The protonation of a simple meso-tetraphenylporphyrin in an organic-aqueous system was found to be induced by the counteranions. During the process of protonation, the counteranion of the proton sources binds with the porphyrin core and thus promotes the complexation of the porphyrin and protons. The interaction of porphyrin and anion was characterized by fluorescence, UV-visible, cyclic voltammetry, (1)H NMR, and IR. Moreover, it could be exploited in selective fluorescent sensing of Cl(-). The sensing mechanism was based on extraction of protons from the aqueous phase into the organic phase by free base porphyrin and simultaneous coextraction of Cl(-), which promoted porphyrin protonation, and hence resulted in significant changes of the porphyrin fluorescence spectra. Selectivity trends turned out to be dependent upon the lipophilicity of anion and the binding affinity and structure complementarity between the protonated porphyrin and anions. The fluorescence enhancement of the porphyrin band at 684 nm showed modest selectivity for Cl(-) and NO(3)(-).
We report here on the synthesis and photophysical/electrochemical properties of three functional triarylamine organic dyes (MXD5-7) as well as their application in dye-sensitized nanocrystalline TiO 2 solar cells (DSSCs). For the designed dyes, the nonplanar structures of bis-hexapropyltruxeneamino take the role of electron donor. The introduction of bis-hexapropyltruxeneamino units brought about superior performance over the simple triphenylamine dye, in terms of light-capturing abilities and suppressing dye aggregation. Among three dyes, the DSSCs based on the dye MXD7 showed the best photovoltaic performance: a short-circuit photocurrent density (J SC ) of 11.8 mA cm -2 , an open-circuit photovoltage (V OC ) of 772 mV, and a fill factor (ff) of 0.68, corresponding to an overall conversion efficiency of 6.18% under 100 mW cm -2 irradiation. These dyes exhibited high V OC values, possible origin for which was investigated regarding the TiO 2 surface blocking, conduction band movement, and electrolyte-dye interaction.
BackgroundThree-dimensional joint kinematics during canine locomotion are commonly measured using skin marker-based stereophotogrammetry technologies. However, marker-related errors caused by the displacement of the skin surface relative to the underlying bones (i.e., soft tissue artifacts, STA) may affect the accuracy of the measurements and obscure clinically relevant information. Few studies have assessed STA in canine limbs during kinematic analysis. The magnitudes and patterns of the STA and their influence on kinematic analysis remain unclear. Therefore, the current study aims to quantify the in vivo STA of skin markers on the canine thigh and crus during passive joint motion. The stifle joints of ten dogs were passively extended while the skin markers were measured using a motion capture system, and skeletal kinematics were determined using a CT-to-fluoroscopic image registration method.ResultsThe skin markers exhibited considerable STA relative to the underlying bones, with a peak amplitude of 27.4 mm for thigh markers and 28.7 mm for crus markers; however, the amplitudes and displacement directions at different attachment sites were inconsistent. The markers on the cranial thigh and lateral crus closer to the stifle joint had greater STA amplitudes in comparison to those of other markers. Most markers had STA with linear and quadratic patterns against the stifle flexion angles. These STA resulted in underestimated flexion angles but overestimated adduction and internal rotation when the stifle was flexed to greater than 90°.ConclusionsMarker displacements relative to the underlying bones were prominent in the cranial aspect of the thigh and the proximal-lateral aspect of the crus. The calculated stifle kinematic variables were also affected by the STA. These findings can provide a reference for marker selection in canine motion analysis for similar motion tasks and clarify the relationship between STA patterns and stifle kinematics; the results may therefore contribute to the development of STA models and compensation techniques for canine motion analysis.Electronic supplementary materialThe online version of this article (10.1186/s12917-018-1714-7) contains supplementary material, which is available to authorized users.
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