(m, 3H), 2.93 (dd, J = 13.8, 4.6 Hz, 1H), 2.88 (dd, J = 13.9, 8.6
Hz, 1H), 2.67 (dd, J = 14.0, 9.0 Hz, 1H), 1.79 (s, 3H); 13C NMR
(126 MHz, DMSO-D6, 10% TFA-D) d 173.0, 171.2, 170.2, 168.6,
137.9, 137.8, 129.7, 129.5, 128.6, 128.4, 126.8, 126.6, 83.1, 73.9,
71.1, 70.9, 61.0, 54.3, 54.0, 53.8, 38.1, 37.0, 32.3, 22.7; ESI-MS:
Calculated for C28H35N3O9S: 589.21 Da [M+], Observed: 589.1 Da
[M+H].
2, 3, were also dissolved in DMSO at a concentration of 60 mM
then diluted in pure water at a concentration of 6 mM.
Transmission Electron Microscopy: After two hours and 24 h,
10 mL the nanostructures solutions were loaded on carbon coated
copper grid, dried and stained with uranyl acetate, followed by
imaging.
Scanning Electron Microscopy: After two hours and 24 h, 10
mL of the nanostructures solutions were deposited on slides, and
then coated with gold. SEM measurements were performed on a
JSM JEOL 6300 SEM operating at 5 kV.
S-a-glucopyranosyl-(1→3)-D-glucosamine diphenylalanine (5)
1H NMR (500 MHz, DMSO-D6, 10% TFA-D) d 8.35 (d, J =
7.8 Hz, 1H), 8.04 (d, J = 8.5 Hz, 1H), 7.63 (d, J = 6.9 Hz, 1H),
7.23–7.15 (m, 10H), 5.39 (d, J = 5.3 Hz, 1H), 4.49–4.45 (m, 1H),
4.39–4.33 (m, 2H), 3.91 (dt, J = 11.0, 5.6 Hz, 1H), 3.67–3.63 (m,
2H), 3.45 (dd, J = 11.9, 5.4 Hz, 1H), 3.33 (t, J = 9.5, 1H), 3.28–
3.24 (m, 1H), 3.17–3.13 (m, 1H), 3.12–2.88 (m, 9 H), 2.85 (dd, J =
Fourier Transform Infrared Spectroscopy: infrared spectra were
recorded using Nicolet Nexus 470 FT-IR spectrometer with DTGS
detector. Nanostructure solution sample were dried on polyethy-
lene card to form thin film. The nanostructures deposits were
resuspended with D2O and dried. The resuspension procedure
was repeated twice to ensure maximal hydrogen to deuterium
exchange. The measurements were taken using a 4 cm-1 resolution
and 1000 scans averaging. The transmittance minima values were
determined by OMNIC analysis program (Nicolet).
13.9, 8.9 Hz, 1H), 2.64 (dd, J = 13.8, 9.0 Hz, 1H), 1.75 (s, 3H); 13
C
NMR (126 MHz, DMSO-D6) d 171.6, 169.8, 168.8, 166.9, 136.5,
136.4, 128.2, 128.0, 127.1, 126.9, 125.4, 125.1, 101.5, 81.4, 79.2,
76.1, 75.4, 72.2, 68.9, 67.6, 60.0, 59.3, 52.6, 52.5, 51.3, 40.6, 36.6,
35.5, 30.6, 21.5; ESI-MS: Calculated for C34H45N3O14S: 751.80 Da
[M+], Observed: 751.2 Da [M+H].
Acknowledgements
The work was supported by the Edmond J. Safra Foundation
(A.B).
Synthesis of glycopeptide 6
Procedure for glycosylation of 11. Protected Neu5Ac-thiol
(309 mg, 0.56 mmol) was dissolved in DMF (1.17 mL) and was
added to the resin (230 mg, 0.30 mmol). To this, freshly distilled
diethylamine (350 mL, 3.37 mmol) was added, shaken for 5 h and
washed with DMF (¥3).
Notes and references
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0.5 M HCl was added dropwise to adjust the pH to 4. The reaction
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acetonitrile–water and HPLC purification as described above
afforded the glycopeptide 6.
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1H NMR (500 MHz, DMSO-D6, 10% TFA-D) d 8.40 (d, J =
2.8 Hz, 1H), 8.39 (d, J = 3.5 Hz, 1H), 8.13 (d, J = 7.8 Hz, 1H),
7.35–7.22 (m, 10H), 4.55 (dd, J = 9.9, 4.4 Hz, 1H), 4.49 (dd, J =
8.7, 5.4 Hz, 1H), 3.72–3.59 (m, 4H), 3.53–3.47 (m, 2H), 3.41 (dd,
J = 8.7, 1.7 Hz, 1H), 3.36–3.31 (m, 2H), 3.13 (dd, J = 13.9, 5.3 Hz,
1H), 3.03 (dd, J = 14.4, 4.8 Hz, 1H), 2.98 (dd, J = 14.0, 8.8 Hz, 1H),
2.78 (dd, J = 13.8, 9.8 Hz, 1H), 2.63 (dd, J = 12.5, 4.2 Hz, 1H),1.94
(d, J = 0.8 Hz, 3H), 1.67 (dd, J = 12.3, 10.9 Hz, 1H); 13C NMR
(126 MHz, DMSO-D6, 10% TFA-D) d 172.7, 171.9, 171.3, 171.1,
171.0, 167.0, 137.8, 137.5, 129.4, 129.3, 128.4, 128.2, 126.6, 126.4,
81.8, 76.1, 68.5, 62.9, 54.1, 53.9, 53.6, 53.5, 52.3, 52.2, 41.0, 37.5,
36.7, 32.7, 22.7; ESI-MS: Calculated for C31H39N3O12S: 677.72 Da
[M+], Observed: 678.1 Da [M+H].
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Nanostructure sample preparation and imaging
Nanostructure preparation: the lyophilized powder of each of the
synthesized glycopeptides, diphenylalanine 2, 3, 4, 5, 6, were dis-
solved in pure water at a concentration of 6 mM, diphenylalanine
2 was incubated at 40 ◦C for 30 min. Glycosylated diphenylalanine
11 M. Broncel, J. A. Falenski, S. C. Wagner, C. P. R. Hackenberger and B.
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5760 | Org. Biomol. Chem., 2011, 9, 5755–5761
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