Co-reporter:Ruoyao Zhang, Yuming Sun, Minggang Tian, Ge Zhang, Ruiqing Feng, Xuechen Li, Lifang Guo, Xiaoqiang Yu, Jing Zhi Sun, and Xiuquan He
Analytical Chemistry June 20, 2017 Volume 89(Issue 12) pp:6575-6575
Publication Date(Web):May 17, 2017
DOI:10.1021/acs.analchem.7b00710
In situ and directly imaging mitochondria in tissues instead of isolated cells can offer more native and accurate information. Particularly, in the clinical diagnose of mitochondrial diseases such as mitochondrial myopathy, it is a routine examination item to directly observe mitochondrial morphology and number in muscle tissues from patients. However, it is still a challenging task because the selectivity of available probes is inadequate for exclusively tissue imaging. Inspired by the chemical structure of amphiphilic phospholipids in mitochondrial inner membrane, we synthesized a phospholipid-biomimetic amphiphilic fluorescent probe (Mito-MOI) by modifying a C18-alkyl chain to the lipophilic side of carbazole-indolenine cation. Thus, the phospholipid-like Mito-MOI locates at mitochondrial inner membrane through electrostatic interaction between its cation and inner membrane negative charge. Simultaneously, the C18-alkyl chain, as the second targeting group, is deeply embedded into the hydrophobic region of inner membrane through hydrophobic interaction. Therefore, the dual targeting groups (cation and C18-alkyl chain) actually endow Mito-MOI with ultrahigh selectivity. As expected, high-resolution microscopic photos showed that Mito-MOI indeed stained mitochondrial inner membrane. Moreover, in situ and high-fidelity tissue imaging has been achieved, and particularly, four kinds of mitochondria and their crystal-like structure in muscle tissues were visualized clearly. Finally, the dynamic process of mitochondrial fission in living cells has been shown. The strategy employing dual targeting groups should have reference value for designing fluorescent probes with ultrahigh selectivity to various intracellular membranous components.
Co-reporter:Xiao Wang;Wenjie Wang;Yanmei Wang;Jing Zhi Sun;Ben Zhong Tang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 15) pp:2353-2362
Publication Date(Web):2017/04/11
DOI:10.1039/C6PY02246D
A conjugated alternative copolymer (P0), containing tetraphenylethylene (TPE) and phenylene-ethynylene (PE) units, was prepared by the Sonogashira coupling polymerization with high yield (96.8%). With the aid of activated ester on the PE unit, differently functionalized copolymers (P1 and P2) were derived from P0, and their structures were well characterized using multiple spectroscopic methods. Due to the incorporation of TPE units into the polymer structure, all of these copolymers (P0, P1 and P2) showed aggregation enhanced emission (AEE) properties as revealed by the fluorescence behaviors observed in THF/water and THF/hexane mixtures. As AEE-active polymers, they were investigated for use as fluorescent probes for explosive detection. Using picric acid (PA) as a model explosive, the Stern–Volmer curves showed a super-amplification effect for all these copolymers, and the largest fluorescence quenching constant (kSV) was calculated to be 56 100 M−1 for P1 in THF/water mixture with 90% water fraction. This value is comparable to that reported for TPE-containing hyperbranched polymers. By the reaction of the chiral primary amine with P0, the chiral dichroism (CD) signal was recorded for the derived copolymer P1 and the evident Cotton effect shifted to around 380 nm, indicating that the chirality was transferred from the side chain to the main chain. By the substitution of the hydrophobic activated ester with the highly hydrophilic poly(ethylene glycol) (PEG1000), the obtained copolymer P2 could be molecularly dispersed in water and gave a clear aqueous solution. The film casting from the P2 THF solution displayed a moderate hydrophilic surface static contact angle of 66.8°, which varied to 33.6° after immersion in THF/water mixture (1 : 1 by volume) for hours, and the microstructural morphology underwent a change from coarse spheres to microfibers, as suggested by scanning electron microscope (SEM) images.
Co-reporter:Xiaoying Gao;Guangxue Feng;Purnima Naresh Manghnani;Fang Hu;Nan Jiang;Jianzhao Liu;Bin Liu;Jing Zhi Sun;Ben Zhong Tang
Chemical Communications 2017 vol. 53(Issue 10) pp:1653-1656
Publication Date(Web):2017/01/31
DOI:10.1039/C6CC09307H
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.
Co-reporter:Rui Chen;Xiaoying Gao;Xiao Cheng;Anjun Qin;Jing Zhi Sun;Ben Zhong Tang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 40) pp:6277-6282
Publication Date(Web):2017/10/17
DOI:10.1039/C7PY01378G
We report the synthesis and properties of a cationic hyperbranched polymer containing tetraphenylethene (TPE) and pyridinium moieties. The polymerization was efficient under mild conditions (60 °C, 12 h) and the yield was as high as 92%. Due to the existence of the TPE moieties, the polymer exhibits an evident aggregation-enhanced emission (AEE) property, and the fluorescence quantum yield is 13.5% and 6.5% as a solid and in a dilute solution, respectively. The conjugation of TPE with the pyridinium moieties bestows the hyperbranched polymer with an extremely large Stokes shift of over 200 nm, and low susceptibility to external stimuli such as mechanical grinding in solid, solvent polarity in solution, and pH change in aqueous medium. The cationic characteristic gives the red-emitting polymer good membrane permeability, and the results of living cell stain experiments suggest that it may find applications as a stable fluorescent probe for bioimaging.
Co-reporter:Wenjie Wang;Yang Shi;Xiao Wang;Anjun Qin;Jing Zhi Sun;Ben Zhong Tang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 17) pp:2630-2639
Publication Date(Web):2017/04/27
DOI:10.1039/C7PY00109F
We report a new synthetic strategy to derive functional poly(disubstituted acetylenes) (PDSAs) through “phenol–yne click reaction”. The phenol-containing PDSA was prepared by the polymerization of the triisopropylsilane (TIPS)-protected 4-((4-fluorophenyl)ethynyl)phenol monomer and by a subsequent de-protection step. Then, different functional groups (e.g., ester and amide) were grafted onto the PDSA side chains via the highly efficient “phenol–yne click reaction”. The post-polymerization modification was carried out under mild conditions (at 40 °C, in common solvent) under an air atmosphere for a short time (4 h). The structures of the products were well characterized by GPC, NMR, and FTIR techniques and satisfactory data were collected. The data indicated that the phenol groups on the precursor PDSA were highly active to react with activated acetylenic compounds bearing functional groups intolerable to direct polymerization. This is the first example of the preparation of phenol-containing PDSA and the use of it as a precursor to prepare functional PDSAs. Besides the activated ester, thiol–ene click reaction, Michael addition reaction and Cu(I) catalysed alkyne–azide click reaction, we added a new tool in the tool-box for the synthesis of functional polymers.
Co-reporter:Jiaqi Tong;Ting Hu;Anjun Qin;Jing Zhi Sun;Ben Zhong Tang
Faraday Discussions 2017 (Volume 196) pp:285-303
Publication Date(Web):2017/02/20
DOI:10.1039/C6FD00165C
The binding behaviours of a transport protein, bovine serum albumin (BSA), in its native, unfolding and refolding states have been probed by monitoring the emission changes of two exogenous AIE-active fluorescent probes, M2 and M3, which are designed to be anionic and cationic, respectively. Due to their AIE properties, both M2 and M3 display emission enhancement when bound to the hydrophobic cavity of BSA. The binding site of M2 and M3 is found to be subdomain IIA. Then, the BSA + M2 and BSA + M3 systems are utilized to fluorescently signal the conformation changes of BSA caused by various external stimuli, including thermally or chemically induced denaturation. The data confirmed the multi-step unfolding process and the existence of a molten-globule intermediate state. The unfolding process consists of the rearrangement of subdomain IIA, the exposure of a negatively charged binding site in domain I that prefers interacting with cationic species, and the transformation of the molten-globule intermediate into the final random coil. The anionic and cationic modifications of the probes enable us to observe that electrostatic interactions play a role in the folding and unfolding of BSA.
Co-reporter:Yanmei Wang;Wenjie Wang;Xiao Wang;Xiao Cheng;Anjun Qin;Jing Zhi Sun;Ben Zhong Tang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 36) pp:5546-5553
Publication Date(Web):2017/09/19
DOI:10.1039/C7PY01110E
We report the synthesis of a poly(1-chloro-2-phenylacetylene) derivative with an electron-withdrawing substituent on the phenyl group. A combination of an N-heterocyclic carbene-based Pd catalyst (NHC-Pd) with silver trifluoromethyl sulfonate (AgOTf) formed an active catalytic system for the polymerization of 1-chloro-2-(para-substituted)-phenylacetylenes. Based on this active catalytic system, functional poly(di-substituted acetylene) (PDSA) bearing an aldehyde group (P3) was obtained in high yield. The exceptional P3 bearing a reactive aldehyde group on its side chain was used as a precursor to be subsequently modified with amines to generate a novel PDSA (P3-ppm) possessing Schiff-base functionalities in good yield.
Co-reporter:Zhaoyang Wang, Wei Bai, Jiaqi Tong, Yi Jia Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2016 vol. 52(Issue 68) pp:10365-10368
Publication Date(Web):19 Jul 2016
DOI:10.1039/C6CC02851A
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.
Co-reporter:Xiao Wang, Yuan Gao, Wenjie Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Polymer Chemistry 2016 vol. 7(Issue 33) pp:5312-5321
Publication Date(Web):27 Jul 2016
DOI:10.1039/C6PY01175F
A series of poly(diphenyl substituted acetylenes) (PDSAs) were prepared through a post-polymerization modification strategy. Primary amine, tertiary amine and quaternized ammonium functionalities were successfully and efficiently attached onto the skeleton of poly(1,2-diphenylacetylene) via the precursor PDSA (P0) with activated ester moieties. The structures of the derived amine-functionalized PDSAs, the modification processes and the efficiency of the post-polymerization modification were characterized by multiple spectroscopic techniques. With the aid of the protection and de-protection of tert-butyloxyl carbonyl (P1), PDSA bearing terminal primary amine groups (P2) were obtained. The plentiful amine groups on the side-chains helped in grafting P2 onto graphene oxide (GO) and the resultant hybrids not only showed a greatly improved dispersing ability in organic solvents, but also emitted strong yellow-greenish fluorescence. The polymer bearing tertiary amine functionalities on side chains (P3) could be directly derived from reacting P0 with 3-N,N′-dimethyl-1-propylamine under mild conditions and in high yield. P3 showed evident pH-dependent fluorescence emission behaviour. Based on P3, cationic PDSA P4 was readily obtained by the transition of tertiary amine to quaternized ammonium functionalities. This transition afforded a novel fluorescent and polyelectrolytic PDSA. P4 was tried as a water soluble fluorescent probe in calf thymus DNA (ct-DNA) detection. The experimental data indicated that P4 at a low concentration of 0.1 ppm can respond to the existence of 10−11 g L−1ct-DNA in aqueous solution. The working mechanism was associated with the aggregation-induced emission enhancement. The present work, together with our previous reports, suggests that the PDSA with an activated ester precursor can be employed as a broad platform to construct different functional PDSAs.
Co-reporter:Huanting Huang, Yin Liao, Weifeng Bu, Wenjie Wang and Jing Zhi Sun
Soft Matter 2016 vol. 12(Issue 22) pp:5011-5021
Publication Date(Web):26 Apr 2016
DOI:10.1039/C6SM00259E
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.
Co-reporter:Yi Jia Wang, Lei Lin, Xing Zhang, Victor Schultz, Fuming Zhang, Jing Zhi Sun, Robert J. Linhardt
Analytical Biochemistry 2016 Volume 514() pp:48-54
Publication Date(Web):1 December 2016
DOI:10.1016/j.ab.2016.09.007
Abstract
A positively charged tetraphenylethene (TPE) derivative, TPE-4MN, was synthesized as a probe for heparin based on aggregation induced emission. On the addition of 5.0 μg/mL of heparin, TPE-4MN showed an enhanced emission of about 10-fold. The change in fluorescence at 475 nm was linear over a range of heparin concentrations of 0–1.0 μg/mL with an R = 0.99988 and the limit of detection (LOD) was calculated to be 0.75 μg/mL. The mechanism of the detection was proven to be through an ion pairing interaction. TPE-4MN showed good selectivity for heparin over other types of polysaccharides and could easily distinguish heparin from heparan sulfate, a glycosaminoglycan having a similar structure to that of heparin.
Co-reporter:Yi Jia Wang;Yang Shi;Zhaoyang Wang;Zhenfeng Zhu;Xinyuan Zhao;Han Nie; Jun Qian; Anjun Qin; Jing Zhi Sun; Ben Zhong Tang
Chemistry - A European Journal 2016 Volume 22( Issue 28) pp:9784-9791
Publication Date(Web):
DOI:10.1002/chem.201600125
Abstract
A tetraphenylethene (TPE) derivative modified with the strong electron acceptor 2-dicyano-methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) was obtained in high yield by a simple two-step reaction. The resultant TPE-TCF showed evident aggregation-induced emission (AIE) features and pronounced solvatochromic behavior. Changing the solvent from apolar cyclohexane to highly polar acetonitrile, the emission peak shifted from 560 to 680 nm (120 nm redshift). In an acetonitrile solution and in the solid powder, the Stokes shifts are as large as 230 and 190 nm, respectively. The solid film emits red to near-IR (red-NIR) fluorescence with an emission peak at 670 nm and a quantum efficiency of 24.8 %. Taking the advantages of red-NIR emission and high efficiency, nanoparticles (NPs) of TPE-TCF were fabricated by using tat-modified 1,2-distearoylsn-glycero-3-phosphor-ethanol-amine-N-[methoxy-(polyethyl-eneglycol)-2000] as the encapsulation matrix. The obtained NPs showed perfect membrane penetrability and high fluorescent imaging quality of cell cytoplasm. Upon co-incubation with 4,6-diamidino-2-phenylindole (DAPI) in the presence of tritons, the capsulated TPE-TCF nanoparticles could enter into the nucleus and displayed similar staining properties to those of DAPI.
Co-reporter:Yi Jia Wang, Zeyu Li, Jiaqi Tong, Xiao Yuan Shen, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2015 vol. 3(Issue 15) pp:3559-3568
Publication Date(Web):26 Feb 2015
DOI:10.1039/C4TC02550D
Two tetraphenylethene (TPE) modified perylenebisimides (PBIs) were synthesized through linking the TPE moieties to the PBI core at the imide positions. Theoretical calculations predict that, in both of the mono-TPE and di-TPE substituted derivatives (i.e. TPE-N-PBI and DTPE-N-PBI), the TPE and PBI units are orthogonal to each other, and thus have no electronic conjugation. Thus the two compounds are TPE–PBI dyads rather than TPE–PBI conjugates. This property is supported by absorption and emission spectral features. In solution, aggregate and solid film, the fluorescence from both TPE and PBI subunits is evidently quenched. The underlying mechanism is the photo-induced charge transfer between the electron donor TPE and electron acceptor PBI subunits. In a highly polar tetrahydrofuran–water mixture with a large fraction of water, TPE-N-PBI can form H-aggregates. In low polar hydrophobic dichloromethane–hexane mixtures, due to the bulky size and rigidity of the TPE subunit, the dyad molecules cannot take a parallel alignment to form classical J- or H-aggregates, but have to exist in a large offset angle. Consequently, X-aggregates are formed, which was confirmed by the absorption features, morphological observations and comparative investigation of the reference compound.
Co-reporter:Ting Hu, Bicheng Yao, Xiujuan Chen, Weizhang Li, Zhegang Song, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2015 vol. 51(Issue 42) pp:8849-8852
Publication Date(Web):16 Apr 2015
DOI:10.1039/C5CC02138C
A pyridinium modified tetraphenylethene-based salt shows aggregation-induced emission enhancement properties and irreversible mechanochromic behaviours.
Co-reporter:Wei Bai, Zhaoyang Wang, Jiaqi Tong, Ju Mei, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2015 vol. 51(Issue 6) pp:1089-1091
Publication Date(Web):24 Nov 2014
DOI:10.1039/C4CC06510G
Dibenzo[24]crown-8 (host) and benzylamine (guest) modified tetraphenylethenes are prepared and used to construct supramolecular polymers, which demonstrate the merits of reversible assembling–disassembling and tunable aggregation-induced emission by acid–base treatments.
Co-reporter:Xiao Wang, Han Hu, Wenjie Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Polymer Chemistry 2015 vol. 6(Issue 46) pp:7958-7963
Publication Date(Web):22 Sep 2015
DOI:10.1039/C5PY01408E
We report synthetic routes to functional poly(disubstituted acetylenes) (PDSAs) through the combination of the activated ester strategy and Cu(I) catalyzed azide–alkyne cycloaddition (CuAAC) reaction. Direct polymerization of a disubstituted acetylene monomer with an end-alkyne group under the catalysis of WCl6-Ph4Sn led to the poly(monosubstituted acetylene) by-product (P1) but not the expected PDSA bearing end-alkyne groups. Protection of the end-alkyne group could lead to the expected product but this route has low efficiency. Using the activated ester functionalized PDSA as a precursor (P0) and propargylamine as the modifier, the end-alkyne groups were easily attached onto the side chains of PDSA (P2). Based on the intermediate, the functional group could be efficiently modified onto the intermediate by reacting with azide containing reagents (using benzyl azide as a model) through the CuAAC click reaction, and finally the triazole functionalized PDSA (P3) was derived. The combination of the activated ester and the CuAAC click reaction strategy bestows the synthetic route with the advantages of high efficiency, mild reaction conditions and potentially plentiful functionalities (due to the versatile azide reagents).
Co-reporter:Yuan Gao;Xiao Wang;Jing Zhi Sun;Ben Zhong Tang
The Chemical Record 2015 Volume 15( Issue 2) pp:524-532
Publication Date(Web):
DOI:10.1002/tcr.201402064
Abstract
We report the recent progress in the preparation of functional poly(disubstituted acetylene)s (PDSAs) through post-polymerization modification routes. The metathesis polymerization of disubstituted acetylene monomers activated by Mo/W–Sn complex catalysts, which do not tolerate highly polar functionalities, was assumed to be a key step in the polymer synthetic procedures. We and other groups have explored several approaches to prepare PDSAs with latent reactive functionalities, which are inactive to Mo/W–Sn complex catalysts but can be used as highly reactive sites for post-polymerization modification. Click chemistry, Michael-type addition reactions, the use of activated esters and other strategies are demonstrated by recently published examples. These works indicate that post-polymerization modification is an efficient route to the synthesis of various functional PDSAs.
Co-reporter:Jiaqi Tong
The Journal of Physical Chemistry C 2015 Volume 119(Issue 38) pp:21875-21881
Publication Date(Web):September 2, 2015
DOI:10.1021/acs.jpcc.5b06088
Co-reporter:Xiao Yuan Shen, Yi Jia Wang, Haoke Zhang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2014 vol. 50(Issue 63) pp:8747-8750
Publication Date(Web):10 Jun 2014
DOI:10.1039/C4CC03024A
Diketopyrrolopyrrole (ACQ-gen) and tetraphenylethenes (AIE-gen) are linked together with phenyl bridges. The derivatives show substantially enhanced and red-shifted emission in the solid state.
Co-reporter:Xiao Wang, Yuan Gao, Hui Zhao, Xiao-Qing Liu, Zhengke Wang, Anjun Qin, Qiaoling Hu, Jing Zhi Sun and Ben Zhong Tang
Polymer Chemistry 2014 vol. 5(Issue 21) pp:6216-6224
Publication Date(Web):04 Jul 2014
DOI:10.1039/C4PY00809J
Monosaccharide-functionalized poly(phenylacetylenes) (PPAs) are synthesized with high yield and molecular weight, but it shows no solvating power to multiwalled carbon nanotubes (MWCNTs) by simply blending them together. Polymerization of monosaccharide-functionalized monomers in the presence of MWCNTs (in situ polymerization) leads to the hybrids of monosaccharide-functionalized PPAs/MWCNTs, and the content of MWCNTs is over 2% by weight. The characterization data indicates that the π–π interaction between the styrene-like moieties in the polymer backbone and the MWCNTs plays crucial role in the dispersing capacity. Based on the in situ precipitation method, CS rods containing monosaccharide-functionalized PPAs/MWCNTs hybrids were fabricated. The bending strength and modulus of the hybrid-reinforced CS rods showed substantial improvement in comparison with the CS rods made from pristine and hydroxyapatite-reinforced CS.
Co-reporter:Yuan Gao, Xiao Wang, Li Tong, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Polymer Chemistry 2014 vol. 5(Issue 7) pp:2309-2319
Publication Date(Web):25 Nov 2013
DOI:10.1039/C3PY01164J
Two disubstituted acetylenes bearing a vinyl group at one end (M1 and M2) were synthesized and polymerized by WCl6–Ph4Sn catalyst. The expected poly(disubstituted acetylenes) PDSAs (P1 and P2) were obtained in high yields. Both P1 and P2 have reactive vinyl groups on their side chains, thus they were used as precursors to be subsequently modified with a mercapto compound through the thiol–ene click reaction to produce the novel PDSAs (P1S and P2S) in good yield. The chemical structures of the polymers were carefully characterized by standard spectroscopic methods such as gel permeation chromatography (GPC), NMR, NMR and FTIR techniques, and satisfactory data were collected. The post-polymerization modification of P1 took a long reaction time (3 days) to convert P1 to P1S because the ene-functionality at the end of side chain of P1 links to a saturated alkyl segment. By using an activated ene-functionality (a,ß-unsaturated vinyl), the modification of P2 to P2S took only 1 day under mild conditions. Moreover, the activated end-ene group allowed the post-polymerization modification of P2 by Michael addition, which was confirmed using butylamine as the representative amine compound and the characterization data indicated the validity of the expected P2N. The thermal analysis results indicated that the modified polymers were highly stable thermally with a decomposition temperature over at least 240 °C, except for P2N, which showed lower stability due to unstable imine groups. Meanwhile, it was found that the modified polymers P1S and P2S were fluorescent and showed similar emission efficiency to their precursors P1 and P2. These results indicated that the thiol–ene click reaction and Michael addition reaction are accessible routes for post-polymerization modification to generate novel functional PDSAs.
Co-reporter:Minggang Tian, Fuqiang Guo, Yuming Sun, Weijia Zhang, Fang Miao, Yong Liu, Guofen Song, Cheuk-Lam Ho, Xiaoqiang Yu, Jing Zhi Sun and Wai-Yeung Wong
Organic & Biomolecular Chemistry 2014 vol. 12(Issue 32) pp:6128-6133
Publication Date(Web):03 Jul 2014
DOI:10.1039/C4OB00382A
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 (30–200 μM) due to its high intracellular concentration (1–10 mM). In this work, an off–on 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 30–200 μM cysteine over 1–10 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.
Co-reporter:Yong Liu, Weijia Zhang, Yuming Sun, Guofen Song, Fang Miao, Fuqiang Guo, Minggang Tian, Xiaoqiang Yu, Jing Zhi Sun
Dyes and Pigments 2014 Volume 103() pp:191-201
Publication Date(Web):April 2014
DOI:10.1016/j.dyepig.2013.12.005
•Two low molecular weight ribonucleic acid probes were designed and synthesized.•Both displayed better photostability than the commercially available probe.•Both possessed large two-photon fluorescence action absorption cross-sections.•Both can achieve one- and two-photon image of ribonucleic acid in living cells.Two low molecular weight, indole-based, mono-cationic probes, were designed and synthesized. According to their spectral response to ribonucleic acid in vitro and direct fluorescence imaging in living cell lines, the two compounds were identified as ribonucleic acid-selective fluorescent turn-on probes with large two-photon excited fluorescence action absorption cross-sections when binding to ribonucleic acid. Moreover, both dyes with good membrane permeability have been successfully used to image ribonucleic acid in nucleoli and cytoplasm in living cells by confocal and two-photon fluorescence microscopy. Furthermore, the dyes possess good counterstain compatibility with Hoechst 33342, important deoxyribonucleic acid-staining dyes for ribonucleic acid–deoxyribonucleic acid colocalization.
Co-reporter:Jiaqi Tong;Yijia Wang;Dr. Ju Mei;Dr. Jian Wang; Anjun Qin; Jing Zhi Sun; Ben Zhong Tang
Chemistry - A European Journal 2014 Volume 20( Issue 16) pp:4661-4670
Publication Date(Web):
DOI:10.1002/chem.201304174
Abstract
A tetraphenylethene (TPE) derivative substituted with the electron-acceptor 1,3-indandione (IND) group was designed and prepared. The targeted IND-TPE reserves the intrinsic aggregation-induced emission (AIE) property of the TPE moiety. Meanwhile, owing to the decorated IND moiety, IND-TPE demonstrates intramolecular charge-transfer process and pronounced solvatochromic behavior. When the solvent is changed from apolar toluene to highly polar acetonitrile, the emission peak redshifts from 543 to 597 nm. IND-TPE solid samples show an evident mechanochromic process. Grinding of the as-prepared powder sample induces a redshift of emission from green (peak at 515 nm) to orange (peak at 570 nm). The mechanochromic process is reversible in multiple grinding–thermal annealing and grinding–solvent-fuming cycles, and the emission of the solid sample switches between orange (ground) and yellow (thermal/solvent-fuming-treated) colors. The mechanochromism is ascribed to the phase transition between amorphous and crystalline states. IND-TPE undergoes a hydrolysis reaction in basic aqueous solution, thus the red-orange emission can be quenched by OH− or other species that can induce the generation of sufficient OH−. Accordingly, IND-TPE has been used to discriminatively detect arginine and lysine from other amino acids, due to their basic nature. The experimental data are satisfactory. Moreover, the hydrolyzation product of IND-TPE is weakly emissive in the resultant mixture but becomes highly blue-emissive after the illumination for a period by UV light. Thus IND-TPE can be used as a dual-responsive fluorescent probe, which may extend the application of TPE-based molecular probes in chemical and biological categories.
Co-reporter:Xiujuan Chen, Xiao Yuan Shen, Erjia Guan, Yi Liu, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2013 vol. 49(Issue 15) pp:1503-1505
Publication Date(Web):04 Jan 2013
DOI:10.1039/C2CC38246F
A pyridinyl-functionalized tetraphenylethene (Py-TPE) was synthesized and it demonstrated colorimetric and ratiometric fluorescent responses to trivalent metal cations (M3+, M = Cr, Fe, Al) over a variety of mono- and divalent metal cations.
Co-reporter:Jing Zhi Sun, Anjun Qin and Ben Zhong Tang
Polymer Chemistry 2013 vol. 4(Issue 2) pp:211-223
Publication Date(Web):14 Aug 2012
DOI:10.1039/C2PY20469J
Functional polyacetylenes (PAs) have attracted great interest and a series of tutorial reviews dealing with the recent progress in the related fields can be found in the literature. The investigation of the hybrids of functional PAs and inorganic nanostructures is a newly asserted and developing area. In this review, we summarise the related works on the hybrids of functional PAs and carbon nanotubes (CNTs) reported in the last decade. The effects of the structural parameters such as the polymer mainchain, functional pendants and the linker between them on the solvating power towards CNTs are explored step-by-step. Concerning the mechanisms of dispersing CNTs into solvents, a novel factor, or donor–acceptor interaction, has been singled out, thus providing a novel concept to design functional polymers for the fabrication of CNT-based processable hybrids. The strong solvating power of properly designed functional PAs facilitates the non-harmful surface functionalization of CNTs and permits using the hybrids of PAs/CNTs as templates to derive multi-component nanocomposites. Different nanostructures including Ag nanoparticles, ZnO nanocrystallites, CdS nanorods and γ-Fe3O4 nanoparticles are successfully incorporated into the functional PAs/CNTs hybrid systems, which show efficient charge transfer, charge carrier transport, enhanced solvatochromism, and superparamagnetic properties. Rationally functionalized PAs demonstrate good biocompatibility and their hybrids with CNTs can be used as active additives to reinforce the bending strength and modulus of chitosan rods. Finally, a brief outlook of the promising directions in this promising research area is contributed.
Co-reporter:Fuqiang Guo, Minggang Tian, Fang Miao, Weijia Zhang, Guofen Song, Yong Liu, Xiaoqiang Yu, Jing Zhi Sun and Wai-Yeung Wong
Organic & Biomolecular Chemistry 2013 vol. 11(Issue 44) pp:7721-7728
Publication Date(Web):05 Sep 2013
DOI:10.1039/C3OB41414K
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.
Co-reporter:Shuang Zhang, Ji-Ming Yan, An-Jun Qin, Jing-Zhi Sun, Ben-Zhong Tang
Chinese Chemical Letters 2013 Volume 24(Issue 8) pp:668-672
Publication Date(Web):August 2013
DOI:10.1016/j.cclet.2013.05.014
Cu(II) detection is important because it plays crucial role in several biological processes and ecological systems. Fluorescent techniques have attracted more and more attention in Cu(II) detection. In this report, we contribute a novel strategy to use fluorescence spectroscopy for Cu(II) specific detection. The specificity relies on the fact that, of the many metal cations, only Cu(II) can catalyze the hydrolyzation of α-amino acid ester. The novelty originates from the unique aggregation-induced emission (AIE) property of the fluorescent label. We designed a model α-amino acid ester (TPE-Ala) constructed with alanine and tetraphenylethene-functionalized methanol (TPE-methanol). In comparison with the precursor TPE-Ala, TPE-methanol has lower solubility and is easy to form aggregates in water, thereby displaying a higher fluorescent response. Thus, the Cu(II) catalyzed hydrolyzation can be monitored by recording the fluorescence enhancement and fluorescent detection Cu(II) is rationally achieved.Within a series of metal cations, only Cu(II) can catalyze the hydrolyzation of tetraphenylethene-modified alanine ester. The released TPE-methanol exhibits lower solubility and higher fluorescence intensity than the ester, which allows Cu(II) to be detected by fluorescence enhancement.
Co-reporter:Ju Mei;Yijia Wang;Jiaqi Tong;Jian Wang;Dr. Anjun Qin;Dr. Jing Zhi Sun;Dr. Ben Zhong Tang
Chemistry - A European Journal 2013 Volume 19( Issue 2) pp:613-620
Publication Date(Web):
DOI:10.1002/chem.201202969
Abstract
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.
Co-reporter:Shuang Zhang;JiMing Yan;AnJun Qin;Ben Zhong Tang
Science China Chemistry 2013 Volume 56( Issue 9) pp:1253-1257
Publication Date(Web):2013 September
DOI:10.1007/s11426-013-4932-7
We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain’s dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.
Co-reporter:Xiao Yuan Shen, Yi Jia Wang, Engui Zhao, Wang Zhang Yuan, Yi Liu, Ping Lu, Anjun Qin, Yuguang Ma, Jing Zhi Sun, and Ben Zhong Tang
The Journal of Physical Chemistry C 2013 Volume 117(Issue 14) pp:7334-7347
Publication Date(Web):March 19, 2013
DOI:10.1021/jp311360p
Luminescent materials with aggregation-induced emission (AIE) property have attracted considerable interests for their promising applications in light-emitting and display devices and fluorescent probes for chemo- and biosensors. Tetraphenylethene (TPE) derivatives are the most attractive species for their notable AIE performance, facile synthesis, and flexible structure modification. To study the effects of donor and acceptor substitutions and extend the applications of TPE-based materials, three TPE kindred, TTPE, BTPEFN, and BATPEFN, are employed. TTPE film displays efficient green fluorescence (λem = 494 nm, ΦF = 100%), evident AIE characteristic (αAIE = 154), and reversible mechanochromism by grinding-fuming: from blue (λem = 472 nm) to green emission (λem = 505 nm). Replacing two phenyls by two cyano (A) groups on the central TPE moiety derives BTPEFN, whose film shows efficient orange fluorescence (λem = 575 nm, ΦF = 100%) and evident AIE (αAIE = 13). The mechanochromic behavior of BTPEFN (from yellow to orange emission, λem from 541 to 563 nm) is reversible by repeating both the grinding-fuming and grinding-annealing processes. The cyano groups bestow BTPEFN with evident intramolecular charge transfer (ICT) property, the emission color can be tuned from green to red-orange by changing solvent from hexane to THF, while the emission of TTPE shows much less response to solvent polarity. Cyanos also endow BTPEFN with better self-assemble ability in proper conditions, and the obtained regular microribbons emit bright green fluorescence. Further decoration of BTPEFN with N,N-diethyamino (D) groups results in BATPEFN. Due to the cooperative effects of D and A groups, BATPEFN shows dramatic red-shifted fluorescence (λem = 713 nm), evident ICT process, and enhanced solvatochromism (from red to infrared).
Co-reporter:Jian Wang ; Ju Mei ; Rongrong Hu ; Jing Zhi Sun ; Anjun Qin ;Ben Zhong Tang
Journal of the American Chemical Society 2012 Volume 134(Issue 24) pp:9956-9966
Publication Date(Web):May 18, 2012
DOI:10.1021/ja208883h
It has been difficult to decipher the mechanistic issue whether E/Z isomerization is involved in the aggregation-induced emission (AIE) process of a tetraphenylethene (TPE) derivative, due to the difficulty in the synthesis of its pure E and Z conformers. In this work, pure stereoisomers of a TPE derivative named 1,2-bis{4-[1-(6-phenoxyhexyl)-4-(1,2,3-triazol)yl]phenyl}-1,2-diphenylethene (BPHTATPE) are successfully synthesized. Both isomers show remarkable AIE effect (αAIE ≥ 322) and high fluorescence quantum yield in the solid state (ΦF 100%). The conformers readily undergo E/Z isomerization upon exposure to a powerful UV light and treatment at a high temperature (>200 °C). Such conformational change, however, is not observed under normal fluorescence spectrum measurement conditions, excluding the involvement of the E/Z isomerization in the AIE process of the TPE-based luminogen. The molecules of (E)-BPHTATPE self-organize into ordered one-dimensional nanostructures such as microfibers and nanorods that show obvious optical waveguide effect. BPHTATPE shows rich chromic effects, including mechano-, piezo-, thermo-, vapo-, and chronochromisms. Its emission peak is bathochromically shifted by simple grinding and pressurization and the spectral change is reversed by fuming with a polar solvent, heating at a high temperature, or storing at room temperature for some time. The multiple chromic processes are all associated with changes in the modes of molecular packing.
Co-reporter:Qiuli Zhao, Shuang Zhang, Yi Liu, Ju Mei, Sijie Chen, Ping Lu, Anjun Qin, Yuguang Ma, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 vol. 22(Issue 15) pp:7387-7394
Publication Date(Web):08 Mar 2012
DOI:10.1039/C2JM16613E
Perylene bisimides (PBIs) are one class of the most explored organic fluorescent materials due to their high fluorescence quantum efficiency, electron transport behaviour, and ready to form well-tailored supramolecular structures. However, they suffer from heavy aggregation-caused quenching (ACQ) effect which has greatly limited their potential applications. We successfully tackle this problem by chemical modification of the PBI core with two tetraphenylethene (TPE) moieties at the bay positions. This modification resulted in a pronounced fluorescence red-shift (over 120 nm) and rendered the derivatives (1,6-/1,7-DTPEPBI) with evident aggregation-induced emission (AIE) behaviour. Both 1,6-DTPEPBI and 1,7-DTPEPBI emit bright red fluorescence in the solid state. The fluorescence quantum efficiency of the aggregates of 1,7-DTPEPBI (ΦF, solid = 29.7%, formed in a hexane/dichloromethane mixture, fh = 90%) is about 424 times higher than that in dichloromethane solution (ΦF, solut = 0.07%). Electrochemical investigation results indicated that 1,7-DTPEPBI sustained the intrinsic n-type semiconductivity of PBI moiety. In addition, morphological inspection demonstrated that 1,7-DTPEPBI molecules easily form well-organized microstructures despite the linkage of the PBI core with bulky TPE moieties.
Co-reporter:J. Mei, J. Wang, A. Qin, H. Zhao, W. Yuan, Z. Zhao, H. H. Y. Sung, C. Deng, S. Zhang, I. D. Williams, J. Z. Sun and B. Z. Tang
Journal of Materials Chemistry A 2012 vol. 22(Issue 10) pp:4290-4298
Publication Date(Web):23 Sep 2011
DOI:10.1039/C1JM12673C
Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch between different solid states, and a typical mechanofluorochromism was observed by cyclic operation of the grinding–heating–cooling processes. In addition, two single crystals (O and R) were successfully obtained in proper conditions, and the crystallographic data indicated that crystal O and R had reasonable hollow structures, inside which different solvent molecules were selectively encapsulated. More importantly, we have presented a proof-of-concept example of the strategy for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability. This design strategy is instructive to design and construct organic soft porous crystals with other conjugated building blocks and develop novel smart and stimuli-responsive photo/electronic materials.
Co-reporter:Ju Mei, Jiaqi Tong, Jian Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 vol. 22(Issue 33) pp:17063-17070
Publication Date(Web):03 Jul 2012
DOI:10.1039/C2JM32892E
A novel fluorescence probe capable of discriminatively and simultaneously detecting Cys, Hcy and GSH has been developed. This specially designed probe can selectively react with Cys and Hcy to form thiazinane and thiazolidine derivatives in the presence of diverse amino acids, protected Cys and glucose and display the expected aggregation-induced emission (AIE) properties. Relying on the differences in kinetics, Cys can be easily and discriminately detected over Hcy by the observation of FL responses. GSH shows great interference with the detection of Cys and Hcy and it can be quantitatively detected by the FL spectroscopic titration method. The threshold of the FL turn-off concentration for GSH is measured to be 1 mM. This is the first report of using a single fluorescent probe to discriminately detect Cys, Hcy and GSH by FL turn-on and turn-off strategies. The discrimination relies on the reaction-dependent fluorophore aggregation, or the solubility of adducts of the probe molecule and analytes. The present strategy is intrinsically a fluorescent titration, which combines the high sensitivity of FL spectroscopy and the reliability of precipitate titration methodology. The threshold concentration of Cys (375 μM, at which the FL is turned-on) coincides with the upper margin of the deficient Cys levels in human plasma, and the primary investigation of the FL response to deproteinized human plasma indicates that this FL probe is a promising one for the discriminatory detection of Cys over Hcy and GSH on a clinical level.
Co-reporter:Qiuli Zhao, Kai Li, Sijie Chen, Anjun Qin, Dan Ding, Shuang Zhang, Yi Liu, Bin Liu, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 vol. 22(Issue 30) pp:15128-15135
Publication Date(Web):28 May 2012
DOI:10.1039/C2JM31368E
Organic fluorescent probes are widely used in bioimaging and bioassays, but the notorious photobleaching hampers their applications. Encapsulation of organic dyes into nanoparticles (NPs) is an effective strategy to minimize photobleaching, but classical organic dye molecules tend to have their fluorescence quenched in aggregate states, which is termed aggregation-caused quenching (ACQ). Here we demonstrate our attempt to tackle this problem through the aggregation-induced emission (AIE) strategy. 3,4:9,10-Tetracarboxylic perylene bisimide (PBI) is a well-known organic dye with a serious ACQ problem. By attaching two tetraphenylethene (TPE) moieties to the 1,7-positions, the ACQ-characteristic PBI-derivative was converted to an AIE-characteristic molecule. The obtained PBI derivative (BTPEPBI) exhibits several advantages over classical PBI derivatives, including pronounced fluorescence enhancement in aggregate state, red to near infrared emission, and facile fabrication into uniform NPs. Studies on the staining of MCF-7 breast cancer cells and in vivo imaging of a tumor-bearing mouse model with BTPEPBI-containing NPs reveal that they are effective fluorescent probes for cancer cell and in vivo tumor diagnosis with high specificity, high photostability and good fluorescence contrast.
Co-reporter:Qiuli Zhao, Xiao A Zhang, Qiang Wei, Jian Wang, Xiao Yuan Shen, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2012 vol. 48(Issue 95) pp:11671-11673
Publication Date(Web):09 Oct 2012
DOI:10.1039/C2CC36060H
Perylene bisimide derivatives substituted with one and two tetraphenylethene moieties at 1 and 1,7-postions show distinct optical properties. The former displays characteristic emission features of perylene bisimides in solution and red emission in the aggregate state, while the latter is nonemissive in solution but highly red-emissive in the aggregate state.
Co-reporter:Zhiguang Yang, Ning Zhao, Yuming Sun, Fang Miao, Yong Liu, Xin Liu, Yuanhong Zhang, Wentao Ai, Guofen Song, Xiaoyuan Shen, Xiaoqiang Yu, Jingzhi Sun and Wai-Yeung Wong
Chemical Communications 2012 vol. 48(Issue 28) pp:3442-3444
Publication Date(Web):14 Feb 2012
DOI:10.1039/C2CC00093H
Two highly selective two-photon fluorescent probes for cysteine over homocysteine, N-acetyl-L-cysteine, dithiothreitol, glutathione and other amino acids, and their fluorescent imaging in living cells have been shown.
Co-reporter:Xiao A Zhang, Anjun Qin, Li Tong, Hui Zhao, Qiuli Zhao, Jing Zhi Sun, and Ben Zhong Tang
ACS Macro Letters 2012 Volume 1(Issue 1) pp:75
Publication Date(Web):November 16, 2011
DOI:10.1021/mz200024a
We demonstrate a facile synthetic route to functional disubstituted polyacetylenes bearing highly polar groups based on polymer reactions. A pentafluorophenyl (PFP) ester-containing diphenylacetylene was designed and polymerized to obtain PFP activated ester-functionalized disubstituted polyacetylene (P1). P1 was used as a parent polymer to further react separately with diverse amines, giving rise to a series of functional disubstituted polyacetylenes with a chiral moiety and hydroxyl and carboxyl groups in high yields under mild condition. Spectral characterization data indicated that the polymers’ structures were well consistent with the expected results. The helicity and emission property of polymers were also studied.
Co-reporter:Jian Wang, Ju Mei, Engui Zhao, Zhegang Song, Anjun Qin, Jing Zhi Sun, and Ben Zhong Tang
Macromolecules 2012 Volume 45(Issue 19) pp:7692-7703
Publication Date(Web):September 24, 2012
DOI:10.1021/ma3017037
Cu(I)-catalyzed azide–alkyne click polymerization, developed based on the click reaction, has become a powerful tool for the construction of functional polytriazoles with linear and hyperbranched structures. This method has, however, rarely been used for the preparation of functional hyperbranched conjugated polytriazoles (hb-CPTA). In this paper, soluble ethynyl-capped hb-CPTA with weight-averaged molecular weight of 39 500 was synthesized in high yield (84.4%) by the Cu(I)-catalyzed azide–alkyne click polymerization of tetraphenylethene containing diazide [1,2-bis(4-azidophenyl)-1,2-diphenylethene] and tetrayne [1,1,2,2-tetrakis(4-ethynylphenyl)ethane] in equal concentration. By taking advantage of the ethynyl groups on its periphery, the polymer could be efficiently postfunctionalized by azide–alkyne and thiol–yne click reactions. The polymers are thermally stable and loss 5% of their weights at temperatures higher than 340.0 °C. hb-CPTA also possesses high char yield (74.8%) at 800 °C. The polymers feature the unique characteristics of aggregation-enhanced emission. Furthermore, the PL intensities of the hb-CPTA and thiol–yne postfunctionalized polytriazoles increase linearly with water fraction in THF/water mixtures. Thanks to their rigid structures, the polymers could be fabricated into unimolecular nanoparticles with sizes of ca. 100 nm. Thus, this paper provides a powerful method to synthesize soluble ethynyl-capped hyperbranched polymers, which could be a useful platform for preparation of versatile functional polymers via postreactions.
Co-reporter:Xiao Yuan Shen, Wang Zhang Yuan, Yi Liu, Qiuli Zhao, Ping Lu, Yuguang Ma, Ian D. Williams, Anjun Qin, Jing Zhi Sun, and Ben Zhong Tang
The Journal of Physical Chemistry C 2012 Volume 116(Issue 19) pp:10541-10547
Publication Date(Web):April 24, 2012
DOI:10.1021/jp303100a
By integrating N,N-dimethyl (donor, D) and fumaronitrile (acceptor, A) groups with the biphenyl fluorogen, which has an aggregation-induced emission (AIE) property, we have obtained the target molecule 2-(4-bromophenyl)-3-(4′-(dimethylamino)-biphenyl-4-yl) fumaronitrile (BDABFN). BDABFN is a red-to-near-infrared-emitting fluorogen with emission peaks at 653 and 710 nm for its amorphous and crystal solids, respectively. BDABFN shows an evident aggregation-induced emission property, and the fluorescence quantum efficiency of its solid is 26.5%. Cystallographic data indicate that there is no π–π stacking, and neither J- nor H-aggregates are observed between the adjacent molecules. The existence of multiple C–H···π bonds between the adjacent molecules restricts the intramolecular rotation of the D and A moieties and enables the fluorogen to emit intensely in the solid states. Meanwhile, because of strong intramolecular D–A interaction, BDABFN exhibits pronounced solvatochromism, and the fluorescence peak red-shifts from 552 nm in hexane (nonpolar and hydrophobic solvent) to 750 nm in tetrahydrofuran (polar and hydrophilic solvent. BDABFN also displays a typical twisted intramolecular charge transfer property in polar solvents because of the interaction between the N,N-dimethyl and fumaronitrile moieties.
Co-reporter:Yu Mao, Hai Peng Xu, Hui Zhao, Wang Zhang Yuan, Anjun Qin, Yong Yu, Mahtab Faisal, Zhang Xiao A, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2011 vol. 21(Issue 35) pp:13627-13633
Publication Date(Web):01 Aug 2011
DOI:10.1039/C1JM11459J
Suspensions containing quaternized poly(pyridylacetylene) (PPyA) and AgX (X = Br and I) were obtained by simply mixing PPyA with water soluble silver salts. The suspensions were stable in the dark at room temperature, and could be cast into uniform films. After exposure to UV-light for sufficient time, Ag nanoparticles were in situ generated in the polymer matrix via photochemical reaction. By adjusting the Ag+ contents and the halide counterions, the size of Ag particles, the conductivity of the composite films, and the surface morphology of the composites were tuned. The quaternized PPyA absorbed UV-light efficiently and the photogenerated halogen caused fast degradation of the polymers. Thus the photo-chemical process concomitantly resulted in the formation of Ag nanoparticles and highly porous films. These properties offer the composite materials potential in the construction of UV-eroding conductive patterns, embedded metal nanostructures, and porous films for loading metal particles as catalyst.
Co-reporter:Zhengke Wang, Hui Zhao, Li Fan, Jun Lin, Pengyu Zhuang, Wang Zhang Yuan, Qiaoling Hu, Jing Zhi Sun, Ben Zhong Tang
Carbohydrate Polymers 2011 Volume 84(Issue 3) pp:1126-1132
Publication Date(Web):17 March 2011
DOI:10.1016/j.carbpol.2011.01.001
Chitosan (CS) rods are a good candidate as temporary mechanical supports in bone regeneration, however the bending strength and bending modulus should be improved to match commercially available devices used for bone fracture internal fixation. Poly(p-amino-phenylacetylene)/multi-walled carbon nanotubes (PaPA/MWCNTs) hybrids with superparamagnetic Fe3O4 nanoparticles (Fe3O4@PaPA/MWCNTs) are applied to reinforce the CS rods. Fe3O4@PaPA/MWCNTs could be uniformly dispersed in CS solution and aligned by an external magnetic field, in the direction parallel to the axis of CS rod. This greatly helped to resist the bending stress, thus the bending strength and modulus of the reinforced CS rods are 124.6 MPa and 5.3 GPa, respectively; which are 34.8% and 29.3% stronger than pure CS rods. As a result, the magnetic-field-assisted in situ precipitation method offers one feasible route for the reinforcement of CS-based devices with nano-scaled one-dimensional additives such as MWCNTs. In addition, CS-based biomaterials containing Fe3O4@PaPA/MWCNTs could obviously promote MG63 cells proliferation, so CS rods modified with Fe3O4@PaPA/MWCNTs are good candidates for bone fracture internal fixation.
Co-reporter:Xiao A Zhang, Min Rui Chen, Hui Zhao, Yuan Gao, Qiang Wei, Shuang Zhang, Anjun Qin, Jing Zhi Sun, and Ben Zhong Tang
Macromolecules 2011 Volume 44(Issue 17) pp:6724-6737
Publication Date(Web):August 17, 2011
DOI:10.1021/ma2014657
Pentafluorophenyl (PFP) ester-functionalized poly(phenylacetylene)s (PPAs, P1, P2, and P3) were designed and synthesized in desirable yields and molecular weight by using organorhodium complexes as catalysts. Furthermore, these PFP-containing PPAs were used as precursors to prepare a series of mono- and dual-functionalized PPAs by the substitution of the activated ester moieties with functional amines. The structures of the PFP-containing PPAs and the derived functional PPAs were characterized by using multiple spectroscopic techniques including GPC, FTIR, 1H NMR, 13C NMR, and 19F NMR. The experimental details and the characterization data demonstrate that activated ester synthetic route to functional PPAs is facile (just stirring the precursor polymer with proper amine(s) at room temperature for hours), efficient (complete transition from ester to amide has been confirmed), and quantitative (the relative content of a specific functionality can be precisely preset by controlling the feed ratio of the functional amines). By reacting three PFP-containing PPAs with chiral amines or with chiral and nonchiral alkyl amines in a step-by-step way, a series of seven different PPAs with asymmetric carbon in the side chains were obtained. CD measurements indicated that the incorporation of chiral amine into polymer side chains induced helicity formation of P1 backbone. P1-C*Ph(L) and P1-C*Ph(D) backbones adopt predominantly right-handed and left-handed helical conformation, respectively. While the flexible spacer between the chiral center and the rigid PPA backbone blocked the induction of main-chain helicity by chiral pendants, thus no CD signals were recorded for P2-C*Ph(L) and P3-C*Ph(L). Substitution of PFP ester with amine-functionalized PEGs transited the hydrophobic PPAs to hydrophilic. All of the PEG-containing PPAs can be dissolved in water and form clear solutions. Meanwhile, all of the aqueous solutions exhibit LCST behavior and the hydrophilic PEG chains and hydrophobic alkyl spacers have positive and negative impact on the cloud point, respectively. Contact angles measurements showed that the length and content of the PEG chains contribute greatly to the hydrophilic property, and the length of the alkyl spacers and the content of the alkyl amine component played a contrary role. By controlling the ratio of the PEGylated and alkyl amines, the amphiphilic property of the PPAs can be well tailored.
Co-reporter:Xiao A.-Zhang, Hui Zhao, Yuan Gao, Jiaqi Tong, Liang Shan, Yufei Chen, Shuang Zhang, Anjun Qin, Jing Zhi Sun, Ben Zhong Tang
Polymer 2011 Volume 52(Issue 23) pp:5290-5301
Publication Date(Web):27 October 2011
DOI:10.1016/j.polymer.2011.09.026
Functional poly(phenylacetylene)s (PPAs) bearing different azobenzene pendants were synthesized in desirable yields and molecular weight by using organorhodium complexes [Rh(diene)Cl]2 as catalysts. The structure of the derived azobenzene-functionalized PPAs was characterized by NMR, IR, and UV spectroscopic techniques. Their photoinduced isomerization behavior was monitored with UV–visible spectroscopy. The thermal stability was evaluated by TGA technique. Polarized optical microscope (POM) observations indicated that the PPAs constructed by linking azobenzene moieties via a longer flexible alkyl spacer to PPA backbone showed typical liquid-crystalline property and the mesophase was assigned to SmA phase. Their phase transition behaviors were further investigated by differential scanning calorimetric (DSC) measurements. The molecular packing modes were analyzed by using X-ray diffraction (XRD) measurement and theoretical simulation. These results revealed some details about the interactions between the polymer backbone, flexible alkyl spacer, and azobenzene functional moiety, which are constructive to design and synthesize novel functional conjugated polymers.
Co-reporter:Yi Liu; Anjun Qin;Xiujuan Chen;Xiao Yuan Shen;Li Tong;Rongrong Hu; Jing Zhi Sun; Ben Zhong Tang
Chemistry - A European Journal 2011 Volume 17( Issue 52) pp:14736-14740
Publication Date(Web):
DOI:10.1002/chem.201102613
Co-reporter:Li Tong;AnJun Qin;XiaoA Zhang;Yu Mao
Science China Chemistry 2011 Volume 54( Issue 12) pp:1948-1954
Publication Date(Web):2011 December
DOI:10.1007/s11426-011-4376-x
We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WCl6-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.
Co-reporter:Yu Mao;Xiao-a Zhang;Hai-peng Xu;Wang-zhang Yuan
Chinese Journal of Polymer Science 2011 Volume 29( Issue 2) pp:133-140
Publication Date(Web):2011 March
DOI:10.1007/s10118-011-1032-z
Functional polyacetylenes containing pyridinium side groups (PPyA-MX, X = Br and I) were successfully synthesized. Spectroscopic techniques such as 1H-NMR, 13C-NMR, and FTIR spectroscopy were used to characterize the structure of the obtained polymers. The characterization data were well consistent with the expected macromolecular structures. PPyA-MI had good solubility in polar organic solvents and low solubility in water, while PPyA-MBr had good solubility in both polar organic solvents and water.
Co-reporter:Jian Wang;Ju Mei;AnJun Qin;Ben Zhong Tang
Science China Chemistry 2010 Volume 53( Issue 12) pp:2409-2428
Publication Date(Web):2010 December
DOI:10.1007/s11426-010-4106-9
Fluorescent hyperbranched polymers (FHBPs), which combine the versatile fluorescent property with unique characteristics of hyperbranched architecture, are desirable candidates for stimulus responsive materials. This review demonstrates the structure and environment-dependent emission behaviors of a series of FHBPs. AEE active FHBPs showing opposite performance to ACQ effect are used to sensitively detect explosives and a superamplification effect is found. Specially designed FHBPs can complex with metal ions, leading to fluorescence turn-off due to complex quenching effect. The protonation of amino-containing FHBPs exhibits pH-dependent fluorescence responses to solution acidity. Some FHBPs containing responsive moieties are photo- and thermo-sensitive, and show potential applications as smart materials.
Co-reporter:Wang Zhang Yuan, Xiao Yuan Shen, Hui Zhao, Jacky W. Y. Lam, Li Tang, Ping Lu, Chunlei Wang, Yang Liu, Zhiming Wang, Qiang Zheng, Jing Zhi Sun, Yuguang Ma and Ben Zhong Tang
The Journal of Physical Chemistry C 2010 Volume 114(Issue 13) pp:6090-6099
Publication Date(Web):March 10, 2010
DOI:10.1021/jp909388y
Phosphorescence has rarely been observed in pure organic chromophore systems at room temperature. We herein report efficient phosphorescence from the crystals of benzophenone and its derivatives with a general formula of (X-C6H4)2C═O (X = F, Cl, Br) as well as methyl 4-bromobenzoate and 4,4′-dibromobiphenyl under ambient conditions. These luminogens are all nonemissive when they are dissolved in good solvents, adsorbed on TLC plates, and doped into polymer films, because active intramolecular motions such as rotations and vibrations under these conditions effectively annihilate their triplet excitons via nonradiative relaxation channels. In the crystalline state, the intramolecular motions are restricted by the crystal lattices and intermolecular interactions, particularly C−H···O, N−H···O, C−H···X (X = F, Cl, Br), C−Br···Br−C, and C−H···π hydrogen bonding. The physical constraints and multiple intermolecular interactions collectively lock the conformations of the luminogen molecules. This structural rigidification effect makes the luminogens highly phosphorescent in the crystalline state at room temperature.
Co-reporter:Li Tang, Jia Ke Jin, Anjun Qin, Wang Zhang Yuan, Yu Mao, Ju Mei, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2009 (Issue 33) pp:4974-4976
Publication Date(Web):10 Jul 2009
DOI:10.1039/B907382E
Poly(N-isopropylacrylamide) was labelled using a fluorogen with an aggregation-induced emission feature by direct polymerization; the label served as a fluorogenic probe that reveals fine details in the thermal transitions in the aqueous solution of the polymer; the working mode was readily tuned between non-monotonic and monotonic by changing the labelling degree of the polymer.
Co-reporter:Jia-Ke Jin, Jing-Zhi Sun, Yong-Qiang Dong, Hai-Peng Xu, Wang-Zhang Yuan, Ben Zhong Tang
Journal of Luminescence 2009 Volume 129(Issue 1) pp:19-23
Publication Date(Web):January 2009
DOI:10.1016/j.jlumin.2008.07.009
A new fluorescence technique for monitoring layer-by-layer self-assembling processes of polycations and polyanions is developed in this work. The fluorescent probe is a fluorogenic dye named 1,1-bis[p-(diethylaminomethyl)phenyl]-2,3,4,5-tetraphenylsilole (A2HPS). Whereas fluorescence of a “normal” fluorophore is often quenched by aggregate formation, the protonated salt of A2HPS, i.e., [H2A2HPS]2+, emits strong light in the suspensions of its nanoaggregates and in the solid films of its blends with poly(diallyldimethylammonium chloride) (PDDAC), thanks to its novel aggregation-induced emission (AIE) characteristics. When ([H2A2HPS]2++PDDAC) cations and poly(styrenesulfonate) (PSS) anions were used to fabricate thin films via layer-by-layer deposition processes on quartz and glass substrates, the emission intensity of [H2A2HPS]2+ showed linear relationship with the number of ([H2A2HPS]2++PDDAC)/PSS bilayers, due to the uniform co-deposition of [H2A2HPS]2+ cations into the PDDAC/PSS bilayers. This proves that the AIE fluorophore is an excellent probe for monitoring the layer-by-layer self-assembling processes of the polyelectrolytes on various substrates.
Co-reporter:Hui Zhao;Wang Zhang Yuan;Ju Mei;Li Tang;Xiao Qing Liu;Ji Ming Yan;Xiao Yuan Shen;Jing Zhi Sun;Anjun Qin;Ben Zhong Tang
Journal of Polymer Science Part A: Polymer Chemistry 2009 Volume 47( Issue 19) pp:4995-5005
Publication Date(Web):
DOI:10.1002/pola.23552
Abstract
Phenylacetylene derivatives containing carbazole (1) and fluorene (2) moieties were polymerized by [Rh(nbd)Cl]2 into corresponding polymers P1 and P2 of high molecular weights (Mw ∼ 150 × 103–465 × 103) in high yields (up to 98%). The polymers were characterized by NMR, IR, UV, PL, and CV techniques. Hybrids of the polymers with multiwalled carbon nanotubes (MWNTs) were prepared by simply mixing the two components in common organic solvents such as dichloromethane. The solvating power of the polymer carrying the electron-donating carbazolyl pendant (P1) is stronger than that of its counterpart carrying fluorenyl pendant (P2), due to the stronger donor–acceptor (D–A) interaction between the P1 chains and the MWNT walls. This work clearly manifests that D–A effect plays an important role in the polymer-aided MWNT dispersion in organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4995–5005, 2009
Co-reporter:Li Tang;JiaKe Jin;Shuang Zhang;Yu Mao
Science China Chemistry 2009 Volume 52( Issue 6) pp:755-759
Publication Date(Web):2009 June
DOI:10.1007/s11426-009-0119-7
We report a fluorescence “turn-on” method to detect the critical micelle concentration (CMC) of surfactants. This method works well for both cationic and anionic surfactants. It employs an unprecedented mechanism (aggregation-induced emission, or AIE) to determine the CMC values, and the results are consistent with the data obtained by the classical techniques. In addition, this method renders the convenient detection of the CMC values. Any large and professional instruments are unnecessary, instead, a portable UV lamp and an ultrasonic generator are enough to carry out the detection in an ordinary laboratory. Considering that micelles are interesting entities and have found applications in many important fields such as emulsion polymerization, template of nanosized materials synthesis, controllable drug delivery and macromolecular self-assembling. Our experimental results may offer a facile, sensitive and promising method to detect the formation of micelles constructed by the new amphiphilic molecules and macromolecules.
Co-reporter:Wang Zhang Yuan, Li Tang, Hui Zhao, Jia Ke Jin, Jing Zhi Sun, Anjun Qin, Hai Peng Xu, Jiahao Liu, Feng Yang, Qiang Zheng, Erqiang Chen and Ben Zhong Tang
Macromolecules 2009 Volume 42(Issue 1) pp:52-61
Publication Date(Web):December 8, 2008
DOI:10.1021/ma801978x
Acetylenic monomers containing highly polar functional groups, especially those with active hydrogen atoms, have been difficult to polymerize because their toxic interactions with transition metal complexes deactivate catalyst systems. In this work, we succeeded in direct polymerizations of a series of highly polar phenylacetylene derivatives. The polymerizations of 4-ethynylbenzoic acid (1), 4-hydroxybutyl 4-ethynylbenzoate (2), 6-(4-ethynylphenoxy)hexanoic acid (3), 4-ethynylaniline (4), and 1-ethynyl-4-nitrobenzene (5) catalyzed by organorhodium complexes afforded corresponding polymers (P1−P5) of high molecular weight (Mw as high as 488 500) and low polydispersity index (Mw/Mn as low as 1.03). The structures of the polymers were characterized spectroscopically. Treatments by base and acid readily transformed neutral polymers P1 and P4 to polyelectrolytes P1− and P4+, respectively. Simple mixing of the conjugated polyelectrolytes with multiwalled carbon nanotubes (MWNTs) afforded polyacetylene/MWNT nanohybrids with water solubility of up to 316 mg/L. The hybrids were facilely decorated by metal (oxide) nanoparticles, furnishing multicomponent composites of P1−/MWNT/Ag, P4+/MWNT/Ag, and P4+/MWNT/ZnO.
Co-reporter:Wang Zhang Yuan, Jacky W. Y. Lam, Xiao Yuan Shen, Jing Zhi Sun, Faisal Mahtab, Qiang Zheng and Ben Zhong Tang
Macromolecules 2009 Volume 42(Issue 7) pp:2523-2531
Publication Date(Web):March 10, 2009
DOI:10.1021/ma802510e
Multifunctional polyacetylenes and their nanohybrids with liquid crystallinity, light emission, and electrical conductivity are developed in this work. New acetylene monomers containing biphenyl mesogens and polynuclear chromophores, namely 4-[3-(1-pyrenyl)propylcarbonyloxy]-4′-biphenylyl 11-(4-ethynylphenoxy)undecanoate (1), 4-[3-(1-pyrenyl)propylcarbonyloxy]-4′-biphenylyl 10-undecynoate (2), and (9-fluorenyl)methyl-4-[(9-decynyl)-carbonyloxy]-4′-biphenylyloxycarbonylmethyl carbamate (3), were synthesized and transformed to their corresponding polymers (P1−P3) by the polymerization reactions catalyzed by organorhodium complexes of Rh+(nbd)[C6H5B−(C6H5)3] and [Rh(diene)Cl]2. Whereas none of the monomers were mesomorphic, P1 and P2 were liquid crystalline. The pyrene pendants enabled P1 and P2 to function as dispersants for short (s)- and long (l)-multiwalled carbon nanotubes (MWNTs). P1 assisted the dissolution of s- and l-MWNTs in THF, with respective solubilities as high as 723 and 625 mg/L. The resultant P1/l-MWNT hybrid maintained the smectic mesomorphism of P1 and emitted bluish-green light in THF upon photoexcitation. The hybrid solid readily redissolved in common organic solvents and formed solid films upon solution casting. The hybrid films showed high electrical conductivity. This work demonstrates that polyacetylenes with multiple functionalities can be generated by attaching appropriate functional pendants to the conjugated polyene backbones.
Co-reporter:Hai Peng Xu, Yu Mao, Jian Wang, Bo Yu Xie, Jia Ke Jin, Jing Zhi Sun, Wang Zhang Yuan, Anjun Qin, Mang Wang and Ben Zhong Tang
The Journal of Physical Chemistry C 2009 Volume 113(Issue 33) pp:14623-14627
Publication Date(Web):July 27, 2009
DOI:10.1021/jp902624k
Polymer nanowires were found to respond to external perturbations and to undergo transfiguration upon exposure to the irradiation of high-flux electron beams. The phenomenon is general, observable in the nanowires of conjugated and nonconjugated polymers with linear and hyperbranched structures. The transfiguration ceased to occur after the nanowires had been annealed at temperatures higher than the glass transition temperatures of the polymers. The phenomenon is rationalized to be associated with the residual internal stress in the nanowires that is relieved through the electron-beam irradiation and/or thermal annealing. This work thus offers cautionary advice that a proper annealing treatment should be exercised, if one wishes to fabricate polymer nanostructures and miniature devices with reliable stability and durable performance.
Co-reporter:Feng Yang, Bo Yu Xie, Jing Zhi Sun, Jia Ke Jin, Mang Wang
Materials Letters 2008 Volume 62(8–9) pp:1302-1304
Publication Date(Web):31 March 2008
DOI:10.1016/j.matlet.2007.08.069
Zinc–aluminum layered double hydroxide (Zn–Al LDH) thin films were prepared by direct precipitation on the surface of porous anodic alumina oxide (AAO) template. The Zn–Al LDH was assigned to Zn6All2(OH)16CO3·nH2O according to the XRD and EDX data. The nano-pores provided channels and the nano-sized wall-edges for supplying Al3+and highly active reaction sites, thereby the Zn–Al LDH films can be grown more efficiently on porous AAO membrane than those on flat bulk alumina oxide surface. The water contact angle (CA) of the as-prepared Zn–Al LDH films was measured to be 122°, indicating a hydrophobic surface, but after calcination at 600 °C for 2 h, the water CA became 65°, suggesting a hydrophilic surface. Comparative analyses of the surface morphological characteristics and elements with respect to the as-prepared and calcined films implied a thermal induced reconstruction of the Zn–Al LDH structure, which was ascribed to the changes of surface wettability.
Co-reporter:Feng Yang, Jia Ke Jin, Qing Chen, Jing Zhi Sun, Mang Wang
Materials Letters 2008 Volume 62(Issue 20) pp:3579-3581
Publication Date(Web):31 July 2008
DOI:10.1016/j.matlet.2008.04.002
We report an unparallel route to synthesize ZnO nanocrystallines by using dodecythiol as ligand. Different from other reported solvotherml synthetic routes, the route reported here related to a two-phase reaction system. Primary ZnO particles were generated in aqueous phase and spontaneously capped by dissolved thiol molecules. When a critical size was reached, the thiol-capped particles transferred from aqueous to thiol phase, and their growth was stopped there. After calcining the thiol-capped precursor particles, ZnO nanoparticles were obtained. The derived ZnO nanocrystallines were characterized with X-ray diffraction, energy dispersion X-ray analysis, transmission electron microscopy techniques.
Co-reporter:BoYu Xie;YaFeng Cao;XinGuo Yang;Mang Wang
Science Bulletin 2008 Volume 53( Issue 2) pp:209-214
Publication Date(Web):2008 January
DOI:10.1007/s11434-007-0496-2
The molecular aggregation state of a porphyrin-perylenediimide dyad can be changed by treating with trifluoroacetic acid. Transmittance electron microscopy (TEM) images revealed that lamella microstructures were formed when the dyad precipitated from neutral solvent, but spherical nano-particles were obtained when precipitating from acidic solution. X-ray diffraction patterns showed that the lamella microstructures and the nanoparticles were polycrystalline and amorphous solids, respectively. By using rational perylenediimide and porphyrin as reference compounds, careful analyses on the UV-visible spectra of the dyad and the references under different conditions were conducted and the results demonstrated that both the porphyrin and perylendiimide subunits of the dyad took J-aggregation in neutral solvent, but after being treated with trifluoroacetic acid and chloroform solution, the perylenediimide subunit changed to an H-aggregation while the porphyrin subunits changed to a random packing mode.
Co-reporter:Hui Zhao, Wang Zhang Yuan, Li Tang, Jing Zhi Sun, Haipeng Xu, Anjun Qin, Yu Mao, Jia Ke Jin and Ben Zhong Tang
Macromolecules 2008 Volume 41(Issue 22) pp:8566-8574
Publication Date(Web):October 28, 2008
DOI:10.1021/ma8014323
A group of triphenylamine-functionalized polyacetylenes (TPA-PAs) were synthesized using [Rh(nbd)Cl]2 as catalyst in high yields (up to 93%). The polymers were characterized by NMR, IR, UV, PL, and CV analyses. The TPA pendants endowed the polymers with desirable redox activity and high photoconductivity. When an electron-withdrawing formyl group was attached to the TPA unit, the resultant polymer (P3) displayed solvatochromism. Simply mixing the polymers with multiwalled carbon nanotubes (MWNTs) in appropriate solvents resulted in the formation of TPA-PA/MWNT hybrids. With the aid of the polymer bearing styryl-TPA pendant (P2), ∼21% of MWNTs were loaded into the hybrid and a solubility of MWNTs in dichloromethane as high as 720 mg/L was achieved, which is among the highest solubilities of MWNTs in organic solvents. The great solvating power of the TPA-PAs for the MWNTs is attributed to the polymer wrapping processes aided by the additive effects of π−π electronic interaction and donor−acceptor (D−A) complexation. This is the first report demonstrating the involvement of D−A interaction in the solubilization of MWNTs by a conjugated polymer. A single-layer photoreceptor with P3/MWNT hybrid as charge-generation material displayed a photosensitivity as high as ∼9091 mm2/mW·s, which is the highest value recorded for a polyacetylene-based device. The excellent photoconductivity is ascribed to the efficient charge separation in the D−A system and the fast transport of the photogenerated holes and electrons in the polymer and MWNT, respectively.
Co-reporter:Haipeng Xu, Jia Ke Jin, Yu Mao, Jing Zhi Sun, Feng Yang, Wang Zhang Yuan, Yong Qiang Dong, Mang Wang and Ben Zhong Tang
Macromolecules 2008 Volume 41(Issue 11) pp:3874-3883
Publication Date(Web):April 30, 2008
DOI:10.1021/ma702337z
It has been a challenge to synthesize thiol-functionalized polyacetylenes because of the poisoning effect of mercapto group on the early transition-metal catalysts. Rhodium complexes such as [Rh(cod)Cl]2 can catalyze the polymerizations but the products are insoluble and intractable. In this work, we tackled this challenge. Sulfur-containing polyacetylenes with macroscopic processability were successfully synthesized by separating thiol pendant from polyene backbone with a flexible spacer (in P1), capping free mercapto group with acetyl or alkyl group (in P2 or P3), and using a zwitterionic complex Rh+[η6-C6H5(nbd)B–(C6H5)3] as catalyst. The soluble polymers were characterized by NMR, IR, UV, PL, and TGA analyses. Due to the specific interactions between thiol group and zinc cation, ZnO nanoparticles were chemisorbed onto the surfaces of polymer films, as verified by AFM analysis. Polymer P2 and ZnO nanoparticles could be readily hybridized by simply mixing the two components in an organic solvent such as chloroform, THF, or DMF. SEM images revealed that the morphology of the film cast from the solution of the P2/ZnO hybrid was dominated by well-dispersed nanoparticles and smooth surface.
Co-reporter:Kin Hei Cheng, Yongchun Zhong, Bo Yu Xie, Yong Qiang Dong, Yuning Hong, Jing Zhi Sun, Ben Zhong Tang and Kam Sing Wong
The Journal of Physical Chemistry C 2008 Volume 112(Issue 45) pp:17507-17511
Publication Date(Web):2017-2-22
DOI:10.1021/jp805158b
We fabricated tetraphenylethylene (TPE)-doped poly(methyl methacrylate) (PMMA) nanowires in the channels of anodic aluminum oxide template. Strong blue photoluminescence from the TPE aggregates in the polymer nanowires was observed. Room temperature ultraviolet lasing can be achieved in as-prepared TPE/PMMA nanowires. Lasing from isolated individual nanowires at 372 nm with emission width of 0.3 nm was also observed at low temperature. Ultrafast emission decay of ∼34 ps from the 372 nm peak pumped above threshold verified the stimulated emission nature of the lasing process. Our result shows that combining small molecules with highly processable PMMA can result in high-quality polymer nanowires and meanwhile maintain or even enhance the original functionality of the small molecules.
Co-reporter:Wang Zhang Yuan, Jing Zhi Sun, Jian Zhao Liu, Yongqiang Dong, Zhen Li, Hai Peng Xu, Anjun Qin, Matthias Häussler, Jia Ke Jin, Qiang Zheng and Ben Zhong Tang
The Journal of Physical Chemistry B 2008 Volume 112(Issue 30) pp:8896-8905
Publication Date(Web):July 2, 2008
DOI:10.1021/jp801892t
A group of ferrocene-containing poly(phenylacetylene)s (PPAs) with different alkyl spacers were synthesized by using organorhodium complexes [Rh(diene)Cl]2 and Rh+(nbd)[C6H5B−(C6H5)3] as catalysts. With the aid of π−π interactions between the walls of carbon nanotubes (CNTs) and the PPA skeleton together with the ferrocene pendants, the polymer (P1, P2(5) and P2(10)) chains effectively wrapped round the shells of both single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs). The “additive effect” of the PPA skeleton and the ferrocene pendants in dispersing the SWNTs and MWNTs resulted in the generation of highly soluble hybrids. The solubilities of P1-functionalized SWNTs and MWNTs in tetrahydrofuran (THF) are up to 633 mg/L and 967 mg/L, respectively. They are much higher than the solubilities of M1-modified SWNTs and MWNTs, which are only 167 mg/L and 133 mg/L in THF. The results indicate the existence of a powerful polymer effect on dispersing CNTs. The high solubilities of the hybrids in organic solvents allowed us to fabricate high-quality and large-area films. Meanwhile, the desirable loading of ferrocene-containing PPAs onto the CNTs offered polymer/CNTs hybrids with multiple redox centers and ferrocene-featured electrochemical properties. The P1/MWNT hybrid exhibits evident optical-limiting properties. At high incident laser fluence, the optical-limiting power of P1/MWNT is higher than that of C60, a well-known optical limiter. Thermal analyses indicate that the decomposition temperatures (Td, the temperature at which a sample loses its 5% weight) for P1 and P1/MWNT are 342 and 346 °C, respectively, much higher than that for PPA (225 °C). Thus the attachment of a ferrocene pendant to a PPA backbone, followed by hybridization with CNTs, improved the thermal stability. Upon pyrolysis, both the polymer and the polymer/CNTs hybrid gave rise to superparamagnetic ceramics; the saturation magnetizations (Ms) of the ceramics derived from P1 and P1/MWNT are 29.9 and 26.9 emu/g, respectively. The latter datum is in the list of the best results reported for the magnetic nanocomposites obtained by the attachment of magnetic nanoparticles onto CNTs.
Co-reporter:Hai-Peng Xu, Bo-Yu Xie, Wang-Zhang Yuan, Jing-Zhi Sun, Feng Yang, Yong-Qiang Dong, Anjun Qin, Shuang Zhang, Mang Wang and Ben Zhong Tang
Chemical Communications 2007 (Issue 13) pp:1322-1324
Publication Date(Web):23 Feb 2007
DOI:10.1039/B617595C
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.
Co-reporter:Hanying Li, Jingzhi Sun, Mang Wang
Materials Letters 2006 Volume 60(Issue 19) pp:2379-2382
Publication Date(Web):August 2006
DOI:10.1016/j.matlet.2006.01.023
Highly ordered spin-coating films of a conjugated molecule, trans-2,3,4,5,6-pentafluorostilbene were fabricated on quartz substrate by making use of the C–F–––H noncovalent intermolecular interaction, whose strength is as high as that of hydrogen bond. The C–F–––H–O interactions are strong enough to drive the molecules in the foundation layer erecting over the substrate and the C–F–––H–C interactions between adjacent molecules maintain such a molecular orientation in the subsequent layers. X-diffraction patterns and polarized raman spectral data confirmed the ordered structure in the spin-coating films.
Co-reporter:J. Cao;J.-Z. Sun;J. Hong;H.-Y. Li;H.-Z. Chen;M. Wang
Advanced Materials 2004 Volume 16(Issue 1) pp:
Publication Date(Web):16 JAN 2004
DOI:10.1002/adma.200306100
Co-reporter:Jian Cao, Jing-Zhi Sun, Han-Ying Li, Jian Hong and Mang Wang
Journal of Materials Chemistry A 2004 vol. 14(Issue 7) pp:1203-1206
Publication Date(Web):23 Feb 2004
DOI:10.1039/B313541A
We have prepared functional TiO2@CdS core/sheath heterostructure nanowires using a simple chemical reduction method at room temperature. The core/sheath nanowires were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-visible spectroscopic techniques. It was found that the thickness of the CdS sheath could be controlled by the concentration of the precursors. The continuous and polycrystalline CdS outer layer could be formed on the TiO2 nanowires when the concentration of the S precursor was higher than 0.2 mmol. A possible multi-site growth mechanism of the formation of the composite nanowires was proposed.
Co-reporter:Jian Cao, Jingzhi Sun, Gaoquan Shi, Hongzheng Chen, Qinglin Zhang, Dejun Wang, Mang Wang
Materials Chemistry and Physics 2003 Volume 82(Issue 1) pp:44-48
Publication Date(Web):28 September 2003
DOI:10.1016/S0254-0584(03)00188-3
The electronic properties of the polythiophene nano-tubule films were studied with surface photovoltage spectrum (SPS) and field-induced surface photovoltage spectrum (FISPS). The surface photovoltaic responses were resulted from the π–π∗ transition of polythiophene chains. Two extra photovoltaic responses in the near-IR region were observed under the external electric field. Based on the band theory and the principle of FISPS, these responses were ascribed to the charged surface electronic states, which were led by the interaction between polythiophene nano-tubules and the oxygen absorbed on the surface.
Co-reporter:Minggang Tian, Yong Liu, Yuming Sun, Ruoyao Zhang, Ruiqing Feng, Ge Zhang, Lifang Guo, Xuechen Li, Xiaoqiang Yu, Jing Zhi Sun, Xiuquan He
Biomaterials (March 2017) Volume 120() pp:
Publication Date(Web):March 2017
DOI:10.1016/j.biomaterials.2016.12.016
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.
Co-reporter:Yi Liu ; Chunmei Deng ; Li Tang ; Anjun Qin ; Rongrong Hu ; Jing Zhi Sun ;Ben Zhong Tang
Journal of the American Chemical Society () pp:
Publication Date(Web):December 20, 2010
DOI:10.1021/ja107086y
A conceptually new “light-up” biosensor with a high specificity for d-glucose (Glu) in aqueous media has been developed. The emission from a tetraphenylethene (TPE)-cored diboronic acid (1) was greatly boosted when the fluorogen was oligomerized with Glu because of restriction of the intramolecular rotations of the aryl rotors of TPE by formation of the oligomer. Little change in the light emission was observed when 1 was mixed with d-fructose, d-galactose, or d-mannose, as these saccharides are unable to oligomerize with the fluorogen.
Co-reporter:Qiuli Zhao and Jing Zhi Sun
Journal of Materials Chemistry A 2016 - vol. 4(Issue 45) pp:NaN10609-10609
Publication Date(Web):2016/10/17
DOI:10.1039/C6TC03359H
Aggregation-induced emission (AIE) materials show faint emission or even non-emission when dissolved in good solvents but strong emission in the aggregate and/or solid states. Owing to the bright solid-state luminescence and a unique emission “turn on” process, AIE materials have captured scientists' intensive attention since the report of the AIE phenomenon in 2001. A great quantity of AIE molecules have been synthesized and widely applied in many areas such as organic light-emitting devices (OLEDs), chemical sensors, fluorescence bioimaging and diagnosis. Whereas, the vast majority of AIE luminogens are blue or green emissive, only few emit red light. However, red and near infrared (NIR) emissive AIE materials are highly important in the fields of full-color display and bioimaging. As one of the three primary colours, red is an indispensable element in the areas of full-color display systems and white-light lightings. Besides their application in optoelectronic devices, red/NIR-emitting materials are promising fluorescence probes in biology due to their large penetration depth, faint background autofluorescence and trivial irradiation harm to cells. The nanoparticles based on red/NIR emissive AIE materials possess high resistance to photobleaching, low toxicity and efficient emission, which are expected to be alternatives to inorganic quantum dots in the fields of biological assays and bioimaging. Therefore, the design and preparation of red/NIR emissive AIE materials have recently become a hot topic. This review summarizes the advances in red/NIR emissive AIE materials from the viewpoint of molecular design, and puts forward proposals for the future development of red/NIR emissive AIE materials.
Co-reporter:Fuqiang Guo, Minggang Tian, Fang Miao, Weijia Zhang, Guofen Song, Yong Liu, Xiaoqiang Yu, Jing Zhi Sun and Wai-Yeung Wong
Organic & Biomolecular Chemistry 2013 - vol. 11(Issue 44) pp:NaN7728-7728
Publication Date(Web):2013/09/05
DOI:10.1039/C3OB41414K
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.
Co-reporter:Minggang Tian, Fuqiang Guo, Yuming Sun, Weijia Zhang, Fang Miao, Yong Liu, Guofen Song, Cheuk-Lam Ho, Xiaoqiang Yu, Jing Zhi Sun and Wai-Yeung Wong
Organic & Biomolecular Chemistry 2014 - vol. 12(Issue 32) pp:NaN6133-6133
Publication Date(Web):2014/07/03
DOI:10.1039/C4OB00382A
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 (30–200 μM) due to its high intracellular concentration (1–10 mM). In this work, an off–on 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 30–200 μM cysteine over 1–10 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.
Co-reporter:Wei Bai, Zhaoyang Wang, Jiaqi Tong, Ju Mei, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2015 - vol. 51(Issue 6) pp:NaN1091-1091
Publication Date(Web):2014/11/24
DOI:10.1039/C4CC06510G
Dibenzo[24]crown-8 (host) and benzylamine (guest) modified tetraphenylethenes are prepared and used to construct supramolecular polymers, which demonstrate the merits of reversible assembling–disassembling and tunable aggregation-induced emission by acid–base treatments.
Co-reporter:Xiao Yuan Shen, Yi Jia Wang, Haoke Zhang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2014 - vol. 50(Issue 63) pp:NaN8750-8750
Publication Date(Web):2014/06/10
DOI:10.1039/C4CC03024A
Diketopyrrolopyrrole (ACQ-gen) and tetraphenylethenes (AIE-gen) are linked together with phenyl bridges. The derivatives show substantially enhanced and red-shifted emission in the solid state.
Co-reporter:Xiujuan Chen, Xiao Yuan Shen, Erjia Guan, Yi Liu, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2013 - vol. 49(Issue 15) pp:NaN1505-1505
Publication Date(Web):2013/01/04
DOI:10.1039/C2CC38246F
A pyridinyl-functionalized tetraphenylethene (Py-TPE) was synthesized and it demonstrated colorimetric and ratiometric fluorescent responses to trivalent metal cations (M3+, M = Cr, Fe, Al) over a variety of mono- and divalent metal cations.
Co-reporter:Yu Mao, Hai Peng Xu, Hui Zhao, Wang Zhang Yuan, Anjun Qin, Yong Yu, Mahtab Faisal, Zhang Xiao A, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2011 - vol. 21(Issue 35) pp:NaN13633-13633
Publication Date(Web):2011/08/01
DOI:10.1039/C1JM11459J
Suspensions containing quaternized poly(pyridylacetylene) (PPyA) and AgX (X = Br and I) were obtained by simply mixing PPyA with water soluble silver salts. The suspensions were stable in the dark at room temperature, and could be cast into uniform films. After exposure to UV-light for sufficient time, Ag nanoparticles were in situ generated in the polymer matrix via photochemical reaction. By adjusting the Ag+ contents and the halide counterions, the size of Ag particles, the conductivity of the composite films, and the surface morphology of the composites were tuned. The quaternized PPyA absorbed UV-light efficiently and the photogenerated halogen caused fast degradation of the polymers. Thus the photo-chemical process concomitantly resulted in the formation of Ag nanoparticles and highly porous films. These properties offer the composite materials potential in the construction of UV-eroding conductive patterns, embedded metal nanostructures, and porous films for loading metal particles as catalyst.
Co-reporter:Qiuli Zhao, Kai Li, Sijie Chen, Anjun Qin, Dan Ding, Shuang Zhang, Yi Liu, Bin Liu, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 - vol. 22(Issue 30) pp:NaN15135-15135
Publication Date(Web):2012/05/28
DOI:10.1039/C2JM31368E
Organic fluorescent probes are widely used in bioimaging and bioassays, but the notorious photobleaching hampers their applications. Encapsulation of organic dyes into nanoparticles (NPs) is an effective strategy to minimize photobleaching, but classical organic dye molecules tend to have their fluorescence quenched in aggregate states, which is termed aggregation-caused quenching (ACQ). Here we demonstrate our attempt to tackle this problem through the aggregation-induced emission (AIE) strategy. 3,4:9,10-Tetracarboxylic perylene bisimide (PBI) is a well-known organic dye with a serious ACQ problem. By attaching two tetraphenylethene (TPE) moieties to the 1,7-positions, the ACQ-characteristic PBI-derivative was converted to an AIE-characteristic molecule. The obtained PBI derivative (BTPEPBI) exhibits several advantages over classical PBI derivatives, including pronounced fluorescence enhancement in aggregate state, red to near infrared emission, and facile fabrication into uniform NPs. Studies on the staining of MCF-7 breast cancer cells and in vivo imaging of a tumor-bearing mouse model with BTPEPBI-containing NPs reveal that they are effective fluorescent probes for cancer cell and in vivo tumor diagnosis with high specificity, high photostability and good fluorescence contrast.
Co-reporter:Hai-Peng Xu, Bo-Yu Xie, Wang-Zhang Yuan, Jing-Zhi Sun, Feng Yang, Yong-Qiang Dong, Anjun Qin, Shuang Zhang, Mang Wang and Ben Zhong Tang
Chemical Communications 2007(Issue 13) pp:NaN1324-1324
Publication Date(Web):2007/02/23
DOI:10.1039/B617595C
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.
Co-reporter:Qiuli Zhao, Shuang Zhang, Yi Liu, Ju Mei, Sijie Chen, Ping Lu, Anjun Qin, Yuguang Ma, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 - vol. 22(Issue 15) pp:NaN7394-7394
Publication Date(Web):2012/03/08
DOI:10.1039/C2JM16613E
Perylene bisimides (PBIs) are one class of the most explored organic fluorescent materials due to their high fluorescence quantum efficiency, electron transport behaviour, and ready to form well-tailored supramolecular structures. However, they suffer from heavy aggregation-caused quenching (ACQ) effect which has greatly limited their potential applications. We successfully tackle this problem by chemical modification of the PBI core with two tetraphenylethene (TPE) moieties at the bay positions. This modification resulted in a pronounced fluorescence red-shift (over 120 nm) and rendered the derivatives (1,6-/1,7-DTPEPBI) with evident aggregation-induced emission (AIE) behaviour. Both 1,6-DTPEPBI and 1,7-DTPEPBI emit bright red fluorescence in the solid state. The fluorescence quantum efficiency of the aggregates of 1,7-DTPEPBI (ΦF, solid = 29.7%, formed in a hexane/dichloromethane mixture, fh = 90%) is about 424 times higher than that in dichloromethane solution (ΦF, solut = 0.07%). Electrochemical investigation results indicated that 1,7-DTPEPBI sustained the intrinsic n-type semiconductivity of PBI moiety. In addition, morphological inspection demonstrated that 1,7-DTPEPBI molecules easily form well-organized microstructures despite the linkage of the PBI core with bulky TPE moieties.
Co-reporter:Xiaoying Gao, Guangxue Feng, Purnima Naresh Manghnani, Fang Hu, Nan Jiang, Jianzhao Liu, Bin Liu, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2017 - vol. 53(Issue 10) pp:NaN1656-1656
Publication Date(Web):2017/01/03
DOI:10.1039/C6CC09307H
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.
Co-reporter:Zhiguang Yang, Ning Zhao, Yuming Sun, Fang Miao, Yong Liu, Xin Liu, Yuanhong Zhang, Wentao Ai, Guofen Song, Xiaoyuan Shen, Xiaoqiang Yu, Jingzhi Sun and Wai-Yeung Wong
Chemical Communications 2012 - vol. 48(Issue 28) pp:NaN3444-3444
Publication Date(Web):2012/02/14
DOI:10.1039/C2CC00093H
Two highly selective two-photon fluorescent probes for cysteine over homocysteine, N-acetyl-L-cysteine, dithiothreitol, glutathione and other amino acids, and their fluorescent imaging in living cells have been shown.
Co-reporter:Li Tang, Jia Ke Jin, Anjun Qin, Wang Zhang Yuan, Yu Mao, Ju Mei, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2009(Issue 33) pp:NaN4976-4976
Publication Date(Web):2009/07/10
DOI:10.1039/B907382E
Poly(N-isopropylacrylamide) was labelled using a fluorogen with an aggregation-induced emission feature by direct polymerization; the label served as a fluorogenic probe that reveals fine details in the thermal transitions in the aqueous solution of the polymer; the working mode was readily tuned between non-monotonic and monotonic by changing the labelling degree of the polymer.
Co-reporter:J. Mei, J. Wang, A. Qin, H. Zhao, W. Yuan, Z. Zhao, H. H. Y. Sung, C. Deng, S. Zhang, I. D. Williams, J. Z. Sun and B. Z. Tang
Journal of Materials Chemistry A 2012 - vol. 22(Issue 10) pp:NaN4298-4298
Publication Date(Web):2011/09/23
DOI:10.1039/C1JM12673C
Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch between different solid states, and a typical mechanofluorochromism was observed by cyclic operation of the grinding–heating–cooling processes. In addition, two single crystals (O and R) were successfully obtained in proper conditions, and the crystallographic data indicated that crystal O and R had reasonable hollow structures, inside which different solvent molecules were selectively encapsulated. More importantly, we have presented a proof-of-concept example of the strategy for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability. This design strategy is instructive to design and construct organic soft porous crystals with other conjugated building blocks and develop novel smart and stimuli-responsive photo/electronic materials.
Co-reporter:Qiuli Zhao, Xiao A Zhang, Qiang Wei, Jian Wang, Xiao Yuan Shen, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2012 - vol. 48(Issue 95) pp:NaN11673-11673
Publication Date(Web):2012/10/09
DOI:10.1039/C2CC36060H
Perylene bisimide derivatives substituted with one and two tetraphenylethene moieties at 1 and 1,7-postions show distinct optical properties. The former displays characteristic emission features of perylene bisimides in solution and red emission in the aggregate state, while the latter is nonemissive in solution but highly red-emissive in the aggregate state.
Co-reporter:Ting Hu, Bicheng Yao, Xiujuan Chen, Weizhang Li, Zhegang Song, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2015 - vol. 51(Issue 42) pp:NaN8852-8852
Publication Date(Web):2015/04/16
DOI:10.1039/C5CC02138C
A pyridinium modified tetraphenylethene-based salt shows aggregation-induced emission enhancement properties and irreversible mechanochromic behaviours.
Co-reporter:Zhaoyang Wang, Wei Bai, Jiaqi Tong, Yi Jia Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Chemical Communications 2016 - vol. 52(Issue 68) pp:NaN10368-10368
Publication Date(Web):2016/07/19
DOI:10.1039/C6CC02851A
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.
Co-reporter:Yi Jia Wang, Zeyu Li, Jiaqi Tong, Xiao Yuan Shen, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 15) pp:NaN3568-3568
Publication Date(Web):2015/02/26
DOI:10.1039/C4TC02550D
Two tetraphenylethene (TPE) modified perylenebisimides (PBIs) were synthesized through linking the TPE moieties to the PBI core at the imide positions. Theoretical calculations predict that, in both of the mono-TPE and di-TPE substituted derivatives (i.e. TPE-N-PBI and DTPE-N-PBI), the TPE and PBI units are orthogonal to each other, and thus have no electronic conjugation. Thus the two compounds are TPE–PBI dyads rather than TPE–PBI conjugates. This property is supported by absorption and emission spectral features. In solution, aggregate and solid film, the fluorescence from both TPE and PBI subunits is evidently quenched. The underlying mechanism is the photo-induced charge transfer between the electron donor TPE and electron acceptor PBI subunits. In a highly polar tetrahydrofuran–water mixture with a large fraction of water, TPE-N-PBI can form H-aggregates. In low polar hydrophobic dichloromethane–hexane mixtures, due to the bulky size and rigidity of the TPE subunit, the dyad molecules cannot take a parallel alignment to form classical J- or H-aggregates, but have to exist in a large offset angle. Consequently, X-aggregates are formed, which was confirmed by the absorption features, morphological observations and comparative investigation of the reference compound.
Co-reporter:Ju Mei, Jiaqi Tong, Jian Wang, Anjun Qin, Jing Zhi Sun and Ben Zhong Tang
Journal of Materials Chemistry A 2012 - vol. 22(Issue 33) pp:NaN17070-17070
Publication Date(Web):2012/07/03
DOI:10.1039/C2JM32892E
A novel fluorescence probe capable of discriminatively and simultaneously detecting Cys, Hcy and GSH has been developed. This specially designed probe can selectively react with Cys and Hcy to form thiazinane and thiazolidine derivatives in the presence of diverse amino acids, protected Cys and glucose and display the expected aggregation-induced emission (AIE) properties. Relying on the differences in kinetics, Cys can be easily and discriminately detected over Hcy by the observation of FL responses. GSH shows great interference with the detection of Cys and Hcy and it can be quantitatively detected by the FL spectroscopic titration method. The threshold of the FL turn-off concentration for GSH is measured to be 1 mM. This is the first report of using a single fluorescent probe to discriminately detect Cys, Hcy and GSH by FL turn-on and turn-off strategies. The discrimination relies on the reaction-dependent fluorophore aggregation, or the solubility of adducts of the probe molecule and analytes. The present strategy is intrinsically a fluorescent titration, which combines the high sensitivity of FL spectroscopy and the reliability of precipitate titration methodology. The threshold concentration of Cys (375 μM, at which the FL is turned-on) coincides with the upper margin of the deficient Cys levels in human plasma, and the primary investigation of the FL response to deproteinized human plasma indicates that this FL probe is a promising one for the discriminatory detection of Cys over Hcy and GSH on a clinical level.
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