Discovery of Photoexcited 2-Chloro-3,5-Dinitrobenzoic Acid as a Chemical Deprenylase of i6A RNA.

RNA modifications play crucial roles in regulating gene expression and cellular homeostasis. Modulating RNA modifications, particularly by targeting the enzymes responsible for their catalysis, has emerged as a promising therapeutic strategy. However, limitations, such as the lack of identified modifying enzymes and compensatory mechanisms, hinder targeted interventions. Chemical approaches independent of enzymatic activity offer an alternative strategy for RNA modification modulation. Here, we present the identification of 2-chloro-3,5-dinitrobenzoic acid as a highly effective photochemical deprenylase of i6A RNA. This method demonstrates exceptional selectivity towards i6A, converting its substituent into a "N-doped" ozonide, which upon hydrolysis releases natural adenine. We believe that this chemical approach will pave the way for a better understanding of RNA modification biology and the development of novel therapeutic modalities.

Chemical Modulation of Metal-Insulator Transition toward Multifunctional Applications in Vanadium Dioxide Nanostructures.

The metal-insulator transition (MIT) of vanadium dioxide (VO2 ) has been of great interest in materials science for both fundamental understanding of strongly correlated physics and a wide range of applications in optics, thermotics, spintronics, and electronics. Due to the merits of chemical interaction with accessibility, versatility, and tunability, chemical modification provides a new perspective to regulate the MIT of VO2 , endowing VO2 with exciting properties and improved functionalities. In the past few years, plenty of efforts have been devoted to exploring innovative chemical approaches for the synthesis and MIT modulation of VO2 nanostructures, greatly contributing to the understanding of electronic correlations and development of MIT-driven functionalities. Here, this comprehensive review summarizes the recent achievements in chemical synthesis of VO2 and its MIT modulation involving hydrogen incorporation, composition engineering, surface modification, and electrochemical gating. The newly appearing phenomena, mechanism of electronic correlation, and structural instability are discussed. Furthermore, progresses related to MIT-driven applications are presented, such as the smart window, optoelectronic detector, thermal microactuator, thermal radiation coating, spintronic device, memristive, and neuromorphic device. Finally, the challenges and prospects in future research of chemical modulation and functional applications of VO2 MIT are also provided.

Interlayer Chemical Modulation of Phase Transitions in Two-Dimensional Metal Chalcogenides.

Two-dimensional metal chalcogenides (2D-MCs) with complex interactions are usually rich in phase transition behavior, such as superconductivity, charge density wave (CDW), and magnetic transitions, which hold great promise for the exploration of exciting physical properties and functional applications. Interlayer chemical modulation, as a renewed surface modification method, presents congenital advantages to regulate the phase transitions of 2D-MCs due to its confined space, strong guest-host interactions, and local and reversible modulation without destructing the host lattice, whereby new phenomena and functionalities can be produced. Herein, recent achievements in the interlayer chemical modulation of 2D-MCs are reviewed from the aspects of superconducting transition, CDW transition, semiconductor-to-metal transition, magnetic phase transition, and lattice transition. We systematically discuss the roles of charge transfer, spin coupling, and lattice strain on the modulation of phase transitions in the guest-host architectures of 2D-MCs established by electrochemical intercalation, solution-processed intercalation, and solid-state intercalation. New physical phenomena, new insight into the mechanism of phase transitions, and derived functional applications are presented. Finally, a prospectus of the challenges and opportunities of interlayer chemical modulation for future research is pointed out.

Highly Responsive Plasmon Modulation in Dopant-Segregated Nanocrystals.

Electron transfer to and from metal oxide nanocrystals (NCs) modulates their infrared localized surface plasmon resonance (LSPR), revealing fundamental aspects of their photophysics and enabling dynamic optical applications. We synthesized and chemically reduced dopant-segregated Sn-doped In2O3 NCs, investigating the influence of radial dopant segregation on LSPR modulation and near-field enhancement (NFE). We found that core-doped NCs show large LSPR shifts and NFE change during chemical titration, enabling broadband modulation in LSPR energy of over 1000 cm-1 and of peak extinction over 300%. Simulations reveal that the evolution of the LSPR spectra during chemical reduction results from raising the surface Fermi level and increasing the donor defect density in the shell region. These results establish dopant segregation as a useful strategy to engineer the dynamic optical modulation in plasmonic semiconductor NC heterostructures going beyond what is possible with conventional plasmonic metals.

Discretized hexagonal boron nitride quantum emitters and their chemical interconversion.

Quantum emitters in two-dimensional hexagonal boron nitride (hBN) are of significant interest because of their unique photophysical properties, such as single-photon emission at room temperature, and promising applications in quantum computing and communications. The photoemission from hBN defects covers a wide range of emission energies but identifying and modulating the properties of specific emitters remain challenging due to uncontrolled formation of hBN defects. In this study, more than 2000 spectra are collected consisting of single, isolated zero-phonon lines (ZPLs) between 1.59 and 2.25 eV from diverse sample types. Most of ZPLs are organized into seven discretized emission energies. All emitters exhibit a range of lifetimes from 1 to 6 ns, and phonon sidebands offset by the dominant lattice phonon in hBN near 1370 cm-1. Two chemical processing schemes are developed based on water and boric acid etching that generate or preferentially interconvert specific emitters, respectively. The identification and chemical interconversion of these discretized emitters should significantly advance the understanding of solid-state chemistry and photophysics of hBN quantum emission.

Recent Advances towards the Reversible Chemical Modification of Proteins.

Proteins are intriguing biomacromolecules for all living systems, not only as essential building blocks of organisms, but also as participants in almost every aspect of cellular activity such as metabolism and gene transcription/expression. Developing chemical biology tools that are capable of labeling/modifying proteins is a powerful method for decoding their detailed structures and functions. However, most current approaches heavily rely on the installation of permanent tags or genetic engineering of unnatural amino acids. There has been slow development in reversible chemical labeling using small organic probes and bioorthogonal transformations to construct site-selectively modified proteins and conditionally restore their activities or structures. This review summarizes recent advances in the field of chemical regulation of proteins with reversible transformations towards distinct motifs, including amino acid residues, amide backbones and native post-translational lysine. Finally, current challenges and future perspectives are discussed.

Selective Chemical Modulation of Interlayer Excitons in Atomically Thin Heterostructures.

Strongly bound interlayer excitons (XIs) in atomically thin transition metal dichalcogenide (TMDC) heterostructures such as MoS2/WSe2 show promising optoelectronic properties for spin-valleytronics and excitonic devices. The ability to probe and control XIs is critical for the development of such applications. This Letter introduces a versatile chemical method for selectively tailoring interlayer excitons in TMDC heterostructures. We show that two organic layers form uniform layers on a WSe2/MoS2 heterostructure and that the XI photoluminescence may be either preserved or quenched. The interlayer emission can also be modulated differently by the formation of the organic layer on either side of the TMDC/TMDC heterostructure. We find that the resulting interlayer emission is dominated by selective photoinduced charge transfer over dark-state p-doping effects. These results shed critical insights on interlayer excitons at the TMDC/TMDC heterointerfaces and provide a versatile approach for selectively tailoring them for optoelectronic applications.

Biocatalysts based on nanozeolite-enzyme complexes: Effects of alkoxysilane surface functionalization and biofuel production using microalgae lipids feedstock.

Nanozeolites with different crystallographic structures (Nano/TS1, Nano/GIS, Nano/LTA, Nano/BEA, Nano/X, and Nano-X/Ni), functionalized with (3-aminopropyl)trimethoxysilane (APTMS) and crosslinked with glutaraldehyde (GA), were studied as solid supports for Thermomyces lanuginosus lipase (TLL) immobilization. Physicochemical characterizations of the surface-functionalized nanozeolites and nanozeolite-enzyme complexes were performed using XRD, SEM, AFM, ATR-FTIR, and zeta potential measurements. The experimental enzymatic activity results indicated that the nanozeolitic supports functionalized with APTMS and GA immobilized larger amounts of enzymes and provided higher enzymatic activities, compared to unfunctionalized supports. Correlations were observed among the nanozeolite surface charges, the enzyme immobilization efficiencies, and the biocatalyst activities. The catalytic performance and reusability of these enzyme-nanozeolite complexes were evaluated in the ethanolysis transesterification of microalgae oil to fatty acid ethyl esters (FAEEs). TLL immobilized on the nanozeolite supports functionalized with APTMS and GA provided the most efficient biocatalysis, with FAEEs yields above 93% and stability during five reaction cycles. Lower FAEEs yields and poorer catalytic stability were found for nanozeolite-enzyme complexes prepared only by physical adsorption. The findings indicated the viability of designing highly efficient biocatalysts for biofuel production by means of chemical modulation of nanozeolite surfaces. The high biocatalyst catalytic efficiency observed in ethanolysis reactions using a lipid feedstock that does not compete with food production is an advantage that should encourage the industrial application of these biocatalysts.

Structural Mapping of Adenosine Receptor Mutations: Ligand Binding and Signaling Mechanisms.

The four adenosine receptors (ARs), A1, A2A, A2B, and A3, constitute a subfamily of G protein-coupled receptors (GPCRs) with exceptional foundations for structure-based ligand design. The vast amount of mutagenesis data, accumulated in the literature since the 1990s, has been recently supplemented with structural information, currently consisting of several inactive and active structures of the A2A and inactive conformations of the A1 ARs. We provide the first integrated view of the pharmacological, biochemical, and structural data available for this receptor family, by mapping onto the relevant crystal structures all site-directed mutagenesis data, curated and deposited at the GPCR database (available through http://www.gpcrdb.org). This analysis provides novel insights into ligand binding, allosteric modulation, and signaling of the AR family.

Mature neurons modulate neurogenesis through chemical signals acting on neural stem cells.

The discovery of neural stem cells has revealed a much higher structural and functional plasticity in the adult nervous system than previously anticipated. Progenitor cells are able to give rise to new neurons and glial cells when needed, thanks to their surveillance of the environment from the germinal niches. Multiple different factors define neural stem cell niches, including cellular and non-cellular components. Innervation of neurogenic centers is crucial, as it allows the functional connection between stem cell behavior and surrounding neuronal activity. Although the association between organismal behavior and neurogenesis is well documented, much less is known about the cellular and molecular mechanisms by which neurons control stem cell activity. In this review we discuss the existing data on this type of regulation from the three best characterized germinal niches in the adult nervous system: the subventricular zone, the hippocampal subgranular zone, and the carotid body. In all cases, neuronal activity modulates stem cell behavior either by neurotransmitter spillover or by synaptic-like contacts. Currently, the molecular mechanisms underlying mature neuron-stem cell interaction are being clarified. Functional consequences and potential clinical relevance of these phenomena are also discussed.

Chemical modulation of bioactive compounds via oligopeptide or amino acid conjugation.

Conjugation of an oligopeptide or an amino acid to bioactive compounds is one of the simplest chemical modifications to modulate the biological functions of the compounds. Recently, numerous methods have been proposed for the modification of their properties, including the alteration of their chemical and physical properties, and of their original bioactivities. We review the current knowledge of the adaptability of oligopeptide or amino acid conjugation for modulating the biological activities of biomolecules.