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Abstract
The present review deals with some factors determining the anti-aging as well as the aging process. In order to get a deeper insight in
the subject matter, firstly some less known spectroscopic and kinetic data of antioxidant vitamins (C, E, b-carotene) acting as anti-aging
factors by electron transfer are briefly discussed. The generation of oxygen transients (OH, ROOd, 1O2, ozone radicals, etc.) by sunlight,
ultrasonic and microwave radiation are causing ‘‘oxygen stress’’ and contribute to early ageing is also reviewed. Particular attention is
paid to external environmental aging factors. Their action is based on the incorporation of various pollutants contained in water and air
in the human organism. In this respect the polycyclic aromatic hydrocarbons (PAHs) play an essential role by initiating DNA-mutation,
leading to an accelerate aging, carcinogenesis and diseases.
r 2007 Elsevier Ltd. All rights reserved.
0969-806X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2007.01.002
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1578 N. Getoff / Radiation Physics and Chemistry 76 (2007) 1577–1586
3. Antioxidant vitamins
of vit.Ed+ by electron transfer from vit.E to DMSOd+ hydrolysis, where OH radicals are formed or it is
proceeds with a rate constant, k ¼ 1 109 L mol1 s1 and regenerated to b-car by electron acception from, surround-
the resulting vit.Ed+ decays by a second order reaction ing molecules (see later).
with k ¼ 4.7 108 L mol1 s1. The transient absorption It was further established that b-carotene can also react
spectrum as well as the molar extinction coefficients with e d
aq , yielding the corresponding radical anion (b-car ).
(e-values) of the corresponding maxima are presented in The absorption spectrum of b-carotene radical anion
Fig. 2. The radical cation of vitamin E-acetate has been (b-card) is shown in Fig. 4. It was registered by pulse
also determined by pulse radiolysis (Getoff, 2001). radiolysis in an airfree solvent mixture of 86% ethanol and
Preliminary experiments showed that vitamin E under 14% three times distilled water (Getoff, 1999). The transient
certain conditions can also react with e aq generating absorption spectrum possesses a strong absorption band at
vit.Ed (radical anion). Studies by various researchers 850 nm (e ¼ 1.3 104 L mol1 cm1) as well as a small one
(see e.g. Machlin, 1991; Kammerer et al., 2001) have shown at about 270 nm. The b-card radical anion is formed with
that vitamin E, likewise as vitamin C is a very potent k ¼ 4.3 109 L mol1 s1 and disappears by a first order
scavenger of oxidizing species: OH, peroxyl and ozone reaction with k1 ¼ 3.8 103 s1, forming a dimer radical
radicals, etc. Hence, it protects the cell components against anion, ðbcarÞd 2 . The ability of vitamin E to form various
destruction, operating as anti-aging agent. types of transients can explaine, at least to certain extent, its
The formation of b-carotene radical cation (b-card+) was versatile biological properties. Naturally, the formation of
determined in oxygenated DMSO solution and is pre- either b-card+ or b-card radical ions in the organism
sented in Fig. 3 at various times (ms) after the end of a should strongly depend on the redox-processes of the
0.1 ms pulse of 10 MeV electrons. The spectrum shows a involved systems. Based on its multiple reactivity b-car
strong absorption maximum at 942 nm (e ¼ 1.6 plays an important role in the aging process as a mediator in
104 L mol1 cm1), whereas the absorption band of b-car redox processes (see next chapter).
triplet state at 520–680 nm is strongly quenched by oxygen The antioxidant properties of the vitamin C, E and
at the same time (Getoff, 2000). b-carotene have been also studied from various points of
Based on the kinetics (Fig. 3, insert) it was established view (e.g. Benssason et al., 1983; Sies and Stahl, 1995).
that the species are formed with a rate constant
k ¼ 4.8 108 L mol1 s1. They disappear in a first order
reaction, k1 ¼ 2.1 103 s1, resulting in a dimer radical 4. Protection of cell membrane damage by antioxidant
cation (b-car)d+
2 . For further details about b-car
d+
species vitamins
see the original paper (Getoff, 2000). It might be mentioned
that b-card+ is a oxidizing specie. In addition to the In general the biological cell membrane consists of
formation of dimer radical cation, it can also undergo lipoproteins, where also enzymes and 3–5% antioxidant
vitamins (b-carotene, vitamin E and C) are also contained.
Based on the above briefly mentioned spectroscopic and
kinetic data of vitamins, an attempt was made to investigate
their effect on the membrane protection. The studies
concerned the electron transfer between them in airfree
DMSO solutions. It was established a cascade electron
transfer process with the following pathway: b-carotene
(b-car) contained at distinct areas at the outer layer of the
cell membrane is getting first in contact with oxidizing
agents (e.g. OH radicals). The ejected electron from b-car
forms the passive OH ions and a strong oxidizing b-card+
radical cation. The last one as an oxidizing specie could
destroy the membrane layer, however, it is regenerated to
b-car by electron transfer from vitamin E (formation of
vit.Ed+). In turn each vit.Ed+ specie is regenerated to vit.E
by an electron provided by vitamin C (AH). The resulting
AHd radicals undergo disproportion, forming DHA. This
Fig. 2. Transient absorption spectrum (5 ms after 0.4 ms electron pulse)
resulting from 9.3 104 mol L1 a-tocopherol in aerated DMSO (OD/
cascade electron transfer can be illustrated by the reactions
cm-values normalized to 10 Gy). Insert: spectroscopic data of Vit. Edþ and the scheme shown in Fig. 5. It appears, therefore,
transients. vitamin C to be the most important electron source for the
Formation and decay reactions: Vit:E þ DMSOdþ ! Vit:Edþ þ protecting process (Getoff, 2001).
DMSO ðk ¼ 1 109 L mol1 s1 Þ; Vit:Edþ þVit:Ed þ ! products ðk ¼ It should be mentioned that the electron transfer
4:7 108 L mol1 s1 Þ: (Reprinted from Radiat. Phys. Chem. 55, 699–704,
1999 by N. Getoff, I. Platzer and C. Winkelbauer: Transients and
reaction in the cell membrane, very likely the lipoproteins
cooperative action of b-carotene, vitamin E and C in biological systems in as well as enzymes are involved. These processes are
vitro under irradiation, with permission from Elsevier). connected with the mechanisms concerning the rather
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1580 N. Getoff / Radiation Physics and Chemistry 76 (2007) 1577–1586
Fig. 3. Absorption spectra and kinetic traces of bcardþ resulting by 0.1 ms pulse of 10 MeV electrons of 1.5 105 mol L1 b-carotene in aerated DMSO
solution.
Formation: bcar þ DMSOdþ ! bcardþ þ DMSO ðk ¼ 4:8 108 L mol1 s1 Þ: Decay: bcardþ þ bcar ! ðbcarÞ2dþ ðdimer radical cationÞ ðk1 ¼
2:1 103 s1 Þ: (Reprinted from Radiat. Res. 154, 692–696, 2000, by N. Getoff: Pulse radiolysis studies of b-carotene in oxygenated DMSO solution.
Formation of b-carotene radical cation, with permission of Radiation Research Journal).
Fig. 6. (A) Total absorption at pulse end (OH-adduct) resulting from 2 104 mol dm3 4-chlorobenzaldhyde saturated with N2O. (B) Saturated with
1.4 102 mol dm3 N2O and 0.62 103 mol dm3 O2 at pulse end. (C) The same medium, spectrum measured at 155 ms after pulse end; pH ¼ 10:4,
absorbed dose: 5 Gy/0.4 ms electron pulse. Kinetic profiles: (a) decay of OH-adducts, (b) formation of peroxyl radicals in solution (B). (Reprinted from
Radiat. Phys. Chem. 65, 437–446, 2002, by N Getoff: Factors influencing the efficiency of radiation-induced degradation of water pollutants, with
permission from Elsevier).
Table 2
Rate constants (k, L mol1 s1) for reactions of some free radicals and pollutants. In Scheme 3 the stepwise ozonation course of
singlet oxygen (1O2) with antioxidant vitamins
aqueous trichloroethylene (TClE) is given as an example.
Vitamin Rate constant (k, L mol1 s1) of As final products of the process very toxic phosgene,
OH e
aq ROOd 1
O2 chloroaldehyde and hydrogen peroxide are formed. The
first two products undergo hydrolysis. The products of
Ascorbate 3 109a 3.5 108a 2 108c 1 107c such processes can seriously contribute to accelerated
Ascorbic acid 1 1010a – – –
Vitamin E 4.6 109b 4.6 109a 5 108c 8 107c
aging, cell damage and carcinogenesis.
b-Carotene – 2 108a 1.5 109c 5 109c
a
8. Ultrasonic radiation
Buxton et al. (1988).
b
Getoff (1999).
c
Sies and Stahl (1995). Electromagnetic radiation with a frequency in the range
of 2 105 to about 108 Hz is indicated as ultrasonic
radiation. It can lead to sonolysis of water, meaning water
A particular role in the aging process is attributed to splitting to H and OH radicals, whereby in the presence of
ozone. It is a very strong oxidant and in addition to this by air peroxyl radicals are formed (El’Piner, 1964; Getoff,
reaction with the free radicals generated in the human 1995):
organism, a number of various oxidizing species are
H 2O H + OH (1)
formed. In order to give an impression in this respect,
some reactions of ozone degradation and corresponding
H þ O2 ! HO2d ðk ¼ 2 1010 L mol1 s1 Þ; (2)
rate constants (k-values) are compiled in Table 3 (Getoff,
1997 and references therein).
HO2d "Hþ þ Od
2
ðpK ¼ 4:8Þ: (3)
As mentioned above, ozone like OH radicals, attack
preferentially the double bonds in organic compounds. For It might be noted that under certain conditions ultra-
illustration of such reactions, the gradual course of the sonic treatment of nutrients can evoke chemical changes,
ozone attack on tyrosine is presented in Scheme 2. which consequently may contribute to the aging process.
Naturally, each of the shown intermediate products can Summing up, as a sequence of the sonolysis of aerated
be involved in a number of other processes, e.g. formation aqueous solutions and water containing food, oxidizing
of peroxyl radicals, etc., leading to harmful consequences radicals: OH, HO2d =Od d
2 , ROO , etc. are produced. They
to living systems and contributing to the aging process of can initiate numerous of chemical and biological processes
men. as already discussed above. Naturally, the implemented
Interesting features in this respect appears the ozone frequency and duration of the ultrasonic treatment are
action on halogenated organic compounds, which are air determining factors for the biological damage. Hence,
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N. Getoff / Radiation Physics and Chemistry 76 (2007) 1577–1586 1583
Scheme 1. Photo-generation of oxygen transients from biological sensitizers, e.g. b-carotene, flavines, pigments, chlorophyll, etc.
Table 3
Formation of ozone- and peroxyl transients in aqueous media (Getoff,
1997)
H þ O3 ! HOd 3
3.6 1010
e d
aq þ O3 ! O3
3.7 1010
(a) 3.3 102a
(b) 5.2 1010
(a) 3.3 103a
Scheme 4. Possible enzymatic oxidation and hydratization of diphenylether (DPE) leading to DNA-mutation of a cell.
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