A Novel Tool for Visualization of Water Molecular Structure and Its Changes, Expressed on the Scale of Temperature Influence
2. Results and Discussion
2.1. Results of Temperature Experiment
2.2. Results of Potassium Chloride Experiment
3. Materials and Methods
3.2. The Temperature Experiment
3.3. The Potassium Chloride Experiment
3.4. NIR Spectral Acquisition
3.5. Statistical Data Analysis
3.5.1. Calculation Protocol of “Classic” Aquagram
3.5.2. Calculation Protocol for Newly Developed (Temperature-Based) Aquagram
- Step 1.
- The dataset of the temperature experiment (i.e., the spectra of the Milli-Q water samples acquired during the temperature experiment in the temperature range between 20–70 °C) is defined as the reference dataset.The dataset of the experiment of interest is defined as the experimental dataset.
- Step 2.
- The average spectra of the consecutive scans are calculated for each temperature step, yielding 26 single, unique spectra in the reference dataset.The average spectra of the groups of interest (in this case, salt concentration levels) are calculated in the experimental dataset together with their respective confidence intervals using the Bootstrap method , yielding as many single, unique spectra as there are groups are in the experimental dataset (plus their upper and lower 95% confidence interval limits).
- Step 3.
- The area under the spectrum for every single average spectrum—in the reference dataset and in the experimental dataset—at the wavelength range of 1336 to 1348 nm (C01) is calculated taking into account the baseline estimated by linear fitting on the two edges of the first overtone region (i.e., 1300 and 1600 nm). In case of the experimental dataset, the areas of the respective confidence interval limits are also calculated in addition to the area of the average spectrum. Figure 8 provides graphical interpretation of the relevant areas and the wavelength regions used for the 12 coordinates.
- Step 4.
- The ratio of the area under the curve for each single coordinate is calculated with respect to the full area under the curve for the first overtone OH region (i.e., the area of C01 is divided by the full area under the spectrum in the range of 1300 to 1600 nm). This is done for every single average spectrum, in the reference dataset and the experimental dataset (together with the respective confidence interval limits for the experimental dataset). This calculation step provides normalized values and avoids possible differences due to scattering and/or pathlength effects.
- Step 5.
- Based on the reference dataset, a continuous array of values for the relative area of C01 (as calculated in Step 1) is calculated for a continuous temperature range from 20 to 70 °C using local polynomial regression. This is an essential step in order to accommodate the data from an experiment performed at specific temperature—see Step 6.
- Step 6.
- The basic principle of the temperature-based aquagram method is to compare the effect of the perturbation used on the system under study which resulted in a certain water spectral pattern to the effect the temperature changes would induce in pure water. Thus, any perturbation can be expressed as an equivalent temperature effect on a Milli-Q water sample. It is necessary to perform a “local calibration” with the reference dataset around the temperature of the experimental dataset. Therefore, in this step, the temperature calibration range is defined. This range is used to express the effect of perturbation in degrees Celsius equivalent. For this, a symmetrical scale is defined from the reference dataset (calculated at Step 5) using two degrees, plus and minus around the temperature of the experiment (hence, a span of 4 °C). For example, if the experiment was performed at 25.0 °C, then the calibration range of 23.0 to 27.0 °C would be used.
- Step 7.
- The temperature calibration equation, the relationship between the change of the temperature and change of the area of C01 at the temperature of the experiment, is determined based on the calculation performed in Step 5 on the reference dataset. (It is known how the area of C01 changes as a function of temperature described by a linear function). Therefore, it is easy to compare the changes for areas for C01 for the experimental dataset (calculated at Step 3) to the changes of the area of C01 caused by temperature, i.e., to express the changes in C01 in units of temperature (degrees Celsius) equivalent.
- Step 8.
- The calculated temperature (degrees Celsius) equivalent value for every group of the experimental dataset is finally visualized together with the respective 95% confidence intervals in a radar chart, where the units of the axes are in degrees Celsius.
- Step 9.
Conflicts of Interest
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Sample Availability: Samples of the compounds KCl are available from the authors.
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Kovacs, Z.; Pollner, B.; Bazar, G.; Muncan, J.; Tsenkova, R. A Novel Tool for Visualization of Water Molecular Structure and Its Changes, Expressed on the Scale of Temperature Influence. Molecules 2020, 25, 2234. https://doi.org/10.3390/molecules25092234
Kovacs Z, Pollner B, Bazar G, Muncan J, Tsenkova R. A Novel Tool for Visualization of Water Molecular Structure and Its Changes, Expressed on the Scale of Temperature Influence. Molecules. 2020; 25(9):2234. https://doi.org/10.3390/molecules25092234Chicago/Turabian Style
Kovacs, Zoltan, Bernhard Pollner, George Bazar, Jelena Muncan, and Roumiana Tsenkova. 2020. "A Novel Tool for Visualization of Water Molecular Structure and Its Changes, Expressed on the Scale of Temperature Influence" Molecules 25, no. 9: 2234. https://doi.org/10.3390/molecules25092234