Chemical Society Reviews

doi: 10.1039/d4cs90085epmid: N/A

doi: 10.1039/d4cs90086cpmid: N/A

doi: 10.1039/d4cs90087apmid: N/A

Lin, Zhixing; Liu, Hai; Richardson, Joseph J.; Xu, Wanjun; Chen, Jingqu; Zhou, Jiajing; Caruso, Frank

doi: 10.1039/d3cs00273jpmid: 39364569

Composites with tailored compositions and functions have attracted widespread scientific and industrial interest. Metal–phenolic networks (MPNs), which are composed of phenolic ligands and metal ions, are amorphous adhesive coordination polymers that have been combined with various functional components to create composites with potential in chemistry, biology, and materials science. This review aims to provide a comprehensive summary of both fundamental knowledge and advancements in the field of MPN composites. The advantages of amorphous MPNs, over crystalline metal–organic frameworks, for fabricating composites are highlighted, including their mild synthesis, diverse interactions, and numerous intrinsic functionalities. The formation mechanisms and state-of-the-art synthesis strategies of MPN composites are summarized to guide their rational design. Subsequently, a detailed overview of the chemical interactions and structure–property relationships of composites based on different functional components (e.g., small molecules, polymers, biomacromolecules) is provided. Finally, perspectives are offered on the current challenges and future directions of MPN composites. This tutorial review is expected to serve as a fundamental guide for researchers in the field of metal–organic materials and to provide insights and avenues to enhance the performance of existing functional materials in applications across diverse fields.

Fu, Fangqin; Crespy, Daniel; Landfester, Katharina; Jiang, Shuai

doi: 10.1039/d4cs00507dpmid: 39291461

Nanoparticles (NPs) inevitably interact with proteins upon exposure to biological fluids, leading to the formation of an adsorption layer known as the “protein corona”. This corona imparts NPs with a new biological identity, directly influencing their interactions with living systems and dictating their fates in vivo. Thus, gaining a comprehensive understanding of the dynamic interplay between NPs and proteins in biological fluids is crucial for predicting therapeutic effects and advancing the clinical translation of nanomedicines. Numerous methods have been established to decode the protein corona fingerprints. However, these methods primarily rely on prior isolation of NP–protein complex from the surrounding medium by centrifugation, resulting in the loss of outer-layer proteins that directly interact with the biological system and determine the in vivo fate of NPs. We discuss here separation techniques as well as in situ characterization methods tailored for comprehensively unraveling the inherent complexities of NP–protein interactions, highlighting the challenges of in situ protein corona characterization and its significance for nanomedicine development and clinical translation.

Xie, Chao; Chen, Wei; Wang, Yanyong; Yang, Yahui; Wang, Shuangyin

doi: 10.1039/d3cs00756apmid: 39382539

Reactions on electrocatalytic interfaces often involve multiple processes, including the diffusion, adsorption, and conversion of reaction species and the interaction between reactants and electrocatalysts. Generally, these processes are constantly changing rather than being in a steady state. Recently, dynamic evolution processes on electrocatalytic interfaces have attracted increasing attention owing to their significant roles in catalytic reaction kinetics. In this review, we aim to provide insights into the dynamic evolution processes in electrocatalysis to emphasize the importance of unsteady-state processes in electrocatalysis. Specifically, the dynamic structure evolution of electrocatalysts, methods for the characterization of the dynamic evolution and the strategies for the regulation of the dynamic evolution for improving electrocatalytic performance are summarized. Finally, the conclusion and outlook on the research on dynamic evolution processes in electrocatalysis are presented. It is hoped that this review will provide a deeper understanding of dynamic evolution in electrocatalysis, and studies of electrocatalytic reaction processes and kinetics on the unsteady-state microscopic spatial and temporal scales will be given more attention.

Wu, Qiong; Xu, Wei; Shang, Jinhua; Li, Jiajing; Liu, Xiaoqing; Wang, Fuan; Li, Jinghong

doi: 10.1039/d4cs00046cpmid: 39400237

Autocatalysis, a self-sustained replication process where at least one of the products functions as a catalyst, plays a pivotal role in life's evolution, from genome duplication to the emergence of autocatalytic subnetworks in cell division and metabolism. Leveraging their programmability, controllability, and rich functionalities, DNA molecules have become a cornerstone for engineering autocatalytic circuits, driving diverse technological applications. In this tutorial review, we offer a comprehensive survey of recent advances in engineering autocatalytic DNA circuits and their practical implementations. We delve into the fundamental principles underlying the construction of these circuits, highlighting their reliance on DNAzyme biocatalysis, enzymatic catalysis, and dynamic hybridization assembly. The discussed autocatalytic DNA circuitry techniques have revolutionized ultrasensitive sensing of biologically significant molecules, encompassing genomic DNAs, RNAs, viruses, and proteins. Furthermore, the amplicons produced by these circuits serve as building blocks for higher-order DNA nanostructures, facilitating biomimetic behaviors such as high-performance intracellular bioimaging and precise algorithmic assembly. We summarize these applications and extensively address the current challenges, potential solutions, and future trajectories of autocatalytic DNA circuits. This review promises novel insights into the advancement and practical utilization of autocatalytic DNA circuits across bioanalysis, biomedicine, and biomimetics.

Gunathilake, Chamila; Soliman, Ibrahim; Panthi, Dhruba; Tandler, Peter; Fatani, Omar; Ghulamullah, Noman Alias; Marasinghe, Dinesh; Farhath, Mohamed; Madhujith, Terrence; Conrad, Kirt; Du, Yanhai; Jaroniec, Mietek

doi:

Qu, Rui; Jiang, Xiqun; Zhen, Xu

doi: 10.1039/d4cs00599fpmid: 39380344

Conventional optical imaging, particularly fluorescence imaging, often encounters significant background noise due to tissue autofluorescence under real-time light excitation. To address this issue, a novel optical imaging strategy that captures optical signals after light excitation has been developed. This approach relies on molecular probes designed to store photoenergy and release it gradually as photons, resulting in delayed photon emission that minimizes background noise during signal acquisition. These molecular probes undergo various photophysical processes to facilitate delayed photon emission, including (1) charge separation and recombination, (2) generation, stabilization, and conversion of the triplet excitons, and (3) generation and decomposition of chemical traps. Another challenge in optical imaging is the limited tissue penetration depth of light, which severely restricts the efficiency of energy delivery, leading to a reduced penetration depth for delayed photon emission. In contrast, X-ray and ultrasound serve as deep-tissue energy sources that facilitate the conversion of high-energy photons or mechanical waves into the potential energy of excitons or the chemical energy of intermediates. This review highlights recent advancements in organic molecular probes designed for delayed photon emission using various energy sources. We discuss distinct mechanisms, and molecular design strategies, and offer insights into the future development of organic molecular probes for enhanced delayed photon emission.

Balhara, Reena; Chatterjee, Ritwika; Jindal, Garima

doi: 10.1039/d4cs00742epmid: 39392229

Constructing highly proficient C–X (X = O, N, S, etc.) and C–C bonds by leveraging TMs (transition metals) (Fe, Cu, Pd, Rh, Au, etc.) and enzymes to catalyze carbene insertion into X–H/C(sp2)–H is a highly versatile strategy. This is primarily achieved through the in situ generation of metal carbenes from the interaction of TMs with diazo compounds. Over the last few decades, significant advancements have been made, encompassing a wide array of X–H bond insertions using various TMs. These reactions typically favor a stepwise ionic pathway where the nucleophilic attack on the metal carbene leads to the generation of a metal ylide species. This intermediate marks a critical juncture in the reaction cascade, presenting multiple avenues for proton transfer to yield the X–H inserted product. The mechanism of C(sp2)–H insertion reactions closely resembles those of X–H insertion reactions and thus have been included here. A major development in carbene insertion reactions has been the use of engineered enzymes as catalysts. Since the seminal report of a non-natural “carbene transferase” by Arnold in 2013, “P411”, several heme-based enzymes have been reported in the literature to catalyze various abiological carbene insertion reactions into C(sp2)–H, N–H and S–H bonds. These enzymes possess an extraordinary ability to regulate the orientation and conformations of reactive intermediates, facilitating stereoselective carbene transfers. However, the absence of a suitable stereochemical model has impeded the development of asymmetric reactions employing a lone chiral catalyst, including enzymes. There is a pressing need to investigate alternative mechanisms and models to enhance our comprehension of stereoselectivity in these processes, which will be crucial for advancing the fields of asymmetric synthesis and biocatalysis. The current review aims to provide details on the mechanistic aspects of the asymmetric X–H and C(sp2)–H insertion reactions catalyzed by Fe, Cu, Pd, Rh, Au, and enzymes, focusing on the detailed mechanism and stereochemical model. The review is divided into sections focusing on a specific X–H/C(sp2)–H bond type catalyzed by different TMs and enzymes.