Efficient Self-Sorting Behaviours of Metallacages with Subtle Structural Differences.

Investigating the self-sorting behaviour of assemblies with subtle structural differences is a captivating yet challenging endeavour. Herein, we elucidate the unusual self-sorting behaviour of metallacages with subtle structural differences in batch reactors and microdroplets. Narcissistic self-sorting of metallacages has been observed for two ligands with identical sizes, shapes, and symmetries, with only minor differences in the substituted groups. In particular, the self-sorting process in microdroplets occurs within 1 min at room temperature, in stark contrast to batch reactors, which require equilibration for 30 min. To reveal the mechanism of self-sorting and the role of microdroplets, we conducted a series of experiments and theoretical calculations, including competitive self-assembly, cage-to-cage transformation, control experiments involving model metallacages with larger cavities, noncovalent interaction analysis, and root mean square deviation (RMSD) analysis. This research demonstrates an unusual case of self-sorting of very similar assemblies and provides a new strategy for facilitating the self-sorting efficiency of supramolecular systems.

A Carbon-Caged Rhodamine Generating Nitrosoperoxycarbonate for Photoimmunotherapy.

Photoimmunotherapy is a promising cancer treatment modality. While potent 1-e- oxidative species are known to induce immunogenic cell death (ICD), they are also associated with unspecific oxidation and collateral tissue damage. This difficulty may be addressed by post-generation radical reinforcement. Namely, non-oxidative radicals are first generated and subsequently activated into powerful oxidative radicals to induce ICD. Here, we developed a photo-triggered molecular donor (NPCD565) of nitrosoperoxycarbonate (ONOOCO2 -), the first of its class to our knowledge, and further evaluated its feasibility for immunotherapy. Upon irradiation of NPCD565 by light within a broad spectral region from ultraviolet to red, ONOOCO2 - is released along with a bright rhodamine dye (RD565), whose fluorescence is a reliable and convenient build-in reporter for the localization, kinetics, and dose of ONOOCO2 - generation. Upon photolysis of NPCD565 in 4T1 cells, damage-associated molecular patterns (DAMPs) indicative of ICD were observed and confirmed to exhibit immunogenicity by induced maturation of dendritic cells. In vivo studies with a bilateral tumor-bearing mouse model showcased the potent tumor-killing capability of NPCD565 of the primary tumors and growth suppression of the distant tumors. This work unveils the potent immunogenicity of ONOOCO2 -, and its donor (NPCD565) has broad potential for photo-immunotherapy of cancer.

Computational Modeling Oriented Substructure Splicing Application in the Identification of Thiazolidine Derivatives as Potential Low Honeybee Toxic Neonicotinoids.

With the aim of identifying novel neonicotinoid insecticides with low bee toxicity, a series of compounds bearing thiazolidine moiety, which has been shown to be low bee toxic, were rationally designed through substructure splicing strategy and evaluated insecticidal activities. The optimal compounds A24 and A29 exhibited LC50 values of 30.01 and 17.08 mg/L against Aphis craccivora, respectively. Electrophysiological studies performed on Xenopus oocytes indicated that compound A29 acted on insect nAChR, with EC50 value of 50.11 µM. Docking binding mode analysis demonstrated that A29 bound to Lymnaea stagnalis acetylcholine binding protein through H-bonds with the residues of D_Arg55, D_Leu102, and D_Val114. Quantum mechanics calculation showed that A29 had a higher highest occupied molecular orbit (HOMO) energy and lower vertical ionization potential (IP) value compared to the high bee toxic imidacloprid, showing potentially low bee toxicity. Bee toxicity predictive model also indicated that A29 was nontoxic to honeybees. Our present work identified an innovative insecticidal scaffold and might facilitate the further exploration of low bee toxic neonicotinoid insecticides.

Naphtho[1,8-ef]isoindole-7,8,10(9H)-trione as Novel Theranostic Agents for Photodynamic Therapy and Multi-Subcellular Organelles Localization.

A series of naphtho[1,8-ef]isoindole-7,8,10(9H)-trione derivatives as novel theranostic agents for photodynamic therapy and multi-subcellular organelles localization were designed and synthesized. Most of them possess moderate fluorescence quantum yield and long wavelength absorption simultaneously, which made them possible for dual effects of imaging and therapy. Notably, compounds 7 b and 7 d exhibited significant light-toxicity but slight dark-toxicity. Confocal fluorescence microscopy experiments demonstrated that compound 7 b can locate and image in special multi-subcellular organelles. All the research results implied that naphtho[1,8-ef] isoindole-7,8,10(9H)-trione derivatives can be applied as a new series of theranostic agents with the characteristics of photodynamic therapy and multi-subcellular organelles imaging.

Microfluidic-Based dsRNA Delivery Nanoplatform for Efficient Spodoptera exigua Control.

Nanotechnology-based RNA interference (RNAi) offers a promising approach to pest control. However, current methods for producing RNAi nanopesticides are mainly implemented in a batch-to-batch manner, lacking consistent quality control. Herein, we present a microfluidic-based nanoplatform for RNA nanopesticide preparation using lipid nanoparticles (LNPs) as nanocarriers, taking advantage of the enhanced mass transfer and continuous processing capabilities of microfluidic technology. The dsRNA@LNPs were rapidly formed within seconds, which showed uniform size distribution, improved leaf wettability, and excellent dispersion properties. The delivery efficiency of dsRNA@LNPs was evaluated by targeting the chitin synthetase B (CHSB) gene ofSpodoptera exigua. The dsRNA@LNPs can effectively resist nuclease-rich midgut fluid degradation. Importantly, dsCHSB@LNPs exhibited increased mortality rates, significant reduction of larvae growth, and enhanced gene suppression efficiency. Therefore, a continuous nanoplatform for RNAi nanopesticide preparation is demonstrated by utilizing microfluidic technology, representing a new route to produce RNAi nanopesticides with enhanced quality control and might accelerate their practical applications.

An all-glass based micro gas chromatographic column for light hydrocarbon separation with HKUST-1 as stationary phase.

BACKGROUND: The gas chromatography column is one of the key components of the gas chromatograph and typically be miniaturized using micro-electro-mechanical system (MEMS) technology. Due to the limited area of the Si wafer, the column length of micro gas chromatographic column (µGCC) is usually much smaller than that of commercial chromatographic columns. Therefore, it is always difficult to use µGCCs to separate small molecule gas components such as light hydrocarbons. More importantly, the heterogeneous microchannel surface formed by silicon glass bonding causes uneven stationary phase coating, further preventing the improvement of separation performance. RESULTS: In this paper, a novel all-glass based µGCC with 2 m length for the separation of light hydrocarbons is proposed. The microchannels of the µGCC were directly prepared in the glass substrate by ultrafast laser assisted chemical etching (ULAE). The all-glass microchannels make the coating of the hydrophilic metal-organic frameworks (MOFs) stationary phase continuously because of the homogeneous material composition. Therefore, a widely used copper based hydrophilic MOFs HKUST-1 was used as stationary phase for coating and testing. The test results show that the µGCC which is an open tubular column can realize the baseline separation of light hydrocarbons at 100 °C. And the resolution of difficult separated compounds, methane and ethane, can reach 12.98, which is 201.86 % higher than the silica-based monolithic capillary column in the relevant research. The resolution of ethane and ethylene reaches 6.81 at 120 °C. SIGNIFICANCE: The µGCC fabricated by ULAE method is composed of all-glass and has the uniform stationary phase coating because of the homogeneous microchannel surface which greatly improve the separation performance, resulting in a large resolution for methane and ethane. The all-glass µGCC has broad application prospects in light hydrocarbon separation.