View source for Transformation of PGJ2 to 15-D-PGJ2

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In aqueous solutions containing serum albumin, PGJ2 is subject to an additional non-enzymatic dehydration reaction at the hydroxyl group of C15 to yield 15-deoxy-PGJ2. The products of these dehydration reactions have higher activity than the parent compound PGD2 <ref>Straus, D. S. Glass, C. K., ''Cyclopentenone prostaglandins: new insights on biological activities and cellular targets'', Med Res Rev (2001), 21, 185-210.</ref>.

== Reaction ==
[[File:R9_PGJ2_-_D15PGJ2.jpg|center|500px]]

==Chemical equation==

<center><math> FA \rightleftharpoons AA </math></center>

== Rate equation ==

[[File:R09.PNG|center|500px]]

== Parameters ==
Note that the literature values are the same as [[Transformation of PGD2 to PGJ2 |reaction 8]].

===  Association Rate Constant (Kf) ===

{|class="wikitable sortable" 
|+  style="text-align: left;" | Literature values
|-
! Value
! Units
! Conditions
! Substrate
! Weight
! Reference
|-
|3.3E+6 (excluded)
|M-1 min-1
|25°C and 0.055 ionic strength
|H2CO3 to CO2
|32
|<ref name="Gibbons1963”>[http://www.jbc.org/content/238/10/3502.full.pdf B. Gibbons "Rate of Hydration of Carbon Dioxide and Dehydration of Carbonic Acid at 25" J Biol Chem. 1963 Oct;238:3502-7]</ref>
|-
|4.5
|M-1 min-1
|20°C
|HC(OH)2COOH
|32
|<ref name="Turyan1998”>[hrcak.srce.hr/file/195437 Y.I. Tur'yan, "Kinetics and Equilibrium of the Dehydration-Hydration and Recombination-Dissociation Reactions of Glyoxylic Acid Investigated by Electrochemical Methods", CCACAA 71 (3) 727¿743 (1998)]</ref>
|-
|0.42
|M-1 min-1
|20°C
|HC(OH)2COO–
|32
|<ref name="Turyan1998”>[hrcak.srce.hr/file/195437 Y.I. Tur'yan, "Kinetics and Equilibrium of the Dehydration-Hydration and Recombination-Dissociation Reactions of Glyoxylic Acid Investigated by Electrochemical Methods", CCACAA 71 (3) 727¿743 (1998)]</ref>
|-
|}

{| class="wikitable"
|+  style="text-align: left;" | Description of the reaction 9 Kf distribution
! Mode (M-1 s-1) !! Confidence Interval !! Location parameter (µ) !! Scale parameter (σ)
|-
| 4.48E+00 || 1.09E+03 || 7.34E+00 || 2.42E+00
|}

[[Image:27.jpg|none|thumb|500px|The estimated probability distribution for reaction 9 Kf. The value and weight of the literature values used to define the distribution are indicated by an orange dashed line. The x axis is plotted on a log-scale.   ]]


=== Dissociation Rate Constant (Kr) ===
This is a “Dependent parameter”, meaning that the log-normal distribution for this parameter was calculated using multivariate distributions  (this is discussed in detail[[Quantification of parameter uncertainty | here]]). As a result, no confidence interval factor or literature values were cited for this parameter. 
{| class="wikitable"
|+  style="text-align: left;" | Description of the reaction 9 Kr distribution
! Mode (M-1 s-1) !! Location parameter (µ) !! Scale parameter (σ)
|-
| 9.25E-04 || -6.07E+00 || 9.57E-01
|- 
|}

[[Image:28.jpg|none|thumb|500px|The estimated probability distribution for reaction 9 Kr. The value and weight of the literature values used to define the distribution are indicated by an orange dashed line. The x axis is plotted on a log-scale.   ]]

===  Dissociation Constant ===
{|class="wikitable sortable" 
|+  style="text-align: left;" | Literature values
|-
! Value
! Units
! Conditions
! Substrate
! Weight
! Reference
|-
|< 8E-04
|N/A
|OH Radicals in the Presence of Added Gas Phase HNO3 (3 ppmv n-pentadecane, 0.25, 0.50, 1.0, or 2.0 ppmv HNO3, 10 ppmv O3, and 2 ppmv TME were added from a glass bulb in a flow of N2)
|Acid-Catalyzed Dehydration of Cyclic Hemiacetals (n-Pentadecane) in SOA
[[File:Cyclic Hemiacetals.PNG ‎|center|100px]]
|8
|<ref name="Ranney2016”>[http://pubs.acs.org/doi/pdf/10.1021/acs.jpca.6b01402 A. Ranney "Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor"  J. Phys. Chem. A, 2016, 120 (16), pp 2561–2568]</ref>
|-
|4E-04
|N/A
|PH of 100 cc. 0-02N NaHCO3, saturated with C02, into which 0 95 cc.
|H2CO3
|8
|<ref name="BUYTENDYK1927”>[https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1251954/pdf/biochemj01144-0128.pdf F. BUYTENDYK "A Study of the System Carbonic Acid, Carbon Dioxide and Water - Determination of the True Dissociation-constant of Carbonic Acid"  Biochem J. 1927; 21(3): 576–584.]</ref>
|-
|4.4E-4
|N/A
|In a 0O008 mol. solution of carbonic acid at 4°, 1-23 % is present as H2CO3
|H2CO3
|8
|<ref name="Thiel1914”>[http://onlinelibrary.wiley.com/doi/10.1002/cber.191404701173/epdf Thiel and Strohecker (1914). Ber. deutsch. chem. Gem. 47, 945, 1061.]</ref>
|-
|}

{| class="wikitable"
|+  style="text-align: left;" | Description of the reaction 9 KD distribution
! Mode (M-1 s-1) !! Confidence Interval !! Location parameter (µ) !! Scale parameter (σ)
|-
| 4.49E-04 || 1.38E+00 || -7.61E+00 || 3.07E-01
|- 
|}

[[Image:R9 kd.jpg|none|thumb|500px|The estimated probability distribution for reaction 9 KD. The value and weight of the literature values used to define the distribution are indicated by an orange dashed line. The x axis is plotted on a log-scale.   ]]

== Related Reactions ==
* [[Transformation of PGD2 to PGJ2 |Transformation of PGD2 to PGJ2]]