Aggregation-induced emission (AIE)-active luminogens (AIEgens) have demonstrated exciting potential for the application in cancer phototheranostics. However, simultaneously achieving tumor-activated bright emission, enhanced reactive oxygen species (ROS) generation, high tumor accumulation, and minimized ROS depletion remains challenging. Here, a metal−organic framework (MOF) hybrid AIEgen theranostic platform is designed, termed A-NUiO@DCDA@ZIF-Cu, composed of an AIEgen-loaded hydrophobic UiO-66 (A-NUiO@DCDA) core and a Cu-doped hydrophilic ZIF-8 (ZIF-Cu) shell. The fluorescence emission and therapeutic ROS activity of AIEgens are restrained during delivery. After uptake by tumor tissues, ZIF-Cu decomposition occurs in response to an acidic tumor microenvironment (TME), and the hydrophobic A-NUiO@ DCDA cores self-assemble into large particles, extremely increasing the tumor accumulation of AIEgens. This results in enhanced fluorescence imaging (FLI) and highly improved 1 O 2 generation ability during photodynamic therapy (PDT). Meanwhile, the released Cu 2+ reacts to glutathione (GSH) to generate Cu + , which provides an extra chemodynamic therapy (CDT) function through Fenton-like reactions with overexpressed H 2 O 2 , resulting in the GSH depletion-enhanced ROS therapy. As a result of these characteristics, the MOF hybrid AIEgens can selectively kill tumors with excellent efficacy.
In this work, two series of chemically reactive polymers, silane coupling agents (SCAs) and water-soluble polymers, were specifically designed as an additive to improve the ductility of slag geopolymer paste by vibration pressure technique. The influences of organic polymers on the fluidity, rheological behavior, mechanical property, porosity, and toughening mechanism of slag geopolymer were investigated. The polycondensation and bonding characteristics of organic–inorganic products were calculated by 1H liquid nuclear magnetic resonance (NMR) technology and Fourier transform infrared (FT-IR). The polymerization degree of composite geopolymer was evaluated by 29Si NMR and X-ray photoelectron spectroscopy (XPS). The microscopic morphology of the geopolymer matrix was analyzed using scanning electron microscopy (SEM). The results showed that the dosage of the KH570 and PAA-Na with 5 wt% behaved best in improving the flexural strength and the compressive strength of geopolymer in their corresponding organic series, respectively. The addition of polymers decreased the fluidity and the fluidity loss ratio of geopolymer slurry but reduced the harmful pores of hardened geopolymer. The organic polymers acting as bridge-fixed water molecules weakened the repulsion force, and formed a three-dimensional network through molecular interweaving in a geopolymer matrix. Methacryloxy in silane coupling agents and carboxyl group in water-soluble polymers may contribute to the improvement of hydration product structure through strong bonding with C-A-S-H. Microscopic measurements indicated that the addition of KH570 and PAA-Na in geopolymer could form 73.55% and 72.48% Si-O-Si with C-A-S-H gel, higher than the reference, and increase the polycondensation degree of C-A-S-H phase, reflected by the increased generation of Q2 and Q2(1Al) and the longer chain length, leading to a higher densified geopolymer matrix with high ductility.
Controllable self-assembly of the DNA-linked gold nanoparticle (AuNP) architecture for in vivo biomedical applications remains a key challenge. Here, we describe the use of the programmed DNA tetrahedral structure to control the assembly of three different types of AuNPs (∼20, 10, and 5 nm) by organizing them into defined positioning and arrangement. A DNA-assembled “core–satellite” architecture is built by DNA sequencing where satellite AuNPs (10 and 5 nm) surround a central core AuNP (20 nm). The density and arrangement of the AuNP satellites around the core AuNP were controlled by tuning the size and amount of the DNA tetrahedron functionalized on the core AuNPs, resulting in strong electromagnetic field enhancement derived from hybridized plasmonic coupling effects. By conjugating with the Raman molecule, strong surface-enhanced Raman scattering photoacoustic imaging signals could be generated, which were able to image microRNA-21 and tumor tissues in vivo. These results provided an efficient strategy to build precision plasmonic superstructures in plasmonic-based bioanalysis and imaging.
Continuous-time dynamic models are often required for controller design, process monitoring, and operation optimization. This paper proposes an approach to estimate unknown parameters of multiple first-order continuous-time dynamic models from special segments in historical data. The approach is composed by two main steps. First, special segments are defined as the ones with two ends in steady states and the middle part having significant amplitude variations in transient states; the special segments are found automatically by exploiting a piece-wise linear representation technique from a large amount of historical data samples. Second, static gains are estimated by solving a set of linear equations based on steady-state values of inputs and outputs; sums of time constants and delays are obtained by solving another set of linear equations based on integrals of model output errors from data samples in transient states; the sums are used as an optimization constraint for maximizing the fitness value between measured and simulated outputs, from which separated estimates of time constants and delays are yielded. Numerical examples are provided to illustrate the proposed approach and compare with existing ones.INDEX TERMS Continuous-time model identification, steady states, transient states, model validation.
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