Multifunctional composite materials are currently highly desired for sustainable energy applications. A general strategy to integrate atomically precise Au (SG) with ZIF-8 (Zn(MeIm) , MeIm = 2-methylimidazole), is developed via the typical Zn-carboxylate type of linkage. Au (SG) are uniformly encapsulated into a ZIF-8 framework (Au (SG) @ZIF-8) by coordination-assisted self-assembly. In contrast, Au (SG) integrated by simple impregnation is oriented along the outer surface of ZIF-8 (Au (SG) /ZIF-8). The porous structure and thermal stability of these nanocomposites are characterized by N adsorption-desorption isothermal analysis and thermal gravimetric analysis. The distribution of Au (SG) in the two nanocomposites is confirmed by electron microscopy, and the accessibility of Au (SG) is evaluated by the 4-nitrophenol reduction reaction. The as-prepared nanocomposites retain the high porosity and thermal stability of the ZIF-8 matrix, while also exhibiting the desired catalytic and optical properties derived from the integrated Au (SG) nanoclusters (NCs). Au (SG) @ZIF-8 with isolated Au sites is a promising heterogenous catalyst with size selectivity imparted by the ZIF-8 matrix. The structural distinction between Au (SG) @ZIF-8 and Au (SG) /ZIF-8 determines their different emission features, and provides a new strategy to adjust the optical behavior of Au (SG) for applications in bioimaging and biotherapy.
Catalytic deoxyribozyme has great potential for gene regulation, but the poor efficiency of the cleavage of mRNA and the lack of versatile DNAzyme vehicles remain big challenges for potent gene therapy. By the rational designing of a diverse vehicle of polydopamine-Mn 2+ nanoparticles (MnPDA), we demonstrate that MnPDA has integrated functions as an effective DNAzyme delivery vector, a self-generation source of DNAzyme cofactor for catalytic mRNA cleavage, and an inherent therapeutic photothermal agent as well as contrast agent for photoacoustic and magnetic resonance imaging. Specifically, the DNAzyme-MnPDA nanosystem protects catalytic deoxyribozyme from degradation and enhances cellular uptake efficiency. In the presence of intracellular glutathione, the nanoparticles are able to in situ generate free Mn 2+ as a cofactor of DNAzyme to effectively trigger the catalytic cleavage of mRNA for gene silencing. In addition, the nanosystem shows high photothermal conversion efficiency and excellent stability against photothermal processing and degradation in complex environments. Unlike previous DNAzyme delivery vehicles, this vehicle exhibits diverse functionalities for potent gene regulation, allowing multimodal imaging-guided synergetic gene regulation and photothermal therapy both in vitro and in vivo.
The extreme complexity and heterogeneity of fatal tumors requires the development of combination phototherapy considering the limited therapeutic efficiency of conventional monomodal photodynamic therapy (PDT) or photothermal therapy (PTT).
Laser-ablated group 2 metal atoms exhibit different reactivities with (CN) 2 in excess argon and neon during condensation at 4 K. UV irradiation (220−290 nm) is required to activate Be to produce the linear CNBeNC di-isocyanide molecule with a strong antisymmetric C−N stretching band at 2104.3 cm −1 and a C-N-Be-N-C stretching mode at 1265.7 cm −1 . The di-isocyanide appears at lower frequency and exhibits more nitrogen and less carbon isotopic shift than the cyanide counterpart, which is confirmed by B3LYP isotopic frequency calculations. Two weak bands were observed for the cyanide NCBeCN, and three absorptions were found for the mixed ligand CNBeCN molecule, which would be difficult to synthesize and put into a bottle. Mg reacts with (CN) 2 to form the CNMgNC counterpart at 2085.8 cm −1 on annealing to 25 K. Absorptions for the Ca(NC) 2 , Sr(NC) 2 , and Ba(NC) 2 molecules at 2060.8, 2048.1, and 2045.9 cm −1 increase on sample annealing with these more reactive heavier alkaline earth metal atoms, which have calculated twisted bowtie side-bound (CN) structures of C 2 symmetry with shorter computed M−N than M−C distances. NBO calculations for the latter molecules reveal natural charges of +1.54, 1.64, 1.71 e on the metal centers and − 0.77, 0.82, and 0.855 e on the corresponding CN subunits, with a doubly occupied sp−sp σ and two p−p π bonds on each (CN), which supports an ionic model for bonding in these molecules. A weaker band at 2056.6 cm −1 behaves nearly the same as the Ca bowtie band in the spectrum on 25 K annealing and photolysis, and it is assigned to the 6 kJ/mol higher-energy linear CNCaNC isomer. Additional similar sharp absorptions for a new Ca, Sr, and Ba reaction product at 2036.3, 2040.6, and 2036.0 cm −1 increase on annealing at the expense of adjacent broader bands: B3LYP and NBO calculations validate their assignment to ionic hexagonal C 2h (MNC) 2 rings from the reaction of two M atoms with (CN) 2 .
Programmable metal–organic frameworks were prepared as efficient delivery vehicles for targeted and stimuli-responsive release of multi-therapeutics with excellent antitumor activity.
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