ACS Nanoscience Au最新文献

RNA-based agents (siRNA, miRNA, and mRNA) can selectively manipulate gene expression/proteins and are set to revolutionize a variety of disease treatments. Nanoparticle (NP) platforms have been developed to deliver functional mRNA or siRNA inside cells to overcome their inherent limitations. Recent studies have focused on siRNA to knock down proteins causing drug resistance or mRNA technology to introduce tumor suppressors. However, cancer needs multitargeted approaches to selectively manipulate multiple gene expressions/proteins. In this proof-of-concept study, we developed NPs containing Luc-mRNA and siRNA-GFP as model agents ((M+S)-NPs) and showed that NPs can simultaneously deliver functional mRNA and siRNA and impact the expression of two genes/proteins in vitro. Additionally, after in vivo administration, (M+S)-NPs successfully knocked down GFP while introducing luciferase into a TNBC mouse model, indicating that our NPs have the potential to develop RNA-based anticancer therapeutics. These studies pave the way to develop RNA-based, multitargeted approaches for complex diseases like cancer.

RNA-based agents (siRNA, miRNA, and mRNA) can selectively manipulate gene expression/proteins and are set to revolutionize a variety of disease treatments. Nanoparticle (NP) platforms have been developed to deliver functional mRNA or siRNA inside cells to overcome their inherent limitations. Recent studies have focused on siRNA to knock down proteins causing drug resistance or mRNA technology to introduce tumor suppressors. However, cancer needs multitargeted approaches to selectively manipulate multiple gene expressions/proteins. In this proof-of-concept study, we developed NPs containing Luc-mRNA and siRNA-GFP as model agents ((M+S)-NPs) and showed that NPs can simultaneously deliver functional mRNA and siRNA and impact the expression of two genes/proteins in vitro. Additionally, after in vivo administration, (M+S)-NPs successfully knocked down GFP while introducing luciferase into a TNBC mouse model, indicating that our NPs have the potential to develop RNA-based anticancer therapeutics. These studies pave the way to develop RNA-based, multitargeted approaches for complex diseases like cancer.

Colloidal nanoparticle assembly methods can produce intricate superlattice structures and often use knowledge of atomic crystallization behaviors to guide their design. While this analogy has enabled multiple routes to programming colloidal crystallization thermodynamics, fewer tools or strategies exist to manipulate nanoparticle superlattice growth kinetics in a controlled manner. Here we investigate how small-molecule additives can be used to modulate the thermodynamics and kinetics of supramolecular-chemistry-driven nanoparticle assembly. Specifically, we introduce monovalent binding agents into the superlattice growth solution that compete with the multivalent interparticle bonding interactions driving particle assembly, thereby altering interparticle bond strength by reducing the number of bridging complexes formed between particles. In this manner, the assemblies can be steered to avoid kinetic traps and crystallize into faceted single crystals under isothermal conditions, alleviating the need for precise thermal control that has conventionally been required to produce large, faceted crystals in prior assembly methods.

Colloidal nanoparticle assembly methods can produce intricate superlattice structures and often use knowledge of atomic crystallization behaviors to guide their design. While this analogy has enabled multiple routes to programming colloidal crystallization thermodynamics, fewer tools or strategies exist to manipulate nanoparticle superlattice growth kinetics in a controlled manner. Here we investigate how small-molecule additives can be used to modulate the thermodynamics and kinetics of supramolecular-chemistry-driven nanoparticle assembly. Specifically, we introduce monovalent binding agents into the superlattice growth solution that compete with the multivalent interparticle bonding interactions driving particle assembly, thereby altering interparticle bond strength by reducing the number of bridging complexes formed between particles. In this manner, the assemblies can be steered to avoid kinetic traps and crystallize into faceted single crystals under isothermal conditions, alleviating the need for precise thermal control that has conventionally been required to produce large, faceted crystals in prior assembly methods.

The dynamic control of chiral (enantiomeric) responses in chiral host-guest complexes through external stimuli is a significant challenge in modern chemistry for developing smart stimuli-responsive materials. Herein, we report the (chir)optical properties and chiral recognition behavior of water-soluble chiral naphthotubes (1) under the influence of hydrostatic pressure as an external stimulus. The hydrostatic pressure spectral profiles compared to those obtained at normal pressure revealed the dynamic behavior of 1 under hydrostatic pressure, owing to the flexible linker. In chiral recognition experiments, hydrophilic amino acids such as phenylalanine (Phe) and tryptophan (Trp) exhibited reaction volume changes (ΔV°) of -0.9 cm³ mol^-1 for d-Phe, -1.2 cm³ mol^-1 for l-Phe, -5.6 cm³ mol^-1 for d-Trp, and -7.0 cm³ mol^-1 for l-Trp, with enantioselectivity ranging from 1.2 to 1.6. In contrast, hydrophobic chiral styrene oxide (2) showed ΔV° values of 1.5 cm³ mol^-1 for R-2 and 3.5 cm³ mol^-1 for S- 2, with a relatively higher enantioselectivity of up to 7.6. These contrasting effects of hydrostatic pressure primarily originate from the dynamics of chiral naphthotubes.

The dynamic control of chiral (enantiomeric) responses in chiral host–guest complexes through external stimuli is a significant challenge in modern chemistry for developing smart stimuli-responsive materials. Herein, we report the (chir)optical properties and chiral recognition behavior of water-soluble chiral naphthotubes (1) under the influence of hydrostatic pressure as an external stimulus. The hydrostatic pressure spectral profiles compared to those obtained at normal pressure revealed the dynamic behavior of 1 under hydrostatic pressure, owing to the flexible linker. In chiral recognition experiments, hydrophilic amino acids such as phenylalanine (Phe) and tryptophan (Trp) exhibited reaction volume changes (ΔV°) of −0.9 cm³ mol^–1 for d-Phe, −1.2 cm³ mol^–1 for l-Phe, −5.6 cm³ mol^–1 for d-Trp, and −7.0 cm³ mol^–1 for l-Trp, with enantioselectivity ranging from 1.2 to 1.6. In contrast, hydrophobic chiral styrene oxide (2) showed ΔV° values of 1.5 cm³ mol^–1 for R-2 and 3.5 cm³ mol^–1 for S-2, with a relatively higher enantioselectivity of up to 7.6. These contrasting effects of hydrostatic pressure primarily originate from the dynamics of chiral naphthotubes.

Wide band gap AInSe₂ (A = K, Rb, Cs) is an important interlayer material for improving the efficiency of Cu(In,Ga)(S,Se)₂ (CIGS) solar cells. Compared to high-vacuum deposition and solid-state synthesis, a less energy-intensive method is of interest for its fabrication. Herein, we present the rapid, low-temperature colloidal synthesis of AInSe₂ nanocrystals that opens a pathway for convenient solution processing. The crystal structures and electronic band structures of the nanocrystals were studied, and their particle morphology was found to be dependent on the choice of alkali metal and selenium precursors. Homogeneous solid solution (K,Rb,Cs)InSe₂ nanocrystals were synthesized using a mixture of alkali metal precursors. Their compositions, lattice parameters, and band gaps were easily tuned based on the K:Rb:Cs precursor ratio, providing potential for interface engineering of CIGS nanocrystal-based solar cells.

Wide band gap AInSe₂ (A = K, Rb, Cs) is an important interlayer material for improving the efficiency of Cu(In,Ga)(S,Se)₂ (CIGS) solar cells. Compared to high-vacuum deposition and solid-state synthesis, a less energy-intensive method is of interest for its fabrication. Herein, we present the rapid, low-temperature colloidal synthesis of AInSe₂ nanocrystals that opens a pathway for convenient solution processing. The crystal structures and electronic band structures of the nanocrystals were studied, and their particle morphology was found to be dependent on the choice of alkali metal and selenium precursors. Homogeneous solid solution (K,Rb,Cs)InSe₂ nanocrystals were synthesized using a mixture of alkali metal precursors. Their compositions, lattice parameters, and band gaps were easily tuned based on the K:Rb:Cs precursor ratio, providing potential for interface engineering of CIGS nanocrystal-based solar cells.

Destructive quantum interference (DQI) leads to a decrease in the conductance of certain well-documented molecules. Experimental observations have revealed both direct and indirect manifestations of DQI, although a comprehensive understanding of the underlying causes of these distinct outcomes remains elusive. In both cases, DQI lowers the conductance, but only the direct case exhibits a characteristic V-shaped dip in differential conductance. Currently, the direct signature has exclusively been observed in monolayers and gated single-molecule systems. In this study, we employ density functional theory to elucidate a plausible explanation for the absence of a direct DQI signature in single molecules. Specifically, we attribute the direct DQI signature to a resonance shift induced by intermolecular interactions, which are absent in the individual molecules. By illustrating the impact of these intermolecular interactions, we emphasize the need for explicit treatment of intermolecular interactions when simulating monolayers.

Destructive quantum interference (DQI) leads to a decrease in the conductance of certain well-documented molecules. Experimental observations have revealed both direct and indirect manifestations of DQI, although a comprehensive understanding of the underlying causes of these distinct outcomes remains elusive. In both cases, DQI lowers the conductance, but only the direct case exhibits a characteristic V-shaped dip in differential conductance. Currently, the direct signature has exclusively been observed in monolayers and gated single-molecule systems. In this study, we employ density functional theory to elucidate a plausible explanation for the absence of a direct DQI signature in single molecules. Specifically, we attribute the direct DQI signature to a resonance shift induced by intermolecular interactions, which are absent in the individual molecules. By illustrating the impact of these intermolecular interactions, we emphasize the need for explicit treatment of intermolecular interactions when simulating monolayers.