106

5 Summary[61] 

The oxidation[4]  and reduction[55]  of the ascorbic acid / dehydroascorbic acid redox system as well as the alkaline hydrolysis[70]  from dehydroascorbic (DHA) to diketogulonic acid (DKG) were[53A]  analyzed[5]  in this dissertation. With the help of[64]  the ascertained[6]  band[63]  parameters, standard and calibration spectra[85]  from the infrared measurements[7] in substances, which contain[8] H–O - and C=O - bond groups[9], both[30A] , the me­tho­do­lo­gy for observing[62]  the reactions with infrared[10]  spectroscopy and[30A]  the interpretation received[11]  an essential[12]  support.

In this context, the problems of the keto-enol tautomerism were[53A]  studied on acetylacetone and (iso-)ascorbic acids. Furthermore[47], it turned out[13], that the square root values of the integral[65]  extinction[56] coefficient of the O=C-stretching[66]  vibration modes, which are proportional to the dipole moment changes, varied[76]  themselves comparably[75]  through the substitution[14]  of neighboring[48][49] bond groups[15] . The phenomenon[50]  of the hydration[69]  of keto groups was able to be pursued[43][59]  infrared spectroscopically[16] on a simple molecule (butanal[17]). For[46] the de­hy­dro­as­cor­bic acids in solution, the interpretation is still ambiguous[18]  because[86]  of several[19]  effects of mutual influence[20] . However, between crys­tal­li­ne bis-DHA and the hydrated[68]  DHA form, clear differences appeared[21]  in the H–O- and O=C-stretching[66]  vibration area. Unambiguously[22] successful[42] was the deuteration[23]  of the HO groups for bis-DHA. For the process of saponification[70]  of the DHA, functional relationships[24] of temperature and pH[54]  with an activation energy of 79.3 kJ / mol[73]  were[53A]  determined[6] . With the help of[64]  the electronic data processing (EDP), up to three infrared standard spectra[85] , namely[45] of DHA, DKG, and another one reductone-like[67]  substance, were able to be separated[60]  from D₂O solutions. The pK_a value of the soap making[70]  product (DKG), determined[6]  by pH-titration[58]  and by infrared spectroscopy, cor­res­ponds[57]  to known pK_a values of oxocarboxylic acids (oxocarbonic acids). The evolution[25]  of CO₂ in spectra[85]  of pellets can be backtracked[26]  to the decarboxylating DKG[27] . However, DKG is still[81]  quite[82]  stable in high concentrations in solution at 37°C. The DKG decomposition reactions were[53A]  examined qualitatively[51] , starting[28]  from DKG-stock solutions also in the neutral and alkaline pH[54]  range, except with the infrared spectroscopy, still with[72]  the spectrophotometry, the fluorescence and also the electron paramagnetic resonance (EPR)[77]  spectroscopy. The ruby-red substance, evolved[29]  at high pH[54]  value from both[30] , DHA and[30]  DKG, unstable opposite[31]  to aerial influences, can be associated[32]  with free radical processes. It was[53]  found one EPR signal, indicating R–O ● radicals.

It is problematic[52] that reduction[55]  and oxidation[4]  are[53C]  influenced[33A] by instabilities[34]  of DHA and DKG. Thus[35], equimolar NADH con­cen­tra­tions reduce[55A]  the DHA only incompletely[36] in the physiological pH[54]  range because[86]  of the additional DHA saponification[70] . The same thing is valid[37]  with reductions[55]  by H–S-group containing[8] substances for those[38]  an apparent[79X]  reaction order[79]  similar to the DHA saponification[70]  was[53]  found. However, one intermediate state[84]  to which[39] the real reduction[55]  reaction of DHA follows is[53B]  proven[40]  infrared spec­tro­sco­pi­cal­ly[16] during reactions by H–S groups. Clear infrared spectroscopic differences were[53A]  found at oxidation[4]  reactions between derivatives[83] , which are incapable or capable of C(6)–O–C(3) - cyclization[41].

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Nota:	English synonyms: Words of the same sense (words of common sense): Words of similar meaning: Englische Synonyme:
0)	with the subject with the topic is entitled is titled
1)	on to
2)	... reactions from dehydroascorbic [acid] and [from] diketogulonic acid ... Grammatical ellipsis/ellipse: ... reactions from dehydroascorbic and diketogulonic acid ...
3)	presented submitted
4)4)4)	oxidation oxydation oxidisation oxidization
5)	analyzed analysed [britische Schreibeweise, für Commonwealth ausser für Canada]
6)a)b)	ascertained determined (by measure) found-out get out identified investigated discovered explored observed
7)	With the help of the ascertained band parameters, standard and calibration spectra[85]  from the infrared measurements ... Relative clause, reduced by past participle: With the help of the band parameters, standard and calibration spectra[85] , ascertained from the infrared measurements ...
8)a)	... containing substances [entspricht am ehesten dem dts. Ausdruck] substances containing ... substances, which contain ... [für Sprachen, die kein Partizip Präsens gebrauchen]
9)9)9)9)9)9)9)	functional groups bond groups
10)	infrared ultrared ultra red
11)	experienced gained received underwent was given
12)	an essential a significant a substantial
13)	it turned out it became apparent it became manifest it was evident it resulted in it emerged it came out
14)	substitution replacement application
15)	neighboring bond groups[9] neighbouring bond groups[9] adjacent bond groups[9]
16)16)	with infrared spectroscopy infrared spectroscopically
17)	butanal butyraldehyde
18)	ambiguous equivocal
19)	several a number of a lot of multiple
20)	effects of mutual influence cross-influence effects effects of interaction
21)	appeared resulted arose were inferd
22)	unambiguously unequivocally clearly
23)	deuteration deuteriation deuterizing deuterization isotopic labeling with deuterium isotopic labelling with deuterium selective incorporation of deuterium in place of hydrogen
24)	functional relationships [Pl.] functional coherencies functional correlations
25)	development evolution
26)	backtracked to traced back to referred to followed back to followed up to derived from attributed to retraced to Note: the prefix "re-" means "again" or "back"
27)	decarboxylating[27A]  DKG DKG which decarboxylates DKG which releases the carboxyl group
27A)	decarboxylating [often] decarboxylizing [rare] decarboxylising [very rare] decarboxylation doing [extremely rare] carboxyl group releasing carboxyl group losing
28)	starting from beginning with
29)	evolved developed itself generated itself
30)	from both, ... and ... from ... as well as ...
30A)	, both, ... and ... , not only ... but also ... , ... as well as ... , as well ... as ... ["as well" stands postpositional]
31)	opposite to ... influences (↔) against ... influences (↔) under ... influences (↧)
32)	associated with related to
33)	are influenced by are affected by
33A)	[Passiv:] that reduction and oxidation are influenced[33] by instabilities of DHA and DKG [Pseudo-Passiv:] that reduction and oxidation are under influence of instabilities of DHA and DKG [Aktiv:] that instabilities of DHA and DKG are taking effect on reduction and oxidation
34)	instabilities unstablenesses
35)	thus so therefore consequently
36)	[pl.-noun] reduce[55A]  ... only incompletely [pl.-noun] make reduction[55]  ... only incompletely [pl.-noun] do not reduce[55A]  ... completely [pl.-noun] do not make reduction[55]  ... completely [pl.-noun] don't make reduction[55]  ... completely
37)	is valid with applies to does apply to goes for happens with
38)	for which for those for what wherefore for that
39)	intermediate state[44]  to which the (...) follows intermediate state[44]  after which the (...) follows intermediate state[44]  to that one the (...) follows intermediate state[44]  which the (...) follows to intermediate state[44]  which the (...) follows after intermediate state[44]  that the (...) follows to intermediate state[44]  the (...) follows to mit: (...) = real reduction[55]  reaction of DHA
40)	proven [Partizip Perfekt; schottisch-englische Variante] proved [Partizip Perfekt; Imperfekt] controlled checked tested shown
41)	cyclization cyclisation ring forming ring closure
42)	succeeded [↔ dts., and., frz.] came out well [↔ esp., prt.] had success [↔ esp.] was successful [↔ prt., gal.] was done successfully was performed successfully
43)	pursued persecuted followed
44)	transitional state intermediate state interstate
45)	namely by name
46)	with in the case of for
47)	furthermore in addition moreover
48)	neighboring neighbouring
49)	neighboring bond groups bond groups in neighborhood
50)	appearence phenomenon
51)	qualitatively in qualitative manner concerning the quality pertaining to quality with regard to quality
52)	It is problematic It is problematical There is a problem There are problems
53)	Hilfsverben für den PASSIV /"passive voice" (eng.) was got
53A)	Hilfsverben für den PASSIV /"passive voice" (eng.) were got
53B)	Hilfsverben für den PASSIV /"passive voice" (eng.) is get
53C)	Hilfsverben für den PASSIV /"passive voice" (eng.) are get
54)	pH the negative common logarithm of the activity of hydrogen ion in solution the common cologarithm of the activity of hydrogen ion in solution [less precise:] the cologarithm with base 10 of the concentration of hydrogen ion in solution
55)	reduction(s) deoxidation(s)
55A)	reduce deoxidize deoxidise do reduction
56)	extinction (act of) extinguishing attenuation
57)	corresponds to is set in line to agrees with matches with coincides with congruates with
58)	titration titrimetry volumetry
59)	one[59X] managed[59Y] to pursue [active voice] the phenomenon ... the phenomenon ... was able to be pursued [passive voice]
59X)	one the author
59Y)	managed enabled was able
60)	one[59X] managed[59Y] to separate [active voice] ... 3 spectra[85]  ... ... 3 spectra[85]  ... were able to be separated [passive voice]
61)	conclusion summary resume
62)	observation observing watching
63)	band zone stripe
64)64)64)	with the help of by means of by dint of
65)	contiguous integral
66)a)	stretching extension
67)	reductonely substance reductone-like substance substance like a reductone substance being similar to reductone substance which is similar to reductone
68)	hydrated water-attached
69)	hydration water-attachment
70)70)70)70)70)	saponification soap making alkaline hydrolysis
71)	calculator-supported computerized computerised
72)	in addition to ... still with ... except with ... still with ... except with ... even with ... except with ... or with ...
73)	79.3 kJ/mol seventy nine point three kilojoules per mole
74)	inaugural dissertation opening doctoral thesis introductory doctoral thesis
75)	comparably in a comparable manner
76)	varied changed amended modified altered
77)	ESR: electron spin[78]  resonance EPR: electron paramagnetic resonance
78)	spin intrinsic angular momentum
79)	(sum of) exponent(s) of rate law equation[80]  of chemical reaction reaction order (sum of) partial order(s) of reaction (overall order of reaction)
79X)	apparent reaction-order pseudo reaction order
80)	rate law equation rate law rate equation
81)	still always yet
82)	entirely quite
83)	derivate derivative
84)	intermediate state transition state
85)	plural forms: spectra spectrums
86)	because of [+ Objekt/Nomen] due to [+ Objekt/Nomen] for the reason that [+ Subjekt/Nomen + Verb]

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Keywords (/index term):

Detlef, Pagel, Giessen, 1992, DHA, DKG, EPR, NADH, pH, pKa, acetyl, acetone, acid, activation, alkaline, ascorbic, bis, bond, butanal, calibration, carbonic, carboxylic, coefficient, concentration, crystallin, cyclization, decomposition, dehydro, deuteration, diketo, dipole, dissertation, electron, energy, enol, fluorescence, group, gulonic, hydration, hydrolysis, inaugural, infrared, instabilities, integral, intermediate, interpretation, iso, keto, making, measurement, moment, neutral, order, oxidation, oxo, paramagnetic, parameter, pellet, photometry, physiological, radical, range, reactions, redox, reduction, reductone, relationship, resonance, saponification, solution, soap, spectro, spectroscopic, spectroscopy, state, stock, stretching, subject, substitution, summary, tautomerism, temperature, titration, ultrared, value, vibration