卟啉-二芳基乙烯分子及其金属配合物的合成与光致变色特性

以苯甲醛和吡咯为初始原料,经多步反应合成了5-[2,3-双(2,4,5-三甲基-3-噻吩基)马来酰亚胺-N-苯基]-10,15,20-三苯基卟啉(TPPMA)及其金属锌配合物(ZnTPPMA)与铜配合物(CuTPPMA),通过IR,MS,1H NMR和13C NMR确认了化合物的结构,并利用UV-Vis光谱探讨了化合物的光致变色性能.实验结果表明,无论在聚乙烯醇缩丁醛(PVB)膜还是在溶液中,TPPMA在254 nm紫外光照射下,没有光致变色现象,而在254和650 nm的光照下其金属配合物CuTPPMA和ZnTPPMA在溶液及PVB膜中皆可以发生可逆的光致变色反应.     

Cargo Encapsulation in Photochromic Supramolecular Hydrogels Depends on Specific Guest-Gelator Supramolecular Interactions

Photochromic supramolecular hydrogels are prospective materials for light-triggered drug release and bionanotechnology. Here we present a structural analysis of peptide-derived photochromic supramolecular hydrogels, which were physically loaded with a selection of biologically related compounds, using advanced techniques of nuclear magnetic resonance. The results enable detailed and correct understanding of the loading process and will allow for correct design of pharmacologically relevant systems for phototriggered drug delivery.     

Kinetics of refractive index changes in polymeric photochromic films

Methacrylate copolymers containing, in side chain azobenzene groupings with heterocyclic sulfonamide substituents: N-(2,6-dimethylpyrimidin-4-yl)sulfamoyl (sulfisomidine) and N-(5-methylisoxazol-3-yl) sulfamoyl (sulfamethoxazole) were investigated. The materials undergo reversible trans-cis isomerisation during illumination with light. This results in changes of dipole moment, polarizability and refractive index. Ellipsometric measurements showed a distinct decreasing refractive index during illumination with light corresponding to absorption band (ca. 450 nm). Depending on the polymer, the change of real part of refractive index in spin-coated films was between 0.016 and 0.031. The dynamics of growth and decay of refractive index changes, was described by biexponential function approach.     

Methacrylic Polymers Bearing in the Side-Chain an Optically Active Moiety Linked to the trans-4-Azobenzene Chromophore: Chiroptical Properties of Poly[(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene]

The synthesis by radical homopolymerization of a novel optically active methacrylic polymer containing a side-chain chiral moiety linked to a photochromic chromophore has been carried out starting from the related monomer trans-(S)-(+)-N-methyl-(2-methacryloyloxypropanoyl)-4-aminoazobenzene. The chiroptical properties in solution of the polymer have been investigated by circular dichroism and compared with those of the corresponding low molecular weight model compound, trans-(S)-(+)-N-methyl-(2-pivaloyloxypropanoyl)-4-aminoazobenzene. The optical activity displayed by the polymer is discussed in terms of extent of chiral conformations assumed by the macromolecules as a consequence of dipole-dipole interactions between the azoaromatic chromophores.     

Faraday Effect of BSO and BTO Crystals Doped with Cr,Mn and Cu

The influence of both photochromic doping and photochromic transitions on the effect of magneto‐optical rotation (Farady effect ‐ FE) of undoped and doped with Cr, Mn and Cu Bi₁₂SiO₂0 (BSO) and Bi₁₂TiO₂0 (BTO) crystals is studied. The present results show, that Cr, Mn and Cu increase the FE. The influence of Cr, whose affect on the optical activity (OA) of BSO is most significant, here is too negligible (Verdet coefficient (V) increases only with 1‐2 % in the range 700 ‐ 590 nm). The Mn‐doping of BSO led to a V‐increase with about of 11 % in the range 400 ‐ 700 nm, as at 460 nm the relative increase of V reaches to about 30 %. The influence of Cu on FE in BSO (likely the case of the natural optical rotation) is again significant. Thus, the influence of V in the case of BSO:Cu is about 18 % in the range 700 ‐ 480 nm as reaches 28 % in the shortwave region at 480 nm. However, in BTO:Cu (0.02 mol.% Cu) the influence of Cu is opposite in respect of both effects. Now the values of V increase with 21 % at 630 nm, 22 % at 590 nm, 42 % at 520 nm, and 73 % at 480 nm in comparison to BTO‐undoped.