مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Density and Viscosity of Amino Acid Serine in Aqueous Dimethyl Sulfoxide Solution at Different Temperatures Z.A. AL-Dulaimy , Z. W. AL-Amel ,R. S. AL-Khalisy , Z. H. Hussein Departme nt of Chemistry, College of Education Ibn-Al-Haitham Unive rsity of Baghdad Received in : 23 August 2011 , Accepted in:10 November 2011 Abstract Densities  and viscosity  of serine in 20, 40, and 60% (w/w) dimethy l sulfoxide (DM SO)-water mixtures were measured at 298.15, 303.15 and 308.15k. From these exp erimental data, app arent molal volume v  , limiting app arent molal volume v o , the slop v S , transfer volume v o(tr), Jones-Dole coefficients A and B were calculated. The results are v odiscussed the solute-solvent and solute-solute interaction, and showed that serine behaves as st ructure-breaker in aqueous DM SO solvent. Key word: Density , Viscosity , Amino Acid, Serine, dimethy l sulfoxide Introduction Amino acid which are the fundamental substances for building blocks of p roteins are used as model comp ounds to st udy the interactions of p roteins in water and different solutions. A number of workers studied the volumetric and viscometric p rop erties of amino acids in water [1-3]. Ali and Shahjaham [4] st udied the volumetric and viscometric behaviour of L- serine, L-threonime, L-glutamine, L-ly sine, L-arginine and L-hist idine amino acids and their group contributions in aqueous tetramethy l ammonium bromide at different t emp eratures. It is well known that the mixed aqueous solvents (with different p ercent w/w) can influence the solubility behavior of amino acids. Consequently thermody namic p rop erties, enthalpies, heat cap acities, app arent molal volumes and viscosities of amino acids and peptide in mixed aqueous solvents are useful to obt ain information about various ty p es of interactions in these solutions [5-6]. Serine (abbreviated as Ser or S) [7], is an amino acid with t he formula HO2CCH(NH2)CH2OH.. It is one of the p roteinogenic amino acids. By virtue of the hy droxy l group , serine is classified as a polar amino acid. Patel and workers [8] demonst rate the interaction of some amino acids(L-serine, L- threonime, L-glutamine, L-ly sine, L-arginine and L-hist idine) in aqueous caffeine they got p ositive values of p artial molal volume of transfer of amino acid from water to aqueous- مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 caffeine v o (tr) ( v o,caffeine- v o,water) which indicate the diminishing of electrost rictive effect of amino acids and addition of caffeine. They related the diminishing to shielding of the amino acids z witterionic group s from water. The p artial molar volumes of tranfere v o(tr) of amino acids from aqueous to aqueous tetramethy l ammonium bromide solution were interp reted in the light of cosp here overlap model. The cosp here overlap model [9] can be used for interp retation of negative v o(tr) values, according to which the overlap of two hy dration sp heres is dest ructive. HO - CH2 - C - COO NH3 H CH3 CH3 S O Serine (Ser) M= 105.1 g.mol -1 Dimethyl sulfoxide (DMSO) M=78.13 g.mol -1 In p resent work viscosities  and densities  of serine (0.1, 0.15, 0.20, 0.25, 0.30 and 0.35 molar concentration) were measured in 20, 40 and 60% (w/w) DM SO + water mixtures at 298.15, 303.15 and 308.15k. Then the app arent molal volumes v  , limiting molal volumes at infinite dilution v o, transfer volumes at infinite dilution v o(tr) and Jones-Dole coefficients B and D were calculated. Experimental Amino acid serine obt ained from Fluka comp any is Analar and used wit hout any furt her t reat ment . Dimet hy l sulfoxide (DMSO) is apro t ic polar liquid wit h a high dielect ric const ant obtained from Fluka co mp any (purit y >99.7%) used wit ho ut further purificat ion . Wat er used for pr eparat ion for all t he solut ion doubly distilled (Sp.conduct ivit y ~10 -6 ohm - 1 cm -1 ). T he serin e co ncent rat ion in t hese mixt ures was ranged from ( 0.1-0 .35) mo l.dm -3 .The viscosity  were determined using a susp ended-level ubbelohde viscometer described by findly [10], in a bath controlled to ±0.01K for all measurements. Densities  of all solutions were measured using a vibrating tube with digital Ant on Parr densimeter (DM A 60/602) according to shuklu etal. Procedure[11], in athermostated bath controlled to ±0.01K. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 . Re sults and Discussion The results of absolute viscosities  and densities  are list ed in table 1. The app arent molal volume v  of serine in aqueous dimethy l sulfoxide (DM SO+H2O) is measured at 298.15, 303.15 and 308.15K using the following relation [12]. 3 31 10 10 [ ] .............(1)v m M m       o Where  and o are the densities of solution and solvent resp ectively, M is molecular weight of solute and m is the molality of solution. m is calculated using the following relation m=1/(P/C –M /10 3 )where C is the molar concentration. The results of v  are tabulated in table (1). Table (1) shows that the value of v  decrease with the increase of concentration of serine but v  increases with increasing DM SO% content and temp erature increase in solution suggesting that the solute-solvent interaction increase with t he increase of DM SO%. Since the limting app arent molal voiume v  were obtained from the realation [13]. v v= .............(2 )vS m   o Where the intercep t v o, which is measure of solute-solvent interaction, and the exp erimental slop v S , which is aparameter of solute-solte interaction were obtained by the molality fitt ing of v  values to eqution(2)in figure(1) and tabulated in table(2). Table 2 reveals that v oare p ositive and increase with the increase of temp erature, indicating the p resence of solute-solvent interactions. The increase in v oon going from 20% to 60% DM SO indicates t he increasing trends of solute-solvent interaction. Table 2 shows that all the values of v S are negative p ointing the p resence of weak solute-solute interactions in solutions. M oreover, the values of v S become more negative with the increase of DM SO content suggesting decreasing in solute-solute interaction with DM SO-rich solvent. In fact negative v S values are often obtained in solvent of high dielectric const ant such as (DM SO + Water Solvent) [14]. The transfer volumes v o(tr) of serine when transferred from water to (DM SO+Water) mixture solution are found using this equation: v o(tr) = v o(DM SO + Water) - v o, water مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 The values of v o, water for serine are 68.07, 66.28 and 65.28 cm 3 .mol -1 at 298.15, 303.15 and 308.15K resp ectively which are est imated from our previous work[15]. The v o(tr) results are list ed in table (3). A p erusal of table 3 indicates that v o of serine in mixed liquids (DM SO+ Water) are lower than those in p ure water, v o(tr) values are negative for all solutions st udied. It is known that zwitterionic group s of amino acids induce a considerable concentration in volume of p erip heral solvent (water) due to electrost rictive effect ,which is diminished on addition of DM SO. Viscosity data were analy zed employing Jone-Dole equation [16]. ŋre l -1/ C =A+B C ………….(3) Where  and o are the viscosity of solution and solvent resp ectively, the Jones-Dole coefficient, A, reflects the effect of solute-solute interaction and B, is a measure of st ructural modifications induced by the solute-solvent interaction. The viscosity coefficient A and B were obtained from the intercep t and slop e of the plots ŋre l -1/ C against C . The values of A and B are list ed in table (2). Table (2) shows that the values of A-coefficient are negative whereas those of B-coefficients are p ositive, suggesting weak solute-solute and st rong solute- solvent interaction. The variation of B with T is depicted graphically in figure 1, revealed that the slop e ( /B T  ) is p ositive for serine in 20, 40 and 60% DM SO content in solution, serine in all solutions act as st ructure-breakers[17]. Conclusions, the values coefficient A and B sup p ort the behaviors of v S and v o(tr) which all suggest st ronger solute-solvent interactions as comp ared to solute-solute interactions. The p ositive ( /B T  ) values for all solutions which p ointed that t he serine acts as a structure-breaker when DM SO added to solutions. Re ferences 1. Frank, H.S. and Wen, W.Y.(1957) Ion-Solvent interaction strructual asp ects of ion-solvent interaction in aqueous solution asuqqested p icture of water st ructure. Discuss Faraday Soc., 24:133. 2. Ty rrell, H.J.V. and Kennerley, M . (1968)A, Viscosity B- coefficients between 5 o and 20 o for glycolamide, glycine, and N- methy latde glycines in aqueous solution. J. Chem. Soc 90: 2724. 3. Devine, W. and Lowe, B.M .( 1971)A, Ap p arent molar volumes and viscosity B- coefficients of same α-amino acids in aqueous solutions from 278.15K to 308.15K 2113 J. chem.. Soc.. 4. A Ali A. and Shahjahan, Z.(2008)Volumetric and viscomitrc behavior of some amino acids and thir group contribution in aqueous tetramethy l ammonium bromide at different temp eratures, p hy s. Chem. 222:1519. 5. Phangs , Aust. (1977) The viscosity of glycine and DL-alanine in dimethy l formamid- water mixtures at 298.15K, J. chem., 30:1605. 6. Prasad, K. P. and Ahluwalia, J. C. (1980)Biopolymers, Heat capacity changes and partial molal heat cap acities of some and tripeptides in water, 19:263. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 7. Λ "Nomencluture and Sy mbolism for amino acids and p eptides (IUPAC-IUB Recommendations 1983)" Pure Ap p l. Chem., 56(5): 595-624, 1984. 8. Ali, A.; Sabir, S.; Nain, A.K.; Hgder, S.;Ahmed, S.;Tariq, M . and Patel, R. (2007) J. Chin. Chem. Soc., Interaction of p henylalanine , ty rosine and hitadine in aqueous caffeine solution at different t emp eratures, 54:659. 9. Friedman, H.L.; Krishnan, C.V.(1973)Water-Acomp rehensive Treatise. F. Franks (Ed.), Plenump ress, New York, 10. Findly, A. " Practical Phy sical Chemistry ", 8 th ed., J. A. Kitchrer (London: Longman), 1954. 11. James, A. M . and Prichard ,E. F. (1974) Practical p hy sical chemistry , Wiley , New York. 12. Pal, A. and Kumar, S. ( 2005) Volumetric st udies of some amino acids in binary aqueous solution of M gCl2.6H2O at 288.15 and 308.15K, T. Chem. Soc. 117 (3):267. 13. Hedwig, G.R. and Reading, J.(1991) Faraday Trans, Aqueous solutions containing amino acids and p eptides p art 27-p artial molar heat capacities and partial molar volumes of some N-acety l amino acids amides and tow p eptides at 25 o C, J. Chem. Soc. 87:1751. 14. Ali, A, ;Nain, A.K.; Kumar, N. and Ibrahim, M .(2002)Densities viscosities of magnesium sulp hate in formamide+ethy lene glycol mixed solvents, Proc. Indian Acad. Sci. (Chem. Sci.) 114:495. 15. AL-Dulaimy, Z. A. H.;AL-Jawary , A. A.; AL- Saidi, S. F.(2009) Viscosity and volumetric st udies of amino acids in solution at different temp eratures, J. of Kerbala University 7:289-295 . 16. Jones, G.and Dole, M .(1929) The viscosity of aqueous solutions of st rong electrolytes with sp ecial reference of st rong electrolytes with sp ecial reference to barium chloride, J. AM . Chem. Soc., 51:2950. 17. Ali, A.; Hy der, S.; Sabir, S.; Chand, D.and Nain, A. K.(2006) Thermody n., Volumatric, viscometric and refractive index behavior of α-amino acids and their group s , contribution in aqueous D-glucose solution at different t emp eratures J. Chem..38:136. مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Table(2): Partial molal volume at infi ni te diluti on v o, v S , Jone s-Dole coeffi cie nts A and B of serine in various water + DMS O mixtures at different temperatures. 298.15k 303.15k 308.15k Solu. Ser. + H2O + 20 % DMSO v o cm3.mol-1 59.41 58.803 59.925 v S cm3.mol-2kg -7 .0466 -8 .586 -1 0.482 A L 1/2 .mol -1/2 -0 .3308 -0 .3374 -0 .3455 B L.m ol -1 1.5051 1.5296 1.5900 Solu. Ser. + H2O + 40 % DMSO v o cm3.mol-1 61.193 62.401 63.727 v S cm3.mol-2kg -1 0.606 -1 0.636 -1 1.306 A L 1/2 .mol -1/2 -0 .3152 -0 .3421 -0 .3653 B L.m ol -1 2.3072 2.6084 2.9695 Solu. Ser. + H2O + 60 % DMSO v o cm3.mol-1 64.131 65.121 65.259 v S cm3.mol-2kg -1 1.508 -1 2.028 -1 2.441 A L 1/2 .mol -1/2 -0 .3270 -0 .3631 -0 .3927 B L.m ol -1 0.4727 2.9637 3.1620 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Table(3): Partial molal volume s of transfer at infini te diluti on v o(tr) of se rine from water to mixe d liqui d (DMS O + Water) at different temperatures. ( ) v tro (cm3. mMol-1) Serin e in mixed liquid (DMSO + W at er) 298.15k 303.15k 308.15k 20 % DMSO -8 .660 -7 .477 -5 .355 40 % DMSO -6 .877 -3 .879 -1 .553 60 % DMSO -3 .930 -1 .159 -0 .021 20% DMSO 56 56.5 57 57.5 58 58.5 59 59.5 0 0.1 0.2 0.3 0.4 298.15 303.15 308.15 40% DMS O 57 58 59 60 61 62 63 0 0.1 0.2 0.3 0.4 m 298.15 303.15 308.15 V V m مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 60% DMSO 60 61 62 63 64 65 66 0 0.1 0.2 0.3 0.4 m 298.15 303.15 308.15 Against m for se rine in variou s wate r+DMSO mix tu re at di fferen t V Fig.(1): tem pe rature Fi g. (2 ): B-coe fficient ve rses T for seri ne in vari ous wate r +DMSO mixtu res 0 0.5 1 1.5 2 2.5 296 298 300 302 304 306 308 310 T B 20%DMSO 40%DMSO 60%DMSO V مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 دراسة لزوجیة وكثافة الحامض االمیني سیرین في المحلول المائي لداي مثیل سلفوكساید بدرجات حراریة مختلفة زینة حمودي حسین ، رقیة سمیر الخالصي ، زینب وجدي العامل ، زینب عباس الدلیمي بغداد جامعة، أبن الھیثم –كلیة التربیة ، قسم الكیمیاء 2011 تشرین الثاني 10: قبل البحث في 2011 آب23: استلم البحث في الخالصة (w/w)% 60، % 40، %20 محالیل الحامض االمیني سیرین في محالیل لتركیـز  ولزوجة قیست كثافة DMلداي مثیل مثیل سلفوكساید SO كلفن استخدمت هـذه النتـائج 298.15 , 303.15 , 308.15 بدرجات حراریة مختلفة حجـــم المــواللي الظـــاهري فــي حــساب ال v  والحجــم المــواللي الظـــاهري المحــدد v o والمیـــل v S حجــم االنتقــال (tr), v o .B , Aومعاملي جونس ودول مذاب وقد اظهرت النتائج ان السیرین یـسلك سـلوك - مذیب ومذاب-تمت مناقشة طبیعة التداخالت من نوع مذاب . سلفوكسایدمهدم للتركیب في المحالیل المائیة لداي مثیل . داي مثل سلفوكساید، السیرین، الحوامض االمینیة، اللزوجة، الكثافة:الكلمات المفتاحیة مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 Tabl e (1): Densities (ρ) an d Viscosi ties (η) with calculate d apparent molal volu me ( v  ), and the (ŋrel -1/ C ) of se rine i n wate r at different pe rcen t (w/w) of di meth yl sulfoxi de mixtures at di ffe ren t tempe ratures . 20% 40% C mol.d m - 3 C m mol.kg- 1 ρ g.cm -3 η cp v  cm 3 .mol - 1 ŋ rel - 1/ C m mol.kg - 1 ρ g.cm -3 η cp v  cm3.mol- 1 ŋ rel - 1/ C m mol.kg 1 0.00 0.0000 1.0582 1.0838 0.0000 1.0595 1.1203 0.0000 0.1 0.3162 0.0950 1.0625 1.1403 58.6604 0.1642 0.0949 1.0636 1.2789 60.4768 0.4477 0.0929 0.15 0.3873 0.1430 1.0647 1.1820 58.3692 0.2339 0.1428 1.0658 1.3658 59.5420 0.5658 0.1419 0.2 0.4472 0.1912 1.0669 1.2433 58.2064 0.3291 0.1910 1.0680 1.4655 59.0794 0.6890 0.1898 0.25 0.5000 0.2397 1.0692 1.3125 57.7382 0.4220 0.2394 1.0703 1.5786 58.4142 0.8182 0.2378 0.3 0.5477 0.2886 1.0715 1.3819 57.4413 0.5022 0.2884 1.0726 1.6911 57.9882 0.9303 0.2863 0.35 0.5916 0.3374 1.0739 1.4450 56.9198 0.5633 0.3372 1.0748 1.8459 57.9407 1.0948 0.3350 298.15k 0.00 0.0000 1.0556 0.9889 0.0000 1.0546 1.0698 0.0000 0.1 0.3162 0.0953 1.0599 1.0365 58.8323 0.1522 0.0954 1.0586 1.2459 61.7253 1.6461 0.0950 0.15 0.3873 0.1435 1.0621 1.0877 58.5618 0.2579 0.1435 1.0608 1.3374 60.4553 1.6676 0.1430 0.2 0.4472 0.1917 1.0643 1.1365 58.3551 0.3337 0.1919 1.0629 1.4504 60.2946 1.7788 0.1913 مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012 0.25 0.5000 0.2403 1.0666 1.1977 57.8808 0.4228 0.2407 1.0651 1.5742 59.8395 1.8859 0.2399 0.3 0.5477 0.2891 1.0690 1.2610 57.2409 0.5024 0.2896 1.0673 1.7064 59.5111 1.9835 0.2888 0.35 0.5916 0.3383 1.0714 1.3250 56.8013 0.5744 0.3389 1.0697 1.8503 58.7552 2.0845 0.3379 303.15k 0.00 0.0000 1.0530 0.9869 0.0000 1.0533 1.0289 0.0000 0.1 0.3162 0.0955 1.0573 1.0360 58.9617 0.1520 0.0955 1.0572 1.2243 62.7404 1.8991 0.0952 0.15 0.3873 0.1437 1.0595 1.0901 58.6584 0.2699 0.1437 1.0593 1.3375 61.7946 1.9995 0.1433 0.2 0.4472 0.1922 1.0619 1.1499 57.5616 0.3693 0.1922 1.0614 1.4610 61.3237 2.0998 0.1917 0.25 0.5000 0.2409 1.0642 1.2064 57.2710 0.4448 0.2410 1.0635 1.5947 61.0424 2.1996 0.2403 0.3 0.5477 0.2893 1.0665 1.2699 57.0667 0.5236 0.2901 1.0656 1.7388 60.8546 2.2997 0.2893 0.35 0.5916 0.3391 1.0690 1.3360 56.3999 0.5979 0.3394 1.0682 1.8931 59.3639 2.3997 0.3389 308.15k مجلة إبن الھیثم للعلوم الصرفة و التطبیقیة 2012 السنة 25 المجلد 1 العدد Ibn A l-Haitham Journal f or Pure and Applied Science No. 1 Vol. 25 Year 2012