Surface modification of a polymer substrate with a mercapto functionality is crucial in many applications such as flexible circuitry and point-of-care biosensors. We present here a novel bifunctional molecular adhesive, 3-mercaptopropylsilatrane (MPS), as an interface between polymer and metal surfaces. Under ambient conditions, surface modification of polymer surfaces with a mercapto functionality can be achieved with low concentration (0.46 mM) of MPS in aqueous solvent (50% ethanol) in a short time (<30 min). Three popular polymers for optical sensors, polycarbonate, polyethylene terephthalate, and poly(methyl methacrylate), were employed as substrates, and MPS films formed on these substrates were examined and compared with that on a glass substrate. The films were characterized by UV-vis spectroscopy, water contact angle, X-ray photoelectron spectroscopy, and atomic force microscopy. MPS was also used as a bifunctional linker for the construction of a gold nanoparticle (AuNP) sub-monolayer on these polymer surfaces. Under optimized preparation conditions, the absorbance and full width at half-maximum of the plasmon band are comparable to those of a AuNP-modified glass substrate. Hence, MPS may have a potential to be a key component in polymer substrate-based localized surface plasmon resonance sensors. A self-catalytic surface reaction mechanism is also proposed to account for the results. As compared to a glass surface with a high number of silanol groups, the successful formation of an MPS film on polymer surfaces with relatively few reactive sites is probably due to the lateral polymerization of MPS starting from a condensed MPS molecule on a reactive site of a polymer surface.

The one-step catalytic stamp pattern transfer process is described for producing arrays of hierarchical nanoparticle assemblies. The method simply combines in situ nanoparticle synthesis triggered by free residual Si−H groups on PDMS stamps and the lift-off pattern transfer technique. No additional nanoparticle synthesis procedure is required before the pattern transfer process. Exquisitely uniform and precisely spaced hierarchical nanoparticle assemblies with designed geometry can be rapidly produced using the catalytic stamp pattern transfer process. Sequential catalytic stamp pattern transfer also is described to generate multilayered, hierarchical nanoparticle assemblies with various geometries. The hierarchical nanoparticle assemblies catalytically transferred onto the surface are not just nanoparticles but nanoparticle− polydimethylsiloxane residue composites. The in situ-synthesized nanoparticles retain optical properties. The hierarchical nanoparticle assemblies with precisely controlled geometry further show potential in the application of surface-enhanced Raman scattering. The capability of one-step catalytic stamp pattern transfer allows the scalable and reproducible fabrication of welldefined hierarchical nanoparticle assemblies.

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Steroid ligands can easily diffuse through the cell membrane and this property makes it feasible to be used for in-situ staining of the nuclear receptors. However, nonspecific binding of the internalized ligand probe with the cellular components has caused serious interferences for the detection of receptor-expressing cells. We report a novel gold nanocluster (AuNC)-conjugated estrogen probe that can eliminate nonspecific internalization and accelerate nuclear localization to achieve selective and rapid detection of estrogen receptors (ERs) in live cells. The AuNC, protected by bovine serum albumin (BSA), BSA-AuNCs, was prepared by the synthesis and confirmed to be 1.9 nm in core size and 18 nm in diameter. Ethinyl estradiol was used as the precursor of 17β-estradial (E2) to conjugate with BSA-protected AuNCs via polyethylene glycol linker (E2-PEG/BSA-AuNCs) or to conjugate with Cy3 dyes (E2-Cy3). The conjugated probe was determined to contain five E2 molecules per BSA-AuNC by mass spectrometry and exhibit an emission maximum of around 640 nm, which was not altered by E2 conjugation indicating that the structural integrity of BSA-AuNCs was conserved. E2-PEG/BSA-AuNCs probes were quickly internalized by MCF-7 (ER+) cells and localized to the nuclei in 2 h. Such internalization was sensitive to competition by free E2 and was rarely detected in the controls using either non-conjugated BSA-AuNCs in MCF-7 (ER+) cells or E2-PEG/BSA-AuNCs in MDA-MB-231 (ER-) cells. In contrast to the high specificity of E2-PEG/BSA-AuNCs probe, the uptake of E2-Cy3 probe could not differentiate between MCF-7(ER+) and MDA-MB-231(ER-) cells during the early phases of the treatment. Moreover, nuclear targeting by E2-Cy3 was three times slower than that by the E2-PEG/BSA-AuNC probe. Such accelerated nuclei targeting was consistent with the enhanced cell viability by conjugating E2 with BSA-AuNC. In conclusion, the E2-PEG/BSA-AuNC probes are promising candidates that can be used for the detection of ER+ tumor tissues and the same strategy can be applied to fabricate other steroid probes.