Topics in Current Chemistry最新文献

Photodynamic therapy is a minimally invasive treatment of tumors using photosensitizers, light, and reactive oxygen species, which can destroy cellular structures. With the development of photodynamic therapy, significant efforts have been made to create new efficient photosensitizers with improved delivery to cells, stability, and selectivity against cancer tissues. Naturally occurring tetrapyrrolic macrocycles, such as porphyrins and chlorins, are very attractive as photosensitizers, and their structural modification and conjugation with other biologically active molecules are promising approaches for creating new photosensitizers specifically targeting cancer cells. The present review aims to highlight recent developments in the design, preparation, and investigation of complex conjugates of tetrapyrrolic macrocycles, which can potentially be used as sensitizers for target-oriented photodynamic therapy of cancer. In this review, we discuss the structure, photodynamic effect, and anticancer activity of the following conjugates of tetrapyrrolic macrocycles: (1) conjugates obtained by modifying peripheral substituents in porphyrins and chlorins; (2) conjugates of porphyrins and chlorins with lipids, carbohydrates, steroids, and peptides; (3) conjugates of porphyrins and chlorins with anticancer drugs and some other biologically active molecules; (4) metal-containing conjugates. The question of how the conjugate structure affects its specificity, internalization, localization, and photoinduced toxicity within cancer cells is the focus of this review.

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Recently, several experimental and theoretical studies have demonstrated the feasibility of enhancing the sonochemical production of hydrogen via methanol pyrolysis within acoustic cavitation bubbles (i.e. sonolysis of aqueous methanol solution). This review includes both the experimental and theoretical achievements in the field of hydrogen production by methanol sonolysis. Additionally, the limits of the process’s applicability and plausible solutions are highlighted. The impact of different parameters influencing the process performance is discussed. Finally, the effects of methanol concentration on the size distribution of active cavitation bubbles are analyzed.

Photochromic compounds of the spiropyran family have two main isomers capable of inter-switching with UV or visible light. In the current review, we discuss recent advances in the synthesis, investigation of properties, and applications of spiropyran derivatives. Spiropyrans of the indoline series are in focus as the most promising representatives of multi-sensitive spirocyclic compounds, which can be switched by a number of external stimuli, including light, temperature, pH, presence of metal ions, and mechanical stress. Particular attention is paid to the structural features of molecules, their influence on photochromic properties, and the reactions taking place during isomerization, as the understanding of the structure–property relationships will rationalize the synthesis of compounds with predetermined characteristics. The main prospects for applications of spiropyrans in such fields as smart material production, molecular electronics and nanomachinery, sensing of environmental and biological molecules, and photopharmacology are also discussed.

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The incorporation of aryl substituents at the meso-positions of calix[4]pyrrole (C4P) scaffolds produces aryl-extended (AE) and super-aryl-extended (SAE) calix[4]pyrroles. The cone conformation of the all-α isomers of “multi-wall” AE-C4Ps and SAE-C4Ps displays deep aromatic clefts or cavities. In particular, “four-wall” receptors feature an aromatic polar cavity closed at one end with four convergent pyrrole rings and fully open at the opposite end. This makes AE- and SAE-C4P scaffolds effective receptors for the molecular recognition of negatively charged ions and neutral guest molecules with donor–acceptor and hydrogen bonding motifs. In addition, adequately functionalized all-α isomers of multi wall AE- and SAE-C4P scaffolds self-assemble into uni-molecular and supra-molecular aggregates displaying capsular and cage-like structures. The self-assembly process requires the presence of template ions or molecules that lock the C4P cone conformation and complementing the inner polar functions and volumes of their cavities. We envisioned performing an in-depth revision of AE- and SAE-C4P scaffolds owing to their importance in different domains such as supramolecular chemistry, biology, material sciences and pharmaceutical chemistry. Herewith, besides the synthetic details on the elaboration of their structures, we also draw attention to their diverse applications. The organization of this review is mainly based on the number of “walls” present in the AE-C4P derivatives and their structural modifications. The sections are further divided based on the C4P functions and applications. The authors are convinced that this review will be of interest to researchers working in the general area of supramolecular chemistry as well as those involved in the study of the binding properties and applications of C4P derivatives.

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Graphene (G) has been a game-changer for conductive optical devices and has shown promising aspects for its implementation in the power industry due to its diverse structures. Graphene has played an essential role as electrodes, hole transport layers (HTLs), electron transport layers (ETLs), and a chemical modulator for perovskite layers in perovskite solar cells (PSCs) over the past decade. Nitrogen-doped graphene (N-DG) derivatives are frequently evaluated among the existing derivatives of graphene because of their versatility of design, easy synthesis process, and high throughput. This review presents a state-of-the-art overview of N-DG preparation methods, including wet chemical process, bombardment, and high thermal treatment methods. Furthermore, it focuses on different structures of N-DG derivatives and their various applications in PSC applications. Finally, the challenges and opportunities for N-DG derivatives for the continuous performance improvement of PSCs have been highlighted.

The possibility to tune the solid catalyst morphology and the unique chemical and physical stability of organosilica-entrapped sol–gel catalysts allow the application of these catalysts to the synthesis of a wide variety of valued molecules, including polymers, manufactured by the fine-chemical industry. Referring to selected independent research achievements, we provide a practice oriented insight on these materials that will hopefully be useful in new, unified catalysis education aimed to foster the uptake of heterogeneous catalysis in the fine and specialty chemical industry.

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Owing to the prevalence of nitrogen-containing compounds in natural products and important pharmaceutical agents, chemists, have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon–nitrogen bonds. Over the last decade, transition metal-catalyzed C–N bond construction via electrophilic amination reaction has emerged as an attractive approach for the synthesis of various organic molecules and pharmaceuticals. Particularly, O-benzoylhydroxylamines as an electrophilic aminating agent have proven to be the best and most widely used in both academic and industrial research. In this review, we highlight the key contributions to the recent transition metal-catalyzed C–N bond formation reactions using O-benzoylhydroxylamines as an aminating agent and their relevant mechanistic insights.

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Carbon monoxide-releasing molecules (CORMs) are promising candidates for producing carbon monoxide in the mammalian body for therapeutic purposes. At higher concentrations, CO has a harmful effect on the mammalian organism. However, lower doses at a controlled rate can provide cellular signaling for mandatory pharmacokinetic and pathological activities. To date, exploring the therapeutic implications of CO dose as a prodrug has attracted much attention due to its therapeutic significance. There are two different methods of CO insertion, i.e., indirect and direct exogenous insertion. Indirect exogenous insertion of CO suggests an advantage of reduced toxicity over direct exogenous insertion. For indirect exogenous insertion, researchers are facing the issue of tissue selectivity. To solve this issue, developers have considered the newly produced CORMs. Herein, metal carbonyl complexes (MCCs) are covalently linked with CO molecules to produce different CORMs such as CORM-1, CORM-2, and CORM-3, etc. All these CORMs required exogenous CO insertion to achieve the therapeutic targets at the optimized rate under peculiar conditions or/and triggering. Meanwhile, the metal residue was generated from i-CORMs, which can propagate toxicity. Herein, we explain CO administration, water-soluble CORMs, tissue accumulation, and cytotoxicity of depleted CORMs and the kinetic profile of CO release.

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Coumarins (2H-1-benzopyran-2-ones) are an important group of biological heterocyclic compounds present in various parts of many plant species, encompassing an array of biological and pharmaceutical activities. In view of the importance of coumarins in heterocyclic chemistry and biological sciences and recent advances in the design of magnetic nanocatalysts, we present herein recent developments pertaining to their synthesis exclusively using magnetic nanoparticles, which can be retrieved easily and thus conform to the tenets of greener synthesis. The preparation of various types of coumarins such as Pechmann-based coumarins, bis coumarins, pyranocoumarins, and coumarin derivatives bearing amine moiety, linked to nicotinonitriles, N-coumarin-2-furanone, and pyrrole-linked chromene derivatives using nanocatalysts with a Fe₃O₄ core are described. This review covers the synthetic developments in the recent years 2012–2021 and focuses entirely on the synthesis of coumarins in the presence of magnetic nanocatalysts using greener approaches such as solvent-free conditions or deploying alternative activation methods, namely microwave or ultrasound irradiation.

Dimethyl sulfoxide (DMSO), as extremely important aprotic polar solvent and reaction medium, has attracted widespread attention from chemists in recent years due to its wide range of uses and the multiple functions it displays in various chemical processes. Especially in the past decade, dimethyl sulfoxide has become increasingly favored as a synthon in organic chemistry, resulting in great progress in this research field. In this context, this review provides a comprehensive summary of the literature on the recent progress in organic synthesis using dimethyl sulfoxide as a synthon, covering all the reports from 1 January 2016 to 11 May 2022. This type of reaction is mainly performed by transferring one or more units of dimethyl sulfoxide, such as oxygen (–O–, =O), methyl (–CH₃), methylene (–CH₂–), methylidene (=CH₂), methine (=CH–), donor of formylation (–CHO), sulfur (–S–), methylthio (–SMe), methyl sulfoxide (–SOMe), donor of methyl thiomethylation (–CH₂SMe), or donor of methyl sulfoxide methylation (–CH₂SOMe), to the target molecules. At the same time, we hope that this review will stimulate future studies and promote developments in this area.

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