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Volumetric, acoustic, viscometric, calorimetric and

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Cite this: DOI: 10.1039/c9fo00872a

spectroscopic studies to elucidate the effects of
citrate and tartrate based food preservatives on
the solvation behaviors of acidic amino acids at
different temperatures†
Aashima Beri, Gagandeep Kaur, Palwinder Singh, Parampaul K. Banipal and
Tarlok S. Banipal *

Received 25th April 2019,
Accepted 20th November 2019
DOI: 10.1039/c9fo00872a
rsc.li/food-function
The effects of trisodium citrate (TSC) and disodium tartrate (DST) based food preservatives on the
hydration behaviors of the amino acids L-aspartic acid (ASP) and L-glutamic acid (GLU) have been studied
using thermodynamic, transport, calorimetric and spectroscopic studies. The volumetric, acoustic and
viscosity data suggest that hydrophilic–ionic/hydrophilic interactions are predominant in these systems.
The calculated parameters are worthwhile for exploring the solutes as structure-breakers, and the solutes
undergo pairwise interactions with the co-solutes. The sweetness of both amino acids decreases in the
presence of the preservatives. The hydration number and solvation data suggest that these solutes are
more hydrated in water. The dominance of dehydration effects in relation to TSC is observed from the
positive enthalpy changes in calorimetry studies and the negative chemical shifts in 1H NMR studies.

1. Introduction on the list of antioxidants. It has been mentioned in the litera-

Food preservation is carried out to maintain the quality and
physicochemical properties of raw food.1 Preservatives are gen-
erally additives, which enhance the life spans of foods and
drinks through preventing microorganism growth.2 As legis-
lation has restricted the use and the levels of some preserva-
tives in different foods, these preservatives must be approved
by food safety authorities.3 Organic acids (citric and tartaric
acid) are traditional preservatives. Organic acids are added to
foods as acidulants, flavorants, or preservatives, inactivating
the growth of spoilage microorganisms and foodborne patho-
gens.4 Citric and tartaric acid show various biological activi-
ties. They exhibit metal ion complexing properties with amino
acids and, thus, they are preferably used for some common
applications in food and agricultural industries as seques-
trants, antioxidants, etc. The use of disodium tartrate (DST)
and trisodium citrate (TSC) as food additives has been
approved by the European Food Safety Authority. They have
been assigned with the E numbers 335 and 331, respectively,
Department of Chemistry, UGC Sponsored Center for Advanced Studies-1,
Guru Nanak Dev University, Amritsar-143005, Punjab, India.
E-mail: tsbanipal@yahoo.com
† Electronic supplementary information (ESI) available: DETAILS. See DOI:
10.1039/c9fo00872a
ture that sodium salts of citrate and tartrate have been used as
anticaking agents, flavour enhancers, etc.5,6 Salts are effective
preservatives because they reduce the water activity of foods.
As well as their food-related value, DST can extend the range of
plant growth promoters and TSC can help in the production of
soil amendments for organic crop production.
L-Glutamate and L-aspartate are key molecules in cellular
metabolism. Dietary proteins are broken down in humans
through digestion into amino acids, which act as metabolic
fuel for other functional activities in the body.7 Casein, lactal-
bumin, Promine-D (soy protein), and wheat gluten contain sig-
nificant amounts of racemized L-aspartic acid (ASP) and
8
L-glutamic acid (GLU). GLU is an important nonessential
amino acid that acts as a neurotransmitter. It is not considered
to be an essential nutrient because it can be manufactured in
the human body from simpler compounds. GLU is a building
block in protein synthesis. This dicarboxylic amino acid is
available in a wide variety of foods and is an important mole-
cule for the metabolism of sugars and fats.9 It is also used to
enhance the flavour of foods.10 ASP is used for the generation
of adenosine triphosphate, which is a required fuel for cell
activity.11 Water is ubiquitous in biochemical processes
because its presence generates hydrophobic forces.12 The
physicochemical properties of studied solutes have been used
to provide insights into hydrophobicity, hydration properties

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and solute–solvent interactions.13 The use of citrate and tar-
trate based salts, along with other additives, not only makes
flavours sharper but also improves the stability of food pro-
ducts in many cases. The present report aims to study the sol-
vation and taste quality behaviors of acidic amino acids (ASP
and GLU) in the presence of citrate (TSC) and tartrate (DST)
food preservatives.
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a set temperature, adjusted using a built-in Peltier thermostat
(PT-100) having an accuracy of ±0.001 K. The speed of sound is
measured via a propagation time technique. Calibration adjust-
ments were performed at 293.15 K with triple-distilled degassed
water, and with dry air at atmospheric pressure. The uncertain-
ties in the temperature, density and speed of sound measure-
ments are 0.03 K, 0.06 kg m−3 and 0.6 m s−1, respectively.
2.2.2. Viscosity. Viscosities, η, were determined using a
suspended level Ubbelohde-type capillary viscometer having

2. Experimental temperature stability within ±0.01 K (model: MC 31A Julabo/

2.1. Materials
All the chemicals used in the present study are of high-purity
analytical grade. The purity of the studied chemicals is ≥99%.
Details relating to the chemicals are given in Table 1. Before
using the chemicals, they have all been dried in vacuo over
anhydrous CaCl2.
2.2. Equipment and procedures
All stock solutions have been prepared using deionised,
double-distilled and degassed water with a specific conduc-
tance less than 1.3 × 10−4 S m−1. The solutions were prepared
on a mass basis using a Mettler balance (Model: AB265-S) with
a precision of ±0.01 mg. The standard uncertainty in molality
is ±2.8 × 10−4 mol kg−1.
2.2.1. Density and speed of sound. The densities and
speeds of sound were measured simultaneously using a vibrat-
ing-tube digital density and sound velocity meter (DSA 5000M,
Anton Paar). The two-in-one instrument is designed with two
cells, i.e., a density cell and a sound velocity cell. Both cells have
Germany). Flow time measurements were done using a stop-
watch with a resolution of ±0.01 s. The viscometer has been
calibrated with deionized, double-distilled and degassed
water. The efflux time data for water was recorded at T =
288.15, 298.15, 308.15 and 318.15 K. Final efflux times are the
means of at least six readings. The standard uncertainty in vis-
cosity, u(η), on an average basis is ±0.012 mPa s. The reliability
of the apparatus was checked through measuring the viscos-
ities of aqueous solutions of glycine at T = 298.15 K, and the
results agreed very well with the literature values.14 The viscos-
ities of pure water have been taken from the literature.15
2.2.3. Enthalpy of dilution. An isothermal titration calori-
meter, (iTC200, MicroCal USA) was used to perform calori-
metric titrations at 298.15 ± 0.005 K for the determination of
enthalpy of dilution values. 100, 250, and 500 mM DST/TSC
solutions were added to a sample cell with a capacity of 200 μl
and the syringe was filled with 40 μl of 30 mM ASP/GLU. A
total of 19 injections of 2 μl of ASP/GLU was titrated into the
sample cell containing DST/TSC and the contents of the cell
were stirred at a fixed speed of 500 rpm to ensure complete

Table 1 Sources and solubilities of the chemicals used

Molar mass Solubility in

S. no. Compound Structure (g mol−1) Source Puritya CAS number watera (mg ml−1)

1 L-Aspartic acid 133.10 Siso Research Laboratories, India 99% 56–86–0 ≈4.5

2 L-Glutamic acid 147.13 Siso Research Laboratories, India 99% 2419–94.5 ≈7.5

3 Di-sodium tartrate 230.08 Central Drug House, India 99% 6132–24–7 ≈290

4 Tri-sodium citrate 294.10 Siso Research Laboratories, India 99% 6132–04–3 ≈92

a
As provided by the supplier.

Food Funct. This journal is © The Royal Society of Chemistry 2019


Food & Function
mixing. The time between successive injections was 120 s,
which was managed using the software provided with the
instrument. The standard uncertainty in the enthalpy values is
±0.5 kJ mol−1.
2.2.4. Chemical shift measurements. 1H NMR spectra were
obtained using a Bruker spectrometer (AVANCE-III, HD
500 MHz) with a probe temperature of 300.15 K. The centre of
the HDO signal (4.650 ppm) is considered as the internal refer-
ence for the other nuclei. NMR spectra of ASP and GLU in
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water and in the presence of aqueous solutions of DST and
TSC (mB = 0.1–0.75 mol kg−1) have been studied in 9 : 1 (w/w)
H2O–D2O solution. From these spectra, the chemical shift
changes (Δδ) were recorded.
3. Results and discussion
3.1. Volumetric measurements
3.1.1. Apparent molar Volumes, V2,ϕ. The densities, ρ, of
the studied amino acids (ASP and GLU) as a function of molal-
ity (mA) in water, and in aqueous solutions of DST and TSC at
mB (molality of DST/TSC) values of 0.10, 0.25, 0.50, and
0.75 mol kg−1 over a temperature range from 288.15 to
323.15 K are given in Table 2. The ρ values directly rise with
the mA and mB values and decrease with T. The ρ values of
aqueous DST and TSC solutions are in good agreement with
the literature values,16–23 and a comparison is shown graphi-
cally in Fig. 1. The density values of aqueous solutions of ASP
and GLU are also in line with the literature values9,24–28 and
are represented in Fig. 2. The variations in the ρ values of ASP
in aqueous DST solutions at different temperatures are shown
in Fig. 3(a) (density, ρ, versus molality, mA, for ASP in DST at
mB = 0.1 mol kg−1 as a function of temperature). In the present
study, apparent molar volumes, V2,ϕ, have been calculated
from the experimentally measured densities using the relation:
V 2;ϕ ¼ fM=ρg  fðρ  ρ0 Þ=ðmA ρρ0 Þg ð1Þ
where ρ and ρ0 are the densities of the solution and the
solvent (H2O or H2O + DST/TSC), M is the molar mass, and mA
is the molality of the solute. The V2,ϕ values are positive for the
studied amino acids both in aqueous and in mixed aqueous
solutions. The V2,ϕ values increase with the mA, mB and T
values. The V2,ϕ values of the studied solutes in the absence,
as well as in the presence, of aqueous solutions of DST and
TSC at mB values of 0.10, 0.25, 0.50, and 0.75 mol kg−1 and at
temperatures from 288.15 to 323.15 K are given in ESI
Table S1.† A representative plot of V2,ϕ versus mA for GLU in
aqueous TSC solutions at mB = 0.25 mol kg−1 and different T
values is shown in Fig. 3(b).
3.1.2. Partial molar volumes, V2,ϕ0. The V2,ϕ0 values have
been evaluated by fitting the corresponding data to the given
equation as follows:
V 2;ϕ ¼ V 2;ϕ 0 þ Sv m ð2Þ
The volumetric virial coefficient, i.e., Sv, is the experimental
slope in the given equation. The V2,ϕ0 values and the standard
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deviation values are tabulated in Table 3. The V2,ϕ0 values for
aqueous solutions of amino acids agree well with those
reported in the literature (Table 3).24–30
The V2,ϕ0 values of both amino acids increase with an
increase in the concentrations of the studied salts and also
with an increase in temperature. As the V2,ϕ0 values increase
with an increase in molecular weight, the V2,ϕ0 values are
higher in GLU than ASP, because of the extra –CH2 group. The
V2,ϕ0 values for both ASP and GLU are higher in aqueous solu-
tions of TSC than in DST.
3.1.3. Apparent specific volume, vϕ. The apparent specific
volume, vϕ, is calculated as follows
vϕ ¼ V 2;ϕ =M: ð3Þ
The apparent specific volume, vϕ, bears a relationship to
taste quality in the order salty < sour < sweet < bitter and,
probably, the entire range of human taste perception is con-
fined to molecules with apparent specific volumes between 0.1
and 0.95 cm3 g−1.31 The vϕ values for the studied systems are
given in Table S2.† In water, the vϕ values for ASP and GLU fall
within the sweet taste range32 (0.52–0.71 cm3 g−1). ASP is
sweeter than GLU in water. However, in aqueous solutions of
DST and TSC, the vϕ values increase and, therefore, the sweet-
nesses of both ASP and GLU decrease as the mB values
increase.
3.1.4. Partial molar volumes of transfer, ΔtrV2,ϕ0. The
ΔtrV2,ϕ0 values of the studied solutes, from water to aqueous
solutions of DST and TSC, are calculated as follows:
Δtr V 2;ϕ 0 ¼ V 2;ϕ 0 ðin aqueous solutions of DST=TSCÞ
 V 2;ϕ 0 ðin waterÞ ð4Þ
The ΔtrV2,ϕ0 values are positive for the studied amino acids
and increase with the co-solute concentrations at all tempera-
tures, as shown in Fig. 4(a, d, g and j). The ΔtrV2,ϕ0 values of
ASP and GLU decrease with temperature. The ΔtrV2,ϕ0 values of
both amino acids are greater in the case of TSC compared to
DST, due to the high charge density.5 The magnitude of trans-
fer is greater in the case of ASP compared to GLU.
The magnitude of ΔtrV2,ϕ0 initially increases sharply, and
the increase is less at higher co-solute concentrations. A co-
sphere overlap model33 is used to interpret these results.
According to this model, hydrophilic (the –NH2 and –COOH
parts of the solute)-ionic (the Na+ and −COO− parts of the co-
solute) and hydrophilic (the –NH2 and –COOH groups of the
solute)-hydrophilic (the –OH groups of the co-solute) inter-
actions contribute positively, and hydrophobic (the alkyl
groups of the solute)-hydrophilic (the –OH groups of the co-
solute) and hydrophobic (the alkyl groups of the solute)-
ionic (the Na+ and −COO− parts of the co-solute) interactions
contribute negatively to the ΔtrV2,ϕ0 values. Therefore, in the
present system, the positive ΔtrV2,ϕ0 values for these amino
acids over the co-solute concentration range studied suggest
that hydrophilic–ionic and hydrophilic–hydrophilic inter-
actions dominate over hydrophobic–hydrophilic and hydro-
phobic–ionic interactions. Furthermore, the decrease in the
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Table 2 Densities, ρ, of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium citrate at T
values from 288.15 to 323.15 K and P = 101.3 kPa

10−3·ρ/kg m−3

mA/mol kg−1 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

L-Aspartic acid in water

0.00000 0.999102 0.998224 0.997047 0.995670 0.994040 0.992238 0.990220 0.988069
0.00517 0.999445 0.998547 0.997360 0.995990 0.994375 0.992558 0.990553 0.988378
0.00712 0.999563 0.998665 0.997477 0.996108 0.994492 0.992674 0.990669 0.988494
0.00921 0.999690 0.998791 0.997602 0.996232 0.994617 0.992799 0.990794 0.988618
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0.01109 0.999803 0.998904 0.997715 0.996345 0.994729 0.992911 0.990905 0.988729

0.01300 0.999918 0.999018 0.997829 0.996460 0.994843 0.993024 0.991018 0.988842
0.01506 1.000042 0.999141 0.997952 0.996582 0.994965 0.993147 0.991140 0.988964
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.1 mol kg
0.00000 1.014500 1.012800 1.010169 1.008856 1.006932 1.004950 1.002974 1.000950
0.00502 1.014789 1.013089 1.010457 1.009144 1.007220 1.005238 1.003261 1.001237
0.00741 1.014926 1.013226 1.010594 1.009280 1.007356 1.005374 1.003398 1.001374
0.01180 1.015178 1.013477 1.010730 1.009531 1.007607 1.005624 1.003648 1.001624
0.01306 1.015249 1.013548 1.010844 1.009603 1.007678 1.005695 1.003719 1.001695
0.01732 1.015492 1.013791 1.010916 1.009845 1.007921 1.005938 1.003960 1.001936
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
0.00000 1.032450 1.030457 1.028594 1.026540 1.025089 1.023450 1.020973 1.018500
0.00584 1.032778 1.030784 1.028920 1.026866 1.025415 1.023775 1.021298 1.018824
0.00817 1.032908 1.030914 1.029050 1.026995 1.025544 1.023904 1.021427 1.018953
0.01106 1.033069 1.031075 1.029211 1.027156 1.025704 1.024064 1.021586 1.019112
0.01337 1.033198 1.031203 1.029338 1.027283 1.025832 1.024191 1.021713 1.019239
0.01555 1.033319 1.031323 1.029459 1.027404 1.025952 1.024311 1.021833 1.019358
0.01667 1.033380 1.031385 1.029520 1.027465 1.026013 1.024372 1.021894 1.019419
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.50 mol kg
0.00000 1.063200 1.061500 1.059301 1.057450 1.055350 1.053240 1.050971 1.048200
0.00638 1.063544 1.061843 1.059644 1.057793 1.055692 1.053582 1.051313 1.048542
0.00782 1.063620 1.061920 1.059721 1.057870 1.055769 1.053659 1.051389 1.048619
0.00982 1.063726 1.062027 1.059828 1.057976 1.055876 1.053765 1.051495 1.048725
0.01307 1.063899 1.062200 1.060001 1.058150 1.056049 1.053938 1.051667 1.048897
0.01509 1.064006 1.062307 1.060109 1.058257 1.056156 1.054044 1.051774 1.049004
0.01539 1.064074 1.062375 1.060178 1.058325 1.056225 1.054113 1.051842 1.049072
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
0.00000 1.093900 1.091750 1.090008 1.087450 1.085611 1.083560 1.080970 1.078900
0.00547 1.094183 1.092032 1.090289 1.087731 1.085892 1.083841 1.081250 1.079180
0.00739 1.094282 1.092131 1.090387 1.087829 1.085990 1.083938 1.081348 1.079278
0.01025 1.094429 1.092278 1.090532 1.087975 1.086135 1.084084 1.081493 1.079423
0.01347 1.094595 1.092443 1.090697 1.088138 1.086298 1.084247 1.081656 1.079585
0.01664 1.094758 1.092605 1.090856 1.088298 1.086458 1.084407 1.081816 1.079743
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
0.00000 1.017603 1.01651 1.015194 1.013658 1.011929 1.010035 1.007541 1.005738
0.00576 1.017926 1.016832 1.015515 1.013979 1.012250 1.010356 1.007861 1.006058
0.00754 1.018025 1.016931 1.015614 1.014077 1.012348 1.010454 1.007960 1.006157
0.01002 1.018164 1.017069 1.015752 1.014214 1.012485 1.010592 1.008097 1.006294
0.01189 1.018267 1.017173 1.015855 1.014317 1.012588 1.010695 1.008200 1.006397
0.01520 1.018451 1.017357 1.016038 1.014500 1.012770 1.010878 1.008383 1.006579
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
0.00000 1.044743 1.043390 1.041855 1.040130 1.038238 1.036425 1.033088 1.030213
0.00624 1.045084 1.043730 1.042194 1.040469 1.038576 1.036762 1.033425 1.030549
0.00784 1.045171 1.043816 1.042281 1.040555 1.038662 1.036848 1.033510 1.030635
0.01080 1.045332 1.043976 1.042441 1.040715 1.038821 1.037007 1.033668 1.030794
0.01208 1.045401 1.044045 1.042510 1.040784 1.038889 1.037075 1.033736 1.030862
0.01490 1.045554 1.044197 1.042663 1.040936 1.039040 1.037225 1.033886 1.031012
0.01825 1.045735 1.044377 1.042843 1.041116 1.039218 1.037403 1.034064 1.031189
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.50 mol kg
0.00000 1.089975 1.088190 1.086290 1.084250 1.082085 1.078250 1.075665 1.072453
0.00597 1.090285 1.088499 1.086598 1.084557 1.082393 1.078558 1.075973 1.072761
0.00809 1.090395 1.088608 1.086707 1.084666 1.082501 1.078666 1.076081 1.072869
0.00985 1.090485 1.088699 1.086797 1.084757 1.082591 1.078756 1.076171 1.072959
0.01284 1.090639 1.088852 1.086951 1.084910 1.082744 1.078909 1.076323 1.073111
0.01520 1.090760 1.088973 1.087071 1.085030 1.082863 1.079029 1.076443 1.073232
0.01810 1.090908 1.089120 1.087219 1.085177 1.083010 1.079176 1.076589 1.073378
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
0.00000 1.135208 1.132990 1.130725 1.128370 1.125933 1.122547 1.118243 1.115480
0.00626 1.135513 1.133294 1.131029 1.128673 1.126237 1.122852 1.118548 1.115786
0.00788 1.135591 1.133373 1.131107 1.128752 1.126315 1.122930 1.118627 1.115864
0.01082 1.135733 1.133514 1.131249 1.128893 1.126457 1.123073 1.118769 1.116006

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Table 2 (Contd.)

10−3·ρ/kg m−3

mA/mol kg−1 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

0.01180 1.135779 1.133562 1.131296 1.128940 1.126505 1.123120 1.118816 1.116052

0.01461 1.135914 1.133696 1.131431 1.129075 1.126640 1.123255 1.118952 1.116188
0.01732 1.136042 1.133825 1.131560 1.129204 1.126769 1.123384 1.119082 1.116318
L-Glutamic acid in water
0.01104 0.999776 0.998875 0.997680 0.996307 0.994687 0.992865 0.990860 0.988682
0.01308 0.999894 0.998992 0.997796 0.996423 0.994802 0.992978 0.990973 0.988794
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0.01522 1.000019 0.999115 0.997919 0.996544 0.994921 0.993096 0.991091 0.988912

0.02078 1.000341 0.999434 0.998235 0.996857 0.995233 0.993404 0.991399 0.989217
0.02517 1.000595 0.999686 0.998485 0.997104 0.995479 0.993645 0.991640 0.989457
0.03030 1.000890 0.999978 0.998775 0.997390 0.995765 0.993927 0.991922 0.988735
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.1 mol kg
0.01288 1.015222 1.013518 1.010883 1.009568 1.007642 1.005658 1.003681 1.001656
0.01523 1.015352 1.013648 1.011011 1.009697 1.007770 1.005787 1.003808 1.001782
0.01930 1.015577 1.013873 1.011235 1.009919 1.007992 1.006010 1.004028 1.002001
0.02496 1.015890 1.014184 1.011546 1.010228 1.008300 1.006318 1.004335 1.002307
0.03127 1.016238 1.014530 1.011890 1.010571 1.008642 1.006659 1.004674 1.002645
0.03591 1.016492 1.014782 1.012142 1.010819 1.008890 1.006909 1.004920 1.002892
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
0.01410 1.033219 1.031223 1.029358 1.027302 1.025850 1.024208 1.021730 1.019255
0.01537 1.033286 1.031291 1.029426 1.027369 1.025917 1.024276 1.021797 1.019322
0.01930 1.033499 1.031503 1.029638 1.027580 1.026127 1.024485 1.022006 1.019531
0.02391 1.033747 1.031750 1.029885 1.027826 1.026372 1.024730 1.022250 1.019775
0.03000 1.034075 1.032075 1.030211 1.028150 1.026695 1.025053 1.022572 1.020096
0.03235 1.034200 1.032200 1.030334 1.028271 1.026819 1.025176 1.022695 1.020217
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.50 mol kg
0.01228 1.063847 1.062143 1.059940 1.058089 1.055985 1.053871 1.051601 1.048830
0.01354 1.063912 1.062208 1.060005 1.058153 1.056049 1.053935 1.051666 1.048892
0.01654 1.064069 1.062363 1.060160 1.058307 1.056202 1.054088 1.051818 1.049043
0.02018 1.064258 1.062551 1.060347 1.058492 1.056388 1.054274 1.052003 1.049227
0.02585 1.064553 1.062844 1.060638 1.058782 1.056675 1.054561 1.052290 1.049512
0.03703 1.065130 1.063412 1.061210 1.059350 1.057240 1.055124 1.052854 1.050070
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
0.01159 1.094489 1.092337 1.090661 1.087995 1.086187 1.084131 1.081540 1.079468
0.01375 1.094597 1.092445 1.090767 1.088101 1.086294 1.084236 1.081645 1.079572
0.01765 1.094792 1.092640 1.090960 1.088293 1.086486 1.084426 1.081835 1.079760
0.01995 1.094907 1.092755 1.091073 1.088405 1.086599 1.084538 1.081945 1.079870
0.02676 1.095245 1.093095 1.091407 1.088740 1.086931 1.084867 1.082275 1.080198
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
0.01247 1.018281 1.017186 1.015870 1.014333 1.012603 1.010708 1.008213 1.006409
0.01463 1.018396 1.017301 1.015986 1.014449 1.012719 1.010823 1.008329 1.006524
0.01634 1.018487 1.017392 1.016077 1.014541 1.012811 1.010913 1.008420 1.006615
0.02218 1.018800 1.017706 1.016391 1.014854 1.013124 1.011224 1.008729 1.006926
0.02857 1.019140 1.018044 1.016732 1.015194 1.013464 1.011563 1.009067 1.007265
0.03390 1.019423 1.018324 1.017015 1.015478 1.013747 1.011844 1.009348 1.007545
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
0.01213 1.045383 1.044029 1.042489 1.040763 1.038868 1.037053 1.033716 1.030842
0.01438 1.045500 1.044146 1.042605 1.040879 1.038983 1.037169 1.033832 1.030956
0.01771 1.045674 1.044320 1.042778 1.041051 1.039155 1.037340 1.034000 1.031126
0.02308 1.045954 1.044600 1.043055 1.041328 1.039430 1.037615 1.034274 1.031400
0.02531 1.046069 1.044715 1.043170 1.041442 1.039542 1.037728 1.034386 1.031512
0.03401 1.046520 1.045167 1.043619 1.041888 1.039985 1.038168 1.034828 1.031953
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.50 mol kg
0.01104 1.090520 1.088735 1.086830 1.084790 1.082623 1.078787 1.076200 1.072989
0.01239 1.090585 1.088800 1.086896 1.084854 1.082687 1.078851 1.076265 1.073054
0.01547 1.090735 1.088950 1.087047 1.085003 1.082836 1.078999 1.076412 1.073202
0.02012 1.090960 1.089176 1.087272 1.085226 1.083059 1.079222 1.076634 1.073426
0.02521 1.091205 1.089423 1.087517 1.085470 1.083303 1.079465 1.076874 1.073670
0.03006 1.091438 1.089657 1.087749 1.085700 1.083535 1.079694 1.077100 1.073900
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
0.01088 1.135703 1.133485 1.131216 1.128861 1.126424 1.123036 1.118734 1.115969
0.01408 1.135848 1.133629 1.131360 1.129005 1.126566 1.123180 1.118877 1.116112
0.01532 1.135903 1.133683 1.131415 1.129059 1.126620 1.123235 1.118932 1.116166
0.02000 1.136113 1.133892 1.131625 1.129267 1.126827 1.123443 1.119140 1.116373
0.02799 1.136469 1.134249 1.131980 1.129622 1.127179 1.123796 1.119494 1.116725
0.03107 1.136605 1.134385 1.132115 1.129756 1.127314 1.123930 1.119629 1.116855

mA is the molality of the solute in water or water + DST/TSC. mB is the molality of DST/TSC in water. Standard uncertainties, u, are u(T ) = 0.03 K,
u(P) = 0.5 kPa, u(m) = 2.8 × 10−4 mol kg−1, u(ρ) = 0.06 kg m−3.

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Fig. 1 (a) Plots of density, ρ, versus molality, mB, for aqueous solutions
of TSC and comparisons with the literature values at different tempera-
tures. (b) Plots of density, ρ, versus molality, mB, for aqueous solutions of
DST and comparisons with the literature values at different
temperatures.

magnitude of ΔtrV2,ϕ0 from ASP to GLU indicates the building
up of hydrophobic–ionic interactions due to the extra
–CH2 group. The additional –CH2 group exerts a destructive
effect on the polar and charged group hydration spheres of
Fig. 2 (a) Plots of density, ρ, versus molality, mA, for aqueous solutions
of ASP and comparisons with the literature values at different tempera-
tures. (b) Plots of density, ρ, versus molality, mA, for aqueous solutions of
GLU and comparisons with the literature values at different
temperatures.

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Fig. 3 Representative plots of: (a) density, ρ, versus molality, mA, for L-aspartic acid in aqueous DST solutions (mB = 0.1 mol kg−1) as a function of
temperature, T; (b) apparent molar volume, V2,ϕ, versus molality, mA, for L-glutamic acid in aqueous TSC solutions (mB = 0.25 mol kg−1) as a function
of temperature, T; (c) speed of sound, u, versus molality, mA, for L-aspartic acid in aqueous TSC solutions (mB = 0.1 mol kg−1) as a function of temp-
erature, T; and (d) viscosity, η, versus molality, mA, for L-glutamic acid in aqueous DST solutions (mB = 0.1 mol kg−1) as a function of temperature, T.

the amino acids. The low ΔtrV2,ϕ0 values for GLU are in line
with the observation that ΔtrV2,ϕ0 values decrease with an
increase in the lengths of the alkyl side chains of amino
acids.18
3.1.5. Hydration number, Nh. The hydration number, Nh of
the amino acids in water and in aqueous DST/TSC solutions
can be calculated by using the following equation.34
N h ðin waterÞ ¼ V elect =ðV 0e  V 0b Þ
In the above equation, V0e = molar volume of electrostricted
water and V0b = molar volume of bulk water/solvent. The
(V0e − V0b ) values are approximately −2.9 cm3 mol−1 at 288.15 K,
−3.3 cm3 mol−1 at 298.15 K and −4.0 cm3 mol−1 at 308.15 K.35
The Velect values have been calculated from the corresponding
V2,ϕ0 values using the equation:
V elect ¼ V 2;ϕ 0  V 0int ð6Þ
where the intrinsic molar volume, V0int, can be estimated from
the crystallographic volume, Vcryst as follows:36
V 0int ¼ ð0:7=0:634ÞV cryst: ð7Þ
ð5Þ The Nh data in Table S3† indicate that the dehydration of
ASP and GLU increases with the co-solute molality. The Nh
values for ASP are higher than for GLU and, also, the decreases
in the Nh values with mB are larger in the case of ASP com-
pared to GLU. TSC is found to be an effective preservative for
dehydration processes, therefore, its use in the food industry

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Table 3 Partial molar volumes, V2,ϕ0, of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium citrate at T values from 288.15 to 323.15 K and
P = 101.3 kPa
Paper

Food Funct.
106 V2,ϕ0 m−3 mol−1
−1
mB/mol kg
288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

L-Aspartic acid in an aqueous solution of di-sodium tartrate

0.0 71.73 ± 0.01 72.02 ± 0.04 72.35 ± 0.04 72.55 ± 0.03 72.74 ± 0.01 72.98 ± 0.01 73.25 ± 0.01 73.46 ± 0.02
71.8a, 72.21b (46.19 ± 5.10) 72.30a, 73.14b, 74.13c, 74.13d 72.78a, 74.17b, 76.01c, 76.01d 73.23a (28.61 ± 2.80)
73.34c, 73.33d 75.04c, 75.03d
(45.37 ± 1.47) (42.67 ± 4.86) (34.31 ± 3.92) (31.06 ± 1.65) (26.65 ± 1.77) (28.96 ± 1.71)
0.1 75.06 ± 0.03 75.19 ± 0.02 75.44 ± 0.01 75.50 ± 0.02 75.59 ± 0.02 75.62 ± 0.01 75.68 ± 0.02 75.75 ± 0.02
(25.48 ± 2.70) (23.27 ± 2.25) (12.64 ± 1.18) (14.64 ± 2.36) (14.35 ± 1.97) (17.57 ± 1.30) (20.99 ± 2.31) (19.66 ± 2.38)
0.25 76.04 ± 0.02 76.24 ± 0.03 76.48 ± 0.01 76.54 ± 0.01 76.65 ± 0.02 76.74 ± 0.02 76.85 ± 0.01 76.93 ± 0.01
(26.40 ± 2.07) (25.89 ± 2.66) (19.64 ± 1.52) (23.10 ± 1.49) (20.60 ± 2.26) (25.38 ± 1.75) (26.12 ± 1.01) (32.56 ± 0.59)
0.50 77.27 ± 0.03 77.39 ± 0.02 77.60 ± 0.03 77.69 ± 0.04 77.75 ± 0.02 77.79 ± 0.02 77.93 ± 0.03 77.98 ± 0.01
(44.41 ± 3.76) (34.32 ± 2.84) (19.91 ± 3.35) (20.86 ± 4.10) (24.55 ± 2.27) (33.46 ± 2.14) (33.36 ± 3.21) (32.24 ± 1.61)
0.75 78.46 ± 0.002 78.56 ± 0.02 78.71 ± 0.03 78.82 ± 0.01 78.90 ± 0.008 78.95 ± 0.03 79.11 ± 0.02 79.16 ± 0.01
(4.23 ± 0.33) (11.50 ± 1.97) (27.31 ± 3.02) (24.49 ± 1.40) (28.81 ± 0.85) (31.10 ± 3.68) (28.16 ± 2.30) (38.43 ± 1.57)
L-Aspartic acid in an aqueous solution of tri-sodium citrate
0.1 76.51 ± 0.02 76.71 ± 0.01 76.92 ± 0.01 76.98 ± 0.03 77.02 ± 0.03 77.12 ± 0.01 77.22 ± 0.007 77.26 ± 0.01
(22.38 ± 2.38) (17.03 ± 1.23) (16.05 ± 1.44) (24.68 ± 3.87) (28.24 ± 3.78) (15.76 ± 1.46) (18.43 ± 0.90) (23.00 ± 1.39)
0.25 77.20 ± 0.005 77.40 ± 0.02 77.61 ± 0.01 77.72 ± 0.01 77.78 ± 0.03 77.95 ± 0.02 78.12 ± 0.05 78.18 ± 0.01
(17.99 ± 0.52) (22.63 ± 2.29) (10.25 ± 1.13) (12.55 ± 0.90) (28.84 ± 2.86) (27.47 ± 2.32) (31.73 ± 4.68) (30.23 ± 1.34)
0.50 78.26 ± 0.01 78.48 ± 0.01 78.71 ± 0.01 78.82 ± 0.02 78.84 ± 0.02 79.00 ± 0.02 79.05 ± 0.02 79.11 ± 0.02
(22.48 ± 1.16) (20.19 ± 1.23) (13.71 ± 1.08) (15.64 ± 2.03) (25.68 ± 1.57) (21.00 ± 1.76) (27.61 ± 1.83) (28.47 ± 2.25)
0.75 79.23 ± 0.02 79.42 ± 0.01 79.64 ± 0.02 79.75 ± 0.02 79.79 ± 0.02 79.81 ± 0.02 79.88 ± 0.01 79.94 ± 0.03
(33.88 ± 2.43) (24.78 ± 1.52) (17.23 ± 1.73) (18.05 ± 1.71) (16.40 ± 2.20) (18.86 ± 2.20) (21.13 ± 1.20) (27.03 ± 3.29)
L-Glutamic acid in an aqueous solution of di-sodium tartrate
0.0 88.34 ± 0.01 88.78 ± 0.04 89.70 ± 0.02 90.01 ± 0.01 90.64 ± 0.03 91.19 ± 0.03 91.46 ± 0.03 91.90 ± 0.02
88.35a, 88.88b 86.68e 89.65a, 90.19b, 87.84e, 89.25e 90.54a, 91.05b 89.87e 91.20a 90.64e
89 f, 90.06 f, 89.64g, 89.65g
(17.83 ± 0.51) (22.72 ± 2.42) (11.13 ± 1.08) (19.88 ± 0.86) (12.77 ± 1.80) (20.83 ± 1.91) (16.57 ± 1.49) (18.29 ± 1.26)
0.1 90.37 ± 0.03 90.62 ± 0.01 91.10 ± 0.04 91.23 ± 0.02 91.46 ± 0.03 91.72 ± 0.03 91.86 ± 0.03 92.01 ± 0.06
(16.23 ± 1.31) (18.16 ± 0.54) (14.97 ± 2.09) (19.55 ± 1.23) (19.40 ± 1.29) (13.04 ± 1.30) (21.12 ± 1.63) (23.46 ± 2.93)
0.25 91.16 ± 0.03 91.32 ± 0.01 91.57 ± 0.03 91.73 ± 0.04 91.92 ± 0.03 92.17 ± 0.01 92.31 ± 0.02 92.52 ± 0.03
(13.60 ± 1.74) (17.47 ± 0.62) (13.77 ± 1.55) (18.93 ± 2.12) (17.61 ± 1.49) (15.50 ± 0.58) (17.96 ± 1.29) (18.35 ± 1.96)
0.50 91.59 ± 0.03 91.86 ± 0.03 92.35 ± 0.02 92.41 ± 0.06 92.75 ± 0.04 93.17 ± 0.01 93.33 ± 0.02 93.49 ± 0.07
(14.53 ± 1.57) (20.06 ± 1.32) (11.94 ± 0.78) (19.37 ± 2.88) (18.96 ± 1.89) (13.09 ± 0.68) (13.05 ± 1.14) (21.08 ± 3.37)
0.75 91.76 ± 0.01 92.05 ± 0.04 92.50 ± 0.04 92.71 ± 0.05 93.06 ± 0.01 93.56 ± 0.02 93.77 ± 0.03 93.95 ± 0.06
(23.58 ± 1.05) (17.30 ± 3.03) (24.03 ± 3.00) (24.22 ± 4.05) (18.56 ± 0.63) (19.44 ± 1.54) (19.24 ± 2.84) (25.87 ± 4.95)
L-Glutamic acid in an aqueous solution of tri-sodium citrate
0.1 91.83 ± 0.07 92.00 ± 0.04 92.14 ± 0.02 92.25 ± 0.01 92.36 ± 0.01 92.50 ± 0.05 92.59 ± 0.03 92.87 ± 0.03
(23.01 ± 3.57) (22.73 ± 2.30) (14.79 ± 1.09) (14.51 ± 0.75) (14.67 ± 0.54) (21.27 ± 2.74) (23.33 ± 1.76) (16.12 ± 1.57)
0.25 92.28 ± 0.03 92.44 ± 0.03 92.90 ± 0.03 93.01 ± 0.03 93.28 ± 0.03 93.50 ± 0.02 93.60 ± 0.07 93.70 ± 0.06
(16.13 ± 1.84) (13.40 ± 1.49) (12.20 ± 1.89) (15.75 ± 1.74) (19.07 ± 1.39) (16.54 ± 1.35) (23.30 ± 3.89) (23.59 ± 3.50)
0.50 93.16 ± 0.03 93.35 ± 0.03 93.74 ± 0.02 93.83 ± 0.04 94.18 ± 0.03 94.40 ± 0.03 94.54 ± 0.03 94.80 ± 0.02
(25.23 ± 2.01) (17.86 ± 1.69) (13.98 ± 1.20) (24.25 ± 2.27) (16.30 ± 2.00) (20.15 ± 1.60) (27.98 ± 1.56) (13.29 ± 1.05)
0.75 94.09 ± 0.01 94.23 ± 0.05 94.65 ± 0.01 94.74 ± 0.03 94.86 ± 0.05 95.17 ± 0.01 95.30 ± 0.03 95.51 ± 0.04
(16.50 ± 0.48) (17.87 ± 2.86) (11.21 ± 0.60) (15.94 ± 1.76) (21.36 ± 2.53) (14.19 ± 0.79) (15.59 ± 1.39) (21.00 ± 2.14)
a
Ref. 24. b Ref. 25. c Ref. 26. d Ref. 27. e Ref. 28. f Ref. 29. g Ref. 30; parentheses contain Sv (m3 kg mol−2) values; standard uncertainties, u, are u(T ) = 0.03 K, u(p) = 0.5 kPa, u(m) = 2.8 × 10−4
mol kg−1.
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Fig. 4 (a, d, g and j) Partial molar volume of transfer values, ΔtrV2,ϕ0, of L-aspartic acid and L-glutamic acid vs. mB for aqueous solutions of di-
sodium tartrate and tri-sodium citrate at T = (◆) 288.15 K; (■) 293.15 K; (▲) 298.15 K; (×) 303.15 K; (*) 308.15 K; (●) 313.15 K; (+) 318.15 K; and (−)
323.15 K. (b, e, h and k) partial molar isentropic compression of transfer values, ΔtrKs,2,ϕ0, of L-aspartic acid and L-glutamic acid vs. mB for aqueous
solutions of di-sodium tartrate and tri-sodium citrate at T = (◆) 288.15 K; (■) 293.15 K; (▲) 298.15 K; (×) 303.15 K; (*) 308.15 K; (●) 313.15 K; (+)
318.15 K; and (−) 323.15 K. (c, f, i and l) Viscosity B-coefficient of transfer values, ΔtrB, of L-aspartic acid and L-glutamic acid vs. mB for aqueous solu-
tions of di-sodium tartrate and tri-sodium citrate at T = (◆) 288.15 K; (■) 298.15 K; (▲) 308.15 K; and (×) 308.15 K.

is more preferred than DST.37 TSC has also been found to be a water and creating a firmer texture. Thus, it helps in the pro-
better food emulsifier than DST in the literature.5 TSC helps cessing of baked foods.38,39 Therefore, the Nh data also indi-
control the stickiness of some doughs through removing extra cate that TSC is a better food preservative than DST.

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3.1.6. Partial molar expansion, E2,ϕ0. To discuss the effects
of temperature on the V2,ϕ0 values, the partial molar expansion
values, E2,ϕ0 (E2,ϕ0 = (∂V2,ϕ0/∂T )P), along with the 2nd order
derivatives, (∂2V2,ϕ0/∂T2)P, have been calculated by the method
of least-squares using the following equation:
V 2;ϕ 0 ¼ a þ bT þ cT 2 ð8Þ
where a, b and c are constants, and T is the temperature in
Kelvin. The (∂V2,ϕ0/∂T )P values are positive for the
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studied solutes (Table S4†), except for ASP in TSC at mB =
0.75 mol kg−1 and at T = 323.15 K. The (∂V2,ϕ0/∂T )P values
decrease with temperature, except for GLU in DST at mB =
0.25 mol kg−1 at higher temperatures and GLU in TSC at mB =
0.1 mol kg−1 at all temperatures. However, the (∂V2,ϕ0/∂T )P
values do not follow any regular trend in relation to the mB
values.
Hepler40 used a general thermodynamic equation,
{(∂CP,20/∂P)T = −T (∂2V2,ϕ0/∂T2)P}, to determine the capacity of a
solute to act as a structure-maker or a structure-breaker in
solution. If the term (∂2V2,ϕ0/∂T2)P < 0, the solute is a
structure-breaker and if (∂2V2,ϕ0/∂T2)P > 0, the solute is a struc-
ture-maker. The negative values of (∂2V2,ϕ0/∂T2)P in aqueous
solutions of the co-solutes suggest that ASP and GLU act as
structure-breaking solutes. However, at mB = 0.1 mol kg−1, GLU
acts as a structure-maker in the case of TSC.
3.1.7. Interaction coefficients. Interaction coefficients have
been calculated using the McMillan–Mayer equation41 from
the transfer volume, ΔtrV2,ϕ0, data for the studied solutes as
follows:
Δtr V 2;ϕ 0 ¼ 2V AB  mB þ 3V ABB  mB 2 þ … ð9Þ
where A stands for the solute and B for the co-solute, and VAB
and VABB are the volumetric pair and triplet interaction coeffi-
cients, respectively (Table S5†). The higher magnitudes of VAB
( positive values) in comparison to VABB (negative values, except
for GLU in DST at T = 323.15 K) for the studied solutes at all
temperatures suggest the predominance of pair-wise inter-
actions. This suggests the dominance of hydrophilic–ionic/
hydrophilic interactions, which again strengthens the above-
mentioned views.
3.2. Acoustic measurements
3.2.1. Speed of sound, u. The speed of sound, u, of amino
acids (ASP and GLU) in water and in aqueous solutions of DST
and TSC at mB = 0.10, 0.25, 0.50 and 0.75 mol kg−1 and at
temperatures from 288.15 to 323.15 K are given in Table 4. The
u values of water are in agreement with the literature values.42
The u values in aqueous solutions of DST and TSC match well
with the available literature data,16–21,23 as seen in Fig. 5. The
u values of ASP and GLU in water are in close agreement with
the available literature data, as seen in Fig. 6.25–27 The u values
increase with the mA, mB and T values, as is evident from the
3-D plot (Fig. 3(c)) of u versus mA for ASP at different tempera-
tures in TSC at mB = 0.1 mol kg−1.
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3.2.2. Apparent molar isentropic compression, Ks,2,ϕ. The
Ks,2,ϕ values for solutes in water and in aqueous solutions of
DST and TSC at mB = 0.10, 0.25, 0.50, and 0.75 mol kg−1 and at
temperatures from 288.15 to 323.15 K (given in Table S6†)
have been calculated using the following relationship:
K s;2;ϕ ¼ ðκs M=ρÞ  fðκs o ρ  κs ρ0 Þ=ðmA ρρ0 Þg ð10Þ
The Ks,2,ϕ values are negative, and their magnitudes
decrease with increases in the temperature and in the concen-
trations of both the solute and co-solute. ρ and ρ0, and κs and
κso are the densities and isentropic compressibilities of the
solution and solvent, respectively. The isentropic compressibil-
ities (κs) were calculated from the measured speed of sound (u)
as follows:
κs ¼ 1=u 2 ρ: ð11Þ
3.2.3. Partial molar isentropic compression, Ks,2,ϕ0. The
Ks,2,ϕ0 values have been calculated using the least squares
fitting of the respective data to the given equation:
K s;2;ϕ ¼ K s;2;ϕ 0 þ Sk m: ð12Þ
At infinite dilution, Ks,2,ϕ0, the apparent molar isentropic
compression, and the partial molar isentropic compression,
Ks,20, become the same. The Ks,2,ϕ0 values of the studied
solutes in water agree well with the literature values.25–27,29,30
The Ks,2,ϕ0 values of the solutes are negative in water as well as
in aqueous solutions of the co-solutes, which may be due to
the hydration of the solutes, as the hydrated water molecules
are already compressed and are thus less compressible than
those present in the bulk. The magnitudes of the Ks,2,ϕ0 values
decrease with temperature and with the co-solute concen-
trations (Table 5).
3.2.4. Partial molar isentropic compression of transfer,
ΔtrKs,2,ϕ0. The partial molar isentropic compression of transfer
values (ΔtrKs,2,ϕ0) were calculated using the following equation:
Δtr K s;2;ϕ 0 ¼ K s;2;ϕ 0 ðin aqueous solutions of DST=TSCÞ
 K s;2;ϕ 0 ðin waterÞ: ð13Þ
The ΔtrKs,2,ϕ0 values are positive for all solutes; this suggests
the predominance of hydrophilic–ionic/hydrophilic inter-
actions and the strengthening of these interactions over the
entire studied concentration range. The magnitudes decrease
with an increase in temperature, as shown in Fig. 4(b, e, h and
k). Due to interactions between the hydrophilic sites of the
amino acids and the citrate and tartrate ions of the co-solutes,
the less compressible water molecules in the hydration shells
of the solute molecules come out in the bulk water, hence
exhibiting positive ΔtrKs,2,ϕ0 values. Higher ΔtrKs,2,ϕ0 values are
observed for the studied solutes in the case of TSC compared
to DST.
3.3. Viscosity measurements
Viscosities have been determined for ASP and GLU in water
and in aqueous solutions of DST and TSC, over an mB
value range from 0.1–0.75 mol kg−1 and from T = 288.15 to
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Table 4 The speed of sound values, u, of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium
citrate at T values from 288.15 to 323.15 K and P = 101.3 kPa

u/m sec−1

mA/mol kg−1 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

L-Aspartic acid in water

0.00000 1466.83 1483.03 1497.10 1510.02 1519.83 1529.98 1536.40 1542.99
0.00517 1467.53 1483.68 1497.71 1510.59 1520.34 1530.45 1536.84 1543.38
0.00712 1467.78 1483.92 1497.94 1510.81 1520.54 1530.62 1536.99 1543.52
0.00921 1468.04 1484.17 1498.18 1511.04 1520.75 1530.80 1537.15 1543.67
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0.01109 1468.28 1484.39 1498.40 1511.25 1520.94 1530.96 1537.30 1543.80

0.01300 1468.51 1484.62 1498.62 1511.46 1521.13 1531.12 1537.45 1543.94
0.01506 1468.76 1484.86 1498.85 1511.68 1521.33 1531.29 1537.60 1544.08
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.1 mol kg
0.00000 1478.73 1494.57 1511.87 1522.45 1534.08 1543.75 1550.05 1557.45
0.00502 1479.25 1495.10 1512.40 1522.98 1534.59 1544.18 1550.48 1557.85
0.00741 1479.50 1495.34 1512.65 1523.23 1534.83 1544.38 1550.68 1558.04
0.01180 1479.95 1495.80 1513.28 1523.69 1535.27 1544.75 1551.05 1558.39
0.01306 1480.07 1495.93 1513.34 1523.82 1535.39 1544.85 1551.16 1558.48
0.01732 1480.51 1496.36 1514.04 1524.26 1535.81 1545.21 1551.51 1558.82
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
0.00000 1504.97 1519.22 1533.45 1544.85 1554.33 1561.75 1569.19 1577.89
0.00584 1505.61 1519.86 1534.09 1545.48 1554.91 1562.23 1569.64 1578.31
0.00817 1505.86 1520.11 1534.34 1545.73 1555.14 1562.42 1569.82 1578.47
0.01106 1506.17 1520.43 1534.65 1546.04 1555.42 1562.65 1570.03 1578.67
0.01337 1506.42 1520.67 1534.90 1546.28 1555.64 1562.83 1570.20 1578.82
0.01555 1506.65 1520.91 1535.13 1546.51 1555.85 1563.00 1570.36 1578.97
0.01667 1506.77 1521.03 1535.25 1546.63 1555.95 1563.08 1570.43 1579.04
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.50 mol kg
0.00000 1549.36 1558.64 1569.41 1579.85 1588.09 1595.45 1601.10 1609.00
0.00638 1550.10 1559.37 1570.12 1580.54 1588.70 1595.96 1601.62 1609.47
0.00782 1550.27 1559.53 1570.28 1580.69 1588.84 1596.07 1601.74 1609.57
0.00982 1550.50 1559.76 1570.50 1580.89 1589.02 1596.22 1601.90 1609.72
0.01307 1550.87 1560.12 1570.85 1581.23 1589.33 1596.47 1602.16 1609.95
0.01509 1551.10 1560.35 1571.07 1581.44 1589.52 1596.62 1602.31 1610.09
0.01639 1551.24 1560.49 1571.20 1581.57 1589.63 1596.72 1602.41 1610.18
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
0.00000 1588.75 1597.00 1605.38 1615.75 1621.84 1628.04 1633.00 1641.75
0.00547 1589.45 1597.68 1606.03 1616.37 1622.42 1628.51 1633.50 1642.22
0.00739 1589.69 1597.92 1606.26 1616.58 1622.62 1628.67 1633.67 1642.38
0.01025 1590.05 1598.27 1606.59 1616.90 1622.91 1628.90 1633.92 1642.62
0.01347 1590.45 1598.66 1606.97 1617.25 1623.26 1629.16 1634.20 1642.89
0.01664 1590.84 1599.04 1607.33 1617.60 1623.57 1629.41 1634.48 1643.15
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
0.00000 1487.73 1503.57 1517.21 1529.07 1539.24 1548.45 1555.13 1562.78
0.00576 1488.28 1504.12 1517.76 1529.62 1539.76 1548.87 1555.53 1563.15
0.00754 1488.45 1504.29 1517.93 1529.79 1539.91 1549.00 1555.65 1563.27
0.01002 1488.69 1504.52 1518.16 1530.02 1540.13 1549.18 1555.82 1563.42
0.01189 1488.86 1504.70 1518.34 1530.19 1540.30 1549.31 1555.94 1563.54
0.0152 1489.17 1505.01 1518.65 1530.49 1540.59 1549.55 1556.16 1563.75
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
0.00000 1517.97 1533.22 1545.99 1557.02 1566.44 1574.85 1580.99 1587.00
0.00624 1518.60 1533.83 1546.57 1557.57 1566.95 1575.25 1581.36 1587.34
0.00784 1518.76 1533.98 1546.71 1557.71 1567.08 1575.35 1581.45 1587.42
0.01080 1519.05 1534.27 1546.98 1557.97 1567.31 1575.53 1581.62 1587.58
0.01208 1519.18 1534.39 1547.10 1558.08 1567.41 1575.61 1581.69 1587.65
0.01490 1519.46 1534.66 1547.35 1558.32 1567.63 1575.78 1581.85 1587.79
0.01825 1519.79 1534.97 1547.65 1558.61 1567.90 1575.99 1582.03 1587.96
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.50 mol kg
0.00000 1568.36 1582.64 1593.94 1603.61 1611.76 1618.75 1624.10 1630.01
0.00597 1569.02 1583.27 1594.55 1604.20 1612.28 1619.16 1624.48 1630.34
0.00809 1569.26 1583.49 1594.77 1604.40 1612.46 1619.30 1624.61 1630.46
0.00985 1569.45 1583.67 1594.95 1604.57 1612.61 1619.42 1624.72 1630.56
0.01284 1569.77 1583.98 1595.26 1604.86 1612.85 1619.62 1624.91 1630.73
0.01520 1570.03 1584.22 1595.50 1605.08 1613.05 1619.77 1625.05 1630.86
0.0181 1570.34 1584.46 1595.78 1605.35 1613.28 1619.95 1625.22 1631.03
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
0.00000 1618.75 1632.06 1641.90 1650.20 1657.08 1662.45 1667.20 1673.45
0.00626 1619.55 1632.82 1642.62 1650.89 1657.68 1662.89 1667.60 1673.84
0.00788 1619.75 1633.01 1642.80 1651.06 1657.83 1663.00 1667.70 1673.94
0.01082 1620.12 1633.36 1643.13 1651.38 1658.10 1663.21 1667.89 1674.13

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Table 4 (Contd.)

u/m sec−1

mA/mol kg−1 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

0.01180 1620.24 1633.47 1643.24 1651.48 1658.18 1663.28 1667.95 1674.19

0.01461 1620.59 1633.80 1643.55 1651.77 1658.44 1663.48 1668.13 1674.36
0.01732 1620.92 1634.12 1643.85 1652.05 1658.68 1663.67 1668.30 1674.53
L-Glutamic acid in water
0.01104 1467.12 1483.26 1497.44 1510.18 1520.06 1530.36 1536.68 1543.40
0.01308 1467.16 1483.31 1497.49 1510.23 1520.12 1530.42 1536.73 1543.45
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0.01522 1467.21 1483.36 1497.54 1510.28 1520.17 1530.47 1536.79 1543.51

0.02078 1467.34 1483.49 1497.68 1510.43 1520.32 1530.62 1536.94 1543.66
0.02517 1467.45 1483.60 1497.79 1510.54 1520.44 1530.74 1537.06 1543.79
0.03030 1467.57 1483.72 1497.92 1510.68 1520.57 1530.88 1537.21 1543.93
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.1 mol kg
0.01288 1479.08 1494.93 1512.24 1522.82 1534.46 1544.13 1550.43 1557.83
0.01523 1479.15 1495.00 1512.31 1522.89 1534.53 1544.20 1550.50 1557.91
0.01930 1479.27 1495.11 1512.43 1523.01 1534.65 1544.32 1550.63 1558.03
0.02496 1479.43 1495.28 1512.59 1523.18 1534.82 1544.49 1550.80 1558.20
0.03127 1479.61 1495.46 1512.78 1523.37 1535.01 1544.68 1550.99 1558.40
0.03591 1479.74 1495.60 1512.92 1523.52 1535.16 1544.82 1551.14 1558.55
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
0.01410 1505.42 1519.67 1533.90 1545.31 1554.79 1562.22 1569.66 1578.36
0.01930 1505.89 1520.15 1534.39 1545.80 1555.29 1562.71 1570.16 1578.86
0.02391 1506.10 1520.36 1534.60 1546.01 1555.50 1562.92 1570.37 1579.07
0.03000 1506.41 1520.67 1534.92 1546.33 1555.82 1563.25 1570.69 1579.40
0.03535 1506.52 1520.79 1535.03 1546.45 1555.94 1563.37 1570.82 1579.52
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.50 mol kg
0.01104 1549.82 1559.11 1569.89 1580.33 1588.57 1595.94 1601.59 1609.49
0.01239 1549.87 1559.16 1569.94 1580.38 1588.62 1595.99 1601.64 1609.54
0.01547 1549.99 1559.28 1570.05 1580.50 1588.74 1596.11 1601.76 1609.67
0.02012 1550.13 1559.42 1570.20 1580.64 1588.89 1596.26 1601.91 1609.82
0.02521 1550.34 1559.64 1570.42 1580.87 1589.12 1596.49 1602.14 1610.05
0.03006 1550.78 1560.09 1570.86 1581.32 1589.57 1596.95 1602.60 1610.51
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
0.01159 1589.26 1597.51 1605.79 1616.32 1622.37 1628.57 1633.54 1642.29
0.01375 1589.35 1597.60 1605.89 1616.42 1622.47 1628.67 1633.64 1642.39
0.01765 1589.52 1597.78 1606.07 1616.60 1622.64 1628.86 1633.82 1642.58
0.01995 1589.63 1597.88 1606.17 1616.71 1622.75 1628.97 1633.93 1642.69
0.02676 1589.93 1598.18 1606.49 1617.02 1623.07 1629.29 1634.25 1643.01
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
0.01247 1488.11 1503.95 1517.59 1529.46 1539.63 1548.84 1555.52 1563.17
0.01463 1488.18 1504.02 1517.66 1529.52 1539.67 1548.91 1555.59 1563.23
0.01634 1488.23 1504.07 1517.72 1529.58 1539.75 1548.97 1555.65 1563.29
0.02218 1488.41 1504.26 1517.90 1529.76 1539.94 1549.16 1555.84 1563.47
0.02857 1488.62 1504.47 1518.11 1529.97 1540.14 1549.36 1556.05 1563.67
0.03390 1488.79 1504.64 1518.28 1530.14 1540.32 1549.54 1556.22 1563.84
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
0.01213 1518.40 1533.65 1546.43 1557.46 1566.88 1575.30 1581.44 1587.45
0.01438 1518.48 1533.73 1546.52 1557.55 1566.97 1575.39 1581.53 1587.54
0.01771 1518.60 1533.86 1546.64 1557.67 1567.10 1575.51 1581.66 1587.66
0.02308 1518.79 1534.05 1546.84 1557.87 1567.31 1575.72 1581.86 1587.87
0.02531 1518.88 1534.13 1546.92 1557.96 1567.39 1575.80 1581.95 1587.96
0.03401 1519.19 1534.45 1547.24 1558.29 1567.73 1576.14 1582.28 1588.29
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.50 mol kg
0.01104 1568.85 1583.14 1594.44 1604.12 1612.26 1619.26 1624.61 1630.52
0.01239 1568.92 1583.20 1594.51 1604.18 1612.33 1619.32 1624.67 1630.58
0.01547 1569.06 1583.34 1594.65 1604.32 1612.47 1619.47 1624.82 1630.72
0.02012 1569.27 1583.55 1594.86 1604.54 1612.69 1619.69 1625.04 1630.94
0.02521 1569.51 1583.79 1595.10 1604.78 1612.93 1619.93 1625.28 1631.17
0.03006 1569.73 1583.96 1595.33 1605.02 1613.16 1620.16 1625.52 1631.40
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
0.01088 1619.34 1632.66 1642.51 1650.81 1657.69 1663.06 1667.81 1674.06
0.01408 1619.52 1632.83 1642.69 1650.99 1657.87 1663.24 1667.99 1674.24
0.01532 1619.59 1632.90 1642.75 1651.06 1657.94 1663.31 1668.06 1674.31
0.02000 1619.85 1633.17 1643.02 1651.32 1658.21 1663.57 1668.32 1674.58
0.02799 1620.29 1633.61 1643.47 1651.78 1658.66 1664.03 1668.77 1675.03
0.03107 1620.47 1633.79 1643.64 1651.95 1658.84 1664.20 1668.95 1675.21

mA is the molality of the solute in water or water + DST/TSC. mB is the molality of DST/TSC in water. Standard uncertainties, u, are u(T ) = 0.03 K,
u(P) = 0.5 kPa, u(m) = 2.8 × 10−4 mol kg−1, u(u) = 0.6 m s−1.

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Fig. 5 (a) Plots of speed of sound values, u, versus molality, mB, for
aqueous solutions of TSC and comparisons with the literature values at
different temperatures. (b) Plots of speed of sound values, u, versus mol-
ality, mB, for aqueous solutions of DST and comparisons with the litera-
ture values at different temperatures.
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Fig. 6 (a) Plots of speed of sound values, u, versus molality, mA, for
aqueous solutions of ASP and comparisons with the literature values at
different temperatures. (b) Plots of speed of sound values, u, versus mol-
ality, mA, for aqueous solutions of GLU and comparisons with the litera-
ture values at different temperatures.
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Table 5 Partial molar isentropic compression values, Ks,2,ϕ0, of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium citrate at T values from
288.15 to 323.15 K and P = 101.3 kPa
Paper

Food Funct.
1014·Ks,2,ϕ0/m3 mol−1 Pa−1

mB/mol kg−1 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 318.15 K 323.15 K

L-Aspartic acid in an aqueous solution of di-sodium tartrate

0 −7.51 ± 0.01 −7.09 ± 0.02 −6.63 ± 0.01 −6.26 ± 0.01 −5.60 ± 0.84 −4.50 ± 0.01 −4.11 ± 0.02 −3.64 ± 0.01
(11.45 ± 0.80) (16.68 ± 1.44) −3.61a, −6.67b, −7.14c (18.28 ± 0.88) −3.06 a (12.76 ± 0.52) (17.70 ± 2.30) (13.34 ± 0.63)
(17.12 ± 0.28) −6.24b,c (19.59 ± 0.84) −4.53b,c
−5.60b, −5.61c
0.1 −5.39 ± 0.01 −5.29 ± 0.01 −5.19 ± 0.02 −5.08 ± 0.01 −4.75 ± 0.01 −3.86 ± 0.01 −3.81 ± 0.01 −3.50 ± 0.01
(7.39 ± 0.89) (7.88 ± 0.50) (7.62 ± 1.33) (6.25 ± 0.35) (7.20 ± 0.75) (8.42 ± 0.95) (7.48 ± 0.56) (8.02 ± 0.98)
0.25 −5.09 ± 0.01 −4.94 ± 0.01 −4.82 ± 0.01 −4.63 ± 0.01 −4.18 ± 0.01 −3.23 ± 0.02 2.96 ± 0.01 −2.63 ± 0.01
(11.00 ± 0.42) (8.48 ± 0.57) (10.92 ± 0.44) (8.86 ± 0.84) (13.29 ± 0.45) (11.71 ± 1.23) (12.61 ± 0.69) (12.95 ± 0.88)
0.50 −4.40 ± 0.01 −4.27 ± 0.01 −4.05 ± 0.01 −3.82 ± 0.01 −3.23 ± 0.01 −2.50 ± 0.01 −2.56 ± 0.01 −2.19 ± 0.01
(8.57 ± 0.66) (10.48 ± 1.03) (10.40 ± 1.22) (13.37 ± 0.64) (8.73 ± 0.86) (12.56 ± 1.16) (9.18 ± 0.56) (9.62 ± 0.58)
0.75 −4.10 ± 0.01 −3.88 ± 0.01 −3.60 ± 0.01 −3.34 ± 0.01 −3.01 ± 0.01 −2.18 ± 0.01 −2.39 ± 0.01 −2.16 ± 0.01
(9.10 ± 0.50) (7.71 ± 0.36) (7.67 ± 0.74) (9.43 ± 0.55) (8.06 ± 0.33) (10.92 ± 0.25) (10.13 ± 0.81) (8.75 ± 0.43)
L-Aspartic acid in an aqueous solution of tri-sodium citrate
0.1 −4.66 ± 0.01 −4.50 ± 0.01 4.37 ± 0.01 −4.29 ± 0.01 −3.89 ± 0.01 −2.99 ± 0.01 −2.77 ± 0.01 −2.47 ± 0.01
(8.65 ± 0.43) (7.58 ± 1.05) (8.51 ± 0.54) (12.76 ± 0.81) (9.43 ± 0.61) (9.30 ± 0.98) (11.02 ± 1.23) (7.58 ± 1.05)
0.25 −4.20 ± 0.01 −3.89 ± 0.01 −3.56 ± 0.01 −3.30 ± 0.01 −2.89 ± 0.01 −2.01 ± 0.01 −1.79 ± 0.02 −1.54 ± 0.01
(8.33 ± 1.12) (7.91 ± 0.96) (9.29 ± 0.72) (8.03 ± 0.55) (8.54 ± 0.62) (9.38 ± 0.80) (10.16 ± 1.24) (8.07 ± 0.52)
0.50 −3.61 ± 0.01 −3.27 ± 0.01 −3.04 ± 0.02 −2.87 ± 0.02 −2.39 ± 0.02 −1.59 ± 0.02 −1.40 ± 0.02 −1.04 ± 0.01
(9.93 ± 0.74) (10.41 ± 0.81) (2.97 ± 1.65) (10.01 ± 1.44) (13.60 ± 1.70) (8.54 ± 1.65) (8.33 ± 1.46) (1.07 ± 0.37)
0.75 −3.31 ± 0.01 −3.01 ± 0.01 −2.74 ± 0.01 −2.50 ± 0.01 −2.01 ± 0.01 −1.10 ± 0.01 −0.88 ± 0.01 −0.84 ± 0.01
(9.49 ± 0.62) (9.41 ± 0.30) (9.33 ± 0.69) (8.00 ± 0.59) (10.11 ± 1.13) (0.61 ± 0.39) (11.17 ± 0.72) (1.11 ± 0.37)
1016·Ks,2,ϕ0/m3 mol−1 Pa−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate
0 −3.86 ± 0.01 −3.50 ± 0.01 −3.18 ± 0.01 −2.75 ± 0.02 −2.46 ± 0.01 −2.18 ± 0.01 −2.06 ± 0.02 −1.92 ± 0.01
−3.37a (5.81 ± 0.60) −3.20a, −3.18d, −3.92e (5.79 ± 1.08) −2.20a (6.80 ± 0.54) (6.58 ± 0.89) (8.64 ± 0.61)
(5.87 ± 0.67) (6.25 ± 0.56) (7.16 ± 0.68)
0.1 −2.58 ± 0.02 −2.44 ± 0.01 −2.30 ± 0.01 −2.16 ± 0.01 −2.03 ± 0.01 −1.85 ± 0.01 −1.80 ± 0.02 −1.71 ± 0.01
(4.57 ± 0.63) (4.63 ± 0.44) (4.42 ± 0.59) (4.91 ± 0.26) (5.26 ± 0.52) (4.91 ± 0.33) (4.81 ± 0.67) (5.47 ± 0.44)
0.25 −2.45 ± 0.01 −2.34 ± 0.01 −2.13 ± 0.01 −2.02 ± 0.01 −1.94 ± 0.01 −1.80 ± 0.01 −1.72 ± 0.01 −1.60 ± 0.01
(4.13 ± 0.20) (4.10 ± 0.53) (4.86 ± 0.47) (3.95 ± 0.28) (4.30 ± 0.54) (6.42 ± 0.53) (4.91 ± 0.46) (4.51 ± 0.36)
0.50 −2.33 ± 0.02 −2.23 ± 0.01 −2.07 ± 0.02 −1.93 ± 0.03 −1.75 ± 0.02 −1.63 ± 0.02 −1.57 ± 0.03 −1.46 ± 0.01
(4.55 ± 0.93) (4.83 ± 0.61) (5.03 ± 0.74) (5.28 ± 1.13) (4.76 ± 0.80) (5.48 ± 0.73) (4.85 ± 1.26) (5.25 ± 0.60)
0.75 −2.28 ± 0.02 −2.16 ± 0.02 −2.00 ± 0.01 −1.87 ± 0.02 −1.73 ± 0.02 −1.58 ± 0.02 −1.47 ± 0.02 −1.40 ± 0.01
(6.44 ± 1.12) (6.33 ± 0.81) (5.86 ± 0.44) (6.13 ± 1.23) (6.46 ± 1.04) (7.82 ± 1.12) (6.15 ± 1.23) (6.94 ± 0.58)
L-Glutamic acid in an aqueous solution of tri-sodium citrate
0.1 −2.19 ± 0.02 −2.04 ± 0.02 −1.94 ± 0.02 −1.77 ± 0.02 −1.69 ± 0.01 −1.47 ± 0.02 −1.43 ± 0.01 −1.33 ± 0.02
(5.49 ± 0.67) (4.35 ± 0.71) (5.21 ± 0.96) (5.62 ± 0.74) (5.27 ± 0.59) (4.55 ± 0.66) (5.82 ± 0.61) (5.91 ± 0.80)
0.25 −2.05 ± 0.02 −1.90 ± 0.02 −1.77 ± 0.01 −1.62 ± 0.02 −1.49 ± 0.02 −1.31 ± 0.02 −1.27 ± 0.02 −1.15 ± 0.01
(5.71 ± 0.68) (6.24 ± 1.06) (4.68 ± 0.56) (6.34 ± 0.87) (4.84 ± 0.91) (6.43 ± 0.91) (6.40 ± 0.87) (4.43 ± 0.62)
0.50 −1.90 ± 0.01 −1.77 ± 0.01 −1.60 ± 0.02 −1.46 ± 0.01 −1.35 ± 0.01 −1.23 ± 0.02 −1.08 ± 0.01 −1.03 ± 0.01
(4.97 ± 0.71) (6.04 ± 0.54) (6.09 ± 0.83) (6.47 ± 0.56) (5.19 ± 0.66) (3.18 ± 1.05) (1.61 ± 0.43) (1.04 ± 0.16)
0.75 −1.76 ± 0.02 −1.65 ± 0.01 −1.49 ± 0.01 −1.36 ± 0.01 −1.23 ± 0.02 −1.07 ± 0.01 −1.01 ± 0.01 −1.00 ± 0.01
(5.66 ± 0.89) (5.70 ± 0.67) (6.84 ± 0.68) (5.43 ± 0.60) (4.89 ± 0.81) (0.59 ± 0.12) (0.15 ± 0.01) (0.45 ± 0.22)
a
Ref. 25. b Ref. 26. c Ref. 27. d Ref. 29. e Ref. 30; parentheses contain Sk (m3 mol−2 kg Pa−1) values; standard uncertainties, u, are u(T ) = 0.03 K, u(P) = 0.5 kPa, u(m) = 2.8 × 10−4 mol kg−1.
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318.15 K, from flow time measurements using the following
expression:
η=ρ ¼ At  B=t ð14Þ
where ρ is the density of the solution, t is the flow time, and A
and B are viscometric constants (A = 0.0000669 mPa m3 kg−1
and B = 0.2244 mPa m3 s2 kg−1). The η values of TSC and GLU
in water at 298.15 K matched well with the literature data
(Fig. S1, ESI†).22,28 The η values increase with an increase in
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the concentration of amino acid in water and in aqueous solu-
tions of DST/TSC, and decrease with temperature (Table 6).
The variation in η values for solutions of GLU in aqueous DST
at different temperatures are shown in Fig. 3(d) (viscosity, η,
versus molality, mA, for GLU in DST at mB = 0.1 mol kg−1 as a
function of temperature).
3.3.1. Viscosity B-coefficient. The relative viscosities are
given by
ηr ¼ η=η0 ð15Þ
where, η and η0 are the viscosities of the solution and solvent,
respectively. The B-coefficients were evaluated by fitting the ηr
values to the Jones–Dole equation43 via a least squares method
as follows:
ηr ¼ 1 þ BC ð16Þ
where C is the molar concentration (calculated from the molal-
ity and density data). The viscosity B-coefficient or B value pro-
vides knowledge about the solvation behaviour of solutes. The
B values of ASP and GLU in water at 298.15 K are in line with
the literature values.14 The B values for the studied amino
acids in water and in aqueous solutions of DST and TSC
increase with temperature and with the molality of the co-
solutes and they are given in Table S7.† The increase is greater
in the case of TSC compared to DST. As the B-coefficient is
directly dependent upon the size of the solute, the B value of
GLU is slightly greater compared to ASP. Moreover, due to the
greater ionic strength of TSC, the observed B values are larger
compared to DST. The increase in the B values with the DST
and TSC solution concentrations indicates a progressively
more structured environment.
The derivative of the B-coefficient with respect to T (dB/dT )
is a far better parameter for investigating the effects of addi-
tives on the structure of water, because it provides better infor-
mation about the structure-making or structure-breaking be-
havior of the solute compared with the B-coefficient. A positive
value of dB/dT indicates that a solute is a structure-breaker,
whereas a negative value indicates that a solute is a structure-
maker.44 The dB/dT values for ASP and GLU in water and in
aqueous solutions of DST and TSC at different temperatures
are given in Table S7.† The dB/dT values for ASP and GLU are
positive in water and in aqueous DST and TSC solutions,
which classifies these solutes as structure-breakers due to the
dominating effects of the hydrophilic groups (–NH2 and
–COOH) over the R-groups.
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3.3.2. Viscosity B-coefficient of transfer, ΔtrB. The viscosity
B-coefficients of transfer, ΔtrB, from water to aqueous DST and
TSC solutions have been calculated as follows:
Δtr B ¼ B-coefficient ðin aqueous DST=TSC solutionÞ-B-
ð17Þ
coefficient ðin waterÞ:
The B-coefficient values for the ASP and GLU amino acids
in aqueous solutions of DST and TSC are higher than the
values in water, which results in positive ΔtrB values. Plots of
the ΔtrB values as a function of the DST and TSC molality are
shown in Fig. 4(c, f, i, l). The transfer values increase with an
increase in the concentration of DST/TSC. For both solutes,
the ΔtrB values decrease with temperature in both aqueous
DST and TSC solutions. The ΔtrB values have greater magni-
tudes in the case of TSC, which may again be attributed to the
high charge density.
3.3.3. Ratio of the B-coefficient to the partial molar
volume, B/V2,ϕ0. The solvation can be judged by the ratio of
the B-coefficient to the partial molar volume (B/V2,ϕ0).
Unsolvated spherical species have B/V2,ϕ0 values ranging
between 0 and 2.5.14 Solvated spherical species have B/V2,ϕ0
values higher than 2.5. In the present study, the lesser magni-
tudes of the B/V2,ϕ0 values of the studied amino acids in the
presence of the co-solutes compared to in water indicate that
these amino acids are more solvated in water (Table S7†).
3.4. Enthalpy measurements from calorimetry
The q values for ASP/GLU (30 mmol kg−1) in the absence, as
well as in the presence, of aqueous solutions of DST and TSC
over an mB range from 100–500 mmol kg−1 at T = 298.15 K
have been measured using ITC. Positive q values for the
solutes have been observed in water and in the presence of
TSC/DST, whereas in some cases involving DST, negative q
values have also been observed (Table 7). These values
decrease with the molality of the solutes in water and increase
in the presence of the co-solutes. The ΔdilH0 values (Table S8†)
have been calculated by fitting the q and mA data to the follow-
ing equations:
q ¼ Δdil H 0 þ mA Sw ð18Þ
q ¼ Δdil H 0 þ mA Sw1 þ mA 2 Sw2 þ ::: ð19Þ
where Sw is the slope obtained via linear regression. In some
cases, ΔdilH0 values have been obtained using high order poly-
nomial fitting with the constants Sw1, Sw2, etc. Positive ΔdilH0
values, except for ASP in 100 mM DST and GLU in 100 and
250 mM DST, are observed for the studied amino acids in
aqueous media and in the presence of the co-solutes. The posi-
tive ΔdilH0 values indicate the dominance of dehydration
effects over hydrophilic–ionic/hydrophilic interactions. These
dehydration effects encourage their use to prevent against
microbial activity. Negative ΔdilH0 values indicate the predomi-
nance of hydrophilic–ionic/hydrophilic interactions. The mag-
nitude of endothermicity for ASP/GLU is greater in the case of
TSC than in the case of DST, which is in accordance with the
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Table 6 Viscosities, η, of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium citrate at T
values from 288.15 to 318.15 K and P = 101.3 kPa

η/mPa s

mA T/K T/K T/K T/K

mol kg−1 288.15 298.15 308.15 318.15

L-Aspartic acid in water

η0 = 1.1382 mPa s η0 = 0.8904 mPa s η0 = 0.7194 mPa s η0 = 0.5963 mPa s
0.00517 1.1390 0.8910 0.7197 0.5967
0.00712 1.1392 0.8912 0.7200 0.5968
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0.00921 1.1395 0.8915 0.7202 0.5970

0.01109 1.1397 0.8917 0.7205 0.5972
0.01300 1.1400 0.8919 0.7206 0.5973
0.01506 1.1404 0.8921 0.7208 0.5975
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.10 mol kg
η0 = 1.1631 mPa s η0 = 0.9518 mPa s η0 = 0.7783 mPa s η0 = 0.6644 mPa s
0.00502 1.1637 0.9525 0.7787 0.6647
0.00741 1.1640 0.9528 0.7790 0.6650
0.01180 1.1643 0.9529 0.7792 0.6651
0.01306 1.1646 0.9531 0.7794 0.6653
0.01732 1.1651 0.9534 0.7797 0.6655
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
η0 = 1.2425 mPa s η0 = 1.0248 mPa s η0 = 0.8544 mPa s η0 = 0.7244 mPa s
0.00584 1.2434 1.0255 0.8550 0.7247
0.00817 1.2436 1.0257 0.8553 0.7250
0.01106 1.2439 1.0260 0.8555 0.7253
0.01337 1.2442 1.0264 0.8556 0.7255
0.01555 1.2446 1.0266 0.8559 0.7256
0.01667 1.2451 1.0269 0.8561 0.7258
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.5 mol kg
η0 = 1.4178 mPa s η0 = 1.1996 mPa s η0 = 0.9924 mPa s η0 = 0.8446 mPa s
0.00638 1.4186 1.2005 0.9931 0.8448
0.00782 1.4188 1.2008 0.9933 0.8453
0.00982 1.4193 1.2011 0.9936 0.8456
0.01307 1.4199 1.2013 0.9939 0.8460
0.01509 1.4203 1.2017 0.9942 0.8462
0.01639 1.4209 1.2021 0.9944 0.8465
−1
L-Aspartic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
η0 = 1.6087 mPa s η0 = 1.3980 mPa s η0 = 1.1562 mPa s η0 = 0.9866 mPa s
0.00547 1.6099 1.3990 1.1570 0.9873
0.00739 1.6102 1.3992 1.1573 0.9875
0.01025 1.6107 1.3999 1.1577 0.9878
0.01347 1.6111 1.4001 1.1580 0.9881
0.01664 1.6115 1.4005 1.1583 0.9885
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
η0 = 1.2165 mPa s η0 = 0.9856 mPa s η0 = 0.8023 mPa s η0 = 0.6650 mPa s
0.00576 1.2170 0.9862 0.8029 0.6655
0.00754 1.2172 0.9865 0.8031 0.6656
0.01002 1.2175 0.9868 0.8033 0.6658
0.01189 1.2178 0.9871 0.8035 0.6660
0.0152 1.2180 0.9874 0.8037 0.6662
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
η0 = 1.4206 mPa s η0 = 1.1424 mPa s η0 = 0.9460 mPa s η0 = 0.7902 mPa s
0.00624 1.4217 1.1431 0.9467 0.7906
0.00784 1.4220 1.1434 0.9469 0.7908
0.01080 1.4224 1.1438 0.9473 0.7912
0.01208 1.4228 1.1442 0.9475 0.7914
0.01490 1.4231 1.1445 0.9478 0.7917
0.01825 1.4234 1.1448 0.9480 0.7921
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.5 mol kg
η0 = 1.7327 mPa s η0 = 1.4619 mPa s η0 = 1.2096 mPa s η0 = 1.0194 mPa s
0.00597 1.7340 1.4631 1.2103 1.0199
0.00809 1.7344 1.4634 1.2107 1.0204
0.00985 1.7347 1.4638 1.2111 1.0207
0.01284 1.7352 1.4640 1.2114 1.0209
0.01520 1.7356 1.4644 1.2118 1.0212
0.01810 1.7361 1.4649 1.2120 1.0215
−1
L-Aspartic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
η0 = 1.9928 mPa s η0 = 1.7555 mPa s η0 = 1.4983 mPa s η0 = 1.2697 mPa s
0.00626 1.9941 1.7569 1.4992 1.2703
0.00788 1.9946 1.7574 1.4999 1.2709
0.01082 1.9952 1.7578 1.5003 1.2712

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Table 6 (Contd.)

η/mPa s

mA T/K T/K T/K T/K

mol kg−1 288.15 298.15 308.15 318.15

0.01180 1.9958 1.7582 1.5007 1.2717

0.01461 1.9964 1.7587 1.5011 1.2720
L-Glutamic acid in water
0.01104 1.1404 0.8921 0.7205 0.5974
0.01308 1.1407 0.8923 0.7209 0.5976
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0.01522 1.1411 0.8927 0.7214 0.5978

0.02078 1.1417 0.8932 0.7218 0.5982
0.02517 1.1422 0.8937 0.7221 0.5986
0.03030 1.1429 0.8942 0.7225 0.5990
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.1 mol kg
0.01288 1.1646 0.9525 0.7789 0.6650
0.01523 1.1653 0.9534 0.7797 0.6655
0.01930 1.1661 0.9543 0.7803 0.6661
0.02496 1.1669 0.9549 0.7810 0.6666
0.03127 1.1676 0.9556 0.7815 0.6670
0.03591 1.1681 0.9564 0.7820 0.6675
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.25 mol kg
0.01410 1.2443 1.0262 0.8556 0.7250
0.01537 1.2450 1.0268 0.8563 0.7257
0.01930 1.2459 1.0275 0.8567 0.7262
0.02391 1.2464 1.0281 0.8571 0.7268
0.03000 1.2471 1.0287 0.8577 0.7273
0.03235 1.2478 1.0296 0.8583 0.7278
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.5 mol kg
0.01228 1.4199 1.2015 0.9935 0.8452
0.01354 1.4209 1.2023 0.9944 0.8462
0.01654 1.4217 1.2029 0.9952 0.8469
0.02018 1.4223 1.2034 0.9958 0.8475
0.02585 1.4230 1.2043 0.9963 0.8481
0.03703 1.4238 1.2052 0.9971 0.8488
−1
L-Glutamic acid in an aqueous solution of di-sodium tartrate at mB = 0.75 mol kg
0.01159 1.6114 1.4004 1.1582 0.9877
0.01375 1.6125 1.4011 1.1588 0.9886
0.01765 1.6131 1.4017 1.1592 0.9895
0.01995 1.6139 1.4027 1.1602 0.9904
0.02676 1.6149 1.4036 1.1608 0.9908
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.1 mol kg
0.01247 1.2182 0.9874 0.8036 0.6660
0.01463 1.2188 0.9878 0.8039 0.6663
0.01634 1.2193 0.9882 0.8043 0.6667
0.02218 1.2198 0.9889 0.8050 0.6671
0.02857 1.2205 0.9893 0.8055 0.6676
0.03390 1.2212 0.9899 0.8060 0.6682
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.25 mol kg
0.01213 1.4232 1.1442 0.9474 0.7914
0.01438 1.4237 1.1446 0.9479 0.7919
0.01771 1.4243 1.1457 0.9484 0.7924
0.02308 1.4250 1.1462 0.9490 0.7929
0.02531 1.4257 1.1467 0.9497 0.7934
0.03401 1.4271 1.1475 0.9507 0.7938
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.5 mol kg
0.01104 1.7359 1.4646 1.2114 1.0211
0.01239 1.7362 1.4652 1.2122 1.0217
0.01547 1.7370 1.4659 1.2129 1.0223
0.02012 1.7381 1.4670 1.2138 1.0227
0.02521 1.7392 1.4677 1.2144 1.0239
0.03006 1.7410 1.4686 1.2154 1.0246
−1
L-Glutamic acid in an aqueous solution of tri-sodium citrate at mB = 0.75 mol kg
0.01088 1.9955 1.7581 1.5003 1.2716
0.01408 1.9973 1.7596 1.5010 1.2726
0.01532 1.9978 1.7604 1.5017 1.2735
0.02000 1.9991 1.7614 1.5034 1.2740
0.02799 2.0009 1.7626 1.5050 1.2752
0.03107 2.0019 1.7636 1.5057 1.2766

mA is the molality of the solute in water or water + DST/TSC (solvent). mB is the molality of DST/TSC in water. Standard uncertainties are u(T ) =
0.03 K, u(P) = 0.5 kPa, u(m) = 2.8 × 10−4 mol kg−1 and u(η) = 0.012 mPa s.

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Table 7 Enthalpy of dilution values, q, of aqueous solutions of L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium
tartrate and tri-sodium citrate at a T value of 298.15 K and P = 101.3 kPa

q/J mol−1

mA/ mB = 0 mB = 100 mB = 250 mB = 500 mB = 100 mB = 250 mB = 500

mmol kg−1 mmol kg−1 mmol kg−1 mmol kg−1 mmol kg−1 mmol kg−1 mmol kg−1 mmol kg−1

L-Asparticacid in an aqueous solution of di-sodium tartrate L-Asparticacid in an aqueous solution of tri-sodium citrate
0.05897 2331.13 −445.97 1478.99 1412.85 2981.24 3639.50 5972.42
0.35207 1928.97 116.10 1553.81 1366.52 3057.06 3758.56 6016.78
0.64226 1120.55 607.86 1638.12 1309.33 3208.70 3843.82 6063.55
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0.92955 707.04 961.64 1708.83 1264.60 3285.24 3932.01 6113.76

1.21394 538.85 1196.41 1772.46 1249.85 3345.96 3995.34 6156.42
1.49542 450.80 1354.93 1822.87 1227.90 3481.98 4032.45 6214.78
1.77400 393.72 1449.52 1871.82 1215.09 3571.76 4136.79 6251.32
2.04968 351.35 1514.27 1926.90 1244.20 3661.63 4165.05 6306.43
2.32246 317.49 1549.66 1986.88 1273.96 3736.21 4183.07 6347.57
2.59233 286.92 1587.42 2050.69 1335.26 3839.65 4259.48 6396.35
2.85929 263.99 1618.50 2123.13 1445.36 3905.29 4307.43 6452.41
3.12336 238.77 1655.39 2188.19 1518.47 3987.36 4361.31 6488.21
3.38452 228.07 1678.46 2299.31 1603.81 4084.03 4485.43 6537.78
3.64278 209.37 1677.83 2398.92 1708.21 4179.06 4562.62 6577.24
3.89813 198.41 1677.24 2456.84 1802.71 4256.64 4622.75 6627.50
4.15058 183.65 1697.28 2512.35 1915.64 4342.19 4726.03 6665.68
4.40013 168.35 1698.79 2561.23 2008.51 4432.38 4812.32 6705.08
4.64677 164.13 1698.79 2606.28 2090.75 4508.28 4868.91 6749.22
4.89051 154.10 1704.97 2703.05 2171.57 4565.64 4934.77 6798.33
L-Glutamic acid in an aqueous solution of Di-sodium tartrate L-Glutamic acid in an aqueous solution of tri-sodium citrate
0.05897 397.36 −953.53 −868.11 345.92 1126.24 3303.28 4329.99
0.35207 339.42 −479.12 −816.65 423.73 1194.15 3343.50 4411.15
0.64226 274.18 −67.00 −772.47 469.41 1256.93 3391.24 4510.22
0.92955 251.38 145.23 −714.45 555.31 1314.97 3441.71 4593.43
1.21394 216.36 248.50 −662.62 644.28 1414.14 3491.56 4659.79
1.49542 179.98 306.75 −628.30 697.72 1465.35 3537.03 4727.20
1.77400 160.58 352.91 −592.38 753.07 1556.91 3589.88 4792.46
2.04968 141.98 394.64 −536.11 850.51 1635.86 3641.27 4837.82
2.32246 122.06 417.21 −502.91 902.46 1692.17 3696.22 4900.68
2.59233 105.23 431.29 −475.78 949.48 1768.96 3750.99 4945.44
2.85929 94.52 456.15 −437.47 999.15 1852.31 3807.83 5001.87
3.12336 72.25 487.66 −384.81 1045.31 1917.93 3849.69 5042.00
3.38452 58.34 490.60 −355.74 1094.73 1973.39 3908.89 5115.39
3.64278 42.74 493.88 −315.97 1190.22 2064.57 3953.95 5176.35
3.89813 36.68 478.74 −280.04 1237.70 2142.39 3998.64 5224.55
4.15058 28.84 499.50 −236.68 1275.55 2256.46 4032.62 5272.35
4.40013 19.63 501.58 −194.97 1326.44 2323.28 4079.62 5345.51
4.64677 10.21 504.97 −153.45 1382.78 2392.10 4130.85 5397.24
4.89051 4.70 504.22 −125.31 1448.78 2468.88 4180.52 5466.93

The standard uncertainties, u, are u(m) = 2.8·10−4 mol kg−1, u(q) = 0.5 kJ mol−1, u(T ) = 0.03 K, and u(P) = 0.5 kPa.

greater dehydration effects of TSC compared to DST. This
shows that hydrophilic–ionic/hydrophilic interactions are
more predominant in the case of DST.
The ΔtrΔdilH0 values, i.e., the standard molar enthalpy of
transfer, for the studied amino acids, from water to DST/
TSC(aq.) are evaluated using the equation:
Δtr Δdil H 0 ¼ Δdil H 0 ðin DST=TSCðaq:Þ Þ  Δdil H 0 ðin waterÞ:
ð20Þ
Negative ΔtrΔdilH0 values for ASP in 100 mM TSC, ASP in
DST and GLU in DST at all molalities, and positive ΔtrΔdilH0
values for ASP in 250 mM and 500 mM TSC and GLU in TSC at
all molalities have been observed (Fig. S2, ESI†). The more
positive magnitudes of the ΔtrΔdilH0 values in the case of GLU
than ASP are due to the presence of an extra –CH2 (hydro-
phobic) group. The negative ΔtrΔdilH0 values suggest the domi-
nance of hydrophilic-ionic/hydrophilic interactions and posi-
tive ΔtrΔdilH0 values may be due to the predominance of co-
solute dehydration effects. Overall, the positive ΔtrΔdilH0 values
in the case of TSC (greater dehydration effects) and the nega-
tive ΔtrΔdilH0 values in the case of DST coincide with the
results obtained from the volumetric studies.
3.5. Analysis of NMR spectra
1
H spectra have been recorded for ASP and GLU in the
absence, as well as in the presence, of DST and TSC using a
Bruker (AVANCE-III, HD 500 MHz) spectrometer at a probe
temperature of 300.15 K. D2O was used for the deuterium lock
and its signal at 4.650 ppm was taken as the internal reference
for the other nuclei. The NMR spectra of ASP and GLU in
water (mA = 0.01 and 0.02 mol kg−1) and in the presence of

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1
Table 8 H data for L-aspartic acid and L-glutamic acid in water and in aqueous solutions of di-sodium tartrate and tri-sodium citrate.
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T = triplet, Q = quartet, M = multiplet.

aqueous solutions of DST and TSC (mB = 0.75 mol kg−1) have
been examined in 9 : 1 H2O–D2O solution. The changes in
chemical shifts (δ) in ppm are summarized in Table 8.
In the 1H NMR spectra of ASP and GLU in aqueous solu-
tions of DST and TSC (mB = 0.75 mol kg−1), the protons go
upfield compared to in the D2O : H2O system (Fig. S3†). This
shows that the hydrogen bonding of the solutes with water
molecules decreases in the presence of DST/TSC owing to the
dominance of dehydration effects over hydrophilic–ionic/
hydrophilic interactions.
presence of the studied preservatives. The values of the inter-
action parameter predict pairwise interactions between the
amino acids and preservatives. Volumetric and viscometric
results indicate that the amino acids behave as structure-
breakers in both salt solutions, except in the case of GLU in
TSC at mB = 0.1 mol kg−1. The hydration number and B/V2,ϕ0
values suggest that these amino acids are more solvated in
water. Calorimetric and spectroscopic results support the fact
that these preservatives stimulate the effects of dehydration on
the studied amino acids.

4. Conclusions Abbreviations
Volumetric, acoustic, viscometric, calorimetric and NMR spec- GLU L-Glutamic acid
troscopic studies have been performed in the present study. ASP L-Asparticacid
The values of ΔtrV2,ϕ0, ΔtrK2,ϕ0 and ΔtrB suggest that hydro- DST Disodium tartrate
philic–ionic/hydrophilic interactions dominate in the present TSC Trisodium citrate
study. The sweet tastes of both amino acids decrease in the DSA Density and sound velocity meter

This journal is © The Royal Society of Chemistry 2019 Food Funct.


Paper
ITC Isothermal titration calorimetry
NMR Nuclear magnetic resonance
Conflicts of interest
The authors declare that there are no conflicts of interest.
Published on 20 November 2019. Downloaded by University of Georgia on 1/3/2020 3:38:16 AM.
Acknowledgements
One of the authors (Aashima Beri) is grateful to the
Department of Science and Technology, New Delhi for the
award of an Inspire Fellowship. The authors also acknowledge
the DST-PURSE scheme of the Department of Science and
Technology, New Delhi and the UPE-Scheme of the University
Grants Commission, New Delhi for research facilities.
References
1 K. Jeevaratnam, M. Jamuna and A. S. Bawa, Biological pres-
ervation of foods-Bacteriocins of lactic acid bacteria, Indian
J. Biotechnol., 2005, 4, 446–454.
2 W. C. Friezer, Contamination, Spoilage and Preservation of
Yoghurt, AVI Publishers, U.S.A., 1989, pp. 13–29.
3 L. Angiolillo, A. Conte and M. A. D. Nobile, Food Additives:
Natural Preservatives. Reference Module in Food Science,
in Encyclopedia of Food Safety, 2014, vol. 2, pp. 474–476.
4 J. B. Gurtler and T. L. Mai, Preservatives | Traditional
Preservatives-Organic Acids. Reference Module in Food
Science, in Encyclopedia of Food Microbiology (2nd edn),
2014, pp. 119–130.
5 T. S. Banipal, H. Kaur, A. Kaur and P. K. Banipal, Effect of
tartarate and citrate based food additives on the micellar
properties of sodium dodecylsulfate for prospective use as
food emulsifier, Food Chem., 2016, 190, 599–606.
6 J. S. L. Velez, A. R. Azzoni, P. De. Alcantara and P. Filho,
Precipitation of lysozyme with sodium succinate, sodium
tartrate and sodium citrate: solubility and osmotic second
virial coefficient data, J. Chem. Thermodyn., 2017, 110, 25–
32.
7 S. A. A. Sajadi, Metal ion-binding properties of L-glutamic
acid and L-aspartic acid, a comparative investigation, Nat.
Sci., 2010, 2, 85–90.
8 P. M. Masters and M. Friedman, Racemization of Amino
Acids in Alkali-Treated Food Proteins, J. Agric. Food Chem.,
1979, 27, 507–511.
9 Y. S. Nahum, A. Apelbla and E. Manzurola, Volumetric
Properties of Aqueous Solutions of L-Glutamic Acid and
Magnesium-L-Glutamate, J. Solution Chem., 2008, 37, 391–
401.
10 K. D. Umaley, G. B. Pethe and A. S. Aswar, Volumetric,
Viscometric, Acoustical, and Optical Studies of Glutamic
Acid in Aqueous Zinc and Copper Chloride Solutions,
Russ. J. Phys. Chem. B, 2013, 7, 11–22.
Food Funct.
View Article Online
Food & Function
11 M. Contineanu, I. Contineanu, A. Neacsu and S. Perisanu,
A DSC Study on Gamma Irradiated Isomers of the Aspartic
Acid, Rev. Chim. (Bucharest), 2010, 61, 774–777.
12 A. K. Nain, R. Pal and P. Droliya, Study of (solute+solute)
and (solute+solvent) interactions of homologous series of
some α-amino acids in aqueous streptomycin sulphate
solutions at different temperatures by using physico-
chemical methods, J. Chem. Thermodyn., 2016, 95, 77–98.
13 C. M. Romero and F. Negrete, Effect of Temperature on
Partial Molar Volumes and Viscosities of Aqueous
Solutions of α-Dl-Aminobutyric Acid, Dl-Norvaline and Dl-
Norleucine, Phys. Chem. Liq., 2004, 42, 261–267.
14 H. Zhao, Viscosity B-coefficient and Standard Partial Molar
Volume of Amino Acids and Their Role in Interpreting the
Protein (Enzyme) Stabilization, Rev. Biophys. Chem., 2006,
122, 157–183.
15 J. Kestin, M. Sokolov and W. A. Wakeham, Viscosity of
liquid water in the range −8 °C to 150 °C, J. Phys. Chem.
Ref. Data, 1978, 7, 941–948.
16 R. Sadeghi and F. Ziamajidi, Apparent Molar Volume and
Isentropic Compressibility of Trisodium Citrate in Water
and in Aqueous Solutions of Polyvinylpyrrolidone at T =
(283.15 to 308.15) K, J. Chem. Eng. Data, 2007, 52,
1037–1044.
17 H. Kumar, Sheetal and S. K. Sharma, Volumetric and
Acoustic Behavior of D ( + )-glucose and D (-)-fructose in
Aqueous Trisodium Citrate Solutions at Different
Temperatures, J. Solution Chem., 2016, 45, 1–27.
18 R. Sadeghi, R. Golabiazar and H. Shekaari, The Salting-Out
Effect and Phase Separation in Aqueous Solutions of Tri-
Sodium Citrate and 1-Butyl-3-Methylimidazolium Bromide,
J. Chem. Thermodyn., 2010, 42, 441–453.
19 H. Kumar, K. Kaur, S. P. Kaur and M. Singla, Studies of
Volumetric and Acoustic Properties of Trisodium Citrate
and Tripotassium Citrate in Aqueous Solutions of N-Acetyl
Glycine at Different Temperatures, J. Chem. Thermodyn.,
2013, 59, 173–181.
20 H. Kumar, M. Singla and R. Jindal, Interactions of Glycine,
L-Alanine and L-Valine with Aqueous Solutions of
Trisodium Citrate at Different Temperatures: A Volumetric
and Acoustic Approach, J. Chem. Thermodyn., 2013, 67,
170–180.
21 H. Kumar and C. Chadha, Densities, Sound Speed, and UV
Absorption Studies of Trisodium Citrate and Tripotassium
Citrate in Aqueous Solutions of 1–Hexyl-3-methyl-
imidazolium Chloride [C6mim][Cl], J. Chem. Eng. Data,
2014, 59, 4049–4061.
22 A. Salabat, L. Shamshiri and F. Sahrakar, Thermodynamic
and transport properties of aqueous trisodium citrate
system at 298.15 K, J. Mol. Liq., 2005, 118, 67–70.
23 M. T. Z. Moattar and S. Hosseinzadeh, Refractive Index,
Viscosity, Density, and Speed of Sound of Aqueous Sodium
Tartrate Solutions at Various Temperatures, J. Chem. Eng.
Data, 2006, 51, 1190–1193.
24 T. S. Banipal, K. Singh and P. K. Banipal, Volumetric
Investigations on Interactions of Acidic/Basic Amino Acids
This journal is © The Royal Society of Chemistry 2019

Food & Function
with Sodium Acetate, Sodium Propionate and Sodium
Butyrate in Aqueous Solutions, J. Solution Chem., 2007, 36,
1635–1667.
25 R. Gaba, A. Pal, D. Sharma, H. Kumar and A. Kumar,
Molecular Interactions of Some Non-Essential Amino Acids
in Aqueous Solutions of 1-Methylimidazolium Chloride at
Different Temperatures, J. Mol. Liq., 2019, 279, 711–718.
26 M. A. Jamal, B. Naseem, M. K. Khosa, M. Muneer and
J. H. Khan, Effect of Anionic Micellar Medium on Thermo
Published on 20 November 2019. Downloaded by University of Georgia on 1/3/2020 3:38:16 AM.
Acoustical Parameters of Aspartic Acid and Serine
Solutions, J. Mol. Liq., 2017, 237, 14–22.
27 M. A. Jamal, B. Naseem, J. H. Khan and I. Arif, Temperature
Dependent Solution Properties of Amino Acids in Colloidal
Solutions, J. Mol. Liq., 2019, 275, 105–115.
28 O. Iulian and A. Stefaniu, Volumetric and Viscometric
Analyses for L-Glutamic Acid in NaCl Aqueous Solutions at
Different Temperatures, J. Solution Chem., 2013, 42, 676–
689.
29 Riyazuddeen and S. Afrin, Effect of NaCl and NaNO3 on the
Partial Molar Volumes and Partial Molar Isentropic
Compressibilities of Some Amino Acids at Several Different
Temperatures (298.15–328.15) K, J. Solution Chem., 2012,
41, 1144–1155.
30 Riyazuddeen and T. Altamash, Study of Interactions of
L-Histidine/L-Glutamic Acid/L-Tryptophan/Glycylglycine
With KCl/KNO3 at Different Temperatures: 298.15, 303.15,
308.15, 313.15, 318.15, 323.15 K, Thermochim. Acta, 2010,
501, 72–77.
31 S. Shamil, G. G. Birch, M. Mathlouthi and M. N. Clifford,
Apparent molar volumes and tastes of molecules with more
than one sapophore, Chem. Senses, 1987, 12, 397–409.
32 M. B. Vranes, J. J. Panic, A. S. Tot and S. M. Papovic, The
solvation properties and effect of D-fructose on taste behav-
iour of citrus aurantium active components in aqueous
solutions, Food Funct., 2018, 9, 5569–5579.
33 R. W. Gurney, Ionic Processes in Solution, McGraw Hill,
New York, vol. 3, 1953, ch. 1, pp. 1–20.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Paper
34 F. Shahidi and P. G. Farrell, Partial molar volumes of some
α-aminocarboxylic acids in water, J. Chem. Soc., Faraday
Trans., 1981, 77, 963–968.
35 Z. Yan, J. Wang, K. W. Kong and J. Lu, Effect of temperature
on volumetric and viscometric properties of some α-amino
acids in aqueous calcium chloride solutions, Fluid Phase
Equilib., 2004, 215, 143–150.
36 E. Berlin and M. J. Pallansch, Densities of several proteins
and L-amino acids in the dry state, J. Phys. Chem., 1968, 72,
1887–1889.
37 C. K. Reddy, T. V. S. Sivapriya, U. A. Kumar and
C. Ramalimgam, Optimization of Food Acidulant to
Enhance the Organoleptic Property in Fruit Jellies, J. Food
Process. Technol., 2016, 7, DOI: 10.4172/2157-7110.1000635.
38 T. Hutton, Sodium: Technological functions of salt in the
manufacturing of food and drink products, Br. Food J.,
2002, 104, 126–152.
39 T. P. Guinee and P. F. Fox, Salt in cheese: Physical, chemi-
cal and biological aspects, in Cheese: Chemistry, physics and
microbiology, ed. P. F. Fox, P. L. H. McSweeney, T. M. Cogan
and T. P. Guinee, 2004, Elsevier, Amsterdam, general
aspects 3rd edn, vol. 1, pp. 207–259.
40 L. G. Hepler, Thermal Expansion and Structure in Water
and Aqueous Solutions, Can. J. Chem., 1969, 47, 4613–4617.
41 W. G. McMillan and J. E. Mayor, The Statistical
Thermodynamics of Multicomponent Systems, J. Chem.
Phys., 1945, 13, 276–305.
42 M. Kikuchi, M. Sakurai and K. Nitta, Partial Molar Volumes
and Isentropic Compressibilities of N-Acetyl Amino Acid
Amides in Dilute Aqueous Solutions at (5, 15, 25, 35, and
45) °C, J. Chem. Eng. Data, 1996, 41, 1439–1445.
43 G. Jones and M. Dole, The Viscosity of Aqueous Solutions
of Strong Electrolytes with Special Reference of Barium
Chloride, J. Am. Chem. Soc., 1929, 51, 2950–2964.
44 T. S. Sarma and J. C. Ahluwalia, Experimental Studies on
the Structure of Aqueous Solutions of Hydrophobic
Solutes, Chem. Soc. Rev., 1973, 2, 203–232.
Food Funct.