Effect of amino acids and B-group vitamins on nucleation of calcium oxalate monohydrate crystals

Journal of Crystal Growth 531 (2020) 125368

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Effect of amino acids and B-group vitamins on nucleation of calcium oxalate monohydrate crystals

T

Y.V. Taranets , O.N. Bezkrovnaya, I.M. Pritula ⁎

Institute for Single Crystals, SSI “Institute for Single Crystals“ NAS of Ukraine, Nauky Ave. 60, Kharkiv 61072, Ukraine

ARTICLE INFO

ABSTRACT

Communicated by S.R. Qiu

Studied is the influence of amino acids (L-Asp, L-Arg, L-Thr) and B-group vitamins (B1, B6, B12) on the processes of nucleation and the value of surface energy of calcium oxalate monohydrate (COM) crystals. It is established that L-Asp and L-Arg molecules inhibit nucleation of COM, that increases their induction time tenfold in comparison with the one of the pure crystals. L-Thr amino acid is shown to promote the processes of COM nucleation and to diminish the induction time by two times. At the introduction of L-Asp and L-Arg molecules into the solution the degree of COM crystal growth inhibition is 32.0–90.2% and 10.2–86.0% respectively. It is found that B1 and B6 vitamins inhibit the growth of COM crystals practically completely (the inhibition degree exceeds 95%) and lead to 70-fold increase in the induction time of pure COM. The value of surface energy of COM crystals diminishes to 19.8–20.8 mJ/m2 at the introduction of the crystallization inhibitor molecules (L-Asp, LArg, B1, B6) into COM solution.

Keywords: A1. Biocrystallization A1. Nucleation A1. Supersaturated solutions A2. Growth from solutions B1. Calcium compounds B1. Nanomaterials

1. Introduction Formation of oxalate kidney stones based on calcium oxalate monohydrate (COM) is considerably influenced by modifier molecules which may be both inhibitors and promoters of crystallization. As shown in a number of papers [1–3], the mechanism of COM formation essentially depends on the crystallization conditions (pH, supersaturation, ionic strength) and the presence of different modifier molecules in the solution. In particular, the process of COM nucleation and growth is substantially defined by the presence of inorganic (magnesium, phosphorus, etc.) and organic (proteins, amino acids and vitamins) additives in the solution [4,5]. Some of them (glutamic acid, lysine, glycine) are COM crystallization inhibitors, whereas proline, valine and serine are the promoters [2,6–8]. In a number of papers there is reported the influence of molecules of some modifiers, in particular, acidic amino acids (L-glutamic and Laspartic (L-Asp) acids), on the processes of COM formation [7,9,10]. As shown in [11,12], L-Asp inhibits the processes of nucleation and growth of COM crystals due to adsorption of its molecules on COM surface. At the same time, described in [13] is promotion of COM nucleation bound up with formation of complexes of calcium with carboxyl groups of LAsp. The contribution of L-threonine (L-Thr) amino acid to the pro-

⁎

cesses of COM formation is ambiguous. In particular, it is reported that L-Thr either accelerates the crystallization process [13], or does not influence COM formation [11]. As is known, there exist amino acids that possess basic properties (e.g. L-lysine, L-arginine (L-Arg)). However, their influence on the processes of pathogenic crystallization of calcium oxalate practically has not been studied. Vitamins are known to be of a great significance for human organism, but their role in COM nucleation has not been established so far. Shown in [14] is the dependence between avitaminosis and development of stone formation for animals. According to clinical trials, A and E vitamins are able to increase excretion of oxalate in physiological liquid and, consequently, risk of COM crystallization [15,16]. The influence of most significant B-group vitamins, in particular, thiamine (B1), pyridoxine (B6) and cyanocobalamin (B12), on the processes of COM formation has not been investigated up to now. The aim of the present work was to study the influence of organic growth modifier molecules (L-Asp, L-Arg, L-Thr amino acids and B1, B6, B12 vitamins) on the kinetics of nucleation of COM crystals, regularities of their crystallization, morphology and size.

Corresponding author. E-mail address: [email protected] (Y.V. Taranets).

https://doi.org/10.1016/j.jcrysgro.2019.125368 Received 11 October 2019; Received in revised form 18 November 2019; Accepted 19 November 2019 Available online 20 November 2019 0022-0248/ © 2019 Elsevier B.V. All rights reserved.

Journal of Crystal Growth 531 (2020) 125368

Y.V. Taranets, et al.

Fig. 1. Typical COM crystallization curve at S = 6.0 (a); kinetic curves of COM crystallization without additives at different supersaturations: 4.6 (1), 6.0 (2), 8.0 (3), 10.0 (4), 12.0 (5), 14.0 (6) (b).

log

Table 1 Effect of L-Asp, L-Arg and L-Thr molecules on COM induction time (S = 4.6–14.0). S*

τCOM, s

τ

(COM+amino acids),

4.6 6.0 8.0 10.0 12.0 14.0

300 100 75 50 40 25

CL-Arg, mM

CL-Thr, mM

4

8

20

4

8

20

4

8

20

500 410 120 100 50 50

630 600 480 220 150 120

1400 990 700 300 170 120

200 130 130 100 70 40

360 280 240 100 70 60

650 600 400 100 70 60

170 50 50 50 40 25

170 50 50 50 40 25

170 50 50 50 40 25

S*– supersaturation of COM solutions; C** – the concentration of amino acids in the oxalate system, mM.

2. Experimental COM crystals were obtained by the method of spontaneous crystallization under the conditions close to physiological ones [17–19]. The process of COM crystallization was realized in aqueous solution at a constant temperature of 37 °C, 0.15 M ionic strength and pH = 5.8, the stoichiometry of the model solution was [Ca2+]/[C2O42–] = 20:1 (S = 4.6, [Ca2+] = 4 mM, [C2O42–] = 0.2 mM). In our case, the concentration of COM was very low, so the value of ionic strength was defined by the concentration of the indifferent electrolyte (potassium chloride) and the acetate buffer solution. The ionic strength of the 0.15 M corresponding to the ionic strength of the biological system [17,18]. The solution supersaturation (S) was calculated according to the formula used in [20–22]:

S = ·{([Ca2 +]·[C2 O24 ])/K sp}1/2

0.3I ],

where A is the Debye-Huckel constant (A = 0.5115); z1 and z2 – the ion charges (z1 = z2 = 2); I, the ionic strength of the solution (I = 0.5⋅Σ (z2c)). The model system of COM was formed on the base of calcium chloride, potassium oxalate, potassium chloride, acetate buffer solution, distilled water, organic additives (L-Asp, L-Arg, L-Thr, B1, B6, B12). In each experiment the said amino acids and vitamins were added to the model system of COM prior to the reaction onset, each additive had its own concentration range. The concentrations of the added amino acids varied from 1 to 20 mM, that being comparable with their biological concentrations. The concentration range for B1 and B6 varied within the limits of 5–50 mM, whereas the concentrations of B12 in the oxalate system were 10–100 µM, that did not exceed the biological concentrations of each vitamin in human organism [23,24]. The crystals synthesized both without the additives and in the presence of the mentioned amino acids and vitamins introduced into the growth solution in a wide range of concentrations after termination of the crystallization cycle, were centrifuged and washed with distilled water to remove residual buffer solution and potassium chloride. The obtained COM crystals were used for studies by the methods of scanning electron microscopy (a JSM-6390LV microscope), IR-spectroscopy (a Spectrum One PerkinElmer spectrophotometer) and X-ray structure analysis (a Siemens D500 diffractometer). The crystallization kinetics for the model COM solutions without additives and for those containing L-Asp, L-Arg, L-Thr amino acids and B1, B6, B12 vitamins were studied by measuring the solution turbidity [25–27]. The optical density of the COM solutions was measured at 620 nm wavelength immediately after mixing the solutions (the optical density of the solution was directly proportional to the mass of COM crystals formed per unit volume) using a spectrophotometer of Optizen 3220UV type [25,28,29]. The moment of the addition of potassium oxalate to the studied system was considered to be the onset of the reaction of COM crystallization. The characteristic curve of COM crystallization (Fig. 1, a) without additives ([Ca2+]/[C2O42–] = 20:1, S = 6.0) comprised the stages of nucleation of the crystals (the steepest fragment of the curve), their further growth and aggregation (the flat fragment gradually

s

C**L-Asp, mM

= Az1 z2 ·[((I 1/2)/(1 + I 1/2 ))

1,

where [Ca2+] is the molar concentration of calcium ions; [C2O42–], the molar concentration of oxalate ions; Ksp, the solubility product of calcium oxalate (equal to 2.8⋅10–9 Mol2/l2 at 37 °C). The activity coefficient γ was determined from the expression:

2

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concentration of the additive the induction time was calculated individually and the initial absorption of the solution was taken as zero. The induction time corresponds to the period between the addition of potassium oxalate to the solution and the moment when the growth of COM crystals can be measured experimentally, i.e. when the changes in the solution absorption amount to 2.5% of the maximum absorption value. The kinetics of COM nucleation in the presence of the considered additives was investigated in a supersaturations range of 4.6–14.0 (S = 6.0 was the most acceptable). At S > 8 the reaction of COM crystallization without additives was very fast, that led to an error in determination of the induction time. Relatively low solution supersaturation values (S < 4) did not permit to obtain reliable results, too, because at high concentrations of the additives in the solution the process of COM crystallization slows down. The degree of COM crystal growth inhibition is a quantitative value and shows a tendency of the influence of the introduced organic molecules on the crystallization process. Calculation of the inhibition degree is based on comparison of the slopes of the turbidity of COM crystals without additives and of those doped with the amino acids (LAsp, L-Arg, L-Thr) and vitamins (B1, B6, B12). The slope of the turbidity curve was experimentally determined from the time dependence of the optical absorption of the solution at λ = 620 nm. The degree of COM crystal growth inhibition (I, %) by the molecules of the additives was determined from the formula [25]:

I = [1

(1)

Tsi/ Tsc]·100,

where Tsc is the slope of the turbidity curve for COM crystals without additives; Tsi, the slope of the turbidity curve of the doped COM crystals. The value of the surface energy (σ) of the undoped and doped COM crystals was found from the Gibbs-Thomson equation:

J = A exp[ 16

3 2 /3k 3 T3m2 (ln

S)2],

(2)

-1

where J is the nucleation rate (c ); A, the pre-exponential factor; σ, the surface energy (J/m2); ν, the volume of a COM molecule (1.10⋅10–22 cm3); k, the Boltzmann constant (1.38⋅10–23 J/K); T, the temperature (K); m, the number of ions into which calcium oxalate dissociates in the solution (m = 2); S, the solution supersaturation. The induction time depends on the nucleation rate τ ~ 1/J. The tangent of the slope angle a of the dependence ln1/τ on 1/ln2S is 16πσ3 ν2 /3k3T3m2, therefore, 3

=

3k3T3m2a/16

2

(3)

Accordingly, one can calculate the value of the surface energy for pure and the doped COM crystals. 3. Results and discussion 3.1. Effect of different concentrations of the amino acids (L-Asp, L-Arg, LThr) on the induction time of COM crystal growth Investigation of the kinetic parameters of crystallization for pure and the doped COM crystals shows the tendency of the influence of the organic molecules and supersaturation on the stage of COM nucleation. At the supersaturations ranging between 4.6 and 14.0 the induction time (τ) for pure COM crystals varies from 25 s to 300 s (Fig. 1, b). The induction time diminishes with the growth of the solution supersaturation: at S = 4.6 and 6.0 it is equal to 300 s and 100 s, respectively, and so on (Table 1).

Fig. 2. Kinetic curves of COM crystallization (S = 6.0) in the presence of L-Asp (a), L-Arg (b) and L-Thr (c) with the concentrations of: 0 (1), 1 (2), 2 (3), 4 (4), 8 (5), 14 (6), 20 (7) mM.

transforming into a plateau). For the nucleation stage the key factor was the induction time (τ) determined from the kinetic curves as a function of the turbidity slope depending on the time (Fig. 1, a). For each

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Table 2 Effect of B1, B6 and B12 molecules on COM induction time (S = 4.6–14.0). S*

τCOM, s

τ(COM+vitamins), s C**B1, mM

4.6 6.0 8.0 10.0 12.0 14.0

300 100 75 50 40 25

CB6, mM

CB12, mM

10

20

50

10

20

50

20

40

100

500 300 160 100 40 25

1000 1000 300 200 120 100

> 7200 > 7200 > 6600 300 140 100

700 700 200 100 50 40

1500 1500 500 300 130 100

> 7200 > 7200 > 6600 400 300 100

200 100 75 50 40 25

250 100 90 50 40 40

250 250 90 50 40 40

S*– supersaturation of COM solutions; C**– the concentration of vitamins in the oxalate system, mM.

L-Asp, L-Arg, L-Thr amino acids introduced into the model system of COM lead to changes in the induction time. The contribution of the said amino acids to these changes depends on their concentration and the solution supersaturation (Table 1). The induction time in the presence of L-Asp and L-Arg in COM solutions diminishes proportionally to the rise of their supersaturation (Table 1). The most essential influence of these amino acids on the stage of COM nucleation is observed at S = 4.6–8.0, however, further increase of the supersaturation value (up to S = 10,0–14.0) reduces this effect. To reveal the influence of 1–20 mM L-Asp, L-Arg and L-Thr amino acids on the induction time and the degree of COM inhibition, we investigated the kinetic parameters of COM crystallization at S = 6.0. LAsp molecules favor the rise of the induction time proportionally to the concentration of the introduced amino acid (Table 1). The introduction of low (1–2 mM) L-Asp concentrations leads to the three-fold increase of τ, at 8 mM and 20 mM L-Asp the value of τ rises by six and ten times, respectively. In the case of the introduction of L-Arg molecules into the model system of COM, the induction time increases only at the concentrations higher than 4 mM. With 20 mM L-Arg in the solution the value of rises up to 660 s (Table 1). This testifies to the fact that the inhibiting influence of L-Arg on COM nucleation is less pronounced in comparison with the one of L-Asp. At the same time, the effect of L-Thr molecules on COM nucleation is opposite to that of L-Asp and L-Arg molecules (Fig. 2). L-Thr amino acid contained in 2–20 mM concentrations in the solution COM promotes the processes of COM nucleation, and at S = 4.6–8.0 accelerates the reaction by two fold in comparison with the one for pure COM. If S = 10.0–14.0, the time induction of COM in the presence of L-Thr and, correspondingly, the nucleation rate are similar to those obtained for COM solution without additives (Table 1). This is explained by the fact that, unlike L-Asp and L-Arg molecules, L-Thr molecule is a promoter of COM crystallization due to the increase of the quantity of crystallization nuclei in the model system, as well as of the rate of COM crystallization. This confirms the results obtained in our previous studies of the promoting influence of L-Thr on COM crystallization [30].

Fig. 3. Kinetic curves of COM crystallization (S = 6.0) in the presence of B1 (a) and B6 (b) with the concentrations of: 0 (1), 5 (2), 10 (3), 20 (4), 40 (5), 50 (6) mM; and in the presence of B12 (c) with the concentrations of: 0 (1), 10 (2), 20 (3), 40 (4), 70 (5), 100 (6) μM.

3.2. Effect of different concentrations of the vitamins (B1, B6, B12) on the induction time of COM crystal growth

model COM solutions with 20 mM B1 and B6 at S = 4.6–14.0 rises as the supersaturation of COM solution diminishes. In particular, at the introduction of 20 mM B6 and B1 τ increases by five and three times, respectively, in comparison with the corresponding value for pure COM

When introduced into the model system of COM (S = 4.6–14.0) B1, B6 and B12 vitamins increase the time of COM induction (Table 2). At 10 mM concentration in the solution the vitamins B1 and B6 increase τ up to 500 s and 700 s, respectively (Table 2). The induction time for the

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3.3. Effect of amino acids and vitamins on the degree of inhibition of COM crystals

Table 3 Effect of different concentrations of the amino acids on the induction time (τ) and the degree of inhibition (I) of COM crystal growth (S = 6.0). COM + amino acids

Camino

pure COM COM + L-Asp

– 1 2 4 8 14 20 1–2 4 8 14 20 1 2–20

COM + L-Arg

COM + L-Thr

acids,

mM

τ, s

I, %

100 300 300 410 600 970 990 100 130 280 570 600 100 50

– 32.0 42.8 64.6 72.2 89.5 90.2 0 0.5 10.2 66.7 86.0 0 0

To estimate the quantitative influence of the introduced L-Asp, LArg, L-Thr amino acids and B1, B6, B12 vitamins on the processes of COM nucleation (S = 6.0), there was determined the degree of COM growth inhibition (I). This degree was shown to increase as L-Asp concentrations rise up to 20 mM, and to vary within the limits of 32.0–90.2% (Table 3). At low concentrations of L-Arg (1–2 mM) inhibition of the growth is not observed, at 4 mM I = 0.5%, and at 20 mM L-Asp – increases to 86.0%. L-Thr is a promoter of crystallization and accelerates the nucleation of COM (Table 3). At the introduction of B1 the degree of COM growth inhibition increases when the concentration of the vitamin rises (for the lowest B1 concentration of 5 mM such a degree is equal to 57.2%). Similar situation is also observed for the vitamin B6, however, at its concentration of 5 mM the inhibition degree increases up to 68.8%. (Table 4). The introduction of B1 and B6 vitamins in 50 mM concentration leads to practically complete crystal growth inhibition (I > 95%). Unlike B1 and B6, B12 vitamin insignificantly influences COM crystallization: at 10–60 μM concentration it does not affect the processes of COM nucleation, and the rise of the concentration up to 100 μM results in 34.7% inhibition degree.

Table 4 Effect of different concentrations of the vitamins on the induction time (τ) and the degree of inhibition (I) of COM crystal growth (S = 6.0). COM + vitamins

Cvitamins, mM

τ, s

I, %

pure COM COM + B1

– 5 10 20 40 50 5 10 20 40 50 0.01–0.06 0.07–0.1

100 280 300 1000 > 7200 > 7200 400 700 1500 > 7200 > 7200 100 250

– 57.2 73.8 74.9 > 95 > 95 68.8 72.0 72.4 > 95 > 95 0 34.7

COM + B6

COM + B12

3.4. Effect of amino acids and vitamins on the surface energy of COM crystals To confirm the interaction of COM crystals with the introduced organic additives L-Asp, L-Arg, L-Thr, B1, B6, B12, there was determined the value of surface energy (σ) of the crystals. It was found using the Gibbs–Thomson equation from the dependence of the nucleation rate on the supersaturation ranging from 4.6 to 14.0 (Figs. 4 and 5). For pure COM crystals and the above-said supersaturations, the value of surface energy is equal to 22.0 mJ/m2 (Table 5). The kinetic curves of COM nucleation (Figs. 4 and 5) are described by the linear dependence that does not contradict the classic theory of nucleation. In the presence of L-Asp amino acid with 4 mM concentration in the model COM system, the value of the surface energy of COM diminishes insignificantly to 21.8 mJ/m2, that practically correlates with the one of pure COM. The increase of L-Asp concentration up to 20 mM diminishes σ to 19.8 mJ/m2. At the introduction of L-Arg the surface energy of COM changes from 20.6 to 21.0 mJ/m2 (Table 5). Adsorption of L-Asp and L-Arg molecules on COM crystallization nuclei probably favors decrease of the surface energy of COM. The mechanism of such an absorption is bound up with the charge state of LAsp and L-Arg molecules in the solution. In this connection, the degree of the interaction between the amino acid molecules and the calcium and oxalate ions which reach the surface of the faces {1 0 0} and {0 1 0} of COM, will change. As earlier shown in our paper [22], L-Asp molecule in the studied system at pH = 5.8 is in anionic form, whereas the form of L-Arg molecule is cationic. L-Asp is adsorbed on the surface of COM crystal due to electrostatic interaction between the negatively charged carboxyl groups of the amino acid and the positively charged calcium ions present on the surface of {1 0 0} and {0 1 0} COM faces [22]. At the same time, the structure of L-Arg is more branched due to the presence of guanidine group, and its skeleton is longer than the one of L-Asp, that enhances adsorption according to the Duclaux-Traube rule. Therefore, the amino acid can be absorbed on the surface of {0 1 0} and {1 2 1} COM crystal faces owing to the formation of

(Table 2). The strongest inhibiting influence of B1 and B6 vitamins on the stage of COM nucleation is observed at S = 4.6–8.0. At the same time, at 100 μM B12 the time of COM induction at S = 4.6 diminishes insignificantly and remains practically unchanged at S = 8.0–14.0. The kinetic curves of COM crystallization in the presence of 5–50 mM B1 and B6, as well as of 10–100 μM contents of B12 make it possible to reveal their influence on COM nucleation (Fig. 3). The induction time for pure COM (S = 6.0) is equal to 100 s and rises in proportion to the growth of B1 concentration (Table 2, Fig. 3): τ = 280–300 s at 5–10 mM B1, whereas at 40–50 mM τ = 7200 s. This testifies to a considerable inhibiting influence of B1 molecules on COM nucleation. According to the data from Table 1, in comparison with B1, the vitamin B6 exerts an essential influence on the induction time: at 20 mM B6 (S = 4.6–6.0) τ increases by fifteen times as against its value in pure COM. As concerns B12, its effect on the kinetics of COM nucleation is less pronounced: the induction time at 70–100 μM B12 (S = 4.6–6.0) is 250 s (for pure COM τ = 100 s). Thus, among B1, B6 and B12 vitamins, it is B6 that has the most essential inhibiting effect on the processes of nucleation of COM crystals. This is caused by the formation of hydrogen bonds between the nitrogen atoms of the pyridine ring of B6 molecule and the hydrogen atoms which reach the surface of the faces {1 0 0} and {0 1 0} of COM crystal.

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Fig. 4. Kinetic curves of nucleation of COM crystals without additives (1) and in the presence of: 4 mM L-Asp (2), 4 mM L-Arg (3), 4 mM L-Thr (4) (a); 8 mM L-Asp (2), 8 mM L-Arg (3), 8 mM L-Thr (4) (b); 20 mM L-Asp (2), 20 mM L-Arg (3), 20 mM L-Thr (4) (c) with S = 4.6–14.0.

hydrogen bonds between the nitrogen atoms of L-Arg and the protons on the surface of COM. The introduction of B1, B6 and B12 vitamins also diminishes the surface energy of COM (Table 5). In particular, the presence of B12 with 20–100 μM concentration in COM solution leads to changes in σ within (21.7–21.9) mJ/m2 range that correlates with the corresponding values of σ for pure COM. The introduction of B1 and B6 vitamins with 10–20 mM concentration reduces the value of σ insignificantly – to 21.8 and 21.7 mJ/m2, respectively (Table 5). The rise of B1 and B6 concentration up to 50 mM (at S = 4.6–8.0) results in the surface energy decrease down to 8.2 mJ/m2. At the mentioned concentration of the vitamins and S = 8.0–14.0 the values of σ for B1 and B6 are equal to 32.4 mJ/m2 and 33.1 mJ/m2, respectively. An essential distinction in COM nucleation in the presence of B6 vitamin is caused by the formation of hydrogen bonds bound up with the existence of a large quantity of hydrogen and oxygen atoms in B6 molecules. Therefore, one B6 molecule may directly interact with several oxalate groups which reach the surface of the faces {1 0 0} and {0 1 0} of COM crystal. Moreover, due to its flat structure, B6 molecule is able to be adsorbed by the crystal growth steps and block the growth of COM. The kink at S = 8.0 observed on the kinetic curve of COM nucleation in the presence of B1 and B6 vitamins (Fig. 5) points to the transition from the heterogenic nucleation at S = 4.6–8,0 to the homogeneous one at S > 8 (Fig. 5).

4. Conclusions L-Thr amino acid was found to promote COM crystallization, and at 2–20 mM in COM solution (S = 6.0) leads to the diminution of the induction time of COM to 50 s, that is less by half than the corresponding value of pure COM (100 s). It is shown that at 1–20 mM L-Asp concentrations the inhibition degree of COM rises as the concentration of L-Asp grows, and changes from 32.0% to 90.2%. In the case of L-Arg the inhibition degree varies from 10.2% (at 8 mM) to 86.0% (at 20 mM). B1 and B6 vitamins exert an inhibiting influence on the processes of nucleation and growth of COM crystals, and at 50 mM concentration favor 70-fold increase in COM induction time. It is shown that at the introduction of the inhibitor molecules L-Asp, L-Arg, B1, B6 into the solution, the surface energy of COM crystals diminishes to 19.8–20.8 mJ/m2, whereas in pure COM it is equal to 22.0 mJ/m2. The curve of COM nucleation in the presence of the additives (B1 and B6 in 40–50 mM) has two kinetic nucleation regions (at S = 4.6–8.0 and S = 8.0–14.0) with a kink at S = 8.0, that is caused by the transition from the heterogenic nucleation to the homogeneous one at high supersaturations.

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Fig. 5. Kinetic curves of nucleation of COM crystals without additives (1) and in the presence of: 10 mM B1 (2), 10 mM B6 (3), 20 μM B12 (4) (a); 20 mM B1 (2), 20 mM B6 (3), 40 μM B12 (4) (b); 50 mM B1 (2), 50 mM B6 (3), 100 μM B12 (4) (c) with S = 4.6–14.0. Table 5 Effect of amino acids and vitamins on the surface energy (σ) of COM crystals. COM + additives

Cadditives, mM

σ, mJ/m2

pure COM COM + L-Asp

– 4 8–20 4 8–20 4–20 10–20 50 10–20 50 0.02–0.04 0.1

22.0 21.8 19.8 21.0 20.6 22.1 20.8 8.2 (S = 4.6–8.0), 32.4 (S = 8.0–14.0) 20.7 8.2 (S = 4.6–8.0), 33.1 (S = 8.0–14.0) 21.9 21.7

COM + L-Arg COM + L-Thr COM + B1 COM + B6 COM + B12

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Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments This work was supported by the National Academy of Sciences of Ukraine by the budget program “Support for the development of priority areas of scientific research” (KPKVK 6541230), project “Photonics”. References [1] A. Millan, Crystal morphology and texture in calcium oxalate monohydrate renal calculi, J. Mat. Sci.: Mater. Medicine. 8 (1997) 247–250, https://doi.org/10.1023/

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