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Thermochemistry of sarcosine and sarcosine anhydride: Theoretical and experimental studies
Accepted Manuscript Thermochemistry of sarcosine and sarcosine anhydride: Theoretical and exper‐ imental studies Luísa M.P.F. Amaral, Ana Filipa L.O.M. Santos, Maria das Dores M.C. Ribeiro da Silva, Rafael Notario PII: DOI: Reference:
S0021-9614(12)00443-0 http://dx.doi.org/10.1016/j.jct.2012.11.019 YJCHT 3369
To appear in:
J. Chem. Thermodynamics
Please cite this article as: L.M.P. Amaral, A.F.L.O. Santos, d.D.M.C. Ribeiro da Silva, R. Notario, Thermochemistry of sarcosine and sarcosine anhydride: Theoretical and experimental studies, J. Chem. Thermodynamics (2012), doi: http://dx.doi.org/10.1016/j.jct.2012.11.019
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Journal of Chemical Thermodynamics 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
Thermochemistry of Sarcosine and Sarcosine Anhydride: Theoretical and Experimental Studies
Luísa M.P.F. Amaral,a Ana Filipa L.O.M. Santos,a Maria das Dores M.C. Ribeiro da Silva,a,* and Rafael Notariob,* a
Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of
Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal b
Instituto de Química Física “Rocasolano”, CSIC, Serrano 119, 28006 Madrid, Spain
________________________________________________________________________ *
Corresponding authors
[email protected] (M.D.M.C.R.S) [email protected] (R.N.)
1
Abstract 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of sarcosine, –(388.0 ± 1.0) kJ.mol-1, and sarcosine anhydride, –(334.5 ± 1.6) kJ.mol-1, were calculated by combining, for each compound, the standard molar enthalpy of formation, in the crystalline phase, and the standard molar enthalpy of sublimation, derived from measurements of the standard massic energies of combustion by static bomb combustion calorimetry, and from measurements of vapor pressures by the Knudsen mass-loss effusion method, respectively. The standard (po = 0.1 MPa) molar enthalpies, entropies and Gibbs functions of sublimation, at T = 298.15 K, were also calculated. A theoretical study at the G3 and G4 levels has been carried out, and the calculated enthalpies of formation have been compared with the experimental ones.
KEYWORDS: Enthalpy of combustion; Enthalpy of sublimation; Enthalpy of formation; Static bomb combustion calorimetry; Knudsen effusion; Vapor pressure; G3 and G4 calculations; Sarcosine; Sarcosine anhydride;
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1. Introduction 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The amino acids are essential species present on the biochemical processes and the understanding of their role on the biological activity depends on the knowledge of thermochemical data related with the formation and dissociation of chemical bonds. The need of reliable data for this class of compounds lead us to the study of selected molecules, in order to improve the situation. In previous papers the thermochemical properties of L-cysteine, L-cystine (sulphur containing amino acids) [1], N-benzylalanines [2], α-alanine (DL) and β- alanine [3] were reported. More recently, we reported the study of the cyclic anhydrides of glycine and alanine [4]. The present work continues our thermochemical characterization of amino acids, presenting the study of two other important molecules, the sarcosine (N-methylglycine) and the sarcosine anhydride (1,4-dimethyl-2,5-piperazinedione) (see Figure 1).
Figure 1. Schematic formulae of sarcosine 1 and sarcosine anhydride 2.
Sarcosine is a natural amino acid with a significant role in metabolic process of living cells as a source of serine, creatine, purines or glutathione, and as an important intermediate in the metabolism of the choline, being found in muscles and other body tissues. Several studies [58] indicate the use of sarcosine in adjunctive treatment of patients with schizophrenia and depression. It has been also recently pointed as a potencial urine biomarker for prostate cancer diagnosis and prognosis [9], since its levels increases greatly during prostate cancer progression to metastasis, being detected in urine. This subject has been analysed by other researchers with different results [10,11], although very recent papers reported that the doubt on its utility as a biomarker is related to the methods used for its quantification [12,13]. Sarcosine anhydride, as a 2,5-diketopiperazine, is a cyclic polyfunctional peptide with ideal characteristics to be used as starting material for synthesis of new heterocyclic compounds 3
with potential application on the development of new bioactive compounds for pharmaceutical 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
and agrochemical industries [14]. Some studies have shown that diketopiperazines present activities as antifungal, antibacterial, antitumour and antiviral, among other [15]. The standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, at the temperature T = 298.15 K, of sarcosine and sarcosine anhydride, were derived from the values of energies of combustion, measured by static bomb combustion calorimetry. The standard molar enthalpies of sublimation of these compounds were obtained from the temperature dependence of the vapor pressure using the Knudsen mass-loss effusion technique. Additionally, computational determinations of the gas-phase enthalpies of formation at the G3 and G4 levels were also performed.
2. Experimental
2.1. Compounds and purity control The two studied compounds were obtained commercially and purified by sublimation under reduced pressure. Further details of the origin and purification of the samples were presented in table 1. The average ratio of the mass of carbon dioxide recovered after combustion to that calculated from the mass of samples used in each experiment, together with the uncertainties (twice the standard deviation of the mean) was (0.99995 ± 0.00010) for sarcosine and (0.99991 ± 0.00022) sarcosine anhydride. The specific densities used to calculate the true mass from the apparent mass in air were 0.9997 g.cm-3 for sarcosine and 1.1318 g.cm-3 for sarcosine anhydride [16].The relative atomic masses used were those recommended by the IUPAC Commission [17].
TABLE 1 near here 2.2. Combustion calorimetry The standard (po = 0.1 MPa) massic energies of combustion of sarcosine and sarcosine anhydride were determined with an isoperibol static bomb calorimeter, using a twin valve bomb, type 1105 of Parr Instrument Company [18,19]. For calibration of the system, benzoic acid NIST Standard Reference Material, sample 39j, with a certified massic energy of combustion, under the bomb conditions, of –(26434 ± 3) J·g-1 [20], was used according to the procedure described by Coops et al. [21]. The calibration results 4
were corrected to give the energy equivalent, calor, corresponding to the average mass of water 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
added to the calorimeter of 3119.6 g. For the combustion experiments of sarcosine, calor = (15905.0 ± 0.8) J·K-1, whereas for sarcosine anhydride, the value of calor used was (15906.6 ± 1.9) J·K-1 The uncertainties quoted are the standard deviations of the mean of six measurements. Both crystalline compounds were burnt in pellet form, in oxygen, at p = 3.04 MPa, with 1.00 cm3 of deionised water added to the bomb. Sarcosine, as a hygroscopic compound, was handled under nitrogen and the pellets were burnt in sealed melinex bags using the technique described by Skinner and Snelson [22], who determined the specific energy of combustion of dry melinex as cuo = –(22902 ± 5) Jg–1. The mass of melinex used in each experiment was corrected for the mass fraction of water (w = 0.0032). For all the experiments, ignition was made at T = (298.150 ± 0.001) K by the discharge of a 1400 µF capacitor through a platinum ignition wire of diameter
= 0.05 mm. The calorimeter temperatures were measured every 10 s, with a precision of ±(1·10-4) K, using a quartz crystal thermometer (Hewlett Packard HP 2804 A), interfaced to a PC programmed to data acquisition, control of the calorimeter temperatures and calculate the adiabatic temperature change, by means of the LABTERMO program [23]. The electrical energy for ignition, U(ign), was determined from the change in potential difference across a capacitor when discharged through the platinum ignition wire. For the cotton thread fuse, empirical formula, CH1.686O0.843, cuo = –16240 J·g-1 [24]. The corrections for nitric acid formation U(HNO3) were based –59.7 kJ.mol-1 [25], for the molar energy of formation of 0.1 mol.dm-3 HNO3(aq), from N2(g), O2(g) and H2O(l). An estimated pressure coefficient of specific energy, at T = 298.15 K, (u/p)T, was assumed to be –0.2 J.g-1.MPa-1, a common value for organic compounds [26]. The amount of substance, m(cpd), used in each experiment and on which the energy of combustion was based, was determined from the total mass of carbon dioxide produced, after allowance for that formed from the cotton thread fuse and of melinex. For each compound, the standard massic energy of combustion, Δcuº, was calculated by the procedure given by Hubbard et al. [27].
2.3. Knudsen effusion technique
The vapor pressures of the two studied compounds as a function of temperature were measured by the mass-loss Knudsen effusion technique using an apparatus previously described. A detailed description of the apparatus and measuring procedure, as well as the results obtained 5
with several test compounds has been reported before [28]. This apparatus enables the 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
simultaneous operation of nine aluminum effusion cells, which are placed in cylindrical holes inside three aluminum blocks, each one with three cells. Each block is maintained at a constant temperature, different from the other two blocks. There are three different groups of effusion cells according to their different areas of effusion orifices: series A (small orifices; Ao ≈ 0.5 mm2), series B (medium orifices; Ao ≈ 0.8 mm2), and series C (large orifices; Ao ≈ 1.1 mm2). The exact areas and the transmission probability factors (Clausing factors) of each effusion orifice, made in platinum foil of 0.0125 mm thickness, are presented in the Supporting Information, Table S1. The Clausing factors were calculated by equation (1) where l is the thickness of the effusion hole and r its radius: wo = {1 + (3 l /8r)}-1.
(1)
For each compound, the measurements were extended through a chosen temperature interval corresponding to measured vapor pressures in the range 0.1 Pa to 1.0 Pa. In a typical effusion experiment the loss of mass m of the samples, during a convenient effusion time period t, is determined by weighing the effusion cells to ± 0.01 mg before and after the effusion period in a system evacuated to a pressure near (1.10-4) Pa. At the temperature T of the experiment, the vapor pressure p is calculated by equation (2), p = (m / Aowo t) (2RT / M)1/2,
(2)
where Ao represents the area of the effusion orifice, wo is the respective Clausing factor, R is the gas constant and M is the molar mass of the effusing vapor.
3. Computational Details
Standard ab initio molecular orbital calculations [29] were performed with the Gaussian 09 series of programs [30]. The energies of the compounds studied were calculated using two different theoretical model chemistry Gaussian-n methods, at the G3 [31] and G4 [32] levels. Details on these methods have been given in our previous paper on glycine and alanine anhydrides [4].
6
Due to the lack of symmetry and the internal rotational degrees of freedom by free 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
rotation of the NHMe, COOH, and OH groups with respect to the carbon skeleton, sarcosine exhibits a large number of low-energy conformers. In this study we have optimized the molecular structures of 6 of its lowest-energy conformers, taking into account only those conformers that contribute significantly to the populated states. Energies at 0 K and enthalpies at 298 K, calculated at the G3 and G4 levels, for sarcosine anhydride and the lowest-energy conformers of sarcosine are collected in Tables S2 to S4 of the Supporting Information.
4. Experimental Results
Tables 2 and 3 show the combustion results obtained for sarcosine and sarcosine anhydride, in which m(H2O) represents the deviation of the mass of water added to the calorimeter from 3119.6 g, the mass assigned to calor, Tad is the calorimeter temperature change corrected for the heat exchange and the work of stirring, U is the correction to the standard state and the remaining terms are as previously defined [27,33].
As
samples were ignited at T =
(298.150 ± 0.001) K, the internal energy associated to the isothermal bomb process, U(IBP), was calculated through: U(IBP) = –{calor + cp(H2O, l)·m(H2O) + f } Tad + U(ign).
(3)
The values of cuo are referred to the combustion reactions, represented by equations (4) and (5) for sarcosine and sarcosine anhydride, respectively
C3H7NO2 (cr) + 3.75O2 (g) 3CO2 (g) + 0.5 N2 (g) + 3.5 H2O (l)
(4)
C6H10O2N2 (cr) + 7.5 O2 (g) 6CO2 (g) + 5H2O (l) + N2 (g)
(5)
TABLES 2 and 3 near here Table 4 list the derived standard molar energies and enthalpies of combustion and the standard molar enthalpies of formation for the compounds in the crystalline phase, at T = 298.15 K. In accordance with normal thermochemical practice, [34,35] the uncertainties assigned to the
7
standard molar energies and enthalpies of combustion are, in each case, twice the overall 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
standard deviation of the mean and include the uncertainties in calibration and in the values of o o auxiliary quantities used. To derive Δ f H m (cr) the standard molar enthalpies (cr) from Δ c H m
of formation of CO2(g) and H2O(l), at T = 298.15 K, –(393.51 ± 0.13) kJ.mol-1 [36] and – (285.830 ± 0.040) kJ.mol-1 [36], respectively, were used. TABLE 4 near here Table 5 presents the experimental results obtained through the effusion experiments. The subscripts A, B, C of the variables m and p stand, respectively, for the results obtained through the small (A1, A2, A3), the medium (B4, B5, B6), and the large (C7, C8, C9) effusion orifices. Table 6 presents, for each series of effusion orifices (A, B, C) and for the global treatment of all results, the parameters of the Clausius–Clapeyron equation, ln(p/Pa) = a – b.(T/K)–1, where a is a constant and b = gcr H mo (T) / R. The entropies of sublimation, at equilibrium conditions, were calculated as gcr S m {T, p(T = T)} = gcr H mo (T)/T.
(6)
TABLES 5 and 6 near here The plots of ln (p/ Pa) = f (1/T) for the global results of the two compounds studied experimentally are presented in figure 2. FIGURE 2 near here Sublimation enthalpies, at the temperature T = 298.15 K, were derived from the sublimation enthalpies calculated at the mean temperature T of the experiments as a result of the expression,
gcr H mo T 298.15 K gcr H mo T gcr Cp,o m 298.15 T ,
(7)
using gcr C op ,m (sarcosine) = –13.0 J·K-1·mol-1 and gcr C op ,m (sarcosine anhydride) = –27.0 J·K-1·mol-1,
calculated
from
the
values
of
the
gas-phase
molar
heat
capacities,
C op, m (g, sarcosine) = 105.2 J·K-1·mol-1 and C op, m (g, sarcosine anhydride) = 159.5 J·K-1·mol-1, at
8
T = 298.15 K, obtained in this work from statistical thermodynamics using the vibrational 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
frequencies from B3LYP/6-31G(d) calculations (scaled by the factor 0.9613 [37]), and from the respective literature values of molar heat capacities, in the crystalline phase: C op,m (cr, sarcosine) = 118.2 J·K-1·mol-1 [38] and C op,m (cr, sarcosine anhydride) = 186.5 J·K-1·mol-1 [39]. Table 7 presents, for each compound, the values, at T = 298.15 K, of the standard molar enthalpies of sublimation, the standard molar entropies of sublimation calculated by the equation (8), where po = 105 Pa, and the standard molar Gibbs energies of sublimation.
gcr S mo (T = 298.15 K) = gcr S m T , p( T ) + gcr Cp,o m ln(298.15K
/ T )
Rln p o /p(T )
(8)
For the studied compounds the standard molar enthalpies of formation in the gaseous state, at T = 298.15 K, obtained by the addition of the derived standard molar enthalpies of formation in the crystalline state with the standard molar enthalpies of sublimation, are summarized in Table 8. TABLE 7 near here 5. Theoretical Results
5.1. Molecular structures
The crystal structure of sarcosine was determined by X-ray diffraction by Mostad and Natarajan, in 1989 [40]. Amino acids exist as zwitterions in the crystalline state [41] as well as in aqueous solution, stabilized by electrostatic, polarization and hydrogen-bonding interactions with their environment. To our knowledge, there is not any experimental determination of the crystal structure of sarcosine anhydride. In the gas phase, where the intermolecular interactions have no effect, amino acids are intrinsically flexible systems, existing as their nonionized forms. To our knowledge, no experimental gas-phase structure determinations of sarcosine or sarcosine anhydride have been reported in the literature. B3LYP/6-31G(2df,p)-optimized geometries of sarcosine anhydride and the six lowest-energy conformers of sarcosine are shown in Figures3 and 4, respectively.
9
FIGURES 3 and 4 near here 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The molecule of sarcosine anhydride is no planar, the atoms in one half molecule, the group
are almost exactly coplanar, but there is a slight twist of one of these groups with respect to the other half of the molecule, as it was observed in our previous study of amino acid anhydrides [4]. The most stable conformer I of sarcosine presents by a N–H···O=C hydrogen bond (2.60 Å) between the oxygen of the carboxylic group and the hydrogen atom of the NHMe group. The B3LYP/6-31G(2df,p)-optimized geometrical parameters for sarcosine anhydride and the most stable conformer of sarcosine have been collected in Tables S5 and S6 of the Supporting Information.
5.2. Theoretical Determination of the Enthalpies of Formation
Sarcosine anhydride G3 and G4-calculated energies at T = 0 K, and enthalpies at T = 298 K, for sarcosine anhydride are given in Table S2 in the Supporting Information. The values of the enthalpies of formation calculated at the G3 and G4 levels, using the standard procedure through atomization reactions [42,43] are shown in Table 8. There is a very good agreement between the experimental and calculated values.
TABLE 8 near here Sarcosine G3 and G4-calculated energies at T = 0 K, enthalpies at T = 298 K, and entropies, for the six lowest-energy conformers of sarcosine are given in Tables S3 and S4 of the Supporting Information, respectively. The conformational composition of sarcosine in the gas phase, at T = 298 K, can be calculated through equation (9):
10
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
xi
e
Grel ( i ) RT
n
e
(9)
Grel ( i ) RT
i 1
where ∆Grel(i) is the relative Gibbs energy of conformer i to the lowest energy conformer I, and can be calculated as:
Grel (i) Hrel (i) T Srel (i) [ H (i) H (I)] T [ S (i) S (I)]
(10)
∆Grel(i) values calculated at the G3 and G4 levels are collected in Tables S3 and S4 of the Supporting Information, respectively. Boltzmann weighted populations derived from Gibbs energies have also been collected in the same Tables. As can be observed, the lowest energy conformer of sarcosine, conformer I, accounts for 53.9 % (G3) and 63.4 % (G4) of the composition in the gas phase. Using equation (11): n
o f H m (X )
xi f H mo (i)
(11)
i 1
the final value for the enthalpy of formation of sarcosine is calculated as –387.4 and –387.3 kJ·mol-1, at the G3 and G4 levels, respectively, in perfect agreement with the experimental value determined in this work (see Table 8).
5. Discussion 5.1. Condensed phase and phase transition Sabbah and Laffitte [44] have measured the enthalpy of sublimation of sarcosine between 380–413 K and they have obtained the value of (146 ± 1) kJ·mol-1, which corrected to 298.15 K yields (147 ± 1) kJ·mol-1. They have also determined the standard molar enthalpy of formation, in the solid phase of sarcosine as, –(513.24 ± 0.26) kJ·mol-1 [45]. Cox and Pilcher [46] have reanalyzed the value of the standard molar enthalpy of formation obtained by Breitenbach, o (cr) = –(508.6 ± 1.3) kJ·mol-1 for Derkosch, et al. [47] and they recommended the value Δ f H m
11
sarcosine. There is a poor agreement between these reported values and the corresponding ones 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
determined in this work. With respect to the enthalpy of sublimation, our value differs of 17.8 kJ.mol-1 from the one determined by Sabbah and Laffitte. Regarding the values of enthalpies of o formation, our Δ f H m (cr) differs only 4 kJ.mol-1 from the value obtained by Sabbah and about 9
kJ.mol-1 from the reanalyzed value of Cox and Pilcher. Theoretical calculations of the gas phase standard molar enthalpy of formation of sarcosine were performed by Dorofeeva and Ryzhova [48] using the high-level Gaussian 4 method and they found a significant discrepancy between theoretical and experimental values, suggesting an inaccuracy of experimental data for this compound. In fact, the calculated value of Dorofeeva, –(389.0 ± 4) kJ.mol-1 is in agreement with our results, either the experimental and the computational ones.
5.2. Final Remarks Looking for data on related nitrogen heterocyclic compounds in order to evaluate the consistency of the present result for the enthalpy of formation of gaseous sarcosine anhydride and the previous one for the glycine anhydride [4], we have selected the uracil [49,50] and the 1,3-dimethyluracil [51]. Scheme 1 shows that the enthalpic increment for the methylation on the two nitrogens of the cycle of uracil is similar to that obtained for identical methylation on glycine anhydride. The coherency of these results constitutes another support for the reliableness of our studies on these cyclic polyfunctional peptides.
Scheme 1 near here
Acknowledgments Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal and to FEDER for financial support given to Centro de Investigação em Química da Universidade do Porto and to Programa Ciência 2008 (PEst-C/QUI/UI0081/2011). A.F.L.O.M.S thanks FCT and The European Social Fund (ESF) under the Community Support Framework (CSF) for the award of a post-doctoral fellowship (SFRH/BPD/41601/2007). The support of the Spanish Ministerio de Economía y Competitividad under Project CTQ2010-16402 is gratefully acknowledged.
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Appendix A. Supporting information 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
This supporting information includes detailed data of the effusion orifices (diameter and Clausing factors) of the Knudsen apparatus the data, the G3 and G4-calculated energies and enthalpies and calculated bond distances and bond angles for the studied compounds. Supplementary data associated with this article can be found, in the online version, at doi:……..
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Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian, Inc., Wallingford CT, 2009. [31] L.A. Curtiss, K. Raghavachari, P.C. Redfern, V. Rassolov, J.A. Pople, J. Chem. Phys. 109 (1998) 7764-7776. [32] L.A. Curtiss, P.C. Redfern, K. Raghavachari, J. Chem. Phys. 126 (2007) 084108. [33] E.F. Westrum, in: S. Sunner and M. Månsson, (Eds.), Combustion Calorimetry, Pergamon Press, Oxford, 1979 (Chapter 7). [34] F.D. Rossini, in: F.D. Rossini (Ed.), Experimental Thermochemistry, vol.1, Interscience, New York 1956 (Chapter 14). [35] G. Olofsson in: S. Sunner, M. Månsson (Eds.), Combustion Calorimetry, Pergamon Press, Oxford 1979 (Chapter 6). [36] J.D.Cox, D D. Wagman, V.A. Medvedev, CODATA Key Values for Thermodynamics, Hemisphere, New York 1989. [37] J.P. Merrick, D. Moran, L. Radom, J. Phys. Chem. A 111 (2007) 11683-11700. [38] M.V. Roux, R. Notario, M. Segura, R. Guzmán-Mejía, E. Juaristi, J.S. Chickos, J. Chem. Eng. Data 56 (2011) 3807-3812. [39] L. Abate, B. Pałecz, C. Giancola, G. Della Gatta, J. Chem. Thermodyn. 29 (1997) 359-368. [40] A. Mostad, S. Natarajan, Acta Chem. Scand. 43 (1989) 1004-1006 [41] F.H. Allen, Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 58 (2003) 380388. [42] R. Notario, O. Castaño, J.-L.M. Abboud, R. Gomperts, L.M. Frutos, R. Palmeiro, J. Org. Chem. 64 (1999) 9011-9014. [43] R. Notario, O. Castaño, R. Gomperts, L.M. Frutos, R. Palmeiro, J. Org. Chem. 65 (2000) 42984302. [44] R. Sabbah, M. Laffitte, Bull. Soc. Chem. France 1 (1978) 50-52. [45] R. Sabbah, M. Laffitte, J. Chem. Thermodyn. 9 (1977) 1107-1108. [46] J.D. Cox, G. Pilcher, Thermochemistry of Organic and Organometallic Compounds, Academic Press, New York 1970. [47] J.W. Breitenbach, J. Derkosch, F. Wessely, Monatsh. Chem. 83 (1952) 591-593. [48] O.V. Dorofeeva, O.N Ryzhova, J. Chem Thermodyn. 42 (2010) 1056-1062. [49] P.M. Nabavian, R. Sabbah, R. Chastel, M. Laffitte, J. Chim. Phys. 74 (1977) 115-126. [50] P. Szterner, M. Kamiński, A. Zielenkiewicz, J. Chem. Thermodyn. 34 (2002) 1005-1012.
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17
TABLE 1 Provenance and purity of the compounds studied
Chemical Name
Sarcosine (cr)
CAS
Provenance
107-97-1
Aldrich Chemical Co.
Initial Molar Final Molar Purification Fraction Fraction Method Purity Purity 0.98
Sarcosine anhydride 5076-82-4 Acros Organics 0.99 (cr) ª Quantity of carbon dioxide recovered in the combustion experiments
Analysis Method
Sublimation
0.99995
a
CO2 recovery
Sublimation
0.99991
a
CO2 recovery
TABLE 2 Standard massic energy of combustion of sarcosine, at T = 298.15 K
m(cpd) / g
1 0.77367
2 0.62211
3 0.71851
4 0.74125
5 0.80945
6 0.83540
m’(fuse) / g
0.00260
0.00235
0.00231
0.00278
0.00274
0.00331
m’’(melinex) / g
0.04589
0.04198
0.04547
0.04206
0.04596
0.04627
Tad / K
0.97930
0.79503
0.91392
0.93610
1.02217
1.05294
16.71
16.24
16.46
16.51
16.73
16.87
m(H2O) / g
0.0
0.0
0.0
0.0
0.0
0.0
U(IBP)a / J
15591.55
12657.25
14550.32
14903.46
16274.04
16764.15
U(melinex) / J
1050.86
961.54
1041.26
63.36
1052.69
1059.77
U(fuse) / J
42.22
38.16
37.51
45.15
44.50
53.75
U(HNO3) / J
43.94
37.67
50.98
47.10
48.48
48.77
U(ign) / J
0.58
0.64
0.62
0.67
0.67
0.62
U / J
11.09
8.86
10.20
10.48
11.58
11.97
18668.73
18663.93
18664.14
18667.62
18675.38
18661.59
f / (J.K-1)
cuo / J.g-1
cuo / J.g-1 a
U(IBP) already includes the U(ign)
TABLE 3 Standard massic energy of combustion of sarcosine anhydride, at T = 298.15 K
m(cpd) / g
1 0.61843
2 0.72154
3 0.75961
4 0.79499
5 0.79672
6 0.81277
7 0.81367
m’(fuse) / g
0.00295
0.00275
0.00287
0.00301
0.00245
0.00245
0.00312
Tad / K
0.92275
1.07502
1.13114
1.18435
1.18600
1.21013
1.21342
15.92
16.18
16.28
16.36
16.38
16.45
16.37
m(H2O) / g
0.0
0.0
0.0
0.0
0.0
0.1
0.0
U(IBP)a / J
14691.80
17116.60
18010.30
18857.66
18884.06
19268.81
19320.44
U(fuse) / J
47.91
44.66
46.61
48.88
39.79
39.79
50.67
U(HNO3) / J
49.79
49.79
51.82
61.37
59.40
57.43
65.67
U(ign) / J
0.70
0.71
0.71
0.70
0.59
0.66
0.81
U / J
9.98
11.85
12.53
13.07
13.10
13.44
13.35
23582.49
23574.99
23563.86
23565.50
23561.31
23571.43
23585.42
f / (J.K-1)
cuo / J.g-1
cuo / J.g-1 a
U(IBP) already includes the U(ign)
m(cpd) is the mass of compound burnt in each experiment; m’(fuse) is the mass of the fuse (cotton) used in each experiment; ; m’’(melinex) is the mass of melinex; Tad is the corrected temperature rise; f is the energy equivalent of the contents in the final state; m(H2O) is the deviation of mass of water added to the calorimeter from 3119.6 g; U(IBP) is the energy change for the isothermal combustion reaction under actual bomb conditions; U(melinex) is the energy of combustion of melinex; U(fuse) is the energy of combustion of the fuse (cotton); U(HNO3) is the energy correction for the nitric acid formation; U(ign) is the electric energy for the ignition; U is the standard state correction; cuo is the standard massic energy of combustion.
TABLE 4 Derived standard (po = 0.1 MPa) molar energy of combustion, c U mo , standard molar enthalpy of combustion, c H mo , and standard molar enthalpy of formation, f H mo , for the crystalline compounds, at T = 298.15 K
Compound
c U mo cr kJ mol 1
c H mo cr kJ mol 1
f H mo cr kJ mol 1
Sarcosine
1663.1 ± 0.6
1663.7 ± 0.6
517.2 ± 0.7
Sarcosine anhydride
3350.9 ± 1.3
3352.1 ± 1.3
438.1 ± 1.5
TABLE 5 Knudsen effusion results for sarcosine and sarcosine anhydride T/K
t/s
Orifices
m / mg mA
mB
mC
p / Pa pA
pB
pC
Sarcosine 403.16
10442
A1-B4-C7
12.27
19.16
27.31
1.151
1.164
1.166
401.15
10442
A2-B5-C8
10.53
16.22
23.52
0.972
0.971
0.978
399.14
10442
A3-B6-C9
8.59
13.45
19.39
0.801
0.794
0.800
397.13
16623
A1-B4-C7
10.97
16.99
24.18
0.641
0.644
0.644
395.10
16623
A2-B5-C8
8.97
14.02
19.68
0.516
0.523
0.510
393.14
16623
A3-B6-C9
7.43
11.47
16.24
0.432
0.422
0.418
391.12
23947
A1-B4-C7
9.02
13.74
19.31
0.363
0.359
0.354
389.10
23947
A2-B5-C8
7.35
11.23
15.14
0.291
0.289
0.271
387.14
23957
A3-B6-C9
5.83
9.07
12.75
0.233
0.230
0.226
385.13
27335
A1-B4-C7
5.67
8.75
12.25
0.198
0.198
0.195
383.12
27335
A2-B5-C8
4.65
7.16
10.08
0.160
0.160
0.156
381.15
27335
A3-B6-C9
3.80
5.80
8.15
0.132
0.128
0.126
Sarcosine anhydride 351.10
10492
A1-B4-C7
17.26
26.32
37.54
1.190
1.176
1.179
349.14
10492
A2-B5-C8
14.47
22.17
30.57
0.982
0.975
0.935
347.16
10492
A3-B6-C9
12.41
18.26
25.31
0.796
0.793
0.768
345.09
14552
A1-B4-C7
13.48
21.10
28.62
0.664
0.674
0.642
343.14
14552
A2-B5-C8
11.20
16.90
23.59
0.543
0.532
0.516
341.17
14552
A3-B6-C9
8.86
13.91
19.23
0.423
0.432
0.417
339.08
15407
A1-B4-C7
7.25
11.45
16.33
0.335
0.342
0.343
337.13
15407
A2-B5-C8
5.96
9.42
13.34
0.271
0.277
0.273
335.18
15407
A3-B6-C9
5.36
7.81
11.03
0.240
0.227
0.224
333.08
15137
A1-B4-C7
3.85
5.97
8.43
0.179
0.180
0.179
331.13
15137
A2-B5-C8
3.10
4.73
6.63
0.142
0.140
0.137
329.18
15137
A3-B6-C9
2.62
3.84
5.46
0.118
0.112
0.112
TABLE 6 Experimental results for sarcosine and sarcosine anhydride, where a and b are from the Clausius-Clapeyron equation, ln (p/Pa) = a – b · (K/T) and b = gcr H mo T / R; R = 8.314472 J·K - 1 ·mol - 1 Orifices
a
b
T
pT
gcr H mo T
gcr S m T , pT
K
Pa
kJ mol1
J K 1 mol 1
Sarcosine A1-A2-A3
37.91 0.32
15226 125
126.6 ± 1.0
B4-B5-B6
38.31 0.33
15386 130
127.9 ± 1.1
C7-C8-C9
38.82 0.42
15590 163
129.6 ± 1.4
Global results
38.34 0.22
15400 85
392.16
0.395
128.0 ± 0.7
326.4 ± 1.8
Sarcosine anhydride A1-A2-A3
35.13 0.39
12274 134
102.0 1.1
B4-B5-B6
35.49 0.25
12396 84
103.1 0.7
C7-C8-C9
35.18 0.26
12298 88
102.2 0.7
Global results
35.27 0.20
12322 66
340.14
0.384
102.5 0.5
301.3 1.5
TABLE 7 Values of the standard (po = 0.1 MPa) molar enthalpy, gcr H mo , entropy, gcr S mo , and Gibbs energy gcr Gmo , of sublimation, at T = 298.15 K, for sarcosine and sarcosine anhydride gcr H mo kJ mol 1
gcr S mo J K 1 mol 1
gcr Gmo kJ mol 1
Sarcosine
129.2 0.7
226.5 1.8
61.7 0.9
Sarcosine anhydride
103.6 ± 0.5
201.2 ± 1.5
43.6 ± 0.7
Compound
TABLE 8 G3- and G4-calculated enthalpies of formation of sarcosine and sarcosine anhydride f H mo g kJ mol 1
Compound
G3
G4
experimental
Sarcosine
387.4
387.3
(388.0 ± 1.0)a (367.2 ± 1.0)b
Sarcosine anhydride
340.1
337.8
(334.5 ± 1.6)a
a
This work. b Taken from ref [44].
0.5 OH
0.0
O NH
ln (p / Pa)
-0.5
-1.0
O
-1.5 N
N
-2.0 O
-2.5 2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
1000 K / T
FIGURE 2. Plots of ln(p / Pa) against 1 / T for sarcosine and sarcosine anhydride
FIGURE 3. B3LYP/6-31G(2df,p)-optimized structure of sarcosine anhydride
I
II
III
IV
V
VI
FIGURE4. B3LYP/6-31G(2df,p)-optimized structures of the six lowest-energy conformers of sarcosine
Figure
HN
O
N
(14.9 ± 4.6) kJ·mol-1 O
N H
N
uracil 1,3-dimethyluracil (313.6 ± 1.5) kJ·mol-1[51]
(298.7 ± 4.4) kJ·mol-1[49,50]
H N
O
(13.5 ± 2.5) kJ·mol
O
N H
N
O
-1
O
N
glycine anhydride (321.0 ± 1.9) kJ·mol-1[4]
sarcosine anhydride (334.5 ± 1.6) kJ·mol-1
Scheme 1. Enthalpic increments for the methylation on the two nitrogen atoms in uracil and glycine anhydride.
Figure
0.5 OH
0.0
O NH
ln (p / Pa)
-0.5
-1.0
O
-1.5 N
N
-2.0 O
-2.5 2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
1000 K / T
FIGURE 2. Plots of ln(p / Pa) against 1 / T for sarcosine and sarcosine anhydride
FIGURE 3. B3LYP/6-31G(2df,p)-optimized structure of sarcosine anhydride
I
II
III
IV
V
VI
FIGURE 4. B3LYP/6-31G(2df,p)-optimized structures of the six lowest-energy conformers of sarcosine
Scheme
HN
O
N
(14.9 ± 4.6) kJ·mol-1 O
N H
N
uracil 1,3-dimethyluracil (313.6 ± 1.5) kJ·mol-1[51]
(298.7 ± 4.4) kJ·mol-1[49,50]
H N
O
(13.5 ± 2.5) kJ·mol
O
N H
N
O
-1
O
N
glycine anhydride (321.0 ± 1.9) kJ·mol-1[4]
sarcosine anhydride (334.5 ± 1.6) kJ·mol-1
Scheme 1. Enthalpic increments for the methylation on the two nitrogen atoms in uracil and glycine anhydride.
*Highlights (for review)
Study on the Energetics of the Sarcosine and Sarcosine Anhydride Experimental and Computational Thermochemistry of Sarcosine and its Anhydride Ab initio calculations for two amino acid derivatives by G3(MP2)//B3LYP method
S0021-9614(12)00443-0 http://dx.doi.org/10.1016/j.jct.2012.11.019 YJCHT 3369
To appear in:
J. Chem. Thermodynamics
Please cite this article as: L.M.P. Amaral, A.F.L.O. Santos, d.D.M.C. Ribeiro da Silva, R. Notario, Thermochemistry of sarcosine and sarcosine anhydride: Theoretical and experimental studies, J. Chem. Thermodynamics (2012), doi: http://dx.doi.org/10.1016/j.jct.2012.11.019
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Journal of Chemical Thermodynamics 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
Thermochemistry of Sarcosine and Sarcosine Anhydride: Theoretical and Experimental Studies
Luísa M.P.F. Amaral,a Ana Filipa L.O.M. Santos,a Maria das Dores M.C. Ribeiro da Silva,a,* and Rafael Notariob,* a
Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of
Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal b
Instituto de Química Física “Rocasolano”, CSIC, Serrano 119, 28006 Madrid, Spain
________________________________________________________________________ *
Corresponding authors
[email protected] (M.D.M.C.R.S) [email protected] (R.N.)
1
Abstract 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of sarcosine, –(388.0 ± 1.0) kJ.mol-1, and sarcosine anhydride, –(334.5 ± 1.6) kJ.mol-1, were calculated by combining, for each compound, the standard molar enthalpy of formation, in the crystalline phase, and the standard molar enthalpy of sublimation, derived from measurements of the standard massic energies of combustion by static bomb combustion calorimetry, and from measurements of vapor pressures by the Knudsen mass-loss effusion method, respectively. The standard (po = 0.1 MPa) molar enthalpies, entropies and Gibbs functions of sublimation, at T = 298.15 K, were also calculated. A theoretical study at the G3 and G4 levels has been carried out, and the calculated enthalpies of formation have been compared with the experimental ones.
KEYWORDS: Enthalpy of combustion; Enthalpy of sublimation; Enthalpy of formation; Static bomb combustion calorimetry; Knudsen effusion; Vapor pressure; G3 and G4 calculations; Sarcosine; Sarcosine anhydride;
2
1. Introduction 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The amino acids are essential species present on the biochemical processes and the understanding of their role on the biological activity depends on the knowledge of thermochemical data related with the formation and dissociation of chemical bonds. The need of reliable data for this class of compounds lead us to the study of selected molecules, in order to improve the situation. In previous papers the thermochemical properties of L-cysteine, L-cystine (sulphur containing amino acids) [1], N-benzylalanines [2], α-alanine (DL) and β- alanine [3] were reported. More recently, we reported the study of the cyclic anhydrides of glycine and alanine [4]. The present work continues our thermochemical characterization of amino acids, presenting the study of two other important molecules, the sarcosine (N-methylglycine) and the sarcosine anhydride (1,4-dimethyl-2,5-piperazinedione) (see Figure 1).
Figure 1. Schematic formulae of sarcosine 1 and sarcosine anhydride 2.
Sarcosine is a natural amino acid with a significant role in metabolic process of living cells as a source of serine, creatine, purines or glutathione, and as an important intermediate in the metabolism of the choline, being found in muscles and other body tissues. Several studies [58] indicate the use of sarcosine in adjunctive treatment of patients with schizophrenia and depression. It has been also recently pointed as a potencial urine biomarker for prostate cancer diagnosis and prognosis [9], since its levels increases greatly during prostate cancer progression to metastasis, being detected in urine. This subject has been analysed by other researchers with different results [10,11], although very recent papers reported that the doubt on its utility as a biomarker is related to the methods used for its quantification [12,13]. Sarcosine anhydride, as a 2,5-diketopiperazine, is a cyclic polyfunctional peptide with ideal characteristics to be used as starting material for synthesis of new heterocyclic compounds 3
with potential application on the development of new bioactive compounds for pharmaceutical 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
and agrochemical industries [14]. Some studies have shown that diketopiperazines present activities as antifungal, antibacterial, antitumour and antiviral, among other [15]. The standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, at the temperature T = 298.15 K, of sarcosine and sarcosine anhydride, were derived from the values of energies of combustion, measured by static bomb combustion calorimetry. The standard molar enthalpies of sublimation of these compounds were obtained from the temperature dependence of the vapor pressure using the Knudsen mass-loss effusion technique. Additionally, computational determinations of the gas-phase enthalpies of formation at the G3 and G4 levels were also performed.
2. Experimental
2.1. Compounds and purity control The two studied compounds were obtained commercially and purified by sublimation under reduced pressure. Further details of the origin and purification of the samples were presented in table 1. The average ratio of the mass of carbon dioxide recovered after combustion to that calculated from the mass of samples used in each experiment, together with the uncertainties (twice the standard deviation of the mean) was (0.99995 ± 0.00010) for sarcosine and (0.99991 ± 0.00022) sarcosine anhydride. The specific densities used to calculate the true mass from the apparent mass in air were 0.9997 g.cm-3 for sarcosine and 1.1318 g.cm-3 for sarcosine anhydride [16].The relative atomic masses used were those recommended by the IUPAC Commission [17].
TABLE 1 near here 2.2. Combustion calorimetry The standard (po = 0.1 MPa) massic energies of combustion of sarcosine and sarcosine anhydride were determined with an isoperibol static bomb calorimeter, using a twin valve bomb, type 1105 of Parr Instrument Company [18,19]. For calibration of the system, benzoic acid NIST Standard Reference Material, sample 39j, with a certified massic energy of combustion, under the bomb conditions, of –(26434 ± 3) J·g-1 [20], was used according to the procedure described by Coops et al. [21]. The calibration results 4
were corrected to give the energy equivalent, calor, corresponding to the average mass of water 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
added to the calorimeter of 3119.6 g. For the combustion experiments of sarcosine, calor = (15905.0 ± 0.8) J·K-1, whereas for sarcosine anhydride, the value of calor used was (15906.6 ± 1.9) J·K-1 The uncertainties quoted are the standard deviations of the mean of six measurements. Both crystalline compounds were burnt in pellet form, in oxygen, at p = 3.04 MPa, with 1.00 cm3 of deionised water added to the bomb. Sarcosine, as a hygroscopic compound, was handled under nitrogen and the pellets were burnt in sealed melinex bags using the technique described by Skinner and Snelson [22], who determined the specific energy of combustion of dry melinex as cuo = –(22902 ± 5) Jg–1. The mass of melinex used in each experiment was corrected for the mass fraction of water (w = 0.0032). For all the experiments, ignition was made at T = (298.150 ± 0.001) K by the discharge of a 1400 µF capacitor through a platinum ignition wire of diameter
= 0.05 mm. The calorimeter temperatures were measured every 10 s, with a precision of ±(1·10-4) K, using a quartz crystal thermometer (Hewlett Packard HP 2804 A), interfaced to a PC programmed to data acquisition, control of the calorimeter temperatures and calculate the adiabatic temperature change, by means of the LABTERMO program [23]. The electrical energy for ignition, U(ign), was determined from the change in potential difference across a capacitor when discharged through the platinum ignition wire. For the cotton thread fuse, empirical formula, CH1.686O0.843, cuo = –16240 J·g-1 [24]. The corrections for nitric acid formation U(HNO3) were based –59.7 kJ.mol-1 [25], for the molar energy of formation of 0.1 mol.dm-3 HNO3(aq), from N2(g), O2(g) and H2O(l). An estimated pressure coefficient of specific energy, at T = 298.15 K, (u/p)T, was assumed to be –0.2 J.g-1.MPa-1, a common value for organic compounds [26]. The amount of substance, m(cpd), used in each experiment and on which the energy of combustion was based, was determined from the total mass of carbon dioxide produced, after allowance for that formed from the cotton thread fuse and of melinex. For each compound, the standard massic energy of combustion, Δcuº, was calculated by the procedure given by Hubbard et al. [27].
2.3. Knudsen effusion technique
The vapor pressures of the two studied compounds as a function of temperature were measured by the mass-loss Knudsen effusion technique using an apparatus previously described. A detailed description of the apparatus and measuring procedure, as well as the results obtained 5
with several test compounds has been reported before [28]. This apparatus enables the 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
simultaneous operation of nine aluminum effusion cells, which are placed in cylindrical holes inside three aluminum blocks, each one with three cells. Each block is maintained at a constant temperature, different from the other two blocks. There are three different groups of effusion cells according to their different areas of effusion orifices: series A (small orifices; Ao ≈ 0.5 mm2), series B (medium orifices; Ao ≈ 0.8 mm2), and series C (large orifices; Ao ≈ 1.1 mm2). The exact areas and the transmission probability factors (Clausing factors) of each effusion orifice, made in platinum foil of 0.0125 mm thickness, are presented in the Supporting Information, Table S1. The Clausing factors were calculated by equation (1) where l is the thickness of the effusion hole and r its radius: wo = {1 + (3 l /8r)}-1.
(1)
For each compound, the measurements were extended through a chosen temperature interval corresponding to measured vapor pressures in the range 0.1 Pa to 1.0 Pa. In a typical effusion experiment the loss of mass m of the samples, during a convenient effusion time period t, is determined by weighing the effusion cells to ± 0.01 mg before and after the effusion period in a system evacuated to a pressure near (1.10-4) Pa. At the temperature T of the experiment, the vapor pressure p is calculated by equation (2), p = (m / Aowo t) (2RT / M)1/2,
(2)
where Ao represents the area of the effusion orifice, wo is the respective Clausing factor, R is the gas constant and M is the molar mass of the effusing vapor.
3. Computational Details
Standard ab initio molecular orbital calculations [29] were performed with the Gaussian 09 series of programs [30]. The energies of the compounds studied were calculated using two different theoretical model chemistry Gaussian-n methods, at the G3 [31] and G4 [32] levels. Details on these methods have been given in our previous paper on glycine and alanine anhydrides [4].
6
Due to the lack of symmetry and the internal rotational degrees of freedom by free 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
rotation of the NHMe, COOH, and OH groups with respect to the carbon skeleton, sarcosine exhibits a large number of low-energy conformers. In this study we have optimized the molecular structures of 6 of its lowest-energy conformers, taking into account only those conformers that contribute significantly to the populated states. Energies at 0 K and enthalpies at 298 K, calculated at the G3 and G4 levels, for sarcosine anhydride and the lowest-energy conformers of sarcosine are collected in Tables S2 to S4 of the Supporting Information.
4. Experimental Results
Tables 2 and 3 show the combustion results obtained for sarcosine and sarcosine anhydride, in which m(H2O) represents the deviation of the mass of water added to the calorimeter from 3119.6 g, the mass assigned to calor, Tad is the calorimeter temperature change corrected for the heat exchange and the work of stirring, U is the correction to the standard state and the remaining terms are as previously defined [27,33].
As
samples were ignited at T =
(298.150 ± 0.001) K, the internal energy associated to the isothermal bomb process, U(IBP), was calculated through: U(IBP) = –{calor + cp(H2O, l)·m(H2O) + f } Tad + U(ign).
(3)
The values of cuo are referred to the combustion reactions, represented by equations (4) and (5) for sarcosine and sarcosine anhydride, respectively
C3H7NO2 (cr) + 3.75O2 (g) 3CO2 (g) + 0.5 N2 (g) + 3.5 H2O (l)
(4)
C6H10O2N2 (cr) + 7.5 O2 (g) 6CO2 (g) + 5H2O (l) + N2 (g)
(5)
TABLES 2 and 3 near here Table 4 list the derived standard molar energies and enthalpies of combustion and the standard molar enthalpies of formation for the compounds in the crystalline phase, at T = 298.15 K. In accordance with normal thermochemical practice, [34,35] the uncertainties assigned to the
7
standard molar energies and enthalpies of combustion are, in each case, twice the overall 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
standard deviation of the mean and include the uncertainties in calibration and in the values of o o auxiliary quantities used. To derive Δ f H m (cr) the standard molar enthalpies (cr) from Δ c H m
of formation of CO2(g) and H2O(l), at T = 298.15 K, –(393.51 ± 0.13) kJ.mol-1 [36] and – (285.830 ± 0.040) kJ.mol-1 [36], respectively, were used. TABLE 4 near here Table 5 presents the experimental results obtained through the effusion experiments. The subscripts A, B, C of the variables m and p stand, respectively, for the results obtained through the small (A1, A2, A3), the medium (B4, B5, B6), and the large (C7, C8, C9) effusion orifices. Table 6 presents, for each series of effusion orifices (A, B, C) and for the global treatment of all results, the parameters of the Clausius–Clapeyron equation, ln(p/Pa) = a – b.(T/K)–1, where a is a constant and b = gcr H mo (T) / R. The entropies of sublimation, at equilibrium conditions, were calculated as gcr S m {T, p(T = T)} = gcr H mo (T)/T.
(6)
TABLES 5 and 6 near here The plots of ln (p/ Pa) = f (1/T) for the global results of the two compounds studied experimentally are presented in figure 2. FIGURE 2 near here Sublimation enthalpies, at the temperature T = 298.15 K, were derived from the sublimation enthalpies calculated at the mean temperature T of the experiments as a result of the expression,
gcr H mo T 298.15 K gcr H mo T gcr Cp,o m 298.15 T ,
(7)
using gcr C op ,m (sarcosine) = –13.0 J·K-1·mol-1 and gcr C op ,m (sarcosine anhydride) = –27.0 J·K-1·mol-1,
calculated
from
the
values
of
the
gas-phase
molar
heat
capacities,
C op, m (g, sarcosine) = 105.2 J·K-1·mol-1 and C op, m (g, sarcosine anhydride) = 159.5 J·K-1·mol-1, at
8
T = 298.15 K, obtained in this work from statistical thermodynamics using the vibrational 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
frequencies from B3LYP/6-31G(d) calculations (scaled by the factor 0.9613 [37]), and from the respective literature values of molar heat capacities, in the crystalline phase: C op,m (cr, sarcosine) = 118.2 J·K-1·mol-1 [38] and C op,m (cr, sarcosine anhydride) = 186.5 J·K-1·mol-1 [39]. Table 7 presents, for each compound, the values, at T = 298.15 K, of the standard molar enthalpies of sublimation, the standard molar entropies of sublimation calculated by the equation (8), where po = 105 Pa, and the standard molar Gibbs energies of sublimation.
gcr S mo (T = 298.15 K) = gcr S m T , p( T ) + gcr Cp,o m ln(298.15K
/ T )
Rln p o /p(T )
(8)
For the studied compounds the standard molar enthalpies of formation in the gaseous state, at T = 298.15 K, obtained by the addition of the derived standard molar enthalpies of formation in the crystalline state with the standard molar enthalpies of sublimation, are summarized in Table 8. TABLE 7 near here 5. Theoretical Results
5.1. Molecular structures
The crystal structure of sarcosine was determined by X-ray diffraction by Mostad and Natarajan, in 1989 [40]. Amino acids exist as zwitterions in the crystalline state [41] as well as in aqueous solution, stabilized by electrostatic, polarization and hydrogen-bonding interactions with their environment. To our knowledge, there is not any experimental determination of the crystal structure of sarcosine anhydride. In the gas phase, where the intermolecular interactions have no effect, amino acids are intrinsically flexible systems, existing as their nonionized forms. To our knowledge, no experimental gas-phase structure determinations of sarcosine or sarcosine anhydride have been reported in the literature. B3LYP/6-31G(2df,p)-optimized geometries of sarcosine anhydride and the six lowest-energy conformers of sarcosine are shown in Figures3 and 4, respectively.
9
FIGURES 3 and 4 near here 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
The molecule of sarcosine anhydride is no planar, the atoms in one half molecule, the group
are almost exactly coplanar, but there is a slight twist of one of these groups with respect to the other half of the molecule, as it was observed in our previous study of amino acid anhydrides [4]. The most stable conformer I of sarcosine presents by a N–H···O=C hydrogen bond (2.60 Å) between the oxygen of the carboxylic group and the hydrogen atom of the NHMe group. The B3LYP/6-31G(2df,p)-optimized geometrical parameters for sarcosine anhydride and the most stable conformer of sarcosine have been collected in Tables S5 and S6 of the Supporting Information.
5.2. Theoretical Determination of the Enthalpies of Formation
Sarcosine anhydride G3 and G4-calculated energies at T = 0 K, and enthalpies at T = 298 K, for sarcosine anhydride are given in Table S2 in the Supporting Information. The values of the enthalpies of formation calculated at the G3 and G4 levels, using the standard procedure through atomization reactions [42,43] are shown in Table 8. There is a very good agreement between the experimental and calculated values.
TABLE 8 near here Sarcosine G3 and G4-calculated energies at T = 0 K, enthalpies at T = 298 K, and entropies, for the six lowest-energy conformers of sarcosine are given in Tables S3 and S4 of the Supporting Information, respectively. The conformational composition of sarcosine in the gas phase, at T = 298 K, can be calculated through equation (9):
10
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
xi
e
Grel ( i ) RT
n
e
(9)
Grel ( i ) RT
i 1
where ∆Grel(i) is the relative Gibbs energy of conformer i to the lowest energy conformer I, and can be calculated as:
Grel (i) Hrel (i) T Srel (i) [ H (i) H (I)] T [ S (i) S (I)]
(10)
∆Grel(i) values calculated at the G3 and G4 levels are collected in Tables S3 and S4 of the Supporting Information, respectively. Boltzmann weighted populations derived from Gibbs energies have also been collected in the same Tables. As can be observed, the lowest energy conformer of sarcosine, conformer I, accounts for 53.9 % (G3) and 63.4 % (G4) of the composition in the gas phase. Using equation (11): n
o f H m (X )
xi f H mo (i)
(11)
i 1
the final value for the enthalpy of formation of sarcosine is calculated as –387.4 and –387.3 kJ·mol-1, at the G3 and G4 levels, respectively, in perfect agreement with the experimental value determined in this work (see Table 8).
5. Discussion 5.1. Condensed phase and phase transition Sabbah and Laffitte [44] have measured the enthalpy of sublimation of sarcosine between 380–413 K and they have obtained the value of (146 ± 1) kJ·mol-1, which corrected to 298.15 K yields (147 ± 1) kJ·mol-1. They have also determined the standard molar enthalpy of formation, in the solid phase of sarcosine as, –(513.24 ± 0.26) kJ·mol-1 [45]. Cox and Pilcher [46] have reanalyzed the value of the standard molar enthalpy of formation obtained by Breitenbach, o (cr) = –(508.6 ± 1.3) kJ·mol-1 for Derkosch, et al. [47] and they recommended the value Δ f H m
11
sarcosine. There is a poor agreement between these reported values and the corresponding ones 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
determined in this work. With respect to the enthalpy of sublimation, our value differs of 17.8 kJ.mol-1 from the one determined by Sabbah and Laffitte. Regarding the values of enthalpies of o formation, our Δ f H m (cr) differs only 4 kJ.mol-1 from the value obtained by Sabbah and about 9
kJ.mol-1 from the reanalyzed value of Cox and Pilcher. Theoretical calculations of the gas phase standard molar enthalpy of formation of sarcosine were performed by Dorofeeva and Ryzhova [48] using the high-level Gaussian 4 method and they found a significant discrepancy between theoretical and experimental values, suggesting an inaccuracy of experimental data for this compound. In fact, the calculated value of Dorofeeva, –(389.0 ± 4) kJ.mol-1 is in agreement with our results, either the experimental and the computational ones.
5.2. Final Remarks Looking for data on related nitrogen heterocyclic compounds in order to evaluate the consistency of the present result for the enthalpy of formation of gaseous sarcosine anhydride and the previous one for the glycine anhydride [4], we have selected the uracil [49,50] and the 1,3-dimethyluracil [51]. Scheme 1 shows that the enthalpic increment for the methylation on the two nitrogens of the cycle of uracil is similar to that obtained for identical methylation on glycine anhydride. The coherency of these results constitutes another support for the reliableness of our studies on these cyclic polyfunctional peptides.
Scheme 1 near here
Acknowledgments Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal and to FEDER for financial support given to Centro de Investigação em Química da Universidade do Porto and to Programa Ciência 2008 (PEst-C/QUI/UI0081/2011). A.F.L.O.M.S thanks FCT and The European Social Fund (ESF) under the Community Support Framework (CSF) for the award of a post-doctoral fellowship (SFRH/BPD/41601/2007). The support of the Spanish Ministerio de Economía y Competitividad under Project CTQ2010-16402 is gratefully acknowledged.
12
Appendix A. Supporting information 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
This supporting information includes detailed data of the effusion orifices (diameter and Clausing factors) of the Knudsen apparatus the data, the G3 and G4-calculated energies and enthalpies and calculated bond distances and bond angles for the studied compounds. Supplementary data associated with this article can be found, in the online version, at doi:……..
13
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15
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65
Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian, Inc., Wallingford CT, 2009. [31] L.A. Curtiss, K. Raghavachari, P.C. Redfern, V. Rassolov, J.A. Pople, J. Chem. Phys. 109 (1998) 7764-7776. [32] L.A. Curtiss, P.C. Redfern, K. Raghavachari, J. Chem. Phys. 126 (2007) 084108. [33] E.F. Westrum, in: S. Sunner and M. Månsson, (Eds.), Combustion Calorimetry, Pergamon Press, Oxford, 1979 (Chapter 7). [34] F.D. Rossini, in: F.D. Rossini (Ed.), Experimental Thermochemistry, vol.1, Interscience, New York 1956 (Chapter 14). [35] G. Olofsson in: S. Sunner, M. Månsson (Eds.), Combustion Calorimetry, Pergamon Press, Oxford 1979 (Chapter 6). [36] J.D.Cox, D D. Wagman, V.A. Medvedev, CODATA Key Values for Thermodynamics, Hemisphere, New York 1989. [37] J.P. Merrick, D. Moran, L. Radom, J. Phys. Chem. A 111 (2007) 11683-11700. [38] M.V. Roux, R. Notario, M. Segura, R. Guzmán-Mejía, E. Juaristi, J.S. Chickos, J. Chem. Eng. Data 56 (2011) 3807-3812. [39] L. Abate, B. Pałecz, C. Giancola, G. Della Gatta, J. Chem. Thermodyn. 29 (1997) 359-368. [40] A. Mostad, S. Natarajan, Acta Chem. Scand. 43 (1989) 1004-1006 [41] F.H. Allen, Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 58 (2003) 380388. [42] R. Notario, O. Castaño, J.-L.M. Abboud, R. Gomperts, L.M. Frutos, R. Palmeiro, J. Org. Chem. 64 (1999) 9011-9014. [43] R. Notario, O. Castaño, R. Gomperts, L.M. Frutos, R. Palmeiro, J. Org. Chem. 65 (2000) 42984302. [44] R. Sabbah, M. Laffitte, Bull. Soc. Chem. France 1 (1978) 50-52. [45] R. Sabbah, M. Laffitte, J. Chem. Thermodyn. 9 (1977) 1107-1108. [46] J.D. Cox, G. Pilcher, Thermochemistry of Organic and Organometallic Compounds, Academic Press, New York 1970. [47] J.W. Breitenbach, J. Derkosch, F. Wessely, Monatsh. Chem. 83 (1952) 591-593. [48] O.V. Dorofeeva, O.N Ryzhova, J. Chem Thermodyn. 42 (2010) 1056-1062. [49] P.M. Nabavian, R. Sabbah, R. Chastel, M. Laffitte, J. Chim. Phys. 74 (1977) 115-126. [50] P. Szterner, M. Kamiński, A. Zielenkiewicz, J. Chem. Thermodyn. 34 (2002) 1005-1012.
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[51] A. Imamura, K. Takahashi, S. Murata, M. Sakiyama, J. Chem. Thermodyn. 21 (1989) 237246.
17
TABLE 1 Provenance and purity of the compounds studied
Chemical Name
Sarcosine (cr)
CAS
Provenance
107-97-1
Aldrich Chemical Co.
Initial Molar Final Molar Purification Fraction Fraction Method Purity Purity 0.98
Sarcosine anhydride 5076-82-4 Acros Organics 0.99 (cr) ª Quantity of carbon dioxide recovered in the combustion experiments
Analysis Method
Sublimation
0.99995
a
CO2 recovery
Sublimation
0.99991
a
CO2 recovery
TABLE 2 Standard massic energy of combustion of sarcosine, at T = 298.15 K
m(cpd) / g
1 0.77367
2 0.62211
3 0.71851
4 0.74125
5 0.80945
6 0.83540
m’(fuse) / g
0.00260
0.00235
0.00231
0.00278
0.00274
0.00331
m’’(melinex) / g
0.04589
0.04198
0.04547
0.04206
0.04596
0.04627
Tad / K
0.97930
0.79503
0.91392
0.93610
1.02217
1.05294
16.71
16.24
16.46
16.51
16.73
16.87
m(H2O) / g
0.0
0.0
0.0
0.0
0.0
0.0
U(IBP)a / J
15591.55
12657.25
14550.32
14903.46
16274.04
16764.15
U(melinex) / J
1050.86
961.54
1041.26
63.36
1052.69
1059.77
U(fuse) / J
42.22
38.16
37.51
45.15
44.50
53.75
U(HNO3) / J
43.94
37.67
50.98
47.10
48.48
48.77
U(ign) / J
0.58
0.64
0.62
0.67
0.67
0.62
U / J
11.09
8.86
10.20
10.48
11.58
11.97
18668.73
18663.93
18664.14
18667.62
18675.38
18661.59
f / (J.K-1)
cuo / J.g-1
cuo / J.g-1 a
U(IBP) already includes the U(ign)
TABLE 3 Standard massic energy of combustion of sarcosine anhydride, at T = 298.15 K
m(cpd) / g
1 0.61843
2 0.72154
3 0.75961
4 0.79499
5 0.79672
6 0.81277
7 0.81367
m’(fuse) / g
0.00295
0.00275
0.00287
0.00301
0.00245
0.00245
0.00312
Tad / K
0.92275
1.07502
1.13114
1.18435
1.18600
1.21013
1.21342
15.92
16.18
16.28
16.36
16.38
16.45
16.37
m(H2O) / g
0.0
0.0
0.0
0.0
0.0
0.1
0.0
U(IBP)a / J
14691.80
17116.60
18010.30
18857.66
18884.06
19268.81
19320.44
U(fuse) / J
47.91
44.66
46.61
48.88
39.79
39.79
50.67
U(HNO3) / J
49.79
49.79
51.82
61.37
59.40
57.43
65.67
U(ign) / J
0.70
0.71
0.71
0.70
0.59
0.66
0.81
U / J
9.98
11.85
12.53
13.07
13.10
13.44
13.35
23582.49
23574.99
23563.86
23565.50
23561.31
23571.43
23585.42
f / (J.K-1)
cuo / J.g-1
cuo / J.g-1 a
U(IBP) already includes the U(ign)
m(cpd) is the mass of compound burnt in each experiment; m’(fuse) is the mass of the fuse (cotton) used in each experiment; ; m’’(melinex) is the mass of melinex; Tad is the corrected temperature rise; f is the energy equivalent of the contents in the final state; m(H2O) is the deviation of mass of water added to the calorimeter from 3119.6 g; U(IBP) is the energy change for the isothermal combustion reaction under actual bomb conditions; U(melinex) is the energy of combustion of melinex; U(fuse) is the energy of combustion of the fuse (cotton); U(HNO3) is the energy correction for the nitric acid formation; U(ign) is the electric energy for the ignition; U is the standard state correction; cuo is the standard massic energy of combustion.
TABLE 4 Derived standard (po = 0.1 MPa) molar energy of combustion, c U mo , standard molar enthalpy of combustion, c H mo , and standard molar enthalpy of formation, f H mo , for the crystalline compounds, at T = 298.15 K
Compound
c U mo cr kJ mol 1
c H mo cr kJ mol 1
f H mo cr kJ mol 1
Sarcosine
1663.1 ± 0.6
1663.7 ± 0.6
517.2 ± 0.7
Sarcosine anhydride
3350.9 ± 1.3
3352.1 ± 1.3
438.1 ± 1.5
TABLE 5 Knudsen effusion results for sarcosine and sarcosine anhydride T/K
t/s
Orifices
m / mg mA
mB
mC
p / Pa pA
pB
pC
Sarcosine 403.16
10442
A1-B4-C7
12.27
19.16
27.31
1.151
1.164
1.166
401.15
10442
A2-B5-C8
10.53
16.22
23.52
0.972
0.971
0.978
399.14
10442
A3-B6-C9
8.59
13.45
19.39
0.801
0.794
0.800
397.13
16623
A1-B4-C7
10.97
16.99
24.18
0.641
0.644
0.644
395.10
16623
A2-B5-C8
8.97
14.02
19.68
0.516
0.523
0.510
393.14
16623
A3-B6-C9
7.43
11.47
16.24
0.432
0.422
0.418
391.12
23947
A1-B4-C7
9.02
13.74
19.31
0.363
0.359
0.354
389.10
23947
A2-B5-C8
7.35
11.23
15.14
0.291
0.289
0.271
387.14
23957
A3-B6-C9
5.83
9.07
12.75
0.233
0.230
0.226
385.13
27335
A1-B4-C7
5.67
8.75
12.25
0.198
0.198
0.195
383.12
27335
A2-B5-C8
4.65
7.16
10.08
0.160
0.160
0.156
381.15
27335
A3-B6-C9
3.80
5.80
8.15
0.132
0.128
0.126
Sarcosine anhydride 351.10
10492
A1-B4-C7
17.26
26.32
37.54
1.190
1.176
1.179
349.14
10492
A2-B5-C8
14.47
22.17
30.57
0.982
0.975
0.935
347.16
10492
A3-B6-C9
12.41
18.26
25.31
0.796
0.793
0.768
345.09
14552
A1-B4-C7
13.48
21.10
28.62
0.664
0.674
0.642
343.14
14552
A2-B5-C8
11.20
16.90
23.59
0.543
0.532
0.516
341.17
14552
A3-B6-C9
8.86
13.91
19.23
0.423
0.432
0.417
339.08
15407
A1-B4-C7
7.25
11.45
16.33
0.335
0.342
0.343
337.13
15407
A2-B5-C8
5.96
9.42
13.34
0.271
0.277
0.273
335.18
15407
A3-B6-C9
5.36
7.81
11.03
0.240
0.227
0.224
333.08
15137
A1-B4-C7
3.85
5.97
8.43
0.179
0.180
0.179
331.13
15137
A2-B5-C8
3.10
4.73
6.63
0.142
0.140
0.137
329.18
15137
A3-B6-C9
2.62
3.84
5.46
0.118
0.112
0.112
TABLE 6 Experimental results for sarcosine and sarcosine anhydride, where a and b are from the Clausius-Clapeyron equation, ln (p/Pa) = a – b · (K/T) and b = gcr H mo T / R; R = 8.314472 J·K - 1 ·mol - 1 Orifices
a
b
T
pT
gcr H mo T
gcr S m T , pT
K
Pa
kJ mol1
J K 1 mol 1
Sarcosine A1-A2-A3
37.91 0.32
15226 125
126.6 ± 1.0
B4-B5-B6
38.31 0.33
15386 130
127.9 ± 1.1
C7-C8-C9
38.82 0.42
15590 163
129.6 ± 1.4
Global results
38.34 0.22
15400 85
392.16
0.395
128.0 ± 0.7
326.4 ± 1.8
Sarcosine anhydride A1-A2-A3
35.13 0.39
12274 134
102.0 1.1
B4-B5-B6
35.49 0.25
12396 84
103.1 0.7
C7-C8-C9
35.18 0.26
12298 88
102.2 0.7
Global results
35.27 0.20
12322 66
340.14
0.384
102.5 0.5
301.3 1.5
TABLE 7 Values of the standard (po = 0.1 MPa) molar enthalpy, gcr H mo , entropy, gcr S mo , and Gibbs energy gcr Gmo , of sublimation, at T = 298.15 K, for sarcosine and sarcosine anhydride gcr H mo kJ mol 1
gcr S mo J K 1 mol 1
gcr Gmo kJ mol 1
Sarcosine
129.2 0.7
226.5 1.8
61.7 0.9
Sarcosine anhydride
103.6 ± 0.5
201.2 ± 1.5
43.6 ± 0.7
Compound
TABLE 8 G3- and G4-calculated enthalpies of formation of sarcosine and sarcosine anhydride f H mo g kJ mol 1
Compound
G3
G4
experimental
Sarcosine
387.4
387.3
(388.0 ± 1.0)a (367.2 ± 1.0)b
Sarcosine anhydride
340.1
337.8
(334.5 ± 1.6)a
a
This work. b Taken from ref [44].
0.5 OH
0.0
O NH
ln (p / Pa)
-0.5
-1.0
O
-1.5 N
N
-2.0 O
-2.5 2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
1000 K / T
FIGURE 2. Plots of ln(p / Pa) against 1 / T for sarcosine and sarcosine anhydride
FIGURE 3. B3LYP/6-31G(2df,p)-optimized structure of sarcosine anhydride
I
II
III
IV
V
VI
FIGURE4. B3LYP/6-31G(2df,p)-optimized structures of the six lowest-energy conformers of sarcosine
Figure
HN
O
N
(14.9 ± 4.6) kJ·mol-1 O
N H
N
uracil 1,3-dimethyluracil (313.6 ± 1.5) kJ·mol-1[51]
(298.7 ± 4.4) kJ·mol-1[49,50]
H N
O
(13.5 ± 2.5) kJ·mol
O
N H
N
O
-1
O
N
glycine anhydride (321.0 ± 1.9) kJ·mol-1[4]
sarcosine anhydride (334.5 ± 1.6) kJ·mol-1
Scheme 1. Enthalpic increments for the methylation on the two nitrogen atoms in uracil and glycine anhydride.
Figure
0.5 OH
0.0
O NH
ln (p / Pa)
-0.5
-1.0
O
-1.5 N
N
-2.0 O
-2.5 2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
1000 K / T
FIGURE 2. Plots of ln(p / Pa) against 1 / T for sarcosine and sarcosine anhydride
FIGURE 3. B3LYP/6-31G(2df,p)-optimized structure of sarcosine anhydride
I
II
III
IV
V
VI
FIGURE 4. B3LYP/6-31G(2df,p)-optimized structures of the six lowest-energy conformers of sarcosine
Scheme
HN
O
N
(14.9 ± 4.6) kJ·mol-1 O
N H
N
uracil 1,3-dimethyluracil (313.6 ± 1.5) kJ·mol-1[51]
(298.7 ± 4.4) kJ·mol-1[49,50]
H N
O
(13.5 ± 2.5) kJ·mol
O
N H
N
O
-1
O
N
glycine anhydride (321.0 ± 1.9) kJ·mol-1[4]
sarcosine anhydride (334.5 ± 1.6) kJ·mol-1
Scheme 1. Enthalpic increments for the methylation on the two nitrogen atoms in uracil and glycine anhydride.
*Highlights (for review)
Study on the Energetics of the Sarcosine and Sarcosine Anhydride Experimental and Computational Thermochemistry of Sarcosine and its Anhydride Ab initio calculations for two amino acid derivatives by G3(MP2)//B3LYP method