Liquid water (D2O): a dynamic model emerging from near-infrared DO-D stretching overtone studies

Khoshtariya, Dimitri E.; Dolidze, Tina D.; Lindqvist‐Reis, Patric; Neubrand, Anton; Eldik, Rudi van

doi:10.1016/s0167-7322(01)00326-9

Cited by 31 publications

(61 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For the case of liquid heavy water (D 2 O), we have disclosed five types of OD-D oscillators, three of which are of major importance for liquid water under ambient conditions. [38,39] We note that recent results from picosecond and sub-picosecond mid-IR transient (pump-probe) spectroscopy of liquid water also revealed the participation of at least three major substates of O-H (O-D) oscillators. [40,41] In Figure 1 we present the results of totally independent DO-D (ref.…”

Section: Resultsmentioning

confidence: 81%

“…Recently [38,39] we have introduced an advanced, physically substantiated, and rigorous method for the deconvolution of composite IR or NIR (as well as Raman) spectra. This method is based on a combined procedure, which includes the generation of difference and double-difference spectra and a global compositional (Gaussian or similar) analysis.…”

Section: Resultsmentioning

confidence: 99%

“…[40,41] In Figure 1 we present the results of totally independent DO-D (ref. [38]) and HO-H (this work) composite stretching overtone (2n OD and 2n OH ) band deconvolutions into five component sub-bands (25 8C, ambient pressure). For the case of H 2 O, the wavenumber axis is reduced by a factor of 1.355 (close to the "ideal" deuteron/hydrogen mass factor of ffiffi ffi 2 p = 1.414 [42] ) to allow a direct comparison between all subband parameters (which are presented also in Table 1).…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Local Dense Structural Heterogeneities in Liquid Water from Ambient to 300 MPa Pressure: Evidence for Multiple Liquid–Liquid Transitions

et al. 2004

View full text Add to dashboard Cite

Difference and double-difference near-infrared DO-D and HO-H stretching overtone (2nuOD and 2nuOH) spectroscopy and a rigorous (physically substantiated) band deconvolution technique were applied to reveal three different kinds of inherent (interstitial) structures of liquid water, which determine its high density (compared to ice lh under ambient conditions), its compressibility (under hydrostatic pressure, up to 300MPa), and its high fragility (manifested under temperature variation). Our data processing allowed the rigorous discrimination of up to six vibrational components. On the basis of an extensive comparative analysis combined with available structural data (X-ray and neutron scattering) and molecular dynamics (MD) simulations for liquid water, as well as with experimental and computed data for small non-tetrahedrally arranged water clusters, the major four components could be ascribed to: i) The basic lh icelike substructure; ii) the temperature-dependent remote interstitial "defects" due to tetrahedral displacements (primarily responsible for transport properties); iii) the interstitial "defects" most probably arranged in quasiplanar noncyclic tetramers (totally absent in the ice structure); and iv) the interstitial "defects" formed with increasing pressure, probably arranged in cubic water octamers and composed of two pairs of noncyclic and cyclic tetramer fragments. The latter structures include, essentially, bent hydrogen bonds stabilized by resonance effects.

show abstract

Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Local Dense Structural Heterogeneities in Liquid Water from Ambient to 300 MPa Pressure: Evidence for Multiple Liquid–Liquid Transitions

et al. 2004

View full text Add to dashboard Cite

show abstract

“…The above-mentioned property of water is probably due to the peculiar multicomponent nature of this liquid. [65] Thus, moderately high pressure (up to 200-300 MPa) affects those structural components that are not responsible for transport properties including fluidity and diffusion.…”

Section: Impact Of Stabilizingmentioning

confidence: 99%

Kinetic, Thermodynamic, and Mechanistic Patterns for Free (Unbound) Cytochrome c at Au/SAM Junctions: Impact of Electronic Coupling, Hydrostatic Pressure, and Stabilizing/Denaturing Additives

Khoshtariya

Dolidze²,

Seifert

et al. 2006

Chemistry A European J

View full text Add to dashboard Cite

Combined kinetic (electrochemical) and thermodynamic (calorimetric) investigations were performed for an unbound (intact native-like) cytochrome c (CytC) freely diffusing to and from gold electrodes modified by hydroxyl-terminated self-assembled monolayer films (SAMs), under a unique broad range of experimental conditions. Our approach included: 1) fine-tuning of the charge-transfer (CT) distance by using the extended set of Au-deposited hydroxyl-terminated alkanethiol SAMs [-S-(CH(2))(n)-OH] of variable thickness (n=2, 3, 4, 6, 11); 2) application of a high-pressure (up to 150 MPa) kinetic strategy toward the representative Au/SAM/CytC assemblies (n=3, 4, 6); 3) complementary electrochemical and microcalorimetric studies on the impact of some stabilizing and denaturing additives. We report for the first time a mechanistic changeover detected for "free" CytC by three independent kinetic methods, manifested through 1) the abrupt change in the dependence of the shape of the electron exchange standard rate constant (k(o)) versus the SAM thickness (resulting in a variation of estimated actual CT range within ca. 15 to 25 A including ca. 11 A of an "effective" heme-to-omega-hydroxyl distance). The corresponding values of the electronic coupling matrix element vary within the range from ca. 3 to 0.02 cm(-1); 2) the change in activation volume from +6.7 (n=3), to approximately 0 (n=4), and -5.5 (n=6) cm(3) mol(-1) (disclosing at n=3 a direct pressure effect on the protein's internal viscosity); 3) a "full" Kramers-type viscosity dependence for k(o) at n=2 and 3 (demonstrating control of an intraglobular friction through the external dynamic properties), and its gradual transformation to the viscosity independent (nonadiabatic) regime at n=6 and 11. Multilateral cross-testing of "free" CytC in a native-like, glucose-stabilized and urea-destabilized (molten-globule-like) states revealed novel intrinsic links between local/global structural and functional characteristics. Importantly, our results on the high-pressure and solution-viscosity effects, together with matching literature data, strongly support the concept of "dynamic slaving", which implies that fluctuations involving "small" solution components control the proteins' intrinsic dynamics and function in a highly cooperative manner as far as CT processes under adiabatic conditions are concerned.

show abstract

“…The presence of nearly-isosbestic points in the infrared spectra of water at different temperatures has usually been taken as support of the mixture model. However, both models need to be taken into account in order to explain the many anomalous properties of water [19].…”

Section: Appendix More Detailed Interpretation Of the Water Temperatumentioning

confidence: 99%

Pre‐processing in biochemometrics: correction for path‐length and temperature effects of water in FTIR bio‐spectroscopy by EMSC

Martens

Bruun

Adt

et al. 2006

Journal of Chemometrics

View full text Add to dashboard Cite

The term 'biochemometrics' is proposed. Methodology is presented for simplifying high-resolution phenotyping measurements, in terms of multivariate modelling methods in order to stabilise FTIR bio-spectroscopy data. Irrelevant gas contributions from water vapour and CO 2 in the instrument light path are modelled and removed, in order to avoid having to wait for N 2 purging. Variations in the infrared spectroscopy (IR) spectrum of water with temperature are described in terms of two model component spectra. These additive water variations are quantified and eliminated by Extended Multiplicative Signal Correction (EMSC), along with various physical signal variations of additive and multiplicative nature due to, for example, sample or instrument temperature. Sample temperature is predicted from the EMSC model parameters. The models developed for Attenuated Total Reflection (ATR) measurements of pure water at different temperatures are tested successfully in independent water samples as well as in the in vivo monitoring of Candida albicans growing and decaying on the ATR crystal of the same instrument.

show abstract

Liquid water (D2O): a dynamic model emerging from near-infrared DO-D stretching overtone studies

Cited by 31 publications

References 57 publications

Local Dense Structural Heterogeneities in Liquid Water from Ambient to 300 MPa Pressure: Evidence for Multiple Liquid–Liquid Transitions

Local Dense Structural Heterogeneities in Liquid Water from Ambient to 300 MPa Pressure: Evidence for Multiple Liquid–Liquid Transitions

Kinetic, Thermodynamic, and Mechanistic Patterns for Free (Unbound) Cytochrome c at Au/SAM Junctions: Impact of Electronic Coupling, Hydrostatic Pressure, and Stabilizing/Denaturing Additives

Pre‐processing in biochemometrics: correction for path‐length and temperature effects of water in FTIR bio‐spectroscopy by EMSC

Contact Info

Product

Resources

About