Chemical functionalization of silicon oxide (SiO(2)) surfaces with silane molecules is an important technique for a variety of device and sensor applications. Quality control of self-assembled monolayers (SAMs) is difficult to achieve because of the lack of a direct measure for newly formed interfacial Si-O bonds. Herein we report a sensitive measure of the bonding interface between the SAM and SiO(2), whereby the longitudinal optical (LO) phonon mode of SiO(2) provides a high level of selectivity for the characterization of newly formed interfacial bonds. The intensity and spectral position of the LO peak, observed upon silanization of a variety of silane molecules, are shown to be reliable fingerprints of formation of interfacial bonds that effectively extend the Si-O network after SAM formation. While the IR absorption intensities of functional groups (e.g., >C=O, CH(2)/CH(3)) depend on the nature of the films, the blue-shift and intensity increase of the LO phonon mode are common to all silane molecules investigated and their magnitude is associated with the creation of interfacial bonds only. Moreover, results from this study demonstrate the ability of the LO phonon mode to analyze the silanization kinetics of SiO(2) surfaces, which provides mechanistic insights on the self-assembly process to help achieve a stable and high quality SAM.
Photodynamic therapy (PDT) is an emerging clinical modality for the treatment of a variety of diseases. Most photosensitizers are hydrophobic and poorly soluble in water. Many new nanoplatforms have been successfully established to improve the delivery efficiency of PS drugs. However, few reported studies have investigated how the carrier microenvironment may affect the photophysical properties of PS drugs and subsequently, their biological efficacy in killing malignant cells. In this study, we describe the modulation of type I and II photoactivation processes of the photosensitizer, 5,10,15,20-tetrakis(meso-hydroxyphenyl)porphyrin (mTHPP), by the micelle core environment. Electron-rich poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) micelles increased photoactivations from type II to type I mechanisms, which significantly increased the generation of O2•− through the electron transfer pathway over 1O2 production through energy transfer process. The PDPA micelles led to enhanced phototoxicity over the electron-deficient poly(D,L-lactide) control in multiple cancer cell lines under argon-saturated conditions. These data suggest that micelle carriers may not only improve the bioavailability of photosensitizer drugs, but also modulate photophysical properties for improved PDT efficacy.
Low-doped silicon multi-nanowire field effect transistors with high ON/OFF ratio over 10(7) and a low subthreshold swing of 60-120 mV dec(-1) are fabricated using lithographic semiconductor processes. The use of multi-nanowires instead of a single nanowire as sensing elements has shown improved device uniformity and stability in buffer solutions. The device stability is further improved with surface silanization and biasing with a solution gate rather than a backgate. pH sensing with a linear response over a range of 2-9 is achieved using these devices. Selective detection of bovine serum albumin at concentrations as low as 0.1 femtomolar is demonstrated.
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