Several important photophysical properties of the cyanine dye Cy3 have been determined by laser flash photolysis. The triplet-state absorption and photoisomerization of Cy3 are distinguished by using the heavy-atom effects and oxygen-induced triplet --> triplet energy transfer. Furthermore, the triplet-state extinction coefficient and quantum yield of Cy3 are also measured via triplet-triplet energy-transfer method and comparative actinometry, respectively. It is found that the triplet --> triplet (T1-->Tn) absorptions of trans-Cy3 largely overlap the ground-state absorption of cis-Cy3. Unlike what occurred in Cy5, we have not observed the triplet-state T1-->Tn absorption of cis-Cy3 and the phosphorescence from triplet state of cis-Cy3 following a singlet excitation (S0-S1) of trans-Cy3, indicating the absence of a lowest cis-triplet state as an isomerization intermediate upon excitation in Cy3. The detailed spectra of Cy3 reported in this paper could help us interpret the complicated photophysics of cyanine dyes.

The optical spectra of the dimethoxy-p-phenylene-ethynylene oligomers (up to n ) 10) are calculated by DFT and TD-DFT methods. It is found that the conformational rotations around the cylindrical triple-bonded carbon links impact significantly the optical spectrum. The effective conjugation length (ECL) of the oligomer is obtained by extrapolating the HOMO-LUMO gap to infinite chain length with an alternative exponential function. The spectral shift is mainly dependent on the high π-conjugation segment of oligomers, resulting from the planarization of the backbone. Although the rotational barrier is very low, the calculated results further indicate that rotation about the cylindrical triple bond still interrupts the conjugation of rod-like oligomers to some extent, and leads to an angle-dependent HOMO-LUMO gap. The results are helpful to interpret the conformational-dependent spectroscopic phenomena of p-phenyleneethynylene oligomers and polymers (PPEs) observed in ensemble and single molecule spectroscopy.

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The tremendous progress of the wearable intelligent system has brought an urgent demand for flexible pressure sensors, especially for those possessing high sensing performances, simple manufacture technology, and efficient integration. In this work, hierarchical core−shell piezoresistive yarns (HCPYs), which contain internal silver-plated nylon electrodes and surface microporous structured carbon nanotubes (CNTs)/thermoplastic polyurethane (TPU) sensing layer, are designed and manufactured via facile wet-spinning accompanied by a water vapor coagulating bath. The obtained HCPY can either be inserted into traditional textiles to assemble a single-pressure sensor, or be woven into a textile-based flexible pressure sensors array with expected size and resolution, without compromising their comfort, breathability, and three-dimensional (3D) conformability. Simultaneously, to further enhance the sensing performance, the surface microporous structures of HCPYs are optimized by altering the treatment humidity and exposure time during the process of water vapor-induced phase separation. The wearable pressure sensors assembled by the optimal HCPY achieved a high sensitivity up to 84.5 N −1 , a good durability over 5000-cycle tests, a fast response time of 2.1 ms, and a recovery time of 2.4 ms. Moreover, the wearable pressure sensors have been successfully used to monitor physical signals and human motions. The textile-based flexible pressure sensors array has also been seamlessly integrated with sportswear to detect movements of the elbow joint and map spatial pressure distribution, which makes HCPY a promising candidate for constructing next-generation wearable electronics.

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