Ruffolo R, Evans CE, Liu XH, Ni Y, Pang Z, Park P, McWilliams AR, Gu X, Lu X, Yekta A, Winnik MA, Manners I
Department of Chemistry, University of Toronto, Ontario, Canada.
Anal Chem. 2000 Apr 15;72(8):1894-904. doi: 10.1021/ac9909610.
We examine the use of thionylphosphazene-based block copolymers as matrixes for oxygen sensor applications. Poly(aminothionylphosphazene)-b-poly(tetrahydrofuran) (PATPy-PTHFx) block copolymers were prepared via reaction of ring-opened poly(chlorothionylphosphazene) with THF and subsequently with excess n-butylamine (to form PBATPy-PTHFx) or methylamine (to form PMATPy-PTHFx). The block copolymers were characterized by NMR, gel permeation chromatography, and differential scanning calorimetry. Films of PBATPy-PTHFx block copolymers containing platinum octaethylporphyrin or [Ru(dpp)3]Cl2 (dpp = 4,7-diphenyl-1,10-phenanthroline) as the oxygen-sensitive chromophore were prepared, and time-scan experiments were carried out to determine the diffusion coefficients, Do2, and solubilities, So2, of oxygen therein. Despite microphase separation, the data fit well to a simple Fick's law description of oxygen diffusion and gave Do2 values smaller than that for the n-butylamino-substituted PBATP635. For films freshly annealed above the melting point of PTHFx, the Do2 values were 35-50% (dye-dependent) larger than after aging 3 days at room temperature. Films with [Ru(dpp)3]Cl2 as the dye were evaluated as media for phosphorescent pressure-sensing. The dye-containing polymer films exhibit linear Stern-Volmer-like plots, even at high dye concentrations, as well as good photostability, and significantly higher sensitivity to oxygen quenching than simple mixtures of the analogous homopolymers.
我们研究了基于亚硫酰磷腈的嵌段共聚物作为氧传感器应用基质的用途。通过开环聚（氯代亚硫酰磷腈）与四氢呋喃反应，随后与过量正丁胺（形成PBATPy - PTHFx）或甲胺（形成PMATPy - PTHFx）反应制备了聚（氨基亚硫酰磷腈）-b-聚（四氢呋喃）（PATPy - PTHFx）嵌段共聚物。通过核磁共振、凝胶渗透色谱和差示扫描量热法对嵌段共聚物进行了表征。制备了含有八乙基铂卟啉或[Ru(dpp)3]Cl2（dpp = 4,7 - 二苯基 - 1,10 - 菲咯啉）作为氧敏发色团的PBATPy - PTHFx嵌段共聚物薄膜，并进行了时间扫描实验以确定其中氧气的扩散系数Do2和溶解度So2。尽管存在微相分离，但数据很好地符合氧扩散的简单菲克定律描述，并且给出的Do2值小于正丁氨基取代的PBATP635的Do2值。对于在高于PTHFx熔点的温度下新鲜退火的薄膜，Do2值比在室温下老化3天后大35 - 50%（取决于染料）。以[Ru(dpp)3]Cl2作为染料的薄膜被评估为磷光压力传感介质。含染料的聚合物薄膜即使在高染料浓度下也呈现出类似线性斯特恩 - 沃尔默的曲线，以及良好的光稳定性，并且对氧猝灭的灵敏度明显高于类似均聚物的简单混合物。
