Shaping Luminescent Properties of Yb3+ and Ho3+ Co‐Doped Upconverting Core–Shell β‐NaYF4 Nanoparticles by Dopant Distribution and Spacing

At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, a series of core@shell NaYF₄ UCNPs doped with Yb³⁺ and Ho³⁺ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@…, …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core–shell NPs. As revealed by quantitative steady‐state and time‐resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical impact on their luminescence characteristics. Although the increased amount of Yb³⁺ ions boosts UCNP performance by amplifying the absorption, the Yb³⁺ ions can also efficiently dissipate the energy stored in the material through energy migration to the surface, thereby reducing the overall energy transfer efficiency to the activator ions. The results provide yet another proof that UC phosphor chemistry combined with materials engineering through intentional core@shell structures may help to fine‐tune the luminescence features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and display technologies.     

Multicolor Photo‐Crosslinkable AIEgens toward Compact Nanodots for Subcellular Imaging and STED Nanoscopy

Aggregation induced emission (AIE) has attracted considerable interest for the development of fluorescence probes. However, controlling the bioconjugation and cellular labeling of AIE dots is a challenging problem. Here, this study reports a general approach for preparing small and bioconjugated AIE dots for specific labeling of cellular targets. The strategy is based on the synthesis of oxetane‐substituted AIEgens to generate compact and ultrastable AIE dots via photo‐crosslinking. A small amount of polymer enriched with oxetane groups is cocondensed with most of the AIEgens to functionalize the nanodot surface for subsequent streptavidin bioconjugation. Due to their small sizes, good stability, and surface functionalization, the cell‐surface markers and subcellular structures are specifically labeled by the AIE dot bioconjugates. Remarkably, stimulated emission depletion imaging with AIE dots is achieved for the first time, and the spatial resolution is significantly enhanced to ≈95 nm. This study provides a general approach for small functional molecules for preparing small sized and ultrastable nanodots.     

3D Orientational Control in Self‐Assembled Thin Films with Sub‐5 nm Features by Light

While self‐assembled molecular building blocks could lead to many next‐generation functional organic nanomaterials, control over the thin‐film morphologies to yield monolithic sub‐5 nm patterns with 3D orientational control at macroscopic length scales remains a grand challenge. A series of photoresponsive hybrid oligo(dimethylsiloxane) liquid crystals that form periodic cylindrical nanostructures with periodicities between 3.8 and 5.1 nm is studied. The liquid crystals can be aligned in‐plane by exposure to actinic linearly polarized light and out‐of‐plane by exposure to actinic unpolarized light. The photoalignment is most efficient when performed just under the clearing point of the liquid crystal, at which the cylindrical nanostructures are reoriented within minutes. These results allow the generation of highly ordered sub‐5 nm patterns in thin films at macroscopic length scales, with control over the orientation in a noncontact fashion.     

Microfluidic Production of Biodegradable Microcapsules for Sustained Release of Hydrophilic Actives

Biodegradable microcapsules with a large aqueous lumen and ultrathin membrane are microfluidically designed for sustained release of hydrophilic bioactives using water‐in‐oil‐in‐water double‐emulsion drops as a template. As a shell phase, an organic solution of poly(lactic‐co‐glycolic acid) is used, which is consolidated to form a biodegradable membrane. The encapsulants stored in the lumen are released over a long period of time as the membranes degrade. The period can be controlled in a range of —three to five months at neutral pH condition by adjusting membrane thickness, providing highly sustained release and potentially enabling the programed release of multiple drugs. At acidic or basic condition, the degradation is accelerated, leading to the release in the period of approximately two months. As the membrane is semipermeable, the microcapsules respond to the osmotic pressure difference across the membrane. The microcapsules are inflated in hypotonic condition and deflated in hypertonic condition. Both conditions cause cracks on the membrane, resulting in the fast release of encapsulants in a day. The microcapsules implanted in mice also show sustained release, despite the period is decreased to a month. It is believed that the microcapsules are promising for the in vivo sustained release of drugs for high and long‐term efficacy.     

Non‐oscillatory and non‐singular asymptotic solutions to stress fields at interface cracks

This work concerns the complex oscillatory singularities revealed in Williams's asymptotic solutions to stress fields around arbitrary interface cracks, which are the foundation of phenomenological interface fracture mechanics. First, we highlight the fatal discrepancy between the asymptotic stress fields for cracks in a homogeneous material obtained by assigning an identical material on both regions embracing an interface crack, and the solutions directly derived from cracks in a single material. Next, following a brief introduction to Williams's formulation process, we adopt the method of repeatedly eliminating variables instead of solving the determinant equation for the coefficient matrix to reformulate the asymptotic analysis of stress fields at arbitrary interface cracks. The resultant stresses get rid of oscillatory character. Further, under two specific loading conditions, namely, remotely uniaxial tension or shear, non‐oscillatory and non‐singular asymptotic solutions to stress fields around interface cracks are obtained.     

Fracture mechanics‐based progressive damage modelling of adhesively bonded fibre‐reinforced polymer joints

A quasi‐static progressive damage model for prediction of the fracture behaviour and strength of adhesively bonded fibre‐reinforced polymer joints is introduced in this paper. The model is based on the development of a mixed‐mode failure criterion as a function of a master R‐curve derived from the experimental results obtained from standard fracture mechanics joints. Consequently, the developed failure criterion is crack‐length and mode‐mixity dependent, and it takes into account the contribution of the fibre‐bridging effect. Energy release rate values for adhesively bonded double‐lap joints are obtained by using the virtual crack closure technique method in a finite element model, and the numerically obtained strain energy release rate is compared to the critical strain energy release rate given by the mixed‐mode failure criterion. The entire procedure is implemented in a numerical algorithm, which was successfully used for predicting the strength and R‐curve response of adhesively bonded double‐lap structural joints made of pultruded glass fibre‐reinforced polymers and epoxy adhesives.