2D polyaniline derivatives as turn-on fluorescent probe for efficient triethylamine detection at room temperature.

Due to the severe toxicity of triethylamine (TEA), the preparation of chemsensors with high sensitivity, low cost and visualization for TEA detection has been a research hotspot. However, based on the fluorescence turn-on detection of TEA remains rare. In this work, three two-dimensional conjugated polymers (2D CPs) were prepared by chemical oxidation polymerization. These sensors show a quick response and excellent selectivity toward TEA at room temperature. The minimum limit of detection (LOD) for TEA was 3.6 nM in the range of 10 µM âˆ¼ 30 µM. Interestingly, the paper sensor based on P2-HCl can quantitatively detect TEA gas within 20 s, which showed great application potential in fields of environmental monitoring. Besides, Fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) data were used to thoroughly interpret the sensing mechanism. This work provided an effective method for the development of 2D fluorescent chemosensors for TEA detection.

Poly(3-amino-carbazole) derivatives containing 1,10-phenanthroline and 8-hydroxyquinoline ligands: Synthesis, properties and application as ion sensors.

As we know, excessive metal ions can even damage human health. Herein, two novel kinds of fluorescent sensing materials Poly(3-amino-carbazole) derivatives containing 1,10-phenanthroline and 8-hydroxyquinoline were synthesized and further applied to fluorescence detection for ions. The results show that Ni2+, Cu2+, and Pd2+ have excellent quenching effects on the fluorescence of Poly[9-(1,10-phenanthroline-2-yl)-9H-carbazol-3-amine] (PPNC), the LOD for these ions reaches 5.2 nM, 12.7 nM, 33.5 nM respectively. In the process of ion response, there is no shift of UV absorption peak, combined with IR spectra and theoretical calculation simulation, the quenching is considered to be caused by the coordination between metal ions and the second amine (-NH-) or 1,10-phenanthroline ligand of PPNC, which leads to the charge transfer from ligands to metal ions. In addition, an acid test was done for PPNC to verify and detect the presence of secondary amine (-NH-), and the results show that PPNC has good acid sensing ability which also supports the secondary amine (-NH-) structure. Finally, the paper test was performed on PPNC, indicating that PPNC has the potential for visual application.

Rational design of fluorescent chemosensor for Pd2+ based on the formation of cyclopalladated complex.

According to the assumption that the formation of C-Pd bond becomes a cyclopalladated complex (CPC), we designed and synthesized two C-N-N pincer ligands of BODIPY appended 2,2'-bipyridine derivatives (BP and BPB). It has been confirmed that the C-Pd bond does exist and plays a crucial role in "on-off" fluorescence behavior. Based on it, a coordination-induced fluorescence quenching sensor for Pd2+ was constructed. The results indicated that BP possessed high sensitivity and specificity for Pd2+ in solution. The limit of detection (LOD) of BP is determined to be 0.97 nM within a linear range between 1.0 and 50.0 nM, meanwhile, the platinum-group ions demonstrate no interference. The bio-imaging application of BP was investigated and it exhibited a promising vitro test for fluorescent imaging of Pd2+ ions in MCF-7 cells. Meanwhile, BPB coated sensor label for Pd2+ was set up. The visible color variation was displayed under UV light with increasing concentrations of Pd2+. Briefly speaking, fluorescence probes of BP and BPB offer new approaches for Pd2+ detection in a lab and on-site test, as well as the vivo imaging. Then, with the aid of (TD)DFT calculation, the internal reason for the optical difference between the two ligands was disclosed. This concept of CPC containing a Pd-C covalent bond provides a promising perspective of coordination fluorescence sensors.

Developing strong NIR absorption materials through linear planar π-conjugated cyclopalladated complex dimers.

Near-infrared absorption metal complexes (NIRMCs) have been traditionally associated with the π-expanded macrocycle structure. However, macrocyclic ligands suitable for NIRMCs require a laborious synthetic route, and are a limited few. Herein, we report a kind of NIRMC based on linear large planar π-conjugated cyclopalladated dimers, which can be obtained by a facile base-induced dimerization of corresponding monomers. These dimers show an intense absorption in the NIR region with ε770 nm = 2.5 × 105 cm-1 M-1, and display a fluorescence emission peak at ca. 910 nm. Quinoid thiophene methine (QTM) and the cyclopalladated structure are speculated to be the key factors for their strong NIR absorption, which provides a different perspective of preparing NIR absorption metal complexes.

Two-dimensional nano-layered materials as multi-responsive chemosensors constructed by carbazole- and fluorene-based polyaniline-like derivatives.

The development of multi-responsive chemosensors has a bright application prospect in environmental monitoring and biological diagnosis. In this paper, we report two kinds of fluorescent polyaniline-like derivatives containing of carbazole or fluorene moieties with two-dimensional (2D) nano-layered structure and their applications in the detection of Al3+, Fe3+, Cu2+ and HCl in different environments. Through the analysis of the structure and properties of these two 2D materials, we find that the prepared (Poly(9,9'-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis(9H-carbazol-3-amine))) PDFCA material performs excellent sensing properties for above analytes. Relevant density functional theory (DFT) calculation further confirms the potential application of 2D nano-layered PDFCA material in sensing field. This study presents that 2D nano-layered PDFCA material is considerably competitive in the development of multi-responsive chemosensors, and it will greatly accelerate the research of 2D polymer materials.

Development of highly efficient chemosensors for Cu2+ and N2H4 detection based on 2D polyaniline derivatives by template-free chemical polymerization method.

Chemosensors play an important role in environmental protection, medical diagnosis and energy conservation. Although polyaniline and its derivatives and two-dimensional (2D) materials have been applied as chemosensors in many reports, the concept of two-dimensional (2D) polyaniline derivatives has not been achieved in chemosensors. Here, two kinds of two-dimensional (2D) polyaniline derivatives are designed and synthesized by template-free chemical polymerization. It can be found that these two two-dimensional (2D) chemosensors exhibit high selectivity and sensitivity to Cu2+ and N2H4. Moreover, it is noteworthy that one of the two-dimensional materials can achieve the limit of detection (LOD) of 45 nM and 8 nM for Cu2+ and N2H4, respectively. Especially, these results imply that this two-dimensional polyaniline derivative is promising as the chemosensor in sensing field.

Carbazole and fluorene polyaniline derivatives: Synthesis, properties and application as multiple stimuli-responsive fluorescent chemosensor.

Development of conjugated polymers with fluorescence sensing characteristics has received close attention from researchers in fields of environmental protection, biosensing and toxins detection on food. In this paper, novel polyaniline derivatives of poly(9-methyl-9H-carbazol-3-amine) and poly(9,9-dihexyl-9H-fluoren-2-amine) are prepared by facile chemical polymerization. Then they are characterized with NMR (Nuclear Magnetic Resonance), GPC (Gel Permeation Chromatography), XRD (X-Ray Diffraction), FT-IR (Fourier Transform Infrared spectroscopy), FL (Fluorescence spectrometry) and UV-vis (Ultraviolet-visible spectroscopy) characterizations and further applied to the fluorescence detection of different acids and amines. Moreover, the obtained poly(9-methyl-9H-carbazol-3-amine) displays excellent fluorescence properties in the detection for both acids and amines. Besides, this poly(9-methyl-9H-carbazol-3-amine) can not only be used for fluorescence detection in solution, but also can be prepared into solid state and applied in the gas phase fluorescence detection. This work has greatly expanded the scope of application to these polyaniline derivatives materials, opening a new path for the researches on multi-functional chemosensor.

Nitrogen atom free polythiophene derivative as an efficient chemosensor for highly selective and sensitive Cu2+ and Ag+ detection.

A new nitrogen atom free polythiophene derivative bearing methoxy-ethoxy units of poly{3-[2-(2-methoxy-ethoxy)-ethoxy]-thiophene} (PM) was successfully synthesized by introducing multiple ether bonds on the thiophene unit. The special (ether bonds) coordination structure was constructed and these fluorescence characteristics of PM to metal ions detection were investigated. This polythiophene-based material displays a specific fluorescence quenching effect on Cu2+ and Ag+, and correspondingly emerges some color changes that are visible to the naked eyes. In addition, it even performs a low detection limit to Cu2+ for only 0.45 µM, which exhibits a higher selective detection to Cu2+ than other reported N-containing chemosenors. These discoveries are helpful to indicate an original aspect for development on nitrogen atom free polythiophene-based fluorescent-sensing materials.

A novel preparation of small TiO2 nanoparticle and its application to dye-sensitized solar cells with binder-free paste at low temperature.

TiO(2) nanoparticles with diameter <10 nm were synthesized by a facile, non-hydrothermal method at low temperature. A porous TiO(2) film electrode consisting of the obtained small TiO(2) nanoparticles and commercial TiO(2) nanoparticles without any organic binder was prepared at low temperature. The photovoltaic performance of the solar cell based on the TiO(2) electrode was investigated by the current-voltage and electrochemical impedance spectra. All the experimental results indicate that the addition amount of the small TiO(2) nanoparticles in the binder-free paste affects the photovoltaic performance of the photoelectrode greatly. The overall energy conversion efficiency of the optimized binder-free photoelectrode achieves 3.53% without high-temperature sintering. Additionally, the performance of the small particles derived from this facile method can be comparable with that of small ones obtained from traditionally hydrothermal method, indicating the small particles in our study can be applied to flexible dye-sensitized solar cells. And the present low-temperature preparation of photoelectrode containing small TiO(2) nanoparticles shows an encouraging performance on both conductive glass and plastic substrates and could be suited in the industrial and large-scale application due to its low energy cost and relatively high conversion efficiency.

Solid-state dye-sensitized solar cells fabricated by coupling photoelectrochemically deposited poly(3,4-ethylenedioxythiophene) (PEDOT) with silver-paint on cathode.

A PEDOT-based dye-sensitized solar cell (DSC) is successfully improved by coupling photoelectrochemically deposited PEDOT layer with an Ag paste-paint on the cathode. With a 9.3 µm thick mesoscopic nanocrystalline TiO(2) film, a maximum cell performance of 3.2% with relatively high V(oc) of around 780 mV is achieved.

Influence of doped anions on poly(3,4-ethylenedioxythiophene) as hole conductors for iodine-free solid-state dye-sensitized solar cells.

Poly(3,4-ethylenedioxythiophene) (PEDOT) is an excellent hole-conducting polymer able to replace the liquid I(-)/I3(-) redox electrolyte in dye-sensitized solar cells (DSCs). In this work we applied the in situ photoelectropolymerization technique to synthesize PEDOT and carried out a careful analysis of the effect of different doping anions on overall solar cell performance. The anions analyzed in this work are ClO4(-), CF3SO3(-), BF4(-), and TFSI(-). The best solar cell performance was observed when the TFSI(-) anion was used. Photoelectrochemical and impedance studies reveal that the doped anions in the PEDOT hole conductor system have great influences on I-V curves, conductivity, and impedance. The optimization of these parameters allowed us to obtain an iodine-free solid-state DSC with a maximum J(sc) of 5.3 mA/cm2, V(oc) of 750 mV, and a conversion efficiency of 2.85% which is the highest efficiency obtained so far for an iodine-free solid-state DSC using PEDOT as hole-transport material.

Sputtered Nb2O5 as an effective blocking layer at conducting glass and TiO2 interfaces in ionic liquid-based dye-sensitized solar cells.

The thin Nb(2)O(5) layer works as a remarkable blocking layer when deposited by the rf magnetron sputtering method between fluorine-doped tin oxide and a mesoporous TiO(2) layer, improving open-circuit photovoltage (V(oc)) and fill factor (FF) with power conversion efficiency over 5.5% at 1 sun irradiation of the dye-sensitized TiO(2) solar cells using ionic liquid electrolytes.

Deposition of a thin film of TiOx from a titanium metal target as novel blocking layers at conducting glass/TiO2 interfaces in ionic liquid mesoscopic TiO2 dye-sensitized solar cells.

In dye-sensitized TiO2 solar cells, charge recombination processes at interfaces between fluorine-doped tin oxide (FTO), TiO2, dye, and electrolyte play an important role in limiting the photon-to-electron conversion efficiency. From this point of view, a high work function material such as titanium deposited by sputtering on FTO has been investigated as an effective blocking layer for preventing electron leakage from FTO without influencing electron injection. X-ray photoelectron spectroscopy analysis indicates that different species of Ti (Ti4+, Ti3+, Ti2+, and a small amount of Ti0) exist on FTO. Electrochemical and photoelectrochemical measurements reveal that thin films of titanium species, expressed as TiOx, work as a compact blocking layer between FTO and TiO2 nanocrystaline film, improving Voc and the fill factor, finally giving a better conversion efficiency for dye-sensitized TiO2 solar cells with ionic liquid electrolytes.

A novel ruthenium sensitizer with a hydrophobic 2-thiophen-2-yl-vinyl-conjugated bipyridyl ligand for effective dye sensitized TiO2 solar cells.

A hydrophobic and 2-thiophen-2-yl-vinyl-conjugated ruthenium complex, cis-Ru(dhtbpy)(dcbpy)(NCS)2 [dhtbpy = 4,4'-di(hexylthienylvinyl)-2,2'-bipyridyl; dcbpy = 4,4'-dicarboxy-2,2'-bipyridyl], was newly designed, synthesized and applied successfully to sensitization of nanocrystalline TiO2-based solar cells, giving a conversion efficiency of 9.5% under irradiation with AM 1.5 solar light.