroaryl substituted 2,3-dihydroquinazolin-4(1H)-ones, compounds with significant medicinal potential, using concentrated solar radiation (CSR) and lemon juice as a natural catalyst. Traditional methods for synthesizing these compounds often involve complex, energy-intensive processes and toxic reagents. In contrast, the method presented here utilizes solar energy and a biodegradable, non-toxic catalyst, aligning with the principles of green chemistry. The reaction, involving 2-aminobenzamide and various aromatic and heteroaromatic aldehydes, was optimized by varying temperature, catalyst concentration, and solvent. Through optimization, a combination of 0.3 mL of lemon juice and CSR achieved a 97% product yield in 10 minutes. A wide range of aromatic and heteroaromatic aldehydes were tested, all of which produced excellent yields, confirming the method's broad applicability. The substrate scope was explored with different aldehydes, containing groups/structures like chloro, bromo, nitro, methyl, methoxy, fluoro, hydroxy, imidazole, thiazole, chromone, pyrrole, and 1,4-dioxane, yielding up to 97%. Comparative studies with other catalysts and solvents confirmed the superior efficiency of lemon juice. This study not only demonstrates a sustainable approach to synthesizing 2,3-dihydroquinazolin-4(1H)-ones but also highlights the potential of solar energy in organic synthesis, offering a viable alternative to conventional methods. This environmentally benign method offers an efficient and sustainable route for synthesizing 2,3-dihydroquinazolin-4(1H)-one derivatives.
{"title":"Green chemistry approach to the synthesis of 2-aryl/heteroaryl substituted 2,3-dihydroquinazolin-4(1H)-ones using lemon juice under concentrated solar radiations as a renewable source†","authors":"Rehana A. Khan, Vishnu A. Adole, Thansing B. Pawar and Bapu S. Jagdale","doi":"10.1039/D4RA05772D","DOIUrl":"https://doi.org/10.1039/D4RA05772D","url":null,"abstract":"<p >This study explores a novel and eco-friendly synthesis of 22 derivatives of 2-aryl/heteroaryl substituted 2,3-dihydroquinazolin-4(1<em>H</em>)-ones, compounds with significant medicinal potential, using concentrated solar radiation (CSR) and lemon juice as a natural catalyst. Traditional methods for synthesizing these compounds often involve complex, energy-intensive processes and toxic reagents. In contrast, the method presented here utilizes solar energy and a biodegradable, non-toxic catalyst, aligning with the principles of green chemistry. The reaction, involving 2-aminobenzamide and various aromatic and heteroaromatic aldehydes, was optimized by varying temperature, catalyst concentration, and solvent. Through optimization, a combination of 0.3 mL of lemon juice and CSR achieved a 97% product yield in 10 minutes. A wide range of aromatic and heteroaromatic aldehydes were tested, all of which produced excellent yields, confirming the method's broad applicability. The substrate scope was explored with different aldehydes, containing groups/structures like chloro, bromo, nitro, methyl, methoxy, fluoro, hydroxy, imidazole, thiazole, chromone, pyrrole, and 1,4-dioxane, yielding up to 97%. Comparative studies with other catalysts and solvents confirmed the superior efficiency of lemon juice. This study not only demonstrates a sustainable approach to synthesizing 2,3-dihydroquinazolin-4(1<em>H</em>)-ones but also highlights the potential of solar energy in organic synthesis, offering a viable alternative to conventional methods. This environmentally benign method offers an efficient and sustainable route for synthesizing 2,3-dihydroquinazolin-4(1<em>H</em>)-one derivatives.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra05772d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fiona Pescher, Julian Stiegeler, Philipp A. Heizmann, Carolin Klose, Severin Vierrath and Matthias Breitwieser
Particle atomic layer deposition (ALD) is an emerging method for engineering 3D materials, such as powders, for energy applications. In our study, we employ a commercially available and scalable particle ALD system to synthesize Pt/C electrocatalysts for fuel cells. Our method yields Pt/C catalysts characterized by highly dispersed platinum nanoparticles with a narrow particle size distribution of 2.2 ± 0.5 nm for 30 wt% Pt and 2.6 ± 0.6 nm for 40 wt% Pt, as verified through transmission electron microscopy and X-ray diffraction analysis. The performance of the ALD-synthesized catalysts is benchmarked against a state-of-the-art catalyst (TEC10V50E), with both catalysts exhibiting similar beginning-of-test performance (1.6 A cm−2 at 0.65 V) under application-relevant operation conditions (80 °C, 50% relative humidity). After 30 000 voltage cycles, conducted in accordance with the U.S. Department of Energy's accelerated catalyst degradation test, the ALD catalysts demonstrate up to 64% greater electrochemical active surface areas and superior retention of cell performance, with a 34% higher current density at 0.65 V, compared to the reference. Given the scalability of the commercial particle ALD system, these promising results encourage the use of particle ALD as a novel synthesis approach for fuel cell catalyst materials in the industry.
粒子原子层沉积(ALD)是一种新兴的能源应用三维材料(如粉末)工程方法。在我们的研究中,我们采用了一种商用的、可扩展的粒子原子层沉积系统来合成用于燃料电池的 Pt/C 电催化剂。经透射电子显微镜和 X 射线衍射分析验证,我们的方法可制得 Pt/C 催化剂,其特点是铂纳米颗粒高度分散,粒度分布较窄,30 wt% 的铂为 2.2 ± 0.5 nm,40 wt% 的铂为 2.6 ± 0.6 nm。ALD 合成催化剂的性能以最先进的催化剂(TEC10V50E)为基准,在应用相关的操作条件(80 °C、50% 相对湿度)下,两种催化剂都表现出相似的起始测试性能(0.65 V 下 1.6 A cm-2)。根据美国能源部的催化剂加速降解测试,经过 30,000 次电压循环后,ALD 催化剂的电化学活性表面积增加了 64%,电池性能保持得更好,在 0.65 V 电压下的电流密度比对照催化剂高出 34%。考虑到商用颗粒 ALD 系统的可扩展性,这些令人鼓舞的结果鼓励业界使用颗粒 ALD 作为燃料电池催化剂材料的新型合成方法。
{"title":"Pt/C catalysts synthesized in a commercial particle atomic layer deposition system enabling improved durability in fuel cells","authors":"Fiona Pescher, Julian Stiegeler, Philipp A. Heizmann, Carolin Klose, Severin Vierrath and Matthias Breitwieser","doi":"10.1039/D4RA04708G","DOIUrl":"https://doi.org/10.1039/D4RA04708G","url":null,"abstract":"<p >Particle atomic layer deposition (ALD) is an emerging method for engineering 3D materials, such as powders, for energy applications. In our study, we employ a commercially available and scalable particle ALD system to synthesize Pt/C electrocatalysts for fuel cells. Our method yields Pt/C catalysts characterized by highly dispersed platinum nanoparticles with a narrow particle size distribution of 2.2 ± 0.5 nm for 30 wt% Pt and 2.6 ± 0.6 nm for 40 wt% Pt, as verified through transmission electron microscopy and X-ray diffraction analysis. The performance of the ALD-synthesized catalysts is benchmarked against a state-of-the-art catalyst (TEC10V50E), with both catalysts exhibiting similar beginning-of-test performance (1.6 A cm<small><sup>−2</sup></small> at 0.65 V) under application-relevant operation conditions (80 °C, 50% relative humidity). After 30 000 voltage cycles, conducted in accordance with the U.S. Department of Energy's accelerated catalyst degradation test, the ALD catalysts demonstrate up to 64% greater electrochemical active surface areas and superior retention of cell performance, with a 34% higher current density at 0.65 V, compared to the reference. Given the scalability of the commercial particle ALD system, these promising results encourage the use of particle ALD as a novel synthesis approach for fuel cell catalyst materials in the industry.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04708g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Subham Preetam, Arka Ghosh, Richa Mishra, Arunima Pandey, Debanjan Singha Roy, Sarvesh Rustagi and Sumira Malik
Electrical stimulation (ES) has emerged as a powerful therapeutic modality for enhancing biological wound healing. This non-invasive technique utilizes low-level electrical currents to promote tissue regeneration and expedite the wound healing process. ES has been shown to accelerate wound closure, reduce inflammation, enhance angiogenesis, and modulate cell migration and proliferation through various mechanisms. The principle goal of wound management is the rapid recovery of the anatomical continuity of the skin, to prevent infections from the external environment and maintain homeostasis conditions inside. ES at the wound site is a compelling strategy for skin wound repair. Several ES applications are described in medical literature like AC, DC, and PC to improve cutaneous perfusion and accelerate wound healing. This review aimed to evaluate the primary factors and provides an overview of the potential benefits and mechanisms of ES in wound healing, and its ability to stimulate cellular responses, promote tissue regeneration, and improve overall healing outcomes. We also shed light on the application of ES which holds excellent promise as an adjunct therapy for various types of wounds, including chronic wounds, diabetic ulcers, and surgical incisions.
电刺激(ES)已成为促进生物伤口愈合的一种强有力的治疗方式。这种非侵入性技术利用低水平电流促进组织再生,加快伤口愈合过程。研究表明,ES 能通过各种机制加速伤口闭合、减少炎症、促进血管生成以及调节细胞迁移和增殖。伤口处理的主要目标是迅速恢复皮肤解剖学上的连续性,防止外部环境的感染并维持内部的平衡状态。在伤口部位使用 ES 是一种令人信服的皮肤伤口修复策略。医学文献中描述了多种 ES 应用,如交流、直流和 PC,以改善皮肤灌注并加速伤口愈合。本综述旨在评估主要因素,并概述 ES 在伤口愈合中的潜在益处和机制,及其刺激细胞反应、促进组织再生和改善整体愈合效果的能力。我们还对 ES 的应用进行了阐述,ES 作为一种辅助疗法在治疗各种类型的伤口(包括慢性伤口、糖尿病溃疡和手术切口)方面前景广阔。
{"title":"Electrical stimulation: a novel therapeutic strategy to heal biological wounds","authors":"Subham Preetam, Arka Ghosh, Richa Mishra, Arunima Pandey, Debanjan Singha Roy, Sarvesh Rustagi and Sumira Malik","doi":"10.1039/D4RA04258A","DOIUrl":"https://doi.org/10.1039/D4RA04258A","url":null,"abstract":"<p >Electrical stimulation (ES) has emerged as a powerful therapeutic modality for enhancing biological wound healing. This non-invasive technique utilizes low-level electrical currents to promote tissue regeneration and expedite the wound healing process. ES has been shown to accelerate wound closure, reduce inflammation, enhance angiogenesis, and modulate cell migration and proliferation through various mechanisms. The principle goal of wound management is the rapid recovery of the anatomical continuity of the skin, to prevent infections from the external environment and maintain homeostasis conditions inside. ES at the wound site is a compelling strategy for skin wound repair. Several ES applications are described in medical literature like AC, DC, and PC to improve cutaneous perfusion and accelerate wound healing. This review aimed to evaluate the primary factors and provides an overview of the potential benefits and mechanisms of ES in wound healing, and its ability to stimulate cellular responses, promote tissue regeneration, and improve overall healing outcomes. We also shed light on the application of ES which holds excellent promise as an adjunct therapy for various types of wounds, including chronic wounds, diabetic ulcers, and surgical incisions.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04258a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel, clean and efficient protocol for the preparation of disulfides has been developed through the photochemical radical homo- and cross-coupling reaction of sulfenyl chlorides under LED irradiation and without the use of any catalyst and additive. The representative photochemical homo-coupling of trichloromethyl sulfenyl chloride has been successfully conducted on kilogram-scale in a continuous flow mode. The solvent and the main byproduct can be recovered in high yields, which makes the approach be highly atom economical.
在 LED 的照射下,不使用任何催化剂和添加剂,通过亚磺酰氯的光化学自由基同偶联和交叉偶联反应,开发出一种新颖、清洁和高效的二硫化物制备方法。具有代表性的三氯甲基亚磺酰氯光化学均偶联反应已在公斤级规模上以连续流模式成功进行。溶剂和主要副产品的回收率都很高,因此该方法具有很高的原子经济性。
{"title":"A facile, catalyst- and additive-free, and scalable approach to the photochemical preparation of disulfides from organosulfenyl chlorides†","authors":"Wei Liu, Jiayi Wang and Gonghua Song","doi":"10.1039/D4RA04568H","DOIUrl":"https://doi.org/10.1039/D4RA04568H","url":null,"abstract":"<p >A novel, clean and efficient protocol for the preparation of disulfides has been developed through the photochemical radical homo- and cross-coupling reaction of sulfenyl chlorides under LED irradiation and without the use of any catalyst and additive. The representative photochemical homo-coupling of trichloromethyl sulfenyl chloride has been successfully conducted on kilogram-scale in a continuous flow mode. The solvent and the main byproduct can be recovered in high yields, which makes the approach be highly atom economical.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04568h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saeed Hosseinpoor, Mehrdad Pourayoubi, Eliška Zmeškalová and Morgane Poupon
Differences/similarities of supramolecular motifs are discussed in two new thiophosphoramide structures and their Ni molecular complexes: (C2H5O)2P(S)(NHC(S)NHCH2C6H4X) and [{(C2H5O)2P(S)(NC(S)NHCH2C6H4X)}2Ni] (X = Cl/CH3I/II and III/IV). The structures have equal numbers of donor/acceptor sites contributing to classical hydrogen bonds (PS/CS and 2 × NH in ligands and 2 × PS and 2 × NH in the complexes). However, these donor and acceptor sites contribute to inter/intramolecular hydrogen bonding in ligands and intramolecular hydrogen bonding in complexes. In the supramolecular assemblies of the ligands, the classic hydrogen bonds (N–H⋯SC) are restricted in dimer synthons, and the weaker interactions (formed by Cl/CH3 substituents) compete against each other. In the complexes, despite the lack of classic intermolecular hydrogen bond, numerous weak interactions, e.g., C–H⋯Y (Y = S, O, Ni, N, and π), contribute to the molecular assemblies, which do not include the participation of Cl/CH3. Thus, different packing features of ligands, but similar in complexes are observed. Each ligand and the associated complex show nearly equal supramolecular motifs in the slice of the substituted benzyl groups, related to the formation of C–H⋯Cl/π⋯π for the 4-Cl-C6H4CH2 groups in I/III and C–H⋯π for the 4-CH3-C6H4CH2 groups in II/IV. The repeatabilities of the motifs made by 4-Cl-C6H4CH2/4-CH3-C6H4CH2 were checked by surveying 142/844 structures with 178/1482 segments in the CSD, which show that 17% and 12% of the structures exhibited similarities with the title structures. The methods X-ray crystallography, 2D fingerprint plots, electrostatic potential surfaces, QTAIM, and energy framework calculations were applied to present the discussion.
{"title":"Supramolecular motifs formed by CH3/Cl-substituted arene groups: evidence for structural differences in thiophosphoramides and similarities in their complexes†","authors":"Saeed Hosseinpoor, Mehrdad Pourayoubi, Eliška Zmeškalová and Morgane Poupon","doi":"10.1039/D4RA05281A","DOIUrl":"https://doi.org/10.1039/D4RA05281A","url":null,"abstract":"<p >Differences/similarities of supramolecular motifs are discussed in two new thiophosphoramide structures and their Ni molecular complexes: (C<small><sub>2</sub></small>H<small><sub>5</sub></small>O)<small><sub>2</sub></small>P(S)(NHC(S)NHCH<small><sub>2</sub></small>C<small><sub>6</sub></small>H<small><sub>4</sub></small>X) and [{(C<small><sub>2</sub></small>H<small><sub>5</sub></small>O)<small><sub>2</sub></small>P(S)(NC(S)NHCH<small><sub>2</sub></small>C<small><sub>6</sub></small>H<small><sub>4</sub></small>X)}<small><sub>2</sub></small>Ni] (X = Cl/CH<small><sub>3</sub></small> <strong>I</strong>/<strong>II</strong> and <strong>III</strong>/<strong>IV</strong>). The structures have equal numbers of donor/acceptor sites contributing to classical hydrogen bonds (PS/CS and 2 × NH in ligands and 2 × PS and 2 × NH in the complexes). However, these donor and acceptor sites contribute to inter/intramolecular hydrogen bonding in ligands and intramolecular hydrogen bonding in complexes. In the supramolecular assemblies of the ligands, the classic hydrogen bonds (N–H⋯S<img>C) are restricted in dimer synthons, and the weaker interactions (formed by Cl/CH<small><sub>3</sub></small> substituents) compete against each other. In the complexes, despite the lack of classic intermolecular hydrogen bond, numerous weak interactions, <em>e.g.</em>, C–H⋯Y (Y = S, O, Ni, N, and π), contribute to the molecular assemblies, which do not include the participation of Cl/CH<small><sub>3</sub></small>. Thus, different packing features of ligands, but similar in complexes are observed. Each ligand and the associated complex show nearly equal supramolecular motifs in the slice of the substituted benzyl groups, related to the formation of C–H⋯Cl/π⋯π for the 4-Cl-C<small><sub>6</sub></small>H<small><sub>4</sub></small>CH<small><sub>2</sub></small> groups in <strong>I</strong>/<strong>III</strong> and C–H⋯π for the 4-CH<small><sub>3</sub></small>-C<small><sub>6</sub></small>H<small><sub>4</sub></small>CH<small><sub>2</sub></small> groups in <strong>II</strong>/<strong>IV</strong>. The repeatabilities of the motifs made by 4-Cl-C<small><sub>6</sub></small>H<small><sub>4</sub></small>CH<small><sub>2</sub></small>/4-CH<small><sub>3</sub></small>-C<small><sub>6</sub></small>H<small><sub>4</sub></small>CH<small><sub>2</sub></small> were checked by surveying 142/844 structures with 178/1482 segments in the CSD, which show that 17% and 12% of the structures exhibited similarities with the title structures. The methods X-ray crystallography, 2D fingerprint plots, electrostatic potential surfaces, QTAIM, and energy framework calculations were applied to present the discussion.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra05281a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marta Ximenis, Santiago Cañellas, Rosa M. Gomila, Bartomeu Galmés, Antonio Frontera, Antonio Costa and Carmen Rotger
The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (kOH ≈ 10−1 M−1 s−1) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.
{"title":"Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters†","authors":"Marta Ximenis, Santiago Cañellas, Rosa M. Gomila, Bartomeu Galmés, Antonio Frontera, Antonio Costa and Carmen Rotger","doi":"10.1039/D4RA04362F","DOIUrl":"https://doi.org/10.1039/D4RA04362F","url":null,"abstract":"<p >The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (<em>k</em><small><sub>OH</sub></small> ≈ 10<small><sup>−1</sup></small> M<small><sup>−1</sup></small> s<small><sup>−1</sup></small>) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra04362f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xia Chen, Zhaolong He, Shiqiang Xu, Yu Zou and Yonghui Zhang
Aryldihydronaphthalenes (ADHNs) and their derivatives are widely found in many types of natural products, bioactive compounds, and functional materials, and are also important synthetic intermediates in organic chemistry, attracting widespread attention from both organic and pharmaceutical chemists. In the past two decades, the chemical synthesis and biological activity of ADHNs and their derivatives have become two hot spots. This review summarizes the synthetic protocols of ADHN derivatives, introduces some representative examples of the reaction mechanism, and focuses on the research progress of ADHNs in natural product chemistry and chemical biology since 2000.
{"title":"Chemical synthesis and application of aryldihydronaphthalene derivatives","authors":"Xia Chen, Zhaolong He, Shiqiang Xu, Yu Zou and Yonghui Zhang","doi":"10.1039/D4RA06517D","DOIUrl":"https://doi.org/10.1039/D4RA06517D","url":null,"abstract":"<p >Aryldihydronaphthalenes (ADHNs) and their derivatives are widely found in many types of natural products, bioactive compounds, and functional materials, and are also important synthetic intermediates in organic chemistry, attracting widespread attention from both organic and pharmaceutical chemists. In the past two decades, the chemical synthesis and biological activity of ADHNs and their derivatives have become two hot spots. This review summarizes the synthetic protocols of ADHN derivatives, introduces some representative examples of the reaction mechanism, and focuses on the research progress of ADHNs in natural product chemistry and chemical biology since 2000.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06517d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409107","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In recent years, biodegradable medical polymer materials (BMPMs) have stood out among many biomedical materials due to their unique advantages, such as high mechanical strength, good biocompatibility, strong corrosion resistance and excellent processability. In this review, we first provide a brief introduction of biodegradable medical materials from both natural and synthetic perspectives, and then systematically categorize BMPMs based on their applications in clinical medicine and highlight the great progress they have made in recent years. Additionally, we also point out several overlooked areas in the research of BMPMs, offering guidance for comprehensive future exploration of these materials. Finally, in view of the complex challenges faced by BMPMs today, their future directions are scientifically proposed. This work contributes to the ongoing efforts of BMPMs in the biomedical field and provides a steppingstone for developing more effective BMPM-based products for clinical applications.
{"title":"Tremendous advances, multifaceted challenges and feasible future prospects of biodegradable medical polymer materials","authors":"Fulong Li, Chao Chen and Xiaohong Chen","doi":"10.1039/D4RA00075G","DOIUrl":"https://doi.org/10.1039/D4RA00075G","url":null,"abstract":"<p >In recent years, biodegradable medical polymer materials (BMPMs) have stood out among many biomedical materials due to their unique advantages, such as high mechanical strength, good biocompatibility, strong corrosion resistance and excellent processability. In this review, we first provide a brief introduction of biodegradable medical materials from both natural and synthetic perspectives, and then systematically categorize BMPMs based on their applications in clinical medicine and highlight the great progress they have made in recent years. Additionally, we also point out several overlooked areas in the research of BMPMs, offering guidance for comprehensive future exploration of these materials. Finally, in view of the complex challenges faced by BMPMs today, their future directions are scientifically proposed. This work contributes to the ongoing efforts of BMPMs in the biomedical field and provides a steppingstone for developing more effective BMPM-based products for clinical applications.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra00075g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yujie Shi, Ganpeng Li, Ruirui Wang, Xiao-jing Zhao and Yonghui He
A new copper and electrocatalytic synergy strategy for efficiently constructing fused quinazolinones has been developed. In the presence of cupric acetate and oxygen, aryl ketones and 1,2,3,4-tetrahydroisoquinoline can smoothly participate in this transformation, thus providing a variety of substituted quinazolones in an undivided cell. The reaction shows good functional group tolerance and provides universal quinazolinones at a good yield under mild conditions.
{"title":"Copper and electrocatalytic synergy for the construction of fused quinazolinones with 2-aminobenzaldehydes and cyclic amines†","authors":"Yujie Shi, Ganpeng Li, Ruirui Wang, Xiao-jing Zhao and Yonghui He","doi":"10.1039/D4RA06539E","DOIUrl":"https://doi.org/10.1039/D4RA06539E","url":null,"abstract":"<p >A new copper and electrocatalytic synergy strategy for efficiently constructing fused quinazolinones has been developed. In the presence of cupric acetate and oxygen, aryl ketones and 1,2,3,4-tetrahydroisoquinoline can smoothly participate in this transformation, thus providing a variety of substituted quinazolones in an undivided cell. The reaction shows good functional group tolerance and provides universal quinazolinones at a good yield under mild conditions.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra06539e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142409108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}