S. Devouge et al. / Bioorg. Med. Chem. Lett. 15 (2005) 3252–3256
3255
Marchand-Brynaert, J. J. Polym. Sci., Part A: Polym.
Chem. 2002, 40, 770.
acknowledged. J.M.-B. is a senior research associate of
the Fonds National de la Recherche Scientifique
(FNRS, Belgium).
13. Procedure for the preparation of ATR crystal 8: a
solution of 4 (1.1 mg) in benzene (0.5 mL) was sprayed
onto the crystal 5 (5.2 cm · 2.0 cm). After solvent evap-
oration, half of the crystal surface was longitudinally
masked with a black paper and the other half surface was
irradiated during 2 h with three UV lamps of 8 W
(254 nm), placed at a distance of 7 cm. The crystal was
rinsed, under shaking, with chloroform (5 min) and
tetrahydrofuran (10 min). The resulting crystal 6 was
sprayed with a solution of amine 7 (6.2 mg) into benzene
(0.5 mL). After solvent evaporation, the crystal was left
in the dark for surface reaction (nucleophilic displace-
ment of the NHS ester) during 100 min at 20 ꢁC. Rinsing
with benzene (2 · 3 min), under shaking, gave crystal 8
(one half part) and the blank (non-irradiated half part)
for XPS analysis.
References and notes
1. (a) Zammatteo, N.; Hamels, S.; De Longueville, F.;
Alexandre, I.; Gala, J. L.; Brasseur, F.; Remacle, J.
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4385.
14. Calculation of the amount of fixed tag from the XPS data,
assuming that each octadecyl chain has fixed one molecule
4 to give crystal 6: theoretical atomic composition of the
organic layer of crystal 8: C18 + C19N2F6 = C37N2F6; thus,
F/C for 100% grafting of 7 = 0.1622. Experimental F/
C = 0.0704, corresponding to 43% of grafting.
15. (a) Marchand-Brynaert, J.; Detrait, E.; Noiset, O.; Boxus,
T.; Schneider, Y.-J.; Remacle, C. Biomaterials 1999, 20,
1773; (b) Biltresse, S.; Attolini, M.; Dive, G.; Cordi, A.;
Tucker, G. C.; Marchand-Brynaert, J. Bioorg. Med. Chem.
2004, 12, 5379; (c) Biltresse, S.; Attolini, M.; Marchand-
Brynaert, J. Biomaterials 2005, 26, 4576.
3. Kumar, P.; Agrawal, S. K.; Misra, A.; Gupta, K. C.
Bioorg. Med. Chem. Lett. 2004, 14, 1097, and references
cited therein.
4. (a) Deng, L.; Mrksich, M.; Whitesides, G. M. J. Am.
Chem. Soc. 1996, 118, 5136; (b) Liley, M.; Keller, T. A.;
Duschl, C.; Vogel, H. Langmuir 1997, 13, 4190; (c) Stefan,
I.; Schersom, D. Langmuir 2000, 16, 5945.
5. (a) Marchand-Brynaert, J. Recent Res. Dev. Polymer Sci.
1998, 2, 335; (b) Marchand-Brynaert, J. In Polymer
Surface Modification: Relevance to Adhesion; Mittal, K.
L., Ed.; VSP; 2000; Vol. 2, pp 281–303.
6. Bayley, H.; Knowles, J. R. Methods Enzymol. 1977, 46, 69.
7. Synthesis and characterisation of 4: in the dark, and under
argon atmosphere, to acid 38 (0.103 g, 0.5 mmol) in
CH2Cl2 (3 mL) were added successively N-hydroxy-
succinimide (0.111 g, 0.96 mmol), dimethylaminopyridine
(catalyst, 0.005 g), and then, dropwise, diisopropylcarbo-
diimide (0.153 mL, 0.98 mmol) in CH2Cl2 (2 mL), at 0 ꢁC,
under stirring. The mixture was stirred for 1 h at 0 ꢁC and
left overnight at 20 ꢁC. After filtration, washing with
0.05 N HCl (three times) and brine (three times), the
organic layer was dried over MgSO4 and concentrated.
Addition of ethyl acetate to the solid residue and storage
at À20 ꢁC allowed the remaining diisopropylurea to
crystallize. After filtration, the crude ester 4 was chro-
matographed (silica gel; EtOAc). Yield: 0.123 g (81%) as
white crystals. 1H NMR (200 MHz, CDCl3) d: 2.05 (quint,
J = 7.4 Hz, 2H), 2.60 (t, J = 7.4 Hz, 2H), 2.72 (t,
J = 7.4 Hz, 2H), 2.85 (s, 4H), 6.97 (d, J = 8.5 Hz, 2H),
7.20 (d, J = 8.5 Hz, 2H); 13C NMR (50 MHz, CDCl3) ppm
169.6, 168.9, 138.9, 138.1, 130.6, 119.9, 34.6, 30.8, 26.9,
26.3; IR (KBr) m 2944, 2111, 1814, 1785, 1739, 1507, 1368,
16. Salvagnini, C.; Marchand-Brynaert, J.; results to be
published elsewhere.
17. Procedure for the preparation of PBT membrane 9: we
used polybutylene terephthalate Meltblown, Goodfellow,
of 0.133 mm thickness and with a mean flow pore of 5 lm.
Polymer discs (13 mm of diameter) were individually
immersed into a solution of 4 (0.025 g) in acetonitrile
(10 mL) during 5 s. The so-wetted samples were air-dried
in the dark for 30 min. Both sides were then irradiated
during 10 min with three UV lamps of 8 W (254 nm)
placed at a distance of 7 cm. The samples were individ-
ually washed with acetonitrile (2 mL, 10 min, three times)
and air-dried. Blank 1 samples were similarly prepared but
without UV exposition. Blank 2 samples were exposed to
UV without any other treatment.
18. (a) Marchand-Brynaert, J. Surface Functionalization of
Polymer Membranes. In Surface Chemistry and Electro-
chemistry of Membranes; So¨rensen, T. S., Ed.; Marcel
Dekker: NY, 1999, pp 91–124; (b) Boxus, T.; Deldime-
Rubbens, M.; Mougenot, P.; Schneider, Y.-J.; Marchand-
Brynaert, J. Polym. Adv. Technol. 1996, 7, 589.
1289, 1206, 1068, 909, 732, 647 cmÀ1
.
19. Preparation of PBT membrane 11. Procedure A: activated
and blank samples were individually incubated for 2 h at
20 ꢁC with 1 mL of 10À3 M [3H]lysine in a phosphate
buffer (PBS)–CH3CN mixture (1:1); the stock-solution of
lysine was prepared as follows: 250 lL of 0.1 M unlabelled
lysine and 187.5 lL of labelled lysine at 37 MBq/mL in
25 mL PBS buffer (pH 7.2); the samples were washed
successively with PBS–CH3CN (1:1) (1 mL, 2 · 10 min),
water (1 mL, 2 · 5 min), 5 · 10À3 M HCl (1 mL,
2 · 5 min) and water (1 mL, 2 · 10 min). Procedure B:
activated and blank samples were individually incubated
for 12 h at 20 ꢁC with 1 mL of 10À4 M [3H]lysine in a
phosphate buffer (PBS)–CH3CN mixture (1:1); the stock
solution of lysine was prepared as follows: 25 lL of 0.1 M
unlabelled lysine and 18.75 lL of labelled lysine at
37 MBq/mL in 25 mL PBS buffer (pH 7.2). The samples
were washed successively with PBS–CH3CN (1:1) (1 mL,
3 · 10 min), water (1 mL, 2 · 5 min), 5 · 10À3 M HCl
8. Carnazzi, E.; Aumelas, A.; Barberis, C.; Guillon, G.;
Seyer, R. J. Med. Chem. 1994, 37, 1841.
9. Surface chemical modification of optical elements for the
spectroscopic detection of molecules and organic compo-
nents. Marchand-Brynaert J. et al. PCT WO 02/056018
A1, 2002.
10. (a) Sagiv, J. J. Am. Chem. Soc. 1980, 102, 92; (b) Mazao,
R.; Sagiv, J. J. Colloid Interface Sci. 1984, 100, 465; (c)
Duchet, J.; Chapert, B.; Chapel, J. P.; Gerard, J. F.;
Chovelon, J. M.; Jaffrezic-Renault, N. Langmuir 1997, 13,
2271; (d) Duchet, J.; Gerard, J. F.; Chapel, J. P.; Chapert,
B. Composite Interfaces 2001, 8, 177.
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(b) Houska, M.; Brynda, E.; Skvor, J.; Ramsden, J. J.
Biosens. Bioelectron. 1998, 13, 165.
12. (a) Biltresse, S.; Descamps, D.; Boxus, T.; Marchand-
Brynaert, J. J. Polym. Sci., Part A: Polym. Chem. 2000, 38,
3510; (b) Biltresse, S.; Descamps, D.; Henneuse-Boxus, C.;