ABSTRACT
Herein, polysiloxane-based aggregation-induced emission (AIE) polymers and rubbers were prepared which display interesting multi-stimuli responsive fluorescence. TPE-modified polydimethylsiloxanes (PDMS-TPE) as polysiloxane-based AIE polymers were synthesized through Heck reaction of bromo-substituted tetraphenylethene (TPE-Br) and vinyl polysiloxanes. As expected, TPE moiety endows the modified polysiloxane with typical AIE behavior. However, limited by the long polymer chains, the aggregation process of PDMS-TPE shows obvious differences compared with the small molecule TPE-Br. The fluorescence of PDMS-TPE in THF/H2O starts to increase when the H2O fraction (fw) is 70% while TPE-Br is nearly non-luminous until the fw is up to 99%. The fluorescence intensity ratio (I/I0) of PDMS-TPE in the aggregated state and dispersed state is over 1300, greater than that of TPE-Br (I/I0 = 380). More importantly, the exceptional thermal motion of Si-O-Si chains and AIE characteristic of TPE moiety work together, enabling PDMS-TPE to show specific temperature-dependent fluorescence with a wider response range of room temperature to 190°C, which is distinguished from TPE-Br. And such fluorescence responsiveness possess good fatigue-resistance. Furthermore, fluorescent silicone rubbers, r-PDMS-TPE were prepared by using PDMS-TPE as additive of the base gum. They display interesting solvent-controllable fluorescence and higher tensile strength (4.42 MPa) than the control sample without TPE component (1.96 MPa). Notably, a unique stretching-enhanced emission (SEE) phenomenon is observed from these TPE-modified silicone rubbers. When being stretched, the rubbers' fluorescent emission intensity could increase by 143%.
ABSTRACT
Silicone elastomers exhibit a broad range of beneficial properties that are exploited in biomaterials. In some cases, however, problems can arise at silicone elastomer interfaces. With breast implants, for example, the fibrous capsule that forms at the silicone interface can undergo contracture, which can lead to the need for revision surgery. The relationship between surface topography and wound healing--which could impact on the degree of contracture--has not been examined in detail. To address this, we prepared silicone elastomer samples with rms surface roughnesses varying from 88 to 650 nm and examined the growth of 3T3 fibroblasts on these surfaces. The PicoGreen assay demonstrated that fibroblast growth decreased with increases in surface roughness. Relatively smooth (approximately 88 nm) PDMS samples had ca. twice as much fibroblast DNA per unit area than the 'bumpy' (approximately 378 nm) and very rough (approximately 604 and approximately 650 nm) PDMS samples. While the PDMS sample with roughness of approximately 650 nm had significantly fewer fibroblasts at 24h than the TCP control, fibroblasts on the smooth silicone surprisingly reached confluence much more rapidly than on TCP, the gold standard for cell culture. Thus, increasing the surface roughness at the sub-micron scale could be a strategy worthy of consideration to help mitigate fibroblast growth and control fibrous capsule formation on silicone elastomer implants.
