- Email: [email protected]
ESI+ studies of the zwitterionic surfactant-Na+ pair formation
Journal of Molecular Graphics and Modelling 91 (2019) 204e213
Contents lists available at ScienceDirect
Journal of Molecular Graphics and Modelling journal homepage: www.elsevier.com/locate/JMGM
Density Functional Theory and UPLC/MS/ESIþ studies of the zwitterionic surfactant-Naþ pair formation -Manuel Martínez-Magada n a, **, David-Aaron Nieto-Alvarez a, ***, Jose jera a, Rodolfo Cisneros-De vora b, n-Camacho b, Ana-Graciela Servín-Na Ricardo Cero a, * Luis-Silvestre Zamudio-Rivera a b
zaro Ca rdenas Norte 152, San Bartolo Atepehuaca n, Ciudad de M leo, Eje Central La Instituto Mexicano Del Petro exico, 07730, Mexico zaro Ca rdenas Norte 152, Col. San Bartolo Atepehuaca n, Ciudad de M leo, Eje Central La CONACyT-Instituto Mexicano Del Petro exico, 07730, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 January 2019 Received in revised form 13 June 2019 Accepted 20 June 2019 Available online 21 June 2019
The formation in solution of supramolecular complexes type zwitterion-cation have been shown. The industrial grade zwitterion surfactants cocamidopropyl hydroxysultaine and cocamidopropyl betaine with sodium ion were studied. A combined experimental and theoretical point of view was performed, through the use of Ultra-Performance Liquid Chromatography/Mass Spectrometry/ElectroSpray Ionization with positive mode (UPLC/MS/ESIþ) analytic technique and Density Functional Theory (DFT) theoretical approach. Then, the supramolecular complex zwitterion-cation-anion triplets are shown to be viable. Mass/Charge (m/z) relationships have been determined through MS/ESI using positive mode as an ionization source, obtaining five and four molecular species for industrial grade sultaine and betaine chemical products, respectively. Also, molecular zwitterion-NaCl complexes were theoretically studied in three different dielectric constants corresponding to water, methanol, and acetone solvents. It was found that acetone, the lower dielectric constant solvent studied, shows the higher interaction energy. In both vacuum neutral, zwitterion-NaCl, and vacuum positive, zwitterion-Naþ, molecular complexes the interaction of the cocamidopropyl hydroxysultaine pairs is less strong than cocamidopropyl betaine ones. © 2019 Elsevier Inc. All rights reserved.
Keywords: Density functional theory UPLC MS ESIþ Zwitterionic surfactant
1. Introduction Supramolecular chemistry continue being currently a significant area of chemistry research and chemical industry as the part of the study of systems that involve self-assembled aggregates of molecules or ions, such as micelles, inverted micelles, bilayers, bilayer vesicles, that are linked through non-covalent intermolecular interactions such as hydrogen bonds, ion-dipole, ion-ion, zwitterionion, p-p, among others [1]. The new self-assembled macromolecular aggregates formed through this type of intermolecular interactions acquire their own physicochemical properties different from those of the molecules that gave them origin. One of the features to be highlighted is the three-dimensional structure that they can adopt, the case of tertiary structures such as enzymes or
* Corresponding author. ** Corresponding author. *** Corresponding author. E-mail addresses: [email protected] (D.-A. Nieto-Alvarez), [email protected] n), [email protected] (L.-S. Zamudio-Rivera). (J.-M. Martínez-Magada https://doi.org/10.1016/j.jmgm.2019.06.017 1093-3263/© 2019 Elsevier Inc. All rights reserved.
the double-helical structure of DNA [2]. In this sense, this was the reason for the developing of the key-lock concept, widely used in enzymatic systems, but in supramolecular chemistry it is known as the guest-host interaction [3]. By using this concept, there are numerous cases of supramolecular complexes derived from noncovalent intermolecular interactions such as pp, p-cation, panion and ion-ion, which are known as ion-par receptors [4]. The development of supramolecular complexes of the guest-host type with metal ions is becoming increasingly important due to its applications in various fields, such as purification processes, controlled delivery of substances, and sensors [5]. Self-assembled macromolecular aggregates structures in solution can transform one to another when the solution conditions are changed, the electrolyte concentration or pH. The equilibrium structures formed are determined by thermodynamics and intra-aggregate forces, along with the strength of the inter-aggregate forces between aggregates in concentrated systems [6]. In oil industry, the understanding of the influence of salinity and hardness over colloidal systems is of vital importance because this comprehension permits to optimize and improve processes of
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
enhanced recovery of hydrocarbons through the use of chemical products. These products must be tolerant to high temperatures, pressures, salinities and hardness present in oil reservoirs. There exists few cases where the use of zwitterion-cation-anion based supramolecular complexes is reported in the oil industry [7e10], where the macromolecules are given by the interaction of zwitterionic liquids with anionic and/or cationic surfactants. For instance, in reference [11] have described a new state of aggregation anion-cation-zwitterion triplets in solution through the equilibrium constant of the reaction of p-nitrophenol with tetra-nbutylamonium taurine in 95.3 mol % dioxane-water. In Ref. [12], it has been defined the complex formation starting from zwitterioncation surfactant-micelles and anionic polyelectrolyte poly(sodium styrenesulfonate). The complex formation followed by NMR spectroscopy of the deuterated-surfactants CTAB-g-d9 and HDPC-g-d6 cetyltrimethylamonium bromide and hexadecyl phosphocholine, explains that the anion poly(sodium styrenesulfonate) interacts with the micelle through electrostatic interactions favoring the balance of the micelle towards the monomers. Finally, in Refs. [13,14], it has been described the assembled-microcapsules formation entirely of block copolymer micelles from cationzwitterion pair starting from anionic poly [2-(dimeylamino)ethyl methacrylate-block-poly (2-diethylamino) ethyl methacrylate)] PDMA-PDEA and the cationic poly(2-(diethylamino)ethyl) methacrylateeblock-poly(methacrylic acid) PDEA-PMAA. In reference [15], it is demonstrated the formation of pair zwitterion-cation from phosphoryletanolamine with cation Ca2þ using femtosecond infrared (fs-IR) pump-probe spectroscopy. In reference [16] by using ESI()-MS and ESI(þ)-MS analytic techniques it has been showed that formation of supramolecular aggregates cation-anion in solution between 1,3-dialkylimidozolium (cation) and tetrafluroborate (anion), so that the general tendency demonstrates that solvents with smaller dielectric constants favor the ion paring. On the other hand, molecular dynamic simulation studies [17,18] show for carboxybetaine and sulfobetaine that association number and lifetime follow the order Liþ>Naþ>Kþ>Csþ, and carboxybetaine is stronger than sulfobetaine consequently the strong cations Liþ and Naþ associate stronger with carboxybetaine than with sulfobetaine, and cations Kþ and Csþ associate more strongly with sulfobetaine. There exists hard evidence that Naþ-Driven wormlike micelles occurs when NaCl is added to N-alkyl-N0 -carboxymethyl imidazolium inner salts and anionic surfactant sodium dodecyl sulfate, in aqueous solution. The resultant solution displayed a high viscosity upon addition of NaCl. It indicates that the viscoelastic fluid was induced to be formed in the presence of NaCl [19]. Due to, it is known that to maintain viscoelasticity under high temperature, and to get a fast recovery under high shear of the wormlike micelle structure, is a challenge in oilfield applications [20], the determination of zwitterion-cation pairs physicochemical properties are needed on each specific application or chemical technology. For example, it has been demonstrated in literature that surfactants derivative of cocoamidopropyl betaine-sodium a-olefin sulfonate interaction are able to tolerate high temperature and high salinity [21]. While, correspondingly, surfactants derivative of cocoamidopropyl hydroxysultaine-sodium a-olefin sulfonate interaction are able to tolerate ultra-high temperature and ultra-high salinity [22]. Additionally, it has been also determined the synergism in mixtures of zwitterionic and ionic surfactants, showing that the addition of inert electrolytes favors the interactions between the ionic and the zwitterionic surfactants. This fact is due to the reduction of the electrostatic repulsion between surfactant ions. In anionicezwitterionic mixtures of brine solutions, the interaction is reduced as the hydrocarbon length of the zwitterionic surfactant increases [23]. Finally, the identification of several polyfluoroalkyl cationic or zwitterionic analytes in sediment samples, was
205
performed through an analytic procedure optimization of HPLC/MS polarity-switching electrospray ionization technique [24]. In this work, a new theoretical analysis, and experimental UPLC/ MS/ESI þ determination procedure is developed for the determination of zwitterion-cation (Naþ) pair's formation. Up to our knowledge, even though the importance of the zwitterion-cation (Naþ) interaction in surfactants with application in oil industry, cocamidopropyl hydroxysultaine and cocamidopropyl betaine, this is the first evidence that shows its existence. 2. Materials and methods 2.1. Molecular modeling In order to determine the theoretical energetic values for the interactions between cocamidopropyl-hydroxysultaine (S1) with NaþCl, and for cocamidopropyl-betaine (B1) with NaþCl, in water (W), methanol (M) and acetone (A) dielectric environments, the molecular cluster approach, i.e., non-periodic PBC(periodic boundary conditios), DFT methodology was applied. These three dielectric environments are taken into account to show that, with a less dielectric constant of environment the system is more stable, i.e., the system would be less solvated. This conditions were properly simulated through dielectric continuum, specifically by use of the three dielectric constant: W: 78.54; M: 32.63 and A: 20.70, correspondingly, within the Conductor-like Screening Model (COSMO) approach [25]. It was used the Materials Studio (MS) program suite [26] to study molecular interactions of cocamidopropyl-hydroxysultaine (S1) with NaþCl, and cocamidopropyl-betaine (B1) with NaþCl. Critical micelle concentrations (CMC) of both zwitterionic surfactants are 279.34 and 1010 ppm for cocamidopropylhydroxysultaine and cocamidopropyl-betaine, respectively [27,28]. Assuming that micelle-monomer equilibrium is observed around of the CMC value region as previously found [29,30], the maximum monomer concentration in the solution will be present on this region. Then, single-molecule approach is considered appropriate for the molecular modeling study. To obtain the optimized molecular geometries for all supramolecular complexes constructed through the graphic environment of MS Visualizer, DFT computations through MS DMol3 application were executed in W, M and A dielectric environments, respectively. DMol3 runs were performed within the Generalized Gradient Approximations (GGA), using DNP(4.4) basis sets and the Perdew-Burke-Ernzerhof (PBE) functional [31], also the Grimme method for the DFT-Dispersion correction [32] was employed, the Effective Core Potentials for core treatment [33], spin unrestricted, and the three above-mentioned solvents were utilized. All run parameters were set at the fine accuracy option. 2.2. Materials Solvents: Methanol and water, both UPLC-grade were acquired
Fig. 1. Molecular structure of cocamidoproyl-hydroxysultaine.
206
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
from J. T. Baker. Surfactants: The cocamidopropyl hydroxysultaine surfactant (Fig. 1) was provided by Stepan Co. as its commercial product, which contains 43.5% of active substance, 6.5% of NaþCl and 50.0% of water. The cocamidopropyl betaine surfactant (Fig. 2) was provided by Stepan Co. as its commercial product, which contains 30.14% of active material, 5% of NaCl and 64.86.0% of water. 2.3. Equipment UPLC coupled to Mass Spectrometer. The Ultra Performance Liquid Chromatograph coupled to the Mass Spectrometer, Waters model SYNAPT G2 HDMS. The chromatograph contains pump and automatic injector and the spectrometer Synapt G2, we have worked with an ESI source in positive mode, we have used the resolution acquisition mode UPLC/MS/ ESIþ.
resolution was 0.1 Da and the width of the peak was located in 5 s. For the total analysis of the ions it is acquired from 100 a 2000 Da. 2.6. Sample preparation For both commercial grade surfactants, cocamidopropyl hydroxysultaine which contains 43.5% of active, and cocamidopropyl-betaine that contains 30.14% of active, a solution of 400 ppm in water, grade UPLC-MS, was prepared for each. It is important to mention that always in this analytical technique is normal to get a dilution of the sample with the corresponding mobile phase [35]. Specifically, in this work a dilution factor of 1:4 was obtained, this means a concentration in solutions of 66 ppm just before to get into the chromatography column. In this way, it is guaranteed that monomers are always available in both cases. 3. Results and discussion
2.4. Optimization of the UPLC analytical method In connection with the optimization of the analytical methodology, different tests were performed modifying the variables involved: column type, column temperature, flow, mobile phase and injection volume. As a result of the process, the best chromatographic conditions were obtained for analyzing the supramolecular complex studied in this work. In the case of mobile phase, different relationships between methanol-water with 1 mM of formic acid were tested. For the relationships (10:0), (9:1) and (8:2), the retention times of the surfactant and the solvent front are very similar, and the signals are overlapped. It was found that when a relationship methanol-water (7:3) is used, the retention times allow the signals to be perfectly distinguished. In particular, it was observed that when the flow rate was greater than 0.5 mL/min retention time of the surfactant was reduced, causing signal overlapping for surfactant and solvent front. Derived from this analysis, it was found that the optimum flow velocity was 0.20 mL/min. As a result of the different tests, the best conditions for the determination of the supramolecular complex were: UPLC CSH C18 (1.7, 2.1 100 mm); column, temperature of 30 C, flow rate of 0.20 mL/min, methanol-water (7:3) v/v as mobile with 1 mM of formic acid phase, injection volume of 5 mL and a tests series of 18 and 20 min. 2.5. Optimization of MS synapt G2 analytical method For the method optimization in the analytical methodology [34], different tests were performed modifying the variables involved. As a result of the process, the best conditions were obtained for analyzing supramolecular complex used in this work were: The mass spectrometry we worked with a ionization source for positive mode electrospray, the resolution acquisition mode was used, the capillary voltage used was 2010 V, the temperature of the source of 120 C, desolvation temperature 490 C, gas cone flow 50 L/h, desolvation flow 498 L/h and nebulizer gas pressure 6.4 bar. Mass
Fig. 2. Chemical structure of cocamidopropyl betaine.
3.1. DFT study DFT results show that a NaþCl species approaches more closely onto cocamidopropyl-hydroxysultaine (S1) and cocamidopropylbetaine (B1) when the dielectric constant of the solvent is minor forming then a more stable supramolecular complex. In Figs. 3 and 4, it is observed that spatially the conformation of the NaþCl on the zwitterion part of S1 and B1 in each case is the same independently of the solvent used; except for the conformation (c) of the sultaine where it is appreciated that the salt is closer to zwitterion fragment, this suggests a less solvation in the structural complex conformation. These characteristics and understanding helps to efficiently design the laboratory tests and later more efficiently apply the chemicals in real tests in the oil industry. Observing the theoretically obtained energy results that are shown in Tables 1 and 2, we can affirm that the solvent of lower dielectric constant shows a greater energy of interaction zwitterion-cation-anion 15.296 and 26.746 kcal/mol for zwitterion surfactants S1 with NaþCl, and B1 with NaþCl, that this general tendency were previously demonstrated [16] exemplify that the solvents with smaller dielectric constants favor the cation paring. In Tables 3 and 4 of Vacuum neutral and Vacuum positive modes, shows that the formation of the zwitterion-cation, cocamidopropyl hydroxysultaine (S1) with Naþ (Fig. 5) is less strong (79.45 kcal/mol) than cocamidopropyl-betaine (B1) with Naþ (Fig. 6) (86.57 kcal/mol), consequently the Naþ cation associate stronger with B1 that with S1, in the case of neutral mode the interaction energy is more soft. The figures use the standard atom colors of, gray: carbon; white: hydrogen; red: oxygen; blue: nitrogen; yellow: sulphur; green: chlorine; and purple: sodium. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article). 3.2. Methodology for the determination of the supramolecular complex zwitterion-cation molecular ion In the retrosynthetic analysis of cocamidopropyl hydroxysultaine as seen in Fig. 7, the synthetic [36,37] precursors are: N,Ndimethylpropyl alkilamides and 3-chloro-2-hydroxy-1-propanesulfonate which are accompanied by sodium chloride and when this surfactant is produced at the industrial level, the sodium chloride is not removed and remains as part of the final product. This gives rise to the zwitterion-cation-anion triads, from the interaction of the zwitterion [cocamidopropyl hydroxysultaine] with the ionic pair [sodium chloride].
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
207
Fig. 3. Conformations of supramolecular assemble for cocamidopropyl hydroxysultaine (S1) and NaþCl in (a) water, (b) methanol, (c) acetone. Atom color code: gray, carbon; white, hydrogen; red, oxygen; blue, nitrogen; yellow, sulphur; green, chlorine; and purple, sodium, (same code applies in all Figures).
Fig. 4. Conformations of supramolecular assemble for the cocamidopropyl-betaine (B1) and NaþCl in (a) water, (b) methanol, (c) acetone.
Table 1 Energetic value for cocamidopropyl hydroxysultaine (S1), salt NaþCl, supramolecular conformation between both and interaction energetic value.
S1 NaþCl S1þNaþCl DE
(a) Water (kcal/mol)
(b) Methanol (kcal/mol)
(c) Acetone (kcal/mol)
1,048,032.138 390,531.470 1,438,572.553 ¡8.945
1,048,029.672 390,530.248 1,438,573.501 ¡13.581
1,048,028.164 390,529.077 1,438,572.537 ¡15.296
Table 2 Energetic value for cocamidopropyl-betaine (B1), salt NaþCl, supramolecular conformation between both and interaction energetic value.
B1 NaþCl B1 þ NaþCl DE
(a) Water (kcal/mol)
(b) Methanol (kcal/mol)
(c) Acetone (kcal/mol)
678,477.612 390,531.470 1,069,033.176 ¡24.093
678,474.503 390,530.248 1,069,031.081 ¡26.330
678,473.319 390,529.077 1,069,029.143 ¡26.746
Now, in the retrosynthetic analysis of cocamidopropyl betaine, as seen in Fig. 8, the synthetic [36,37] precursors are: N,N-dimethyl propyl alkilamides and sodium chloroacetate which are supplemented by sodium chloride and when this surfactant is produced at the industrial level, the sodium chloride is not removed and remains as part of the final product. This originates the corresponding zwitterion-cation-anion triplet [cocamidopropyl betaine] with
[sodium chloride]. According to the retrosynthetic analysis for both zwitterionic surfactants cocamidopropyl-hydroxysultaine and cocamidopropylbetaine, the sodium chloride is always present giving rise to the interaction of the zwitterionic surfactant with the ionic par, sodium chloride. The supramolecular structures zwitterion-cation-anion, cocamidopropyl hydroxysultaine and cocamidopropyl-betaine,
208
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
Table 3 Energetic value for the sultaine (S1), salt NaþCl, and Naþ in neutral and positive mode for a supramolecular conformation between both and the interaction energetic value. (a) Vacuum neutral mode
(b) Vacuum positive mode
(kcal/mol) S1 NaþCl S þ NaþCl DE
1,047,983.107 390,495.831 1,438,507.912 28.973
S Naþ S þ Naþ DE
1,047,983.107 101,641.483 1,149,704.040 79.449
both with sodium chloride, cannot be characterized by traditional spectroscopic techniques. However, the use of technique UPLC/MS/ ESI/þ allows to unequivocally identify such complexes. Additionally, when dealing with industrial grade products, the supramolecular complexes present in the final product can be separated for UPLC and later through the technique of MS with con soft ionization for ESI, it is possible to know exactly the molecular weight of each of the supramolecular complexes and therefore the average molecular weight of the industrial grade product.
Table 4 Energetic value for the betaine (B1), salt NaþCl, and Naþ in neutral and positive mode for a supramolecular conformation between both and the interaction energetic value. (a) Vacuum neutral mode (kcal/mol) B NaþCl B þ NaþCl DE
678,444.294 390,495.831 1,068,979.273 ¡39.147
(b) Vacuum positive mode (kcal/mol) B Naþ B þ Naþ DE
678,444.294 101,641.483 780,172.343 ¡86.565
Fig. 5. Conformation of supramolecular assemble for the cocamidopropyl hydroxysultaine and NaþCl
Fig. 6. Conformation the supramolecular assemble for the cocamidopropyl betaine, and NaþCl
Fig. 7. Retrosynthetic analysis showing the raw materials for the preparation of the cocamidopropyl hydroxysultaine.
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
209
Fig. 8. Retrosynthetic analysis showing the raw materials for preparation of the cocamidopropyl betaine.
Fig. 9. Commercial product cocamidopropyl hydroxysultaine chromatogram.
3.3. Determination of the supramolecular zwitterion-cation complex, cocamidopropyl hydroxysultaine with sodium chloride and, its average molecular weight The analytical results derived from the UPLC/MS/ESIþ study designed for commercial grade product cocamidopropyl hydroxysultaine, show in the chromatogram (Fig. 9) the presence of five derivatives with retention times in: 1.26, 1.77, 2.96, 6.28, and 15.70 min m/z relationships are determined for each of the elution times by means of electrospray ionization mass spectrometry (ESIMS) using the positive mode ionization source, obtaining the following m/z values: 361.189, 389.216, 417.245, 445.273 and 473.309. It is shown in Fig. 10, the extraction ion chromatogram for each of the aforementioned elution times. The results indicate that for each ratio of m/z corresponds to the molecular weight of the product with sodium cation [MþNa]þ, by checking the presence of the supramolecular complex as shown in Fig. 11, cocamidopropyl hydroxysultaine with sodium cation from zwitterion-cation interaction. It also indicates that the five products differ in the alkyl chain represented in Fig. 11, where n represents the number of carbon units of 4, 6, 8, 10 and 12. For the most abundant species commercial grade product, the elution time is 6.28 min (Fig. 9), the deconvolution for getting the m/z relationships, gives the peak with elution time of 6.36 min,
corresponding to cocamidopropyl hydroxysultaine with sodium cation [MþNa]þ molecular ion, which has a m/z ratio of 445.273 obtained through ESI-MS. From this analysis of the m/z obtained value, the presence of complex zwitterion-cation pair complex is confirmed, as shown in Fig. 11, where the value of n is 10. Thus, in order to recover the molecular weight of supramolecular zwitterion-cation-anion triplet (Fig. 12) it must be added the atomic weight of the chloride ion, obtaining a subsequent molecular weight 480.726 g/mol. Now, for elution time of 15.70 min, the obtained m/z of 473.309 through ESI-MS corresponds to the [MþNa]þ molecular ion. Consequently, this m/z value indicates the presence of the zwitterion-cation complex pair shown in Fig. 11, where the value of n is 12. By adding the atomic weight of the chloride ion, the molecular weight of 508.762 g/mol for the supramolecular zwitterioncation-anion complex is obtained (Fig. 12). Through the same analysis procedure, the molecular weights of the four remaining products are obtained, as presented in Table 5. The analytical results in Table 5 show that the hydrocarbon tail length of the cocamidopropyl hydroxysultaine lies between 4 and 12 carbons, and the average molecular weight of the supramolecular complex derivative of the interaction between cocamidopropyl-hydroxysultaine with NaþCl (zwitterion-cationanion triplet), is 468.171 g/mol. The supramolecular complex of greater abundance is in which the hydrocarbon tail length is 10 (Fig. 12). 3.4. Determination of the zwitterion-cation supramolecular complex, cocamidopropyl betaine with sodium chloride, and its average molecular weight The analysis of the results derived from the UPLC/MS/ESIþ study designed for cocamidopropyl betaine commercial grade product, shows in its chromatogram (Fig. 13) the presence of four derivatives with retention times in: 1.26, 3.22, 6.96, and 17.52 min m/z relationships are determined for each of the elution times by means of electrospray ionization mass spectrometry (ESI-MS) using the positive mode ionization source, obtaining the following m/z values: 327.210, 337.257, 365.289, and 393.316. Fig. 14 shows the extraction ion chromatogram for each of the aforementioned elution times. The results indicate that the interaction of cocamidopropyl betaine with the sodium cation originates the observed zwitterion-cation complex. Their m/z ratio corresponds to the molecular weight of the product with sodium cation [MþNa]þ. It also indicates that the four products differ in the chain length represented in Fig. 15, where n represents the number of carbon
210
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
Fig. 10. Extraction ion chromatogram for each of the elution times for commercial product cocamidopropyl hydroxysultaine.
Fig. 11. Molecular structure of supramolecular complexes zwitterion-cation, Cocamidopropyl hydroxysultaine with sodium cation.
units 6, 8, 10 and 12. Although, only the m/z value of 327.210 correspond to the specie [M þ Na þ H2O]þ where n is for 6 carbon units, this behavior only is observed in this isolated case, here the water molecule is part of sodium hydration sphere. For the most abundant species of the commercial grade product, the elution time is 6.96 min, the deconvolution for getting the m/z relationships, gives two peaks 6.90 and 7.04 as function of elution time. For the 6.90 min Case the corresponding complex is cocamidopropyl betaine-hydrogen cation, [MþH]þ, and the 7.04 min peak, relates to the cocamidopropyl betaine-sodium cation complex, [MþNa]þ, which has an m/z ratio of 365.289 by ESI-MS. From this analysis of the m/z obtained values, the presence of zwitterion-
Fig. 12. Supramolecular zwitterion-cation-anion triads with 46.5% of abundance in the industrial grade product cocamidopropyl hydroxysultaine.
cation pair complex is proven, as illustrated in Fig. 15, where the value of n is 10. Thus, in order to recover the molecular weight of supramolecular zwitterion-cation-anion triads (Fig. 16), it must be added the atomic weight of the chloride ion, obtaining a resulting molecular weight of 400.742 g/mol. Now, for elution time of 17.52 min, the obtained m/z of 393.316 through ESI-MS corresponds to the [MþNa]þ molecular ion. Therefore, this m/z value indicates the presence of the zwitterion-
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213 Table 5 Analytical results obtained through UPLC/MS/ESI þ for the supramolecular zwitterion-cation complexes cocamidopropyl hydroxysultaine with sodium cation. [min]a
[g/mol]b
[n]c
[L2]d
[%]e
[g/mol]f
[g/mol]g
1.26 1.77 2.96 6.28 15.70
361.189 389.216 417.245 445.273 473.309
4 6 8 10 12
14,659.079 96,474.531 74,380.297 234,539.469 84,727.891
2.9 19.1 14.7 46.5 16.8
396.642 424.669 452.698 480.726 508.762
468.171
a b c d e f g
Retention time. Molecular weight of pair zwitterion-cation. Carbon number of the hydrocarbon tail. Area under the curve. Percentage of pair zwitterion-cation as a function of the hydrocarbon tail. Molecular weight of zwitterion-cation-anion triplet. Average molecular weight of zwitterion-cation-anion triplet.
211
cation complex pair shown in Fig. 14, where the value of n is 12. By adding the atomic weight of the chloride ion, the molecular weight of 428.769 g/mol for the supramolecular zwitterion-cation-anion complex is obtained (Fig. 16). Through the same analysis procedure, the molecular weights of the three remaining products are obtained, presenting the results in Table 6. The analytical results in Table 6 show that the average molecular weight of the commercial grade product cocamidopropyl betaine with sodium chloride is 411.027 g/mol, and for the supramolecular complexes considering all the zwitterion-cation-anion triads that has greater abundance, area down curve of 517,489 L2, is that one in which the value of n is 10 with 50.3% of abundance as depicted in Fig. 16.
4. Conclusion
Fig. 13. Commercial grade product cocamidopropyl betaine chromatogram.
In this work it is shown the theoretical determination of threemember supramolecular complex zwitterion-cation-anion bonds and their corresponding experimental characterization by the analytical method UPLC/MS/ESIþ. The corresponding results shows that molecular weights were determined for the cationic fragment in the supramolecular complex, these corresponds to zwitterioncation pair [MþNa] each one of the supramolecular complexes. The zwitterion-cation-anion supramolecular structure, which are part of the industrial grade product formed by intermolecular interactions that take place between cocamidopropyl hydroxysultaine and sodium chloride, and cocamidopropyl betaine and sodium chloride, originating the supramolecular complexes zwitterion-cation-anion triplets. The supramolecular interaction have been good displayed for DFT analysis, highlighting that, the most stable conformations in all systems are observed on the one hand when the solvent is acetone and on the other when it is locked in positive mode.
Fig. 14. Extraction ion chromatogram for each of the elution times for commercial grade product cocamidopropyl betaine.
212
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
CONACyT for its appointment. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.jmgm.2019.06.017. References
Fig. 15. Molecular structure of zwitterion-cation supramolecular complexes, cocamidopropyl betaine with sodium cation.
Fig. 16. Supramolecular complexes zwitterion-cation-anion triplets with 50.3% of abundance in the industrial grade product cocamidopropyl betaine.
Table 6 Analytical results obtained through UPLC/MS/ESIþ for the supramolecular zwitterion-cation complexes, cocamidopropyl betaine with sodium cation. [min]a 1.26 3.22 6.96 17.52 a b c d e f g h
[g/mol]b
[n]c
h
327.210 337.257 365.289 393.316
[L2]d 6 8 10 12
11,406 53,551 517,489 445,982
[%]e 1.1 5.2 50.3 43.4
[g/mol]f 362.663 372.71 400.742 428.769
[g/mol]g h
411.027
Retention time. Molecular weight of pair zwitterion-cation. Carbon number of the hydrocarbon tail. Area under the curve. Percentage of pair zwitterion-cation as a function of the hydrocarbon tail. Molecular weight of zwitterion-cation-anion triplet. Average molecular weight of zwitterion-cation-anion triplet. Molecular weight correspond to [M þ Na þ H2O] þ.
Acknowledgements The authors acknowledge to the Mexican Institute of Petroleum ~ o y síntesis de nuevos prototipos de (IMP), Projects D.61029 “Disen productos químicos multifuncionales con propiedades dispersantes de asfaltenos, modificadoras de la mojabilidad y desemulsificantes” tico Asistido por Agentes Espumantes and H.61057 “Bombeo Neuma vora de Tecnología IMP”, for financial support. Rodolfo Cisneros-De n-Camacho thank to the Direccio n de Ca tedras and Ricardo Cero
[1] J.-M. Lehn, Supramolecular chemistrydscope and perspectives molecules, supermolecules, and molecular devices(nobel lecture), Angew Chem. Int. Ed. Engl. 27 (1988) 89e112, https://doi.org/10.1002/anie.198800891. [2] D. Phlip, softcover, DM 58.00, in: J.-M. Lehn, V.C.H. Weinheim (Eds.), Supramolecular Chemistry: Concepts and Perspectives, x, WILEY-VCH Verlag GmbH, 1995, ISBN 3-527-2931 1-6, p. 271, https://doi.org/10.1002/ adma.19960081029, 1996. [3] Jose Vazquez Tato, Química supramolecular, Rev. Iberoam. Polímeros. 6 (2005) 44e80. [4] D.A. Dougherty, The cation-p interaction, Acc. Chem. Res. 46 (2013) 885e893, https://doi.org/10.1021/ar300265y. [5] H.-R. Yu, J.-Q. Hu, X.-H. Lu, X.-J. Ju, Z. Liu, R. Xie, W. Wang, L.-Y. Chu, Insights into the effects of 2:1 “Sandwich-Type” crown-ether/metal-ion complexes in responsive hosteguest systems, J. Phys. Chem. B 119 (2015) 1696e1705, https://doi.org/10.1021/jp5079423. [6] Intermolecular and Surface Forces, Elsevier, 2011, https://doi.org/10.1016/ C2009-0-21560-1. zar-Vara, L.S. Zamudio-Rivera, E. Buenrostro-Gonza lez, Multifunc[7] L.A. Alca tional evaluation of a new supramolecular complex in enhanced oil recovery, removal/control of organic damage, and heavy crude oil viscosity reduction, Ind. Eng. Chem. Res. 54 (2015) 7766e7776, https://doi.org/10.1021/ acs.iecr.5b01308. [8] L.A. Alc azar-Vara, L.S. Zamudio-Rivera, E. Buenrostro-Gonz alez, R. Hern andezrez, Multifunctional propAltamirano, V.Y. Mena-Cervantes, J.F. Ramírez-Pe erties of zwitterionic liquids. Application in enhanced oil recovery and asphaltene aggregation phenomena, Ind. Eng. Chem. Res. 54 (2015) 2868e2878, https://doi.org/10.1021/ie504837h. [9] C. Zou, Y. Qin, X. Yan, L. Zhou, P. Luo, Study on acidizing effect of cationic bcyclodextrin inclusion complex with sandstone for enhancing oil recovery, Ind. Eng. Chem. Res. 53 (2014) 12901e12910, https://doi.org/10.1021/ ie501569d. n, D. Rodrigue, Evaluation of two new self-assembly [10] B. Wei, L. Romero-Zero polymeric systems for enhanced heavy oil recovery, Ind. Eng. Chem. Res. 53 (2014) 16600e16611, https://doi.org/10.1021/ie5014986. [11] P. Haberfield, J.J. Cincotta, Proximate charge effects. 6. Anion-cationzwitterion triplets in solution, J. Org. Chem. 49 (1984) 4188e4192, https:// doi.org/10.1021/jo00196a017. [12] D.J. Semchyschyn, M.A. Carbone, P.M. Macdonald, Anionic polyelectrolyte binding to mixed CationicZwitterionic surfactant micelles: a molecular perspective from 2 H NMR spectroscopy, Langmuir 12 (1996) 253e260, https://doi.org/10.1021/la950244a. [13] T. Addison, O.J. Cayre, S. Biggs, S.P. Armes, D. York, Polymeric microcapsules assembled from a cationic/zwitterionic pair of responsive block copolymer micelles, Langmuir 26 (2010) 6281e6286, https://doi.org/10.1021/la904064d. [14] T.H. Rehm, C. Schmuck, Ion-pair induced self-assembly in aqueous solvents, Chem. Soc. Rev. 39 (2010) 3597, https://doi.org/10.1039/b926223g. [15] S.T. van der Post, J. Hunger, M. Bonn, H.J. Bakker, Observation of water separated ion-pairs between cations and phospholipid headgroups, J. Phys. Chem. B 118 (2014) 4397e4403, https://doi.org/10.1021/jp411458z. [16] H.K. Stassen, R. Ludwig, A. Wulf, J. Dupont, Imidazolium salt ion pairs in solution, Chem. Eur J. 21 (2015) 8324e8335, https://doi.org/10.1002/ chem.201500239. [17] Q. Shao, Y. He, S. Jiang, Molecular dynamics simulation study of ion interactions with zwitterions, J. Phys. Chem. B 115 (2011) 8358e8363, https:// doi.org/10.1021/jp204046f. cha, D. Touraud, P. Jungwirth, W. Kunz, [18] N. Vlachy, B. Jagoda-Cwiklik, R. Va Hofmeister series and specific interactions of charged headgroups with aqueous ions, Adv. Colloid Interface Sci. 146 (2009) 42e47, https://doi.org/ 10.1016/j.cis.2008.09.010. [19] X. Wang, R. Wang, Y. Zheng, L. Sun, L. Yu, J. Jiao, R. Wang, Interaction between zwitterionic surface activity ionic liquid and anionic surfactant: Na þ -driven wormlike micelles, J. Phys. Chem. B 117 (2013) 1886e1895, https://doi.org/ 10.1021/jp308016a. [20] J. Yang, Viscoelastic wormlike micelles and their applications, Curr. Opin. Colloid Interface Sci. 7 (2002) 276e281, https://doi.org/10.1016/S13590294(02)00071-7. [21] R. Hernandez Altamirano, L.S. Zamudio Rivera, V.Y. Mena Cervantes, E.E. Luna Rojero, E. Serrano Saldana, J.M. Martinez Magadan, R. Oviedo Roa, D.A. Nieto Alvarez, E. Buenrostro Gonzalez, R. Cisneros Devora, M.D.P. Arzola Garcia, M. Pons Jimenez, A.E. Mendoza Aguilar, S.J.K. Kim, J.F. Ramirez Perez, T.E. Chavez Miyauchi, Y. Ruiz Morales, Foaming composition with wettability modifying and corrosion inhibitory properties for high temperature and ultrahigh salinity. http://www.freepatentsonline.com/9469804.html, 2016.
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213 (Accessed 30 April 2019). Dura pez Ramírez, V.C.D.L.A. n, R. Herna ndez Alta[22] L.S. Zamudio Rivera, S. Lo mirano, V.Y. Mena Cervantes, M.N.A. García, A. Ríos Reyes, A. Ortega Rodríguez, L.C.J. Mendoza De, C.M.Y. Lozada, E. Buenrostro Gonz alez, Foaming composition for high temperature and salinity. http://www.freepatentsonline. com/8722588.html, 2014. (Accessed 30 April 2019). pez-Díaz, I. García-Mateos, M.M. Vel [23] D. Lo azquez, Synergism in mixtures of zwitterionic and ionic surfactants, Colloid. Surf. Physicochem. Eng. Asp. 270e271 (2005) 153e162, https://doi.org/10.1016/J.COLSURFA.2005.05.054. [24] G. Munoz, S.V. Duy, P. Labadie, F. Botta, H. Budzinski, F. Lestremau, J. Liu, , Analysis of zwitterionic, cationic, and anionic poly- and perS. Sauve fluoroalkyl surfactants in sediments by liquid chromatography polarityswitching electrospray ionization coupled to high resolution mass spectrometry, Talanta 152 (2016) 447e456, https://doi.org/10.1016/ J.TALANTA.2016.02.021. [25] A. Klamt, G. Schüürmann, COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient, J. Chem. Soc., Perkin Trans. 2 (1993) 799e805, https://doi.org/10.1039/ P29930000799, 0. [26] Accelrys.com, Version 7.0, Accelrys Software Inc., 2012. [27] D.A. Nieto-Alvarez, L.S. Zamudio-Rivera, E.E. Luna-Rojero, D.I. Rodríguez n, R. Herna ndez-Altamirano, V.Y. Mena-Cervantes, Otamendi, A. Marín-Leo T.E. Ch avez-Miyauchi, Adsorption of zwitterionic surfactant on limestone measured with high-performance liquid chromatography: micelleevesicle influence, Langmuir 30 (2014) 12243e12249, https://doi.org/10.1021/ la501945t. [28] C. Dai, J. Zhao, L. Yan, M. Zhao, Adsorption behavior of cocamidopropyl betaine under conditions of high temperature and high salinity, J. Appl. Polym. Sci. (2014) 40424, https://doi.org/10.1002/app.40424. nez, R. Cartas-Rosado, J.M. Martínez-Magada n, R. Oviedo-Roa, [29] M. Pons-Jime vora, H.I. Beltr R. Cisneros-De an, L.S. Zamudio-Rivera, Theoretical and
[30]
[31]
[32]
[33]
[34]
[35] [36]
[37]
213
experimental insights on the true impact of C12TAC cationic surfactant in enhanced oil recovery for heavy oil carbonate reservoirs, Colloid. Surf. Physicochem. Eng. Asp. 455 (2014), https://doi.org/10.1016/j.colsurfa.2014.04.051. K.D. Danov, P.A. Kralchevsky, K.P. Ananthapadmanabhan, Micelleemonomer equilibria in solutions of ionic surfactants and in ionicenonionic mixtures: a generalized phase separation model, Adv. Colloid Interface Sci. 206 (2014) 17e45, https://doi.org/10.1016/j.cis.2013.02.001. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (1996) 3865e3868, https://doi.org/10.1103/ PhysRevLett.77.3865. F. Ortmann, F. Bechstedt, W.G. Schmidt, Semiempirical van der Waals correction to the density functional description of solids and molecular structures, Phys. Rev. B 73 (2006) 205101, https://doi.org/10.1103/ PhysRevB.73.205101. M. Dolg, U. Wedig, H. Stoll, H. Preuss, Energy-adjusted ab initio pseudopotentials for the first row transition elements, J. Chem. Phys. 86 (1987) 866, https://doi.org/10.1063/1.452288. L.-S. Ramirez-Perez, Jorge-Francisco, Ricardo Ceron-Camacho, Davidaaron Nieto-Alvarez, Servin-Najera, Ana-Graciela, Zamudio-Rivera, Metodologia por UPLC/MS/ESI/þ, Para la determinacion de complejos supra n-anio n. Una aplicacio n para la moleculares base tercias zwitterion-catio industria petrolera, 2017, 03-2017-022410430800e01. V. Meyer, John Wiley & Sons., Practical High-Performance Liquid Chromatography, John Wiley, 2004. N. Parris, J.K. Well, W.M. Linfield, Soap-based detergent formulations: XII. Alternate syntheses of surface active sulfobetaines, J. Am. Oil Chem. Soc. 53 (1976) 60e63, https://doi.org/10.1007/BF02637393. N. Parris, C. Pierce, W.M. Linfield, Soap based detergent formulation: XXIV. Sulfobetaine derivatives of fatty amides, J. Am. Oil Chem. Soc. 54 (1977) 294e296, https://doi.org/10.1007/BF02671099.
Contents lists available at ScienceDirect
Journal of Molecular Graphics and Modelling journal homepage: www.elsevier.com/locate/JMGM
Density Functional Theory and UPLC/MS/ESIþ studies of the zwitterionic surfactant-Naþ pair formation -Manuel Martínez-Magada n a, **, David-Aaron Nieto-Alvarez a, ***, Jose jera a, Rodolfo Cisneros-De vora b, n-Camacho b, Ana-Graciela Servín-Na Ricardo Cero a, * Luis-Silvestre Zamudio-Rivera a b
zaro Ca rdenas Norte 152, San Bartolo Atepehuaca n, Ciudad de M leo, Eje Central La Instituto Mexicano Del Petro exico, 07730, Mexico zaro Ca rdenas Norte 152, Col. San Bartolo Atepehuaca n, Ciudad de M leo, Eje Central La CONACyT-Instituto Mexicano Del Petro exico, 07730, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 January 2019 Received in revised form 13 June 2019 Accepted 20 June 2019 Available online 21 June 2019
The formation in solution of supramolecular complexes type zwitterion-cation have been shown. The industrial grade zwitterion surfactants cocamidopropyl hydroxysultaine and cocamidopropyl betaine with sodium ion were studied. A combined experimental and theoretical point of view was performed, through the use of Ultra-Performance Liquid Chromatography/Mass Spectrometry/ElectroSpray Ionization with positive mode (UPLC/MS/ESIþ) analytic technique and Density Functional Theory (DFT) theoretical approach. Then, the supramolecular complex zwitterion-cation-anion triplets are shown to be viable. Mass/Charge (m/z) relationships have been determined through MS/ESI using positive mode as an ionization source, obtaining five and four molecular species for industrial grade sultaine and betaine chemical products, respectively. Also, molecular zwitterion-NaCl complexes were theoretically studied in three different dielectric constants corresponding to water, methanol, and acetone solvents. It was found that acetone, the lower dielectric constant solvent studied, shows the higher interaction energy. In both vacuum neutral, zwitterion-NaCl, and vacuum positive, zwitterion-Naþ, molecular complexes the interaction of the cocamidopropyl hydroxysultaine pairs is less strong than cocamidopropyl betaine ones. © 2019 Elsevier Inc. All rights reserved.
Keywords: Density functional theory UPLC MS ESIþ Zwitterionic surfactant
1. Introduction Supramolecular chemistry continue being currently a significant area of chemistry research and chemical industry as the part of the study of systems that involve self-assembled aggregates of molecules or ions, such as micelles, inverted micelles, bilayers, bilayer vesicles, that are linked through non-covalent intermolecular interactions such as hydrogen bonds, ion-dipole, ion-ion, zwitterionion, p-p, among others [1]. The new self-assembled macromolecular aggregates formed through this type of intermolecular interactions acquire their own physicochemical properties different from those of the molecules that gave them origin. One of the features to be highlighted is the three-dimensional structure that they can adopt, the case of tertiary structures such as enzymes or
* Corresponding author. ** Corresponding author. *** Corresponding author. E-mail addresses: [email protected] (D.-A. Nieto-Alvarez), [email protected] n), [email protected] (L.-S. Zamudio-Rivera). (J.-M. Martínez-Magada https://doi.org/10.1016/j.jmgm.2019.06.017 1093-3263/© 2019 Elsevier Inc. All rights reserved.
the double-helical structure of DNA [2]. In this sense, this was the reason for the developing of the key-lock concept, widely used in enzymatic systems, but in supramolecular chemistry it is known as the guest-host interaction [3]. By using this concept, there are numerous cases of supramolecular complexes derived from noncovalent intermolecular interactions such as pp, p-cation, panion and ion-ion, which are known as ion-par receptors [4]. The development of supramolecular complexes of the guest-host type with metal ions is becoming increasingly important due to its applications in various fields, such as purification processes, controlled delivery of substances, and sensors [5]. Self-assembled macromolecular aggregates structures in solution can transform one to another when the solution conditions are changed, the electrolyte concentration or pH. The equilibrium structures formed are determined by thermodynamics and intra-aggregate forces, along with the strength of the inter-aggregate forces between aggregates in concentrated systems [6]. In oil industry, the understanding of the influence of salinity and hardness over colloidal systems is of vital importance because this comprehension permits to optimize and improve processes of
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
enhanced recovery of hydrocarbons through the use of chemical products. These products must be tolerant to high temperatures, pressures, salinities and hardness present in oil reservoirs. There exists few cases where the use of zwitterion-cation-anion based supramolecular complexes is reported in the oil industry [7e10], where the macromolecules are given by the interaction of zwitterionic liquids with anionic and/or cationic surfactants. For instance, in reference [11] have described a new state of aggregation anion-cation-zwitterion triplets in solution through the equilibrium constant of the reaction of p-nitrophenol with tetra-nbutylamonium taurine in 95.3 mol % dioxane-water. In Ref. [12], it has been defined the complex formation starting from zwitterioncation surfactant-micelles and anionic polyelectrolyte poly(sodium styrenesulfonate). The complex formation followed by NMR spectroscopy of the deuterated-surfactants CTAB-g-d9 and HDPC-g-d6 cetyltrimethylamonium bromide and hexadecyl phosphocholine, explains that the anion poly(sodium styrenesulfonate) interacts with the micelle through electrostatic interactions favoring the balance of the micelle towards the monomers. Finally, in Refs. [13,14], it has been described the assembled-microcapsules formation entirely of block copolymer micelles from cationzwitterion pair starting from anionic poly [2-(dimeylamino)ethyl methacrylate-block-poly (2-diethylamino) ethyl methacrylate)] PDMA-PDEA and the cationic poly(2-(diethylamino)ethyl) methacrylateeblock-poly(methacrylic acid) PDEA-PMAA. In reference [15], it is demonstrated the formation of pair zwitterion-cation from phosphoryletanolamine with cation Ca2þ using femtosecond infrared (fs-IR) pump-probe spectroscopy. In reference [16] by using ESI()-MS and ESI(þ)-MS analytic techniques it has been showed that formation of supramolecular aggregates cation-anion in solution between 1,3-dialkylimidozolium (cation) and tetrafluroborate (anion), so that the general tendency demonstrates that solvents with smaller dielectric constants favor the ion paring. On the other hand, molecular dynamic simulation studies [17,18] show for carboxybetaine and sulfobetaine that association number and lifetime follow the order Liþ>Naþ>Kþ>Csþ, and carboxybetaine is stronger than sulfobetaine consequently the strong cations Liþ and Naþ associate stronger with carboxybetaine than with sulfobetaine, and cations Kþ and Csþ associate more strongly with sulfobetaine. There exists hard evidence that Naþ-Driven wormlike micelles occurs when NaCl is added to N-alkyl-N0 -carboxymethyl imidazolium inner salts and anionic surfactant sodium dodecyl sulfate, in aqueous solution. The resultant solution displayed a high viscosity upon addition of NaCl. It indicates that the viscoelastic fluid was induced to be formed in the presence of NaCl [19]. Due to, it is known that to maintain viscoelasticity under high temperature, and to get a fast recovery under high shear of the wormlike micelle structure, is a challenge in oilfield applications [20], the determination of zwitterion-cation pairs physicochemical properties are needed on each specific application or chemical technology. For example, it has been demonstrated in literature that surfactants derivative of cocoamidopropyl betaine-sodium a-olefin sulfonate interaction are able to tolerate high temperature and high salinity [21]. While, correspondingly, surfactants derivative of cocoamidopropyl hydroxysultaine-sodium a-olefin sulfonate interaction are able to tolerate ultra-high temperature and ultra-high salinity [22]. Additionally, it has been also determined the synergism in mixtures of zwitterionic and ionic surfactants, showing that the addition of inert electrolytes favors the interactions between the ionic and the zwitterionic surfactants. This fact is due to the reduction of the electrostatic repulsion between surfactant ions. In anionicezwitterionic mixtures of brine solutions, the interaction is reduced as the hydrocarbon length of the zwitterionic surfactant increases [23]. Finally, the identification of several polyfluoroalkyl cationic or zwitterionic analytes in sediment samples, was
205
performed through an analytic procedure optimization of HPLC/MS polarity-switching electrospray ionization technique [24]. In this work, a new theoretical analysis, and experimental UPLC/ MS/ESI þ determination procedure is developed for the determination of zwitterion-cation (Naþ) pair's formation. Up to our knowledge, even though the importance of the zwitterion-cation (Naþ) interaction in surfactants with application in oil industry, cocamidopropyl hydroxysultaine and cocamidopropyl betaine, this is the first evidence that shows its existence. 2. Materials and methods 2.1. Molecular modeling In order to determine the theoretical energetic values for the interactions between cocamidopropyl-hydroxysultaine (S1) with NaþCl, and for cocamidopropyl-betaine (B1) with NaþCl, in water (W), methanol (M) and acetone (A) dielectric environments, the molecular cluster approach, i.e., non-periodic PBC(periodic boundary conditios), DFT methodology was applied. These three dielectric environments are taken into account to show that, with a less dielectric constant of environment the system is more stable, i.e., the system would be less solvated. This conditions were properly simulated through dielectric continuum, specifically by use of the three dielectric constant: W: 78.54; M: 32.63 and A: 20.70, correspondingly, within the Conductor-like Screening Model (COSMO) approach [25]. It was used the Materials Studio (MS) program suite [26] to study molecular interactions of cocamidopropyl-hydroxysultaine (S1) with NaþCl, and cocamidopropyl-betaine (B1) with NaþCl. Critical micelle concentrations (CMC) of both zwitterionic surfactants are 279.34 and 1010 ppm for cocamidopropylhydroxysultaine and cocamidopropyl-betaine, respectively [27,28]. Assuming that micelle-monomer equilibrium is observed around of the CMC value region as previously found [29,30], the maximum monomer concentration in the solution will be present on this region. Then, single-molecule approach is considered appropriate for the molecular modeling study. To obtain the optimized molecular geometries for all supramolecular complexes constructed through the graphic environment of MS Visualizer, DFT computations through MS DMol3 application were executed in W, M and A dielectric environments, respectively. DMol3 runs were performed within the Generalized Gradient Approximations (GGA), using DNP(4.4) basis sets and the Perdew-Burke-Ernzerhof (PBE) functional [31], also the Grimme method for the DFT-Dispersion correction [32] was employed, the Effective Core Potentials for core treatment [33], spin unrestricted, and the three above-mentioned solvents were utilized. All run parameters were set at the fine accuracy option. 2.2. Materials Solvents: Methanol and water, both UPLC-grade were acquired
Fig. 1. Molecular structure of cocamidoproyl-hydroxysultaine.
206
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
from J. T. Baker. Surfactants: The cocamidopropyl hydroxysultaine surfactant (Fig. 1) was provided by Stepan Co. as its commercial product, which contains 43.5% of active substance, 6.5% of NaþCl and 50.0% of water. The cocamidopropyl betaine surfactant (Fig. 2) was provided by Stepan Co. as its commercial product, which contains 30.14% of active material, 5% of NaCl and 64.86.0% of water. 2.3. Equipment UPLC coupled to Mass Spectrometer. The Ultra Performance Liquid Chromatograph coupled to the Mass Spectrometer, Waters model SYNAPT G2 HDMS. The chromatograph contains pump and automatic injector and the spectrometer Synapt G2, we have worked with an ESI source in positive mode, we have used the resolution acquisition mode UPLC/MS/ ESIþ.
resolution was 0.1 Da and the width of the peak was located in 5 s. For the total analysis of the ions it is acquired from 100 a 2000 Da. 2.6. Sample preparation For both commercial grade surfactants, cocamidopropyl hydroxysultaine which contains 43.5% of active, and cocamidopropyl-betaine that contains 30.14% of active, a solution of 400 ppm in water, grade UPLC-MS, was prepared for each. It is important to mention that always in this analytical technique is normal to get a dilution of the sample with the corresponding mobile phase [35]. Specifically, in this work a dilution factor of 1:4 was obtained, this means a concentration in solutions of 66 ppm just before to get into the chromatography column. In this way, it is guaranteed that monomers are always available in both cases. 3. Results and discussion
2.4. Optimization of the UPLC analytical method In connection with the optimization of the analytical methodology, different tests were performed modifying the variables involved: column type, column temperature, flow, mobile phase and injection volume. As a result of the process, the best chromatographic conditions were obtained for analyzing the supramolecular complex studied in this work. In the case of mobile phase, different relationships between methanol-water with 1 mM of formic acid were tested. For the relationships (10:0), (9:1) and (8:2), the retention times of the surfactant and the solvent front are very similar, and the signals are overlapped. It was found that when a relationship methanol-water (7:3) is used, the retention times allow the signals to be perfectly distinguished. In particular, it was observed that when the flow rate was greater than 0.5 mL/min retention time of the surfactant was reduced, causing signal overlapping for surfactant and solvent front. Derived from this analysis, it was found that the optimum flow velocity was 0.20 mL/min. As a result of the different tests, the best conditions for the determination of the supramolecular complex were: UPLC CSH C18 (1.7, 2.1 100 mm); column, temperature of 30 C, flow rate of 0.20 mL/min, methanol-water (7:3) v/v as mobile with 1 mM of formic acid phase, injection volume of 5 mL and a tests series of 18 and 20 min. 2.5. Optimization of MS synapt G2 analytical method For the method optimization in the analytical methodology [34], different tests were performed modifying the variables involved. As a result of the process, the best conditions were obtained for analyzing supramolecular complex used in this work were: The mass spectrometry we worked with a ionization source for positive mode electrospray, the resolution acquisition mode was used, the capillary voltage used was 2010 V, the temperature of the source of 120 C, desolvation temperature 490 C, gas cone flow 50 L/h, desolvation flow 498 L/h and nebulizer gas pressure 6.4 bar. Mass
Fig. 2. Chemical structure of cocamidopropyl betaine.
3.1. DFT study DFT results show that a NaþCl species approaches more closely onto cocamidopropyl-hydroxysultaine (S1) and cocamidopropylbetaine (B1) when the dielectric constant of the solvent is minor forming then a more stable supramolecular complex. In Figs. 3 and 4, it is observed that spatially the conformation of the NaþCl on the zwitterion part of S1 and B1 in each case is the same independently of the solvent used; except for the conformation (c) of the sultaine where it is appreciated that the salt is closer to zwitterion fragment, this suggests a less solvation in the structural complex conformation. These characteristics and understanding helps to efficiently design the laboratory tests and later more efficiently apply the chemicals in real tests in the oil industry. Observing the theoretically obtained energy results that are shown in Tables 1 and 2, we can affirm that the solvent of lower dielectric constant shows a greater energy of interaction zwitterion-cation-anion 15.296 and 26.746 kcal/mol for zwitterion surfactants S1 with NaþCl, and B1 with NaþCl, that this general tendency were previously demonstrated [16] exemplify that the solvents with smaller dielectric constants favor the cation paring. In Tables 3 and 4 of Vacuum neutral and Vacuum positive modes, shows that the formation of the zwitterion-cation, cocamidopropyl hydroxysultaine (S1) with Naþ (Fig. 5) is less strong (79.45 kcal/mol) than cocamidopropyl-betaine (B1) with Naþ (Fig. 6) (86.57 kcal/mol), consequently the Naþ cation associate stronger with B1 that with S1, in the case of neutral mode the interaction energy is more soft. The figures use the standard atom colors of, gray: carbon; white: hydrogen; red: oxygen; blue: nitrogen; yellow: sulphur; green: chlorine; and purple: sodium. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article). 3.2. Methodology for the determination of the supramolecular complex zwitterion-cation molecular ion In the retrosynthetic analysis of cocamidopropyl hydroxysultaine as seen in Fig. 7, the synthetic [36,37] precursors are: N,Ndimethylpropyl alkilamides and 3-chloro-2-hydroxy-1-propanesulfonate which are accompanied by sodium chloride and when this surfactant is produced at the industrial level, the sodium chloride is not removed and remains as part of the final product. This gives rise to the zwitterion-cation-anion triads, from the interaction of the zwitterion [cocamidopropyl hydroxysultaine] with the ionic pair [sodium chloride].
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
207
Fig. 3. Conformations of supramolecular assemble for cocamidopropyl hydroxysultaine (S1) and NaþCl in (a) water, (b) methanol, (c) acetone. Atom color code: gray, carbon; white, hydrogen; red, oxygen; blue, nitrogen; yellow, sulphur; green, chlorine; and purple, sodium, (same code applies in all Figures).
Fig. 4. Conformations of supramolecular assemble for the cocamidopropyl-betaine (B1) and NaþCl in (a) water, (b) methanol, (c) acetone.
Table 1 Energetic value for cocamidopropyl hydroxysultaine (S1), salt NaþCl, supramolecular conformation between both and interaction energetic value.
S1 NaþCl S1þNaþCl DE
(a) Water (kcal/mol)
(b) Methanol (kcal/mol)
(c) Acetone (kcal/mol)
1,048,032.138 390,531.470 1,438,572.553 ¡8.945
1,048,029.672 390,530.248 1,438,573.501 ¡13.581
1,048,028.164 390,529.077 1,438,572.537 ¡15.296
Table 2 Energetic value for cocamidopropyl-betaine (B1), salt NaþCl, supramolecular conformation between both and interaction energetic value.
B1 NaþCl B1 þ NaþCl DE
(a) Water (kcal/mol)
(b) Methanol (kcal/mol)
(c) Acetone (kcal/mol)
678,477.612 390,531.470 1,069,033.176 ¡24.093
678,474.503 390,530.248 1,069,031.081 ¡26.330
678,473.319 390,529.077 1,069,029.143 ¡26.746
Now, in the retrosynthetic analysis of cocamidopropyl betaine, as seen in Fig. 8, the synthetic [36,37] precursors are: N,N-dimethyl propyl alkilamides and sodium chloroacetate which are supplemented by sodium chloride and when this surfactant is produced at the industrial level, the sodium chloride is not removed and remains as part of the final product. This originates the corresponding zwitterion-cation-anion triplet [cocamidopropyl betaine] with
[sodium chloride]. According to the retrosynthetic analysis for both zwitterionic surfactants cocamidopropyl-hydroxysultaine and cocamidopropylbetaine, the sodium chloride is always present giving rise to the interaction of the zwitterionic surfactant with the ionic par, sodium chloride. The supramolecular structures zwitterion-cation-anion, cocamidopropyl hydroxysultaine and cocamidopropyl-betaine,
208
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
Table 3 Energetic value for the sultaine (S1), salt NaþCl, and Naþ in neutral and positive mode for a supramolecular conformation between both and the interaction energetic value. (a) Vacuum neutral mode
(b) Vacuum positive mode
(kcal/mol) S1 NaþCl S þ NaþCl DE
1,047,983.107 390,495.831 1,438,507.912 28.973
S Naþ S þ Naþ DE
1,047,983.107 101,641.483 1,149,704.040 79.449
both with sodium chloride, cannot be characterized by traditional spectroscopic techniques. However, the use of technique UPLC/MS/ ESI/þ allows to unequivocally identify such complexes. Additionally, when dealing with industrial grade products, the supramolecular complexes present in the final product can be separated for UPLC and later through the technique of MS with con soft ionization for ESI, it is possible to know exactly the molecular weight of each of the supramolecular complexes and therefore the average molecular weight of the industrial grade product.
Table 4 Energetic value for the betaine (B1), salt NaþCl, and Naþ in neutral and positive mode for a supramolecular conformation between both and the interaction energetic value. (a) Vacuum neutral mode (kcal/mol) B NaþCl B þ NaþCl DE
678,444.294 390,495.831 1,068,979.273 ¡39.147
(b) Vacuum positive mode (kcal/mol) B Naþ B þ Naþ DE
678,444.294 101,641.483 780,172.343 ¡86.565
Fig. 5. Conformation of supramolecular assemble for the cocamidopropyl hydroxysultaine and NaþCl
Fig. 6. Conformation the supramolecular assemble for the cocamidopropyl betaine, and NaþCl
Fig. 7. Retrosynthetic analysis showing the raw materials for the preparation of the cocamidopropyl hydroxysultaine.
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
209
Fig. 8. Retrosynthetic analysis showing the raw materials for preparation of the cocamidopropyl betaine.
Fig. 9. Commercial product cocamidopropyl hydroxysultaine chromatogram.
3.3. Determination of the supramolecular zwitterion-cation complex, cocamidopropyl hydroxysultaine with sodium chloride and, its average molecular weight The analytical results derived from the UPLC/MS/ESIþ study designed for commercial grade product cocamidopropyl hydroxysultaine, show in the chromatogram (Fig. 9) the presence of five derivatives with retention times in: 1.26, 1.77, 2.96, 6.28, and 15.70 min m/z relationships are determined for each of the elution times by means of electrospray ionization mass spectrometry (ESIMS) using the positive mode ionization source, obtaining the following m/z values: 361.189, 389.216, 417.245, 445.273 and 473.309. It is shown in Fig. 10, the extraction ion chromatogram for each of the aforementioned elution times. The results indicate that for each ratio of m/z corresponds to the molecular weight of the product with sodium cation [MþNa]þ, by checking the presence of the supramolecular complex as shown in Fig. 11, cocamidopropyl hydroxysultaine with sodium cation from zwitterion-cation interaction. It also indicates that the five products differ in the alkyl chain represented in Fig. 11, where n represents the number of carbon units of 4, 6, 8, 10 and 12. For the most abundant species commercial grade product, the elution time is 6.28 min (Fig. 9), the deconvolution for getting the m/z relationships, gives the peak with elution time of 6.36 min,
corresponding to cocamidopropyl hydroxysultaine with sodium cation [MþNa]þ molecular ion, which has a m/z ratio of 445.273 obtained through ESI-MS. From this analysis of the m/z obtained value, the presence of complex zwitterion-cation pair complex is confirmed, as shown in Fig. 11, where the value of n is 10. Thus, in order to recover the molecular weight of supramolecular zwitterion-cation-anion triplet (Fig. 12) it must be added the atomic weight of the chloride ion, obtaining a subsequent molecular weight 480.726 g/mol. Now, for elution time of 15.70 min, the obtained m/z of 473.309 through ESI-MS corresponds to the [MþNa]þ molecular ion. Consequently, this m/z value indicates the presence of the zwitterion-cation complex pair shown in Fig. 11, where the value of n is 12. By adding the atomic weight of the chloride ion, the molecular weight of 508.762 g/mol for the supramolecular zwitterioncation-anion complex is obtained (Fig. 12). Through the same analysis procedure, the molecular weights of the four remaining products are obtained, as presented in Table 5. The analytical results in Table 5 show that the hydrocarbon tail length of the cocamidopropyl hydroxysultaine lies between 4 and 12 carbons, and the average molecular weight of the supramolecular complex derivative of the interaction between cocamidopropyl-hydroxysultaine with NaþCl (zwitterion-cationanion triplet), is 468.171 g/mol. The supramolecular complex of greater abundance is in which the hydrocarbon tail length is 10 (Fig. 12). 3.4. Determination of the zwitterion-cation supramolecular complex, cocamidopropyl betaine with sodium chloride, and its average molecular weight The analysis of the results derived from the UPLC/MS/ESIþ study designed for cocamidopropyl betaine commercial grade product, shows in its chromatogram (Fig. 13) the presence of four derivatives with retention times in: 1.26, 3.22, 6.96, and 17.52 min m/z relationships are determined for each of the elution times by means of electrospray ionization mass spectrometry (ESI-MS) using the positive mode ionization source, obtaining the following m/z values: 327.210, 337.257, 365.289, and 393.316. Fig. 14 shows the extraction ion chromatogram for each of the aforementioned elution times. The results indicate that the interaction of cocamidopropyl betaine with the sodium cation originates the observed zwitterion-cation complex. Their m/z ratio corresponds to the molecular weight of the product with sodium cation [MþNa]þ. It also indicates that the four products differ in the chain length represented in Fig. 15, where n represents the number of carbon
210
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
Fig. 10. Extraction ion chromatogram for each of the elution times for commercial product cocamidopropyl hydroxysultaine.
Fig. 11. Molecular structure of supramolecular complexes zwitterion-cation, Cocamidopropyl hydroxysultaine with sodium cation.
units 6, 8, 10 and 12. Although, only the m/z value of 327.210 correspond to the specie [M þ Na þ H2O]þ where n is for 6 carbon units, this behavior only is observed in this isolated case, here the water molecule is part of sodium hydration sphere. For the most abundant species of the commercial grade product, the elution time is 6.96 min, the deconvolution for getting the m/z relationships, gives two peaks 6.90 and 7.04 as function of elution time. For the 6.90 min Case the corresponding complex is cocamidopropyl betaine-hydrogen cation, [MþH]þ, and the 7.04 min peak, relates to the cocamidopropyl betaine-sodium cation complex, [MþNa]þ, which has an m/z ratio of 365.289 by ESI-MS. From this analysis of the m/z obtained values, the presence of zwitterion-
Fig. 12. Supramolecular zwitterion-cation-anion triads with 46.5% of abundance in the industrial grade product cocamidopropyl hydroxysultaine.
cation pair complex is proven, as illustrated in Fig. 15, where the value of n is 10. Thus, in order to recover the molecular weight of supramolecular zwitterion-cation-anion triads (Fig. 16), it must be added the atomic weight of the chloride ion, obtaining a resulting molecular weight of 400.742 g/mol. Now, for elution time of 17.52 min, the obtained m/z of 393.316 through ESI-MS corresponds to the [MþNa]þ molecular ion. Therefore, this m/z value indicates the presence of the zwitterion-
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213 Table 5 Analytical results obtained through UPLC/MS/ESI þ for the supramolecular zwitterion-cation complexes cocamidopropyl hydroxysultaine with sodium cation. [min]a
[g/mol]b
[n]c
[L2]d
[%]e
[g/mol]f
[g/mol]g
1.26 1.77 2.96 6.28 15.70
361.189 389.216 417.245 445.273 473.309
4 6 8 10 12
14,659.079 96,474.531 74,380.297 234,539.469 84,727.891
2.9 19.1 14.7 46.5 16.8
396.642 424.669 452.698 480.726 508.762
468.171
a b c d e f g
Retention time. Molecular weight of pair zwitterion-cation. Carbon number of the hydrocarbon tail. Area under the curve. Percentage of pair zwitterion-cation as a function of the hydrocarbon tail. Molecular weight of zwitterion-cation-anion triplet. Average molecular weight of zwitterion-cation-anion triplet.
211
cation complex pair shown in Fig. 14, where the value of n is 12. By adding the atomic weight of the chloride ion, the molecular weight of 428.769 g/mol for the supramolecular zwitterion-cation-anion complex is obtained (Fig. 16). Through the same analysis procedure, the molecular weights of the three remaining products are obtained, presenting the results in Table 6. The analytical results in Table 6 show that the average molecular weight of the commercial grade product cocamidopropyl betaine with sodium chloride is 411.027 g/mol, and for the supramolecular complexes considering all the zwitterion-cation-anion triads that has greater abundance, area down curve of 517,489 L2, is that one in which the value of n is 10 with 50.3% of abundance as depicted in Fig. 16.
4. Conclusion
Fig. 13. Commercial grade product cocamidopropyl betaine chromatogram.
In this work it is shown the theoretical determination of threemember supramolecular complex zwitterion-cation-anion bonds and their corresponding experimental characterization by the analytical method UPLC/MS/ESIþ. The corresponding results shows that molecular weights were determined for the cationic fragment in the supramolecular complex, these corresponds to zwitterioncation pair [MþNa] each one of the supramolecular complexes. The zwitterion-cation-anion supramolecular structure, which are part of the industrial grade product formed by intermolecular interactions that take place between cocamidopropyl hydroxysultaine and sodium chloride, and cocamidopropyl betaine and sodium chloride, originating the supramolecular complexes zwitterion-cation-anion triplets. The supramolecular interaction have been good displayed for DFT analysis, highlighting that, the most stable conformations in all systems are observed on the one hand when the solvent is acetone and on the other when it is locked in positive mode.
Fig. 14. Extraction ion chromatogram for each of the elution times for commercial grade product cocamidopropyl betaine.
212
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213
CONACyT for its appointment. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.jmgm.2019.06.017. References
Fig. 15. Molecular structure of zwitterion-cation supramolecular complexes, cocamidopropyl betaine with sodium cation.
Fig. 16. Supramolecular complexes zwitterion-cation-anion triplets with 50.3% of abundance in the industrial grade product cocamidopropyl betaine.
Table 6 Analytical results obtained through UPLC/MS/ESIþ for the supramolecular zwitterion-cation complexes, cocamidopropyl betaine with sodium cation. [min]a 1.26 3.22 6.96 17.52 a b c d e f g h
[g/mol]b
[n]c
h
327.210 337.257 365.289 393.316
[L2]d 6 8 10 12
11,406 53,551 517,489 445,982
[%]e 1.1 5.2 50.3 43.4
[g/mol]f 362.663 372.71 400.742 428.769
[g/mol]g h
411.027
Retention time. Molecular weight of pair zwitterion-cation. Carbon number of the hydrocarbon tail. Area under the curve. Percentage of pair zwitterion-cation as a function of the hydrocarbon tail. Molecular weight of zwitterion-cation-anion triplet. Average molecular weight of zwitterion-cation-anion triplet. Molecular weight correspond to [M þ Na þ H2O] þ.
Acknowledgements The authors acknowledge to the Mexican Institute of Petroleum ~ o y síntesis de nuevos prototipos de (IMP), Projects D.61029 “Disen productos químicos multifuncionales con propiedades dispersantes de asfaltenos, modificadoras de la mojabilidad y desemulsificantes” tico Asistido por Agentes Espumantes and H.61057 “Bombeo Neuma vora de Tecnología IMP”, for financial support. Rodolfo Cisneros-De n-Camacho thank to the Direccio n de Ca tedras and Ricardo Cero
[1] J.-M. Lehn, Supramolecular chemistrydscope and perspectives molecules, supermolecules, and molecular devices(nobel lecture), Angew Chem. Int. Ed. Engl. 27 (1988) 89e112, https://doi.org/10.1002/anie.198800891. [2] D. Phlip, softcover, DM 58.00, in: J.-M. Lehn, V.C.H. Weinheim (Eds.), Supramolecular Chemistry: Concepts and Perspectives, x, WILEY-VCH Verlag GmbH, 1995, ISBN 3-527-2931 1-6, p. 271, https://doi.org/10.1002/ adma.19960081029, 1996. [3] Jose Vazquez Tato, Química supramolecular, Rev. Iberoam. Polímeros. 6 (2005) 44e80. [4] D.A. Dougherty, The cation-p interaction, Acc. Chem. Res. 46 (2013) 885e893, https://doi.org/10.1021/ar300265y. [5] H.-R. Yu, J.-Q. Hu, X.-H. Lu, X.-J. Ju, Z. Liu, R. Xie, W. Wang, L.-Y. Chu, Insights into the effects of 2:1 “Sandwich-Type” crown-ether/metal-ion complexes in responsive hosteguest systems, J. Phys. Chem. B 119 (2015) 1696e1705, https://doi.org/10.1021/jp5079423. [6] Intermolecular and Surface Forces, Elsevier, 2011, https://doi.org/10.1016/ C2009-0-21560-1. zar-Vara, L.S. Zamudio-Rivera, E. Buenrostro-Gonza lez, Multifunc[7] L.A. Alca tional evaluation of a new supramolecular complex in enhanced oil recovery, removal/control of organic damage, and heavy crude oil viscosity reduction, Ind. Eng. Chem. Res. 54 (2015) 7766e7776, https://doi.org/10.1021/ acs.iecr.5b01308. [8] L.A. Alc azar-Vara, L.S. Zamudio-Rivera, E. Buenrostro-Gonz alez, R. Hern andezrez, Multifunctional propAltamirano, V.Y. Mena-Cervantes, J.F. Ramírez-Pe erties of zwitterionic liquids. Application in enhanced oil recovery and asphaltene aggregation phenomena, Ind. Eng. Chem. Res. 54 (2015) 2868e2878, https://doi.org/10.1021/ie504837h. [9] C. Zou, Y. Qin, X. Yan, L. Zhou, P. Luo, Study on acidizing effect of cationic bcyclodextrin inclusion complex with sandstone for enhancing oil recovery, Ind. Eng. Chem. Res. 53 (2014) 12901e12910, https://doi.org/10.1021/ ie501569d. n, D. Rodrigue, Evaluation of two new self-assembly [10] B. Wei, L. Romero-Zero polymeric systems for enhanced heavy oil recovery, Ind. Eng. Chem. Res. 53 (2014) 16600e16611, https://doi.org/10.1021/ie5014986. [11] P. Haberfield, J.J. Cincotta, Proximate charge effects. 6. Anion-cationzwitterion triplets in solution, J. Org. Chem. 49 (1984) 4188e4192, https:// doi.org/10.1021/jo00196a017. [12] D.J. Semchyschyn, M.A. Carbone, P.M. Macdonald, Anionic polyelectrolyte binding to mixed CationicZwitterionic surfactant micelles: a molecular perspective from 2 H NMR spectroscopy, Langmuir 12 (1996) 253e260, https://doi.org/10.1021/la950244a. [13] T. Addison, O.J. Cayre, S. Biggs, S.P. Armes, D. York, Polymeric microcapsules assembled from a cationic/zwitterionic pair of responsive block copolymer micelles, Langmuir 26 (2010) 6281e6286, https://doi.org/10.1021/la904064d. [14] T.H. Rehm, C. Schmuck, Ion-pair induced self-assembly in aqueous solvents, Chem. Soc. Rev. 39 (2010) 3597, https://doi.org/10.1039/b926223g. [15] S.T. van der Post, J. Hunger, M. Bonn, H.J. Bakker, Observation of water separated ion-pairs between cations and phospholipid headgroups, J. Phys. Chem. B 118 (2014) 4397e4403, https://doi.org/10.1021/jp411458z. [16] H.K. Stassen, R. Ludwig, A. Wulf, J. Dupont, Imidazolium salt ion pairs in solution, Chem. Eur J. 21 (2015) 8324e8335, https://doi.org/10.1002/ chem.201500239. [17] Q. Shao, Y. He, S. Jiang, Molecular dynamics simulation study of ion interactions with zwitterions, J. Phys. Chem. B 115 (2011) 8358e8363, https:// doi.org/10.1021/jp204046f. cha, D. Touraud, P. Jungwirth, W. Kunz, [18] N. Vlachy, B. Jagoda-Cwiklik, R. Va Hofmeister series and specific interactions of charged headgroups with aqueous ions, Adv. Colloid Interface Sci. 146 (2009) 42e47, https://doi.org/ 10.1016/j.cis.2008.09.010. [19] X. Wang, R. Wang, Y. Zheng, L. Sun, L. Yu, J. Jiao, R. Wang, Interaction between zwitterionic surface activity ionic liquid and anionic surfactant: Na þ -driven wormlike micelles, J. Phys. Chem. B 117 (2013) 1886e1895, https://doi.org/ 10.1021/jp308016a. [20] J. Yang, Viscoelastic wormlike micelles and their applications, Curr. Opin. Colloid Interface Sci. 7 (2002) 276e281, https://doi.org/10.1016/S13590294(02)00071-7. [21] R. Hernandez Altamirano, L.S. Zamudio Rivera, V.Y. Mena Cervantes, E.E. Luna Rojero, E. Serrano Saldana, J.M. Martinez Magadan, R. Oviedo Roa, D.A. Nieto Alvarez, E. Buenrostro Gonzalez, R. Cisneros Devora, M.D.P. Arzola Garcia, M. Pons Jimenez, A.E. Mendoza Aguilar, S.J.K. Kim, J.F. Ramirez Perez, T.E. Chavez Miyauchi, Y. Ruiz Morales, Foaming composition with wettability modifying and corrosion inhibitory properties for high temperature and ultrahigh salinity. http://www.freepatentsonline.com/9469804.html, 2016.
D.-A. Nieto-Alvarez et al. / Journal of Molecular Graphics and Modelling 91 (2019) 204e213 (Accessed 30 April 2019). Dura pez Ramírez, V.C.D.L.A. n, R. Herna ndez Alta[22] L.S. Zamudio Rivera, S. Lo mirano, V.Y. Mena Cervantes, M.N.A. García, A. Ríos Reyes, A. Ortega Rodríguez, L.C.J. Mendoza De, C.M.Y. Lozada, E. Buenrostro Gonz alez, Foaming composition for high temperature and salinity. http://www.freepatentsonline. com/8722588.html, 2014. (Accessed 30 April 2019). pez-Díaz, I. García-Mateos, M.M. Vel [23] D. Lo azquez, Synergism in mixtures of zwitterionic and ionic surfactants, Colloid. Surf. Physicochem. Eng. Asp. 270e271 (2005) 153e162, https://doi.org/10.1016/J.COLSURFA.2005.05.054. [24] G. Munoz, S.V. Duy, P. Labadie, F. Botta, H. Budzinski, F. Lestremau, J. Liu, , Analysis of zwitterionic, cationic, and anionic poly- and perS. Sauve fluoroalkyl surfactants in sediments by liquid chromatography polarityswitching electrospray ionization coupled to high resolution mass spectrometry, Talanta 152 (2016) 447e456, https://doi.org/10.1016/ J.TALANTA.2016.02.021. [25] A. Klamt, G. Schüürmann, COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient, J. Chem. Soc., Perkin Trans. 2 (1993) 799e805, https://doi.org/10.1039/ P29930000799, 0. [26] Accelrys.com, Version 7.0, Accelrys Software Inc., 2012. [27] D.A. Nieto-Alvarez, L.S. Zamudio-Rivera, E.E. Luna-Rojero, D.I. Rodríguez n, R. Herna ndez-Altamirano, V.Y. Mena-Cervantes, Otamendi, A. Marín-Leo T.E. Ch avez-Miyauchi, Adsorption of zwitterionic surfactant on limestone measured with high-performance liquid chromatography: micelleevesicle influence, Langmuir 30 (2014) 12243e12249, https://doi.org/10.1021/ la501945t. [28] C. Dai, J. Zhao, L. Yan, M. Zhao, Adsorption behavior of cocamidopropyl betaine under conditions of high temperature and high salinity, J. Appl. Polym. Sci. (2014) 40424, https://doi.org/10.1002/app.40424. nez, R. Cartas-Rosado, J.M. Martínez-Magada n, R. Oviedo-Roa, [29] M. Pons-Jime vora, H.I. Beltr R. Cisneros-De an, L.S. Zamudio-Rivera, Theoretical and
[30]
[31]
[32]
[33]
[34]
[35] [36]
[37]
213
experimental insights on the true impact of C12TAC cationic surfactant in enhanced oil recovery for heavy oil carbonate reservoirs, Colloid. Surf. Physicochem. Eng. Asp. 455 (2014), https://doi.org/10.1016/j.colsurfa.2014.04.051. K.D. Danov, P.A. Kralchevsky, K.P. Ananthapadmanabhan, Micelleemonomer equilibria in solutions of ionic surfactants and in ionicenonionic mixtures: a generalized phase separation model, Adv. Colloid Interface Sci. 206 (2014) 17e45, https://doi.org/10.1016/j.cis.2013.02.001. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (1996) 3865e3868, https://doi.org/10.1103/ PhysRevLett.77.3865. F. Ortmann, F. Bechstedt, W.G. Schmidt, Semiempirical van der Waals correction to the density functional description of solids and molecular structures, Phys. Rev. B 73 (2006) 205101, https://doi.org/10.1103/ PhysRevB.73.205101. M. Dolg, U. Wedig, H. Stoll, H. Preuss, Energy-adjusted ab initio pseudopotentials for the first row transition elements, J. Chem. Phys. 86 (1987) 866, https://doi.org/10.1063/1.452288. L.-S. Ramirez-Perez, Jorge-Francisco, Ricardo Ceron-Camacho, Davidaaron Nieto-Alvarez, Servin-Najera, Ana-Graciela, Zamudio-Rivera, Metodologia por UPLC/MS/ESI/þ, Para la determinacion de complejos supra n-anio n. Una aplicacio n para la moleculares base tercias zwitterion-catio industria petrolera, 2017, 03-2017-022410430800e01. V. Meyer, John Wiley & Sons., Practical High-Performance Liquid Chromatography, John Wiley, 2004. N. Parris, J.K. Well, W.M. Linfield, Soap-based detergent formulations: XII. Alternate syntheses of surface active sulfobetaines, J. Am. Oil Chem. Soc. 53 (1976) 60e63, https://doi.org/10.1007/BF02637393. N. Parris, C. Pierce, W.M. Linfield, Soap based detergent formulation: XXIV. Sulfobetaine derivatives of fatty amides, J. Am. Oil Chem. Soc. 54 (1977) 294e296, https://doi.org/10.1007/BF02671099.