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Luminol

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For thebarbituratedrug Luminal, seephenobarbital.

Luminol[1]
Chemical structure of luminol
Ball-and-stick model of luminol
Names
Preferred IUPAC name
5-Amino-2,3-dihydrophthalazine-1,4-dione
Other names
5-Amino-2,3-dihydro-1,4-phthalazinedione
o-Aminophthaloyl hydrazide
o-Aminophthalyl hydrazide
3-Aminophthalhydrazide
3-Aminophthalic hydrazide
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.007.556Edit this at Wikidata
EC Number
  • 208-309-4
UNII
  • InChI=1S/C8H7N3O2/c9-5-3-1-2-4-6(5)8(13)11-10-7(4)12/h1-3H,9H2,(H,10,12)(H,11,13)checkY
    Key: HWYHZTIRURJOHG-UHFFFAOYSA-NcheckY
  • InChI=1/C8H7N3O2/c9-5-3-1-2-4-6(5)8(13)11-10-7(4)12/h1-3H,9H2,(H,10,12)(H,11,13)
    Key: HWYHZTIRURJOHG-UHFFFAOYAB
  • C1=CC2=C(C(=C1)N)C(=O)NNC2=O
Properties
C8H7N3O2
Molar mass 177.16 g/mol
Melting point 319 °C (606 °F; 592 K)
Hazards
NFPA 704(fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
1
0
Safety data sheet(SDS) MSDS for luminol
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).

Luminol(C8H7N3O2) is achemicalthat exhibitschemiluminescence,with a blue glow, when mixed with an appropriateoxidizing agent.Luminol is a white-to-pale-yellow crystalline solid that is soluble in most polar organic solvents but insoluble in water.

Forensicinvestigators use luminol to detect trace amounts ofbloodatcrime scenes,as it reacts with the iron inhemoglobin.Biologists use it in cellularassaysto detectcopper,iron,andcyanidesas well as specificproteinsviawestern blotting.[2]

When luminol is sprayed evenly across an area, trace amounts of an activating oxidant make the luminol emit a blue glow that can be seen in a darkened room. The glow only lasts about 30 seconds but can be documented photographically. The glow is stronger in areas receiving more spray; the intensity of the glow does not indicate the amount of blood or other activator present.

Synthesis

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Luminol is synthesized in a two-step process, beginning with 3-nitrophthalic acid.[3][4]First,hydrazine(N2H4) is heated with the 3-nitrophthalic acid in a high-boiling solvent such astriethylene glycolandglycerol.Acondensation reactionoccurs, with loss of water, forming 3-nitrophthalhydrazide. Reduction of thenitro groupto anamino groupwithsodium dithionite(Na2S2O4), via a transienthydroxylamineintermediate, produces luminol.

The compound was first synthesized in Germany in 1902[5]but was not namedluminoluntil 1934.[3][6]

Chemiluminescence

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Chemiluminescence of luminol

To exhibit its luminescence, the luminol must be activated with an oxidant. Usually, a solution containinghydrogen peroxide(H2O2) andhydroxideions in water is the activator. In the presence of acatalystsuch as anironorperiodatecompound, the hydrogen peroxide decomposes to form oxygen and water:

2 H2O2→O2+ 2 H2O
H2O2+ KIO4→ KIO3+ O2+ H2O

Laboratory settings often usepotassium ferricyanideorpotassium periodatefor the catalyst. In the forensic detection of blood, the catalyst is the iron present inhemoglobin.[7]Enzymesin a variety of biological systems may also catalyse the decomposition of hydrogen peroxide.

The exact mechanism of luminol chemiluminescence is a complex multi-step reaction, especially in aqueous conditions. A recent theoretical investigation has been able to elucidate the reaction cascade as shown below.[8]Luminol is first deprotonated in basic conditions then oxidized to the anionic radical, which in turn has two paths available to give the key intermediate α-hydroxy- peroxide. After cyclization to the endoperoxide, the mono-anion will undergo decompositionwithoutluminescence if the pH is too low (< 8.2) for a second deprotonation. The endoperoxide dianion, however, can give the retro-Diels–Alder product: 1,2-dioxane-3,6-dione dianion, and afterchemiexcitationby two single-electron transfers (SET) gives 3-aminophthalate dianion in its first singlet excited state (S1). This highly instable molecule relaxes to the ground state, thereby emitting light of around 425 nm wavelength (purple-blue), thuschemiluminescence.

Use in criminal investigation

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History

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In 1928, German chemist H. O. Albrecht found thatblood,among other substances, enhanced the luminescence of luminol in an alkaline solution of hydrogen peroxide.[9][10]In 1936, Karl Gleu and Karl Pfannstiel confirmed this enhancement in the presence ofhaematin,a component of blood.[11]In 1937, German forensic scientist Walter Specht made extensive studies of luminol's application to the detection of blood at crime scenes.[12]In 1939, San Francisco pathologists Frederick Proescher and A. M. Moody made three important observations about luminol:[13][14]

  1. although the test is presumptive, large areas of suspected material can be examined rapidly;
  2. dried and decomposed blood gave a stronger and more lasting reaction than fresh blood; and
  3. if the luminescence disappears, it may be reproduced by the application of a fresh luminol–hydrogen-peroxide solution; dried bloodstains may thus be made luminescent repeatedly.

Theory

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Crime scene investigatorsuse luminol to find traces of blood, even if someone has cleaned or removed it. The investigator sprays a solution of luminol and the oxidant. The iron in blood catalyses the luminescence. The amount of catalyst necessary to cause the reaction is very small relative to the amount of luminol, allowing detection of even trace amounts of blood. The blue glow lasts for about 30 seconds per application. Detecting the glow requires a fairly dark room. Any glow detected may be documented by a long-exposurephotograph.

Drawbacks

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Luminol's use in a crime scene investigation is somewhat hampered by the fact that it reacts to iron- andcopper-containing compounds,[15]bleaches,horseradish,fecal matter,and cigarette smoke residue.[14]Application of luminol to a piece of evidence may prevent other tests from being performed on it; however, DNA has been successfully extracted from samples exposed to luminol.[16]

[edit]
  • Luminol: 5-amino-2,3-dihydro-1,4; 3-amino-phthalhydrazide; 1,4-phthalazinedione, 5-amino-2,3-dihydro; CAS: [521-31-3]
    C8H7N3O2– MW: 177.16
    λabs(in 0.1 N NaOH) λmax1: 347 nm & λmax2: 300 nm; EC (at λmax1): 7650 L/mol × cm
    λabs/ λem(MeOH): 355/413 nm
  • Luminol, sodium salt: sodium 3-amino-phthalhydrazide; CAS: [20666-12-0]
    C8H6N3O2Na – MW: 199.12
  • Luminol hemihydrate: ahydrateof sodium 3-amino-phthalhydrazide; CAS: [206658-90-4]
    C8H6N3O2Na·H2O– MW: 217.16
  • Luminol hydrochloride: 3-amino-phthalhydrazide hydrochloride; CAS: [74165-64-3]
    C8H7N3O2· HCl MW: 213.62
  • Isoluminol: 4-aminophthalhydrazide; CAS: [3682-14-1]
    C8H7N3O2– MW: 117.16 (Xi)
  • Isoluminol monohydrate: 4-aminophthalhydrazide monohydrate
    C8H7N3O2·H2O– MW: 195.15
  • Isoluminol ABEI: 4-aminophthalhydrazide monohydrate; CAS: [66612-29-1]

See also

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References

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  1. ^Merck Index,11th Edition,5470.
  2. ^ Khan, Parvez; Idrees, Danish; MOxley, Michael A.; et al. (May 2014)."Luminol-Based Chemiluminescent Signals: Clinical and Non-clinical Application and Future Uses".Applied Biochemical Biotechnology.173(2): 333–355.doi:10.1007/s12010-014-0850-1.PMC4426882.PMID24752935.
  3. ^abErnest Huntress; Lester Stanley; Almon Parker (1934). "The preparation of 3-aminophthalhydrazide for use in the demonstration of chemiluminescence".Journal of the American Chemical Society.56(1): 241–242.doi:10.1021/ja01316a077.
  4. ^Synthesis of luminol
  5. ^See:
    • Aloys Josef Schmitz,"Ueber das Hydrazid der Trimesinsäure und der Hemimellithsäure"Archived2015-01-02 at theWayback Machine(On the hydrazide oftrimesic acid[1,3,5-benzenetricarboxylic acid] and of hemimellitic acid [1,2,3-benzenetricarboxylic acid]), Inaugural Dissertation, Heidelberg University, 1902; pp. 17, 39–43. Schmitz calls luminol "1-amino-2,3-phtalsäurehydrazid".
    • Note: Gill states that luminol was prepared as early as 1853. See: Steven K. Gill (1983) "New developments in chemiluminescence research,"Aldrichimica Acta16(3): 59–61; has footnote 2 on p. 60. Available at:Aldrichimica ActaArchived2015-01-08 at theWayback Machine.However, the sources Gill cites don't mention the preparation of luminol before 1902. Gill probably confused luminol withlophine(2,4,5-triphenyl-1H-imidazole), which the sources he cites do mention. Lophine is also chemiluminescent, and was first prepared in 1844 by Auguste Laurent. (See: Auguste Laurent (1844)"Sur un nouvel alcali organique, la lophine"(On a new organic alkali, lophine),Revue scientifique et industrielle,18:272–278.) The chemiluminescence of lophine was first observed by: Radziszewski, Bronisław L. (1877)"Untersuchungen über Hydrobenzamid, Amarin und Lophin"Archived2015-12-14 at theWayback Machine(Investigations of hydrobenzamide, amarine, and lophine),Berichte der Deutschen chemischen Gesellschaft zu Berlin,10:70–75. In 1853, Ludwig Teichmann developed a test for blood, but it did not rely on chemiluminescence. See: L Teichmann (1853)"Ueber die Krystallisation der organischen Bestandtheile des Bluts"(On the crystallization of the organic components of blood),Zeitschrift für rationelle Medicin,new series,3:375–388.
  6. ^Huntress, Ernest H.; Stanley, Lester N.; Parker, Almon S. (1934). "The oxidation of 3-aminophthalhydrazide (" luminol ") as a lecture demonstration of chemiluminescence".Journal of Chemical Education.11(3): 142.Bibcode:1934JChEd..11..142H.doi:10.1021/ed011p142.
  7. ^Ples, Marek."Chemiluminescence activated by blood".www.weirdscience.eu(in Polish). Archived fromthe originalon 3 January 2015.Retrieved23 December2014.
  8. ^Yue, Ling; Liu, Yi-Tong (3 September 2020)."Mechanistic Insight into pH-Dependent Luminol Chemiluminescence in Aqueous Solution".The Journal of Physical Chemistry B.124(35): 7682–7693.doi:10.1021/acs.jpcb.0c06301.ISSN1520-6106.PMID32790377.S2CID221125324.
  9. ^H. O. Albrecht (1928) "Über die Chemiluminescenz des Aminophthalsäurehydrazids" (On the chemiluminescence of aminophthalic acid hydrazide)Zeitschrift für Physikalische Chemie136:321–330.
  10. ^Stuart H. James and William G. Eckert,Interpretation of Bloodstain Evidence at Crime Scenes,2nd ed. (Boca Raton, Florida: CRC Press LLC, 1998),page 154Archived2017-02-15 at theWayback Machine.
  11. ^Gleu, Karl; Pfannstiel, Karl (1936) "Über 3-aminophthalsaure-hydrazid"Journal für Praktische Chemie146:137–150.
  12. ^Specht, Walter (1937) "Die Chemiluminescenz des Hämins, ein Hilfsmittel zur Auffindung und Erkennung forensisch wichtiger Blutspuren" (The chemiluminescence of haemin, an aid to the finding and recognition of forensically significant blood traces),Angewandte Chemie50(8): 155–157.
  13. ^Proescher F. and Moody A.M. (1939) "Detection of blood by means of chemiluminescence,"Journal of Laboratory and Clinical Medicine,24:1183–1189.
  14. ^abJames, Stuart; Kish, Paul E.; Sutton, Paulette Sutton (2005).Principles of Bloodstsain Pattern Analysis.Boca Raton, London, New York, Singapore: Taylor and Francis Group. p.376.ISBN0-8493-2014-3.
  15. ^Ples, Marek."Chemiluminescence of luminol activated by copper compound".www.weirdscience.eu(in Polish). Archived fromthe originalon 3 January 2015.Retrieved23 December2014.
  16. ^Technical note aboutHemaglowArchivedJanuary 2, 2015, at theWayback Machine
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