RESUMO
Biomolecular systems actively control their local environment on a sub-nm scale via changes in molecular configuration from their flexible structures and derive emergent functions. Although this functional emergence based on local environmental control is attracting a great deal of attention in chemistry, it remains challenging to realize this artificially. Herein, we report the tuning of the thermo-responsive properties of oligo(ethylene glycol) (OEG) derivatives attached on gold nanoparticles via local environmental control not only by the hydrophobic moiety at their terminus but also by their molecular configuration. OEG-attached alkane thiol-modified AuNPs showed thermo-responsive assembly/disassembly in water through the hydration/dehydration of the OEG portions in a manner dependent both on the hydrophobicity at their terminus and the surface curvature of the core nanoparticles. Further, the assembly temperature (T A) was also tuned by ligand mixing with a non-thermo-responsive ligand with a shorter OEG length. Molecular dynamics simulations show that the distribution of the hydrophobic terminus in the normal direction along the gold surface varied in accordance with the surface curvature, indicating variations in molecular configuration. It is expected that a bent configuration could accelerate the thermo-responsiveness of OEG by allowing them greater accessibility to the hydrophobic terminus. Experimental and simulation results support the notion that local OEG density tuning by surface curvature or ligand mixing with a different OEG length leads to different degrees of accessibility to the hydrophobic terminus via changes in molecular configuration, promoting local environmental control-directed assembly temperature tuning.
RESUMO
Exosomes are participated in the pathogenesis of cardiovascular diseases and can be secreted by mesenchymal stem cells (MSCs). However, the effects of circRNA, delivered by exosomes derived from MSCs, on myocardial injury remain unclear. Hence, this study aims to explore the therapeutic potential of exosomes derived from circRNA_0002113 lacking MSCs in the treatment of myocardial injury in vitro and in vivo. Our results reveal that exosomes derived from circRNA_0002113 lacking MSCs decreased cell apoptosis in anoxia-reoxygenation (A/R) model cells, and reduced myocardial injury by inhibiting nuclear translocation of RUNX1 in vitro and in vivo. Moreover, miR-188-3p, which targets RUNX1 in cardiomyocytes was also found to interact with circRNA_0002113. In conclusion, exosomes derived from circRNA_0002113 lacking MSCs could suppress myocardial infarction by sponging miR-188-3p to regulate RUNX1 nuclear translocation. The circRNA_0002113/miR-188-3p/RUNX1 axis mediated alleviation of apoptosis serves as a novel strategy to treat myocardial I/R injury.
RESUMO
Surface-enhanced Raman scattering (SERS) tags draw much attention due to the ultrasensitivity and multiplex labeling capability. Recently, a new kind of SERS tags was rationally designed by encapsulating metal nanoparticles with phospholipid bilayers, showing great potential in theranostics. The lipid bilayer coating confers biocompatibility and versatility to changing surface chemistry of the tag; however, its "soft" feature may influence SERS signal stability, which is rarely investigated. Herein, we prepared phospholipid-coated AuNR@Ag/Au nanosphere SERS tags by using three different kinds of Raman reporters, i.e., thio-containing 4-nitrothiophenol (NT), nitrogen-containing hydrophobic chromophore cyanine 7 monoacid (Cy7), and alkyl chain-chromophore conjugate 1,1'-dioctadecyl-3,3,3',3'-tetramethylindodicarbocyanine (DiD). It was found that signal responses were different upon additional stimulation which the tags may encounter in theranostic applications including the presence of detergent Triton X-100, lipid membrane, and photothermal treatment. Living-cell imaging also showed signal changing distinction. The different SERS signal performances were attributed to the different Raman reporter releasing behaviors from the tags. This work revealed that Raman reporter structure determined signal stability of lipid-coated SERS tags, providing guidance for the design of stimulus responsive tags. Moreover, it also implied the potential of SERS technique for real time drug release study of lipid based nanomedicine.