2D Hierarchical Microbarcodes with Expanded Storage Capacity for Optical Multiplex and Information Encryption

The design of nanosegregated fluorescent tags/barcodes by geometrical patterning with precise dimensions and hierarchies could integrate multilevel optical information within one carrier and enhance microsized barcoding techniques for ultrahigh-density optical data storage and encryption. However, precise control of the spatial distribution in micro/nanosized matrices intrinsically limits the accessible barcoding applications in terms of material design and construction. Here, crystallization forces are leveraged to enable a rapid, programmable molecular packing and rapid epitaxial growth of fluorescent units in 2D via crystallization-driven self-assembly. The fluorescence encoding density, scalability, information storage capacity, and decoding techniques of the robust 2D polymeric barcoding platform are explored systematically. These results provide both a theoretical and an experimental foundation for expanding the fluorescence storage capacity, which is a longstanding challenge in state-of-the-art microbarcoding techniques and establish a generalized and adaptable coding platform for high-throughput analysis and optical multiplexing

Regulation of Two-Dimensional Platelet Micelles with Tunable Core Composition Distribution via Coassembly Seeded Growth Approach

Seeded growth termed “living” crystallization-driven self-assembly (CDSA) has been identified as a powerful method to create one- or two-dimensional nanoparticles. Epitaxial crystallization is usually regarded as the growth mechanism for the formation of uniform micelles. From this perspective, the unimer depositing rate is largely related to the crystallization temperature, which is a key factor to determine the crystallization rate and regulate the core composition distribution among nanoparticles. In the present work, the coassembly of two distinct crystallizable polymers is explored in detail in a one-pot seeded growth protocol. Results have shown that polylactone containing a larger number of methylene groups (−CH2−) in their repeating units such as poly(η-octalactone) (POL) has a faster crystallization rate compared to poly(ε-caprolactone) (PCL) with a smaller number of −CH2– at ambient temperature (25 °C), thus a block or blocky platelet structure with heterogeneous composition distribution is formed. In contrast, when the crystallization temperature decreases to 4 °C, the difference of crystallization rate between both cores become negligible. Consequently, a completely random component distribution within 2D platelets is observed. Moreover, we also reveal that the core component of seed micelles is also paramount for the coassembly seeded growth, and a unique structure of flower-like platelet micelle is created from the coassembly of PCL/POL using POL core-forming seeds. This study on the formation of platelet micelles by one-pot seeded growth using two crystallizable components offers a considerable scope for the design of 2D polymer nanomaterials with a controlled core component distribution

Synthesis of hollow platelet polymer particles by spontaneous precision fragmentation

The creation of anisotropic core–shell nanoparticles using the living crystallization-driven self-assembly method results in colloidally stable solid particles. The fragmentation or degradation of crystallization-driven self-assembly nanomaterials is currently accessible only when intensive external stimuli are exerted. Controlling the stability of the crystalized core material may also allow structural evolution and fragmentation to be achieved. Here we report that two-dimensional (2D) platelets containing less stable domains specifically fragment upon ageing, providing a simple method to create hollow platelet polymer particles in one step. Mechanistic studies reveal that a high concentration of low-molecular-weight homopolymer in 2D platelet that crystallizes at low temperatures results in less stable domains, which fragment upon ageing. To illustrate the utility of spontaneous fragmentation, spatially selective fragmentation of 2D segmented platelets is used to prepare 2D hollow platelets that are usually inaccessible from a thermodynamic process

Synthesis of hollow platelet polymer particles by spontaneous precision fragmentation

The creation of anisotropic core–shell nanoparticles using the living crystallization-driven self-assembly method results in colloidally stable solid particles. The fragmentation or degradation of crystallization-driven self-assembly nanomaterials is currently accessible only when intensive external stimuli are exerted. Controlling the stability of the crystalized core material may also allow structural evolution and fragmentation to be achieved. Here we report that two-dimensional (2D) platelets containing less stable domains specifically fragment upon ageing, providing a simple method to create hollow platelet polymer particles in one step. Mechanistic studies reveal that a high concentration of low-molecular-weight homopolymer in 2D platelet that crystallizes at low temperatures results in less stable domains, which fragment upon ageing. To illustrate the utility of spontaneous fragmentation, spatially selective fragmentation of 2D segmented platelets is used to prepare 2D hollow platelets that are usually inaccessible from a thermodynamic process

Biodegradable Lipid-Modified Poly(Guanidine Thioctic Acid)s: A Fortifier of Lipid Nanoparticles to Promote the Efficacy and Safety of mRNA Cancer Vaccines

Lipid nanoparticles (LNPs)-based messenger RNA (mRNA) therapeutics have emerged with promising potentials in the fields of infectious diseases, cancer vaccines, and protein replacement therapies; however, their therapeutic efficacy and safety can still be promoted by the optimization of LNPs formulations. Unfortunately, current LNPs suffer from increased production of reactive oxygen species during translation, which leads to a decreased translation efficiency and the onset of inflammation and other side effects. Herein, we synthesize a lipid-modified poly(guanidine thioctic acid) polymer to fabricate novel LNPs for mRNA vaccines. The acquired G-LNPs significantly promote the translation efficiency of loaded mRNA and attenuate inflammation after vaccination through the elimination of reactive oxygen species that are responsible for translational inhibition and inflammatory responses. In vivo studies demonstrate the excellent antitumor efficacy of the G-LNPs@mRNA vaccine, and two-dose vaccination dramatically increases the population and infiltration of cytotoxic T cells due to the intense antitumor immune responses, thus generating superior antitumor outcomes compared with the mRNA vaccine prepared from traditional LNPs. By synergy with immune checkpoint blockade, the tumor inhibition of G-LNPs@mRNA is further boosted, indicating that G-LNPs-based mRNA vaccines will be powerful and versatile platforms to combat cancer