Proach to that employed to estimate the relative prices of hydrolysis was also applied for the calculation on the successful Arrhenius parameters for racemisation. We estimated the “scaling” elements that create the most beneficial alignment from the data across the three temperatures (see Section three.1.three) by fitting a thirdorder polynomial towards the raw D/L data and utilised the relative prices therefore obtained to calculate the productive kinetic parameters (Table five anda[(1D/L)/(1K’D/L)]1.[(1D/L)/(1K’D/L)]y = 2E05x 0.0449 two R = 0.b140 110 80y = 3E05x 0.4433 2 R = 0.140 110 8012 ten 8 six y = 6E07x 0.1713 four two 0 0 5000000 R2 = 0.10 y = 9E07x 0.1769 5 R = 0.y = 3E08x 0.0122 two R = 0.y = 4E08x 0.012 2 R = 0.9899 10000000 15000000 200000000 10000000 15000000 20000000 25000000 0Heating time (s)Heating time (s)cSum of R2 for three temperaturesIle 3.Asx Minimumd0.0023 0 2 0.0024 n=1 n=1.2 0.0025 1/T (K)0.0026 0.0027 0.0028 0.2.GlxLn k Ile2.Val6 8 y = 15747x 26.093 R= 0.9918 (n=1.0)2.four Ala Leu two.12 14 y = 16041x 27.228 R= 0.9937 (n=1.2)2.0 0 0.5 1 1.5 2 two.5 3 three.5 4 four.518 Exponent (n)Fig. 7. (a) Ile epimerisation rates at 140 C, 110 C and 80 C estimated by raising the integrated firstorder rate equation towards the exponent n 1.2, which yields great linearization with the experimental information for many with the amino acids. (b) Ile epimerisation rates at 140 C, 110 C and 80 C estimated by raising the integrated firstorder rate equation to the exponent that yielded the most effective fit to the experimental information (n 1). (c) Evaluation from the “best fit” exponent to become used to linearise the experimental data at 140 C, 110 C and 80 C for several amino acids; the maximum of every curve represents the highest worth from the sum on the R2 for the correlation involving the modified price equation plus the experimental information and indicates the ideal value from the exponent n to be utilised in Eq. (3). (d) Arrhenius plot for Ile epimerisation.B. Demarchi et al. / Quaternary Geochronology 16 (2013) 158eTable four Racemisation rate constants (two k, s) for THAA Asx, Ala, Ser, Val, Ile and Leu obtained by applying Eq. (three); exponent n employed to transform the firstorder rate equation; coefficients of determination (R2) for the linear regression at every temperature; kinetic parameters (Ea and a) and coefficients of determination (R2) for the Arrhenius relation. CPK Asx Asx Glx Glx Sera Sera Alab Alab Val Val Leu Leu Ile Ile n 1.two 1.9 1.two 1.three 1.two two.eight 1.2 1.7 1.two 0.five 1.two 0.four 1.two 1 2 k 140 C (s) 9E05 1E03 9E05 1E04 6E04 2E02 1E04 6E04 7E05 5E06 1E04 8E06 3E05 2E05 R2 140 C 0.91 0.98 0.98 0.97 0.96 0.97 0.89 0.95 0.9 0.99 0.91 0.99 0.98 0.99 2 k 110 C (s) 1E05 9E05 2E06 2E06 4E05 3E04 9E06 4E05 9E07 2E07 4E06 4E07 9E07 6E07 R2 110 C 0.Buy55477-80-0 98 0.6-Chloroquinoline-2-carboxylic acid Order 99 0.PMID:23329650 97 0.98 0.79 0.96 0.95 0.91 0.99 0.97 0.92 0.99 0.99 0.98 2 k 80 C (s) 4E07 2E06 8E08 9E08 4E07 9E06 2E07 6E07 4E08 1E08 7E08 2E08 4E08 3E08 R2 80 C 0.98 0.99 0.91 0.92 0.88 0.93 0.99 0.99 0.97 0.96 0.99 0.98 0.99 0.98 Ea (kJ/mol) 110 131 141 141 135 149 126 140 150 125 147 121 133 131 A (s) 4E9 3E3 3E3 3E3 3E3 5E6 5E1 2E4 2E4 2E0 2E4 7E9 7E1 2E1 R2 0.99 0.99 0.99 0.99 0.96 0.99 0.99 0.99 0.98 0.99 0.99 0.99 0.99 0.a Ser values integrated only up to Ser THAA D/L 0.91 (140 C experiment) and Ser THAA D/L 0.86 (110 C experiment) and excluded the 120 h time point for the 110 C experiment (outlier). b Excluding the 840 h time point for the 110 C experiment (outlier).Supplementary Info 1). Table five reports the values obtained when two pairs of data series (i.e. 80 C and 110 C, 140.
