Difference between revisions of "Transformation of PGJ2 to 15-D-PGJ2"
(6 intermediate revisions by the same user not shown) | |||
Line 1: | Line 1: | ||
[[Welcome to the In-Silico Model of Cutaneous Lipids Wiki | Return to overview]] | [[Welcome to the In-Silico Model of Cutaneous Lipids Wiki | Return to overview]] | ||
+ | |||
+ | 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 == | == Reaction == | ||
+ | [[File:R9_PGJ2_-_D15PGJ2.jpg|center|500px]] | ||
==Chemical equation== | ==Chemical equation== | ||
Line 8: | Line 12: | ||
== Rate equation == | == Rate equation == | ||
+ | [[File:R09.PNG|center|500px]] | ||
== Parameters == | == Parameters == | ||
+ | Note that the literature values are the same as [[Transformation of PGD2 to PGJ2 |reaction 8]]. | ||
+ | |||
+ | === Association Rate Constant (Kf) === | ||
− | {|class="wikitable" | + | {|class="wikitable sortable" |
− | + | |+ style="text-align: left;" | Literature values | |
+ | |- | ||
! Value | ! Value | ||
! Units | ! Units | ||
− | ! | + | ! Conditions |
+ | ! Substrate | ||
+ | ! Weight | ||
! Reference | ! Reference | ||
|- | |- | ||
− | | | + | |3.3E+6 (excluded) |
− | | Y | + | |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]] |
Latest revision as of 08:11, 21 August 2019
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 [1].
Contents
Reaction
Chemical equation
Rate equation
Parameters
Note that the literature values are the same as reaction 8.
Association Rate Constant (Kf)
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 | [2] |
4.5 | M-1 min-1 | 20°C | HC(OH)2COOH | 32 | [3] |
0.42 | M-1 min-1 | 20°C | HC(OH)2COO– | 32 | [3] |
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 |
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 here). As a result, no confidence interval factor or literature values were cited for this parameter.
Mode (M-1 s-1) | Location parameter (µ) | Scale parameter (σ) |
---|---|---|
9.25E-04 | -6.07E+00 | 9.57E-01 |
Dissociation Constant
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 | 8 | [4] |
4E-04 | N/A | PH of 100 cc. 0-02N NaHCO3, saturated with C02, into which 0 95 cc. | H2CO3 | 8 | [5] |
4.4E-4 | N/A | In a 0O008 mol. solution of carbonic acid at 4°, 1-23 % is present as H2CO3 | H2CO3 | 8 | [6] |
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 |
Related Reactions
- Transformation of PGD2 to PGJ2
- ↑ Straus, D. S. Glass, C. K., Cyclopentenone prostaglandins: new insights on biological activities and cellular targets, Med Res Rev (2001), 21, 185-210.
- ↑ B. Gibbons "Rate of Hydration of Carbon Dioxide and Dehydration of Carbonic Acid at 25" J Biol Chem. 1963 Oct;238:3502-7
- ↑ 3.0 3.1 [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)]
- ↑ 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
- ↑ 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.
- ↑ Thiel and Strohecker (1914). Ber. deutsch. chem. Gem. 47, 945, 1061.