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Review on Synthesis of 2-(2-Hydroxyaryl) Benzothiazoles (HBT) for Excited-State Intra-molecular Proton Transfer (ESIPT)-Based Detection of Ions and Biomolecules. 基于激发态分子内质子转移 (ESIPT) 的离子和生物大分子检测的 2-(2-羟基芳基) 苯并噻唑 (HBT) 的合成综述。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-07-18 DOI: 10.1007/s41061-024-00472-x
Amandeep Kaur, R P Chaudhary

In this review, we present a systematic and comprehensive summary of the recent developments in the synthetic strategies of 2-(2-hydroxyarylsubstituted)-benzothiazole (HBT) framework along with incorporation of various substituents on phenolic and benzothiazole rings which affect the emission process. The literature, spanning the years 2015-2024, on excited-state intramolecular proton transfer (ESIPT)-based studies of HBT derivatives comprising the effects of solvent polarity, substituents, and extended conjugation on fluorophores has been searched. ESIPT, intramolecular charge transfer, and aggregation-induced emissions enable these fluorescent probes to specifically interact with analytes, thereby altering their luminescence characteristics to achieve analyte detection. These fluorescent probes exhibit large Stokes shifts, high quantum yields, and excellent color transitions. Finally, the applications of HBTs as ESIPT-based fluorescent probes for the detection of cations, anions, and biomolecules have been summarized. We anticipate that this review will provide a comprehensive overview of the current state of research in this field and encourage researchers to develop novel ESIPT-based fluorophores with new applications.

在这篇综述中,我们系统而全面地总结了 2-(2-羟基芳基取代)-苯并噻唑(HBT)框架合成策略的最新进展,以及在酚醛环和苯并噻唑环上加入各种取代基对发射过程的影响。我们搜索了 2015-2024 年间基于激发态分子内质子转移(ESIPT)研究 HBT 衍生物的文献,包括溶剂极性、取代基和扩展共轭对荧光团的影响。ESIPT、分子内电荷转移和聚集诱导发射使这些荧光探针能够与分析物发生特异性相互作用,从而改变其发光特性,实现分析物检测。这些荧光探针具有较大的斯托克斯位移、较高的量子产率和出色的颜色转换。最后,我们总结了 HBT 作为基于 ESIPT 的荧光探针在检测阳离子、阴离子和生物分子方面的应用。我们希望这篇综述能全面概述该领域的研究现状,并鼓励研究人员开发基于 ESIPT 的新型荧光探针,以实现新的应用。
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引用次数: 0
Significance of Chalcone Scaffolds in Medicinal Chemistry. Chalcone 支架在药物化学中的意义。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-06-27 DOI: 10.1007/s41061-024-00468-7
Rishav Mazumder, Ichudaule, Ashmita Ghosh, Subrata Deb, Rajat Ghosh

Chalcone is a simple naturally occurring α,β-unsaturated ketone with biological importance, which can also be easily synthesized in laboratories by reaction between two aromatic scaffolds. In plants, chalcones occur as polyphenolic compounds of different frameworks which are bioactive molecules that have been in traditional medicinal practice for many years. Chalcone-based lead molecules have been developed, possessing varied potentials such as antimicrobial, antiviral, anti-inflammatory, anticancer, anti-oxidant, antidiabetic, antihyperurecemic, and anti-ulcer effects. Chalcones contribute considerable fragments to give important heterocyclic molecules with therapeutic utilities targeting various diseases. These characteristic features have made chalcone a topic of interest among researchers and have attracted investigations into this widely applicable structure. This review highlights the extensive exploration carried out on the synthesis, biotransformations, chemical reactions, hybridization, and pharmacological potentials of chalcones, and aims to provide an extensive, thorough, and critical review of their importance, with emphasis on their properties, chemistry, and biomedical applications to boost future investigations into this potential scaffold in medicinal chemistry.

查尔酮是一种简单的天然α,β-不饱和酮,具有重要的生物学意义,也可以通过两个芳香族支架之间的反应在实验室中轻松合成。在植物中,查耳酮以不同结构的多酚化合物形式出现,是具有生物活性的分子,多年来一直被用于传统医药中。查耳酮类先导分子已被开发出来,具有抗菌、抗病毒、抗炎、抗癌、抗氧化、抗糖尿病、抗高血压和抗溃疡等多种功效。查耳酮可提供大量片段,形成重要的杂环分子,具有针对各种疾病的治疗作用。这些特点使查尔酮成为研究人员感兴趣的话题,并吸引了人们对这种广泛应用的结构进行研究。这篇综述重点介绍了在查耳酮的合成、生物转化、化学反应、杂交和药理潜力等方面进行的广泛探索,旨在对其重要性进行广泛、深入和批判性的评述,重点关注其性质、化学性质和生物医学应用,以推动未来对这一药物化学潜在支架的研究。
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引用次数: 0
Properties, Synthesis and Emerging Applications of Graphdiyne: A Journey Through Recent Advancements. Graphdiyne 的特性、合成和新兴应用:最新进展之旅。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-05-19 DOI: 10.1007/s41061-024-00466-9
H V Nidhi, Vinayaka S Koppad, Ann Mariella Babu, Anitha Varghese

Graphdiyne (GDY) is a new variant of nano-carbon material with excellent chemical, physical and electronic properties. It has attracted wide attention from researchers and industrialists for its extensive role in the fields of optics, electronics, bio-medics and energy. The unique arrangement of sp-sp2 carbon atoms, linear acetylenic linkages, uniform pores and highly conjugated structure offer numerous potentials for further exploration of GDY materials. However, since the material is at its infancy, not much understanding is available regarding its properties, growth mechanism and future applications. Therefore, in this review, readers are guided through a brief discussion on GDY's properties, different synthesis procedures with a special focus on surface functionalization and a list of applications for GDY. The review also critically analyses the advantages and disadvantages of each synthesis route and emphasizes the future scope of the material.

Graphdiyne (GDY) 是一种新型纳米碳材料,具有优异的化学、物理和电子特性。由于其在光学、电子学、生物医学和能源领域的广泛作用,它已引起研究人员和工业家的广泛关注。sp-sp2碳原子的独特排列、线性乙炔链、均匀的孔隙和高度共轭的结构为进一步开发 GDY 材料提供了巨大的潜力。然而,由于这种材料尚处于起步阶段,人们对其性能、生长机制和未来应用的了解还不多。因此,本综述将引导读者简要讨论 GDY 的特性、不同的合成过程(特别关注表面功能化)以及 GDY 的应用清单。综述还批判性地分析了每种合成途径的优缺点,并强调了该材料的未来应用范围。
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引用次数: 0
Indole as a Versatile Building Block in Cycloaddition Reactions: Synthesis of Diverse Heterocyclic Frameworks. 吲哚作为环化反应中的多功能构件:合成多种杂环框架。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-05-17 DOI: 10.1007/s41061-024-00463-y
Biswajita Baruah, Choitanya Dev Pegu, Mohit L Deb

Indole, a ubiquitous and structurally versatile aromatic compound, has emerged as a key player in the synthesis of diverse heterocyclic frameworks via cycloaddition reactions. These reactions are completely atom-economical and, hence, are considered as green reactions. This review article provides a comprehensive overview of the pivotal role played by indole in the construction of complex and biologically relevant heterocyclic compounds. Here we explore the chemistry of indole-based cycloadditions, highlighting their synthetic utility in accessing a wide array of heterocyclic architectures, including cyclohepta[b]indoles, tetrahydrocarbazoles, tetrahydroindolo[3,2-c]quinoline, and indolines, among others. Additionally, we discuss the mechanistic insights that underpin these transformations, emphasizing the strategic importance of indole as a building block. The content of this article will certainly encourage the readers to explore more work in this area.

吲哚是一种无处不在、结构多变的芳香族化合物,是通过环加成反应合成各种杂环框架的关键人物。这些反应完全是原子经济的,因此被认为是绿色反应。这篇综述文章全面概述了吲哚在构建复杂且具有生物相关性的杂环化合物中发挥的关键作用。在此,我们探讨了基于吲哚的环加成反应的化学性质,强调了它们在获得各种杂环结构方面的合成用途,包括环庚基[b]吲哚、四氢咔唑、四氢吲哚并[3,2-c]喹啉和吲哚啉等。此外,我们还讨论了支持这些转化的机理见解,强调了吲哚作为构建基块的战略重要性。本文的内容必将鼓励读者探索这一领域的更多工作。
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引用次数: 0
Water-Soluble Small Organic Fluorophores for Oncological Theragnostic Applications: Progress and Development 用于肿瘤治疗应用的水溶性小型有机荧光团:进展与发展
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-04-26 DOI: 10.1007/s41061-024-00458-9
Ashanul Haque, Khalaf M. Alenezi, Abdulmohsen Khalaf Dhahi Alsukaibi, Ahmed A. Al-Otaibi, Wai-Yeung Wong

Cancer is one of the major noncommunicable diseases, responsible for millions of deaths every year worldwide. Though various cancer detection and treatment modalities are available today, many deaths occur owing to its late-stage detection and metastatic nature. Noninvasive detection using luminescence-based imaging tools is considered one of the promising techniques owing to its low cost, high sensitivity, and brightness. Moreover, these tools are unique and valuable as they can detect even the slightest changes in the cellular microenvironment. To achieve this, a fluorescent probe with strong tumor uptake and high spatial and temporal resolution, especially with high water solubility, is highly demanded. Recently, several water-soluble molecules with emission windows in the visible (400–700 nm), first near-infrared (NIR-I, 700–1000 nm), and second near-infrared (NIR-II, 1000–1700 nm) windows have been reported in literature. This review highlights recently reported water-soluble small organic fluorophores/dyes with applications in cancer diagnosis and therapeutics. We systematically highlight and describe the key concepts, structural classes of fluorophores, strategies for imparting water solubility, and applications in cancer therapy and diagnosis, i.e., theragnostics. We discuss examples of water-soluble fluorescent probes based on coumarin, xanthene, boron–dipyrromethene (BODIPY), and cyanine cores. Some other emerging classes of dyes based on carbocyclic and heterocyclic cores are also discussed. Besides, emerging molecular engineering methods to obtain such fluorophores are discussed. Finally, the opportunities and challenges in this research area are also delineated.

癌症是主要的非传染性疾病之一,每年造成全球数百万人死亡。尽管目前已有各种癌症检测和治疗方法,但由于癌症的晚期检测和转移特性,仍有许多人因此而死亡。由于成本低、灵敏度高、亮度高,使用基于发光的成像工具进行无创检测被认为是最有前途的技术之一。此外,这些工具还能检测到细胞微环境中最细微的变化,因此具有独特的价值。要实现这一目标,对具有强肿瘤吸收能力、高时空分辨率,尤其是高水溶性的荧光探针的要求很高。最近,文献报道了几种发射窗口在可见光(400-700 纳米)、第一近红外(NIR-I,700-1000 纳米)和第二近红外(NIR-II,1000-1700 纳米)窗口的水溶性分子。本综述重点介绍最近报道的可应用于癌症诊断和治疗的水溶性小型有机荧光团/染料。我们系统地强调和描述了关键概念、荧光团的结构类别、赋予水溶性的策略以及在癌症治疗和诊断(即热敏诊断)中的应用。我们讨论了基于香豆素、香蒽、硼-二吡咯并二酮(BODIPY)和氰基核心的水溶性荧光探针的实例。此外,还讨论了基于碳环和杂环核心的其他一些新兴染料类别。此外,还讨论了获得此类荧光团的新兴分子工程方法。最后,还探讨了这一研究领域的机遇和挑战。
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引用次数: 0
Pushing Boundaries: What’s Next in Metal-Free C–H Functionalization for Sulfenylation? 突破界限:无金属 C-H 功能化亚硫酰化的下一步是什么?
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-04-12 DOI: 10.1007/s41061-024-00460-1
Payal Rani, Sandhya Chahal, Rajvir Singh, Jayant Sindhu

The synthesis of thioether derivatives has been explored widely due to the potential application of these derivatives in medicinal chemistry, pharmaceutical industry and material chemistry. Within this context, there has been an increasing demand for the environmentally benign construction of C–S bonds via C–H functionalization under metal-free conditions. In the present article, we highlight recent developments in metal-free sulfenylation that have occurred in the past three years. The synthesis of organosulfur compounds via a metal-free approach using a variety of sulfur sources, including thiophenols, disulfides, sulfonyl hydrazides, sulfonyl chlorides, elemental sulfur and sulfinates, is discussed. Non-conventional strategies, which refer to the development of thioether derivatives under visible light and electrochemically mediated conditions, are also discussed. The key advantages of the reviewed methodologies include broad substrate scope and high reaction yields under environmentally benign conditions. This comprehensive review will provide chemists with a synthetic tool that will facilitate further development in this field.

Graphical Abstract

由于硫醚衍生物在药物化学、制药工业和材料化学中的潜在应用,人们对这些衍生物的合成进行了广泛的探索。在此背景下,人们对在无金属条件下通过 C-H 功能化构建 C-S 键的环境友好性需求日益增加。在本文中,我们将重点介绍过去三年中在无金属亚磺酰化方面的最新进展。文章讨论了利用各种硫源(包括噻吩酚、二硫化物、磺酰肼、磺酰氯、元素硫和硫酸盐)通过无金属方法合成有机硫化合物的过程。此外,还讨论了非常规策略,即在可见光和电化学介导条件下开发硫醚衍生物。所综述方法的主要优点包括:底物范围广,在无害环境的条件下反应产率高。本综述将为化学家提供一种合成工具,促进该领域的进一步发展。
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引用次数: 0
Research Progress in Structure Synthesis, Properties, and Applications of Small-Molecule Silicone Surfactants 小分子有机硅表面活性剂的结构合成、性能和应用研究进展
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-04-08 DOI: 10.1007/s41061-024-00457-w
Wenhui Zhao, Yuqiao Cheng, Jiaqi Pu, Leigang Su, Nan Wang, Yinhao Cao, Lijun Liu

Silicone surfactants have garnered significant research attention owing to their superior properties, such as wettability, ductility, and permeability. Small-molecular silicone surfactants with simple molecular structures outperform polymeric silicone surfactants in terms of surface activity, emulsification, wetting, foaming, and other areas. Moreover, silicone surfactants with small molecules exhibit a diverse and rich molecular structure. This review discusses various synthetic routes for the synthesis of different classes of surfactants, including single-chain, “umbrella” structure, double chain, bolaform, Gemini, and stimulus-responsive surfactants. The fundamental surface/interface properties of the synthesized surfactants are also highlighted. Additionally, these surfactants have demonstrated enormous potential in agricultural synergism, drug delivery, mineral flotation, enhanced oil recovery, separation, and extraction, and foam fire-fighting.

Graphical Abstract

有机硅表面活性剂因其润湿性、延展性和渗透性等优越性能而备受研究关注。分子结构简单的小分子有机硅表面活性剂在表面活性、乳化、润湿、发泡等方面均优于聚合物有机硅表面活性剂。此外,小分子有机硅表面活性剂的分子结构多样而丰富。本综述讨论了合成不同类别表面活性剂的各种合成路线,包括单链、"伞状 "结构、双链、波拉莫夫型、双子型和刺激响应型表面活性剂。此外,还重点介绍了合成表面活性剂的基本表面/界面特性。此外,这些表面活性剂在农业增效、药物输送、矿物浮选、提高石油采收率、分离和萃取以及泡沫灭火等方面都显示出巨大的潜力。
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引用次数: 0
Reaction Pattern and Mechanistic Aspects of Iodine and Iodine-Based Reagents in Selenylation of Aliphatic, Aromatic, and (Hetero)Cyclic Systems 碘和碘基试剂在脂肪族、芳香族和(异)环族体系硒化中的反应模式和机理方面的研究
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-04-08 DOI: 10.1007/s41061-024-00459-8
Pankaj Kumar, Aman Bhalla

Organoselenium compounds have been the subject of extensive research since the discovery of the biologically active compound ebselen. Ebselen has recently been found to show activity against the main protease of the virus responsible for COVID-19. Other organoselenium compounds are also well-known for their diverse biological activities, with such compounds exhibiting interesting physical properties relevant to the fields of electronics, materials, and polymer chemistry. In addition, the incorporation of selenium into various organic molecules has garnered significant attention due to the potential of selenium to enhance the biological activity of these molecules, particularly in conjunction with bioactive heterocycles. Iodine and iodine-based reagents play a prominent role in the synthesis of organoselenium compounds, being valued for their cost-effectiveness, non-toxicity, and ease of handling. These reagents efficiently selenylate a broad range of organic substrates, encompassing alkenes, alkynes, and cyclic, aromatic, and heterocyclic molecules. They serve as catalysts, additives, inducers, and oxidizing agents, facilitating the introduction of different functional groups at alternate positions in the molecules, thereby allowing for regioselective and stereoselective approaches. Specific iodine reagents and their combinations can be tailored to follow the desired reaction pathways. Here, we present a comprehensive review of the progress in the selenylation of organic molecules using iodine reagents over the past decade, with a focus on reaction patterns, solvent effects, heating, microwave, and ultrasonic conditions. Detailed discussions on mechanistic aspects, such as electrophilic, nucleophilic, radical, electrochemical, and ring expansion reactions via selenylation, multiselenylation, and difunctionalization, are included. The review also highlights the formation of various cyclic, heterocyclic, and heteroarenes resulting from the in situ generation of selenium intermediates, encompassing cyclic ketones, cyclic ethers, cyclic lactones, selenophenes, chromones, pyrazolines, pyrrolidines, piperidines, indolines, oxazolines, isooxazolines, lactones, dihydrofurans, and isoxazolidines. To enhance the reader’s interest, the review is structured into different sections covering the selenylation of aliphatic sp2/sp carbon and cyclic sp2 carbon, and then is further subdivided into various heterocyclic molecules.

Graphical Abstract

自生物活性化合物依布硒被发现以来,有机硒化合物一直是广泛研究的主题。最近,人们发现依布硒对 COVID-19 病毒的主要蛋白酶具有抑制作用。其他有机硒化合物也因其多种多样的生物活性而闻名,这些化合物还表现出与电子、材料和聚合物化学领域相关的有趣的物理特性。此外,由于硒有可能增强各种有机分子的生物活性,特别是与具有生物活性的杂环一起使用时,硒与这些分子的结合也引起了人们的极大关注。碘和碘基试剂在合成有机硒化合物的过程中发挥着重要作用,因其成本效益高、无毒、易于操作而备受重视。这些试剂能有效地硒化多种有机底物,包括烯烃、炔烃、环状分子、芳香分子和杂环分子。它们可用作催化剂、添加剂、诱导剂和氧化剂,促进在分子的不同位置引入不同的官能团,从而实现区域选择性和立体选择性方法。特定的碘试剂及其组合可以按照所需的反应途径进行定制。在此,我们全面回顾了过去十年中使用碘试剂对有机分子进行硒化反应的进展,重点介绍了反应模式、溶剂效应、加热、微波和超声条件。书中还详细讨论了机理方面的问题,如亲电、亲核、自由基、电化学以及通过硒化、多硒化和双官能化进行的扩环反应。综述还重点介绍了原位生成硒中间体所形成的各种环状、杂环和杂环烯,包括环酮、环醚、环内酯、硒酚、色酮、吡唑啉类、吡咯烷类、哌啶类、吲哚啉类、噁唑啉类、异噁唑啉类、内酯类、二氢呋喃类和异噁唑烷类。为了提高读者的阅读兴趣,本综述分为不同的章节,涵盖了脂肪族 sp2/sp 碳和环状 sp2 碳的硒化反应,然后又进一步细分为各种杂环分子。
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引用次数: 0
Recent Advances in the Application of P(III)-Nucleophiles to Create New P-C Bonds through Michaelis-Arbuzov-Type Rearrangement. 应用 P(III)-Nucleophiles 通过 Michaelis-Arbuzov 型重排生成新 P-C 键的最新进展。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-03-08 DOI: 10.1007/s41061-024-00456-x
Biquan Xiong, Minjing Yuan, Chonghao Shi, Longzhi Zhu, Fan Cao, Weifeng Xu, Yining Ren, Yu Liu, Ke-Wen Tang

Organophosphorus compounds have long been considered valuable in both organic synthesis and life science. P(III)-nucleophiles, such as phosphites, phosphonites, and diaryl/alkyl phosphines, are particularly noteworthy as phosphorylation reagents for their ability to form new P-C bonds, producing more stable, ecofriendly, and cost-effective organophosphorus compounds. These nucleophiles follow similar phosphorylation routes as in the functionalization of P-H bonds and P-OH bonds. Activation can occur through photocatalytic, electrocatalytic, or thermo-driven reactions, often in coordination with a Michaelis-Arbuzov-trpe rearrangement process, to produce the desired products. As such, this review offers a thorough overview of the phosphorylated transformation and potential mechanisms of P(III)-nucleophiles, specifically focusing on developments since 2010. Notably, this review may provide researchers with valuable insights into designing and synthesizing functionalized organophosphorus compounds from P(III)-nucleophiles, guiding future advancements in both research and practical applications.

长期以来,有机磷化合物一直被认为在有机合成和生命科学领域具有重要价值。作为磷酸化试剂,P(III)-亲核物(如亚磷酸盐、亚磷酸盐和二芳基/烷基膦)尤其值得注意,因为它们能够形成新的 P-C 键,生成更稳定、更环保、更经济的有机磷化合物。这些亲核剂的磷酸化路线与 P-H 键和 P-OH 键的功能化路线相似。活化可通过光催化、电催化或热驱动反应进行,通常与 Michaelis-Arbuzov-trpe 重排过程协调进行,以产生所需的产物。因此,本综述全面综述了亲核物 P(III)的磷酸化转化和潜在机制,特别侧重于 2010 年以来的发展。值得注意的是,这篇综述可为研究人员设计和合成来自 P(III)-nucleophiles 的功能化有机磷化合物提供有价值的见解,为未来的研究和实际应用提供指导。
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引用次数: 0
Chemical Aspects of Halide Perovskite Nanocrystals. 卤化物过氧化物纳米晶体的化学方面。
IF 8.6 2区 化学 Q1 Chemistry Pub Date : 2024-03-02 DOI: 10.1007/s41061-024-00453-0
Mrinmoy Roy, Milan Sykora, M Aslam

Halide perovskite nanocrystals (HPNCs) are currently among the most intensely investigated group of materials. Structurally related to the bulk halide perovskites (HPs), HPNCs are nanostructures with distinct chemical, optical, and electronic properties and significant practical potential. One of the keys to the effective exploitation of the HPNCs in advanced technologies is the development of controllable, reproducible, and scalable methods for preparation of materials with desired compositions, phases, and shapes and low defect content. Another important condition is a quantitative understanding of factors affecting the chemical stability and the optical and electronic properties of HPNCs. Here we review important recent developments in these areas. Following a brief historical prospective, we provide an overview of known chemical methods for preparation of HPNCs and approaches used to control their composition, phase, size, and shape. We then review studies of the relationship between the chemical composition and optical properties of HPNCs, degradation mechanisms, and effects of charge injection. Finally, we provide a short summary and an outlook. The aim of this review is not to provide a comprehensive summary of all relevant literature but rather a selection of highlights, which, in the subjective view of the authors, provide the most significant recent observations and relevant analyses.

卤化物过氧化物纳米晶体(HPNCs)是目前研究最深入的一组材料。在结构上与块状卤化物包晶(HPs)相关,HPNCs 是一种具有独特化学、光学和电子特性的纳米结构,具有巨大的实用潜力。在先进技术中有效利用 HPNCs 的关键之一是开发可控、可重现和可扩展的方法,以制备具有所需成分、相和形状以及低缺陷含量的材料。另一个重要条件是定量了解影响 HPNCs 化学稳定性以及光学和电子特性的因素。在此,我们将回顾这些领域的重要最新进展。在简要回顾历史之后,我们概述了制备 HPNC 的已知化学方法以及用于控制其成分、相、尺寸和形状的方法。然后,我们回顾了有关 HPNC 化学成分与光学特性之间的关系、降解机制以及电荷注入效应的研究。最后,我们进行简短总结和展望。本综述的目的不是对所有相关文献进行全面总结,而是根据作者的主观看法,选取其中最重要的最新观察结果和相关分析。
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引用次数: 0
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Topics in Current Chemistry
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