Solubility and Solid Phase Studies of Isomeric...
Transcript of Solubility and Solid Phase Studies of Isomeric...
Supporting Information
Solubility and Solid Phase Studies of Isomeric Phenolic Acids in Pure Solvents
Sérgio M. Vilas-Boasa,b,c, Paula Brandãod, Mónia A.R. Martinsa,b,d, Liliana P.
Silvad, Tatiana La Banca Schreinera,b, Luciano Fernandesc, Olga Ferreiraa,b,*,
Simão P. Pinhoa,b
aCentro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal
bLaboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Polytechnic Institute of Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal
cUTFPR- Departamento de Engenharia Química, Universidade Tecnológica Federal do Paraná, 84016-210 Ponta Grossa, Brazil
dCICECO − Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
*Corresponding author: Olga Ferreira
Telephone: +351 273 303 087
Fax: +351 273 313 051
E-mail: [email protected]
Table S1: Crystal data and refinement parameters of hydrated protocatechuic acid.
Parameter Protocatechuic AcidEmpirical Formula C14H16O10
Mw 344.27Crystal System Triclinic
Space group P 1a / [Å] 7.927(3)b / [Å] 8.058(3)c / [Å] 12.500(4)α / [º] 77.323(13) / [º] 72.847(13)γ / [º] 72.382(13)V [Å3] 719.7(4)
Z 2Dc [Mg m-3] 1.589 / [mm-1] 0.138
Reflections collected 25521Unique reflections, [Rint] 4453 [0.0459]
Final R indices
R1, wR2 [I>2I] 0.0457, 0.1144[3212]
R1, wR2 (all data) 0.0715, 0.1315
Table S2: Overview of the literature solubility data for the studied phenolic acids.
Solute Solvent Temperature range (K) Reference
gallic acid
water 273.15 – 363.15 Lu and Lu [1]
water 293.15 – 318.15 Noubigh et al. [2]
water 288 – 323 Mota et al. [3]
water, methanol, ethanol, and ethyl acetate 298.2 – 333.2 Daneshfar et al.
[4]
water and methanol 293.15 – 318.15 Noubigh et al. [5]
water, 1-propanol, 2- propanol and acetonitrile 293.15 – 318.15 Dali et al. [6]
water 298 - 343 Dabir ei al. [7]
protocatechuic acid
water 293.15 – 318.15 Noubigh et al. [2]
water 288 – 323 Queimada et al. [8]
water 298.75 – 415.85 Srinivas et al. [9]
methanol, ethanol, methyl acetate and ethyl acetate 293.15 – 318.15 Noubigh et al.
[10]
Temp Cel260.0250.0240.0230.0220.0210.0200.0
DSC
mW
0.000
-1.000
-2.000
-3.000
-4.000
-5.000
-6.000
DDSC
mW
/min
250.3Cel-5.243mW
284.8mJ/mg
249.1Cel-2.912mW
249.8Cel-4.287mW
251.9Cel-1.555mW
Temp Cel215.0210.0205.0200.0195.0190.0
DSC
mW
2.00
0.00
-2.00
-4.00
-6.00
-8.00
-10.00
-12.00
-14.00
DDSC
mW
/min
b)
a)
Temp Cel220.0215.0210.0205.0200.0195.0190.0185.0180.0
DSC
mW0.00
-2.00
-4.00
-6.00
-8.00
-10.00
-12.00
-14.00
-16.00
-18.00
DDSC
mW
/min
c)
Temp Cel245.0240.0235.0230.0225.0
DSC
mW
1.000
0.000
-1.000
-2.000
-3.000
-4.000
-5.000
-6.000
-7.000
-8.000
-9.000
DDSC
mW
/min
d)
Figure S1: Exemplificative DSC thermograms for: a) Gallic acid; b) Protocatechuic acid; c) Gentisic
Acid and d) α-Resorcylic acid.
Table S3: Characterization of the solid samples obtained from evaporating the solvent from the saturated
solutions.
Compound CCDC/ RefcodeSpace
Group/crystal Pattern
Z Solvate Reference
Gallic Acid
820132 Monoclinic, C2/c 8 Anhydrate [11]
811292 Monoclinic, C2/c 8 Anhydrate [12]
837396 Monoclinic, C2/c 8 Anhydrate [13]
927226 Monoclinic, C2/c 4 Anhydrate [14]
Protocatechuic Acid
764265 Monoclinic P21/c 4 Monohydrate[15]
764266 Triclinic P1 6 Anhydrate
Gentisic Acid747937-747942
and 747946-747948
Monoclinic P21/c 4 Anhydrate [16]
α-Resorcylic Acid
762467 Monoclinic Cc 4 Acetylacetone solvate monohydrate
[15]
764268 Monoclinic P21/c 4 1,4-dioxane solvate
764269 Monoclinic Cc 4 tetrahydrofuran solvate monohydrate
764270 Monoclinic, C2/c 4 Anhydrate
764271 Monoclinic, C2/c 24 Anhydrate
Figure S2: Experimental X–ray powder diffraction pattern of protocatechuic acid from supplier and the
powder pattern calculated from the single-crystal X-ray diffraction data.
Figure S3: Experimental X–ray powder diffraction pattern of gallic acid from supplier and the powder
pattern calculated from the single-crystal X-ray diffraction data (CCDC 927226)
Figure S4: Experimental X–ray powder diffraction pattern of resorcylic acid from supplier and the
powder pattern calculated from the single-crystal X-ray diffraction data of resorcylic acid with CCDC
number 764271.
Table S4: Sample ID of the crystals obtained from gravimetry.
Solute Solvent ID
Gallic acid
Water W3Methanol B3
2-Butanone I3Ethyl Acetate F3
DMF 2IR
Protocatechuic Acid
Water 5wrMethanol B5Methanol 4BR
2-Butanone I62-Butanone 5IR
Ethyl Acetate F6DMF l5
α-Resorcylic Acid
Water W12Methanol B12
2-Butanone I12Ethyl Acetate F12
DMF R13
a
b
Figure S5: (a) Molecular structure of I5 sample; (b) Hydrogen bonds between protocatechuic acid
molecules.
Figure S6: Experimental X–ray powder diffraction pattern of W3, B3, I3, F3 and 2lR samples and the
powder pattern of gallic acid from supplier.
Figure S7: Experimental X–ray powder diffraction pattern of I6, 5IR, 4BR samples and the powder
pattern calculated from the single-crystal X-ray diffraction data of protocatechuic acid with CCDC
number 764266 [15].
Figure S8: Experimental X–ray powder diffraction pattern of F6, B5, I5, 5wr samples, the powder
pattern calculated using the single-crystal X-ray diffraction data of protocatechuic acid from supplier and
the protocatechuic acid with CCDC 764265 for comparison (hydrate form identified by Sarma et al. [15].
Figure S9: Experimental X–ray powder diffraction pattern of W12, B12, I12, F12 and R13 samples and
the powder pattern of resorcylic acid from supplier.
295 300 305 310 3150.01
0.1
1 a1-Propanol Exp1-Propanol CalcDMF ExpDMF Calc
Temperature (K)
Mol
e Fr
actio
n So
lubi
lity
295 300 305 310 3150.01
0.1
1 b1-Propanol Exp1-Propanol CalcDMF ExpDMF Calc
Temperature (K)
Mol
e Fr
actio
n So
lubi
lity
295 300 305 310 3150.01
0.1
1 c1-Propanol Exp1-Propanol CalcDMF ExpDMF Calc
Temperature (K)
Mol
e Fr
actio
n So
lubi
lity
296 298 300 302 304 306 308 310 312 314 3160.01
0.1
1 d1-Propanol Exp1-Propanol CalcDMF ExpDMF Calc
Temperature (K)
Mol
e Fr
actio
n So
lubi
lity
Figure S10: Predicted solubility data obtained through NRTL-SAC for: (a) gallic acid, (b) protocatechuic
acid, (c) gentisic acid and (d) α-resorcylic acid.
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