Intense pH Sensitivity Modulation in Carbon Nanotube-Based Field-Effect Transistor by Non-Covalent Polyfluorene Functionalization.

We compare the pH sensing performance of non-functionalized carbon nanotubes (CNT) field-effect transistors (p-CNTFET) and CNTFET functionalized with a conjugated polyfluorene polymer (labeled FF-UR) bearing urea-based moieties (f-CNTFET). The devices are electrolyte-gated, PMMA-passivated, 5 µm-channel FETs with unsorted, inkjet-printed single-walled CNT. In phosphate (PBS) and borate (BBS) buffer solutions, the p-CNTFETs exhibit a p-type operation while f-CNTFETs exhibit p-type behavior in BBS and ambipolarity in PBS. The sensitivity to pH is evaluated by measuring the drain current at a gate and drain voltage of -0.8 V. In PBS, p-CNTFETs show a linear, reversible pH response between pH 3 and pH 9 with a sensitivity of 26 ± 2.2%/pH unit; while f-CNTFETs have a much stronger, reversible pH response (373%/pH unit), but only over the range of pH 7 to pH 9. In BBS, both p-CNTFET and f-CNTFET show a linear pH response between pH 5 and 9, with sensitivities of 56%/pH and 96%/pH, respectively. Analysis of the I-V curves as a function of pH suggests that the increased pH sensitivity of f-CNTFET is consistent with interactions of FF-UR with phosphate ions in PBS and boric acid in BBS, with the ratio and charge of the complexed species depending on pH. The complexation affects the efficiency of electrolyte gating and the surface charge around the CNT, both of which modify the I-V response of the CNTFET, leading to the observed current sensitivity as a function of pH. The performances of p-CNTFET in PBS are comparable to the best results in the literature, while the performances of the f-CNTFET far exceed the current state-of-the-art by a factor of four in BBS and more than 10 over a limited range of pH in BBS. This is the first time that a functionalization other than carboxylate moieties has significantly improved the state-of-the-art of pH sensing with CNTFET or CNT chemistors. On the other hand, this study also highlights the challenge of transferring this performance to a real water matrix, where many different species may compete for interactions with FF-UR.

Large area CMOS bio-pixel array for compact high sensitive multiplex biosensing.

A novel CMOS bio-pixel array which integrates assay substrate and assay readout is demonstrated for multiplex and multireplicate detection of a triplicate of cytokines with single digit pg ml(-1) sensitivities. Uniquely designed large area bio-pixels enable individual assays to be dedicated to and addressed by single pixels. A capability to simultaneously measure a large number of targets is provided by the 128 available pixels. Chemiluminescent assays are carried out directly on the pixel surface which also detects the emitted chemiluminescent photons, facilitating a highly compact sensor and reader format. The high sensitivity of the bio-pixel array is enabled by the high refractive index of silicon based pixels. This in turn generates a strong supercritical angle luminescence response significantly increasing the efficiency of the photon collection over conventional farfield modalities.

Formation of a covalent bond between a polyoxometalate and silica covered by SiH moieties.

Dehydroxylated silica was modified by grafting reaction of SiHMe2 groups. The resulting material was fully characterized by various methods including infrared and one- and two-dimensional solid-state NMR. This material can further react with dehydrated polyoxometalates (POMs), leading to the formation of a covalent POM-silica bond. In the case of H4PVMo11O40, hydrogen released during the grafting reaction reduces the POM. This leads to the formation of two surface species, which can be reoxidized in presence of oxygen. In the case of H3PW12O40, no reduction is observed. In both cases, (29)Si solid-state NMR shows that the POM-silica bond is covalent, contrary to what was observed in homogeneous conditions.

Polyoxometalate grafting onto silica: stability diagrams of H3PMo12O40 on {001}, {101}, and {111} ß-cristobalite surfaces analyzed by DFT.

The process of grafting H(3)PMo(12)O(40) onto silica surfaces is studied using periodic density functional theory methods. For surfaces with a high hydroxyl coverage, the hydroxyl groups are consumed by the polyoxometalate protons, resulting in water formation and the creation of a covalent bond between the polyoxometalate and the surface, and mostly no remaining acidic proton on the polyoxometalate. When the surfaces are partially dehydroxylated and more hydrophobic, after temperature pretreatment, less covalent and hydrogen bonds are formed and the polyoxometalate tends to retain surface hydroxyl groups, while at least one acidic proton remains. Hence the hydroxylation of the surface has a great impact on the chemical properties of the grafted polyoxometalate. In return, the polyoxometalate species affects the compared stability of the partially hydroxylated silica surfaces in comparison with the bare silica case.

Reactivity of anhydrous keggin-type heteropolyacids with alkylsilanes: synthesis and characterization.

Anhydrous tungstic heteropolyacids react with alkylsilanes in the absence of solvent, leading to the evolution of hydrogen and the formation of a new kind of species where silicon is only weakly interacting with the polyoxometalate. The resulting material was characterized by various physicochemical methods including NMR, IR, and Raman spectroscopy. The most interesting feature is the unusual chemical shift of the (29)Si nuclei (ca. +50 ppm), which confirms the formation of a quasi-ionic bond between the organic and inorganic moieties. The weakness of this bond was also evidenced by chemical reactivity with nBu(4)NCl (leading to the formation of R(3)SiCl species) and oxygen. This new kind of structure can be of great interest in the field of microelectronics. Indeed the reactivity described in this article can be used and transferred easily in heterogeneous conditions to introduce defects in semiconductors.

Grafting reaction of organotin complexes on silica catalyzed by tungstic heteropolyacids.

The grafting reaction of tetramethyltin on silica is catalyzed by H(4)SiW(12)O(40) preliminary impregnated on the support. While the reaction proceeds at temperatures higher than 150 degrees C on silica alone, the presence of the polyacid allows the grafting at room temperature. A study as a function of the polyacid coverage has shown that there is a direct correlation between the reaction rate and the number of highly acidic sites on the support, probing that there is a reaction of the tetraalkyltin with them (limiting step) followed by a migration of the grafted fragment on the silica surface. Not only monografted species (as observed on silica) but also multigrafted tin species are formed because of further reactions of the grafted fragments.