Traumatic brain injury (TBI) constitutes a cluster of disorders resulting from external physical forces that undermine the structure or function of the brain. TBI brings high disability and mortality rates to patients. Hence, the early diagnosis of TBI is of utmost importance. Current approaches mainly encompass computed tomography and magnetic resonance imaging; however, there are still constraints in diagnosing TBI due to limited spatial resolution and long scan durations. Herein, based on the advantages of low imaging background, high signal-to-background ratio, excellent tissue penetration, and high sensitivity of afterglow imaging, we have developed a trianthracene derivative (TA)-based nanoparticle for non-invasive afterglow imaging of TBI. Compared with fluorescence imaging, TA-NPs demonstrate a deeper tissue penetration depth (up to 2.5 cm) and a higher signal-to-noise ratio. After injection via the tail vein, TA-NPs can accumulate in the TBI area within the brain parenchyma and achieve in vivo detection of TBI within a short period (within 1 h), which is beneficial for the early diagnosis of TBI. Additionally, TA-NPs can also accomplish precise afterglow imaging of brain injuries with lower severity. The TA-NPs-based afterglow imaging developed herein will significantly facilitate the early diagnosis of TBI and provide robust evidence for its subsequent treatment.
The visible light-driven photoswitches are attracting widespread attention, but it is challenging to leverage their phototriggered structural changes to regulate dynamic bonds, assemblies, and materials. Herein, we incorporated reversible covalent sites of aldehyde ring-chain tautomers into all-visible-light azobenzenes toward a versatile platform for light-controlled formation/exchange of dynamic C—N bonds from secondary amines. The movement of ring-chain equilibrium was attained via manipulating intramolecular multiple hydrogen bonding from E/Z configurational isomers. Such structural regulation further enabled photocontrolled kinetics for the formation and exchange reactions of cyclic hemiaminal ethers from secondary amines exhibiting kinetic rate reversal from E/Z isomers. The varied capability of E/Z configurational isomers in engaging in multiple hydrogen bonds of azo attached carboxylate with ammonium salt accounts for the difference. Moreover, the photoswitching performance of azobenzenes in different solutions was readily regulated by dynamic covalent reactions with amines. The dynamic reactivity control with visible light and associated mechanistic foundation add into the collection of photoswitchable dynamic covalent chemistry and would lay the foundation for subsequent biological and material applications.
RNA plays a pivotal role in genetic information transmission, gene expression regulation, and key biological processes, making its functional regulation critical. In this study, we introduce an iedDA-based strategy for post-synthetic RNA modification, enabling controlled nucleic acid cleavage via the CRISPR-Cas system. By modifying RNA with trans-cyclooctene (TCO), its function is paused, and reactivation is achieved using the repair agent dimethyl-tetrazine (Me2Tz), triggering the iedDA reaction. We demonstrate reversible on/off switching of CRISPR-Cas activity in vitro and further validate the strategy's applicability to other RNA systems, highlighting its potential for gene editing in cells.
With the hypothesis of simple units integration to create new reactivities, a strategy for the synthesis of polyfunctionalized 5-alkenyl-3-carbonylfurans from γ-hydroxyl enal and 1,3-dicarbonyl compounds is established, featuring readily available starting materials, high efficiency, good functional groups compatibility, green chemistry with high atom economy and only water release, etc., to provide a series of polyfunctionalized 5-alkenyl-3-carbonylfurans, which could be applied to the late-stage functionalization of naturally occurring compounds and bioactive molecules, as well as the transformation to pyrroles and polycyclic aromatic hydrocarbon via electrocyclic reaction. The γ-hydroxyl has played an important role in the unexpected process of ring opening isomerization of 2H-pyran to furanones, as confirmed by detailed mechanistic studies.
This study explores the synthesis of calix[4]resorcinarene-based anion receptors and their shape selective recognition properties. Electron withdrawing groups are modified at the bridging site of the resorcinarene scaffold, leading to a reduction in the electron density of the receptors. The number of fluorine atoms in the receptors is adjusted to regulate their ability to bind anions. Our results demonstrate that these receptors bind with anions in two manners: electropositive "H" atoms in the concave cavity bind with non-spherical anion [MeSO3]− and the lower "crown" binds with spherical anion [Cl]−. The two binding modes are both driven by C—H∙∙∙anion hydrogen bonding. Besides, mass spectrometric experiments and density functional theory (DFT) calculations also verified the binding mechanism.
N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules. However, effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date. Herein, we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals. This methodology exhibits broad substrate scope, good functional group compatibility, and potential synthetic utility by a scale-up reaction, diverse product derivatizations and late-stage functionalization of complex biorelevant molecule. Notably, this transformation selectively allows for the formation of three new chemical bonds (C–O, C–C, and C–N) and one spiro quaternary carbon center across C-C double bonds.
An innovative visible-light-driven direct hydrogen atom transfer (d-HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10-phenanthraquinone (PCHAT9) serves as an efficient photocatalyst for the generation of germanium-centered radicals from germanium hydrides including Ph3GeH, nBu3GeH, and Ph2GeH2. By employing hypervalent iodine reagents as SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β-cleavage of a carboxyl radical to yield a diverse array of ethynyl-, vinyl-, nitrile-, and phenyl-functionalized germanes. The methodological leap signifies a noteworthy departure from the previous photocatalytic indirect hydrogen atom transfer (i-HAT) relying on combined usage of PCSET with abstractors, which not only advances the methodology for creating germanium radicals in a photocatalytic fashion but also provides access to structurally novel and pharmaceutically promising organogermanium compounds that are difficult to synthesize by routine methods.
Radical hydrogenation facilitated by metal (Fe, Co, Mn, etc.) hydride-mediated hydrogen atom transfer (mHAT) has emerged as a powerful technique in organic synthesis. However, nickel-hydride (NiH) catalyzed radical hydrogenation has remained largely unexplored. Herein, we develop a NiH catalytic system that achieves the hydrogenation of enamides in high efficiency. This strategy stands out for its ability to hydrogenate challenging quinolines at room temperature, avoiding the catalyst poisoning and deactivation by quinolines and their hydrogenation products. Furthermore, the deuteration of alkenes was achieved with high deuteration rates (up to > 99%), underscoring its potential in the synthesis of deuterium-containing molecules.
Arylamines constitute a fundamental class of organic compounds critical to pharmaceuticals, dyes, and advanced materials. The direct synthesis of arylamines from nitro compounds demonstrates significant advantages in step economy, cost efficiency, and functional group compatibility. However, conventional methodologies frequently necessitate transition metal catalysts or excessive reducing agents, limiting their practical applicability. Herein, we introduce a highly efficient photochemical protocol for the synthesis of arylamines from readily accessible nitro compounds and Grignard reagents under purple light (390—395 nm) irradiation, eliminating the requirement for transition metal catalysts or external reducing agents. This protocol exhibits exceptional tolerance to sterically hindered substrates and sensitive functional groups. Preliminary mechanistic investigations suggest the involvement of nitrosoarenes and diarylamine nitrogen radicals as key intermediates in the reaction pathway.
Selective catalysis, particularly when differentiating substrates with similar reactivities in a mixture, is a significant challenge. In this study, anomaly detection algorithms—tools traditionally used for identifying outliers in data cleaning—are applied to catalyst screening. We focus on developing catalytic methods to selectively oxidize cyclic alkanes over linear alkanes in mixtures such as naphtha. By inserting cyclohexane oxidation data one by one into a database of n-hexane oxidization, we used several anomaly detection algorithms to evaluate whether the inserted cyclohexane oxidation data could be considered anomalous. Conditions identified as anomalies imply that they are likely not suitable for n-hexane oxidization. As these anomalies come from conditions for cyclohexane oxidation, they are promising conditions for selective oxidation of cyclohexane while leaving n-hexane unaltered. These anomalies were thus further investigated, leading to the discovery of a specific catalytic approach that selectively oxidizes cyclohexane. This application of anomaly detection offers a novel method to search for selective catalyst for chemical reactions involving mixed substrates.
Given the global resource constraints and substantial energy consumption, the innovative development of efficient and precise thermal management materials represents a significant step forward in improving energy efficiency and promoting ecological and environmental sustainability. The unique structure of natural wood with its porous anisotropy provides new insights and strategies for the design of advanced thermal management materials. However, present reviews often fail to provide a comprehensive and systematic analysis of the inherent structural advantages, as well as the strategies pertinent to the construction and utilization of wood-based and biomimetic materials. This review explores the evolution of wood and its biomimetic structures in the field of thermal management materials, detailing the basic structures and compositions of wood and timber, as well as explaining how these materials can be processed and constructed with physical/chemical strategies. In addition, we highlight recent advances in such materials in the fields of thermal insulation, radiative cooling, heat transfer, and thermal energy storage. Finally, we offer some unique insights on the challenges and future developments for the scale-up of the use of such materials, providing our perspectives on their potential for broader implementation.
Solid oxide fuel cell (SOFC) is recognized as the third-generation fuel cell which transforms the chemical energy of different fuels directly into electrical energy with highly efficient. However, the sulfur poisoning and carbon deposition at high temperatures at the anode side hindered its commercialization. Using perovskite anodes combined with the in-situ exsolution (ISE) method has been extensively developed aimed at alleviating the above problems. This review is trying to depict a systematic overview of the mechanism of the ISE process, the strategies for designing ISE, and its application in SOFC anodes. We hope that this work could give a comprehensive understanding of future anodes for SOFC.
The development of photodynamic therapy (PDT), from its initial discovery of photodynamic effects to its current use in various medical conditions, is a testament to its therapeutic potential. Recent breakthroughs in nanotechnology have significantly enhanced the effectiveness of PDT. Typical nanomaterials (NMs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and nanozymes have been introduced to enhance the photodynamic efficacy because they can enhance the delivery of PSs, and effectively overcome insufficient targeting specificity, limited tissue penetration depth, and hypoxic microenvironments, thereby amplifying its therapeutic efficacy. However, the clinical application of these NMs in PDT faces several challenges, including concerns regarding biocompatibility, long-term biosafety, and economic feasibility. To further advance PDT, researchers should focus on designing NMs to improve therapeutic outcomes, exploring combination therapies with PDT, and conducting translational clinical trials to validate the safety and therapeutic efficacy of these novel PDT approaches. This review summarizes the recent progress in PDT based on NMs, especially MOFs, COFs and nanozymes and their application in disease treatment. We aim to provide guidance for future research and clinical practice in advancing NMs-enhanced PDT, paving the way for more effective therapeutic strategies.
Chiral framework materials, such as chiral metal-organic frameworks (MOFs) and chiral covalent organic frameworks (COFs), have been extensively reported and studied. However, research on chiral hydrogen-bonded organic frameworks (HOFs) is far behind. HOFs present a novel approach for creating chiral materials, thanks to their mild synthesis conditions, solution processability, and ease of repair and regeneration. This review provides a comprehensive overview of the design and synthesis strategies for chiral HOFs, highlighting recent advancements and exploring the applications of emerging chiral HOFs materials.