Anomalous pH-Dependent Enhancement of p-Methyl Benzoic Acid Sum-Frequency Intensities: Cooperative Surface Adsorption Effects.

Vibrational sum-frequency generation (SFG) spectroscopy is used to determine the surface pKa of p-methyl benzoic acid (pMBA) at the air-water interface by monitoring the carbonyl and carboxylate stretching modes over the pH range of 2 to 12. The SFG intensities of pMBA and its conjugate base, p-methyl benzoate (pMBA-), exhibit an anomalously large enhancement over a narrow pH range (∼0.5) centered at pH 6.3 near the SFG-determined surface pKa, 5.9 ± 0.1. The increase in the surface pKa relative to the bulk value of 4.34 is consistent with the trend previously observed for long chain carboxylic acids in which the surface pKa is higher than the bulk solution pKa. SFG polarization studies help distinguish the orientation and number density contributions to this observed anomalous surface phenomenon. The large SFG intensity increase is attributed to an increase in the pMBA and pMBA- surface concentrations in this narrow pH range due to a cooperative adsorption effect between pMBA and pMBA-. This cooperativity is manifested only on the 2D air-water interface, where the interactions between the acid and base are not as dielectrically screened as in the aqueous bulk phase. Surface effects are critical to understanding and controlling the reactivity, solubility, and behavior of organic acids at interfaces and can have an impact on biomedical applications.

Spectroscopic evidence for the origin of odd-even effects in self-assembled monolayers and effects of substrate roughness.

This paper reports the effects of substrate roughness on the odd-even effect in n-alkanethiolate self-assembled monolayers (SAMs) probed by vibrational sum frequency generation (SFG) spectroscopy. By fabricating SAMs on surfaces across the so-called odd-even limit, we demonstrate that differentiation of the vibrational frequencies of CH3 from SAMs derived from alkyl thiols with either odd (SAMO) or even (SAME) numbers of carbons depends on the roughness of the substrate on which they are formed. Odd-even oscillation in SFG susceptibility amplitudes was observed for spectra derived from SAME and SAMO fabricated on flat surfaces (RMS roughness = 0.4 nm) but not on rougher surfaces (RMS roughness = 2.38 nm). In addition, we discovered that local chemical environments for the terminal CH3 group have a chain-length dependence. There seems to be a transition at around C13, beyond which SAMs become "solid-like".

Photochromic copolymers containing 3-indolylfulgides/indolylfulgimides: synthesis and photochemical properties in toluene and as films.

Photochromic indolylfulgimides covalently attached to polymers have beneficial properties for optical switching. A 3-indolylfulgide and two 3-indolylfulgimides with one or two polymerizable styrene groups attached on the nitrogen atom(s) were synthesized. Copolymerization with methyl methacrylate (MMA) provided linear copolymers (one styrene group) or a cross-linked copolymer (two styrene groups). The properties of the monomers and copolymers in toluene or as thin films were characterized. The new copolymers were photochromic (reversible Z-to-C isomerization), absorbed visible light, and revealed good thermal and photochemical stability. At room temperature, all copolymer films showed no loss of absorbance after 5 weeks. At 80 °C in either toluene or as films, the Z-forms copolymers were less stable than the C-form copolymers, which showed little or no degradation after 400 h. The degradation rate due to repeated ring-closing - ring opening cycles was less than 3% per 100 cycles. The cross-linked copolymer showed photochemical stability comparable to monomeric fulgides in toluene, <1% per 100 cycles. In general, the properties of the linear and cross-linked copolymers were similar to the corresponding monomers in toluene. In films, the conformations of the Z-form were restricted due to the matrix indicating that the preparation of films from the C-form is advantageous.