View source for Oxidation/Reduction of Biomolecules

==Introduction==
Electrons are the currency of the chemical world. In an analogy with the financial world, '''''reduction''''' is like income and '''''oxidation''''' is like a payment; deposits and payments are made throughout the day and night resulting in a functioning economy. Although deposits are generally preferred over payments, consumers balance expenditures (payments) to meet our income (deposits). Unlike the financial world, the chemical world does not print/borrow currency, instead the chemical world follows strict conservation of matter. The analogy breaks down when we look at the details of the oxidation-reduction reactions. Because electrons have a strong tendency to pair with each other, the transfer of electrons between chemical species is generally considered in terms of electron pairs.


:Alkane -2e- --> Alcohol -2e- --> Carbonyl -2e- --> Carboxylic acid -2e- --> Carbon dioxide. (replace this with chemical structures)


When oxidation/reduction takes place via a 2-electron process, the chemical reactions are fairly well described. Nearly all of the introductory organic synthesis presented to an undergraduate student involves a 2-electron transfer mechanism.


When a single electron is taken away from a chemical species (chemical oxidation), this results in a '''''radical'''''; a radical is any chemical species with an unpaired electron; radicals can also form via 1-electron reduction. Radicals formed from chemical oxidation have a tendency to re-acquire the lost electron; radicals formed from chemical reduction, have a tendency to give up the gained electron. For this reason radicals are considered harmful since they can take electrons away from or give electrons to biomolecules like DNA, proteins, lipids, and other bioactive chemicals. The term "free radical" is often used in place of the more general term "radical," but has no clear physical or chemical meaning. Although most free radicals are transient (have short half-lives), some chemical structures have the unpaired electron highly delocalized or localized on a chemically unreactive moiety leading to longer half-lives. 

'''Oxidation-reduction reactions which involve the formation of free radical intermediates have product outcomes that are not well understood."

Main goals of this type of research is to:
:1) evaluate whether a biomolecule can undergo oxidation or reduction (mainly focusing on the oxidation),
:2) verify the free radical intermediate in the oxidation/reduction process,
:3) evaluate the products that result from the oxidation/reduction,
:4) determine any bioactivity associated with the products.

''Note: Although these introductory statements about free radicals present them as harmful, this is not always the case.''

==General Chemistry Introduction==
The loss of an electron from a chemical species is referred to as '''''oxidation'''''; the gain of an electron by a chemical species is called '''''reduction'''''. The commonly used acronyms to remember these terms are: '''LEO-GER''' for '''L'''oss of '''E'''lectron is '''O'''xidation – '''G'''ain of '''E'''lectron is '''R'''eduction or '''OIL RIG''' for '''O'''xidation '''I'''s '''L'''oss '''R'''eduction '''I'''s '''G'''ain. Oxidation-reduction chemistry, also known as '''''redox''''' chemistry, is further complicated by the terms '''''reducing agent''''' and '''''oxidizing agent'''''. A reducing agent is a chemical species that reduces another chemical species; in the process the reducing agent becomes oxidized. Likewise, an oxidizing agent is a chemical species that oxidizes another chemical species; in the process the oxidizing agent becomes reduced. An example of a redox reaction is shown below:

:Fe(s) + Cu<sup>2+</sup>(aq) → Fe<sup>3+</sup>(aq) + Cu(s) '''''(eq. 1)'''''

First off, this equation is not balanced. Taking into account that we must balance both elements and electrons:

:2 Fe(s) + 3 Cu<sup>2+</sup>(aq) → 2 Fe<sup>3+</sup>(aq) + 3 Cu(s) '''''(eq. 2)'''''

In this example, Fe(s) is being oxidized and Cu<sup>2+</sup>(aq) is being reduced; Fe(s) is the reducing agent and Cu<sup>2+</sup>(aq) is the oxidizing agent. We often think of these redox reactions in terms of oxidation - reduction half reactions shown in eq 3. and eq. 4:

:Fe(s) → Fe<sup>3+</sup>(aq) + 3e- (oxidation half rxn)	'''''(eq. 3)'''''

:Cu<sup>2+</sup>(aq) + 2e- → Cu(s) (reduction half rxn)	'''''(eq. 4)'''''

The addition of the two half reactions (including the stoichiometric coefficients) results in the cancellation of the electrons generating the overall balanced redox reaction (eq. 2).

Eq. 1 says that if you put a piece of iron metal in a copper (II) solution (like copper chloride – CaCl<sub>2</sub>) then you will form copper metal. Is this true? According to the activity series of metals presented in general chemistry (see [Chemistry Reference Document]), Fe(s) is more reactive then Cu(s), therefore in a solution that contains Fe(s) and Cu<sup>2+</sup>(aq), Fe(s) will react to form Fe<sup>3+</sup>(aq) with the resulting electrons going to reduce Cu<sup>2+</sup>(aq) to Cu(s). The concept of the '''''activity series''''' can be further reinforced by considering the most stable metals (also the least reactive metals) such as silver, platinum, and gold and the least stable metals (also the most reactive metals) such as the alkali metals and the alkaline earth metals. On earth we DO find native silver, platinum, and gold, but we '''do not''' find native sodium instead we find Na<sup>+</sup> salts. When considering eq. 2, as the reaction starts the system will contain Fe(s), Fe<sup>3+</sup>(aq), Cu(s), and Cu<sup>2+</sup>(aq). Since Fe(s) is more reactive then Cu(s), the Fe(s) will react and products will form. If I may digress to the previous financial analogy where electrons were equated to money, Fe(s) is a shopper, Cu<sup>2+</sup>(aq) is the merchant, Fe<sup>3+</sup>(aq) is the "broke" shopper, and Cu(s) is the merchant who has no more goods to sell. The stoichiometry of this reaction can be viewed as the amount of money the shopper is able to spend and the amount of money the merchant can accept based on the amount of goods they are able to sell.

==Analytical Chemistry Introduction==
In the above conversation we used the ''activity series'' to indicate whether a reaction would occur or not (or if the reverse reaction would occur). We can be more quantitative by using the standard reduction potentials (see [[Chemistry02-07-2002.pdf|Chemistry Reference Document]]). Each redox reaction consist of one oxidation reaction and one reduction reaction, but the tabulated values are only for the ''reduction potentials''. We can lookup the reduction half reactions (inverse of Eq. 3 and Eq. 4):
:E<sub>red</sub> (V)
:Fe<sup>3+</sup>(aq) + 3e- → Fe(s) = -0.036
:Cu<sup>2+</sup>(aq) + 2e- → Cu(s) = +0.34

To compensate for the oxidation reaction (Eq. 3), we need to reverse the iron reduction potential to make it oxidation and in doing so we change the sign of the Ered. In addition, if there is a stoichiometric coefficient, we need to multiple the potential by that value:

	E<sub>redox</sub> (V)
	2x [Fe(s) → Fe<sup>3+</sup>(aq) + 3e-]	2x [+0.036] = 0.072 V
	3x [Cu<sup>2+</sup>(aq) + 2e- → Cu(s)]	3x [+0.34] = 1.02 V

Adding together the potentials we arrive at 1.092V. If this redox reaction potential is a positive value, then the reaction will proceed as written. If the reaction was written as;

	Fe3+(aq) + Cu(s) → Fe(s) + Cu2+(aq),

then the overall redox potential for this reaction would be –1.092 V and hence would not proceed as written (in fact you could assume the reverse reaction would occur). When using tabulated redox potentials, it is important that you pay close attention to the details of the table contents that state the standard conditions that apply and the reference potential (in this case the standard hydrogen electrode - SHE).

You might find yourself asking how does one determine the reduction potential for a given chemical species. In general redox potentials can be determined using cyclic voltammetry. See:
http://www-biol.paisley.ac.uk/marco/Enzyme_Electrode/Chapter1/Cyclic_Voltammetry1.htm

Let us consider an example more related to molecules of biological origin, like ascorbic acid and α-tocopherol, also known as vitamin C and E, respectively and glutathione (in the figure below the label is “reduced” glutathione. This is an indication that the thiol moiety is an R–S-H. There is also “oxidized” glutathione where the thiol moiety is R-S-S-R, this is clearly a bad/unclear naming convention).

==Bulk Electrolysis/Electrosynthesis==
[[:Media:cen-09743-cover.pdf|'''AMPING UP THE PHARMA LAB''' Companies explore the potential of electrochemistry]]