Target-Specific Gene Silencing of Layer-by-Layer Assembled Gold–Cysteamine/siRNA/PEI/HA Nanocomplex

Target-specific intracellular delivery of small interfering RNA (siRNA) is regarded as one of the most important technologies for the development of siRNA therapeutics. In this work, a cysteamine modified gold nanoparticles (AuCM)/siRNA/polyethyleneimine (PEI)/hyaluronic acid (HA) complex was successfully developed using a layer-by-layer method for target-specific intracellular delivery of siRNA by HA receptor mediated endocytosis. Atomic force microscopic and zeta potential analyses confirmed the formation of a AuCM/siRNA/PEI/HA complex having a particle size of ca. 37.3 nm and a negative surface charge of ca. −12 mV. With a negligible cytotoxicity, AuCM/siRNA/PEI/HA complex showed an excellent target-specific gene silencing efficiency of ca. 70% in the presence of 50 vol % serum, which was statistically much higher than that of siRNA/Lipofectamine 2000 complex. In the competitive binding tests with free HA, dark-field bioimaging and inductively coupled plasma–atomic emission spectroscopy confirmed the target-specific intracellular delivery of AuCM/siRNA/PEI/HA complex to B16F1 cells with HA receptors. Moreover, the systemic delivery of AuCM/siRNA/PEI/HA complex using apolipoprotein B (ApoB) siRNA as a model drug resulted in a significantly reduced ApoB mRNA level in the liver tissue. Taken together, AuCM/siRNA/PEI/HA complex was thought to be developed as target-specific siRNA therapeutics for the systemic treatment of various liver diseases

¹⁹F Magnetic Resonance Imaging Signals from Peptide Amphiphile Nanostructures Are Strongly Affected by Their Shape

Magnetic resonance imaging (MRI) is a noninvasive imaging modality that provides excellent spatial and temporal resolution. The most commonly used MR probes face significant challenges originating from the endogenous ¹H background signal of water. In contrast, fluorine MRI (¹⁹F MRI) allows quantitative probe imaging with zero background signal. Probes with high fluorine content are required for high sensitivity, suggesting nanoscale supramolecular assemblies containing ¹⁹F probes offer a potentially useful strategy for optimum imaging as a result of improved payload. We report here on supramolecular nanostructures formed by fluorinated peptide amphiphiles containing either glutamic acid or lysine residues in their sequence. We identified molecules that form aggregates in water which transition from cylindrical to ribbon-like shape as pH increased from 4.5 to 8.0. Interestingly, we found that ribbon-like nanostructures had reduced magnetic resonance signal, whereas their cylindrical counterparts exhibited strong signals. We attribute this drastic difference to the greater mobility of fluorinated tails in the hydrophobic compartment of cylindrical nanostructures compared to lower mobility in ribbon-like assemblies. This discovery identifies a strategy to design supramolecular, self-assembling contrast agents for ¹⁹F MRI that can spatially map physiologically relevant changes in pH using changes in morphology

Spectrally Stable Deep-Blue Light-Emitting Diodes Based on Layer-Transferred Single-Crystalline Ruddlesden–Popper Halide Perovskites

A novel approach to producing high-color-purity blue-light-emitting diodes based on single-crystalline Ruddlesden–Popper perovskites (RPPs) is reported. The utilization of a pure bromide composition eliminates any possibility of halide segregation, which can otherwise lead to undesired shifts in the emission wavelength or irreversible degradation of the spectral line width. Phase-pure PEA2MAPb2Br7 single crystals with a lateral size exceeding 1 cm2 can be synthesized using the inverse temperature crystallization method. To prepare RPP layers with a thickness of less than 50 nm, we employ a thinning process of the initially thick bulk crystals, followed by a dry-transfer process to place them onto a hole transport layer and an indium-tin-oxide-coated glass substrate. By utilizing polydimethylsiloxane as a handling layer, deformations of the bulk RPP crystal and exfoliated RPP layer, as well as the formation of defects such as pinholes, can be effectively suppressed. Subsequent depositions of an electron transport layer and a metal contact complete the fabrication of electroluminescence (EL) devices. The EL devices utilizing the single-crystalline RPP demonstrate excellent spectral stability across a broad range of the applied bias voltage spanning from 4.5 to 10 V, exhibiting a significantly narrow line width of 14 nm at an emission wavelength of 440 nm that can potentially cover 99.3% of the Rec. 2020 color gamut. The sharp EL emission spectrum can be effectively preserved, avoiding any broadening of the line width, by suppressing Joule heating throughout the device operation, in addition to the intrinsic stability of single-crystalline RPPs