R4
y&*
R1
R3
R i = (CH3)2N,R2 = (CH3)zN'
RI = NHz, R2 = (CH3)zNi
RI = (CHdNH,Rz = (CH3)Nf
RI = (CH3)zN.R2 = (CH3)N.R6 = CH3
RI = CzHsNH. R2 = CzH5NHf. R4 = R5 = CH3
Ri = HzN, Rz = HzNt
Rx = HzN, Rz = H2Nt, Rs = CH3
R i = (CH3)2N,R2 = (CH3)2N', R3 = NO2
Ri = (CH3)zN.R2 = 0
Oxazines
rate = k[D,I[CHI[OHI
where Do, is the oxidized (blue) form of methylene blue,
and CH is the carbohydrate, glucose.
The following is a simple mechanism for this reaction.
fast D,
O,+D d
R3
Ri=NaO,Rz=O,R7=0
Ri = (CzH5)2N,R2 = HzN,' Rs = CH3
Ri = H2N, R2 = HzNt, Rs and Re = fused benzene
Ri =OH, R2 = (CzH5)2N,R3 = OH, R4 = HzNCO
Azines
where D is the reduced (wlorless) form of the dye methylene blue, and X- represents the oxidation products from
the glucose (arabinoic, formic, oxalic, and erythronic acids
(3,411.The enthalpy of the reaction has been reported to be
5.5 kcal/mol(5).
How Blue?
Are other colors beside blue possible for this reaction?
Methylene blue is a thiazine dye (structure 1 shown in
Table 1).There are manv other dves in the thiazine dve
family that might be usckd, as wcil as dyes in the related
oxazine and azme dye families. Wc havc found that many
Preliminary report presented at the 106th Annual Meeting of the
Indiana Academy of Science, 1990.
'PRISMS Program (Precollege Research In the Sciences for Minority Students)participants during summers of 1990and 1991. Program cosponsored by GTE and Valparaiso University.
'Theodore Roosevelt High School. Gary, IN 46407.
3West Side High School, Gary, IN 46406.
160
of these other dyes also catalyze the oxidation of an alkaline aqueous solution of glucose when mixed with oxygen.
However, the rates of reaction and sometimes the wlors
of the oxidized dyes vary from that observed with methylene blue. The color of the oxidized form of the dye in aqueous base and the relative rates of oxidation of glucose are
shown in Table 2. Two of the oxazine dyes (cresyl violet
acetate and resazuriu) fluoresce red in their oxidized
states when excited by a 365-11111 U V lamp, whereas fluo-