Article pubs.acs.org/jced
Calorimetric Studies of the Interactions between Several Aminophosphonic Acids and Urea in Aqueous Solutions at 298.15 K Bartłomiej Palecz,*,† Aleksandra Grala,† and Zbigniew Kudzin‡ †
Department of Physical Chemistry, and ‡Department of Organic Chemistry, University of Lodz, 90-416 Lodz, Poland ABSTRACT: The enthalpies of solution of 1-aminobutylphosphonic acid (NvalP), 1-amino-2-methylpropylphosphonic acid (ValP), 1-amino-3-(methylthio)propylphosphonic acid (MetP), N-methyl-1-aminopropylphosphonic acid (Me-HalP), and N,N-dimethyl-1-aminopropylphosphonic acid (Me2-HalP) in water and aqueous urea solutions were measured within the molality range from (0.5 to 4) mol (U)·kg−1 (H2O) at a temperature of 298.15 K. The results obtained were used to determine the standard enthalpies of solution, whose values were then used to calculate the enthalpic heterogeneous pair (phosphonic amino acid−urea) interaction coefficients.
1. INTRODUCTION Aminophosphonic acids constitute an important class of the analogue of natural amino acids. They differ from amino acids in the presence of a phosphonic instead of carboxylic group. Their structural similarity results in interesting biological properties such as enzyme inhibition,1−3 antiviral activity,4 antineoplastic activity,5,6 and antagonistic effects against neural receptors.7 Aminophosphonic acids (Figure 1) were discovered in micro-organisms,8,9 especially in marine microorganisms,
urea is used as an additive to cosmetics and occurs in animal foodstuff, it is a component of many chemical fertilizers. The aim of this research was to study the interaction between aminophosphonic acid molecules and urea taking place in water. This paper presents calorimetric studies of the enthalpy of solution of the phosphonic derivatives of valine (ValP and NvalP) and methionine (MetP) and two N-methyl derivatives of homoalanine: N-methyl-1-aminopropylphosphonic acid (MeHalP) and N,N-dimethyl-1-aminopropylphosphonic acid (Me2HalP) in water and aqueous solutions of urea at 298.15 K. The values obtained were used to determine the standard enthalpy of solution of phosphonic amino acids that were used then to calculate the enthalpic heterogeneous pair interaction coefficients (hPU) by means of the modified29,30 theory of McMillan−Mayer.31 The enthalpic coefficients, hPU, describe the energetic effects of the interactions between the molecules of aminophosphonic acid and urea occurring with the competitive participation of solvent molecule, in the case under discussion, water molecules. The enthalpic pair interaction coefficients between aminophosphonic acids and urea one can treat as a parameter describing hydrophilic− hydrophobic properties of a side chains.26 Therefore it is worth investigating the effect of replacing hydrogen atoms in the amino group by methyl substituents.
Figure 1. Structure of aminophosphonic acid.
among other things in sea anemones10 or in invertebrates.11 Trace quantities of aminophosphonic acids, including 2aminoethanphosphonic acid (AEP) were found in the organisms of vertebrates: goat liver,12 bovine brain,13 and human brain.14 Phosphonic derivatives also find their use in agriculture as plant growth regulators, one of the most popular is phosphonomethylglycine (glyphosine, PMG) synthesized by Franz in the seventies.15 Calorimetry is the experimetal method which enables us to determine the efects of the interactions between several solution’s ingredients. Many scientific centers are carrirng out research on physical properties of amino acids, peptides, and proteins using calorimetric method. This technique is useful for measuring the enthalpy of dissolution,16−19 dilution,20−23 and mixing.24,25 Our laboratory has long carried out studies on the interactions of L-α-amino acids with the components of body fluids, among other things, urea.26−28 As aminophosphonic acids are disseminated in the environment, it is of interest to assess their interactions with urea occurring in vertebrate organisms as a component of the urea cycle. In the industry, © 2014 American Chemical Society
2. EXPERIMENTAL SECTION 2.1. Materials. The phosphonic amino acids used in the studies (Table 1) were synthesized in the following way: 1aminobutylphosphonic acid (NvalP),32 1-amino-2-metylhpropylphosphonic acid (ValP,)32 and 1-amino-3-(methylthio)propylphosphonic acid (MetP)33 by Ptc-aminophosphonate method;34 1-(N-methylamino)propyl-phosphonic acid (MeHalP) by the classical hydrophosphonylation35 of propanal Nmethylimine; and 1-(N,N-dimethylamino)propyl-phosphonic acid (Me2-HalP)36 by the classical Kabachnik-Fields condensaReceived: October 9, 2013 Accepted: January 6, 2014 Published: January 13, 2014 426
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
Table 1. Names, Abbreviations, and Structures of Aminophosphonic Acids Discussed in this Worka name
abbreviation
aminomethylphosphonic acid 1-aminoethylphosphonic acid 1-aminopropylphosphonic acid 1-aminobutylphosphonic acid 1-amino-2-methylpropyl-phosphonic acid 1-amino-3-(methylthio)propyl-phosphonic acid 1-(N-methylamino)propyl-phosphonic acid 1-(N,N-dimethylamino)propyl-phosphonic acid
GlyP AlaP HalaP NvalP ValP MetP Me-HalP Me2-HalP
RH CH3 CH3CH2 CH3CH2CH2 (CH3)2CH CH3−S-CH2CH2 CH3CH2 CH3CH2
R′
R″
H H H H H H CH3 CH3
H H H H H H H CH3
a
Applied names were in accordance with the JUPAC rules, and the abbreviations were in agreement with the general rules elaborated by Kudzin at al.34,37
Table 2. Enthalpies of Solution of 1-Amino-2-methylpropylphosphonic Acid (ValP) in Water (W) and Aqueous Urea (W+U) Solutions at 298.15 K and 0.1 MPaa 1.0 mol(U)·kg−1(W)
water (W) ΔsolH0m
m −1
mol(P)·kg (W)
−1
kJ·mol
0.001312 −0.15 0.001438 −0.10 0.001453 −0.12 0.001551 −0.10 0.001175 −0.09 0.001659 −0.08 4.0 mol(U)·kg−1(W) 0.001300 −2.19 0.001400 −2.30 0.001441 −2.32 0.001486 −2.12 0.001561 −2.16
m −1
mol(P)·kg (W+U)
2.0 mol(U)·kg−1(W)
ΔsolH0m
m
−1
−1
kJ·mol
mol(P)·kg (W+U)
−0.70 −0.66 −0.66 −0.69 −0.71
0.000865 0.00154 0.001594 0.001757 0.001819
3.0 mol(U)·kg−1(W)
ΔsolH0m −1
kJ·mol
−1.23 −1.11 −1.09 −1.18 −1.25
0.001031 0.001091 0.001298 0.001328 0.001488
m −1
ΔsolH0m
mol(P)·kg (W+U)
kJ·mol−1
0.000861 0.000922 0.001252 0.001385 0.001433
−2.37 −2.32 −2.26 −2.26 −2.19
a Standard uncertainties are u(T) = 0.005 K, u(p) = 0.1 kPa, u(mU) = 0.001 mol·kg−1, u(mP) = 0.000001 mol·kg−1, the combined expanded uncertainty Uc(ΔsolH0m) is 20 J·mol−1 with a 0.95 level of confidence (k ≈ 2).
Table 3. Enthalpies of Solution of 1-Aminobutylphosphonic Acid (NvalP) in Water (W) and Aqueous Urea (W+U) Solutions at 298.15 K and 0.1 MPaa 0.5 mol(U)·kg−1(W)
water (W) m
ΔsolH0m
mol(P)·kg−1(W)
kJ·mol−1
0.000783 −1.98 0.000810 −1.99 0.000860 −2.18 0.000893 −2.17 0.000957 −2.19 2.5 mol(U)·kg−1(W) 0.000961 −3.73 0.001081 −3.62 0.001094 −3.61 0.001125 −3.69 0.001162 −3.60
m
ΔsolH0m
mol(P)·kg−1(W+U)
kJ·mol−1
1.0 mol(U)·kg−1(W)
0.000939 −2.33 0.000937 −2.33 0.001074 −2.35 0.001095 −2.40 0.001157 −2.35 3.0 mol(U)·kg−1(W) 0.000957 −3.65 0.001022 −3.81 0.000635 −3.69 0.001159 −3.79 0.001229 −3.82
2.0 mol(U)·kg−1(W)
m
ΔsolH0m
m
ΔsolH0m
mol(P)·kg−1(W+U)
kJ·mol−1
mol(P)·kg−1(W+U)
kJ·mol−1
0.000731 0.000853 0.000865 0.000951 0.001157
−2.69 −2.81 −2.64 −2.65 −2.82
0.00078 0.000928 0.000986 0.001045 0.001141
−3.47 −3.58 −3.54 −3.44 −3.56
a Standard uncertainties are u(T) = 0.005 K, u(p) = 0.1 kPa, u(mU) = 0.001 mol·kg−1, u(mP) = 0.000001 mol·kg−1, the combined expanded uncertainty Uc(ΔsolH0m) is 20 J·mol−1 with a 0.95 level of confidence (k ≈ 2).
tion.36 Purity of all phosphonic amino acids is estimated about 0.99 mass fraction. KCl (Sigma, mass fraction ≥ 0.995) used for calibration the calorimeter was dried under vacuum at a temperature 373 K for 48 h. Urea (U; Aldrich, mass fraction ≥ 0.995) and the remaining substances were dried at a temperature of 333 K under vacuum for 48 h. The water used in measurements was
distilled three time and degassed. Urea solutions were prepared by weight with an accuracy of ± (10−2) mol·kg−1. Ampules with the phosphonic amino acids dissolved were prepared with the use of a Mettler AE 240 balance with an accuracy of ± (2·10−5) g. 2.2. Measurements of Enthalpy of Solution. The enthalpy of solution was measured at a temperature of 298.15 427
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
Table 4. Enthalpies of Solution of 1-Amino-3-(methylthio)propylphosphonic Acid (MetP) in Water (W) and Aqueous Urea (W +U) Solutions at 298.15 K and 0.1 MPaa 1.0 mol(U)·kg−1(W)
water (W) m
ΔsolH0m
mol(P)·kg−1(W) 0.000677 0.000694 0.000775 0.000849 0.001032 0.001043
2.5 mol(U)·kg−1(W)
m
ΔsolH0m
kJ·mol−1
mol(P)·kg−1(W+U)
11.69 11.85 11.66 11.70 11.75 11.68
0.000599 0.000815 0.000988 0.001033 0.001066 0.001083
3.0 mol(U)·kg−1(W)
m
ΔsolH0m
m
ΔsolH0m
kJ·mol−1
mol(P)·kg−1(W+U)
kJ·mol−1
mol(P)·kg−1(W+U)
kJ·mol−1
11.15 10.75 11.02 10.86 11.10 10.80
0.000507 0.000626 0.000688 0.000777 0.001003
8.97 8.95 8.87 8.90 8.97
0.000614 0.000752 0.000836 0.000891 0.000957
8.43 8.42 8.39 8.38 8.29
a Standard uncertainties are u(T) = 0.005 K, u(p) = 0.1 kPa, u(mU) = 0.001 mol·kg−1, u(mP) = 0.000001 mol·kg−1, the combined expanded uncertainty Uc(ΔsolH0m) is 40 J·mol−1 with a 0.95 level of confidence (k ≈ 2).
Table 5. Enthalpies of Solution of N-Methyl-1-amino-propylphosphonic (Me-HalaP) in Water (W) and Aqueous Urea (W+U) Solutions at 298.15 K and 0.1 MPaa 1.0 mol(U)·kg−1(W)
water (W) m
ΔsolH0m
mol(P)·kg−1(W)
kJ·mol−1
0.000548 −7.16 0.000864 −7.00 0.000996 −7.23 0.001029 −6.98 0.001118 −7.08 0.001133 −7.05 3.0 mol(U)·kg−1(W) 0.00088 −8.33 0.001005 −8.40 0.001089 −8.32 0.001091 −8.33 0.001212 −8.30
1.5 mol(U)·kg−1(W)
m
ΔsolH0m
mol(P)·kg−1(W+U) 0.000852 0.000897 0.000954 0.001023 0.001139 0.001188
2.0 mol(U)·kg−1(W)
m
ΔsolH0m
m
ΔsolH0m
kJ·mol−1
mol(P)·kg−1(W+U)
kJ·mol−1
mol(P)·kg−1(W+U)
kJ·mol−1
−7.94 −8.00 −7.93 −8.10 −7.96 −8.05
0.000845 0.000908 0.000963 0.00108 0.001188
−7.99 −8.17 −8.04 −7.99 −8.09
0.000931 0.001027 0.001049 0.001091 0.001157
−8.08 −8.10 −8.10 −8.26 −8.03
Standard uncertainties are u(T) = 0.005 K, u(p) = 0.1 kPa, u(mU) = 0.001 mol·kg−1, u(mP) = 0.000001 mol·kg−1, the combined expanded uncertainty Uc(ΔsolH0m) is 30 J·mol−1 with a 0.95 level of confidence (k ≈ 2). a
Table 6. Enthalpies of Solution of N,N-Dimethyl-1-amino-propylphosphonic (Me2-HalaP) in Water (W) and Aqueous Urea (W +U) Solutions at 298.15 K and 0.1 MPaa 1.0 mol(U)·kg−1(W)
water (W) ΔsolH0m
m −1
mol(P)·kg (W) 0.000502 0.000969 0.000855 0.001020 0.001050
−1
kJ·mol
−7.13 −7.18 −7.15 −7.14 −7.17
2.5 mol(U)·kg−1(W) 0.000886 −8.67 0.000844 −8.65 0.000935 −8.67 0.000936 −8.67 0.001026 −8.65 0.001105 −8.65
m −1
mol(P)·kg (W+U)
1.5 mol (U)·kg−1(W)
ΔsolH0m
m
−1
−1
kJ·mol
mol(P)·kg (W+U)
0.001135 −8.30 0.000846 −8.29 0.000791 −8.33 0.000875 −8.38 0.000879 −8.39 0.001069 −8.35 3.0 mol(U)·kg−1(W) 0.000647 −9.88 0.000921 −9.81 0.000946 −9.86 0.001018 −9.88 0.001021 −9.87 0.001064 −9.68
0.000563 0.000576 0.000657 0.000828 0.001019 0.001218
2.0 mol(U)·kg−1(W)
ΔsolH0m −1
kJ·mol
−8.52 −8.56 −8.55 −8.52 −8.51 −8.69
m −1
ΔsolH0m
mol(P)·kg (W+U)
kJ·mol−1
0.000841 0.000849 0.000924 0.000925 0.000990 0.001000
−8.78 −8.63 −8.59 −8.72 −8.54 −8.71
Standard uncertainties are u(T) = 0.005 K, u(p) = 0.1 kPa, u(mU) = 0.001 mol·kg−1, u(mP) = 0.000001 mol·kg−1, the combined expanded uncertainty Uc(ΔsolH0m) is 30 J·mol−1 with a 0.95 level of confidence (k ≈ 2). a
K, using an isoperibol calorimeter38 with a volume of 120 mL. A digital AxioMet AX-178 (Poland) recorder linked to a computer was used instead of analog recorder. Data were calculated in Microsoft Excel 2003 (Office Packet). The
calorimeter was placed in a water thermostat with a temperature stability of ± (5·10−3) K. The uncertainty of experimental measurements, which is connected with uncertainty of every apparatus building the calorimeter, was about 428
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
Table 7. Standard Enthalpies of Solution of α-Aminophosphonic Acids (P) in Water (W) and Aqueous Urea (W+U) Solutions at 298.15 Ka ΔsolHm0 (W + U)/kJ·mol−1 mU/mol(U)·kg
−1
H2O
0 0.5 1.0 1.5 2.0 2.5 3.0 4.0 a
Val
P
−0.11 ± 0.01 −0.68 ± 0.02 −1.17 ± 0.07 −2.28 ± 0.07 −2.22 ± 0.09
MetP
Me-HalP
Me2-HalP
−2.10 ± 0.11 −2.35 ± 0.03 −2.72 ± 0.09
11.72 ± 0.07
−7.08 ± 0.11
−7.16 ± 0.02
10.95 ± 0.14
−3.52 ± 0.09 −3.65 ± 0.06 −3.75 ± 0.09
8.83 ± 0.04
−8.00 ± 0.09 −8.054 ± 0.08 −8.12 ± 0.09
8.38 ± 0.05
−8.33 ± 0.04
Nval
P
−8.34 −8.56 −8.66 −9.46 −9.83
± ± ± ± ±
0.04 0.07 0.09 0.09 0.07
± is the standard deviation.
Table 8. Values of the Heterogenous Pair (hPU) and Triplet Interaction (hPUU) Coefficients for Aminophosphonic Acids with Urea in Water and Heterogenous Pair Interaction Coefficients for Natural Amino Acids with Urea in Water (hAU)26 hAU/J·kg·mol−2
a
Gly Ala Aba (Hala) Val
−390.2 −238.2 −185 −116
Met
−180
hPU/J·kg·mol−2 Pa
Gly AlaPa HalaPa ValP NvalP MetP Me-HalP Me2-HalP
−1151 −666 −476 −354 −387 −637 −466.5 −487
± ± ± ± ± ± ± ±
92 69 32 100 65 150 94 91
hPUU/J·kg2·mol−3 150 67 48 12 22 7 58 11
± ± ± ± ± ± ± ±
24 18 8 9 6 5 21 10
Values from ref 28. ± is the standard deviation.
where mU is the urea molality, hPU is the enthalpic heterogeneous pair interaction coefficient of aminophosphonic acid and urea molecules, and hPUU is the coefficient of the interaction of three molecules. The interpretation of the triplet coefficient will be omitted as it also contains the pairwise interaction terms.44 The enthalpic coefficient, hPU, describes the sum of the thermal effects of interactions between polar and ionic groups of the molecules discussed in an infinitely diluted aqueous solution (exothermic effect). The interacting molecules under discussion are hydrated, so to cause their direct interaction, some water molecules must be removed from their hydration layers constituting a steric hindrance impeding direct approach. The endothermic effect of partial dehydration is intensified by the processes of hydrophobic hydration induced by the nonpolar groups of aminophosphonic side substituents.45 Hydrogen bonds between water molecules in the direct neighborhood of nonpolar chains are strengthened due to the co-operation capability of bonds. This effect is also transmitted on water molecules surrounding polar and ionic groups. The process of hydrophobic hydration causes the necessity of increase in the energy indispensable for their partial dehydration, and thereby the total effect described by enthalpic coefficients, hPU, becomes more endothermic. The pair interaction coefficients determined are negative in the case of all compounds under investigation (Table 8). It was observed in the series of compounds discussed that the values of hPU increase in the following order GlyP < AlaP < HalaP < ValP ≤ NvalP. The substitution of hydrogen atom in the molecule of aminomethylphosphonic acid with an alkyl group increases the endothermic dehydration effect of adjoining polar or ionic functional groups, which results in the attenuation of the summary interaction (see Table 8). Figure 2 shows the dependence of enthalpic interaction coefficients, hPU, on the
1 % of the value measured. The calorimeter was tested by measuring the enthalpy of solution of urea and KCl. Obtained standard enthalpies of solution were (15.31 ± 0.04) kJ·mol−1 for urea and (17.28 ± 0.02) kJ·mol−1 for KCl, and these results were in good agreement with literature data: 15.30 kJ·mol−1 (Desnoyer)39 and 15.29 kJ·mol−1 (Schrier)40 for urea and (17.251 ± 0.018) kJ·mol−1 (Kilday),41 (17.207 ± 0.092) kJ· mol−1 (Sanahuja),42 and 17.29 kJ·mol−1 (Piekarski)43 for KCl. A total of 5 to 6 independent measurements of the enthalpy of solution of the phosphonic amino acids within the concentration range of (0.0005 to 0.002) mol(P)·kg−1(solvent) were made in both water and aqueous urea solutions with concentration from (0.5 to 4) mol(U)·kg−1(H2O). The values of standard enthalpies of solution were determined as mean values of 5−6 measurements of solution enthalpies in every molality of urea in water. 2.3. pH Measurements. The measurements of pH were made by means of an EMU analyzer (Technical University of Wroclaw, Poland) connected to a combined glass electrode ESAgP-301WM (EUROSENSOR, Poland). The pH system was calibrated using standard solutions (2 < pH < 10), and measurements were carried out at a room temperature.
3. RESULTS AND DISCUSSION Tables 2−6 contain values of solution enthalpies of studied compounds in water and urea aqueous solutions. The values of standard enthalpies of solution in water ΔsolH0(W) and aqueous urea solutions ΔsolH0(W+U) (Table 7) were used to calculate the enthalpic pair interaction coefficients of aminophosphonic acid zwitterion and urea molecule, using the equation proposed by Desnoyers:39 0 0 2 Δsol H(W + U) = Δsol H(W) + 2hPU mU + 3hPUU mU + ...
(1) 429
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
Figure 2. Dependence of the enthalpic pair interaction coefficients (hPU) of aminoalkylphosphonic acid−urea molecules in water on the number of CH2 groups in the side chain of aminophosphonic acid molecules.
Figure 3. Relationship between the enthalpic pair interaction coefficients (hPU) of aminoalkylphosphonic acid−urea molecule in water and the enthalpic pair interaction coefficients (hAU) of natural amino acid−urea molecule in water.
the endothermic effect of the dehydration of polar molecules that increases with increasing number of hydrophobic methyl groups at the nitrogen atom; (2) the exothermic effect connected with the interaction of the more acidic zwitterion head of aminophosphonic acid interaction with urea molecule. The acidity of the N-methyl derivatives investigated increases in the following sequence: HalaP < Me-HalP < Me2-HalP. Table 9 contains the pH values of aqueous solutions HalaP, Me-HalP, and Me2-HalP with concentrations from (0.0005 to
number of methylene groups (using Savage and Wood’s conception,46 according to which CH3 = 1.5 CH2; CH = 0.5 CH2). The absence of a linear dependence indicates that the contribution of successive CH2 groups inducing the effect of hydrophobic hydration, more remote from the “zwitterion head”, is weaker. The interaction of 1-amino-3-(methylthio)propylphosphonic acid with urea is stronger than in the case of aminopropylphosphonic acid but weaker than that of aminoethylphosphonic acid. This fact indicates that hydrophobicity of CH3−S-CH2−CH2- substituent is between ethyl and propyl group. The enthalpic heterogeneous pair interaction coefficients of both aminophosphonic acids and natural amino acids are negative and indicate predominating exothermic effects of the interactions. In Table 8, the enthalpic interaction coefficients of aminophosphonic acids with urea, hPU, are compared with the values of the enthalpic interaction coefficients of amino acid− urea pairs, hAU, for natural amino acids.26 The values of the heterogeneous pair interaction coefficients, hPU, are three times lower in relation to the absolute value, which indicates that the contribution made by the “ionic aminophosphonic head” [(H3N+)CH−PO(OH)O−] to the analyzed value of the pair interaction coefficients is higher than that made by the zwitterion head of amino acids [(H3N+)CHCOO−]. Figure 3 shows the dependence of the enthalpic pair interaction coefficients, hPU, on the enthalpic coefficients, hAU. This dependence was described with the equation of a straight line with R2 = 0.966. The course of this dependence suggests a similar contribution made by the correlated amino acid substituents (both in natural amino acids and phosphonic derivatives) to the interaction with urea molecules. The values of the standard enthalpies of solution of N-methyl aminophosphonic acids in water and aqueous urea solutions are listed in Table 6. These values are exothermic and they were used to determine the enthalpic interaction coefficients of the phosphonic amino acid-urea pairs in water according to eq 1. The enthalpic coefficients of interaction between N-methyl derivatives of 1-aminopropylphosphonic acid (Me-HalP and Me2-HalP) and urea are listed in Table 8. The values of the pair interaction coefficients, hPU, are very similar to each other, which seems to be due to the compensation of two effects: (1)
Table 9. Dependence of pH on Concentration of 1Aminopropylphosphonic Acid, N-Methyl-1aminopropylphosphonic Acid and N,N-Dimethyl-1aminopropylphosphonic Acid pH −1
P
c/mol·L
Hala
Me-HalP
Me2-HalP
0.0005 0.0010 0.0015 0.0020 0.0025
5.46 5.24 5.12 4.88 4.85
5.44 5.23 5.06 4.98 4.81
5.31 5.01 4.90 4.70 4.54
0.0025) mol·L−1. The pH values are the lowest for N,Ndimethyl derivative, indicating that the acidity of the ionic head [(HN+)(CH3)2CH−PO(OH)O−] is higher than that for [(H2N+)(CH3)CH−PO(OH)O−] solutions. The acidity translates into the resultant charge of “ionic head” that is the most negative when nitrogen atom is blocked with additional methyl groups.
4. CONCLUSION Investigating the enthalpic pair interaction coefficients between aminophosphonic acids and urea and the interactions of amino acids with urea, one can found a dominating effect of the phosphonic group on the energetics of interaction. Comparing the enthalpic coefficients of interaction, hPU, of 1-aminopropylphosphonic acid and its N-methyl derivatives, it can be observed that the substitution of the hydrogen atom of amine group with a successive hydrophobic group in the molecule of aminophosphonic acid practically does not influence the interactions with urea since the endothermic effect of the dehydration of polar groups and the exothermic effect of the 430
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
(18) Zhang, Z.-H.; Ku, Z.-J.; Liu, Y.; Qu, S.-S. Study on Thermochemistry and Thermal Decomposition Kinetics of Dy(Tyr)(Gly)3Cl3·3H2O. Chin. J. Chem. Study 2005, 23, 1146−1150. (19) Smirnov, V. I.; Badelin, V. G. Thermochemistry of the solution of β-alanine in (H2O + alcohol) mixtures at 298.15 K. Thermochim. Acta 2013, 565, 202−204. (20) Humphrey, R. S.; Hedwig, G. R.; Watson, I. D.; Malcolm, G. N. The Partial Molar Enthalpies in Aqueous Solution of Some Amino Acids with Polar and Non-polar Side Chains. J. Chem. Thermodyn. 1980, 12, 595−603. (21) Stroth, L.; Schönert, H. Excess Enthalpies of Water + Diglycine or Triglycine or Glycyl-L-Alanine + Urea at 298.15 K. J. Chem. Thermodyn. 1980, 12, 595−603. (22) Reading, J. F.; Hedwig, G.. R. Thermodynamic Properties of Peptide Solutions. Part 12. Enthalpies of Dilution of Aqueous Solutions of Some Glycyl Dipeptides at 298.15 K. Thermochim. Acta 1994, 242, 41−50. (23) Liang, H.; Hu, X.; Fang, Gu.; Shao, S.; Guo, A.; Guo, Z. Enthalpic Discrimination of Position Isomerism: Pairwise Interaction of Piperidinecarboxylic Acid Isomers in DMSO + H2O Mixtures at 298.15 K. Thermochim. Acta 2012, 549, 140−147. (24) Węgrzyn, T. F.; Watson, J. D.; Hedwig, G. R. Enthalpies of Mixing of Aqueous Solutions of the Amino Acids Glycine, L-Alanine and L-Serine. J. Solution Chem. 1984, 13, 233−244. (25) Li, G..; Liu, M.; Dong, L.; Wang, L.; Sun, D.; Wei, X.; Di, Y. The Enthalpic Interaction Coefficients of N,N′-hexamethylenebisacetamide and N-methylformamide with Four Types of Amino Acids in Aqueous Sucrose Solutions at 298.15 K. J. Chem. Thermodyn. 2012, 48, 160− 174. (26) Pałecz, B. Enthalpic Pair Interaction Coefficient between Zwitterions of L-α-Amino Acids and Urea Molecule as a Hydrophobicity Parameter of Amino Acid Side Chains. J. Am. Chem. Soc. 2005, 9, 17768−17771. (27) Pałecz, B.; Dunal, J.; Waliszewski, D. Enthalpic Interaction Coefficients of Several L-α-amino Acids in Aqueous Sodium Chloride Solutions at 298.15 K. J. Chem. Eng. Data 2010, 55, 5216−5218. (28) Pałecz, B.; Grala, A.; Kudzin, Z. Interaction of Some Aminophosphonic Acids with Urea in Aqueous Solutions at 298.15 K. J. Chem. Eng. Data 2012, 57, 1515−1519. (29) Friedman, H. L.; Krishnan, C. V. Studies of Hydrophobic Bonding in Aqueous Alcohols: Enthalpy Measurements and Model Calculations. J. Solution Chem. 1973, 2, 119−140. (30) Franks, F.; Pedley, M.; Ried, D. S. Solute Interactions in Dilute Aqueous Solutions. J. Chem. Soc. Faraday Trans. 1 1976, 72, 359−367. (31) McMillan, W. G.; Mayer, J. E. The Statistical Thermodynamics of Multicomponent Systems. J. Chem. Phys. 1945, 13, 276−305. (32) Kudzin, Z. H.; Stec, W. J. Synthesis of 1-Aminoalkanephosphonates via Thioureidoalkane-phosphonates. Synthesis 1978, 469−472. (33) Kudzin, Z. H.; Stec, W. J. Phosphonohomocysteine Derivatives. Synthesis 1980, 1032−1034. (34) Kudzin, M. H.; Kudzin, Z. H.; Drabowicz, J. Nomenclature of Aminoalkylphosphonic acids and derivatives. Ewolution of the Code System. 14th International Symposium, ,Advances in the Chemistry of Heteroorganic Compounds, CBMM PAN, Łodź, Poland, 2011, 11, 18. (35) Kudzin, M. H.; Kudzin, Z. H.; Drabowicz, J. Thioureidoalkylphosphonates in the synthesis of 1-aminoalkylphosphonic acids. The Ptc-aminophosphonate method. Arkiv. 2011, vi, 227−269. (36) Kudzin, Z. H.; Drabowicz, J.; Sochacki, M.; Wiśniewski, W. Characterization of 1-Aminoalkane-phosphonic Acids by Chemical Ionization Mass Spectrometry. Phosphorus, Sulfur Silicon 1994, 92, 77− 94. (37) Kudzin, Z. H.; Kudzin, M. H.; Drabowicz, J.; Stevens, Ch. Aminophosphonic acids - phosphorus analogues of natural amino acids. Curr. Org. Chem. 2011, 15, 2015−2071. (38) Palecz, B. The Enthalpies of Interaction of Glycine with Some Amides and Ureas in Water at 25°C. J. Solution Chem. 1995, 24, 537− 550.
interactions of the ionic head of aminophosphonic acid are compensated.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Tel.:48-42-6355828. Notes
The authors declare no competing financial interest.
■ ■
ACKNOWLEDGMENTS The authors express their thanks to Mr. Paweł Urbaniak for his help in performing pH measurements. REFERENCES
(1) Hanson, J. E.; Kaplan, A. P.; Bartlett, P. A. Phosphonate Analogues of Carboxypeptidase A Substrates Are Potent TransitionState Analogue Inhibitors. Biochemistry 1989, 28, 6294−6305. (2) Giannousis, P. P.; Bartlett, P. A. Phosphorus Amino Acid Analogues as Inhibitors of Leucine Aminopeptidase. J. Med. Chem. 1987, 30, 1603−1609. (3) Poręba, M.; Gajda, A.; Picha, J.; Jiracek, J.; Marschner, A.; Klein, C. D.; Salvesen, G. S.; Drąg, M. S1 Pocket Fingerprints of Human and Bacterial Methionine Aminopeptidases Determined Using Fluorogenic Libraries of Substrates and Phosphorus Based Inhibitors. Biochimie 2012, 94, 704−710. (4) Alonso, E.; Alonso, E.; Solís, A.; del Pozo, C. Synthesis of NAlkyl-(α-Aminoalkyl)Phosphine Oxides and Phosphonic Esters as Potential HIV-Protease Inhibitors, Starting from α-Aminoacids. Synlett 2000, 2000, 698−700. (5) Naydenova, E. D.; Todorov, P. T.; Troev, K. D. Recent synthesis of aminophosphonic acids as potential biological importance. Amino Acids 2010, 38, 23−30. (6) Klimczak, A.; Kuropatwa, A.; Lewkowski, J.; Szemraj, J. Synthesis of New N-arylamino(2furyl)methylphosphonic Acid Diesters, and in Vitro Evaluation of Their Cytotoxicity Against Esophageal Cancer Cells. Med. Chem. Res. 2013, 22, 852−860. (7) Lejczak, B.; Kafarski, P. Biological Activity of Aminophosphonic Acids and Their Short Peptides. Top. Heterocycl. Chem. 2009, 20, 31− 63. (8) Horiguchi, M.; Kandatsu, M. Isolation of 2-aminoethanephosphonic Acid from Rumen Protozoa. Nature 1959, 184, 901−902. (9) Kittredge, J. S.; Roberts, E. A Carbon-Phosphorus Bond in Nature. Science 1969, 164, 37−42. (10) Kittredge, J. S.; Roberts, E.; Simonsen, D. G. The Occurrence of Free 2-aminoethylphosphonic Acid in the Sea Anemone, Anthopleura elegantissima. Biochemistry 1962, 1, 624−628. (11) Quin, L. D. The Presence of Compounds with a Carbonphosphorus Bond in Some Marine Invertebrates. Biochemistry 1965, 4, 324−330. (12) Kandatsu, M.; Horiguchi, M. The Occurrence of Ciliatine (2Aminoethylphosphonic Acid) in the Goat Liver. Agr. Biol. Chem. 1965, 29, 781−782. (13) Shimizu, H.; Kakimoto, Y.; Nakajima, T.; Kanazawa, A.; Sano, I. Isolation and Identification of 2-Aminoethyl-phosphonic Acid from Bovine Brain. Nature 1965, 207, 1197−1198. (14) Alhadeff, J. A.; Daves, G.. D., Jr. Occurrence of 2-Aminoethylphosphonic Acid in Human Brain. Biochemistry 1970, 9, 4866− 4869. (15) Franz, J. E. Herbicidal Compositions and Methods Employing Esters of N-phosphonoglycine. U.S. Patent 3997860, 1976; Chem. Abstr. 1976, 86, 43812. (16) Stimson, E. R.; Schrier, E. E. Calorimetric studies of the interactions of guanidinium hydrochloride and potassium iodide with model amides in aqueous solution. Biopolymers 1975, 14, 509−520. (17) Souillac, P. O.; Constantino, H. R.; Middaugh, C. R.; Rytting, H. J. Investigation of Protein/Carbohydrate Interactions in the Dried State. 1. Calorimetric Studies. J. Pharm. Sci. 2002, 91, 206−216. 431
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432
Journal of Chemical & Engineering Data
Article
(39) Desnoyers, J. E.; Perron, G.; Avedikian, L.; Morel, J.-P. Enthalpies of the urea-tert-butanol-water system at 25°C. J. Solution Chem. 1976, 5, 631−644. (40) Shrier, M. Y.; Turner, P. I.; Shrier, E. E. Thermodynamic Quantities for the Transfer of Urea from Water to Aqueous Electrolyte Solutions. J. Phys. Chem. 1975, 79, 1391. (41) Kilday, M. V. The Enthalpy of Solution of SRM 1655 (KCl) in H2O. J. Res. National Data N.B.S. 1980, 85, 467−481. (42) Sanahuja, A.; Cesari, E. Enthalpy of Solution of KCl and NaCl in water at 298.15 K. J. Chem. Thermodyn. 1984, 16, 1195−1202. (43) Piekarski, H.; Waliszewski, D. Thermochemic properties of NaCl and KCl solutions in mixtures of water with N,Ndimethylacetamide at 25°C. Thermochim. Acta 1991, 190, 299−306. (44) Wood, R. H.; Lilley, T. H; Thomson, P. T. Rapidly Converging Activity Expansions for Representing the Thermodynamic Properties of Fluid Systems: Gases, Non-electrolyte Solutions, Weak and Strong Electrolyte Solutions. J. Chem. Soc. Faraday Trans. 1 1978, 74, 1301− 1323. (45) Palecz, B. The Enthalpies of Interactions of Some L-a-amino Acids with Urea Molecule in Aqueous Solutions at 298.15K. Amino Acids 2004, 27, 299−303. (46) Wood, R. H.; Hiltzik, L. H. Enthalpies of Dilution of Aqueous Solution of Formamide, Acetamide, Propionamide, and N,Ndimetylformamide. J. Solution Chem. 1980, 9, 45−57.
432
dx.doi.org/10.1021/je400900h | J. Chem. Eng. Data 2014, 59, 426−432