solubility and solid phase studies of isomeric...
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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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