Applications of Polyacetylene Derivatives in Gas and Liquid Separation.

As a low energy consumption, simple operation and environmentally friendly separation method, membrane separation has attracted extensive attention. Therefore, researchers have designed and synthesized various types of separation membrane, such as metal organic framework (MOF), covalent organic framework (COF), polymer of intrinsic micro-porosity (PIM) and mixed matrix membranes. Some substituted polyacetylenes have distorted structures and formed micropores due to the existence of rigid main chains and substituted side groups, which can be applied to the field of membrane separation. This article mainly introduces the development and application of substituted polyacetylenes in gas separation and liquid separation based on membrane technology.

A Novel Fluorescent Skeleton from Disubstituted Thiochromenones via Nickel-Catalyzed Cycloaddition of Sulfobenzoic Anhydrides with Alkynes.

Nickel-catalyzed cycloaddition of alkynes and 2-sulfobenzoic anhydrides gives highly functionalized thiochromenones. The reaction undergoes a deoxygenative rather than decarbonylative pathway and shows advantages of an excellent isolated yield (up to 95%), high reaction efficiency, and high regioselectivity. As one of the resulted products, 2,3-di(triphenylamine)-thiolchromenone possesses a typical aggregation-induced emission property and emits efficient near-infrared fluorescence.

Synthesis of surface modified Fe3O4 super paramagnetic nanoparticles for ultra sound examination and magnetic resonance imaging for cancer treatment.

In the present work, Fe3O4 nanoparticles with superparamagnetic properties were prepared and capped by using Chitosan. The synthesized NPs were studied by using transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. Average particle size and surface charge of the synthesized NPs were characterized by using Malvern Zetasizer instrument. TEM images showed the morphology and size distribution of uncoated Fe3O4 NPs, exhibiting the uniform sized NPS with an average particle size of about 10 nm. Vibrating Scanning Magnetometry (VSM) experiments, showed the superparamagnetic nature of the prepared nanoparticles. Fe3O4 NPs showed ferromagnetic magnetization which is very sensitive towards the sample's nanostructure. The results of paramagnetic studies exhibited the substantial reduction in paramagnetic behavior after Chitosan coating but sufficient for responding in magnetic field. Further, the in-vitro ability of the Chitosan coated Fe3O4 NPs as contrast agents in efficient Ultra sound/Magnetic resonance (US/MR) imaging was investigated. These findings demonstrated that the Chitosan coated super para magnetic iron oxide nanoparticles (SPION) have reported significant contrast-enhanced imaging potential for dual-mode US/MR imaging. Hence, the prepared Chitosan coated SPION composites administration serve as potential guide in the diagnosis and treatment of cancers.

Specific Targeting, Imaging, and Ablation of Tumor-Associated Macrophages by Theranostic Mannose-AIEgen Conjugates.

Tumor-associated macrophages (TAMs) that exist in tumor microenvironment promote tumor progression and have been suggested as a promising therapeutic target for cancer therapy in preclinical studies. Development of theranostic systems capable of specific targeting, imaging, and ablation of TAMs will offer clinical benefits. Here we constructed a theranostic probe, namely, TPE-Man, by attaching mannose moieties to a red-emissive and AIE (aggregation-induced emission)-active photosensitizer. TPE-Man can specifically recognize a mannose receptor that is overexpressed on TAMs by the sugar-receptor interaction and enables fluorescent visualization of the mannose-receptor-positive TAMs in high contrast. The histologic study of mouse tumor sections further verifies TPE-Man's excellent targeting specificity being comparable with the commercial mannose-receptor antibody. TAMs can be effectively eradicated upon exposure to white light irradiation via a photodynamic therapy effect. To our knowledge, this is the first small molecular theranostic probe for TAMs that revealed combined advantages of low cost, high targeting specificity, fluorescent light-up imaging, and efficient photodynamic ablation.

A unimolecular theranostic system with H2O2-specific response and AIE-activity for doxorubicin releasing and real-time tracking in living cells.

A theranostic drug delivery system composed of tetraphenyl-ethene (AIEgen), benzyl boronic ester (trigger), and doxorubicin (drug) was designed and synthesized; its utilities for cell imaging, drug delivery tracking, and cancer cell cytociding were evaluated.

Phenol-yne Click Polymerization: An Efficient Technique to Facilely Access Regio- and Stereoregular Poly(vinylene ether ketone)s.

Alkyne-based click polymerizations have been well-established. However, in order to expand the family to synthesize polymers with new structures and novel properties, new types of click polymerizations are highly demanded. In this study, for the first time, we established a new efficient and powerful phenol-yne click polymerization. The activated diynes and diphenols could be facilely polymerized in the presence of the Lewis base catalyst of 4-dimethylaminopyridine (DMAP) under mild reaction conditions. Regio- and stereoregular poly(vinylene ether ketone)s (PVEKs) with high molecular weights (up to 35 200) were obtained in excellent yields (up to 99.0 %). The reaction mechanism was well explained under the assistance of density functional theory (DFT) calculation. Furthermore, since the vinyl ether sequence acts as a stable but acid-liable linkage, the polymers could be decomposed under acid conditions, rendering them applicable in biomedical and environmental fields.

A two-channel responsive fluorescent probe with AIE characteristics and its application for selective imaging of superoxide anions in living cells.

A two-channel responsive and AIE-active fluorescent probe was developed to selectively detect superoxide anions in living cells, which can be used to track the endogenous superoxide anion level when cells undergo apoptosis and inflammation.

A single fluorescent probe enables clearly discriminating and simultaneously imaging liquid-ordered and liquid-disordered microdomains in plasma membrane of living cells.

Liquid-ordered (Lo) and liquid-disordered (Ld) microdomains in plasma membrane play different yet essential roles in various bioactivities. However, discrimination of the two microdomains in living cells is difficult, due to the similarity in their constituents and structures. Up to now, polarity sensitive probes are the only tool for imaging the two microdomains, but their small difference between emission spectra in the two microdomains (less than 50 nm) limited their application in living cells. In this work, we first presented an aggregation/monomer type of fluorescent probe (2,7-9E-BHVC12) with much larger separation in emission wavelength (up to 100 nm), for dual-color visualizing the two membrane microdomains in living cells. The probe can form red-emissive aggregates and yellow-emissive monomers when induced by Lo and Ld microdomains, respectively, and thus enables clear visualization of the two membrane microdomains in living cells with dual colors, and thus high-fidelity images of substructures of plasma membrane have been obtained. According to the images of three kinds of normal cells and three kinds of cancer cells stained with 2,7-9E-BHVC12, significant difference in plasma membrane microstructure of cancer cells was found. In terms of 2,7-9E-BHVC12, normal cells were mainly consisted of either Lo or Ld microdomains all over their membranes, while cancer cells all clearly display coexistence of Lo and Ld membrane microdomains. Therefore, 2,7-9E-BHVC12 can serve as a powerful tool for studies of membrane microdomains, and the different results of normal and cancer cells would also deepen our understanding in cancer science.

A macrocyclic 1,4-bis(4-pyridylethynyl)benzene showing unique aggregation-induced emission properties.

A box-like macrocycle based on 1,4-bis(4-pyridylethynyl)benzene was derived in high yield. The macrocyclic fluorogen shows unique aggregation-induced emission properties.

Going beyond the classical amphiphilicity paradigm: the self-assembly of completely hydrophobic polymers into free-standing sheets and hollow nanostructures in solvents of variable quality.

Self-assembly is well-known to occur in amphiphiles, and the totally hydrophobic ones are never reported to self-assemble. In this work we report for the first time that the latter can self-assemble into free-standing sheets and hollow spheres in toluene/methanol mixed solvents by modulating the solvent quality. The homopolymers studied in this work are polystyrene (PS), polyphenylacetylene (PPA), and poly(3-hexyl thiophene) (P3HT), representing polymers with different rigidity. All the three form a homogenous solution in toluene, but self-assembly occurs in the toluene/methanol mixed solvents. Micrometer sized free-standing sheets were formed for PS, PPA, and P3HT at methanol volume fractions being 43%, 50%, and 67%, respectively, and hollow spheres were observed for PPA at higher methanol fractions of 75 and 90%. Under the latter solvent conditions, PS forms solid spheres, yet ill-defined aggregates and free-standing sheets coexist in the case of P3HT. This non-solvent induced self-assembly was explained by a delicate balance of two "opposing forces": van der Waals attractive and entropic repulsive forces generated between the segments of these homopolymers within a single chain, between two chains, and among more chains in the solvents of worsened quality.

Influence of the number and substitution position of phenyl groups on the aggregation-enhanced emission of benzene-cored luminogens.

The influence of the number and substitution position of phenyl groups on the aggregation-enhanced emission of benzene-cored luminogens is unambiguously revealed.

A fluorescent probe for intracellular cysteine overcoming the interference by glutathione.

Cysteine (Cys) plays important roles in many physiological processes of eukaryotic cells and its detection in cells is of fundamental significance. However, glutathione (GSH), homocysteine, N-acetyl-L-cysteine and other thiols greatly hamper the detection of Cys. In particular, GSH strongly interferes with the detection of cellular Cys (30­200 µM) due to its high intracellular concentration (1­10 mM). In this work, an off­on fluorescent probe (HOTA) for the detection of Cys is presented. This probe possesses both excellent sensitivity and satisfactory selectivity for cellular Cys detection: with the addition of 200 µM Cys, the fluorescence intensity of the probe (10 µM) enhanced 117-fold and the detection limit was calculated to be 13.47 µM, which is lower than the cellular Cys concentration; the probe also selectively detected 30­200 µM cysteine over 1­10 mM glutathione. Consequently, cell imaging experiments were performed with probe HOTA. Furthermore, the results of the thiol-blocking and GSH synthesis inhibiting experiments confirmed that the intracellular emission mainly originates from the interaction between Cys and HOTA.

Lighting up cysteine and homocysteine in sequence based on the kinetic difference of the cyclization/addition reaction.

A novel one- and two-photon fluorescent probe CB1 has been developed for discriminating Cys and Hcy in a successive manner with high selectivity. The discrete time-dependent fluorescent responses enable us to sequentially detect Cys and Hcy in different time windows. Two-step reaction and kinetic modes were used to explain the sensing mechanism. As a promising biosensor for cell imaging, CB1 has been confirmed to exhibit membrane permeability to intact cells, low cytotoxicity to viable cells and photostability to ultraviolet light excitation. Furthermore, the results from the control assay have shown that the one- and two-photon fluorescence of CB1 within cells is associated with intracellular mercapto biomolecules but yet there is little interference with physiological pH value, viscosity and common bioanalytes. Finally one- and two-photon fluorescent images of CB1 within living SiHa cells have been presented.

Discriminatory detection of cysteine and homocysteine based on dialdehyde-functionalized aggregation-induced emission fluorophores.

We demonstrate a concept-proof work of using fluorescence (FL) "turn-on" probes for the discriminatory detection of cysteine (Cys) over homocysteine (Hcy). The fluorogens are provided with aggregation-induced emission (AIE) characteristic and functionalized with two aldehyde-groups (DMTPS-ALD and TPE-ALD). All the detections were carried out in a biocompatible medium (10 mM HEPES buffer and DMSO, pH 7.4). In principle, the formation of thiazinane/thiazolidine through the chemical reaction of aldehydes on the probe molecules and the residue of Cys/Hcy determines the selective recognition of Cys and Hcy over other amino acids and glucose. The FL responses originate from the AIE property of thiazinane/thiazolidine resultants, which have low solubility and precipitate (aggregate) in the detection medium. The discrimination between Cys and Hcy comes from the difference in reaction kinetics of TPE-ALD/DMTPS-ALD with Cys and Hcy, thereby the FL responses show different time courses and intensity enhancement. It is worth noting that TPE-ALD outshined the other two probes in performance with fast response, a high FL enhancement up to 16-fold, high sensitivity, and good specificity and selectivity. Moreover, its FL response threshold at 250 µM is very close to the lower limit of the normal level of Cys in human plasma, which implies that TPE-ALD could be applied as a potential indicator of Cys deficiency.

BSA-tetraphenylethene derivative conjugates with aggregation-induced emission properties: fluorescent probes for label-free and homogeneous detection of protease and α1-antitrypsin.

Herein, BSA-tetraphenylethene derivative conjugates with aggregation-induced emission (AIE) properties were constructed and used as fluorescent probes for label-free detection of protease and α1-antitrypsin. Conjugated AIE probes were formed based on the electrostatic induced assembly between an ammonium cation of quaternized tetraphenylethene salt and carboxyl anion groups of BSA. While water soluble quaternized tetraphenylethene salt showed very low fluorescence in its well-dispersed state, obvious enhancement in the fluorescence of the aggregated tetraphenylethene derivative on the BSA templates was achieved due to the abnormal aggregation-induced emission properties of tetraphenylethene. These BSA-tetraphenylethene derivative conjugates enabled label-free detection of protease. In the presence of trypsin, the BSA templates were enzymatically hydrolyzed and the conjugates decomposed. Therefore the quaternized tetraphenylethene molecules became increasingly isolated from each other. Accordingly, the aggregation to dispersing state change of tetraphenylethene derivative resulted in an obvious decrease in the fluorescence of the conjugates probes and enabled the sensitive and selective detection of trypsin. Furthermore, upon addition of α1-antitrypsin, the enzymatic activity of trypsin was inhibited and the fluorescence was consequently preserved. Sensitive detection of α1-antitrypsin was thus realised. The protein-tetraphenylethene derivative conjugates with aggregation-induced emission properties therefore show great promise for the monitoring of biological processes and cancer diagnostics with simplicity, high sensitivity, and rapid response.

Label-free fluorescence detection of mercury(II) and glutathione based on Hg2+-DNA complexes stimulating aggregation-induced emission of a tetraphenylethene derivative.

Herein, a sensitive and selective sensor for mercury(II) and glutathione based on the aggregation-induced emission (AIE) of a tetraphenylethene derivative stimulated by Hg(2+)-DNA complexes is reported. Aggregation complexes of AIE probes, quaternized tetraphenylethene salt and anti-Hg(2+) aptamer ssDNA, were formed based on the electrostatic interactions between the ammonium cation of AIE probes and the backbone phosphate anions of DNA. In the presence of target Hg(2+), the aptamer ssDNA with thymine (T)-rich sequences selectively bound with Hg(2+) to form an Hg(2+)-bridged T base pair and the ssDNA changed into a hairpin-like structure. Therefore the AIE probing molecules were brought to be positioned closer. Accordingly, the conformational change of aptamer ssDNA resulted in an obvious enhancement in the fluorescence of the probing complex enabling the sensitive and selective detection of Hg(2+). Furthermore, upon reaction of Hg(2+) with biothiols, the compact structure was destroyed and the fluorescence decreased consequently. Sensitive detection of GSH was realised based on the decrease of fluorescence of the probing complex. The target-aptamer complexes stimulating aggregation-induced emission therefore show great promise for environmental and biological process monitoring and disease diagnosis.

Hybridization of thiol-functionalized poly(phenylacetylene) with cadmium sulfide nanorods: improved miscibility and enhanced photoconductivity.

Molecules of a thiol-functionalized phenylacetylene derivative were assembled on the CdS nanorod surface and copolymerized with phenylacetylene, affording an inorganic semiconductor-conjugated polymer hybrid with excellent solubility and high photoconductivity.

Electric field induced cis-to-trans isomerization of polyphenylacetylene in solid state.

A field induced isomerization from cis to trans form in stereoregular cis-rich polyphenylacetylenes (PPAs) was found, and it provides an alternate method to control the order of chromophores in thin solid films.