vanessa hemme 27.04 - fh münster€¦ · luminol glow sticks singlet oxygen siloxene...

Vanessa Hemme

27.04.2016

Introduction History Working Principle Embodiments◦ Mitscherlich Test◦ Luminol◦ Glow Sticks◦ Singlet Oxygen◦ Siloxene◦ Bioluminescence

References

27.04.2016Chemoluminescence

Vanessa Hemme 2

http://www.ruhrstadtregion.de/uploads/tiny/Solmund_Rudlof/GluhwurmchenMM.jpg

lat. luminare – „light up, illuminate“

MechanismExcitation: (Bio-)chemical reaction

Return: Emission of „cold light“

Reaction: X*+ F X + F* X + F + hνF: Fluorescent dye (sensitizer)


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3500 years ago: fireflies (China)

1669: white Phosphorus (Heinrich H. Brand, Hamburg)

1888: Introduction „Chemiluminescence“ (Eilhardt Weidemann)

1928: Luminol (H.O. Albrecht)

1963: Peroxyoxalate system (E.A. Chandross)


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Hennig Brand (Alchemist & Pharmacist, 1630-1690)http://www.elementalmatter.info/images/hennig-brand.jpg

Requirements:

little volume

short time interval

exergonic (∆𝑅G < 0)

predominant oxidation reactions


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http://www.chemie.uni-jena.de/institute/oc/weiss/chemilumi.html

Visible light

∆𝑅𝐻0 = 168 − 294𝑘𝐽

𝑚𝑜𝑙

Quantum yield

Φ𝐶𝐿 =ℎ∗ν𝑒𝑚𝑖𝑡𝑡𝑒𝑑

𝑛𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠= Φ𝑅 ∗ Φ𝐸𝑆 ∗ Φ𝐹

Φ𝑅 − Yield of reacting molecules

Φ𝐸𝑆 − Yield of excited molecules

Φ𝐹 − Fluorescence quantum yield


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http://www.wildlifeonline.me.uk/images/graphics/visible_light.png

Proof of a Phosphorus intoxication

Production of P4O10 + HPO

Emission processes:

2 PO + O2 ⟶ 2 PO2 + hν

HPO + O⟶ HPO2 + hν


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https://lp.uni-goettingen.de/get/image/3910


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Blood proof at a crime scene

Fe2+ as a catalyst

Oxidation with Hydrogenperoxide

http://www.compoundchem.com/2014/10/17/luminol

http://www.elabscience.com/images/article/luminol-experimentation.jpg

Setup:

1-Plastic cover

2-Glass vial with Hydrogenperoxide

3-Enclosed space with chemicals

(Dyes, solvent, oxalic acid ester)

4/5-Breakage of glass vial

chemical reaction proceeds


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http://daten.didaktikchemie.uni-bayreuth.de/umat/chemolumineszenz/chemolumineszenz.htm#voraussetzungen%20f%C3%BCr%20chemolumineszenz

Mechanism (Peroxyoxalate system)

CO2 + Dye∗ Dye + h*ν


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Dye

https://www.simplyscience.ch/teens-wissen/articles/wie-funktioniert-ein-knicklicht.html


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Emission reaction:

2 1O2 (↑↓) ⟶ 3O2 (↑↑) + 3O2 (↓↓) + h*ν (-184kJ

mol)


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Anorganische Chemie; E. Riedel, De Gruyter 2015

http://illumina-chemie.de/upload/5_4245275974ed00c3e9132a.jpg

Synthesis (Mallet reactions)

Hydrogenperoxide + Hypohalide

H2O2 + -OCl ⟶ HO2Cl (instabil) + -OH ⟶ -Cl + H2O + 1O2

Hydrogenperoxide + Halide + Hydroxide

Cl2 + 2 –OH ⟶ -OCl + H2O + -Cl

Set-up: 1-Reaction vessel

2-Glass frit

3-Reaction mixture

4-Security bottle

5-Beaker with ice water


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http://daten.didaktikchemie.uni-bayreuth.de/umat/chemolumineszenz/reaktionsaparatur_versuch3.gif

Synthesis from Calciumdisilicide:3 CaSi2 + 6 HCl + 3 H2O → Si6O3H6 + 3 CaCl2 + 3 H2↑ (0 °C)

Derivates by replacement of H-atoms

Hydroxysiloxenes + HCl + KMnO4

Chemiluminescence-IndicatorCerimetry

Permanganometry


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Zur Chemie von Siloxenen und zur Darstellung von Polysilinen und nanodimensionierten Siliciumteilchen; M.P. Gallo, Dissertation an der Universität Bielefeld 2004

http://illumina-chemie.de/upload/843_83681361352d3ab64ae38e.gif

Occurence:Fire flies, worms, fungis

Jelly fishes, fishes

Unicellular organisms, bacteria

Terms:Catalysis by enzymes luciferases

„Phosphors“ luciferines

Oxidised form oxyluciferine


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http://www.wissenschaft-aktuell.de/extra_rubriken/Biolumineszenz__Wenn_Lebewesen_leuchten.html

https://upload.wikimedia.org/wikipedia/commons/e/e8/PanellusStipticusAug12_2009.jpg

MechanismLuciferase helps excipients (ATP, Ca2+)

to bind to the luciferine

Modified luciferine + Oxygen

Oxyluciferine* Oxyluciferine + h*ν

Byproduct of oxidation: CO2


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http://s.hswstatic.com/gif/bioluminescence-luciferin.gifhttps://upload.wikimedia.org/wiki

pedia/commons/1/18/Firefly_Luciferase_Crystal_Structure.rsh.png

http://www.intechopen.com/source/html/16496/media/image4.png

Ambient lighting by bacteria + algae

+biodegradable

+no electrical consumption

Chemoluminescence concepts?


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https://ignitechannel-production.s3.amazonaws.com/media/images/c478b40b8bbc3e0827090eee1zps3cc5555.focus-none.width-500.png

http://www.teamorca.org/graphics/Biolum/buttons/lldino2_roll.jpg

Photochemie; D. Wöhrle, M. Tausch, W.- D. Stohrer, Wiley-VCH 1998

Anorganische Chemie; E.Riedel, De Gruyter 2015

Zur Chemie von Siloxenen und zur Darstellung von Polysilinen und nanodimensionierten Siliciumteilchen; M.P. Gallo, Dissertation an der Universität Bielefeld 2004

http://www.chemie.uni-jena.de/institute/oc/weiss/chemilumi.html

http://www.chemie.uni-jena.de/institute/oc/weiss/biolumineszenz.htm

http://daten.didaktikchemie.uni-bayreuth.de/umat/chemolumineszenz/chemolumineszenz.htm

What is chemiluminescence?; Science in School, Issue 19 2011

www.chids.de

http://labiotech.eu/bioluminescent-bacteria-and-algae-lighting/


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vanessa hemme 27.04 - fh münster€¦ · luminol glow sticks singlet oxygen siloxene...

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