Cristallographie de monocouches organiques: vers la ... · Introduction Analysis procedure Example: divalent cations Perspectives Cristallographie de monocouches organiques: vers

IntroductionAnalysis procedure

Example: divalent cationsPerspectives

Cristallographie de monocouches organiques: versla resolution atomique

Carry le Rouet, November 28 2005

Cristallographie de monocouches organiques






a

b

(a)

(1 1)-

(1 1)

(0 2)

SHELX 97

virtual axis

Area, Lorentz andpolarizationcorrections




Analysis Procedure I: (J. Phys. Chem. B 44, 22178 (2006))

Molecular model

Azimuth of the

chains




Analysis Procedure I:Phase S arachidic acid

.

Herringboneordering (α1 - α2 =90◦)

Heads and chainscoplanar




New phase, symmetryp2gm

Minimum of latticeenergy but never observed







































Analysis Procedure II: simulated annealing (Thin Solid Films 515,

5691 (2007))




L2 phase of myristic (C14) acid:

without kinks:

χ2 = 24.6

Kinks in the chain:

χ2 = 9.35

.

.

2 water molecules:

χ2 = 4.95





without kinks:

χ2 = 24.6

Kinks in the chain:

χ2 = 9.35

.

.

2 water molecules:

χ2 = 4.95





without kinks:

χ2 = 24.6

Kinks in the chain:

χ2 = 9.35

.

.

2 water molecules:

χ2 = 4.95




Crystalline Langmuir films with divalent cations

Cd2+, Pb2+, Mn2+, Mg 2+ → highly crystalline films at high pH, even for

concentrations � 10−3M (Leveiller et al. Science 1991, P. Dutta’s group)

Pure water

tilted molecules10−4mol .L−1 MnCl2pH 7.5




0.001

0.01

0.1

0 10 20 30 40 50

I [arb.]

Angle [degree]

Mn 0.14mM pH 7.5(45 ions / COO-)

Mg 0.019mM pH 10.5(20 ions / COO-)

(10)/(1-1) (0-1)

(2-1)

(20)/(2-2)

(02)

(3-1)(3-2)

(21)(2-3)

(12)/(1-3)

(4-2)(22)(2-4)

(40)(4-4)

(04)

(0-1)(1-1)

(1-2)/(20)

(02)

(1-3)(11)

(21)(2-3)

(2-2)

(2-1)(2-3)

(12)(1-4)

(20)(2-4)

(04)

1e-04

0.001

0 100 200 300 400 500 600 700 800 900 1000

I

Channel

acid

ions

ion superlattice

Mg2+ 2× 2

Mn2+ 2× 1

Cd2+ 2× 3

Pb2+ (14)

Kmetko et al., J. Phys. Chem. 2001




Mn2+

(a) (b)

(c) (d)




Air-water interface(below a lipid monolayer)

Streptavidin underbiotilynated lipidmonolayer

P.-F. Lenne et al.,

Biophysical Journal

79 496 (2000)




Solid-water interface

Annexin A5 (p6crystal) onmica-supportedDOPC

R.P. Richter et al.,

Biophysical Journal

89 3372 (2005)




Grazing incidence diffraction

2.5:1 DPPC Cholesterol bilayer (water/Si interface)ESRF, BM32, 27 keV

Coll. L. Leiserowitz (Weizmann), G. Fragneto (ILL)

J.D. et al., PNAS, 2005




J. PignatS. Cantin (Cergy-Pontoise)F. Perrot (Cergy-Pontoise)S. Mora (LCVN, Montpellier)O. Konovalov (ESRF)


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Cristallographie de monocouches organiques: vers la ... · Introduction Analysis procedure Example: divalent cations Perspectives Cristallographie de monocouches organiques: vers