High-resolution Broadband Sum Frequency Generation Research Articles

Mechanism by Which Cholesterol Induces Sphingomyelin Conformational Changes at an Air/Water Interface.

This work investigates the interactions in cholesterol and sphingomyelin monolayers at the molecular level by high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The SFG spectra of natural egg sphingomyelin (ESM) as a function of cholesterol concentration are obtained at an air/water interface under different polarization combinations. The analysis of the spectra shows that cholesterol can induce sphingomyelin conformational changes at an air/water interface. The mechanism is proposed. When cholesterol is inserted into the ESM monolayer, the inherent intramolecular hydrogen bonds between the phosphate moiety and 3OH in the sphingosine backbones are destroyed. During this process, the sphingosine backbones become more ordered, while the conformation of the N-linked long acid chain remains unaltered. The OH of the cholesterol head group can bind to the -PO-2 of the ESM molecule, and the orientation of the -PO-2 in the head groups changes to be more parallel to the interface.

Adsorption Structure and Coverage-Dependent Orientation Analysis of Sub-Monolayer Acetonitrile on TiO2(110)

The adsorption structure and orientation of acetonitrile on TiO2(110) have been investigated by temperature-programmed desorption (TPD) and high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) in combination with ab initio molecular dynamics (AIMD) simulation. Sub-monolayer, monolayer, and multilayer states of acetonitrile on TiO2(110) have been unambiguously distinguished in the TPD spectra. The in situ HR-BB-SFG vibrational spectra of acetonitrile on TiO2(110) at 100 K not only show the symmetric stretching mode of the methyl group and the nitrile group, similar to those of vapor acetonitrile on oxide surfaces, but also present an intense antisymmetric stretching mode of the methyl group as well as the sum resonance mode between symmetric C–C stretching and symmetric CH3 deformation. Besides, two adsorption forms for acetonitrile on TiO2(110), including interactions with five-coordinated titanium (Ti5c) and bridge-bonded oxygen (Obr) vacancies, have also been resolved and identified in our SFG vibrational spectra. By the combination of SFG polarization analyses and AIMD simulations, we further found that the tilt angle of CH3CN on TiO2(110) decreases as the coverage increases from sub-monolayer to monolayer. Considering the down shifts of desorption temperature, vibrational frequency, and adsorption energy for acetonitrile on TiO2(110) at higher coverage, we propose that the intermolecular repulsion plays a major role in the coverage-dependent adsorption configuration. Our results not only provide a detailed insight into the adsorption states of acetonitrile on TiO2(110) at a low temperature but also demonstrates the capabilities of high-resolution SFG-VS for investigating the complicated structure and orientation of adsorbates on single-crystal metal oxides.

Flexible high-resolution broadband sum-frequency generation vibrational spectroscopy for intrinsic spectral line widths.

The difficulty in achieving high spectral resolution and accurate line shape in sum-frequency generation vibrational spectroscopy (SFG-VS) has restricted its use in applications requiring precise detection and quantitative analysis. Recently, the development of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution generated by synchronizing two independent amplifier lasers have opened new opportunities for probing an intrinsic SFG response. Here, we present a new flexible approach to achieve HR-BB-SFG-VS. In this system, two regeneration amplifiers shared the same oscillator laser as the seed, and a time-asymmetric visible pulse with a nearly Lorentzian line shape filtered by an etalon was used to overlap with a femtosecond broadband infrared pulse. This Lorentzian line shape of the visible pulse can greatly simplify the spectral fitting and analysis. We also demonstrated that the single-sided long visible pulse provided both high spectral resolution (1.4 cm-1) and effective suppression of the non-resonant background by detuning the time delay between visible and infrared pulses in SFG-VS measurements. With this new SFG setup, a pair of spectral splittings by 3.1 ± 0.7 and 3 ± 0.2 cm-1 for the symmetric and antisymmetric stretching of the CH3 group was resolved at the CH3CN/TiO2(110) surface, which are tentatively attributed to two different orientational methyl groups. These technological advancements can help broaden the applications of HR-BB-SFG-VS and provide solid ground for a better understanding of complex molecular structures and dynamics at interfaces.

High-resolution broadband sum frequency generation vibrational spectroscopy using intrapulse interference.

We theoretically propose a new approach to obtain high-spectral-resolution sum frequency generation (SFG) vibrational spectra using intrapulse interference. By introducing a π-step phase modulation to the broadband 800 nm pulse, the broadband 800 nm laser pulse splits into two distinguishable pulses in the time domain with a fixed time delay. The resolution of the intrapulse interference SFG can be better than 1 cm-1 and is limited only by the spectral resolution of the spectrometer. This approach can accurately retrieve the amplitude and the relative phase of vibrational peaks. Additionally, the sensitivity of SFG is enhanced by adopting femtosecond IR and femtosecond visible pulses.

Ordering effects of cholesterol on sphingomyelin monolayers investigated by high-resolution broadband sum-frequency generation vibrational spectroscopy

This report investigated the ordering of the alky chain of sphingomyelin (SMs) monolayers induced by cholesterol at the air/water interface using high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The SFG spectra of the three nature sphingomyelin/cholesterol mixture monolayers with two concentrations of the cholesterol at the air/water interface are performed under different polarization combination. A new resolved CH2 symmetric stretching (d+, ∼2834cm−1) and the CH3 symmetric stretching (r+, ∼2874cm−1) mode are applied to characterize the conformational order in the sphingomyelin/cholesterol mixture monolayers. It was found that the cholesterol make the sphingosine backbones more conformational order. During this process, the conformational order of the N-linked acyl chain remains unaltered. Moreover, the sphingosine backbones of SMs have much larger contributions to gauche defects of SMs than one in the N-linked acyl chain. These results presented here not only shed lights on understanding of the interactions of sphingomyelin molecules with cholesterol molecules at interface but also demonstrates the ability of HR-BB-SFG to probe such complicated molecular systems.

Effect of Ca2+ to Sphingomyelin Investigated by Sum Frequency Generation Vibrational Spectroscopy

The interactions between Ca2+ ions and sphingomyelin play crucial roles in a wide range of cellular activities. However, little is known about the molecular details of the interactions at interfaces. In this work, we investigated the interactions between Ca2+ ions and egg sphingomyelin (ESM) Langmuir monolayers at the air/water interface by subwavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS). We show that Ca2+ ions can induce ordering of the acyl chains in the ESM monolayer. An analysis of the one alkyl-chain-deuterated ESM revealed that the Ca2+ ions do not affect the N-linked saturated fatty acid chain, although they make the sphingosine backbone become ordered. Further analysis of the SFG-VS spectra shows that the interactions between ESM and Ca2+ ions make the orientation of the methyl group at the end of sphingosine backbone change from pointing downward to pointing upward. Moreover, a large blue shift of the phosphate group at the CaCl2 solution interface indicates, to our knowledge, new cation binding modes. Such binding causes the phosphate moiety to dehydrate, resulting in the conformation change of the phosphate moiety. Based on these results, we propose the molecular mechanism that Ca2+ ions can bind to the phosphate group and subsequently destroy the intramolecular hydrogen bond between the 3-hydroxyl group and the phosphate oxygen, which results in an ordering change of the sphingosine backbone. These findings illustrate the potential application of HR-BB-SFG-VS to investigate lipid-cation interactions and the calcium channel modulated by lipid domain formation through slight structural changes in the membrane lipid. It will also shed light on the interactions of complex molecules at surfaces and interfaces.

Local Environment and Interactions of Liquid and Solid Interfaces Revealed by Spectral Line Shape of Surface Selective Nonlinear Vibrational Probe

Vibrational spectral line shape contains important detailed information on molecular vibration and reports its specific interactions and couplings to its local environment. In this work, recently developed sub-1 cm–1 high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) was used to measure the −C≡N stretch vibration in the 4-n-octyl-4′-cyanobiphenyl (8CB) Langmuir or Langmuir–Blodgett (LB) monolayer as a unique vibrational probe, and the spectral line shape analysis revealed the local environment and interactions at the air/water, air/glass, air/calcium fluoride, and air/α-quartz interfaces for the first time. The 8CB Langmuir or LB film is uniform, and the vibrational spectral line shape of its −C≡N group has been well characterized, making it a good choice as the surface vibrational probe. Line shape analysis of the 8CB −C≡N stretch SFG vibrational spectra suggests the coherent vibrational dynamics and the structural and dynamic inhomogeneity of the −C≡N group at each interface are uniquely different. In addition, it is also found that there are significantly different roles for water molecules in the LB films on different substrate surfaces. These results demonstrated the novel capabilities of the surface nonlinear spectroscopy in characterization and in understanding the specific structures and chemical interactions at the liquid and solid interfaces in general.

Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy.

In this report, we show that the ability to measure the sub-1 cm(-1) resolution phase-resolved and intensity high-resolution broadband sum frequency generation vibrational spectra of the -CN stretch vibration of the Langmuir-Blodgett (LB) monolayer of the 4-n-octyl-4'-cyanobiphenyl (8CB) on the z-cut α-quartz surface allows the direct comparison and understanding of the homogeneous and inhomogeneous broadenings in the imaginary and intensity SFG vibrational spectral line shapes in detail. The difference of the full width at half maximum (FWHM) of the imaginary and intensity sum-frequency generation vibrational spectroscopy spectra of the same vibrational mode is the signature of the Voigt line shape and it measures the relative contribution to the overall line shape from the homogeneous and inhomogeneous broadenings in SFG vibrational spectra. From the phase-resolved and intensity spectra, we found that the FWHM of the 2238.00 ± 0.02 cm(-1) peak in the phase-resolved imaginary and intensity spectra is 19.2 ± 0.2 cm(-1) and 21.6 ± 0.4 cm(-1), respectively, for the -CN group of the 8CB LB monolayer on the z-cut α-quartz crystal surface. The FWHM width difference of 2.4 cm(-1) agrees quantitatively with a Voigt line shape with a homogeneous broadening half width of Γ = 5.29 ± 0.08 cm(-1) and an inhomogeneous standard derivation width Δω = 5.42 ± 0.07 cm(-1). These results shed new lights on the understanding and interpretation of the line shapes of both the phase-resolved and the intensity SFG vibrational spectra, as well as other incoherent and coherent spectroscopic techniques in general.

Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.

Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS)

The lack of understanding of the temporal effects and the restricted ability to control experimental conditions in order to obtain intrinsic spectral lineshapes in surface sum-frequency generation vibrational spectroscopy (SFG-VS) have limited its applications in surface and interfacial studies. The emergence of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution [Velarde et al., J. Chem. Phys., 2011, 135, 241102] offers new opportunities for obtaining and understanding the spectral lineshapes and temporal effects in SFG-VS. Particularly, the high accuracy of the HR-BB-SFG-VS experimental lineshape provides detailed information on the complex coherent vibrational dynamics through direct spectral measurements. Here we present a unified formalism for the theoretical and experimental routes for obtaining an accurate lineshape of the SFG response. Then, we present a detailed analysis of a cholesterol monolayer at the air/water interface with higher and lower resolution SFG spectra along with their temporal response. With higher spectral resolution and accurate vibrational spectral lineshapes, it is shown that the parameters of the experimental SFG spectra can be used both to understand and to quantitatively reproduce the temporal effects in lower resolution SFG measurements. This perspective provides not only a unified picture but also a novel experimental approach to measuring and understanding the frequency-domain and time-domain SFG response of a complex molecular interface.

Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: Resolving interfacial inhomogeneities of “identical” molecular groups

The ability to achieve sub-wavenumber resolution (0.6 cm(-1)) and a large signal-to-noise ratio in high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) allows for the detailed SFG spectral lineshapes to be used in the unambiguous determination of fine spectral features. Changes in the structural spectroscopic phase in SFG-VS as a function of beam polarization and experimental geometry proved to be instrumental in the identification of an unexpected 2.78 ± 0.07 cm(-1) spectral splitting for the two methyl groups at the vapor/dimethyl sulfoxide (DMSO, (CH(3))(2)SO) liquid interface as well as in the determination of their orientational angles.