Ligand-protected nanocluster-mediated photoswitchable fluorescent nanoprobes towards dual-color cellular imaging.

Development of robust multi-color photoswitchable fluorescent probes is critical for many optical applications, but it remains a challenge to rationally design these probes. Here, we report a new design of Förster resonance energy transfer-based dual-color photoswitchable fluorescent nanoparticles (DPF NPs) by taking advantage of the distinct properties of ligand-protected gold nanoclusters (AuNCs). Detailed photophysical studies revealed that ultrasmall-sized AuNCs not only act as the FRET donors due to their intrinsic fluorescence properties, but also play a significant role in regulating the photochromic and aggregate properties of spiropyran through ligand-spiropyran interactions. These DPF NPs exhibit a high fluorescence on/off ratio (∼90%) for both green and red fluorescence emission, and good reversibility during cycled photo-stimulation. Cell imaging experiments showed that DPF NPs could specifically accumulate in lipid droplets, and enable photoswitchable dual-color imaging in living cells. Moreover, by labeling mitochondria with a green-emitting marker, we demonstrated that DPF NPs can distinguish different targets based on dynamic and static fluorescence signals at the sub-cellular level in two emission channels reliably. This study provides a new strategy for designing robust photoswitchable fluorescent probes by modulating the properties of photochromic dyes through ligand-protected nanoclusters, which can be generalized for the development of other photoswitch systems towards advanced optical applications.

Chirality-Dependent Angiogenic Activity of MoS2 Quantum Dots toward Regulatable Tissue Regeneration.

Despite great advances in understanding the biological behaviors of chiral materials, the effect of chirality-configured nanoparticles on tissue regeneration-related biological processes remains poorly understood. Herein, the chirality of MoS2 quantum dots (QDs) is tailored by functionalization with l-/d-penicillamine, and the profound chiral effects of MoS2 QDs on cellular activities, angiogenesis, and tissue regeneration are thoroughly investigated. Specifically, d-MoS2 QDs show a positive effect in promoting the growth, proliferation, and migration of human umbilical vein endothelial cells. The expression of vascular endothelial growth factor (VEGF), endothelial nitric oxide synthase (eNOS), and fibroblast growth factor (FGF) in d-MoS2 QDs group is substantially up-regulated, resulting in enhanced tube formation activity. This distinct phenomenon is largely due to the higher internalization efficiency of d-MoS2 QDs than l-MoS2 QDs and chirality-dependent nano-bio interactions. In vivo angiogenic assay shows the expression level of angiogenic markers in newly-formed skin tissues of d-MoS2 QDs group is higher than that in l-MoS2 QDs group, leading to an accelerated re-epithelialization and improved skin regeneration. The findings of chirality-dependent angiogenesis activity of MoS2 QDs provide new insights into the biological activity of MoS2 nanomaterials, which also opens up a new path to the rational design of chiral nanomaterials for tissue regeneration application.

Surface Engineering of MoS2 Quantum Dots via Cyclodextrin-Based Host-Guest Chemistry as Versatile Platforms for Enhanced Cell Imaging Application.

Transition metal chalcogenide quantum dots (QDs), especially MoS2 QDs, are an emerging class of novel optical probes for versatile bioanalytical applications owing to their distinct physicochemical properties. However, the reasonable use of these QDs for biological imaging has been largely restricted due to the challenge of controllable surface functionalization. In this work, we report a new strategy to engineer the surface of MoS2 QDs by taking advantage of cyclodextrin (CD)-based host-guest chemistry. The prepared ß-CD-modified QDs (ß-CD-MoS2 QDs) exhibit enhanced fluorescence properties, excellent biocompatibility, and good stability, making them promising as novel optical probes for bioimaging. Cellular imaging experiments revealed that these ß-CD-MoS2 QDs can enter living cells through multiple internalization pathways, which differs significantly from pristine QDs. Particularly, we observed that the intracellular accumulation of MoS2 QDs in lipid droplets was enhanced owing to the specific binding of ß-CD to cholesterol, which was then harnessed for monitoring the lipid metabolism in living cells via fluorescence imaging. Furthermore, we also demonstrated the potential use of ß-CD-MoS2 QDs for targeted cell imaging and microplate-based cell recognition, which can be easily achieved via bioconjugation with functional motifs (e.g., folate acid) through host-guest chemistry. Altogether, these results illustrate the great potential of engineering the surface of MoS2 QDs and other analogous materials via CD-based host-guest chemistry for advancing their cell imaging applications.

Chirality-Dependent Dynamic Evolution of the Protein Corona on the Surface of Quantum Dots.

Elucidating the biological behavior of engineered nanoparticles, for example, the protein corona, is important for the development of safe and efficient nanomedicine, but our current understanding is still limited due to its highly dynamic nature and lack of adequate analytical tools. In the present work, we demonstrate the establishment of a fluorescence resonance energy transfer (FRET)-based platform for monitoring the dynamic evolution behavior of the protein corona in complex biological media. With human serum albumin and lysozyme as the model serum proteins, the protein exchange process of the preformed corona on the surface of chiral quantum dots (QDs) upon feeding either individual protein or human serum was monitored in situ by FRET. Important parameters characterizing the evolution process of protein corona could be obtained upon quantitative analysis of FRET data. Further combining real-time FRET monitoring with gel electrophoresis experiments revealed that the nature of the protein initially adsorbed on the surface of QDs significantly affects the subsequent dynamic exchange behavior of the protein corona. Furthermore, our results also revealed that only a limited proportion of proteins are involved in the protein exchange, and the exchange process exhibits a significant dependence on the surface chirality of QDs. This work demonstrates the feasibility of FRET as a powerful tool to exploit the dynamic evolution process of the protein corona, which can provide theoretical guidance for further design of advanced nanomaterials for biomedical applications.

Surface chemistry regulates the optical properties and cellular interactions of ultrasmall MoS2 quantum dots for biomedical applications.

Molybdenum disulfide quantum dots (MoS2 QDs) have drawn increasing attention owing to their distinct optical properties and potential applications in many fields such as biosensing, photocatalysis and cell imaging. Elucidating the relationship between the surface chemistry of MoS2 QDs and their optical properties as well as biological behaviors is critical for their practical applications, which remain largely unclear. Herein, by adopting a sulfur vacancy modification strategy, a toolbox of MoS2 QDs functionalized with different thiolate ligands was prepared. The effect of surface chemistry on the optical properties of MoS2 QDs was systematically explored by various spectroscopic techniques, revealing the important role of surface ligands in defining their absorption band gap and luminescence quantum yield. Furthermore, cellular experiments showed that the cytotoxicity and intracellular fate (i.e., lysosomal accumulation) of MoS2 QDs are closely related to the properties of surface ligands. Our results underscore the important roles of surface ligands in regulating the properties and biological interactions of these QDs, which will facilitate the future development of MoS2-based materials with precisely controlled functions for biomedical applications.

[Research of input water ratio's impact on the quality of effluent water from hydrolysis reactor].

Based on high SS/BOD and low C/N ratio of waste water of municipal wastewater treatment plant, the structure of currently existing hydrolysis reactor was reformed to improve the influent quality. In order to strengthen the sludge hydrolysis and improve effluent water quality, two layers water distributors were set up so that the sludge hydrolysis zone was formed between the two layers distribution. For the purpose of the hydrolysis reactor not only plays the role of the primary sedimentation tank but also improves the effluent water biodegradability, input water ratios of the upper and lower water distributor in the experiment were changed to get the best input water ratio to guide the large-scale application of this sort hydrolysis reactor. Results show, four kinds of input water ratio have varying degrees COD and SS removal efficiency, however, input water ratio for 1 : 1 can substantially increase SCOD/COD ratio and VFA concentration of effluent water compared with the other three input water ratios. To improve the effluent biodegradability, input water ratio for 1 : 1 was chosen for the best input water ratio. That was the ratio of flow of upper distributor was 50%, and the ratio of the lower one was 50%, at this case it can reduce the processing burden of COD and SS for follow-up treatment, but also improve the biodegradability of the effluent.