106
5 Summary
In this dissertation, as well the oxidation and reduction of ascorbic acid and dehydroascorbic acid (redox system) as the alkaline hydrolysis from dehydroascorbic (DHA) to diketogulonic acid (DKG) were analyzed
2) .
With the help of the ascertained
18) band parameters, standard and calibration spectra from the infrared measurements in substances, which contain H–O- and C=O-bond groups, as well methodology for observing the reactions with infrared
4) spectroscopy as the interpretation experienced an essential support.
In this context, the problems of the keto-enol tautomerism were
studied in acetylacetone and (
iso-) ascorbic acids.
Furthermore, it turned out, that the square root values of the integral extinction coefficient of the O=C-stretching vibration modes, which are proportional to the dipole moment changes, varied themselves comparatively through the substitution of neighboring bond groups
14) .
The phenomenon of the hydration of keto groups was able to be pursued with infrared spectroscopy in a simple molecule (butanal
15) ).
With the dehydroascorbic acids in solution, the interpretation is because of several effects of mutual influence still ambiguous.
However, clear differences between crystalline
bis-DHA and the hydrated DHA form resulted
12) from the H–O- and O=C-stretching vibration area.
Unambiguously, the deuteration of the HO groups was successful for
bis-DHA.
For the process of saponification of the DHA, functional coherences of temperature and pH with an activation energy of 79.3 kJ/mol were determined.
With the help of the electronic data processing (EDP), up to three infrared standard spectra, namely of DHA, DKG, and another one reductone-like substance, were able to be separated from D
2O solutions.
The pK
a value of the soap making product (DKG), investigated by pH-titration and by infrared spectroscopy, corresponds to known pK
a values of oxocarboxylic acids (oxocarbonic acids).
The evolution of CO
2 in spectra of pellets can be traced back to the decarboxylating
3) DKG.
However, DKG is still quite stable in high concentrations in solution at 37°C.
The DKG decomposition reactions were qualitatively examined, starting
19) from DKG-stock solutions also in the neutral and alkaline pH range, except with the infrared spectroscopy, still with the spectrophotometry, the fluorescence and also the electron paramagnetic resonance (EPR) spectroscopy.
A ruby-red substance evolved
16) at high pH value from as well
17) DHA as DKG.
It is unstable to aerial influences and can be associated with radicalic processes.
It was found a R–O
• radicals indicating EPR signal.
It is problematic that reduction and oxidation are influenced by
instabilities of DHA and DKG.
Therefore, equimolar NADH concentrations reduce only incompletely the DHA in the physiological pH range because of the additional DHA saponification.
The same is valid
13)
with reductions by H–S-group containing substances for which an apparent reaction order similar to the DHA saponification was found.
However, an intermediate state which the real reduction reaction of DHA follows, is infrared spectroscopically proven
1) by reactions with H–S groups.
Clear infrared spectroscopic differences were found at oxidation reactions between derivatives, which are incapable or capable of C(6)–O–C(3) - cyclization.
Nota: |
English synonyms:
Englische Synonyme: |
1) |
proven [Partizip Perfekt]
proved [Partizip Perfekt; Imperfekt]
|
2) |
analyzed
analysed
|
3) |
decarboxylating [often]
decarboxylizing [rare]
decarboxylising [very rare]
decarboxylation doing [extremely rare]
|
4) |
infrared
ultrared
ultra red
|
5) |
substitution
application
|
6) |
deuteration
deuteriation
|
7) |
several
a number of
|
8) |
effects of mutual influence
cross-influence effects
|
9) |
development
evolution
|
10) |
instabilities
unstablenesses
|
11) |
cyclization
cyclisation
ring forming
|
12) |
resulted from
arose from
|
13) |
is valid
applies
does apply
|
14) |
neighboring bond groups
neighbouring bond groups
adjacent bond groups
|
15) |
butanal
butyraldehyde
|
16) |
evolved
developed itself
|
17) |
from both, ... and ...
from as well ... as ...
|
18) |
ascertained
determined
found-out
identified
|
19) |
starting from
beginning with
|