OH-stretching Frequencies Research Articles

In Situ Probing the Structure Change and Interaction of Interfacial Water and Hydroxyl Intermediates on Ni(OH)2 Surface over Water Splitting.

There is growing acknowledgment that the properties of the electrochemical interfaces play an increasingly pivotal role in improving the performance of the hydrogen evolution reaction (HER). Here, we present, for the first time, direct dynamic spectral evidence illustrating the impact of the interaction between interfacial water molecules and adsorbed hydroxyl species (OHad) on the HER properties of Ni(OH)2 using Au/core-Ni(OH)2/shell nanoparticle-enhanced Raman spectroscopy. Notably, our findings highlight that the interaction between OHad and interfacial water molecules promotes the formation of weakly hydrogen-bonded water, fostering an environment conducive to improving the HER performance. Furthermore, the participation of OHad in the reaction is substantiated by the observed deprotonation step of Au@2 nm Ni(OH)2 during the HER process. This phenomenon is corroborated by the phase transition of Ni(OH)2 to NiO, as verified through Raman and X-ray photoelectron spectroscopy. The significant redshift in the OH-stretching frequency of water molecules during the phase transition confirms that surface OHad disrupts the hydrogen-bond network of interfacial water molecules. Through manipulation of the shell thickness of Au@Ni(OH)2, we additionally validate the interaction between OHad and interfacial water molecules. In summary, our insights emphasize the potential of electrochemical interfacial engineering as a potent approach to enhance electrocatalytic performance.

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents.

NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics. Diffusion coefficients (DB) and rotational correlation times (τB) of benzene in the solvents examined are accurately described as functions of viscosity (η) by DB ∝ η-0.81 and τB ∝ η0.64. Literature values of DB and τB in alkane and normal alcohols, which were not included among the solvents studied here, are systematically faster than predicted by these correlations, indicating that factors beyond solvent viscosity play a role in determining the friction on benzene. In contrast to benzene, water diffusion and rotation are poorly described in terms of viscosity alone, even in the dipolar and ionic solvents measured here. The present data and the substantial literature data already available on dilute water diffusion show a systematic dependence of DW on solvent polarity among isoviscous solvents. The aspect of solvent polarity most relevant to water dynamics is the ability of a solvent to accept hydrogen bonds from water, as conveniently quantified by the frequency of water's OH stretching band, ΔνOH. The friction on translation, ζtr = kBT/DW, and rotation, ζrot = kBTτW, are both well correlated by functions of the form ζ(η, ΔνOH) = a1ηa2 exp (a3ΔνOH), where the ai are adjustable parameters. Molecular dynamics simulations reveal a strong coupling between electrostatic and nonelectrostatic water-solvent interactions, which makes it impossible to dissect the friction on water into additive dielectric and hydrodynamic components. Simulations also provide a tentative explanation for the unusual form of the correlating function ζ(η, ΔνOH), at least in the case of ζrot.

Weak hydrogen bonding to halogens and chirality communication in propanols: Raman and microwave spectroscopy benchmark theory.

Constitutional and conformational isomers of bromopropanol are vibrationally and rotationally characterised with parallels drawn to the structural chlorine analogues. A previous microwave spectroscopic study of the chloropropanols is re-examined and all systems are explored by Raman jet spectroscopy. For bromine, the entire nuclear quadrupole coupling tensors are accurately determined and compared to their chlorine counterparts. Tensor asymmetry parameters are determined and linked with the hydrogen bond strength as indicated by the downshift of the OH-stretching frequency. The spectroscopic constants derived from the observed transitions are used as benchmarks for a large variety of electronic structure methods followed by harmonic and anharmonic rovibrational treatments. The CCSD(T) electronic structure calculations provide the best performance, in particular once anharmonic and relativistic corrections are applied or implied. Standard DFT approaches vary substantially with respect to their systematic error cancellation across the investigated species, and cost-effective compromises for the different observables are proposed.

Structural Investigation of Small Nickel-Ethanol Clusters Using Vibrational Spectroscopy in a Molecular Beam.

The structural identification of small nickel clusters with ethanol can help to understand fundamental steps for heterogenous catalysis. We investigate the rows [Nix (EtOH)1 ]+ with x=1-4, and [Ni2 (EtOH)y ]+ with y=1-3 via IR photodissociation spectroscopy in a molecular beam experiment. Analyzing the CH- and OH-stretching frequencies and comparing these experimental results with density functional theory (DFT) calculations on the PW91/6-311+G(d,p) level leads to the identification of intact motifs for all clusters and hints for C-O cleavage of the ethanol in two particular cases. Furthermore, we analyze the effects of frequency shifts with the increasing clusters sizes using the results of natural bond orbitals (NBO) analyses and an energy decomposition method.

Equilibrium hydrogen isotope fractionation between portlandite/brucite and water: Implication from the vibrational spectra at elevated temperature and pressure

Minerals in brucite-type structure, including brucite (Mg(OH)2) and portlandite (Ca(OH)2), have been studied as important analogs of hydrous silicate minerals for their thermodynamic properties, including equilibrium hydrogen and oxygen isotope fractionations between minerals and water at elevated temperatures and pressures. In this study, Raman and Fourier transform infrared (FTIR) spectra were collected at high-temperature (T) and high-pressure (P) conditions on synthetic hydrogenated and deuterated portlandite samples (i.e., Ca(OH)2 and Ca(OD)2), and their isobaric and isothermal mode Grüneisen parameters, as well as anharmonic parameters, were then evaluated. These high-precision vibrational spectra enable the evaluation of thermodynamic properties of portlandite (ΔU, CV, CP and ΔS) up to 427 °C, to which anharmonicity has positive contributions. More importantly, they help to determine the isobaric (at P = 1 bar) β factors of brucite and portlandite for equilibrium D/H fractionation considering anharmonic effects, and the D/H fractionation factor (103∙lnα) between brucite/portlandite and water at high-P,T conditions. The calculated equilibrium fractionation factor (lnαbrucite-water) agrees with experimental results in the temperature range from 300 to 647 K (∼27 to ∼374 °C, the critical point of water) within analytical uncertainties estimated using Monte Carlo method. The Ab initio calculation using DFT theory and VASP program was also carried out to obtain phonon spectra for brucite and portlandite with three-split hydrogen sites and to evaluate the dispersion effect, which is found to be smaller than the statistical uncertainty at high temperatures. Our results show that the internal OH-stretching modes in brucite/portlandite play a dominant role in determining the β values, and the anharmonic OH-stretching potential (xi parameter) contributes significantly to the D/H fractionation factor. Because previous studies show that OH-stretching frequencies generally decrease with increasing mass of cation in the metallic hydroxide having similar crystal structure, our results imply that the deuterium isotope may be preferentially enriched in the hydroxide phase with the light cation bonded to the hydroxyl group, which is also consistent with the observed D/H fractionations among hydrous silicates.

Probing Hydrogen-Bonding Interactions within Phenol-Benzimidazole Proton-Coupled Electron Transfer Model Complexes with Cryogenic Ion Vibrational Spectroscopy.

Hydrogen-bonding interactions within a series of phenol-benzimidazole model proton-coupled electron transfer (PCET) dyad complexes are characterized using cryogenic ion vibrational spectroscopy. A highly red-shifted and surprisingly broad (>1000 cm-1) transition is observed in one of the models and assigned to the phenolic OH stretch strongly H-bonded to the N(3) benzimidazole atom. The breadth is attributed to a combination of anharmonic Fermi-resonance coupling between the OH stretch and background doorway states involving OH bending modes and strong coupling of the OH stretch frequency to structural deformations along the proton-transfer coordinate accessible at the vibrational zero-point level. The other models show unexpected protonation of the benzimidazole group upon electrospray ionization instead of at more basic remote amine/amide groups. This leads to the formation of HO-+HN(3) H-bond motifs that are much weaker than the OH-N(3) H-bond arrangement. H-bonding between the N(1)H+ benzimidazole group and the carbonyl on the tyrosine backbone is the stronger and preferred interaction in these complexes. The results show that conjugation effects, secondary H-bond interactions, and H-bond soft modes strongly influence the OH-N(3) interaction and highlight the importance of the direct monitoring of proton stretch transitions in characterizing the proton-transfer reaction coordinate in PCET systems.

Machine Learning Approach for Describing Water OH Stretch Vibrations.

A machine learning approach employing neural networks is developed to calculate the vibrational frequency shifts and transition dipole moments of the symmetric and antisymmetric OH stretch vibrations of a water molecule surrounded by water molecules. We employed the atom-centered symmetry functions (ACSFs), polynomial functions, and Gaussian-type orbital-based density vectors as descriptor functions and compared their performances in predicting vibrational frequency shifts using the trained neural networks. The ACSFs perform best in modeling the frequency shifts of the OH stretch vibration of water among the types of descriptor functions considered in this paper. However, the differences in performance among these three descriptors are not significant. We also tried a feature selection method called CUR matrix decomposition to assess the importance and leverage of the individual functions in the set of selected descriptor functions. We found that a significant number of those functions included in the set of descriptor functions give redundant information in describing the configuration of the water system. We here show that the predicted vibrational frequency shifts by trained neural networks successfully describe the solvent-solute interaction-induced fluctuations of OH stretch frequencies.

Intramolecular O-H⋯S hydrogen bonding in threefold symmetry: Line broadening dynamics from ultrafast 2DIR-spectroscopy and ab initio calculations.

The dynamics of intramolecular hydrogen-bonding involving sulfur atoms as acceptors is studied using two-dimensional infrared (2DIR) spectroscopy. The molecular system is a tertiary alcohol whose donating hydroxy group is embedded in a hydrogen-bond potential with torsional C3-symmetry about the carbon-oxygen bond. The linear and 2DIR-spectra recorded in the OH-stretching region of the alcohol can be simulated very well using Kubo's line shape theory based on the cumulant expansion for evaluating the linear and nonlinear optical response functions. The correlation function for OH-stretching frequency fluctuations reveals an ultrafast component decaying with a time constant of 700 fs, which is in line with the apparent decay of the center line slopes averaged over absorption and bleach/emission signals. In addition, a quasi-static inhomogeneity is detected, which prevents the 2DIR line shape to fully homogenize within the observation window of 4 ps. The experimental data were then analyzed in more detail using a full ab initio approach that merges time-dependent structural information from classical molecular dynamics (MD) simulations with an OH-stretching frequency map derived from density functional theory (DFT). The latter method was also used to obtain a complementary transition dipole map to account for non-Condon effects. The 2DIR-spectra obtained from the MD/DFT method are in good agreement with the experimental data at early waiting delays, thereby corroborating an assignment of the fast decay of the correlation function to the dynamics of hydrogen-bond breakage and formation.

A comprehensive infrared spectroscopic and theoretical study on phenol-ethyldimethylsilane dihydrogen-bonded clusters in the S0 and S1 states.

To investigate microscopic characters of Si-H⋯H-O type dihydrogen bonds, we observed OH and SiH stretch bands in both the S0 and S1 states of phenol-ethyldimethylsilane (PhOH-EDMS) clusters by infrared (IR)-ultraviolet (UV) and UV-IR double resonance spectroscopies. Density functional theory (DFT) calculations and energy decomposition analysis were also performed. Structures of two isomers identified were unambiguously determined through the analysis of IR spectra and DFT calculations. To discuss the strength of dihydrogen bond in various systems, we performed theoretical calculations on clusters of EDMS with several acidic molecules in addition to PhOH. It was revealed that charge-transfer interaction energies from a bonding σ orbital of SiH bond to an anti-bonding σ* orbital of OH bond well reflect strengths of dihydrogen bonds. Additionally, it was found that the red shift of SiH stretch frequencies can be used as a crude measure of the strength of dihydrogen bonds. Relationship between the red shifts of OH/SiH stretch frequencies and various electrostatic components of the interaction energy was examined. In the S1 state, large increases in red shifts were observed for both the OH and SiH stretch frequencies. Since the EDMS moiety is not associated with the electronic excitation in a cluster, the strength of dihydrogen bonds in the S1 and S0 states was able to be directly compared based on the red shifts of the SiH stretch bands. A significant increase in the red shift of SiH stretch frequency indicates a strengthening of the dihydrogen bonds during the electronic excitation of the PhOH moiety.

Temperature and Nuclear Quantum Effects on the Stretching Modes of the Water Hexamer.

The water hexamer has many low-lying isomers, e.g., ring, book, cage, and prism, shifting from two- to three-dimensional structures. We show that this dimensionality change is accompanied by a drop in the quantum nature of the cluster, as manifested in the red shift of the quantal OH stretching modes as compared with their classical counterparts. We obtain this “nuclear quantum effect” (NQE) as the mean deviation between the OH stretch frequencies from velocity autocorrelation Fourier transforms from classical trajectories on a high-level water potential (MB-pol) as compared with scaled harmonic frequencies from high-level quantum chemistry calculations. With a universal scaling factor, the predicted OH frequencies agree with experiment to a mean absolute deviation ≤10 cm–1, which allows unequivocal isomer assignments. By assuming temperature-independent NQEs, we produce the temperature dependence of the cage isomer OH stretch spectrum below 70 K, where it is the dominant structure. All bands widen and blue-shift with increasing temperature, most conspicuously the reddest mode, which thus constitutes a “vibrational thermometer”.

Conformer-Specific Photolysis of Pyruvic Acid and the Effect of Water.

The conformer-specific reactivity of gas-phase pyruvic acid following the S1(nπ*) ← S0 excitation at λmax = 350 nm (290-380 nm) and the effect of water are investigated for the two lowest energy conformers. Conformer-specific gas-phase pyruvic acid photolysis rate constants and their respective populations are measured by monitoring their distinct vibrational OH-stretching frequencies. The geometry, relative energies, fundamental vibrational frequencies, and electronic transitions of the pyruvic acid conformers and their monohydrated complexes are calculated with density functional theory and ab initio methods. Results from experiment and theory show that the more stable conformer with an intramolecular hydrogen bond dominates the gas-phase photolysis of pyruvic acid. Water greatly affects the gas-phase pyruvic acid conformer population and photochemistry through hydrogen bonding interactions. The addition of water decreases the gas-phase relative population of the more stable conformer and decreases the molecule's gas-phase photolysis rate constants. The theoretical results show that even a single water molecule interrupts the intramolecular hydrogen bond, which is essential for the efficient photodissociation of gas-phase pyruvic acid. Results of this study suggest that the aqueous-phase photochemistry of pyruvic acid proceeds through hydrogen-bonded conformers lacking an intramolecular hydrogen bond.

Machine Learning for Vibrational Spectroscopic Maps.

Maps that relate spectroscopic properties of a vibrational mode and collective solvent coordinates have proven useful in theoretical vibrational spectroscopy of condensed-phase systems. It has been realized that the predictive power of such an approach is limited and there is no clear systematic way to improve its accuracy. Here, we propose an adaptation of Δ-machine-learning methodology that goes beyond the spectroscopic maps. The machine-learning part of our approach combines Gaussian process regression used to generate the data set with an artificial neural network used to predict spectroscopic properties of interest. A specific application to the OH-stretch frequencies and transition dipoles of water is presented. Our method approximates these properties about two times more accurately than the spectroscopic-maps-only-based approach. Our results suggest that the new approach may become useful in the study of vibrational spectroscopy of condensed-phase systems.

Dealing with Hydrogen Bonding on the Conformational Preference of 1,3-Aminopropanols: Experimental and Molecular Dynamics Approaches.

This study expands the knowledge on the conformational preference of 1,3-amino alcohols in the gas phase and in solution. By employing Fourier transform infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, density functional theory (DFT) calculations, quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) analysis, and molecular dynamics (MD), the compounds 3-aminopropan-1-ol (1), 3-methylaminopropan-1-ol (2), and 3-dimethylaminopropan-1-ol (3) are evaluated. The results show that the most stable conformation of each compound in the gas phase and in nonpolar solvents exhibited an O-H···N intramolecular hydrogen bond (IHB). Based on the experimental and theoretical OH-stretching frequencies, the IHB becomes stronger from 1 to 3. In addition, from the experimental NMR J-couplings, the IHB conformers are predominant in nonbasic solvents, representing 70-80% of the conformational equilibrium, while in basic solvents, such conformers only represent 10%. DFT calculations and QTAIM analysis in the gas phase support the occurrence of IHBs in these compounds. The MD simulation indicates that the non-hydrogen-bonded conformers are the lowest energy conformations in the solution because of molecular interactions with the solvent, while they are absent in the implicit solvation model based on density. NBO analysis suggests that methyl groups attached on the nitrogen atom affect the charge transfer energy involved in the IHB. This effect occurs mostly because of a decrease in the s-character of the LPN orbital along with weakening of the charge transfer from LPN to σ*OH, which is caused by an increase in the C-C-N bond angle.

Effects of methylation in acceptors on the hydrogen bond complexes between 2,2,2-trifluoroethanol and cyclic ethers.

In order to explore the effect of methylation on the stability and spectral shift of hydrogen bond complexes, the complexes of 2,2,2-trifluoroethanol (TFE) with propylene oxide (PO) and isobutylene oxide (IBO) were investigated by Fourier transform infrared (FTIR) spectroscopy and ab initio computations. The comparable OH-stretching red shifts were observed upon complexation, and an enhancement of the OH-stretching band is shown with the partial pressure of monomers increasing. The OH-stretching frequency of TFE is red shifted by 180 and 201 cm-1 with PO and IBO, respectively. By using quantum chemical calculations, we predicted the geometric parameters, binding energies, and spectral shifts of TFEPO/IBO hydrogen bond complexes. The calculated and observed spectral shifts follow the same trends. Compared with the TFEethylene oxide (EO) complex, the strength of the hydrogen bond in complex increases with the addition of methyl group, which likely results from the increase in basicity of the hydrogen bond acceptor. By combining the experimental integrated absorbance and the calculated IR intensity of the OH-stretching vibrational transition, the equilibrium constant for the complex formation was determined. In addition, atoms-in-molecules (AIM) and natural bond orbital (NBO) analyses were carried out to explain the red shift and the nature of the interaction in these complexes.

Spectroscopy and SEM imaging reveal endosymbiont-dependent components changes in germinating kernel through direct and indirect coleorhiza-fungus interactions under stress

In the present study, FTIR spectroscopy and hyperspectral imaging was introduced as a non-destructive, sensitive-reliable tool for assessing the tripartite kernel-fungal endophyte environment interaction. Composition of coleorhizae of Triticum durum was studied under ambient and drought stress conditions. The OH-stretch IR absorption spectrum suggests that the water-deficit was possibly improved or moderated by kernel’s endophytic partner. The OH-stretch frequency pattern coincides with other (growth and stress) related molecular changes. Analysis of lipid (3100–2800 cm−1) and protein (1700–1550 cm−1) regions seems to demonstrate that drought has a positive impact on lipids. The fungal endosymbiont direct contact with kernel during germination had highest effect on both lipid and protein (Amide I and II) groups, indicating an increased stress resistance in inoculated kernel. Compared to the indirect kernel-fungus interaction and to non-treated kernels (control), direct interaction produced highest effect on lipids. Among treatments, the fingerprint region (1800–800 cm−1) and SEM images indicated an important shift in glucose oligosaccharides, possibly linked to coleorhiza-polymer layer disappearance. Acquired differentiation in coleorhiza composition of T. durum, between ambient and drought conditions, suggests that FTIR spectroscopy could be a promising tool for studying endosymbiont-plant interactions within a changing environment.

On the Hydrogen Bond Strength and Vibrational Spectroscopy of Liquid Water

In the present work, we introduce two new metrics i.e. hydrogen-bond strength and charge-transfer between the donor/acceptor water molecules as a measure of hydrogen-bond rearrangement dynamics. Further, we also employ a simple model based on energy flux through the donor-acceptor water pairs to quantify the extent of the local hydrogen-bond network reorganization. Most importantly, we report a linear relationship between the OH stretch frequency and the charge and energy transfer through donor-acceptor water pairs. We demonstrate that the vibrational frequency fluctuations, which are used to determine third-order non-linear spectroscopic observables like the short-time slope of three pulse photon echo, can be used as an analog of the fluctuations in the hydrogen-bond strength and charge-transfer. The timescales obtained from our hydrogen-bond strength correlation and charge-transfer correlation decay are in excellent agreement with the computed frequency-time correlation function, as well as with recent vibrational echo experiments.

Protonation and Sequential Microsolvation of 5-Hydroxyindole: Infrared Photodissociation Spectra of 5HIH+–Ln with L = Ar and N2 (n ≤ 3)

Protonation and solvation of functionalized heterocyclic aromatic molecules, which often occur as biomolecular building blocks, are important processes in (bio-)organic biochemistry. Herein, we study the protonation and microsolvation mechanisms of 5-hydroxyindole (5HI, 1 H-indol-5-ol, C8H7NO), the chromophore of serotonin, produced by electron and and chemical ionization using infrared photodissociation (IRPD) spectroscopy of mass-selected cold 5HIH+-L n clusters (L = Ar/N2, n ≤ 3) and dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). Isomer-selective OH and NH stretch frequencies in the spectral range 3000-3800 cm-1 reveal the coexistence of at least four protonated species: the most stable syn (cis) isomer protonated at the C3 position of indole, both syn- and anti-rotamers protonated at C4 of the phenol ring, and the drastically less stable O-protonated isomer (Δ E0 = 117.1 kJ/mol) stabilized by kinetic trapping. Manipulation of the IRPD conditions (fragmentation channels) facilitates the spectroscopic isolation of O-protonated species. Upon protonation, the acidity of the OH group increases in the order 5HIH+(C3), 5HIH+(C4), and 5HIH+(O), while the acidity of the NH group decreases along this series, strongly affecting the microsolvation motifs of the individual isomers. Comparison of 5HIH+-L to the corresponding neutral and radical cation clusters reveals the impact of both protonation and ionization on the interaction with nonpolar ligands. Furthermore, our results are compared to protonated phenol, for which similar gas-phase protonation mechanisms have been found. Comparison of 5HIH+-L with the corresponding clusters of protonated phenol illustrates the effects of functional substitution and addition of aromatic rings on intermolecular potential.

Origin of Many-Body Vibrational Frequency Shifts in Water Clusters.

We have demonstrated the application of many-body expansions to calculations of the anharmonic, local-mode, OH-stretching vibrational frequencies of water clusters. We focused on five low-lying isomers of the water hexamer and the DD*(20,1) isomer of (H2O)21. Our approach provides accurate OH-stretching vibrational frequencies when treating one- and two-body interactions with the CCSD(T)-F12 level of theory and the three- and four-body interactions with the DF-MP2-F12 level. Additionally, we have investigated the physical origin of the large contribution that two- and three-body interactions make to the shifts of vibrational frequencies using symmetry-adapted perturbation theory (SAPT). We conclude that while two-body vibrational frequency shifts can be correlated linearly with electrostatic energies, all strongly shifted three-body interactions can be correlated to the induction energy with a single regression coefficient of approximately 70 cm-1 (kcal·mol-1)-1.

Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids.

Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm-1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pKA values. Dimers with large pKA differences are found to have features that can extend to frequencies below 1000 cm-1. The relationships between mean OH/NH frequency, aqueous pKA, and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm-1. Understanding how the vibrational features of strongly hydrogen-bonded structures depend on the relative pKA and other structural parameters will guide studies of biological structures and analysis of proton transfer studies using photoacids.

Thermal restraint of a bacterial exopolysaccharide of shallow vent origin

To dynamically characterize the thermal properties of the fructose-rich exopolysaccharide (EPS1-T14), produced by the marine thermophilic Bacillus licheniformis T14, the Attenuated Total Reflectance Fourier Transform Infra-Red spectroscopy was coupled to variable temperature ranging from ambient to 80°C.The spectra were analyzed by the following innovative mathematical tools: i) non-ideal spectral deviation, ii) OH-stretching band frequency center shift, iii) spectral distance, and iv) wavelet cross-correlation analysis.The thermal restraint analysis revealed that the whole EPS1-T14 system possessed high stability until 80°C, and suggested that fucose was mainly involved in the EPS1-T14 thermal stability, whereas glucose was responsible for its molecular flexibility.Our results provide novel insights into the thermal stability properties of the whole EPS1-T14 and into the role of its main monosaccharidic units. As a new biopolymer, the thermostable EPS1-T14 could be used in traditional biotechnology fields and in new biomedical areas, as nanocarriers, requiring high temperature processes.