Interactions of Saccharides in Aqueous Glycine and Leucine Solutions

Article pubs.acs.org/jced

Interactions of Saccharides in Aqueous Glycine and Leucine Solutions at Different Temperatures of (293.15 to 313.15) K: A Viscometric Study Kuldeep Kumar,† Baljeet Singh Patial,‡ and Suvarcha Chauhan*,† †

Department of Chemistry, Himachal Pradesh University, Summer Hill, Shimla-171005, Himachal Pradesh, India Department of Chemistry, BTC DAV College Banikhet (Dalhousie), Chamba-176310, Himachal Pradesh, India

‡

ABSTRACT: The results of viscosity measurements of ribose, maltose, and raffinose at molalities ranging from (0.050 to 0.100) mol·kg−1 in aqueous solutions of glycine and leucine of (0.025, 0.050, and 0.100) mol·kg−1, respectively, over a wide temperature range of (293.15 to 313.15) K, have been reported. The viscosity data have been used to calculate the viscosity B-coefficients by employing the Jones−Dole equation at different temperatures. The temperature derivative of B-coefficients, dB/dT, the viscosity B-coefficient of transfer, ΔtrB, free energy of activation of viscous flow per mole of solvent, Δμo1*, and solute, Δμo2*, respectively, activation entropy, ΔSo2*, and activation enthalpy, ΔHo2* for saccharides in aqueous amino acid solutions have been estimated from viscosity B-coefficient data. These parameters have been discussed in terms of saccharide−amino acid interactions, structure-making behavior of saccharides, and formation of transition state in the presence of amino acids. We have also attempted to investigate the temperature and concentration dependence of these outcomes.

1. INTRODUCTION Saccharides are one of the four major categories of macromolecules (proteins, saccharides, lipids, and nucleic acids) that play critical roles in biological systems. These biological molecules have been involved in energy storage (animal glycogen), structure support (plant cellulose), and signaling, etc. However, sugars like glucose among saccharides are important source of immediate energy for cell processes through respiration. Generally, saccharides appear as part of other biomaterials such as glycoproteins and glycolipids of the membrane, which make cell−cell recognition and nucleic acids. Moreover, there are many molecules that are mostly saccharide in nature with extra properties, for example, mucopolysaccharides or glycosaminoglycans, which give distinct characteristics to materials like mucus, mucins, and chitin. In addition, the interactions of saccharides with macromolecules like proteins have developed a great deal of interest in various aspects of researches due to their important functions in the fields related to biology, medicine, cosmetics, catalysis, etc.1−5 An analysis of literature shows that these interactions are driven by negative enthalpy terms, i.e., heat is released,6 balanced by hydrophobic stacking, van der Waals’ interactions, and hydrogen bonds between protein and saccharide.7 In fact, studies have shown that protein−saccharide interactions are really stronger than corresponding protein−protein interactions in the living organism.8,9 This observation is the manifestation of involvement of electronegative atoms with highly organized hydrogen bonding resulting in greater frequency of hydrogen bonds per unit area leading to a closely spaced © XXXX American Chemical Society

protein−saccharide complex. However, these enthalpy favored interactions are counteracted by an unfavorable entropy term,10 probably due to inflexibility of saccharides. This type of enthalpy−entropy compensation is exclusively common in interactions involving water molecules,11 which easily form hydrogen bonds with proteins as well as with saccharides. Water being a major component of human body plays an essential role in protein−saccharide interactions by mediating network of saccharide epitope to the binding cleft of the protein.12−14 Consequently, most of the protein−saccharide interaction studies have been carried out in aqueous medium. Moreover, viscometric properties of saccharides in aqueous solutions have also been utilized in many technological applications such as the control of gelling processes and the osmoregulation of tissues and organs under cryoprotective provisions.15,16 Therefore, as a part of our previous work on saccharides,17,18 in the present study, we have investigated the viscometric behavior of some saccharides in aqueous solutions of two structurally different amino acids to explore the saccharide−protein interactions in aqueous medium.

2. EXPERIMENTAL SECTION 2.1. Materials. The deionized distilled water with a conductivity of 1·10−6 S·cm−1 to 2·10−6 S·cm−1 and pH 6.8 to pH 7.0 Received: July 11, 2014 Accepted: December 2, 2014

A

dx.doi.org/10.1021/je500647a | J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Specifications of Chemicals Used

a

chemical name

CAS No.

MW/(kg·mol−1)

supplier

purification method

mole fraction puritya

glycine L-leucine D-(−)-ribose D-(+)-maltose monohydrate D-(+)-raffinose pentahydrate

56-40-6 61-90-5 50-69-1 6363-53-7 17629-30-0

0.0751 0.1312 0.1501 0.3603 0.5945

Calbiochem S.D. Fine Chem Limited Loba Chemie PVT. Ltd. Loba Chemie PVT. Ltd. Loba Chemie PVT. Ltd.

recrystallization recrystallization recrystallization recrystallization recrystallization

0.99 0.99 0.99 > 0.95 0.99

Purity as provided by suppliers.

for the solute−solute interactions, while the B-coefficient is a measure of structural modifications induced by the solute− solvent interactions.25,26 The values of A- and B-coefficients have been obtained as the intercepts and slopes from linear regression of ψ vs m1/2 plots, which were found almost linear for all the studied systems as illustrated in Figure 1. The A-coefficients in all the cases were found to be negligible (either close to zero or even negative) when compared to that of electrolytes,27 as also documented in literature,28 indicating weak solute−solute interactions and are, therefore, not reported. Further, the greater positive B-coefficient values for all cases as shown in Table 3 are indicative of strong saccharide−amino acid interactions,29 and these values in pure water are in good agreement with those documented in the literature.30,31 Thus, the values of A- and B-coefficients are fully supported by the nature of partial molar properties, which suggest strong saccharide−amino acid interactions as compared to solute− solute interactions in these studied.17,18 An examination of Table 3 reveals that B-coefficient values of the saccharides increase in the order: ribose < maltose < raffinose, which holds good in all the solvent systems. However, with regards to the dependence of B-coefficient values on solvent systems, it can be seen to increase with amino acid concentration in water and found to be greater in aqueous glycine solutions as compared to aqueous leucine solutions for all the saccharides. This dependence of B-coefficient values on concentration of amino acids indicate a structure to allow the cosolute (amino acids) to act on solvent and reinforce its structure through H-bonding.32 The data in Table 3 and plot of Figure 2 depict that B-coefficient values decrease with temperature for all of the investigated saccharides. A similar increase in B-coefficient values with cosolute concentration has also been reported by Zhuo et al. in their study on monosaccharides in aqueous glycine solutions.30 The sign of temperature derivative of B-coefficient, i.e., dB/dT, provides important information about the structuremaking/breaking nature of any solute.33 The negative values of dB/dT imply structure-making, whereas the positive values reflect the structure-breaking ability of solute.34,35 In the present case, dB/dT values (Figure 2) have been found to be negative for all the studied saccharides, revealing the structure-making nature of saccharides in the presence of both amino acids. In general, the magnitude of the negative dB/dT values has been found to increase with type of saccharide as ribose < maltose < raffinose at all concentrations of both amino acids, hence reinforcing that an increase in structural order of the solution occurs in the same directions. This may be due to strengthening of the hydrophilic−ionic interactions between saccharides and amino acids with type of saccharide, as also observed from their volumetric studies.17,18 These results have been further substantiated by the findings of Banipal et al. on saccharides in aqueous MgCl2 and borax solutions.34,36

(at 298.15 K) was obtained from a Millipore−Elix system. The specifications of all the chemicals used are given in Table 1. All saccharides and amino acids were recrystallized twice in distilled water and dried in vacuum oven. After this they were kept in a vacuum desiccator over anhydrous calcium chloride at room temperature for a minimum of 48 h. 2.2. Equipment and Procedures. Stock solutions of amino acids of (0.025, 0.050, and 0.100) mol·kg−1 were prepared in distilled water and were used as solvents for the preparation of saccharide solutions. These solutions were prepared by using Shimadzu balance with a precision of ± 0.0001 g. The viscosity measurements were carried out using a jacketed Ostwald viscometer. The viscometer was calibrated before use with solvents 1,4-dioxane and dimethyl sulfoxide (both of AR grade with purity 99.5 % were obtained from SISCO Res. Lab. Pvt. Ltd.) at 298.15 K. The viscosity values of water used for calibration purposes were taken from literature.19 However, the density values of all these solvents have been used from our previous study.18 The viscosity values of 1,4-dioxane and dimethyl sulfoxide have been obtained to be (1.1937 and 2.0067) mPa·s, respectively. These values were found in good agreement with the literature values.20,21 The temperature of the viscometer filled with the experimental solutions was maintained by circulating water of desired temperature from a high precision water bath (± 0.01 K) supplied by Narang Scientific Works (NSW) Pvt. Ltd., New Delhi. The efflux time of flow was measured by using a digital stop watch with an uncertainty of ± 0.01 s. The mean of at least three flow time readings was used as the final efflux time. The experimental uncertainty in viscosity measurements was ± 0.0020 mPa·s.

3. RESULTS AND DISCUSSION The viscosity values for ribose, maltose, and raffinose in pure water and aqueous solutions of glycine and leucine (0.025, 0.050, and 0.100) mol·kg−1 as a function of molalities of saccharides (0.050 to 0.100) mol·kg−1 and temperature are summarized in Table 2. However, the density values used to calculate the viscosity values have been reported earlier.17,18 The viscosity values for pure water and amino acids in water are found to be in close agreement (within the limits of experimental errors) with the values already reported in literature (Table 2). The viscosity data have been used to calculate A- and B-coefficients of viscosity using the Jones−Dole equation22 of the form ψ = (ηr − 1)/m1/2 = A + Bm1/2

(1)

where ηr (= η/ηo) is the relative viscosity of the solution, η and ηo are the viscosities of solution and the solvent (aqueous amino acid), respectively, m is the molality of saccharides solutions, A is the Falkenhagen coefficient,23,24 and B is the Jones−Dole coefficient.22 Falkenhagen coefficient, A, accounts B



Article

Table 2. Values of η for Saccharides in Aqueous Glycine and Leucine Solutions at Different Temperatures (T/K) and Experimental Pressure, p = 0.098 MPaa η/(mPa·s) mb mol·kg

saccharides in aqueous glycine solutions −1

0.000

293.15

298.15

303.15

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0019 (1.0020)d 1.0191 1.0210 1.0225 1.0241 1.0261 1.0272 1.0290 1.0314 1.0328 1.0355

0.8903 (0.8903)d 0.9032 0.9047 0.906 0.9073 0.9085 0.9100 0.9114 0.9127 0.9143 0.9168

0.7973 (0.7975)d 0.8071 0.8082 0.8092 0.8101 0.8113 0.8125 0.8135 0.8146 0.8157 0.8183

0.000 0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0112 1.0289 1.0306 1.0323 1.0339 1.0357 1.0377 1.0393 1.0417 1.0428 1.0454

0.8923 0.9062 0.9077 0.9096 0.9105 0.9122 0.9141 0.9152 0.9164 0.9177 0.9204

0.7994 0.8094 0.8106 0.8112 0.8126 0.8133 0.8150 0.816 0.8171 0.8181 0.8208

0.000

1.0161

0.8947 (0.8965)e

0.8017

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0349 1.0371 1.0389 1.0403 1.0422 1.0441 1.0450 1.0480 1.0495 1.0530

0.9100 0.9114 0.9132 0.9149 0.9166 0.9182 0.9195 0.9206 0.922 0.9247

0.8124 0.8135 0.8146 0.8161 0.8173 0.8185 0.8195 0.8206 0.8220 0.8240

0.000

1.0216 (1.0156)g

0.8056 (0.8095)g

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0431 1.0453 1.0482 1.0488 1.0514 1.0534 1.0549 1.0555 1.0578 1.0644

0.9011 (0.9028)e (0.9050)h 0.9164 0.9182 0.9191 0.9207 0.9220 0.9239 0.9250 0.9263 0.9286 0.9321

0.8161 0.8169 0.8183 0.8196 0.8207 0.8217 0.8229 0.8240 0.8252 0.8282

308.15

saccharides in aqueous leucine solutions 313.15

293.15

Ribose mAA/(mol·kg−1) = 0.000c 0.7190 0.6526 1.0019 (0.7195)d (0.6535)d (1.0020)d 0.7261 0.6570 1.0191 0.7270 0.6576 1.0210 0.7277 0.6581 1.0225 0.7286 0.6587 1.0241 0.7292 0.6595 1.0261 0.7302 0.6601 1.0272 0.7313 0.6607 1.0290 0.7321 0.6616 1.0314 0.7333 0.6626 1.0328 0.7353 0.6642 1.0355 mAA/(mol·kg−1) = 0.025 0.7201 0.6549 1.0345 0.7278 0.6587 1.0337 0.7288 0.6593 1.0352 0.7297 0.6601 1.0364 0.7309 0.6612 1.0380 0.7320 0.6617 1.0401 0.7329 0.6621 1.0412 0.7336 0.6629 1.0431 0.7344 0.6634 1.0444 0.7355 0.6645 1.0463 0.7372 0.6660 1.0492 mAA/(mol·kg−1) = 0.050 0.7213 0.6563 1.0223 (0.7248)e 0.7301 0.7315 0.7328 0.7335 0.7346 0.7360 0.7366 0.7376 0.7385 0.7406

0.6605 1.0423 0.6612 1.0446 0.6619 1.0462 0.6626 1.0482 0.6632 1.0501 0.6641 1.0520 0.6648 1.0535 0.6654 1.0548 0.6663 1.0572 0.6681 1.0612 mAA/(mol·kg−1) = 0.100 0.7236 0.6582 1.0263 (0.7291)e (0.6628)g (0.7290)h 0.7340 0.6627 1.0526 0.7352 0.6636 1.0548 0.7364 0.6641 1.0581 0.7372 0.6648 1.0589 0.7384 0.6654 1.0615 0.7394 0.6664 1.0636 0.7406 0.6671 1.0651 0.7416 0.6680 1.0676 0.7429 0.6690 1.0696 0.7451 0.6704 1.0746

C

298.15

303.15

308.15

313.15

0.8903 (0.8903)d 0.9032 0.9047 0.906 0.9073 0.9085 0.9100 0.9114 0.9127 0.9143 0.9168

0.7973 (0.7975)d 0.8071 0.8082 0.8092 0.8101 0.8113 0.8125 0.8135 0.8146 0.8157 0.8183

0.7190 (0.7195)d 0.7261 0.7270 0.7277 0.7286 0.7292 0.7302 0.7313 0.7321 0.7333 0.7353

0.6526 (0.6535)d 0.6570 0.6576 0.6581 0.6587 0.6595 0.6601 0.6607 0.6616 0.6626 0.6642

0.8932 0.9081 0.9095 0.9108 0.9124 0.9141 0.9157 0.9170 0.9184 0.9198 0.9222

0.7948 0.8103 0.8116 0.8129 0.8143 0.8158 0.8172 0.8183 0.8198 0.8210 0.8236

0.7187 0.7281 0.7292 0.7303 0.7313 0.7324 0.7334 0.7342 0.7352 0.7363 0.7384

0.6481 0.6586 0.6597 0.6606 0.6618 0.6629 0.6638 0.6646 0.6656 0.6665 0.6684

0.8936

0.8021

0.6571

0.9126 0.9144 0.9162 0.9179 0.9194 0.9209 0.9225 0.9242 0.9257 0.9293

0.8146 0.8159 0.8169 0.8184 0.8193 0.8210 0.8222 0.8234 0.8245 0.8269

0.7237 (0.7363)e (0.7365)f 0.7318 0.7327 0.7340 0.7347 0.7359 0.7367 0.7379 0.7385 0.7396 0.7417

0.6627 0.6636 0.6644 0.6655 0.6662 0.6669 0.6675 0.6683 0.6691 0.6709

0.8992

0.8011

0.7223

0.6533

0.9183 0.9199 0.9211 0.9227 0.9240 0.9259 0.9272 0.9294 0.9312 0.9353

0.8166 0.8181 0.8196 0.8210 0.8222 0.8236 0.8249 0.8263 0.8278 0.8307

0.7341 0.7356 0.7367 0.7381 0.7393 0.7404 0.7412 0.7426 0.7434 0.7459

0.6657 0.6668 0.6677 0.6685 0.6691 0.6702 0.6709 0.6718 0.6728 0.6742



Article

Table 2. continued η/(mPa·s) m

b

mol·kg−1

saccharides in aqueous glycine solutions 293.15

298.15

303.15

308.15

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0215 1.0254 1.0295 1.0334 1.0365 1.0413 1.0452 1.0495 1.0537 1.0619

0.9029 0.9064 0.9093 0.9119 0.9159 0.9193 0.9231 0.9262 0.9294 0.9361

0.8044 0.8074 0.8099 0.812 0.8144 0.8178 0.8202 0.8230 0.8261 0.833

0.7221 0.7240 0.7266 0.7287 0.7315 0.7341 0.7362 0.7383 0.7406 0.7449

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0281 1.0317 1.0362 1.0400 1.0447 1.0482 1.0514 1.0558 1.0600 1.0682

0.9064 0.9095 0.9131 0.9167 0.9192 0.9229 0.9265 0.9308 0.9341 0.9403

0.8081 0.8107 0.8137 0.8167 0.8190 0.8216 0.8249 0.8279 0.8309 0.8371

0.7246 0.7268 0.7292 0.7313 0.7340 0.7360 0.7383 0.7414 0.7439 0.7489

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0368 1.0399 1.0444 1.0478 1.0533 1.0572 1.0614 1.0651 1.0697 1.0777

0.9102 0.9133 0.9171 0.9203 0.9242 0.9270 0.9310 0.9348 0.9385 0.9451

0.8121 0.8148 0.8179 0.8208 0.8236 0.8270 0.8294 0.8330 0.8359 0.8417

0.7274 0.7300 0.7323 0.7348 0.7379 0.7398 0.7426 0.7447 0.7477 0.7525

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0449 1.0489 1.0532 1.0573 1.0623 1.0667 1.0709 1.0754 1.0795 1.0876

0.9169 0.9202 0.9234 0.9277 0.9307 0.9340 0.9377 0.9417 0.9452 0.9527

0.8181 0.8208 0.8236 0.8270 0.8306 0.8334 0.8363 0.8395 0.8427 0.8486

0.7320 0.7342 0.7367 0.7395 0.7425 0.7448 0.7472 0.7503 0.7533 0.7576

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0555 1.0613 1.0661 1.0714 1.0790 1.0873 1.0948 1.1014 1.1079 1.1179

0.9281 0.9343 0.9400 0.9448 0.9488 0.9553 0.9597 0.9674 0.9724 0.9824

0.8259 0.8302 0.8349 0.8402 0.8435 0.8485 0.8521 0.8569 0.8631 0.8719

0.7393 0.7424 0.7474 0.7516 0.7547 0.7585 0.7625 0.7663 0.7700 0.7775


Maltose mAA/(mol·kg−1) = 0.6529 0.6549 0.6564 0.6586 0.6606 0.6619 0.6645 0.6669 0.6687 0.6724 mAA/(mol·kg−1) = 0.6557 0.6571 0.6588 0.6605 0.6625 0.6642 0.6668 0.6690 0.6713 0.6760 mAA/(mol·kg−1) = 0.6582 0.6602 0.6622 0.6639 0.6655 0.6675 0.6704 0.6727 0.6754 0.6789 mAA/(mol·kg−1) = 0.6621 0.6640 0.6661 0.6685 0.6705 0.6724 0.6748 0.6770 0.6799 0.6839 Raffinose mAA/(mol·kg−1) = 0.6657 0.6688 0.673 0.6764 0.6792 0.6822 0.6857 0.6881 0.6925 0.6980

D

293.15 0.000 1.0215 1.0254 1.0295 1.0334 1.0365 1.0413 1.0452 1.0495 1.0537 1.0619 0.025 1.0312 1.0345 1.0383 1.0423 1.0460 1.0502 1.0540 1.0573 1.0610 1.0689 0.050 1.0396 1.0438 1.0475 1.0520 1.0555 1.0601 1.0639 1.0683 1.0725 1.0796 0.100 1.0484 1.0529 1.0559 1.0633 1.0666 1.0709 1.0754 1.0791 1.0830 1.0906 0.000 1.0555 1.0613 1.0661 1.0714 1.0790 1.0873 1.0948 1.1014 1.1079 1.1179

298.15

303.15

308.15

313.15

0.9029 0.9064 0.9093 0.9119 0.9159 0.9193 0.9231 0.9262 0.9294 0.9361

0.8044 0.8074 0.8099 0.812 0.8144 0.8178 0.8202 0.8230 0.8261 0.833

0.7221 0.7240 0.7266 0.7287 0.7315 0.7341 0.7362 0.7383 0.7406 0.7449

0.6529 0.6549 0.6564 0.6586 0.6606 0.6619 0.6645 0.6669 0.6687 0.6724

0.9085 0.9120 0.9152 0.9187 0.9214 0.9251 0.9286 0.9331 0.9366 0.9434

0.8088 0.8115 0.8144 0.8174 0.8205 0.8241 0.8270 0.8302 0.8330 0.8390

0.7263 0.7288 0.7314 0.7332 0.7355 0.7388 0.7414 0.7439 0.7466 0.7517

0.6551 0.6569 0.6592 0.6616 0.6637 0.6663 0.6683 0.6705 0.6731 0.6774

0.9136 0.9174 0.9210 0.9248 0.9279 0.9320 0.9362 0.9399 0.9435 0.9501

0.8129 0.8163 0.8192 0.8218 0.8250 0.8280 0.8313 0.8343 0.8371 0.8427

0.7302 0.7324 0.7345 0.7372 0.7395 0.7421 0.7452 0.7475 0.7504 0.7548

0.6608 0.6630 0.6646 0.6662 0.6681 0.6700 0.6731 0.6753 0.6779 0.6826

0.9214 0.9253 0.9289 0.9328 0.9364 0.9405 0.9450 0.9484 0.9522 0.9593

0.8191 0.8220 0.8253 0.8283 0.8320 0.8357 0.8386 0.8419 0.8453 0.8516

0.7332 0.7356 0.7384 0.7411 0.7441 0.7467 0.7495 0.7522 0.7552 0.7595

0.6647 0.6664 0.6690 0.6710 0.6725 0.6752 0.6777 0.6806 0.6827 0.6866

0.9281 0.9343 0.9400 0.9448 0.9488 0.9553 0.9597 0.9674 0.9724 0.9824

0.8259 0.8302 0.8349 0.8402 0.8435 0.8485 0.8521 0.8569 0.8631 0.8719

0.7393 0.7424 0.7474 0.7516 0.7547 0.7585 0.7625 0.7663 0.7700 0.7775

0.6657 0.6688 0.673 0.6764 0.6792 0.6822 0.6857 0.6881 0.6925 0.6980



Article

Table 2. continued η/(mPa·s) m

b

mol·kg−1

saccharides in aqueous glycine solutions 293.15

298.15

303.15

308.15

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0614 1.0678 1.0742 1.0795 1.0862 1.0932 1.1005 1.1071 1.1134 1.1263

0.9320 0.9370 0.9425 0.9483 0.9532 0.9586 0.9644 0.9715 0.9763 0.9865

0.8298 0.8345 0.8392 0.8444 0.8494 0.8543 0.8580 0.8628 0.8675 0.8769

0.7422 0.7470 0.7504 0.7554 0.7591 0.7625 0.7659 0.7704 0.7754 0.7823

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0672 1.0741 1.0800 1.0866 1.0920 1.0993 1.1062 1.1143 1.1213 1.1322

0.9363 0.9424 0.9484 0.9541 0.9601 0.9652 0.9714 0.9769 0.9826 0.9923

0.8350 0.8393 0.8442 0.8487 0.8531 0.858 0.8629 0.8681 0.8735 0.8833

0.7459 0.7498 0.7539 0.7582 0.7623 0.7663 0.7697 0.7744 0.7788 0.7867

0.050 0.055 0.060 0.065 0.070 0.075 0.080 0.085 0.090 0.100

1.0766 1.0826 1.0892 1.0956 1.1037 1.1101 1.1174 1.1239 1.1307 1.1435

0.9466 0.9519 0.9577 0.9632 0.9684 0.9747 0.9811 0.9872 0.9934 1.0040

0.8425 0.8467 0.8514 0.8554 0.8605 0.8664 0.8713 0.8762 0.8817 0.8923

0.7516 0.7555 0.7596 0.7639 0.7672 0.7720 0.7767 0.7809 0.7854 0.7939


293.15

mAA/(mol·kg−1) = 0.025 0.6693 1.0646 0.6718 1.0714 0.6749 1.0783 0.6780 1.0840 0.6815 1.0897 0.6848 1.0966 0.6881 1.1049 0.6926 1.1109 0.6954 1.1161 0.7016 1.1273 mAA/(mol·kg−1) = 0.050 0.6710 1.0752 0.6744 1.0806 0.6781 1.0863 0.6817 1.0931 0.6849 1.0990 0.6886 1.1058 0.6917 1.1125 0.6953 1.1199 0.6979 1.1275 0.7046 1.1421 mAA/(mol·kg−1) = 0.100 0.6765 1.0845 0.6802 1.0913 0.6836 1.0976 0.6866 1.1042 0.6898 1.1116 0.6930 1.1191 0.6963 1.1257 0.7007 1.1326 0.7051 1.1410 0.7123 1.1529

298.15

303.15

308.15

313.15

0.9340 0.9390 0.9443 0.9489 0.9547 0.9604 0.9672 0.9731 0.9785 0.9883

0.8314 0.8366 0.8413 0.8459 0.8511 0.8562 0.8610 0.8659 0.8707 0.8809

0.7448 0.7485 0.7527 0.7570 0.7612 0.7649 0.7686 0.7734 0.7778 0.7858

0.6681 0.6716 0.6754 0.6796 0.6832 0.6870 0.6901 0.6937 0.6964 0.7031

0.9429 0.9474 0.9533 0.9592 0.9642 0.9703 0.9762 0.9831 0.9894 1.0019

0.8394 0.8446 0.850 0.8547 0.8592 0.8643 0.8694 0.8749 0.8790 0.8901

0.7513 0.7561 0.7593 0.7644 0.7686 0.7727 0.7758 0.7817 0.7859 0.7932

0.6750 0.6790 0.6824 0.6852 0.6879 0.6912 0.6958 0.6994 0.7027 0.7110

0.9530 0.9595 0.9650 0.9706 0.9777 0.9842 0.9905 0.9964 1.0027 1.0141

0.8498 0.8546 0.8599 0.8662 0.8713 0.8776 0.8826 0.8876 0.8938 0.9036

0.7579 0.7622 0.7671 0.7720 0.7769 0.7805 0.7850 0.7897 0.7944 0.8036

0.6797 0.6839 0.6873 0.6912 0.6946 0.6984 0.7020 0.7061 0.7105 0.7190

Standard uncertainties, u, are u(T) = 0.01 K, u(p) = 0.002 MPa, u(m) = 0.003 mol·kg−1, and u(η) = 0.0020 mPa·s. The combined expanded uncertainties, U, is U(η) = 0.0040 mPa·s (level of confidence = 0.95, k = 2). bm is the molality of saccharide in water and water + amino acid. cmAA is the molality of amino acid in water. dReference 41. eReference 42. fReference 43. gReference 44. hReference 45. a

Further, the viscosity B-coefficient values have been used to calculate the viscosity B-coefficient of transfer, ΔtrB, of saccharides from water to aqueous amino acid solutions by using the equation: Δtr B = B(Aq. A . A . ) − B(water)

get strengthened with temperature and molalities of both amino acids as shown by increase in ΔtrB values (Table 3). These results are in accordance with the conclusions drawn from Δtrϕov and Δtrϕok values as reported in our previous studies.17,18 Eyring and co-workers37 have proposed the following relation for the calculation of the free energy of activation of viscous flow per mole of solvent, Δμo1*:

(2)

The positive ΔtrB values have been summarized in Table 3 and illustrated in Figure 3. A perusal of Table 3 and Figure 3 reveals that ΔtrB values increase with the molalities of both amino acids as well as with the complexity of the saccharides at all temperatures. This suggests that an overall structural increase occurs in solution and this property gets enhanced with the type of the saccharide. A similar pattern of behavior for mono-, di-, and tri-saccharides in the aqueous solutions of KCl and MgCl2 has also been reported in the literature.31,32 Comparatively, for all the studied saccharides, ΔtrB values in aqueous glycine solutions are found to be greater than aqueous leucine solutions, suggesting stronger solute−solvent interactions in aqueous glycine solutions. Moreover, the positive ΔtrB values are indicative of predominance of hydrophilic−ionic interactions over the hydrophobic−ionic interactions, which further

ηo =

⎛ Δμ 0 * ⎞ hNA ⎜⎜ 1 ⎟⎟ exp V1̅ o ⎝ RT ⎠

(3)

where h is the Planck’s constant, NA is the Avogadro’s number, R is the universal gas constant, T is the temperature, and V̅ o1 (= ∑xiMi/d) is the mean volume of the solvent. The terms xi and Mi denote the mole fractions and molecular weights of water and amino acid, and d is the density of solvent mixture (water + amino acid). Rearrangement of above equation yields Δμ10 * E

⎛ η V1̅ o ⎞ = RT ln⎜ o ⎟ ⎝ hNA ⎠

(4)



Article

Table 3. Values of B-Coefficient, and ΔtrB, for Saccharides in Pure Water and Aqueous Solutions of Amino Acids at Different Temperatures and Experimental Pressure, p = 0.098 MPaa ribose T/K

B/(kg·mol−1)

maltose ΔtrB/(kg·mol−1)

293.15 298.15 303.15 308.15 313.15

0.326 0.315 0.298 0.289 0.278

± ± ± ± ±

0.001a 0.001 0.001 0.001 0.001

293.15 298.15 303.15 308.15 313.15

0.331 0.321 0.306 0.297 0.289

± ± ± ± ±

0.001 0.001 0.001 0.001 0.001

0.005 0.006 0.008 0.009 0.011

293.15 298.15 303.15 308.15 313.15

0.337 0.328 0.314 0.306 0.296

± ± ± ± ±

0.001 0.001 0.001 0.001 0.001

0.011 0.013 0.016 0.017 0.019

293.15 298.15 303.15 308.15 313.15

0.346 0.337 0.323 0.315 0.305

± ± ± ± ±

0.003 0.002 0.001 0.001 0.001

0.020 0.022 0.025 0.026 0.027

293.15 298.15 303.15 308.15 313.15

0.329 0.319 0.303 0.295 0.285

± ± ± ± ±

0.001 0.001 0.001 0.001 0.001

0.003 0.004 0.005 0.006 0.007

293.15 298.15 303.15 308.15 313.15

0.333 0.324 0.310 0.302 0.292

± ± ± ± ±

0.001 0.001 0.001 0.001 0.001

0.007 0.009 0.012 0.013 0.014

293.15 298.15 303.15 308.15 313.15

0.340 0.331 0.317 0.309 0.300

± ± ± ± ±

0.002 0.002 0.001 0.001 0.001

0.014 0.016 0.019 0.020 0.022

B/(kg·mol−1)

raffinose ΔtrB/(kg·mol−1)

Pure Water 1.099 ± 0.002 1.081 ± 0.002 1.063 ± 0.001 1.045 ± 0.002 1.028 ± 0.001 mGly/(mol·kg−1) = 0.025b 1.110 ± 0.002 1.094 ± 0.002 1.078 ± 0.001 1.062 ± 0.001 1.047 ± 0.002 mGly/(mol·kg−1) = 0.050 1.117 ± 0.002 1.101 ± 0.001 1.085 ± 0.001 1.071 ± 0.002 1.055 ± 0.002 mGly/(mol·kg−1) = 0.100 1.127 ± 0.002 1.110 ± 0.001 1.094 ± 0.002 1.079 ± 0.002 1.064 ± 0.001 mLeu/(mol·kg−1) = 0.025b 1.108 ± 0.001 1.091 ± 0.002 1.074 ± 0.001 1.058 ± 0.002 1.043 ± 0.001 mLeu/(mol·kg−1) = 0.050 1.113 ± 0.002 1.097 ± 0.002 1.082 ± 0.001 1.065 ± 0.002 1.050 ± 0.003 mLeu/(mol·kg−1) = 0.100 1.121 ± 0.004 1.105 ± 0.002 1.089 ± 0.001 1.073 ± 0.002 1.057 ± 0.002

B/(kg·mol−1)

ΔtrB/(kg·mol−1)

1.489 1.470 1.447 1.425 1.403

± ± ± ± ±

0.002 0.002 0.002 0.001 0.002

0.011 0.013 0.015 0.018 0.019

1.508 1.492 1.469 1.449 1.428

± ± ± ± ±

0.002 0.002 0.003 0.003 0.003

0.019 0.021 0.022 0.024 0.025

0.018 0.020 0.022 0.026 0.027

1.512 1.495 1.474 1.453 1.433

± ± ± ± ±

0.003 0.003 0.002 0.002 0.003

0.023 0.024 0.027 0.028 0.030

0.028 0.029 0.031 0.034 0.036

1.518 1.501 1.481 1.461 1.440

± ± ± ± ±

0.002 0.002 0.003 0.002 0.003

0.029 0.030 0.034 0.036 0.037

0.009 0.010 0.011 0.013 0.015

1.505 1.488 1.465 1.446 1.425

± ± ± ± ±

0.003 0.003 0.001 0.001 0.003

0.016 0.017 0.018 0.021 0.022

0.014 0.016 0.019 0.020 0.022

1.509 1.496 1.470 1.450 1.430

± ± ± ± ±

0.003 0.003 0.002 0.003 0.003

0.020 0.021 0.023 0.025 0.027

0.022 0.024 0.026 0.028 0.029

1.514 1.497 1.476 1.455 1.436

± ± ± ± ±

0.002 0.002 0.002 0.002 0.002

0.025 0.026 0.029 0.030 0.033

Standard deviation. Standard uncertainties, u, are u(T) = 0.01 K, u(p) = 0.002 MPa, and u(m) = 0.003 mol·kg−1. bmGly and mLeu are the molalities of glycine and leucine in water, respectively.

a

The values of V̅ o1, Δμo1*, and Δμo2* have been listed in Table 4. The Δμo2* values in pure water are found to be in good agreement with those as reported in the literature.31 It is also evident from Table 4 that for all saccharides in aqueous amino acid solutions, the Δμo2* values are positive and much larger than those of Δμo1* values. This suggests that the interactions between saccharides and solvent (aqueous−amino acids) molecules in the ground state are stronger than in the transition state. In other words, the formation of the transition state is less favored in the presence of amino acids due to breaking and distortion of the intermolecular bonds,39 and the same has been reported in literature as well.31 The Δμo2* values in aqueous solutions of both amino acids increase in the order

Based on Eyring transition state theory,37 Feakins et al.38 suggested the following equation for the free energy of activation of viscous flow per mole of solute, Δμo2*: B = (V1̅ o − V2̅ o ) +

V1̅ o(Δμ20 * − Δμ10 *) RT

(5)

V̅ o2

where is the partial molar volume of solute and is equivalent to ϕov as calculated in our previous studies.17,18 Equation 5 can be written as follows: ⎛ RT ⎞ Δμ20 * = Δμ10 * + ⎜ o ⎟[B − (V1̅ o − V2̅ o)] ⎝ V1̅ ⎠

(6) F



Article

Figure 1. Representative plot of Ψ versus m1/2 of raffinose in 0.100 mol·kg−1 aqueous glycine solution with error bars within the symbols. ■, T = 293.15 K; ●, T = 298.15 K; ▲, T = 303.15 K; ▼, T = 308.15 K; ◀, T = 313.15 K. The points represent experimental values, and lines represent values calculated from eq 1.

Figure 3. Representative plots of ΔtrB versus mAA of (a) glycine and (b) leucine of ribose with error bars within the symbols. ■, T = 293.15 K; ●, T = 298.15 K; ▲, T = 303.15 K; ▼, T = 308.15 K; ◀, T = 313.15 K. The points and lines represent values calculated from eq 2. Figure 2. Representative plot of B versus T in 0.100 mol·kg−1 aqueous glycine solution with error bars within the symbols. ■, ribose; ●, maltose; ▲, raffinose. The points and lines represent values calculated from eq 1.

saccharides has been calculated with the help of the following relation: ΔH2o * = Δμ20 * + T ΔS2o *

TΔSo2*

The values of and at different temperatures are recorded in Table 4. It is interesting to note that, for all of the saccharides except ribose, TΔSo2* values are negative, while all the ΔHo2* values are positive indicating that the formation of transition state for viscous flow is associated with bond breaking and an increase in order in the system.40 However, the positive values of TΔSo2* in case of ribose suggest a decrease in order of transition state. This type of positive values for these saccharides have also been reported in aqueous solutions of electrolyte.31 The data reveal that the ΔHo2* values of the ternary mixtures increase with the type of the saccharides, thereby suggesting that the formation of activated species for viscous flow becomes difficult as complexity of the saccharide increase. Moreover, the order of the system increases with the type of saccharide as indicated by the TΔSo2* values.

ribose < maltose < raffinose, implying that the formation of the transition state requires more energy with the complexity/ size of the saccharide. Further, the Δμo2* values increase with increase in temperature (except for ribose), indicating that saccharide−amino acid interactions increase with rise in temperature, making the flow of solute molecules difficult.40 It is interesting to note that Δμo2* values also show dependence on the type of amino acid; greater values have been observed in glycine solutions as compared to leucine solutions. The activation entropy (ΔSo2*) for different saccharides studied has also been calculated from the following relation:37 d(Δμ20 *)/dT = −ΔS2o *

(8)

ΔHo2*

(7)

Δμo2*

The slopes of linear plots of versus T represent the values of ΔSo2*. The activation enthalpy (ΔHo2*) for viscous flow of G



Article

Table 4. Values of V̅ o1, Δμo1*, Δμo2*, TΔSo2*, and ΔHo2*, for Saccharides in Pure Water and Aqueous Solutions of Amino Acids at Different Temperatures and Experimental Pressure, p = 0.098 MPaa V̅ o1·106 T/K

−1

m ·mol 3

Δμo2*/(kJ·mol−1)

Δμo1* −1

kJ·mol

ribose

maltose

293.15 298.15 303.15 308.15 313.15

18.032 18.052 18.079 18.104 18.132

9.293 9.161 9.041 8.928 8.825

63.590 62.877 61.241 60.709 59.897

186.036 186.374 186.718 186.973 187.345

293.15 298.15 303.15 308.15 313.15

18.043 18.064 18.089 18.119 18.152

9.317 9.168 9.049 8.934 8.837

64.808 64.260 63.138 62.874 62.414

188.463 189.361 190.075 190.882 191.699

293.15 298.15 303.15 308.15 313.15

18.052 18.074 18.100 18.129 18.163

9.330 9.177 9.057 8.940 8.844

65.792 65.398 64.354 64.049 63.622

189.412 190.326 191.045 192.007 192.848

293.15 298.15 303.15 308.15 313.15

18.078 18.100 18.125 18.155 18.189

9.346 9.198 9.073 8.952 8.856

67.120 66.774 65.720 65.390 64.810

190.587 191.399 192.190 193.099 194.092

293.15 298.15 303.15 308.15 313.15

18.071 18.092 18.118 18.148 18.181

9.340 9.175 9.038 8.933 8.814

64.321 63.632 62.314 61.947 61.278

187.725 188.399 189.003 189.728 190.496

293.15 298.15 303.15 308.15 313.15

18.110 18.131 18.157 18.187 18.221

9.352 9.181 9.067 8.957 8.856

64.789 64.382 63.218 62.860 62.246

188.141 188.997 189.926 190.465 191.292

293.15 298.15 303.15 308.15 313.15

18.193 18.215 18.241 18.271 18.307

9.373 9.208 9.075 8.964 8.877

65.507 65.120 63.956 63.630 63.188

188.545 189.413 190.243 190.916 191.622

TΔSo2*/(kJ·mol−1) raffinose

ribose

Pure Water 261.486 55.992 263.158 56.947 263.862 57.902 264.739 58.857 265.374 59.812 mGly/(mol·kg−1) = 0.025b 265.738 36.057 267.774 36.672 268.969 37.287 270.189 37.902 271.357 38.517 mGly/(mol·kg−1) = 0.050 266.866 33.126 268.818 33.691 270.488 34.256 271.601 34.821 272.920 35.386 mGly/(mol·kg−1) = 0.100 267.597 35.178 269.701 35.778 271.171 36.378 272.559 36.978 273.822 37.578 mLeu/(mol·kg−1) = 0.025b 265.222 45.438 267.262 46.213 268.227 46.988 269.519 47.763 270.602 48.538 mLeu/(mol·kg−1) = 0.050 265.390 38.696 267.443 39.356 268.783 40.016 270.083 40.676 271.252 41.336 mLeu/(mol·kg−1) = 0.100 265.229 35.764 267.214 36.374 268.533 36.984 269.789 37.594 271.192 38.204

ΔHo2*/(kJ·mol−1)

maltose

raffinose

ribose

maltose

raffinose

−18.762 −19.082 −19.402 −19.722 −20.042

−54.819 −55.754 −56.689 −57.624 −58.559

119.581 119.823 119.143 119.565 119.709

167.275 167.293 167.316 167.251 167.304

206.667 207.404 207.173 207.115 206.815

−46.611 −47.406 −48.201 −48.996 −49.791

−80.030 −81.395 −82.760 −84.125 −85.490

100.866 100.932 100.425 100.777 100.931

141.852 141.955 141.874 141.887 141.908

185.708 186.379 186.209 186.064 185.867

−50.129 −50.984 −51.839 −52.694 −53.549

−87.066 −88.551 −90.036 −91.521 −93.006

98.918 99.089 98.610 98.870 99.008

139.283 139.342 139.206 139.313 139.299

179.801 180.267 180.452 180.080 179.915

−51.008 −51.878 −52.748 −53.618 −54.488

−89.704 −91.234 −92.764 −94.294 −95.824

102.298 102.552 102.098 102.368 102.388

−51.008 −51.878 −52.748 −53.618 −54.488

177.894 178.467 178.407 178.265 177.998

−40.162 −40.847 −41.532 −42.217 −42.902

−76.219 −77.519 −78.819 −80.119 −81.419

109.759 109.845 109.302 109.710 109.817

147.564 147.553 147.472 147.511 147.594

189.003 189.743 189.408 189.400 189.183

−45.438 −46.213 −46.988 −47.763 −48.538

−84.134 −85.569 −87.004 −88.439 −89.874

103.485 103.738 103.233 103.535 103.581

142.703 142.783 142.937 142.702 142.754

181.256 181.874 181.779 181.644 181.378

−44.852 −45.617 −46.382 −47.147 −47.912

−85.014 −86.464 −87.914 −89.364 −90.814

101.271 101.495 100.941 101.225 101.392

143.693 143.796 143.861 143.769 143.710

180.215 180.751 180.619 180.425 180.378

a Standard uncertainties, u, are u(T) = 0.01 K, u(p) = 0.002 MPa, and u(m) = 0.003 mol·kg−1. bmGly and mLeu are the molalities of glycine and leucine in water, respectively.

interactions in the presence of glycine than leucine. The Δμo2* values are much larger than those of Δμo1* values, revealing that the formation of the transition state is less favored in the presence of amino acids. Moreover, the negative TΔSo2* values and positive ΔHo2* values are affirming the fact of bond breaking and increase in order, respectively, during the formation of transition state for viscous flow.

4. CONCLUSIONS The viscosity B-coefficients are positive and large in the presence of both the studied amino acids as compared to pure water, suggesting that a more structured medium is offered in the presence of these co-solutes. Moreover, the negative dB/dT values are also revealing the structure-making nature of studied saccharides in the presence of amino acids. The increase in ΔtrB values from ribose to maltose to raffinose suggests that structure of the medium gets enhanced with the complexity of the saccharides due to strengthening of solute−solvent interactions. The greater ΔtrB values in aqueous glycine solutions are indicative of stronger hydrophilic−ionic

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S.C. and K.K. thank UGC for financial assistance under the project (F. No. 42-249/2013/SR) and fellowship (F. No. 7-75/ 2007/BSR), respectively. Notes

The authors declare no competing financial interest.

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Interactions of Saccharides in Aqueous Glycine and Leucine Solutions

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