Supporting Information - Wayne State University

Supporting Information

Structural Features of Europium(II)-Containing Cryptates ThatInfluence Relaxivity

Chamika U. Lenora,[a] Fabio Carniato,[b] Yimin Shen,[c] Zahid Latif,[c, d] E. Mark Haacke,[c, d]

Philip D. Martin,[e] Mauro Botta,*[b] and Matthew J. Allen*[a, d]

chem_201702158_sm_miscellaneous_information.pdf

http://orcid.org/0000-0003-4192-355X

http://orcid.org/0000-0003-4192-355X

http://orcid.org/0000-0002-6868-8759

http://orcid.org/0000-0002-6868-8759

http://orcid.org/0000-0002-6868-8759

Lenora et al. Supporting Information

S1

Page Contents

S1 Table of Contents

S2 Metal complex formation

S3 ICP–MS data and stability studies

S4 Aggregation studies

S5–S6 Dynamic light scattering and 17O-NMR data

S7–S8 Relaxivity data and EPR data

S9 Temperature dependence of proton relaxivity

S10 Contributions of τR, τM, and T1e to τC

S10 Change in relaxivity as a function of τR

S11−S13 Crystallography data

S14−S17 1H- and 13C-NMR spectra


S2

Metal complex formation

Figure S1. Water proton relaxation rates (R1obs) of aqueous solutions of EuCl2 (1 mM) upon addition of different concentrations of the ligand of complex 1 at 37 oC. Error bars represent the standard error of the mean of three independently prepared samples.

Figure S2. Water proton relaxation rates (R1obs) of aqueous solutions of EuCl2 (1 mM) upon addition of different concentrations of the ligand of complex 2 at 37 oC. Error bars represent the standard error of the mean of four independently prepared samples.


S3

ICP–MS data and stability studies

Table S1. ICP–MS data from the study of the formation of complex 3

Ligand to metal ratio

[Ligand] / mM [Eu] before metalation / mM

[Eu] after metalation / mM

1:1 3.0 3.00 2.73 ± 0.03

1:2 3.0 6.00 2.77 ± 0.03

Figure S3. Relaxivity (60 MHz, 37 oC) of complex 2 in PBS with time. Error bars represent the standard error of the mean of three independently prepared samples.


S4

Aggregation studies.

In the region above the inflection point (ic), the relaxation rate is conveniently expressed as the sum of two contributions, one attributable to the monomeric complex (present in solution at the concentration corresponding to the ic) and the second assigned to the aggregate. The relaxation rate of the paramagnetic system can be expressed as in equation S1, where r1

n.a. and r1a are the

proton relaxivities of the non-aggregated and aggregated forms, respectively; R1d corresponds to

the relaxation rate of pure water (0.38 s–1 at 60 MHz and 298 K); and C is the concentration of EuII:

R1obs – R1

d = (r1n.a. – r1

a)ic + r1a C (S1)

The relaxivity of the monomeric, isolated complex, r1n.a., is described by equation S2:

R1obs – R1

d = r1n.a.C (S2)

By plotting R1obs – R1

d as a function of C, values of ic, r1n.a., and r1

a can be obtained by fitting equations S1 and S2.*

* B.C. Webber, C. Cassino, M. Botta, M. Woods, Inorg. Chem. 2015, 54, 2085-2087.


S5

Dynamic light scattering and 17O-NMR data

Figure S4. Intensity percent vs size of complex 3.

17O-NMR data

Table S2. 17O-NMR data for a solution of complex 1 (5 mM in phosphate-buffered saline) and phosphate-buffered saline (pH = 7.4)

Temperature / oC Linewidth / Hz

1 Phosphate-buffered saline

50 47 42

45 53 48

40 60 54

35 70 63

30 82 74

25 100 87

20 121 106


S6

Table S3. 17O-NMR data for a solution of complex 2 (5 mM in phosphate-buffered saline) and phosphate-buffered saline (pH = 7.4)



50 37 30

45 45 34

40 57 41

35 75 52

30 105 71

25 154 102

20 183 126

Table S4. 17O-NMR data for a solution of complex 3 (1.2 mM in phosphate-buffered saline) and phosphate-buffered saline (pH = 7.4)



50 50 43

45 57 48

40 65 55

35 75 64

30 92 75

25 104 89

20 122 107


S7

Relaxivity and EPR data

Table S5. Relaxivity (mM−1 s−1) data at different field strengths.*

Complex 3 T** 7 T** 9.4 T*** 11.7 T***

1 3.8 ± 0.2 4.7 ± 0.5 3.6 ± 0.5 3.2 ± 0.5

2 4.8 ± 0.3 5.7 ± 0.3 4.24 ± 0.01 3.84 ± 0.03

3 6.3 ± 0.2 6.8 ± 0.1 5.6 ± 0.1 4.69 ± 0.07

3/β-CD 10.2 ± 0.4 8.6 ± 0.4 6.7 ± 0.6 6.0 ± 0.3

3/poly-β-CD 12.9 ± 0.3 11.2 ± 0.6 7.85 ± 0.04 6.9 ± 0.3

3/HSA 5.8 ± 0.3 5.5 ± 0.1 4.5 ± 0.3 3.8 ± 0.1

*Errors represent the standard error of the mean of three independently prepared samples; **data obtained at 22 oC; ***data obtained at 25 oC.

EPR data

Figure S5. EPR spectrum of 3/β-CD in phosphate-buffered saline at 110 K under an atmosphere of N2.


S8

Figure S6 EPR spectrum of 3/poly-β-CD in phosphate-buffered saline at 110 K under an atmosphere of N2.


S9

Temperature dependence of proton relaxivity

Figure S7: Temperature dependence of proton relaxivity (9.4 T, pH = 7.4) of (a) 3/β-CD, (b) 3/poly-β-CD, and (c) 3/HSA. Error bars represent the standard error of the mean of three independently prepared samples.


S10

Contributions of τR, τM, and T1e to τC

Figure S8: Contributions of exchange, rotation, and electronic relaxation to the overall correlation time for complex 3 at different field strengths.

Change in relaxivity as a function of τR

Figure S9: Relaxivity of 1 (□), 2 (◊), 3 (■), 3/β-CD (▲), 3/poly-β-CD (●), and 3/HSA (○) at 0.47 T as a function of global rotational correlation times.

0

4

8

12

20 120 300

1/τC /ns–1

Proton Larmor Frequency / MHz

1/τM

1/τRG

1/T1e


S11

Crystallography data

Table S6. Crystallographic properties of 1

Chemical formula C18H36Cl2EuN2O7

Formula weight 615.35

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 11.044(12) Å, α = 90o

b = 13.3244(15) Å, β = 90.199(7)o

c = 16.1349 (18) Å, γ = 90o

Volume 2387.3(5) Å

Z 4

Density (calculated) 1.712 g cm−3

Absorption coefficient)

F(000)

2.891 mm−1

1244


S12

Table S7. Crystallographic properties of 2

Chemical formula C22H40Cl2EuN3O6

Formula weight 665.43

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 8.2489(5) Å, α = 90o

b = 18.1828(13) Å, β = 90.705(3)o

c = 17.2906(12) Å, γ = 90o

Volume 2593.2(3) Å3

Z 4

Density (calculated) 1.704 g cm−3

Absorption coefficient) 2.667 mm−1

F(000) 1352


S13

Table S8. Important bond lengths and bond angles for complexes 1.

Bond lengths (Å) Bond angles (°) Eu1–O5 2.659(3) Eu1–O4 2.681(3) Eu1–O1 2.701(3) Eu1–Cl1 2.8365(8) Eu1–N3 2.859(3) Eu1–O2 2.678(3) Eu1–O6 2.687(3) Eu1–O3 2.708(3) Eu1–N1 2.838(3)

O5–Eu1–O2 58.75(9) O2–Eu1–O4 175.75(10) O2–Eu1–O6 120.32(9) O5–Eu1–O1 103.61(10) O4–Eu1–O1 107.07(10) O5–Eu1–O3 74.19(11) O4–Eu1–O3 78.53(10) O1–Eu1–O3 62.63(8) O2–Eu1–Cl1 88.78(8) O6–Eu1–Cl1 91.35(7) O5–Eu1–O4 122.45(9) O5–Eu1–O6 178.89(9) O4–Eu1–O6 58.52(9) O2–Eu1–O1 75.99(11)

Table S9. Important bond lengths and bond angles for complex 2.

Bond lengths (Å) Bond angles (°) Eu1–O2 2.6735(7) Eu1–O7 2.6961(7) Eu1–O3 2.7503(7) Eu1–Cl1 2.7884(3) Eu1–N2 2.8051(8) Eu1–O1 2.6804(7) Eu1–O5 2.6981(7) Eu1–O4 2.7593(7) Eu1–N3 2.7998(8)

O2–Eu1–O1 62.44(2) O1–Eu1–O7 81.11(2) O1–Eu1–O5 110.10(2) O2–Eu1–O3 75.14(2) O7–Eu1–O3 179.15(2) O2–Eu1–O4 107.15(2) O7–Eu1–O4 124.18(2) O3–Eu1–O4 55.80(2) O1–Eu1–N3 123.82(2) O5–Eu1–N3 60.17(2) O4–Eu1–N3 117.56(2) O2–Eu1–N2 123.55(2) O7–Eu1–N2 63.37(2) O3–Eu1–N2 116.65(2)


S14

1H- and 13C-NMR spectra

O

O

O

O

OCH3

OCH3

4

CL-111-45-bpester-1-23-15-13C

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

Chemical shift (ppm)

CL-III-11-bpester-12-17-14

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0



S15

O

O

O

O

OH

OH

5

CL-III-43-bpacid-12-18-14

10 9 8 7 6 5 4 3 2 1

Chemical shift (ppm) CL-III-43-bpacid-12-17-14-13C-2

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0



S16

CL-V-20-BPdiamide-13C-5hrs-8-17-16

220 200 180 160 140 120 100 80 60 40 20 0 -20


CL-III-43-bpdiamide-1H-1-1-15.esp-integrated and assigned.esp

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5


N

N

O

O

O

O

O

O

O

O

6


S17

N

N

O

O

O

O

O

O

7

Supporting Information - Wayne State University

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