DNA single strands tethered to fused quartz/water interfaces studied by second harmonic generation

Second harmonic generation (SHG) is used to study oligonucleotides at aqueous/solid interfaces for the first time. Detailed thermodynamic state information for interfacial DNA single strands, namely, the interfacial charge density, the interfacial potential, and the change in the interfacial energy density, is obtained. The phosphate groups on the DNA backbone serve as intrinsic labels that do not require DNA modification other than surface attachment. This approach is broadly applicable for the investigation of DNA during its interaction with biological targets, as well as charged biopolymers in general, and has important implications for predicting and controlling macromolecular interactions, improving biodiagnostics, and understanding life processes.     

Tracking oxytetracyline mobility across environmental interfaces by second harmonic generation

This work examines the binding behavior of the antibiotic oxytetracycline (OTC) to mineral oxide/water interfaces in the presence and absence of organic functional groups using the interface-specific technique second harmonic generation (SHG). Studies show that OTC binding to fused quartz, methyl ester, carboxylic acid, and alkyl interfaces is fully reversible and highly dependent on solution pH, with appreciable adsorption occurring only at pH 8. Relative surface coverage at pH 8 is highest for the polar organic-functionalized surfaces, and surface saturation occurs for the methyl ester-functionalized fused quartz/water interface at 2 x 10(-5) M. Adsorption isotherm measurements indicate that the binding process is controlled by hydrogen bonding and hydrophobic interactions, with free energies of adsorption on the order of -40 kJ/mol for all interfaces studied. The results indicate that OTC transport in the environment will depend heavily on soil pH and composition and have implications for the development of bacterial antibiotic resistance.     

Imaging chirality with surface second harmonic generation microscopy

Chirality is a fundamental construct in nature which arises from an antisymmetric arrangement of atoms, molecules, or larger structures, resulting in the formation of nonsuperimposable mirror images. Bulk chiral effects can easily be measured using circular dichroism (CD) or optical rotary dispersion (ORD). However, the imaging of chirality originating from molecular surface films cannot be obtained with these linear optical methods. By using chiral second harmonic generation (C-SHG), with its inherent surface sensitivity and ability to discriminate between the symmetry of surface adsorbed species in combination with a counter-propagating optical geometry, we have developed the first nonlinear chiral microscope. In the study presented here, the intrinsic chirality of R- and S-(+)-1,1'-bi-2-naphthol (RBN, SBN) has been used to image a patterned planar supported lipid bilayer (PSLB) of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) using C-SHG. Spatial resolution of the patterned PSLB is visible when either RBN or SBN is intercalated into the membrane. No image is observed when a racemic mixture of RBN and SBN is present. The C-SHG images are compared with those obtained from fluorescence microscopy to verify the C-SHG imaging technique. The results presented here demonstrate that C-SHG possesses the requisite surface selectivity and sensitivity to detect interfacial chirality and provides a direct route for the visualization of chirality originating from molecular surface films.     

Interaction of nitrate, barium, strontium and cadmium ions with fused quartz/water interfaces studied by second harmonic generation

Inorganic anions and cations are ubiquitous in environmental chemistry. Here, we use second harmonic generation to track the interaction of the environmentally important metal cations barium, strontium, and cadmium and the nitrate anion with fused quartz/water interfaces at pH 7. Using a dynamic flow system, we assess the extent of reversibility in the binding process and report the absolute number density of adsorbed cations, their charge densities, and their free energies of adsorption. We also present resonantly enhanced second harmonic generation experiments that show that nitrate is surface active and report the free energies and binding constants for the adsorption process. The second harmonic generation spectrum of surface-bound nitrate shows a new adsorption band that cuts further into the solar spectrum than nitrate in the aqueous or solid state. The results that we obtain for all four inorganic ions and the implications for tropospheric and aquatic chemistry as well as geochemistry are discussed in the context of fundamental science as well as pollutant transport models.     

Environment-induced surface dynamics of a biomimetic ionomer studied using in situ second harmonic generation

The environmental-induced surface dynamics of the biomimetic phosphoryl choline (PC)-functionalized poly(trimethylene carbonate) ionomer has been studied and compared to its unfunctionalized counterpart using in situ second harmonic generation measurements. Whereas the nonpolar liquid n-hexane did not induce any surface dynamic processes in the ionomer under study, the presence of water initiated a Debye-type dynamic reaction at the surface of the PC ionomer, which had no equivalent in the unfunctionalized material. This first-order reaction was attributed to a surface enrichment process of the functionalized ionomer in the hydrophilic environment involving movement of the PC endgroups from aggregates in the bulk to the surface. The time constant of the process was found to be about 6 min, and the corresponding activation energy was 0.4 eV. The dehydration process of the PC-functionalized ionomer in nitrogen gas atmosphere could be described by two time constants, one slightly below 1 min and the other one just above 13 min. The results presented in this work show that SHG measurements are well suited for the study of polymer surface restructuring dynamics in response to environmental changes. Such information is very important for the successful design and implementation of biomimetic polymers intended for biomedical applications.     

Ion-association aggregation of an anionic porphyrin at the liquid/liquid interface studied by second harmonic generation spectroscopy

Interfacial ion-association adsorption and aggregation of a water-soluble porphyrin, tetrakis(4-sulfonatephenyl)porphyrin (TPPS) diacid, which was promoted by a cationic cetyltrimethylammonium ion (CTA(+)), was studied by second harmonic generation (SHG) spectroscopy. Comparing the interfacial SH spectrum with the transmission absorption spectrum of TPPS in the aqueous solution elucidated the aggregation behavior of TPPS at the heptane/water interface. The time-dependent SHG spectra for TPPS aggregation and the interfacial tension lowering in the presence of CTA(+) were discussed on the basis of an electrostatic adsorption model. Then, it was suggested that TPPS diacid was highly concentrated by the ion-association with CTA(+) at the interface, which was the intermediate state before the final aggregated state.     

Quantitative measurement and interpretation of optical second harmonic generation from molecular interfaces

Second harmonic generation (SHG) has been proven a uniquely effective technique in the investigation of molecular structure and conformations, as well as dynamics of molecular interfaces. The ability to apply SHG to molecular interface studies depends on the ability to abstract quantitative information from the measurable quantities in the actual SHG experiments. In this review, we try to assess recent developments in the SHG experimental methodologies towards quantitative analysis of the nonlinear optical properties of the achiral molecular interfaces with rotational isotropy along the interface normal. These developments include the methodology for orientational analysis of the SHG experimental data, the experimental approaches for more accurate SHG measurements, and a novel treatment of the symmetry properties of the molecular polarizability tensors in association with the experimentally measurable quantities. In the end, the recent developments on the problem of surface versus bulk contribution in SHG surface studies is discussed. These developments can put SHG on a more solid foundation for molecular interface studies, and to pave the way for better understanding and application of SHG surface studies in general.     

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

Even though nanoparticles have dimensions much smaller than the optical wavelength and shapes commonly with inversion symmetry, we show, for the first time, direct experimental evidence that second harmonic generation (SHG) can be detected from the surface layer of metallic nanoparticles, in this case 40 nm radius Ag particles. The SH intensity detected is shown to substantially decrease upon chemical bonding of thiol molecules to the Ag particle surface. The surface generated SH intensity can be used for probing properties and processes at the nanoparticle surface.     

In situ dual-beam coincidence second harmonic generation as a probe of spatially resolved dynamics at electrochemical interfaces

In situ dual-beam coincidence second harmonic generation was used to monitor spatially resolved dynamics at the Pt(111)/CO-saturated 0.1 M HClO4 interface. The results obtained showed that, for potential steps from 30 to about 870 mV vs RHE, the full electrooxidation of CO as evidenced from SHG occurred at different times for the two areas of the Pt(111) surface probed by the beams. On this basis, the diffusional rates of adsorbed CO cannot be assumed to be generally large enough as to render the entire surface in a homogeneous state, as invoked by the mean field approximation model.     

Control of carboxylic acid and ester groups on chromium (VI) binding to functionalized silica/water interfaces studied by second harmonic generation

Resonantly enhanced surface second harmonic generation (SHG) measurements carried out at pH 7 and room temperature were performed to study how surface-bound carboxylic acid and methyl ester functional groups control the interaction of chromate ions with fused silica/water interfaces. These functional groups were chosen because of their high abundance in humic and fulvic acids and related biopolymers commonly found in soils. They were anchored to the silica surface using organosilane chemistry to avoid competing complexation processes in the aqueous solution as well as competitive adsorption of the organic compounds and chromate. The SHG experiments were carried out at room temperature and pH 7 while using environmentally representative chromate concentrations ranging from 1 x10(-6) to 2 x 10(-4) M. Chromate is found to bind to the acid- and ester-functionalized silica/water interfaces in a reversible fashion. In contrast to the plain silica/water interface, chromate binding studies performed on the functionalized silica/water interfaces show S-shaped adsorption isotherms that can be modeled using the Frumkin-Fowler-Guggenheim (FFG) model. This model predicts a coverage-dependent binding constant of K(ads) x exp(gtheta). Values for g are found to be 3.2(2), 2.1(2), and 1.3(2) for the carboxylic acid-, the ester-, and the nonfunctionalized silica/water interfaces, respectively, and are consistent with stabilizing lateral adsorbate-adsorbate interactions among the Cr(VI) species adsorbed to the functionalized surfaces. The FFG model allows for the parametrization of the solid-liquid partition coefficient and chromate retardation factors in silica-rich soil particles whose surfaces contain organic adlayers rich in carboxylic acid and methyl ester groups. The straightforward model presented here predicts that chromate retardation increases by up to 200% when carboxylic acid functional groups are present at the silica/water interface. Increases up to 50% are predicted for methyl ester-containing organic adlayers, and the retardation factor remains effectively near unity for the plain silica/water interface (no siloxanes present).     

Phase transitions in Langmuir monolayer of long chain attached fluorescein studied by second harmonic generation technique

Optical second harmonic generation (SHG) measurements coupled with Π-A isotherms have been shown to be helpful, for the following and comprehension of orientational orders and phase transitions in Langmuir monolayers. Using the SHG-(Π-A) measurements, monolayers of 5-hexadecanoylaminofluorescein on the water surface were examined by monolayer compression. The phase transitions were noticeably revealed. Dependence of the square root of the intensities polarizations quotient in the molecules surface density, allowed establishing tilting orientation alignment phases. In addition, change in the monolayer symmetry C_∞v→C_2v as it goes through the LE–LC phase transition, was clearly recognized. It was concluded that a possible change in β is taking place due to aggregate formation.     

Control of surface tension at liquid-liquid interfaces using nanoparticles and nanoparticle-protein complexes

Subtle changes in the monolayer structure of nanoparticles (NPs) influence the interfacial behavior of both NPs and NP-protein conjugates. In this study, we use a series of monolayer-protected gold NPs to explore the role of particle hydrophobicity on their dynamic behavior at the toluene-water interface. Using dynamic surface tension measurements, we observed a linear decrease in the meso-equilibrium surface tension (γ) and faster dynamics as the hydrophobicity of the ligands increases. Further modulation of γ is observed for the corresponding NP-protein complexes at the charge-neutralization point.     

Dynamics of a surface phase transition as monitored by in situ second harmonic generation

The dynamics of the (2 x 2)-3CO <--> dilute phase transition involving CO adsorbed on Pt(111) microfacets has been monitored in situ in a CO-saturated acidic electrolyte using potential step-second harmonic generation techniques. Apparent time constants derived strictly from the optical data were found to be orders of magnitude slower for the forward process as compared to those of the reverse process. This behavior is consistent with the activated nature of CO electrooxidation, which requires the presence of a neighboring adsorbed oxygenated species, for example, hydroxyl, for the process to ensue.     

Adsorption behavior of lauric acid at heptane/water interface as studied by second harmonic generation spectroscopy and interfacial tensiometry.

Interfacial tensiometry and second harmonic generation (SHG) spectroscopy were applied to examine the adsorption behavior of lauric acid (LA) at a heptane/water interface. From interfacial tensiometry measurements, the adsorption kinetics of LA was revealed to be diffusion-controlled, and the adsorption constant of LA was estimated to be 9.6 x 10(4) M(-1). The adsorption isotherms obtained by SHG measurements were analyzed by taking account of both the molecular orientation of LA at the interface and a surface electric field generated by the adsorbed LA layer. It was confirmed that the carboxylic groups of adsorbed LA molecules were well ordered at the heptane/water interface and the orientation of the carboxylate group was invariant during the adsorption process.     

Optical recognition of surface chirality at Au(hkl) single crystalline surfaces by second harmonic generation rotational anisotropy

Two-dimensional chirality at naturally chiral gold single crystalline surfaces was detected and characterized using optical second harmonic generation (SHG) measurements. SHG rotational anisotropy (SH-RA) patterns at Au(643)S and Au(643)R surfaces were mirror symmetric to each other. Systematic SH-RA measurements at chiral Au(hkl) surfaces with the same step and kink structures but different (111) terrace widths showed a linear correlation between surface step density and SH-RA fitting parameters arising from defects. These results indicate that SH-RA measurements provide information not only on surface chirality but also on density of surface defects.     

Second-order nonlinear optical properties of side-chain liquid crystalline polymers studied by second harmonic generation from thin films

The two independent elements of the second-order nonlinear optical susceptibility tensor of a range of contact poled, donor–acceptor substitued side-chain polymers are reported. The susceptibilities were measured by second harmonic generation from thin films, typically less than 0.5 μm thick, at a fundamental wavelength of 1064 nm. The largest value was χ = 2.64 pm/V which is three times greater than the χ value of KDP and was measured in a nitrobenzylidene side chain, polyhydroxystyrene polymer with an eleven unit alkyl chain spacer attaching the side group to the backbone. Typical susceptibility values obtained were χ～0.3 pm/V and X⁽²⁾₃₃～1 pm/V. The coherence lengths of the materials, which lay in the range 4–12 μm, were measured at 1064 nm by the maker fringe technique using thick, wedge-shaped samples.     

Reversible electrochemical monitoring of surface confined reactions at liquid-liquid interfaces by modulation of ion transfer fluxes

The adsorption of the neutral surfactant Brij35 at a liquid-liquid interface is reversibly monitored via its disturbance of an electrochemically imposed ion flux across the interface, forming a promising experimental tool for the detection of surface confined reactions at such liquids and polymers.     

Dynamic behaviors of molecular assemblies at liquid/liquid interfaces studied by time-resolved quasi-elastic laser scattering spectroscopy.

The dynamic behaviors of molecular assemblies at two immiscible liquid interfaces are intriguing topics in many fields of science and technology. However, it is generally difficult to investigate the dynamic behaviors of such molecular assemblies because of the buried nature of liquid/liquid interfaces. In the present paper, our recent investigations on dynamic behaviors of various molecular self-assemblies at liquid/liquid interfaces are reviewed. We monitored dynamic behaviors of the molecular assemblies by time-resolved quasi-elastic laser scattering (TR-QELS) and fluorescent spectroscopy. The former method allows us to monitor the change in interfacial tension with millisecond time-resolution. As molecular assemblies, bis(2-ethylhexyl)sulfosuccinate (AOT) microemulsion, phospholipid biomembrane models, and liposome-DNA complexes have all been studied, since they are relevant in material sciences and biological technologies. At liquid/liquid interfaces, these molecular assemblies showed characteristic behaviors. We review the finding of rebound response of the interfacial tension at the liquid/liquid interface induced by the adsorption of the AOT microemulsion. We monitored the hydrolysis reaction of phospholipid biomembrane models formed at oil/water interfaces, observing the different types of behavior of liposome-DNA complexes at biomembrane models with different kinds of phospholipids.     

Molecular interactions of proteins and peptides at interfaces studied by sum frequency generation vibrational spectroscopy

Interfacial peptides and proteins are critical in many biological processes and thus are of interest to various research fields. To study these processes, surface sensitive techniques are required to completely describe different interfacial interactions intrinsic to many complicated processes. Sum frequency generation (SFG) spectroscopy has been developed into a powerful tool to investigate these interactions and mechanisms of a variety of interfacial peptides and proteins. It has been shown that SFG has intrinsic surface sensitivity and the ability to acquire conformation, orientation, and ordering information about these systems. This paper reviews recent studies on peptide/protein-substrate interactions, peptide/protein-membrane interactions, and protein complexes at interfaces and demonstrates the ability of SFG on unveiling the molecular pictures of complicated interfacial biological processes.     

Phase transition of lipid-like monolayer characterized by second harmonic generation

Phase transition of a lipid-like hemicyanine compound characterized by second harmonic generation is studied carefully. The phase transition is assigned as the first order transition between solid state and liquid state. The transition temperature increases with an increase in the surface molecular concentration. A monolayer structure parameter a which is very sensitive to the phase transition is introduced.