2 H = ( 2 H / 1 H) Sample vs. ( 2 H / 1 H) Reference 13 C/ 12 C – 15 N/ 14 N – 18 O/ 16 O – 34...
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Transcript of 2 H = ( 2 H / 1 H) Sample vs. ( 2 H / 1 H) Reference 13 C/ 12 C – 15 N/ 14 N – 18 O/ 16 O – 34...
![Page 1: 2 H = ( 2 H / 1 H) Sample vs. ( 2 H / 1 H) Reference 13 C/ 12 C – 15 N/ 14 N – 18 O/ 16 O – 34 S/ 32 S – 37 Cl/ 35 Cl – 81 Br/ 79 Br.](https://reader036.fdocuments.us/reader036/viewer/2022062404/551a92c855034643688b5e0a/html5/thumbnails/1.jpg)
2H = (2H / 1H)Sample vs. (2H / 1H)Reference
13C/12C – 15N/14N – 18O/16O – 34S/32S – 37Cl/35Cl – 81Br/79Br
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Malin SödermanJunior Research Engineer
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• We develop methods – Visitors come and use them
• Self-cost model
• We are available for
-General isotope advice (planning)
- Collaboration - One-off- Short term- Long term- Proposal assist
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… Equilibrium Isotope Effects (EIE) – isotopic phase partitioning… Kinetic Isotope Effects (KIE) – isotopic reaction rates
Zero-point energies…
=(1/2+n)h
(/m)½
Vibrational frequency
Isotope mass
Force constant
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Heavy isotopes favour a strong bond
The Equilibrium Isotope Effect
(2H / 1H)Phase X-H*
(2H / 1H)Phase Y-H*
EIE =
solvent analyte
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The Kinetic Isotope Effect
krate=Ae-Ea/RT
Fre
e en
ergy
Reaction coordinate
Ea LightEEa HeavyE
KIE = kLight / kHeavy
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…KIE = kLight / kHeavy
Holmstrand et al., Chemosphere 69 (2007) 1533–1539
DDT DDE
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R(+)or
S(-)
Catalysis by DL-2-haloacid dehalogenase for stereo isomers as
determined from Kinetic Isotope Effects (KIEs)
Papajak et al., Biochemistry 2006, 45, 6012-6017
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An Equilibrium Isotope EffectMolecular oxygen adducts in metalloenzymes
– side-on or end-on?
Side-on
End-on
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The characterization of intermediates
in oxidation reactions of transition metals – MetalloenzymesSide-on
End-on
The derived oxygen isotopic effects have been used to
(i) differentiate inner-sphere from outer-sphere electron transfer
(ii) identify metal-O2 intermediates
(iii) assess mechanisms of O-O bond-breaking/making reactions
Ashley, Brinkley and Roth, Oxygen Isotope Effects as Structural and Mechanistic Probes in Inorganic Oxidation Chemistry, Inorg. Chem. 2010, 49, 3661–3675
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“No deuterium was incorporated… the active site of the enzyme is probably in a closed conformation during catalysis”
Hydrogen exchange labeling to studya reaction mechnism
- choice of labels and analytical technique
2H label
Natural 2H level
Guangqi et al., Biochimie 92 (2010) 1454e1457
Tracers and labels: - Is natural abundance enough? (safety, cost, feasibility)
- Can KIE or EIE help? (additional information)
- Added value of IRMS instruments? (trace weaker signals)
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Macronutrient sourcing for biosynthesis using 13C analysis of amino acids
– direct routing from diet to tissue
Filled = diet Open = collagen
Diet compositionDiet Protein EnergyD2A C3 C3
D3G C3 C4
D4H C4 C4
D5I C4 C3
Jim et al., British Journal of Nutrition (2006), 95, 1055–1062
C3
C4
-25‰
-12‰
C3 plants = - 25‰ (e.g. rice)C4 plants = - 12‰ (maize)
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?
Chemistry
Labeling
Reactionmechanisms
Reactionmonitoring
Reactionidentification
Linking source &product
Environmentalsciences
Ecology
Plant physiology
Microbiology
Biochemistry
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E-mail: [email protected]
Cell phone: 070 760 7229
Website: http://delta.geo.su.se…where you will find this presentation…