Blood Circulation Assessment by Steadily Fluorescent Near-Infrared-II Aggregation-Induced Emission Nano Contrast Agents.

The dysfunction of the blood circulation system typically induces acute or chronic ischemia in limbs and vital organs, with high disability and mortality. While conventional tomographic imaging modalities have shown good performance in the diagnosis of circulatory diseases, multiple limitations remain for real-time and precise hemodynamic evaluation. Recently, fluorescence imaging in the second region of the near-infrared (NIR-II, 1000-1700 nm) has garnered great attention in monitoring and tracing various biological processes in vivo due to its advantages of high spatial-temporal resolution and real-time feature. Herein, we employed NIR-II imaging to carry out a blood circulation assessment by aggregation-induced emission fluorescent aggregates (AIE nano contrast agent, AIE NPs). Thanks to the longer excited wavelength, enhanced absorptivity, higher brightness in the NIR-II region, and broader optimal imaging window of the AIE NPs, we have realized a multidirectional assessment for blood circulation in mice with a single NIR-II imaging modality. Thus, our work provides a fluorescence contrast agent platform for accurate hemodynamic assessment.

Catalyst-Free Spontaneous Polymerization with 100% Atom Economy: Facile Synthesis of Photoresponsive Polysulfonates with Multifunctionalities.

Photoresponsive polymers have attracted extensive attention due to their tunable functionalities and advanced applications; thus, it is significant to develop facile in situ synthesis strategies, extend polymers family, and establish various applications for photoresponsive polymers. Herein, we develop a catalyst-free spontaneous polymerization of dihaloalkynes and disulfonic acids without photosensitive monomers for the in situ synthesis of photoresponsive polysulfonates at room temperature in air with 100% atom economy in high yields. The resulting polysulfonates could undergo visible photodegradation with strong photoacid generation, leading to various applications including dual-emissive or 3D photopatterning, and practical broad-spectrum antibacterial activity. The halogen-rich polysulfonates also exhibit a high and photoswitched refractive index and could undergo efficient postfunctionalizations to further expand the variety and functionality of photoresponsive heteroatom-containing polyesters.

Aggregate Science: From Structures to Properties.

Molecular science entails the study of structures and properties of materials at the level of single molecules or small interacting complexes of molecules. Moving beyond single molecules and well-defined complexes, aggregates (i.e., irregular clusters of many molecules) serve as a particularly useful form of materials that often display modified or wholly new properties compared to their molecular components. Some unique structures and phenomena such as polymorphic aggregates, aggregation-induced symmetry breaking, and cluster excitons are only identified in aggregates, as a few examples of their exotic features. Here, by virtue of the flourishing research on aggregation-induced emission, the concept of "aggregate science" is put forward to fill the gaps between molecules and aggregates. Structures and properties on the aggregate scale are also systematically summarized. The structure-property relationships established for aggregates are expected to contribute to new materials and technological development. Ultimately, aggregate science may become an interdisciplinary research field and serves as a general platform for academic research.

Economic Sulfur Conversion to Functional Polythioamides through Catalyst-Free Multicomponent Polymerizations of Sulfur, Acids, and Amines.

Sulfur utilization is a global concern because of its abundant nature sources and the safety or environmental problems caused by its burning or oxidation during storage, while sulfur-containing polymers are popular materials in virtue of their fascinating properties such as metal coordination ability, high refractive indices, and semiconducting property. The synthesis of sulfur-containing polymers is challenging, especially directly from elemental sulfur. Herein, catalyst-free and scalable multicomponent polymerizations (MCPs) of all commercially available elemental sulfur, dicarboxylic acids, and diamines were reported to facilely construct 12 polythioamides with diverse and well-defined structures, high molecular weights (Mw's up to 86 200 g/mol), and excellent yields (up to 99%) from elemental sulfur. Besides commonly used aliphatic diamines, aromatic diamine monomers are also applicable to these multicomponent polymerizations, affording polythioamides with unique rigid structures and improved functionality as compared to those of the previously reported polythioamides. These polythioamides can be applied in gold recovery, which could extract a trace amount of Au3+ from practical acidic leaching solution of discarded electronic waste selectively, rapidly (1 min), sensitively (10 ppb), and efficiently (>99.99%) with high extraction capacity up to 0.60 g· Au3+/g to directly afford high-purity elemental gold after pyrolysis. The MCPs could make use of both abundantly existing sulfur waste and trace amounts of precious gold residue in electronic wastes, demonstrating their great potential in resource utilization.

Aggregation-Induced Emission Luminogen with Near-Infrared-II Excitation and Near-Infrared-I Emission for Ultradeep Intravital Two-Photon Microscopy.

Currently, a serious problem obstructing the large-scale clinical applications of fluorescence technique is the shallow penetration depth. Two-photon fluorescence microscopic imaging with excitation in the longer-wavelength near-infrared (NIR) region (>1100 nm) and emission in the NIR-I region (650-950 nm) is a good choice to realize deep-tissue and high-resolution imaging. Here, we report ultradeep two-photon fluorescence bioimaging with 1300 nm NIR-II excitation and NIR-I emission (peak ∼810 nm) based on a NIR aggregation-induced emission luminogen (AIEgen). The crab-shaped AIEgen possesses a planar core structure and several twisting phenyl/naphthyl rotators, affording both high fluorescence quantum yield and efficient two-photon activity. The organic AIE dots show high stability, good biocompatibility, and a large two-photon absorption cross section of 1.22 × 103 GM. Under 1300 nm NIR-II excitation, in vivo two-photon fluorescence microscopic imaging helps to reconstruct the 3D vasculature with a high spatial resolution of sub-3.5 µm beyond the white matter (>840 µm) and even to the hippocampus (>960 µm) and visualize small vessels of ∼5 µm as deep as 1065 µm in mouse brain, which is among the largest penetration depths and best spatial resolution of in vivo two-photon imaging. Rational comparison with the AIE dots manifests that two-photon imaging outperforms the one-photon mode for high-resolution deep imaging. This work will inspire more sight and insight into the development of efficient NIR fluorophores for deep-tissue biomedical imaging.

Novel super-resolution capable mitochondrial probe, MitoRed AIE, enables assessment of real-time molecular mitochondrial dynamics.

Mitochondria and mitochondrial dynamics play vital roles in health and disease. With the intricate nanometer-scale structure and rapid dynamics of mitochondria, super-resolution microscopy techniques possess great un-tapped potential to significantly contribute to understanding mitochondrial biology and kinetics. Here we present a novel mitochondrial probe (MitoRed AIE) suitable for live mitochondrial dynamics imaging and single particle tracking (SPT), together with a multi-dimensional data analysis approach to assess local mitochondrial (membrane) fluidity. The MitoRed AIE probe localizes primarily to mitochondrial membranes, with 95 ms fluorophore on-time delivering 106 photons/ms, characteristics which we exploit to demonstrate live cell 100 fps 3D time-lapse tracking of mitochondria. Combining our experimental and analytical approaches, we uncover mitochondrial dynamics at unprecedented time scales. This approach opens up a new regime into high spatio-temporal resolution dynamics in many areas of mitochondrial biology.

Aggregation-induced emissive nanoparticles for fluorescence signaling in a low cost paper-based immunoassay.

Low cost paper based immunoassays are receiving interest due to their fast performance and small amounts of biomolecules needed for developing an immunoassay complex. In this work aggregation-induced emissive (AIE) nanoparticles, obtained from a diastereoisomeric mixture of 1,2-di-(4-hydroxyphenyl)-1,2-diphenylethene (TPEDH) in a one-step top-down method, are characterized through Dynamic Light Scattering (DLS), Scanning Electron Microscopy (SEM), and Zeta potential. By measuring the Zeta potential before and after labeling the nanoparticles with antibodies we demonstrate that the colloidal system is stable in a wide pH-range. The AIE-active nanoparticles are deposited on chitosan and glutaraldehyde modified paper pads overcoming the common aggregation-caused quenching (ACQ) effect. Analyte concentrations from 1000ng and below are applied in a model immunocomplex using Goat anti-Rabbit IgG and Rabbit IgG. In the range of 7.81ng-250ng, linear trends with a high R(2) are observed, which leads to a strong increase of the blue fluorescence from the TPEDH nanoparticles.