Chemiluminescence (sometimes "chemoluminescence") is the emission of light with limited emission of heat (luminescence), as the result of a chemical reaction. Given reactants A and B, with an excited intermediate ◊,
- [A] + [B] → [◊] → [Products] + light
For example, if [A] is luminol and [B] is hydrogen peroxide in the presence of a suitable catalyst we have:
- luminol + H2O2 → 3-APA[◊] → 3-APA + light
where:
- where 3-APA is 3-aminophthalate
- 3-APA[◊] is the excited state fluorescing as it decays to a lower energy level.
The decay of the excited state[◊] to a lower energy level is responsible for the emission of light. In theory, one photon of light should be given off for each molecule of reactant, or Avogadro's number of photons per mole. In actual practice, non-enzymatic reactions seldom exceed 1% QC, quantum efficiency.
- In a chemical reaction, reactants collide to form a transition state, the enthalpic maximum in a reaction coordinate diagram, which proceeds to the product. Normally under reacting conditions, reactants form products of lesser chemical energy. The difference in energy between reactants and products, represented as ΔHrxn, is turned into heat, physically realized as excitations in the vibrational state of the normal modes of the product. Since vibrational energy is generally much greater than the thermal agitation, it is rapidly dispersed into the solvent through solvent molecules' rotation and translation. This underlies how exothermic reactions make their solutions hotter. In a chemiluminescent reaction, the direct product of a reaction is delivered in an excited electronic state, which then decays into an electronic ground state through either fluorescence or phosphorescence, depending on the spin state of the electronic excited state formed. The reason why this is possible is that chemical bond formation can occur on a timescale faster than electronic transitions, and therefore can result in discrete products in excited electronic states.
- Chemiluminescence differs from fluorescence in that the electronic excited state is derived from the product of a chemical reaction rather than the more typical way of creating electronic excited states, namely absorption. It is the antithesis of a photochemical reaction, in which light is used to drive an endothermic chemical reaction. Here, light is generated from a chemically exothermic reaction.
A standard example of chemiluminescence in the laboratory setting is found in the luminol test, where evidence of blood is taken when the sample glows upon contact with iron. When chemiluminescence takes place in living organisms, the phenomenon is called bioluminescence. A lightstick emits a form of light by chemiluminescence.
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Liquid-phase reactions
- Luminol in an alkaline solution with hydrogen peroxide in the presence of iron or copper[1], or an auxiliary oxidant[2], produces chemiluminescence. The luminol reaction is
- luminol + H2O2 → 3-APA[◊] → 3-APA + light
- Cyalume, as used in a lightstick, emits light by chemiluminescence of a fluorescent dye (also called fluorescor) activated by cyalume reacting with hydrogen peroxide in the presence of a catalyst,such as sodium salicylate. It is the most efficient chemiluminescent reaction known. up to 15% quantum efficiency.[3]
- cyalume + H2O2 + dye → phenol + 2CO2 + dye[◊]
When the activated fluorescent dye decays to a lower energy level, light is given off. The color depends upon the dye.[4].
| Color | Sensitiser |
|---|---|
| Blue | 9,10-Diphenylanthracene |
| Green | 9,10-Bis(phenylethynyl)anthracene |
| Yellow-green | Tetracene |
| Yellow | 1-Chloro-9,10-bis(phenylethynyl)anthracene |
| Orange | 5,12-Bis(phenylethynyl)naphthacene, Rubrene, Rhodamine 6G |
| Red | Rhodamine B |
- Oxalyl chloride (C2O2Cl2) produces light when oxidized - but only in the presence of a sensitiser, similar to the above examples. If oxalyl chloride is treated with H2O2 in non-aqueous media (e.g. CH2Cl2) in the presence of a sensitiser, emission of light is obtained. The colour, intensity and duration of light emission depend on the sensitiser used. Rodamin 6 G gives bright orange light with moderate duration of emission.
- Ru(bipy)32+ is a ruthenium(II) complex which undergoes oxidation to ruthenium(III) if certain oxidizing agents are introduced. If ruthenium(III) complex is then reduced in alkaline medium, emission of light occurs. First, there is a reaction:
- 2Ru(bipy)32+ + PbO2 + 4H+ → 2Ru(bipy)33+ + Pb2+ + 2H2O
- Here, Ru(III) is obtained. Further reaction includes use of solution of sodium tetrahydroborate(III), NaBH4 in alkaline medium. When the solution is added, Ru(III) is reduced to Ru(II) and orange light is emitted.
- TMAE (tetrakis(dimethylamino)ethylene) emits clear blue-green light upon oxidation by air.
- Pyrogallol (1,2,3-trihydroxibenzene) is also capable of light emission. If an aqueous solution of pyrogallol, NaOH and K2CO3 is mixed with formaldehyde, short-lived red emission occurs.
- Singlet oxygen (O2) can also emit light. If solutions of 30% hydrogen peroxide and 5% alkaline sodium hypochlorite (NaClO) are mixed, red light is emitted. It is barely visible, though - for this reason a sensitiser is often included to boost light emission in terms of brightness and intensity. Again, both colour and intensity of light depend on the sensitiser used.
- Lucigenin oxidation is also very well known among chemiluminescence reactions. If an aqueous lucigenin solution is mixed with highly alkaline aqueous solution containing ethanol or acetone and hydrogen peroxide, very bright green emission is produced that decays to greenish blue and finally blue emission. The duration of the emission can be up to a couple of minutes under the right circumstances. [5].
- Solutions containing ions of manganese (VII, IV, III) show chemiluminescence (690 nm) when reduced by sodium borohydride at low pH to Mn(II) [6]
- Other liquid phase chemilumiscence reagents:
- peroxyoxalates
- Aryl oxalates
- Acridiniumesters
- dioxetanes
Gas-phase reactions
- One of the oldest known chemoluminescent reactions is that of elemental white phosphorus oxidizing in moist air, producing a green glow. This is actually a gas-phase reaction of phosphorus vapor, above the solid, with oxygen producing the excited states (PO)2 and HPO.[3]
- Another gas phase reaction is the basis of nitric oxide detection in commercial analytic instruments applied to environmental air quality testing. Ozone is combined with nitric oxide to form nitrogen dioxide in an activated state.
- NO+O3 → NO2[◊]+ O2
- The activated NO2[◊] luminesces broadband visible to infrared light as it reverts to a lower energy state. A photomultiplier and associated electronics counts the photons which are proportional to the amount of NO present. To determine the amount of nitrogen dioxide, NO2, in a sample (containing no NO) it must first be converted to nitric oxide, NO, by passing the sample through a converter before the above ozone activation reaction is applied. The ozone reaction produces a photon count proportional to NO which is proportional to NO2 before it was converted to NO. In the case of a mixed sample containing both NO and NO2, the above reaction yields the amount of NO and NO2 combined in the air sample, assuming that the sample is passed through the converter. If the mixed sample is not passed through the converter, the ozone reaction produces activated NO2[◊] only in proportion to the NO in the sample. The NO2 in the sample is not activated by the ozone reaction. Though unactivated NO2 is present with the activated NO2[◊], photons are only emitted by the activated species which is proportional to original NO. Final step, subtract NO from (NO + NO2) to yield NO2[7]
Bioluminescence
Chemiluminescence takes place in numerous living organisms, the American firefly being a widely studied case of bioluminescence.
The firefly reaction has the highest known quantum efficiency, QC of 88%, for chemiluminescence reactions. ATP (adenosine tri-phosphate), the ubiquitous biological energy source, reacts with luciferin with the aid of the enzyme luciferase to yield an intermediate complex. This complex combines with oxygen to produce a highly chemiluminescent compound.
Enhanced chemiluminescence
Enhanced chemiluminescence is a common technique for a variety of detection assays in biology. A horseradish peroxidase enzyme (HRP) is tethered to the molecule of interest (usually through labeling an immunoglobulin that specifically recognizes the molecule). This enzyme complex, then catalyzes the conversion of the enhanced chemiluminescent substrate into a sensitized reagent in the vicinity of the molecule of interest, which on further oxidation by hydrogen peroxide, produces a triplet (excited) carbonyl which emits light when it decays to the singlet carbonyl. Enhanced chemiluminescence allows detection of minute quantities of a biomolecule. Proteins can be detected down to femtomole quantities (Enhanced CL review), well below the detection limit for most assay systems.
Applications
- gas analysis: for determining small amounts of impurities or poisons in air. Other compounds can also be determined by this method (ozone, N-oxides, S-compounds). Typical example is NO determination with detection limits down to 1 ppb
- analysis of inorganic species in liquid phase
- analysis of organic species: useful with enzymes, where the substrate isn't directly involved in chemiluminescence reaction, but the product is
- detection and quantitation of biomolecules in assay systems such as ELISA and Western blots
- DNA sequencing using pyrosequencing
- Lighting objects. Chemiluminescence kites, emergency lighting, glow sticks (party decorations).
- Combustion analysis: certain radical species (such as CH* and OH*) give off radiation at specific wavelengths. The heat release rate is calculated by measuring the amount of light radiated from a flame at those wavelengths.
- children's toys
See also
References
- ^ a b "Luminol chemistry laboratory demonstration". http://www.3rd1000.com/labs/lumine.htm. Retrieved 2006-03-29.
- ^ a b "Investigating lu.inol" (PDF). Salters Advanced Chemistry. http://www.york.ac.uk/org/seg/salters/chemistry/ResourceSheets/luminol.PDF. Retrieved 2006-03-29.
- ^ a b Rauhut, Michael M. (1985), Chemiluminescence. In Grayson, Martin (Ed) (1985). Kirk-Othmer Concise Encyclopedia of Chemical Technology (3rd ed), pp 247 John Wiley and Sons. ISBN 0-471-51700-3
- ^ Helmenstine, Anne Marie (Aug 10, 2004). Light stick chemistry, retrieved Sept. 22, 2004.
- ^ For more information about how to perform experiments mentioned, see the reference Bassam Z. Shakhashiri: Chemical Demonstrations, Volume 1, University of Wisconsin 1983.
- ^ New light from an old reagent: Chemiluminescence from the reaction of potassium permanganate with sodium borohydride. Neil W. Barnett, Benjamin J. Hindson , Phil Jones, Claire E. Lenehan and Richard A. Russell. Aust. J. Ed. Chem., 2005, 65,
- ^ Air Zoom | Glowing with Pride
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