Miller John S, Finney Tanner J, Ilagan Ethan, Frank Skye, Chen-Izu Ye, Suga Keishi, Kuhl Tonya L
Department of Materials Science and Engineering, University of California Davis, Davis, CA 95616, USA.
Department of Chemical Engineering, University of California Davis, Davis, CA 95616, USA.
Biosensors (Basel). 2025 Jan 7;15(1):27. doi: 10.3390/bios15010027.
Polydiacetylenes (PDAs) are conjugated polymers that are well known for their colorimetric transition from blue to red with the application of energetic stimulus. Sensing platforms based on polymerized diacetylene surfactant vesicles and other structures have been widely demonstrated for various colorimetric biosensing applications. Although less studied and utilized, the transition also results in a change from a non-fluorescent to a highly fluorescent state, making polydiacetylenes useful for both colorimetric and fluorogenic sensing applications. Here, we focus on the characterization and optimization of polydiacetylene vesicles to tune their sensitivity for fluorogenic sensing applications. Particularly, we look at how the structure of the diacetylene (DA) hydrocarbon tail and headgroup affect the self-assembled vesicle size and stability, polymerization kinetics, and the fluorogenic, blue to red phase transition. Longer DA acyl tails generally resulted in smaller and more stable vesicles. The polymerization kinetics and the blue to red transition were a function of both the DA acyl tail length and structure of the headgroup. Decreasing the acyl tail length generally led to vesicles that were more sensitive to energetic stimuli. Headgroup modifications had different effects depending on the structure of the headgroup. Ethanolamine headgroups resulted in vesicles with potentially increased stimuli responsivity. The lower energy stimulus to induce the chromatic transition was attributed to an increase in headgroup hydrogen bonding and polymer backbone strain. Boronic-acid headgroup functionalization led to vesicles that were generally unstable, only weakly polymerized, and unable to fully transform to the red phase due to strong polar, aromatic headgroup interactions. This work presents the design of PDA vesicles in the context of biosensing platforms and includes a discussion of the past, present, and future of PDA biosensing.
聚二乙炔（PDA）是一种共轭聚合物，以在施加能量刺激时从蓝色到红色的比色转变而闻名。基于聚合二乙炔表面活性剂囊泡和其他结构的传感平台已被广泛用于各种比色生物传感应用。尽管研究和利用较少，但这种转变也会导致从非荧光状态转变为高荧光状态，使得聚二乙炔可用于比色和荧光传感应用。在这里，我们专注于聚二乙炔囊泡的表征和优化，以调整其对荧光传感应用的灵敏度。特别是，我们研究了二乙炔（DA）烃尾和头基的结构如何影响自组装囊泡的大小和稳定性、聚合动力学以及荧光性的蓝到红相变。较长的DA酰基尾通常会导致形成更小、更稳定的囊泡。聚合动力学以及蓝到红的转变是DA酰基尾长度和头基结构的函数。缩短酰基尾长度通常会导致囊泡对能量刺激更敏感。头基修饰根据头基的结构有不同的影响。乙醇胺头基导致囊泡的刺激响应性可能增加。诱导颜色转变所需的较低能量刺激归因于头基氢键和聚合物主链应变的增加。硼酸头基功能化导致囊泡通常不稳定，聚合较弱，并且由于强烈的极性、芳香头基相互作用而无法完全转变为红色相。这项工作介绍了在生物传感平台背景下PDA囊泡的设计，并讨论了PDA生物传感的过去、现在和未来。
