Metal-Phenolic-Mediated Assembly of Functional Small Molecules into Nanoparticles: Assembly and Bioapplications.

Small molecules, including therapeutic drugs and tracer molecules, play a vital role in biological processing, disease treatment and diagnosis, and have inspired various nanobiotechnology approaches to realize their biological function, particularly in drug delivery. Desirable features of a delivery system for functional small molecules (FSMs) include high biocompatibility, high loading capacity, and simple manufacturing processes, without the need for chemical modification of the FSM itself. Herein, we report a simple and versatile approach, based on metal-phenolic-mediated assembly, for assembling FSMs into nanoparticles (i.e., FSM-MPN NPs) under aqueous and ambient conditions. We demonstrate loading of anticancer drugs, latency reversal agents, and fluorophores at up to ~80 % that is mostly facilitated by π and hydrophobic interactions between the FSM and nanoparticle components. Secondary nanoparticle engineering involving coating with a polyphenol-antibody thin film or sequential co-loading of multiple FSMs enables cancer cell targeting and combination delivery, respectively. Incorporating fluorophores into FSM-MPN NPs enables the visualization of biodistribution at different time points, revealing that most of these NPs are retained in the kidney and heart 24 h post intravenous administration. This work provides a viable pathway for the rational design of small molecule nanoparticle delivery platforms for diverse biological applications.

ZIFs-Derived Hollow Nanostructures via a Strong/Weak Coetching Strategy for Long-Life Rechargeable Zn-Air Batteries.

Recently, zeolitic imidazolate frameworks (ZIFs) composites have emerged as promising precursors for synthesizing hollow-structured N-doped carbon-based noble-metal materials with diverse structures and compositions. Here, a strong/weak competitive coordination strategy is presented for synthesizing high-performance electrocatalysts with hollow features. During the competitive coordination process, the cubic zeolitic-imidazole framework-8 (Cube-8)@ZIF-67 with core-shell structures are transformed into Cube-8@ZIF-67@PF/POM with yolk-shell nanostructures employing phosphomolybdic acid (POM) and potassium ferricyanide (PF) as the strong chelator and the weak chelator, respectively. After calcination, the hollow Mo/Fe/Co@NC catalyst exhibits superior performance in both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Interestingly, the Mo/Fe/Co@NC catalyst exhibits efficient electrocatalytic performance for Zn-air batteries (ZABs), with a high power density (≈150 mW cm-2 ) and superior cycling life (≈500 h) compared to commercial platinum/carbon (Pt/C) and ruthenium dioxide (RuO2 ) mixture benchmarks catalysts. In addition, the density functional theory further proves that after the introduction of Mo and Fe atoms, the adsorption energy with the adsorption intermediates is weakened by adjusting the d-band center, thus weakening the reaction barrier and promoting the reaction kinetics of OER. Undoubtedly, this study presents novel insights into the fabrication of ZIFs-derived hollow structure bifunctional oxygen electrocatalysts for clean-energy diverse applications.

Direct Assembly of Metal-Phenolic Network Nanoparticles for Biomedical Applications.

Coordination assembly offers a versatile means to developing advanced materials for various applications. However, current strategies for assembling metal-organic networks into nanoparticles (NPs) often face challenges such as the use of toxic organic solvents, cytotoxicity because of synthetic organic ligands, and complex synthesis procedures. Herein, we directly assemble metal-organic networks into NPs using metal ions and polyphenols (i.e., metal-phenolic networks (MPNs)) in aqueous solutions without templating or seeding agents. We demonstrate the role of buffers (e.g., phosphate buffer) in governing NP formation and the engineering of the NP physicochemical properties (e.g., tunable sizes from 50 to 270 nm) by altering the assembly conditions. A library of MPN NPs is prepared using natural polyphenols and various metal ions. Diverse functional cargos, including anticancer drugs and proteins with different molecular weights and isoelectric points, are readily loaded within the NPs for various applications (e.g., biocatalysis, therapeutic delivery) by direct mixing, without surface modification, owing to the strong affinity of polyphenols to various guest molecules. This study provides insights into the assembly mechanism of metal-organic complexes into NPs and offers a simple strategy to engineer nanosized materials with desired properties for diverse biotechnological applications.

Assessment of PCDD/Fs formation and emission characteristics at a municipal solid waste incinerator for one year.

Municipal solid waste incineration (MSWI) has become a predominant emission source of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). Research focusing on the impact of operating conditions, environmental changes, and operating time on the generation and emissions of PCDD/Fs has not been resolved. To this end, this study tracked and investigated the PCDD/Fs and 17 congener emissions of a typical grate incinerator (800 t/d) continuously for one year. Results showed that the PCDD/Fs concentration at the boiler outlet, stack inlet, and bag filter, including normal and abnormal operation conditions, ranges from 2.11E-02-41.86 ng I-TEQ/Nm3, 7.00E-04-6.76 ng I-TEQ/Nm3, and 1.12-2.90E+03 ng I-TEQ/Nm3, respectively. The 2,3,4,7,8-P5CDF has the highest contribution in all samples, in which a proportion of TEQ ranged from 30 % to 77.73 %. Moreover, by applying the correlation analysis between PCDD/Fs and operating parameters, the emission characteristic is mainly affected by incinerators and boilers during the normal period, and it is affected by the whole MSWI process under abnormal conditions. In addition, the PCDD/Fs emission from the MSWI plant gradually increases from spring to winter. This study is beneficial for supporting the control of PCDD/Fs emission reduction and assisting the operators to optimize the relevant operating parameters of the MSWI plant to achieve a stable and up-to-substandard emissions during the operation period.

Investigation on dioxins emission characteristic during complete maintenance operating period of municipal solid waste incineration.

The dioxins (DXN) are a set of pollutants encompass polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F), their emissions from municipal waste incineration processes (MSWI) are normally detected under steady operating conditions. However, limited studies have focused on the PCDD/F emission characteristics under a complete maintenance operating period (CMOP), which includes shut-down, cooling, maintenance, heating, startup, and normal operations. In this article, the shutdown process (SDP) starts from the normal operation, followed by shutdown, and then cooling; while the startup process (SUP) commences from heating, followed by startup, and then normal operation. The detection and analysis were conducted at the SDP and SUP stages. The PCDD/F mass and total toxic equivalent quantity (TEQ) concentrations were measured in the flue gas and bag filter fly ash (BF-FA) during a CMOP of Beijing MSWI plant. The highest PCDD/F concentrations in the flue gas were found in the "cooling" and "startup" phases; in the FA, this condition occurred in the "startup" phase. Further, the results show that the most heightened concentrations were observed for 5-6 chlorinated PCDF and 4-5 chlorinated PCDD among the 17 PCDD/F congeners in most cases. More importantly, the air pollution control devices (APCDs) which include activated carbon, lime, and BF, have high removal efficiency for PCDD/F (especially PCDD) during the "startup" phase. APCDs also easily release a considerable amount of PCDD/F because of the memory effect, which emits more PCDD/F at the "shutdown" phase than at the "startup" one. Besides, the annual PCDD/F emission in the flue gas of the MSWI plant was estimated to be 67.72 mg I-TEQ, of which the emission accounts for approx. 20% during the CMOP. Moreover, the experiment shows that the PCDD/F emissions of the MSWI plant in Beijing under unsteady conditions are more miniature than those reported earlier in other areas.

A stable DNA Tetrahedra-AuNCs nanohybrid: On-site programmed disassembly for tumor imaging and combination therapy.

Despite DNA nanotechnology has spawned a broad variety and taken a giant leap toward cancer theranostic applications over the last decade, the homogeneous DNA nanostructures often suffer from fatal degradation due to their limited stability and specificity. Herein, for the first time, we report a stable DNA tetrahedra-gold nanoclusters (DT/AuNCs) nanohybrid with a self-assembly/programmed disassembly manner for stimuli-responsive tumor imaging and gene-chemo therapy. By utilizing the multifunctional peptides with positive and legumain-specific domains as bioligands, AuNCs were synthesized as signal generators and gate guard attached on the dual-responsive DT, forming the DT/AuNCs with sequential response to legumain-TK1 mRNA & glutathione. The tumorous biomarker of legumain initiated the signal generation relying on the nanosurface energy transfer effect of AuNCs and denudation of DT-Dox (preliminary disassembly). Successively, the dual-responsive DT-Dox administrated a sequential fragmentation along with Dox release in response to the up-regulated glutathione and TK1 mRNA (secondary disassembly), thereby leading to combined gene silencing and chemo-therapy. The results revealed that the DT/AuNCs nanohybrids significantly improved the stability and enhanced the therapeutic efficiency compared to naked DT. Endowing with remarkable stability against biological milieu and site specificity for drug release, our work exhibits a new prospect of fabricating DNA-based nanohybrids for precise tumor theranostics.

Analysis of Pollution in High Voltage Insulators via Laser-Induced Breakdown Spectroscopy.

Surface pollution deposition in a high voltage surface can reduce the surface flashover voltage, which is considered to be a serious accident in the transmission of electric power for the high conductivity of pollution in wet weather, such as rain or fog. Accordingly, a rapid and accurate online pollution detection method is of great importance for monitoring the safe status of transmission lines. Usually, to detect the equivalent salt deposit density (ESDD) and non-soluble deposit density (NSDD), the pollution should be collected when power cut off and bring back to lab, time-consuming, low accuracy and unable to meet the online detection. Laser-induced breakdown spectroscopy (LIBS) shows the highest potential for achieving online pollution detection, but its application in high voltage electrical engineering has only just begun to be examined. In this study, a LIBS method for quantitatively detecting the compositions of pollutions on the insulators was investigated, and the spectral characteristics of a natural pollution sample were examined. The energy spectra and LIBS analysis results were compared. LIBS was shown to detect pollution elements that were not detected by conventional energy spectroscopy and had an improved capacity to determine pollution composition. Furthermore, the effects of parameters, such as laser energy intensity and delay time, were investigated for artificial pollutions. Increasing the laser energy intensity and selecting a suitable delay time could enhance the precision and relative spectral intensities of the elements. Additionally, reducing the particle size and increasing the density achieved the same results.

Effect of inoculants and storage temperature on the microbial, chemical and mycotoxin composition of corn silage.

OBJECTIVE: To evaluate the effect of lactic acid bacteria and storage temperature on the microbial, chemical and mycotoxin composition of corn silage. METHODS: Corn was harvested at 32.8% dry matter, and chopped to 1 to 2 cm. The chopped material was subjected to three treatments: i) control (distilled water); ii) 1×106 colony forming units (cfu)/g of Lactobacillus plantarum; iii) 1×106 cfu/g of Pediococcus pentosaceus. Treatments in triplicate were ensiled for 55 d at 20°C, 28°C, and 37°C in 1-L polythene jars following packing to a density of approximately 800 kg/m3 of fresh matter, respectively. At silo opening, microbial populations, fermentation characteristics, nutritive value and mycotoxins of corn silage were determined. RESULTS: L. plantarum significantly increased yeast number, water soluble carbohydrates, nitrate and deoxynivalenol content, and significantly decreased the ammonia N value in corn silage compared with the control (p<0.05). P. pentosaceus significantly increased lactic acid bacteria and yeast number and content of deoxynivalenol, nivalenol, T-2 toxin and zearalenone, while decreasing mold population and content of nitrate and 3-acetyl-deoxynivalneol in corn silage when stored at 20°C compared to the control (p<0.05). Storage temperature had a significant effect on deoxynivalenol, nivalenol, ochratoxin A, and zearalenone level in corn silage (p<0.05). CONCLUSION: Lactobacillus plantarum and Pediococcus pentosaceus did not decrease the contents of mycotoxins or nitrate in corn silage stored at three temperatures.

A zeolitic imidazolate framework-8-based indocyanine green theranostic agent for infrared fluorescence imaging and photothermal therapy.

Indocyanine green (ICG) is the only near-infrared (NIR) dye approved by the United States Food and Drug Administration (FDA). Although it is highly desirable, some bottlenecks still remain in clinical applications, such as poor photostability, poor thermal stability, and lack of target specificity. To solve these problems, a zeolitic imidazolate framework-8 (ZIF-8)-based ICG theranostic agent was constructed by one-pot synthesis for fluorescence imaging and photothermal therapy (PTT). The as-synthesized ICG@ZIF-8 nanoparticles (NPs) displayed ultrahigh loading capacity, superior photothermal stability, good anti-photobleaching ability, good biocompatibility, efficient cellular uptake, and favourable photothermal killing capacity for human hepatocarcinoma SMMC-7721 cells. Importantly, in vivo experiments showed that ICG@ZIF-8 NPs accurately and sensitively detected tumors by fluorescence molecular imaging. The PTT results indicated that ICG@ZIF-8 NPs efficiently induced a local ablation effect under a single NIR laser irradiation. The tumor was completely suppressed, and no tumor recurrence or treatment-induced toxicity was observed. The described particles have the potential to act as a promising platform for cancer theranostic nanomedicine.