Introduction

Covalently bound functional GAGs orchestrate tissue mechanics through time-dependent characteristics.

Objective

The role of specific glycosaminoglycans (GAGs) at the ligament-cementum and cementum-dentin interfaces within a human periodontal complex were examined. Matrix swelling and resistance to compression under health and modeled diseased states was investigated.

Materials and methods

The presence of keratin sulfate (KS) and chondroitin sulfate (CS) GAGs at the ligament-cementum and cementum-dentin interfaces in human molars (N=5) was illustrated by using enzymes, atomic force microscopy (AFM), and AFM-based nanoindentation. The change in physical characteristics of modeled diseased states through sequential digestion of keratin sulfate (KS) and chondroitin sulfate (CS) GAGs was investigated. One-way ANOVA tests with P<0.05 were performed to determine significant differences between groups. Additionally, the presence of mineral within the seemingly hygroscopic interfaces was investigated using transmission electron microscopy.

Results

Immunohistochemistry (N=3) indicated presence of biglycan and fibromodulin small leucine rich proteoglycans at the interfaces. Digestion of matrices with enzymes confirmed the presence of KS and CS GAGs at the interfaces by illustrating a change in tissue architecture and mechanics. A significant increase in height (nm), decrease in elastic modulus (GPa), and tissue deformation rate (nm/s) of the PDL-C attachment site (215±63-424±94nm; 1.5±0.7-0.4±0.2GPa; 21±7-48±22nm/s), and cementum-dentin interface (122±69-360±159nm; 2.9±1.3-0.7±0.3GPa; 18±4-30±6nm/s) was observed.

Conclusions

The sequential removal of GAGs indicated loss in intricate structural hierarchy of hygroscopic interfaces. From a mechanics perspective, GAGs provide tissue recovery/resilience. The results of this study provide insights into the role of GAGs toward conserved tooth movement in the socket in response to mechanical loads, and modulation of potentially deleterious strain at tissue interfaces.

A versatile and highly tunable synthesis for nanofiber aerogels based on the n-type organic semiconductor perylene tetracarboxylic diimide (PTCDI) is presented. PTCDI nanofiber aerogels are demonstrated to incorporate the organic semiconductor into a high surface area and porous morphology, and can also be graphitized to synthesize carbon nanofiber (CNF) aerogels by thermal annealing. Using this approach, CNF aerogels with variable density and crystallinity are synthesized. Furthermore, by incorporating metal salts into the synthesis, metal-directed assembly yields a variety of nanoscale morphologies. The selection of post-synthesis thermal treatment can result in metal-directed assembly of PTCDI aerogels, low crystallinity graphitic aerogels decorated with metal nanoparticles, or highly crystalline graphitic aerogels with controllable nanoscale morphologies. The high surface area and porosity afforded by the aerogel morphology coupled with the intrinsic properties of PTCDI or CNFs is important for improving their performance in a number of applications including energy storage and catalysis.

The growing interest in two-dimensional imine-based covalent organic frameworks (COFs) is inspired by their crystalline porous structures and the potential for extensive π-electron delocalization. The intrinsic reversibility and strong polarization of imine linkages, however, leads to insufficient chemical stability and optoelectronic properties. Developing COFs with improved robustness and π-delocalization is highly desirable but remains an unsettled challenge. Here we report a facile strategy that transforms imine-linked COFs into ultrastable porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction. The as-formed, quinoline-linked COFs not only retain crystallinity and porosity, but also display dramatically enhanced chemical stability over their imine-based COF precursors, rendering them among the most robust COFs up-to-date that can withstand strong acidic, basic and redox environment. Owing to the chemical diversity of the cycloaddition reaction and structural tunability of COFs, the pores of COFs can be readily engineered to realize pre-designed surface functionality.

Black phosphorus (BP) as a promising two-dimensional (2D) material has gained great attention in nanoelectronic devices because of its intrinsic semiconductor characteristics. However, the poor material availability and solution processability have been major roadblocks that hinder its wider application in microelectronics. Herein, readily available, lost-cost BP was utilized as an effective component that was integrated via a facile solution process for the fabrication of bulk heterojunction organic solar cells (OSCs). An impressive fill factor (FF) of 74.2% and power conversion efficiency (PCE) of 10.5% were realized in the OSCs incorporating 10 wt% of BP in the active layer of the benchmark polymer donor PTB7-Th and PC71BM acceptor, corresponding to a 20% PCE enhancement compared to the BP-free binary devices. The efficiency enhancement can be attributed to BP's high hole carrier mobility that facilitates better carrier extraction and suppression of the recombination. BP has been further demonstrated to be effective in additional solar cells based on other photovoltaic (PV) materials, including non-fullerene OSCs. The successful incorporation of the inexpensive BP in the solution-based fabrication of OSCs opens the door for its application in high performance, low cost flexible electronics.

Inorganic nanocrystals such as quantum dots (QDs) and upconverting nanoparticles (UCNPs) are uniquely suited for quantitative live-cell imaging and are typically functionalized with ligands to study specific receptors or cellular targets. Antibodies (Ab) are among the most useful targeting reagents owing to their high affinities and specificities, but common nanocrystal labeling methods may orient Ab incorrectly, be reversible or denaturing, or lead to Ab-NP complexes too large for some applications. Here, we show that SpyCatcher proteins, which bind and spontaneously form covalent isopeptide bonds with cognate SpyTag peptides, can conjugate engineered Ab to nanoparticle surfaces with control over stability, orientation, and stoichiometry. Compact SpyCatcher-functionalized QDs and UCNPs may be labeled with short-chain variable fragment Ab (scFv) engineered to bind urokinase-type plasminogen activator receptors (uPAR) that are overexpressed in many human cancers. Confocal imaging of anti-uPAR scFv-QD conjugates shows the antibody mediates specific binding and internalization by breast cancer cells expressing uPAR. Time-lapse imaging of photostable scFv-UCNP conjugates shows that Ab binding causes uPAR internalization with a ∼20 min half-life on the cell surface, and uPAR is internalized to endolysosomal compartments distinct from general membrane stains and without significant recycling to the cell surface. The controlled and stable conjugation of engineered Ab to NPs enables targeting of diverse receptors for live-cell study of their distribution, trafficking, and physiology.

This study investigates bony protrusions within a narrowed periodontal ligament space (PDL-space) of a human bone-PDL-tooth fibrous joint by mapping structural, biochemical, and mechanical heterogeneity. Higher resolution structural characterization was achieved via complementary atomic force microscopy (AFM), nano-transmission X-ray microscopy (nano-TXM), and microtomography (MicroXCT™). Structural heterogeneity was correlated to biochemical and elemental composition, illustrated via histochemistry and microprobe X-ray fluorescence analysis (μ-XRF), and mechanical heterogeneity evaluated by AFM-based nanoindentation. Results demonstrated that the narrowed PDL-space was due to invasion of bundle bone (BB) into PDL-space. Protruded BB had a wider range with higher elastic modulus values (2-8GPa) compared to lamellar bone (0.8-6GPa), and increased quantities of Ca, P and Zn as revealed by μ-XRF. Interestingly, the hygroscopic 10-30μm interface between protruded BB and lamellar bone exhibited higher X-ray attenuation similar to cement lines and lamellae within bone. Localization of the small leucine rich proteoglycan biglycan (BGN) responsible for mineralization was observed at the PDL-bone interface and around the osteocyte lacunae. Based on these results, it can be argued that the LB-BB interface was the original site of PDL attachment, and that the genesis of protruded BB identified as protrusions occurred as a result of shift in strain. We emphasize the importance of bony protrusions within the context of organ function and that additional study is warranted.

Free-standing ultrathin (∼2 nm) films of several oxides (Al₂O₃,TiO₂, and others) have been developed, which are mechanically robust and transparent to electrons with E_kin ≥ 200 eV and to photons. We demonstrate their applicability in environmental X-ray photoelectron and infrared spectroscopy for molecular level studies of solid-gas (≥1 bar) and solid-liquid interfaces. These films act as membranes closing a reaction cell and as substrates and electrodes for electrochemical reactions. The remarkable properties of such ultrathin oxides membranes enable atomic/molecular level studies of interfacial phenomena, such as corrosion, catalysis, electrochemical reactions, energy storage, geochemistry, and biology, in a broad range of environmental conditions.

This study investigates bony protrusions within a narrowed periodontal ligament space (PDL-space) of a human bone-PDL-tooth fibrous joint by mapping structural, biochemical, and mechanical heterogeneity. Higher resolution structural characterization was achieved via complementary atomic force microscopy (AFM), nano-transmission X-ray microscopy (nano-TXM), and microtomography (MicroXCT™). Structural heterogeneity was correlated to biochemical and elemental composition, illustrated via histochemistry and microprobe X-ray fluorescence analysis (μ-XRF), and mechanical heterogeneity evaluated by AFM-based nanoindentation. Results demonstrated that the narrowed PDL-space was due to invasion of bundle bone (BB) into PDL-space. Protruded BB had a wider range with higher elastic modulus values (2-8GPa) compared to lamellar bone (0.8-6GPa), and increased quantities of Ca, P and Zn as revealed by μ-XRF. Interestingly, the hygroscopic 10-30μm interface between protruded BB and lamellar bone exhibited higher X-ray attenuation similar to cement lines and lamellae within bone. Localization of the small leucine rich proteoglycan biglycan (BGN) responsible for mineralization was observed at the PDL-bone interface and around the osteocyte lacunae. Based on these results, it can be argued that the LB-BB interface was the original site of PDL attachment, and that the genesis of protruded BB identified as protrusions occurred as a result of shift in strain. We emphasize the importance of bony protrusions within the context of organ function and that additional study is warranted.

The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO2-to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here we utilize in situ infrared nanospectroscopy and surface-enhanced Raman spectroscopy, unveiling an electrochemical bias-induced consecutive bond cleavage mechanism of surface ligands leading to formation of the NP/ordered-ligand interlayer. This real-time molecular insight could influence the design of confined localized fields in multiple catalytic systems. Moreover, the demonstrated capability of capturing nanometre-resolved, dynamic molecular-scale events holds promise for the advancement of using controlled local molecular behaviour to achieve desired functionalities across multiple research domains in nanoscience. (Figure presented.).

We present a study of the effect of gold nanoparticles (Au NPs) on TiO₂ on charge generation and trapping during illumination with photons of energy larger than the substrate band gap. We used a novel characterization technique, photoassisted Kelvin probe force microscopy, to study the process at the single Au NP level. We found that the photoinduced electron transfer from TiO₂ to the Au NP increases logarithmically with light intensity due to the combined contribution of electron-hole pair generation in the space charge region in the TiO₂-air interface and in the metal-semiconductor junction. Our measurements on single particles provide direct evidence for electron trapping that hinders electron-hole recombination, a key factor in the enhancement of photo(electro)catalytic activity.