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12. I. Non-Thermal Plasma Sterilization of Different Surfaces

A significant part of OR oxidation of bioorganic materials is due to the initial dehydrogenization of the substrate organic molecules RH:

OR + RH -+ R + R2

o.
(12-15)

The resulting oxidized substrate bioorganic compound R is a radical and reacts with molecules in chain processes. It could react with oxygen to produce a peroxyl radical, R-OO-:

+ O2 -+ R - 00 - .

(12-16)

The peroxyl radical is highly reactive and can react with another organic substrate, RH, propagating the chain oxidation mechanism:

(R - 00- )

+ RH -+ ROOR + R.

(12-17)

This type of biochemical chain reaction of OR is common in the oxidative damage of fatty acids and other lipids and demonstrates why radicals such as the hydroxyl radical can cause so much more damage than one might have expected. Plasma-generated ozone is at least partially dissociated when immersed into water, liquid-based, or liquid-like bi om a terial:

(12-18)

Atomic oxygen created in the process intensively reacts with the bioorganic molecules
RH, producing R radicals and OR radicals:

o + RH -+ R +
(12-19)

OR,

which then stimulate the same biochemical chain oxidation mechanism (12-15)-(12-17). Thus, ozone (03) can actually be added to the intensive OR-based biochemical oxidation. Similar damage caused by hydroxyl radicals and other reactive oxygen species can occur in proteins and with nucleic acids (mainly DNA). Proteins are highly susceptible to oxidative damage, particularly at sites where sulfur-containing amino acids are found. DNA can be oxidatively damaged at both the nucleic bases (the individual molecules that make up the genetic code) and at the sugars that link the bases. Oxidative damage of DNA results in degradation of the bases, breaking of the DNA strands by oxidation of the sugar linkages, or cross-linking of DNA to protein (a form of damage particularly difficult for the cell to repair). Although all cells have some capability of repairing oxidative damage to proteins and DNA, excess damage can cause mutations or cell death (Christophersen et al., 1991). Thus, nonthermal atmospheric plasma-generated reactive neutral species, particularly OR and 03, are very effective in deactivation of micro-organisms, and generally in the treatment of biomaterials. The reactive neutrals, especially OR, can be not only generated in plasma and transported to the surface ofbiomaterials (as assumed in this section) but also produced in the biomaterials from plasma-generated charged particles (see Section 12.1.4). In the case of direct plasma treatment with sufficiently high electric fields (see the next section), the flux of charged particles can dominate in the production of reactive neutrals in the biomaterial. Otherwise, the reactive neutrals are mostly generated in plasma and then transported to the surface of the biomaterials. Numerical kinetic data on the effect of 03 and OR on deactivation of different micro-organisms are to be summarized later in connection with plasma sterilization of air streams (Section 12.3). Significant sterilization effect can be provided by R2 O2 plasma generated in water. Conventional DBD produces in water more than 10-100 !-LM of R202, which are able to penetrate into cells and stimulate double-strand breaks of DNA after seconds of treatment. Direct treatment of water by air-plasma can lead to higher R202 concentrations.
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