Longyi Zhu

The development of energetic materials with high-energy and low-sensitivity is crucial for their practical applications. Energetic covalent-organic frameworks (ECOFs), with their high thermal stability and facile functionalization, hold great potential for precise regulation of energy and safety at molecular level. However, the current ECOFs remains largely underexplored due to non-energetic or low-density co-monomers. Here we present a dual energetic-monomer strategy to construct two series of ECOFs by using tetrafluoroterephthalaldehyde (TFTA) and 2-nitroterephthalaldehyde (NTA) as co-monomers to condense with triaminoguanidinium salts (TAGX) respectively. The as-synthesized COF-TAGX-TFTA achieves a density of approximately 1.90 g·cm-3, a maximum detonation velocity of 8191 m·s-1, detonation pressures of 22~30 GPa, demonstrating excellent detonation performance. With respect to safety characteristics, all target COFs exhibit impact sensitivity above 60 J and friction sensitivity above 360 N, along with thermal critical temperatures exceeding 210℃ (except TAGNO3-NTA) and favorable compatibility with typical energetic materials. Further mechanism study shows their energy release follows a dual-pathway of bond energy release and redox reactions. The thermal decomposition is initiated by N-N bond cleavage, with the decomposition model transitioning from A2 to L2 as conversion progresses. These results demonstrate that both ECOF series achieve efficient enhancement of energy and safety, showing potential practical applications.

A mitochondrial regulation strategy based on a light-triggered hybrid chain reaction has been designed for controlling mitochondrial aggregation and fusion in living cells.

The accurate identification of energetic heterocyclic compounds (EHCs) is of great significance in munition assessment, environmental monitoring, and biosafety but remains largely underexplored. Herein, a covalent organic frameworks-based fluorescence sensor array (COFx sensor array) for efficient screening of EHCs is reported. The topologies of the COFs were rationally designed by modulating the pore sizes and linkage strategies to achieve the simplified sensor array. Eighteen EHC representatives, including single-, dual-, and three-ring EHCs with multivariate substructures, were successfully discriminated ranging from 10 μM to 1 mM. The sensor array showed robust selectivity against a wide range of interferences. The quantitative structure–activity relationship (QSAR) analysis has been conducted for the mechanistic study of the sensor array. Three multiple linear regression models have been established using molecular descriptors to evaluate and predict Stern–Volmer coefficient values, achieving explicit correlation between EHC structures and the signal outputs of the sensor array. Five molecular descriptors are retained to reveal the governing factors of the sensor array resolution. The QSAR analysis facilitates the design and development of the COFx sensor array, offering a new approach for customized multivariate analysis.

The nonphotodriven electrochemiluminescence (ECL) imageology necessitates concentrated coreacting additives plus longtime exposures. Seeking biosafe and streamlined ensembles can help lower the bar for quality ECL bioimaging to which call the crystallized endo-coreaction in nanoreticula might provide a potent solution. Herein, an exo-coreactant-free ECL visualizer was fabricated out in one-pot, which densified the dyad triethylamine analogue: 1,4-diazabicyclo-[2.2.2]octane (DABCO) in the lamellar hive of 9,10-di(p-carboxyphenyl)anthracene (DPA)-Zn²⁺. This biligated non-noble metal-organic framework (m-MOF) facilitated a self-contained anodic ECL with a yield as much as 70% of Ru(bPy)₃²⁺ in blank phosphate buffered saline. Its featured two-stage emissions rendered an efficient and endurant CCD imaging at 1.0 V under mere 0.5 s swift snapshots and 0.1 s step-pulsed stimulation. Upon structural and spectral cause analyses as well as parametric set optimization, simplistic ECL-graphic immunoassay was mounted in the in situ imager to enact an ultrasensitive measurement of coronaviral N-protein in both signal-on and off modes by the privilege of straight surface amidation on m-MOFs, resulting in a wide dynamic range (10^-4-10 ng/mL), a competent detection limit down to 56 fg/mL, along with nice precision and parallelism in human saliva tests. The overall work manifests a rudimentary endeavor in self-sufficient ECL visuality for brisk, biocompatible, and brilliant production of point-of-care diagnostic "Big Data".

The precision additive manufacturing and tessellated multitasking out of the structural DNA nanotechnology enable a configurable expression of densified electrochemiluminescent (ECL) complexes, which would streamline the bioconjugation while multiplying signals. Herein, a completely DNA-scaffold ECL "polyploid" was replicated out via the living course of rolling circle amplification. The amplicon carried the aptameric sequences of ZnPPIX/TSPP porphyrin as photoreactive centers that rallied at periodical intervals of the persistent extension into a close-packed nanoflower, ZnPDF_I/II. Both microscopies and electrophoresis proved the robust nesting of guests at their deployed gene loci, while multispectral comparisons among cofactor substituents pinpointed the pivotal roles of singlet seclusion and Zn²⁺-chelation for the sake of intensive ECL irradiation. The adversity-resilient hydrogel texture made lipoidal filmogens as porphyrinic ECL prerequisites to be of no need at all, thus not only simplifying assay flows but also inspiring an in situ labeling plan. Upon bioprocessing optimization, an enriched probe ZnPDF_III was further derived that interpolated the binding motif related to calprotectin as validated by molecular docking and affinity titration. With it being a strongly indicative marker of inflammatory bowel disease (IBD), a competitive ECL aptasensing strategy was contrived, managing a signal-on and sensitive detection in mild conditions with a subnanogram-per-milliliter limit of detection by 2 orders of magnitude lower than the standard method as well as a comparable accuracy in clinical stool sample testing. Distinct from those conventional chemophysical rebuilding routes, this de novo biosynthetic fusion demonstrated a promising alternative toward ECL-source bioengineering, which may intrigue vibrant explorations of other ECL-shedding fabrics and, accordingly, a new bioanalytic mode downstream.

Given the lack of timely evaluation of the well-received selenium fortification, a neat lateral-flow chromatographic solution was constructed here by using the recently identified urinary selenosugar (Sel) as a strongly indicative marker. As there are no ready-made receptors for this synthetic standard, phenylboronic acid (PBA) esterification and Dolichos biflorus agglutinin (DBA) affinity joined up to pinch and pin down the analyte into a sandwich-type glycol complex. Pilot lectin screening on homemade glycan microarrays verified such a new pairing between dual recognizers as PBA-Sel-DBA with a firm monosaccharide-binding constant. To quell the sample autofluorescence, europium nanoparticles with efficient long-life afterglow were employed as conjugating probes under 1 μs excitation. After systematic process optimizations, the prepared Sel-dipstick achieved swift and sensitive fluorometry over the physiological level of the target from 0.1 to 10 μM with a detection limit down to 0.06 μM. Further efforts were made to eliminate matrix effects from both temperature and pH via an approximate formula. Upon completion, the test strips managed to quantify the presence of Sel in not just imitated but real human urine, with comparable results to those in the references. As far as we know, this would be the first in-house prototype for user-friendly and facile diagnosis of Se nutrition with fair accuracy as well as selectivity. Future endeavors will be invested to model a more traceable Se-supplementary plan based on the rhythmic feedback of Sel excretion.

Targeted protein degradation (TPD) is a powerful technique for regulation of protein homeostasis. Current TPD mainly focuses on the therapeutical consequences rather than the operation processes of the molecular tools. Herein, we construct a platform for precisely manipulate the protein degradation by activatable lysosome targeting DNA nanodevices. In the design, a lysosome-targeting CD63 aptamer is locked by the single-stranded DNA with a photocleavable group and a disulfide bond. This locked CD63 aptamer is connected with the aptamer targeting the protein of interest via double-stranded DNA linkages to form the logic-gate activated lysosome targeting DNA nanodevice (LALTD). With the UV light and endogenous GSH as inputs, AND logic-gate is built to efficiently manipulate the protein delivery processes by LALTD. The protein of interest could be degraded via efficient lysosome hydrolysis. Further studies shows that the logic-gate operation could be used for modulating the T cell-mediated antitumor immunity. The modularly designed activatable lysosome targeting DNA nanodevices exhibits good stability, controllability, programmability and universality, providing a new prospect for accurate protein degradation and precise therapy. Entry for the Table of Contents: Through rational integration of dual molecular switches with bispecific aptamer systems, a logic-gate activated lysosome targeting DNA nanodevice (LALTD) was developed for precisely controlled process of protein hydrolysis in living cells. The designed LALTD system provide a general platform for designing accurate protein degradation.