Enhancing the thermoelectric performance through the mutual interaction between conjugated polyelectrolytes and single-walled carbon nanotubes

We present a method of constructing composites composed of conjugated polyelectrolytes(CPEs)and singlewalled carbon nanotubes(SWCNTs)to obtain a high-performing flexible thermoelectric generator.In this approach,three kinds of polymers,namely,poly[(1,4-(2,5-didodecyloxybenzene)-alt-2,5-thiophene](P1),poly[(1,4-(2,5-bis-sodium butoxysulfonate-phenylene)-alt-2,5-thiophene](P2),and poly[(1,4-(2,5-bis-acid butoxysulfonic-phenylene)-alt-2,5-thiophene](P3)are designed,synthesized and complexed with SWCNTs as thermoelectric composites.The electrical conductivities of the CPEs/SWCNTs(P2/SWCNTs,and P3/SWCNTs)nanocomposites are much higher than those of non-CPEs/SWCNTs(P1/SWCNTs)nanocomposites.Among them,the electrical conductivity of P2/SWCNTs with a ratio of 1:4 reaches 3686 S·cm^(-1),which is 12.4 times that of P1/SWCNTs at the same SWCNT mass ratio.Moreover,CPEs/SWCNTs composites(P2/SWCNTs)display remarkably improved thermoelectric properties with the highest power factor(PF)of 163μW·m^(-1)·K^(-1).In addition,a thermoelectric generator is fabricated with P2/SWCNTs composite films,and the output power and power density of this generator reach 1.37μW and 1.4 W·m;(cross-section)at△T=70 K.This result is over three times that of the thermoelectric generator composed of non-CPEs/SWCNTs composite films(P1/SWCNTs,0.37μW).The remarkably improved electrical conductivities and thermoelectric properties of the CPEs/SWCNTs composites(P2/SWCNTs)are attributed to the enhanced interaction.This method for constructing CPEs/SWCNTs composites can be applied to produce thermoelectric materials and devices.

Red AIE conjugated polyelectrolytes for long-term tracing and image-guided photodynamic therapy of tumors

Robust photosensitizers with strong red/NIR fluorescence, efficient reactive oxygen species(ROS) generation and high photostability are highly desired for photodynamic therapy(PDT). Herein, three novel red conjugated polyelectrolytes(CPEs) with tetraphenylethene and 2,1,3-benzothiadiazole on the main chains and triphenylphosphonium on the side chains are developed.These CPEs display apparent aggregation-induced emission feature and high fluorescence quantum yields in the aggregated state. They can target lysosome in He La cells for fluorescence bioimaging. By virtue of the good retention effect and high photostability, these CPEs show ultralong-term tracing performance of subcutaneous tumors, and the tumor site can still be visualized for 20 days after injection. Owing to their good biocompatibility and strong ROS generation ability, the image-guided PDT based on these CPEs can effectively inhibit the growth of subcutaneous tumor and significantly prolong the survival of tumor bearing mice. The H&E and IHC staining reveal that the PDT of these CPEs depress the proliferation of tumor cells, and promote apoptosis and necrosis process. These new CPEs may be employed both as fluorescent probes for in vitro and in vivo long-term tracing and as photosensitizers for image-guided PDT of tumors.

Conjugated polyelectrolytes for label-free visual detection of heparin

Conjugated polyelectrolytes (CPEs),with electron-delocalized backbones and charged ionic side chains,are unique sensory materials for the construction of optical biosensors.In this feature article,CPE-based visual detection of heparin is summarized.Three CPE-based heparin probes,including ratiometric,light-up and colormetric probes,are discussed in terms of molecular design,detection selectivity and quantification capability.The work summarized here provides fundamental guidelines for CPE-based label-free visual sensing.

Preparation and Properties of Water-soluble Conjugated Polyelectrolyte

The water-soluble conjugated polyelectrolyte, poly[3-（1′-ethyloxy-2′-N- methylimidazole）thiophene]（PEOIMT）, was prepared. Its photophysical and electrochemical properties, and response characteristics to the external condition（e g, temperature response, solvent response and pH response）, were investigated. The results show the PEOIMT belongs to the organic semiconductor. The interaction between the PEOIMT and the bovine serum albumin（BSA） was investigated using UV-vis spectroscopy. It was found that the PEOIMT could interact with the BSA. The PEOIMT can be used as a biosensor to detect the BSA.

Direct visualization of the charge transfer in conjugated polymers

Ion-induced charge-transfer states in conjugated polyelectrolytes were experimentally investigated by Justin M.Hodgkiss and his co-workers [J Am Chem Soc,2009,131(25):8913].In this work,charged and neutral conjugated polyelectrolytes were further studied with quantum chemistry methods.The calculation result shows that the absorption spectra are roughly in visible and ultraviolet light regions,and the two absorption peaks are located in the wavelength span 300-400 nm for charged polyelectrolytes.However,in neutral conjugated polyelectrolytes,the peaks of the absorption spectra showed a blue shift compared with those of the charged polyelectrolytes.Charge transfer (CT) properties of the studied compounds were also investigated with both the three-dimensional real-space analysis method of transition and charge difference densities,and the two-dimensional real-space analysis method of transition density matrices based on the simulated absorption spectra.The calculation results revealed the charge transfer in conjugated polyelectrolytes on the excitation states.

Conjugated Polyelectrolyte-Ag＋ Fluorescent Switch for Biothiol Sensing

A new ＂off-on＂ switch for sensitive and selective fluorescence detection of biothiols[glutathione（GSH）, cysteine（Cys） and homocysteine（Hcy）] was developed based on an anionic conjugated polyelectrolyte（CPE）, pyridyl-functionalized poly（phenylene ethynylene）（Pl）. The fluorescence of P1 can be significantly quenched by Ag＋ due to complexation-mediated interpolymer aggregation. Furthermore, biothiols can efficiently recover the fluorescence intensity of P1 as a result of the stronger binding between thiol group and Ag＋, which dissociates PI from the P1/Ag＋ complex and disrupts interpolymer aggregation. Under optimum conditions, a good linear relation- ship in a range of 100--4200 nmol/L is obtained for GSH with a detection limit of 80 nmol/L（S/N=3）. As a result of specific interaction between the thiol group and Ag＋, the proposed method shows a high selectivity for biothiols. In addition, the CPE-based fluorescence ＂off-on＂ switch has been used to quantitatively detect total biothiols in cell lysates.

A prototype of benzobis(imidazolium)-embedded conjugated polyelectrolyte: Synthesis by direct C–H arylation and fluorescent responses to anions

We report the convenient synthesis of a benzobis(imidazolium)-embedded conjugated polyelectrolyte pBBI by a Cu-catalyzed direct C–H arylation of a cationic benzobis(imidazolium)monomer with a di-iodide comonomer.pBBI shows weak fluorescence in solution due to rotation of the repeat units in the conjugated backbone,and enhanced fluorescence when electrostatically interacting with a variety of an-ions to form aggregates.Specially,pBBI responds to the bisulfite anion with intensified unique deep-blue fluorescence easily discriminated by naked eye.