Encounter between Gyroid and Lamellae in Janus Colloidal Particles Self-Assembled by a Rod-Coil Block Copolymer.

Controlling the internal structure of block copolymer (BCP) particles has a significant influence on its functionalities. Here, a structure-controlling method is proposed to regulate the internal structure of BCP Janus colloidal particles using different surfactants. Different microphase separation processes take place in two connected halves of the Janus particles. An order-order transition between gyroid and lamellar phases is observed in polymeric colloids. The epitaxial growth during the structural transformation from gyroid to lamellar phase undergoes a two-layered rearrangement to accommodate the interdomain spacing mismatch between these two phases. This self-assembly behavior can be ascribed to the preferential wetting of BCP chains at the interface, which can change the chain conformation of different blocks. The Janus colloidal particles can further experience a reversible phase transition by restructuring the polymer particles under solvent vapor. It is anticipated that the new phase behavior found in Janus particles can not only enrich the self-assembly study of BCPs but also provide opportunities for various applications based on Janus particles with ordered structures.

Osteopontin interacts with dendritic cells and macrophages in pulp inflammation: Comprehensive transcriptomic analysis and laboratory investigations.

AIM: To investigate novel diagnostic markers for pulpitis and validate by clinical samples from normal and inflamed pulp. To explore the relationship between diagnostic markers and immune cells or their phenotypes during pulp inflammation. METHODOLOGY: Two microarray datasets, GSE77459 and GSE92681, and identified differential expression genes were integrated. To understand immune features, gene functions, Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), Disease Ontology (DO) and ImmuneSigDB Gene Set Enrichment Analysis (GSEA) were analysed. For predictive purposes, machine learning techniques were applied to detect diagnostic markers. Immune infiltration in inflamed pulp was studied using CIBERSORT. The relationship between diagnostic markers and immune cells was investigated and validated their gene expression in clinical samples from the normal or inflamed pulp by qRT-PCR. Finally, the correlation between one marker, secreted phosphoprotein 1 (SPP1), encoding osteopontin (OPN), and dendritic cells (DCs)/macrophages was identified via HE staining and multiplex immunohistochemistry. An in vitro inflammatory dental pulp microenvironment model of THP-1 macrophages cocultured with dental pulp cells derived conditioned media (DPCs-CM) to investigate OPN production and macrophage phenotypes was established. RESULTS: Analysis revealed unique immunologic features in inflamed pulp. Three diagnostic markers for pulpitis: endothelin-1 (EDN1), SPP1, and purine nucleoside phosphorylase (PNP), and validated them using qRT-PCR were predicted. Multiplex immunohistochemistry demonstrated OPN co-localized with activated DCs and M2 macrophages during pulp inflammation. In vitro experiments showed that THP-1 macrophages produced the highest levels of OPN when stimulated with DPCs-CM derived from the 20 µg/mL LPS pre-conditioned group, suggesting an M2b-like phenotype by increasing surface marker CD86 and expression of IL6, TNFα, IL10, and CCL1 but not CCL17 and MerTK. Levels of CCL1 and IL10 elevated significantly in the macrophages' supernatant from the 20 µg/mL LPS pre-conditioned CM group. OPN was proven co-localizing with CD86 in the inflamed pulp by immunofluorescence. CONCLUSIONS: The current findings suggest that OPN can serve as a promising biomarker for pulpitis, correlated with DCs and macrophages. OPN+ macrophages in the inflamed pulp are associated with M2b-like phenotypes. These insights offer the potential for improved diagnosis and targeted therapy.

Caesarean-section delivery and caries risk of 3-year-old Chinese children: a retrospective cohort study.

BACKGROUND: Caesarean-section (C-section) may influence children's long-term health by affecting bacterial colonization. However, few studies have focused on the association between C-section delivery (CSD) and dental caries, and previous conclusions have been conflicting. This study aimed to explore whether CSD would increase the risk of early childhood caries (ECC) in preschool children in China. METHODS: This study was a retrospective cohort study. Three-year-old children with full primary dentition were included through the medical records system. Children in the nonexposure group were vaginally delivered (VD), while children in the exposure group were delivered through C-section. The outcome was the occurrence of ECC. After agreeing to participate in this study, guardians of included children completed a structured questionnaire on maternal sociodemographic factors, children's oral hygiene and feeding habits. The chi-square test was used to determine differences in the prevalence and severity of ECC between the CSD and VD groups and to analyse the prevalence of ECC according to sample characteristics. Subsequently, potential risk factors for ECC were preliminarily identified through univariate analysis, and the adjusted odds ratios (ORs) were further calculated through multiple logistic regression analysis after controlling for confounding factors. RESULTS: The VD group included 2115 participants while CSD group included 2996 participants. The prevalence of ECC was higher in CSD children than in VD children (27.6% vs. 20.9%, P < 0.05), and the severity of ECC in CSD children was higher (mean number of decayed, missing, and filled teeth, dmft: 2.1 vs. 1.7, P < 0.05). CSD was a risk factor for ECC in 3-year-old children (OR = 1.43, 95% CI = 1.10-2.83). In addition, irregular tooth brushing and always prechewing children's food were risk factors for ECC (P < 0.05). Low maternal educational attainment (high school or below) or socioeconomic status (SES-5) may also increase the prevalence of ECC in preschool children and CSD children (P < 0.05). CONCLUSIONS: CSD would increase the risk of ECC in 3-year-old Chinese children. Paediatric dentists should devote more attention to the development of caries in CSD children. Obstetricians should also prevent excessive and unnecessary CSD.

Ordered structure constructed from C2-symmetric hexa-peri-hexabenzocoronene linked with oligo(dimethylsiloxane).

The preparation of sub-5-nm ordered structures is very important to the development of today's nanotechnology. Block molecules have the potential to form structures with significantly small characteristic dimensions. Herein two novel organic-inorganic block molecules composed of a hexa-peri-hexabenzocoronene (HBC) core and two oligo(dimethylsiloxane) (ODMS) tails with C2 symmetry are reported. A hierarchical lamello-columnar structure with a two-dimensional rectangular lattice where HBC cores adopt a tilted arrangement was obtained from their bulk self-assembly. The feature sizes are all below 5 nm and can be regulated via the number of ODMS chains. Sub-5-nm line structures were obtained through spin-coating of the block molecules onto silicon substrates modified with poly(dimethylsiloxane). As organic-inorganic hybrid materials, these block molecules may be further applied in sub-5-nm nanopatterning.

Tailored Polymer Particles with Ordered Network Structures in Emulsion Droplets.

The structural control of block copolymer (BCP) particles, which determines their properties and utilities, is quite important. Understanding the structural relationship between solution-cast samples and polymer particles in a confined space is necessary to precisely regulate the internal structure of polymer particles. Therefore, a facile method by choosing an appropriate selective solvent is reported to prepare spherical polymer particles with ordered network structures. The rod-coil BCP, poly(dimethylsiloxane)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS), was chosen as a model polymer because of its strong phase segregation ability. First, the structures of the BCP with a thermodynamically stable lamellar structure cast from different selective solvents were systematically studied. Then, a polymer particle with the same internal structure as that of the solution-cast sample can be easily prepared by self-assembling in an emulsion confined space. The relatively large particle size is of importance in this process because the large value of the particle size to periodicity ratio can provide a weak confined environment. This method helps us understand the inherent self-assembling mechanism of polymer particles in an emulsion confined space and accurately control the internal structure of the polymer particle obtained.

Efficient Access to 3D Mesoscopic Prisms in Polymeric Soft Materials.

The preparation of 3D functional isolated mesoscopic assemblies remains a challenge in the self-assembly of polymers. Here, well-defined 3D hexagonal and hexagram prisms with uniform dimensions are acquired by the crystallization of the inclusion complex composed of a crystalline molecule tris-o-phenylenedioxycyclotriphosphazene (TPP) and a block copolymer. The crystalline TPP plays an important role in the self-assembling process. The faceted morphologies of the hexagonal and hexagram prisms are infrequent in the self-assembly field of soft materials. The formation of the prisms experiences a 3D growth mechanism. The epitaxial growth, accompanied by the heterogeneous nucleation in the edges, yields the growth of inclusion crystals. This study provides a path to construct well-defined polymeric soft materials with broad utility based on numerous supramolecular complexes.

5 nm Ordered Structures Self-Assembled by C2 -Symmetric Hybrids with Polyhedral Oligomeric Silsesquioxane and Hexa-peri-Hexabenzocoronene.

Hybrids consisting of polyhedral oligomeric silsesquioxane (POSS) and hexa-peri-hexabenzocoronene (HBC) with a dumbbell topology and C2 symmetry were designed and synthesized. They self-assemble into 5 nm ordered structures. In particular, the increased steric effect with increasing POSS units stabilizes a square columnar phase (Colsqu ) which is important in nanotemplating. These hybrids containing discotic liquid crystal HBC and POSS units have an excellent etching contrast and present an approach to obtain 5 nm nanopatterns.

Hierarchically ordered structures of disk-cube triads containing hexa-peri-hexabenzocoronene and polyhedral oligomeric silsesquioxane.

Obtaining nanoscale-ordered structures is important for the development of nanotechnology. We designed and synthesized a series of disk-cube triads containing one hexa-peri-hexabenzocoronene (HBC) and two polyhedral oligomeric silsesquioxane (POSS) moieties, HBC-2POSS. The two POSS units were linked via ester or amide bonds. With the amide linkage used, the hydrogen bonding that was introduced affected the balance between the π-π interaction of HBC cores and crystallization interaction of POSS units. Hierarchically ordered structures were obtained from HBC-2POSS triads owing to the synergistic effect of multiple secondary interactions: π-π interaction, hydrogen bonding, and crystallization interaction. As organic-inorganic hybrid materials, these HBC-2POSS triads are promising candidates for templates <10 nm.

Head-Tail Asymmetry as the Determining Factor in the Formation of Polymer Cubosomes or Hexasomes in a Rod-Coil Amphiphilic Block Copolymer.

The self-assembly of a rod-coil amphiphilic block copolymer (ABCP) led to Im3‾ m and Pn3‾ m polymer cubosomes and p6mm polymer hexasomes. This is the first time that these structures are observed in a rod-coil system. By varying the hydrophobic chain length, the initial concentration of the polymer solution, or the solubility parameter of the mixed solvent, head-tail asymmetry is adjusted to control the formation of polymer cubosomes or hexasomes. The formation mechanism of the polymer cubosomes was also studied. This research opens up a new way for further study of the bicontinuous and inverse phases in different ABCP systems.

Multi-Modal Sensing Ionogels with Tunable Mechanical Properties and Environmental Stability for Aquatic and Atmospheric Environments.

Ionogels have garnered significant interest due to their great potential in flexible iontronic devices. However, their limited mechanical tunability and environmental intolerance have posed significant challenges for their integration into next-generation flexible electronics in different scenarios. Herein, the synergistic effect of cation-oxygen coordination interaction and hydrogen bonding is leveraged to construct a 3D supramolecular network, resulting in ionogels with tunable modulus, stretchability, and strength, achieving an unprecedented elongation at break of 10 800%. Moreover, the supramolecular network endows the ionogels with extremely high fracture energy, crack insensitivity, and high elasticity. Meanwhile, the high environmental stability and hydrophobic network of the ionogels further shield them from the unfavorable effects of temperature variations and water molecules, enabling them to operate within a broad temperature range and exhibit robust underwater adhesion. Then, the ionogel is assembled into a wearable sensor, demonstrating its great potential in flexible sensing (temperature, pressure, and strain) and underwater signal transmission. This work can inspire the applications of ionogels in multifunctional sensing and wearable fields.

Strain-Stiffening Ionogel with High-Temperature Tolerance via the Synergy of Ionic Clusters and Hydrogen Bonds.

Highly stretchable and conductive ionogels have great potential in flexible electronics and soft robotic skins. However, current ionogels are still far from being able to accurately duplicate the mechanically responsive behavior of real human skin. Furthermore, durable robotic skins that are applicable under harsh conditions are still lacking. Herein, a strong noncovalent interaction, ionic clusters, is combined with hydrogen bonds to obtain a physically cross-linked ionogel (PCI). Benefiting from the strong ionic bonding of the ionic cluster, the PCI shows strain-stiffening behavior similar to that of human skin, thus enabling it to have a perception-strengthening ability. Additionally, the strong ionic clusters can also ensure the PCI remains stable at high temperatures. Even when the temperature is raised to 200 °C, the PCI can maintain the gel state. Moreover, the PCI exhibits high transparency, recyclability, good adhesion, and high conductivity. Such excellent features distinguish the PCI from ordinary ionogels, providing a new way to realize skin-like sensing in harsh environments for future bionic machines.

White-Light-Emitting AIE/Eu3+-Doped Ion Gel with Multistimuli-Responsive Properties.

A white-light-emitting ion gel composed of a poly[(2-(4-vinylphenyl)ethene-1,1,2-triyl)tribenzene-b-ethylene glycol-b-(2-(4-vinylphenyl)ethene-1,1,2-triyl)tribenzene] aggregation-induced emission (AIE) network and a poly([2,2':6',2″-terpyridin]-4'-yl methacrylate-co-methyl methacrylate) Eu3+-doped network was fabricated via a solution mixing process. This ion gel exhibits special multistimuli-responsive properties, and it can change its luminescent color by changing pH, temperature, or the solvent. The unique color-changing property is attributed to the different luminescent mechanisms of the AIE/Eu3+-doped polymer networks. The former is affected by changes in its aggregation state, while the latter is controlled by the dynamic metal-ligand cross-linking bonds. Furthermore, owing to the interpenetrating networks formed by the two polymers, the hybrid gel has both good mechanical strength and flexibility. It may be used in the fields of sensors, probes, and light-emitting materials.

Ordered structures and sub-5 nm line patterns from rod-coil hybrids containing oligo(dimethylsiloxane).

Sub-5 nm ordered nanostructures including lamellar, double gyroid, and columnar phases are formed by a series of oligo(dimethylsiloxane) (ODMS)-based rod-coil liquid crystals with accurate molecular weights. Films with well-oriented line patterns can be obtained by substrate-induced directed self-assembly, which may be further used as lithographic templates.

Chitosan-based thermosensitive hydrogel for nasal delivery of exenatide: Effect of magnesium chloride.

The aim of this research was to evaluate the potential of two chitosan (CS)-based hydrogel systems for nasal delivery of exenatide (EXT) in rats. Both of the EXT-loaded CS/glycerophosphate (GP)/CaCl2 (EXT/CS/GP/CaCl2) and EXT/CS/GP/MgCl2 hydrogel systems had similar in vitro release profiles. However, a difference in metal salt surprisingly resulted in multifaceted differences between the two hydrogel systems, such as EXT stability, gelation time, transepithelial transport, biodistribution and pharmacokinetics. The gelation time of the EXT/CS/GP/MgCl2 hydrogel (more than 110 min) at 37 °C was much longer than that of the EXT/CS/GP/CaCl2 hydrogel (8.0-20.4 min). Transepithelial transport analysis showed that the CS/GP/MgCl2 hydrogel enhanced EXT transport across the Calu-3 cell monolayers more than the CS/GP/CaCl2 hydrogel (P < 0.05). After nasal administration in the rats, the EXT/CS/GP/MgCl2 hydrogel increased the distribution of EXT in the targeting organs and the relative bioavailability of EXT in the rats more than the EXT/CS/GP/CaCl2 hydrogel. Moreover, both EXT/CS/GP/salt hydrogel formulation treatments in high-fat-fed rats significantly decreased food intake and body weight relative to the EXT solution within ten days (P < 0.05). The aforementioned results suggest that the EXT/CS/GP/MgCl2 hydrogel formulation is more suitable to be used as a nasally delivered EXT formulation for the treatment of weight loss.