Aliphatic Polyesters with White-Light Clusteroluminescence.

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, the first example of linear nonconjugated polyesters with SMWLE is reported. Twenty-four kinds of nonconjugated aliphatic polyesters with tunable clusteroluminescence (CL) colors and efficiency were synthesized by the copolymerization of six epoxides and four anhydrides. Experimental and calculation results prove that, at the primary structure level, the balance of structural flexibility and rigidity via adjusting the side-chain length significantly enhances the efficiency of CL without wavelength change. However, altering the chemical structures of the monomer from succinic anhydride to trans-maleic anhydride (MA), cis-MA, and citraconic anhydride (CA), secondary structures of these polyesters change from helix to straight and folding sheet accompanied by gradually red-shifted CL from 460 to 570 nm due to the increase in through-space n-π* interactions, as demonstrated by the computational and experimental results. Then, pure SMWLE with CIE coordination (0.30, 0.32) based on overlapped short-wavelength and long-wavelength CL is achieved in CA-based polyesters. This work not only provides further insights into the emission mechanism of CL but also provides a new strategy to manipulate the properties of CL by regulating the hierarchical structures of CLgens.

Decomposition-assembly of tetraphenylethylene nanoparticles with uniform size and aggregation-induced emission property.

Tetraphenylethylene (TPE)-substituted poly(allylamine hydrochloride) (PAH-g-TPE) is synthesized by a Schiff base reaction between PAH and TPE-CHO. The PAH-g-TPE forms micelles in water at pH 6, which are further transformed into pure TPE-CHO nanoparticles (NPs) with a diameter of ≈300 nm after incubation in a solution of low pH value. In contrast, only amorphous precipitates are obtained when TPE-CHO methanol solution is incubated in water. The aggregation-induced emission feature of the TPE molecule is completely retained in the TPE NPs, which can be internalized into cells and show blue fluorescence. Formation mechanism of the TPE NPs is proposed by taking into account the guidance effect of linear and charged PAH molecules, and the propeller-stacking manner between the TPE-CHO molecules.

Efficient polymerization of azide and active internal alkynes.

The 1,3-dipolar cycloaddition of azides and active internal alkynes has been well studied, but is rarely utilized as a tool for polymer preparation. In this work, an efficient polymerization route is developed. Polycycloaddition of diazide (4) and bis(benzoylethynyl)-benzenes and -butane (3) at elevated temperature has produced the first examples of soluble 1,4,5-trisubstituted polytriazoles PI with satisfactory molecular weights (M(w) up to 16 400) in excellent yields (up to 98.6%). All the obtained polymers are thermally stable, losing merely 5% of their weights at temperatures higher than 367 °C. They exhibit higher refractive indices than some commercial plastics and can be crosslinked upon UV irradiation to generate a 3D photopattern with high resolution. The metal-free feature of such a methodology offers a facile tool to prepare functional materials free from the contamination of metal species.

Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules.

The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically important PEO-PPO-PEO copolymer, Pluronic F127, was further studied by using the TPE fluorescence spectrum intensity. Our results showed good agreement with those reported in the literature by using other methods. The special advantage of the AIE probe method was further explored to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants. Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can conclude that the TPE method is a promising method for the determination of the CMC and critical micellization temperature (CMT), particularly having a special advantage to determine the assembling/disassembling process of colored amphiphilic molecules.

In situ formation of tetraphenylethylene nano-structures on microgels inside living cells via reduction-responsive self-assembly.

Controlling the assembly of synthetic molecules in living systems is of significance for their adaptive applications. However, it is difficult to achieve, especially for composite self-assemblies, due to the complexity and dynamic change of the intracellular environment, and there exist technical difficulties for the direct visualization of organic and polymer self-assemblies. Herein, we demonstrate a novel strategy for the in situ formation of self-assembled micro-nano composite structures in a cell milieu using reduction-responsive microgels (MGs) as a platform. The MGs were prepared by a templating and crosslinking method using a synthetic amphiphlic polymer as the basic material and porous CaCO3 microparticles as the template. The aggregation-induced emission (AIE) tetraphenylethylene moieties and reduction-labile disulfide bonds in the MGs were employed as the self-assembly building blocks and triggering sites for the intracellular self-assembly, respectively. In the presence of reductive agents such as glutathione, nano-spikes were gradually formed on the MGs. After the MGs were internalized by cells, the in situ formation of microgel/nano-spike composite structures was evidenced by the enhanced fluorescence intensity and was further confirmed by direct transmission electron microscopy observation. This work provides an effective strategy to cope with the challenging task of achieving and probing controlled self-assembly in a cell milieu, leading to new insights into investigating biological self-assembly and promoting the development of micro-/nanomaterials by learning from nature.

Photoluminescent supramolecular hyperbranched polymer without conventional chromophores based on inclusion complexation.

A novel photoluminescent supramolecular hyperbranched polymer (SHP) without conventional chromophores was constructed for the first time by inclusion complexation between α-cyclodextrin and diethylenetriamine. The SHP showed wide-band fluorescence dependent upon the excitation wavelength.