Poly(γ-benzyl-L-glutamate) (PBLG) derivatized at its N-terminus with lipoic acid, a disulfide-containing moiety, self-assembles on gold from helicogenic solvents to give a thin film with the polypeptide α-helices orientation distribution different from the planar orientation in the unlabeled, physisorbed PBLG films (control) and Langmuir-Blodgett monolayers. The SA films were studied by angle-dependent XPS, reflection-absorption FTIR spectroscopy, and ellipsometry. The IR dichroic properties of the amide I and amide II bands were used to infer the orientational distribution of the helices in the self-assembled film and lead to two extreme pictures of the helix axis distribution function: (a) random (hemispherical distribution) and (b) perfect order with a tilt of 53° from the surface normal. Additional characterization is necessary to differentiate between these two distributions.

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Self-assembly (SA) on gold substrates of α-helical poly(γ-benzyl-L-glutamate) [(PBLG); molecular weight ∼20 000 kd] with a disulfide moiety attached at its N-terminus (PBLGSS) was investigated. The SA films were compared with control experiments using unlabeled physisorbed (PS) PBLG and Langmuir–Blodgett (LB) deposited PBLG monolayers. Characterization of the films included angle-dependent x-ray photoelectron spectroscopy, reflection–absorption Fourier transform infrared spectroscopy, ellipsometry, and contact angle measurements. For PBLGSS, a SA monolayer was formed wherein the α-helical conformation was retained and the polypeptides were preferentially bound to gold through the disulfide moiety. This terminal bond to the substrate results in a nonplanar distribution of helix axes (i.e., on average tilted up from the gold surface). This is different from the unlabeled PBLG controls, PS film and LB monolayers, wherein, respectively, less polymer was adsorbed and the helices lie in the plane of the gold substrate. Furthermore, polypeptide aggregation in the solution (e.g., in dichloromethane or 1,4-dioxane) appears to have an influence on the self-assembling behavior of these macromolecules relative to known nonaggregating solvents (N,N-dimethylformamide).

Gold electrodes are important in some devices and certain applications where an inert, highly conductive feature is required. An aqueous gold nanoparticle (AuNP) ink suitable for inkjet printing was synthesized and formulated using starch and microwave-assisted heating. By varying the hydrolysis conditions of starch, the size, yield, and stability of the AuNP suspension can be controlled and optimized to achieve a jettable ink. The optimized formulation has a very low starch loading of only 1.75 wt % relative to gold, forming a highly stable AuNP ink, which upon drying already forms a very conductive film and sinters at low temperature. The overall synthesis protocol thus provides a greener and cheaper alternative to other AuNP synthesis methods. The sintering behavior of the film was monitored, wherein, upon heating, starch is degraded, crystallite growth increased, and the morphology changed from individual nanoparticles to a network of fused particles. The film sheet resistance decreased concomitant with these physical changes. By heating the film to at least 200 °C, a sheet resistance of <1.0 Ω/□ is achieved. This aqueous-formulated ink, therefore, offers an alternative to the usual organic solvent ink formulations used in printed electronics. It proved printing of conductive films on various substrates for possible applications in flexible electronic devices.

Polarized infrared spectroscopy in attenuated total reflection was used to investigate the adsorption of PMMA (polymethylmethacrylate) onto PS (polystyrene) that was previously adsorbed onto oxidized silicon from dilute solution in carbon tetrachloride at 30°C. The carbonyl group of PMMA forms hydrogen bonds with surface silanol groups, giving segment‐surface interaction energy of 4 kT as against 1 kT for PS (k is the Boltzmann constant, T the absolute temperature). The formation of hydrogen‐bonding by PMMA was unaffected, in rate or amount, by preadsorbed PS, but a lesser total amount of PMMA adsorbed onto PS, resulting in a higher average bound fraction. The histogram of the mass adsorbed, attributable to subpopulations of chains with different bound fractions, was inferred by subtracting infrared spectra acquired at successive times. Whereas this histogram was broad and bimodal for adsorption onto bare surface, it was narrower and unimodal for adsorption onto preadsorbed PS. © 1995 John Wiley & Sons, Inc.