SUPPORTING INFORMATION
Novel pyrrolo-quinazolino-quinoline analogues of the natural alkaloids and their inclusion molecular complexes in the native cyclodextrins – experimental vs. theoretical study
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Table S1. The dihedral angles f1 – f4 (Scheme 1) of the synthesised CPTs 14-Aza-(i) and Luot-A-(i) (i = 1 – 5) as well as in the molecular complexes xCD-14-Aza-(i) and xCD-Luot-A-(i) (x = a, b or g; i = 1 – 5); The angles are given in [o].
14-Aza-CPT-(1) / Luot-A-(1) / 14-Aza-CPT-(2) / Luot-A-(2) / 14-Aza-CPT-(3) / Luot-A-(3) / 14-Aza-CPT-(4) / Luot-A-(4) / 14-Aza-CPT-(5) / Luot-A-(5)f1 / 36.3(8) / 10.0(2) / 34.9(5) / 12.4(4) / 35.((0) / 12.9(7) / 35.8(9) / 14.2(2) / 34.6(7) / 20.1(3)
f2 / - / - / 65.3(8) / 47.0(2) / 66.2(5) / 47.8(9) / 65.4(3) / 55.5(3) / 65.4(3) / 170.2(2)
f3 / - / - / - / - / - / - / - / - / 178.5(1) / 179.1(5)
f4 / - / - / - / - / - / - / - / - / 176.4(2) / 178.5(6)
aCD-14-Aza-CPT-(1) / aCD-14-Aza-CPT-(2) / aCD-14-Aza-CPT-(3) / aCD-14-Aza-CPT-(4) / aCD-14-Aza-CPT-(5)
f1 / 63.8(0) / 101.5(7) / 101.3(2) / 102.4(8) / 108.1(9)
f2 / - / 73.2(5) / 77.9(7) / 62.2(1) / 52.9(7)
f3 / - / - / - / - / 159.8(4)
f4 / - / - / - / - / 65.8(9)
aCD-Luot-A-(1) / aCD-Luot-A-(2) / aCD-Luot-A-(3) / aCD-Luot-A-(4) / aCD-Luot-A-(5)
f1 / 27.8(1) / 29.7(7) / 29.6(3) / 30.7(2) / 29.5(6)
f2 / - / 58.8(1) / 59.5(2) / 67.0(1) / 57.3(3)
f3 / - / - / - / - / 174.3(2)
f4 / - / - / - / - / 64.3(2)
bCD-14-Aza-CPT-(1) / bCD-14-Aza-CPT-(2) / bCD-14-Aza-CPT-(3) / bCD-14-Aza-CPT-(4) / bCD-14-Aza-CPT-(5)
f1 / 32.4(5) / 32.2(7) / 34.4(6) / 33.8(2) / 33.0(1)
f2 / - / 64.1(3) / 44.9(0) / 43.2(9) / 93.3(3)
f3 / - / - / - / - / 164.1(0)
f4 / - / - / - / - / 89.6(1)
bCD-Luot-A-(1) / bCD-Luot-A-(2) / bCD-Luot-A-(3) / bCD-Luot-A-(4) / bCD-Luot-A-(5)
f1 / 10.1(4) / 11.4(8) / 12.7(2) / 33.8(6) / 6.0(8)
f2 / - / 52.6(3) / 53.8(5) / 43.2(4) / 60.9(2)
f3 / - / - / - / - / 157.7(1)
f4 / - / - / - / - / 125.8(3)
gCD-14-Aza-CPT-(1) / gCD-14-Aza-CPT-(2) / gCD-14-Aza-CPT-(3) / gCD-14-Aza-CPT-(4) / gCD-14-Aza-CPT-(5)
f1 / 18.9(2) / 16.1(5) / 17.2(5) / 16.8(3) / 15.6(2)
f2 / - / 35.7(0) / 41.3(2) / 78.9(5) / 76.3(1)
f3 / - / - / - / - / 170.4(3)
f4 / - / - / - / - / 60.1(0)
gCD-Luot-A-(1) / gCD-Luot-A-(2) / gCD-Luot-A-(3) / gCD-Luot-A-(4) / gCD-Luot-A-(5)
f1 / 7.0(1) / 4.8(0) / 4.1 / 4.0(2) / 4.9(3)
f2 / - / 66.4(5) / 69.8(7) / 65.6(0) / 48.1
f3 / - / - / - / - / 135.7(1)
f4 / - / - / - / - / 56.9
Table S2. The free Gibbs energie (DG) [kcal/mol] for the studied molecular complexes
-131.6489 / -152.6111 / -154.3185 / -150.008 / -147.3652
aCD-Luot-A-(1) / aCD-Luot-A-(2) / aCD-Luot-A-(3) / aCD-Luot-A-(4) / aCD-Luot-A-(5)
-132.4528 / -134.0004 / -135.5180 / -135.1564 / -132.1779
bCD-14-Aza-CPT-(1) / bCD-14-Aza-CPT-(2) / bCD-14-Aza-CPT-(3) / bCD-14-Aza-CPT-(4) / bCD-14-Aza-CPT-(5)
-135.9165 / -135.9555 / -146.2116 / -147.6067 / -147.600
bCD-Luot-A-(1) / bCD-Luot-A-(2) / bCD-Luot-A-(3) / bCD-Luot-A-(4) / bCD-Luot-A-(5)
-123.6404 / -130.9295 / -132.1768 / -132.7121 / -126.6068
gCD-14-Aza-CPT-(1) / gCD-14-Aza-CPT-(2) / gCD-14-Aza-CPT-(3) / gCD-14-Aza-CPT-(4) / gCD-14-Aza-CPT-(5)
-137.6075 / -137.6871 / -139.3696 / -139.1983 / -131.7304
gCD-Luot-A-(1) / gCD-Luot-A-(2) / gCD-Luot-A-(3) / gCD-Luot-A-(4) / gCD-Luot-A-(5)
-126.8881 / -134.5404 / -136.5022 / -137.9068 / -125.9757
(a) / (b)
/ Figure S1. Electronic absorption spectra (EAs) in solvent mixture methanol:acetonitrile 1:1 (a) of the gCD (1), bCD (2), gCD-14-Aza-CPT-(3) (3), gCD-14-Aza-CPT-(4) (4), and bCD-Laut-A-(4) (5); Curve-fitted EAs after the baseline correction, and non-linear multipeak Gaussian function fitting; A- total area under the curve from the baseline centre of the peak; w2 “sigma”, approximately 3.117 the FWHM; w/2 – is the standard deviation, respectively (b); CD-spectra solvent mixture methanol:water 1:1 (c) of ), gCD-14-Aza-CPT-(4) (1), and bCD-Laut-A-(5) (2) at different molar ratios of the cyclodextrins within 1:1–1:4 labeled with (a)-(d), respectively.
(c)
a-CD-14-Aza-CPT-(1) / a-CD-14-Aza-CPT-(2) / a-CD-14-Aza-CPT-(3) / a-CD-14-Aza-CPT-(4)
a-CD-Luot-A-(1) / a-CD-Luot-A-(2) / a-CD-Luot-A-(3) / a-CD-Luot-A-(4)
b-CD-14-Aza-CPT-(1) / b-CD-14-Aza-CPT-(2) / b-CD-14-Aza-CPT-(3) / b-CD-14-Aza-CPT-(4) / b-CD-Luot-A-(5)
b-CD-Luot-A-(1) / b-CD-Luot-A-(2) / b-CD-Luot-A-(3) / b-CD-Luot-A-(4)
g-CD-14-Aza-CPT-(1) / g-CD-14-Aza-CPT-(2) / g-CD-14-Aza-CPT-(3) / g-CD-14-Aza-CPT-(4) / g-CD-Luot-A-(5)
g-CD-Luot-A-(1) / g-CD-Luot-A-(2) / g-CD-Luot-A-(3) / g-CD-Luot-A-(4)
Scheme S1. Most stable conformers of the xCD-14-Aza-(i) and xCD-Luot-A-(i) (x = a, b or g; i = 1 – 5) molecular complexes, obtained at B3LYP/6-31++G(2d,2p) level of theory; Selected intermolecular hydrogen bonds [Å].
-132.4290 / gCD-14-Aza-CPT-(1)gCD-Luot-A-(1) / -136.6392 / -136.6355
(a) / (a) / (b)
Scheme S2. Conformers of the g-CD-14-Aza-(1) and g-CD-Luot-A-(1) molecular complexes, labeles as (a) and (b), close to the local minimum of the free energie showin in [kcal/mol], obtained at B3LYP/6-31++G(2d,2p) level of theory; Selected hydrogen bonds [Å].
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