Direct Observation of Phenylalanine Orientations in Statherin Bound to Hydroxyapatite Surfaces
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99 GENERAL AND MISCELLANEOUS↗
Engineering topics
Baio, J
Publications and source records attributed to Baio, J.
NEXAFS imaging to characterize the physio-chemical composition of cuticle from African Flower Scarab Eudicella gralli
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99 GENERAL AND MISCELLANEOUS↗
Simultaneous Modification of Bottom-Contact Electrode and Dielectric Surfaces for Organic Thin-Film Transistors Through Single-Component Spin-Cast Monolayers
An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This efficient interface modification is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO{sub 2}) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defined phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C60) and p-channel (pentacene) based OTFTs. Specifically, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO{sub 2} dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec{sup -1}), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm{sup 2} V{sup -1} s{sup -1}, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.
36 MATERIALS SCIENCE↗
Phthalocyaninato Complexes with Peripheral Alkylthio Chains: Disk-like Adsorbate Species for the Vertical Anchoring of Ligands onto Gold Surfaces
Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalized phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, {beta}-positioned, alkylthio substituents SR (1a: R = n-C{sub 8}H{sub 1}7, 1b: R = n-C{sub 12}H{sub 25}), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterized by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to MnII.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NHC-based Self-assembled Monolayers on Solid Gold Substrates
Thin films of 1,3-diethylbenzimidazol-2-ylidene (BIEt) were fabricated from THF solution on solid gold substrates and characterised by high-resolution X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy. The surface-analytical data are in accord with the formation of self-assembled monolayers of BIEt molecules exhibiting an approximately vertical orientation on the substrate. The crystal structure of (BIEt){sub 2} was also determined.
36 MATERIALS SCIENCE↗
Probing the Orientation of Surface-Immobilized Protein G B1 Using ToF-SIMS Sum Frequency Generation and NEXAFS Spectroscopy
The ability to orient active proteins on surfaces is a critical aspect of many medical technologies. An important related challenge is characterizing protein orientation in these surface films. This study uses a combination of time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum frequency generation (SFG) vibrational spectroscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to characterize the orientation of surface-immobilized Protein G B1, a rigid 6 kDa domain that binds the Fc fragment of IgG. Two Protein G B1 variants with a single cysteine introduced at either end were immobilized via the cysteine thiol onto maleimide-oligo(ethylene glycol)-functionalized gold and bare gold substrates. X-ray photoelectron spectroscopy was used to measure the amount of immobilized protein, and ToF-SIMS was used to measure the amino acid composition of the exposed surface of the protein films and to confirm covalent attachment of protein thiol to the substrate maleimide groups. SFG and NEXAFS were used to characterize the ordering and orientation of peptide or side chain bonds. On both substrates and for both cysteine positions, ToF-SIMS data showed enrichment of mass peaks from amino acids located at the end of the protein opposite to the cysteine surface position as compared with nonspecifically immobilized protein, indicating end-on protein orientations. Orientation on the maleimide substrate was enhanced by increasing pH (7.0-9.5) and salt concentration (0-1.5 M NaCl). SFG spectral peaks characteristic of ordered {alpha}-helix and {beta}-sheet elements were observed for both variants but not for cysteine-free wild type protein on the maleimide surface. The phase of the {alpha}-helix and {beta}-sheet peaks indicated a predominantly upright orientation for both variants, consistent with an end-on protein binding configuration. Polarization dependence of the NEXAFS signal from the N 1s to {pi}* transition of {beta}-sheet peptide bonds also indicated protein ordering, with an estimated tilt angle of inner {beta}-strands of 40-50{sup o} for both variants (one variant more tilted than the other), consistent with SFG results. The combined results demonstrate the power of using complementary techniques to probe protein orientation on surfaces.
59 BASIC BIOLOGICAL SCIENCES↗