Rod-like gold nanoparticles are directly embedded in a 1D-polymeric spin crossover (SCO) material leading to singular Au@SCO nanohybrid architectures. The resulting architectures are designed to promote a synergetic effect between ultrafast spin-state photoswitching and photothermal properties of plasmonic nanoparticles. This synergy is evidenced by the strong modulation of the surface plasmon resonance of the gold nanorods through the spin-state switching of the SCO component and also the strong enhancement of the photoswitching efficiency compared to pure SCO particles. This remarkable synergy results from the large modulation of the dielectric properties of the SCO polymer upon its thermal switching and the enhancement of the heating of these hybrid nanostructures upon excitation of the surface plasmon resonance of the gold nanorods.
The catalytic performance and therapeutic effect of nanoparticles varies with shape. Here, we investigated and compared the therapeutic outcomes of ceria nanospheres (Ceria NSs) and ceria nanorods (Ceria NRs) in an in vivo study of mild traumatic brain injury (mTBI). In vivo TBI was induced in a mouse model of open head injury using a stereotaxic impactor. Outcomes including cytoprotective effects, cognitive function, and cerebral edema were investigated after retro-orbital injection of 11.6 mM of ceria nanoparticles. Ceria nanoparticles significantly reduced fluoro-jade B (FJB)-positive cells and terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL)-positive cells, and restored mRNA levels of superoxide dismutase 1 (SOD1) and SOD2. They also decreased the cyclooxygenase-2 (COX-2) expression compared with the untreated control group. Comparing the two nanomaterials, Ceria NRs showed less stable and high-energy (100) and (110) planes, which increased the number of active sites. The Ce3+/Ce4+ molar ratio of Ceria NRs (0.40) was greater than that of Ceria NSs (0.27). Ceria NRs (0.059 ± 0.021) appeared to exhibit better anti-inflammatory effect than Ceria NSs (0.133 ± 0.024), but the effect was statistically insignificant (p = 0.190). Ceria nanoparticles also improved cognitive impairment following mTBI compared with the control group, but the effect did not differ significantly according to the nanoshape. However, Ceria NRs (70.1 ± 0.5%) significantly decreased brain water content compared with Ceria NSs (73.7 ± 0.4%; p = 0.0015), indicating a more effective reduction in brain edema (p = 0.0015). Compared with Ceria NSs, the Ceria NRs are more effective in alleviating cerebral edema following in vivo mTBI.
Spin Crossover (SCO) is a promising switching phenomenon when implemented in electronic devices as molecules, thin films or nanoparticles. Among the properties modulated along this phenomenon, optically induced mechanical changes are of tremendous importance as they can work as fast light-induced mechanical switches or allow to investigate and control microstructural strains and fatigability. The development of characterization techniques probing nanoscopic behaviour with high spatio-temporal resolution allows to trigger and visualize such mechanical changes of individual nanoscopic objects. Here we use Ultrafast Transmission Electron Microscopy (UTEM) to precisely probe the length changes of individual switchable nanoparticles induced thermally by nanosecond laser pulses. This allows us to reveal the mechanisms of spin switching, leading to the macroscopic expansion of SCO materials. This study was conducted on individual pure SCO nanoparticles and SCO nanoparticles encapsulating gold nanorods that serve for plasmonic heating under laser pulses. Length changes are compared with time-resolved optical measurements performed on an assembly of these particles.
Crystalline metal–organic frameworks (MOFs) are extensively used in areas such as gas storage and small-molecule drug delivery. Although Cu-BTC (1, MOF-199, BTC: benzene-1,3,5-tricarboxylate) has versatile applications, its NO storage and release characteristics are not amenable to therapeutic usage. In this work, micro-sized Cu-BTC was prepared solvothermally and then processed by ball-milling to prepare nano-sized Cu-BTC (2). The NO storage and release properties of the micro- and nano-sized Cu-BTC MOFs were morphology dependent. Control of the hydration degree and morphology of the NO delivery vehicle improved the NO release characteristics significantly. In particular, the nano-sized NO-loaded Cu-BTC (NO⊂nano-Cu-BTC, 4) released NO at 1.81 µmol·mg−1 in 1.2 h in PBS, which meets the requirements for clinical usage. The solid-state structural formula of NO⊂Cu-BTC was successfully determined to be [CuC6H2O5]·(NO)0.167 through single-crystal X-ray diffraction, suggesting no structural changes in Cu-BTC upon the intercalation of 0.167 equivalents of NO within the pores of Cu-BTC after NO loading. The structure of Cu-BTC was also stably maintained after NO release. NO⊂Cu-BTC exhibited significant antibacterial activity against six bacterial strains, including Gram-negative and positive bacteria. NO⊂Cu-BTC could be utilized as a hybrid NO donor to explore the synergistic effects of the known antibacterial properties of Cu-BTC.
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