Wei Gan

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = ⟨cos θ ⟩/⟨cos3 θ⟩, and comparison between the PNA me...Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = ⟨cos θ ⟩/⟨cos3 θ⟩, and comparison between the PNA method with the commonly used polarization intensity ratio (PIR) method is discussed. The polarization and incident angle dependencies of the SFG-VS intensity are also reviewed, in the light of how experimental arrangements can be optimized to effectively abstract crucial information from the SFG-VS experiments. The values and models of the local field factors in the molecular layers are discussed. In order to examine the validity and limitations of the bond polarizability derivative model, the general expressions for molecular hyperpolarizability tensors and their expression with the bond polarizability derivative model for C 3 v , C 2 v and C ∞ v molecular groups are given in the two appendixes. We show that the bond polarizability derivative model can quantitatively describe many aspects of the intensities observed in the SFG-VS spectrum of the vapour/neat liquid interfaces in different polarizations. Using the polarization analysis in SFG-VS, polarization selection rules or guidelines are developed for assignment of the SFG-VS spectrum. Using the selection rules, SFG-VS spectra of vapour/diol, and vapour/n-normal alcohol (n∼ 1–8) interfaces are assigned, and some of the ambiguity and confusion, as well as their implications in previous IR and Raman assignment, are duly discussed. The ability to assign a SFG-VS spectrum using the polarization selection rules makes SFG-VS not only an effective and useful vibrational spectroscopy technique for interface studies, but also a complementary vibrational spectroscopy method in general condensed phase studies. These developments will put quantitative orientational and spectral analysis in SFG-VS on a more solid foundation. The formulations, concepts and issues discussed in this review are expected to find broad applications for investigations on molecular interfaces in the future.

Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface

Here we report a detailed study on spectroscopy, structure, and orientational distribution, as well as orientational motion, of water molecules at the air/water interface, investigated with sum frequency generation vibrational spectroscopy (SFG-VS). Quantitative polarization and experimental configuration analyses of the SFG data in different polarizations with four sets of experimental configurations can shed new light on our present understanding of the air/water interface. Firstly, we concluded that the orientational motion of the interfacial water molecules can only be in a limited angular range, instead of rapidly varying over a broad angular range in the vibrational relaxation time as suggested previously. Secondly, because different vibrational modes of different molecular species at the interface has different symmetry properties, polarization and symmetry analyses of the SFG-VS spectral features can help the assignment of the SFG-VS spectra peaks to different interfacial species. These analyses concluded that the narrow 3693 cm(-1) and broad 3550 cm(-1) peaks belong to C(infinityv) symmetry, while the broad 3250 and 3450 cm(-1) peaks belong to the symmetric stretching modes with C2v symmetry. Thus, the 3693 cm(-1) peak is assigned to the free OH, the 3550 cm(-1) peak is assigned to the singly hydrogen-bonded OH stretching mode, and the 3250 and 3450 cm(-1) peaks are assigned to interfacial water molecules as two hydrogen donors for hydrogen bonding (with C2v symmetry), respectively. Thirdly, analysis of the SFG-VS spectra concluded that the singly hydrogen-bonded water molecules at the air/water interface have their dipole vector directed almost parallel to the interface and is with a very narrow orientational distribution. The doubly hydrogen-bonded donor water molecules have their dipole vector pointing away from the liquid phase.

Quantitative Sum-Frequency Generation Vibrational Spectroscopy of Molecular Surfaces and Interfaces: Lineshape, Polarization and Orientation

Sum-frequency generation vibrational spectroscopy (SFG-VS) can provide detailed information and understanding of the molecular composition, interactions, and orientational and conformational structure of surfaces and interfaces through quantitative measurement and analysis. In this review, we present the current status of and discuss important recent developments in the measurement of intrinsic SFG spectral lineshapes and formulations for polarization measurements and orientational analysis of SFG-VS spectra. The focus of this review is to present a coherent description of SFG-VS and discuss the main concepts and issues that can help advance this technique as a quantitative analytical research tool for revealing the chemistry and physics of complex molecular surfaces and interfaces.

Activation of Thiols at a Silver Nanoparticle Surface

Adsorption of organosulfur (thiol) molecules on noble metal surfaces has been widely used to fabricate self-assembled monolayers or modify surface properties in a broad range of novel technological applications. Adsorption of thiols on the surface of noble metals, such as gold or silver, has been intensively studied to gain fundamental understandings on the adsorption process, including its mechanism and rates. It is generally accepted that thiol adsorption onto the gold/ silver surfaces consists of many steps, starting with physical adsorption, followed by the sulfur–metal bonding reaction, the reorientation of the adsorbed thiol molecules, and the formation of a compact self-assembled layer. On the other hand, both diffusion-limited and non-diffusion-limited adsorptions have been reported, though the conditions for the two scenarios have not been consistently defined. 13–16] Thiol adsorption has been widely used to influence the properties of metallic nanoparticles, such as controlling their biomedical functions, tuning optical properties, changing the attached chromophores, and the synthesis of nanoparticles/nanocages of different shapes and size. The adsorption of thiol molecules on metallic nanoparticles have been studied mostly using optical techniques. For example, a sum frequency vibrational spectroscopy study has revealed that long-chain thiol molecules on gold nanoparticles of varying sizes have different conformations. The adsorption free energies of several thiol molecules on gold and silver nanoparticles have been determined using fluorescence or second harmonic generation (SHG) measurements. More than a decade ago, hyper Rayleigh scattering from gold nanoparticles was pursued and first reported as an incoherent second harmonic method for examining nanoparticles, as it was thought that there is an inherent size restriction in SHG such that the method could not be detected from particles with diameters much smaller than the optical wavelength. We have subsequently demonstrated that SHG from the surface of nanometer size particles can be detected at specific scattering angles where phase matching conditions are satisfied. This advancement has led to the detection of SHG from silver nanoparticles (AgNPs). In principle, the SHG signal may arise from the surface and/or bulk of the nanoparticles. In the case of AgNPs, the surface contribution is identified by the response in the SHG signal to the formation of surface bonding that would diminish the polarizability of the free electrons at the surface. The surface portion of the SHG signal can then be used for probing processes occurring at the surface. It was illustrated in our work that the adsorption of thiols onto the AgNP surface can be directly monitored with time using SHG. The SHG intensity generated at the surface layer of the silver particle is sensitive to the formation of the S Ag bonds at the nanoparticle surface. It was found that the majority of the SHG signal from AgNPs of 80 nm diameter can be quenched by the adsorption of thiol molecules as the formation of the S Ag bonds localizes the Ag electrons that are responsible for the nonlinear susceptibility. The change of the SHG intensity can be quantitatively related to the thiol coverage on the surface, and used for the determination of the adsorption and desorption rates as well as the free energy change of the adsorptive reaction process. If there is a barrier associated with the ratelimiting process in the adsorption, temperature dependence of the adsorption rate should enable the determination of the activation energy and reveal which is the activation process. Herein we present experimental observations indicating that the thiol reactions at the silver nanoparticle surface is an activated process and that temperature can be used to control the reaction rates. For the case of 1,2-benzenedithiol adsorption onto a silver nanoparticle, the activation energy was determined as 8.4 kcalmol . This energy barrier is likely associated with the formation of the transition state during the formation of sulfur–silver bond and not from the diffusion-limited process. Figure 1 shows that as 1,2-benzenedithiol at different concentrations was added into Ag colloids at 293 K, the intensity of the SHG light scattered from silver nanoparticles decreased. The decrease is resulted from the reduction of the nonlinear susceptibility of the Ag surface atoms as S Ag bonds form. As indicated by the rate of the SHG intensity decay, which is proportional to the square of the thiol coverage on the surface, the rate of adsorption of thiol molecules is faster when thiol concentration is higher. Figure 1 shows three of the five experimental measurements conducted with added thiol concentrations varying from 0.1 to 0.5 mm. The Langmuir model can be used to describe the adsorption kinetics with adsorption and desorption rate constants ka and kd:

Novel method for accurate determination of the orientational angle of interfacial chemical groups

The common practice for determination of orientational angle of interfacial molecular groups with the interfacial sum frequency generation vibrational spectroscopy (SFG-VS) is to measure the intensity ratio between two SFG intensities at a certain vibrational frequency with different polarization directions. Because sometimes the SFG at one polarization direction is too weak to be measured accurately, this ratio usually has big uncertainty, and consequently it is impossible to obtain accurate orientation parameters. Thus the corresponding orientation angle was not accurately calculated. Through analyzing the basic relationship between the orientation angle and SFG intensity, we found that the null angle method would be suitable for such cases. The null angle measurement is simple, precise and easy to realize, therefore can greatly improve the accuracy of orientation angle. Using this method, we determined the orientation angle of the methyl group of methanol orients about 31.8 ± 2.4° from the surface normal at the air/methanol interface, much more accurate than the previously reported value of < 42°. The null angle method provides a reliable experimental analytical tool for studying the orientation of the chemical group or chemical bond at interfaces.

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.

Graphene quantum dots: recent progress in preparation and fluorescence sensing applications

Fluorescent graphene quantum dots (GQDs) have attracted tremendous attention because of their unique 2D layered structure, large surface area, good water solubility, tunable fluorescence, high photostability, excellent biocompatibility and low toxicity, which make them promising candidates for applications in various fields. In this review, we summarize the latest progress in research on GQDs, focusing on their preparation via both top-down and bottom-up routes and application in fluorescence sensing of inorganic ions, organic molecules and biomaterials. This review provides insight into GQDs to inspire their further development, including their controllable preparation and use in a wider range of sensing applications, by the large community of researchers focusing on graphene.

Evidence of the adsorption of hydroxide ion at hexadecane/water interface from second harmonic generation study

The electric potential and water molecular orientation at oil/water interfaces, as well as the origin of the interfacial potential, have been intensively investigated recently. In some reports, the purity of hexadecane and its influence to the origin of the negative charge at hexadecane/water interface was in debating. In the debate the reliability of sum frequency generation-vibrational spectroscopy in evaluating the influence of chemical impurities on the electric potential and molecular structure at the hexadecane/water interface was called into question. Here we revisited this system using another second order nonlinear spectroscopic technique, Second Harmonic Generation (SHG). The SHG results sensitively reflected the influence of the impurities in hexadecane. As a representative long-chain carboxylic acid, which is generally considered to be the principle impurity in hexadecane, oleic acid at a concentration of several micromolar caused a notable change in the SH intensity of the hexadecane/water interface. The presence of carboxylic-type impurities was confirmed in the as-received hexadecane with 99% purity. After purification with alumina columns, the concentration of the impurities was substantially reduced and the influence on the SH signal was barely detectable. The effect of the hydroxide ion on the structure of water molecules at the hexadecane/water interface was also confirmed, which strongly supports the adsorption of hydroxide ions at oil/water interfaces.

Time-efficient syntheses of nitrogen and sulfur co-doped graphene quantum dots with tunable luminescence and their sensing applications

Heteroatom doped graphene quantum dots (GQDs) are particularly promising in bioimaging and fluorescent sensing because of their better photoluminescence tunability compared to pristine GQDs. Herein, two nitrogen and sulfur co-doped GQDs (N,S-GQDs) with varied fluorescence emission wavelength were synthesized via HNO3 vapour cutting route, in which a porous polythiophene-derived carbon served as the sulfur source while the HNO3 vapour was presented as the scissor and the nitrogen source. The as-prepared N,S-GQDs exhibited blue and yellow-green coloured fluorescence, owing to their varied morphologies and surface states resulted from varied reaction temperature. Compared to the typical top-down syntheses via hydrothermal or solvothermal routes, the present HNO3 vapour cutting method is prominently efficient in time expense and product separation. An application of the obtained greenish-yellow N,S-GQDs for highly selective and sensitive fluorescent detection of Fe3+ was demonstrated, with a linear range of 0–130 μM and a detection limit of 0.07 μM. The protocol reported here can also be readily applied for facial synthesis of other heteroatom doped GQDs.

Molecular interactions at the hexadecane/water interface in the presence of surfactants studied with second harmonic generation

It is important to investigate the influence of surfactants on structures and physical/chemical properties of oil/water interfaces. This work reports a second harmonic generation study of the adsorption of malachite green (MG) on the surfaces of oil droplets in a hexadecane/water emulsion in the presence of surfactants including sodium dodecyl sulfate, polyoxyethylene-sorbitan monooleate (Tween80), and cetyltrimethyl ammonium bromide. It is revealed that surfactants with micromolar concentrations notably influence the adsorption of MG at the oil/water interface. Both competition adsorption and charge-charge interactions played very important roles in affecting the adsorption free energy and the surface density of MG at the oil/water interface. The sensitive detection of the changing oil/water interface with the adsorption of surfactants at such low concentrations provides more information for understanding the behavior of these surfactants at the oil/water interface.