(100 ml ꢀ 3). The organic layer at this stage tested negative for
peracids or peroxides. The chloroform layer was dried (MgSO4)
and reduced to a small volume and absorbed onto a short
(5 ꢀ 5 cm) silica column. Elution with CH2Cl2 and removal of
solvent affordedꢄ a residue that was purified by bulb-to-bulb
distillation (110 C, 0.5 mmHg), after discarding a short initial
fraction, to afford the desired product as a clear colourless liquid.
Yield 3.3 g (78%). Spectroscopic data were consistent with
reported by van As et al.30
H2O in volumetric flasks. The reaction mixtures were gently
warmed to effect complete dissolution of the ligands and diluted
to the appropriate concentration. Samples for SANS measure-
ments were made in a similar manner using D2O.
Small-angle neutron scattering (SANS)
Small-angle neutron scattering experiments were performed
either on (i) the fixed-geometry, time-of flight LOQ diffractom-
eter at the ISIS Spallation Neutron Source, Rutherford Appleton
Laboratory, Didcot, UK which spans a Q range (Q ¼ (4p/l)
2-Methyl-7-hydroxy-2,5-diazaheptadecane (40). To a solution
of 1,2-epoxydodecane (4.61 g, 25 mmol) in freshly distilled dry
ethanol (100 ml) was added N,N,-dimethylethylenediamine (22 g,
250 mmol, 10 equivalents). The reaction mixture was allowed to
stand at room temperature for 5 days. Solvent and excess N,N,-
dimethylethylenediamine were removed using a rotary evapo-
rator. The residue was purified twice by bulb-to-bulb distillation
ꢃ1
˚
sin(q/2)) 0.008 < Q < 0.25 A by using neutron wavelengths
˚
(l) spanning 2.2 to 10 A with a fixed sample-detector of 4.1 m or
(ii) on the D11 or D22 diffractometers at the ILL, Grenoble,
ꢃ1
˚
˚
which span a Q-range of 0.01 < Q < 0.25 A , (l ¼ 8 A) requiring
two or three separate instrument configurations (sample–
detector distances and collimation).
€
using a Kugelrohr apparatus to afford the desired product as
1
a white waxy solid. Yield 5.4 g (79%). H NMR (400 MHz,
Samples were contained in 2 mm path length, UV-spectro-
photometer grade, quartz cuvettes (Hellma, GmBh) and mounted
in aluminium holders on top of an enclosed, computer-
controlled, sample chamber. Sample volumes were around
0.6 cm3. All experiments were conducted at 25 ꢄC (unless
otherwise stated). Temperature control was achieved by using
a thermostatted circulating bath pumping fluid through the base
of the sample chamber, achieving a temperature stability of
ꢂ0.2 ꢄC. Experimental measuring times were approximately
40 min per sample.
CDCl3): d ¼ 0.82 (t, 3H, 6.6 Hz, -CH3), 1.12–1.43 (br m, 18H,
-(CH2)9-), 2.15 (s, 6H, NCH3), 2.36 (m, 3H, HCHN), 2.63
(m, 3H, HCHN), 3.52 (m, 1H, CHOH). 13C NMR (100 MHz,
CDCl3): d ¼ 13.12 (CH3), 21.68 (CH2), 24.76 (CH2), 28.33 (CH2),
28.61 (CH2), 28.79 (CH2), 28.86 (CH2), 33.72 (CH2), 44.33
(N-CH3), 45.88 (N-CH2), 54.58(N-CH2), 58.14(N-CH2), 68.47
(CH(OH)). HR-MS (ESI, MeCN–H2O) (m/z): calculated for
C16H36N2O + H+ (M + H+) 273.2900, found 273.2911.
All scattering data were (a) normalized for the sample trans-
mission, (b) background corrected using a quartz cell filled with
D2O, and (c) corrected for the linearity and efficiency of the
detector response using the instrument specific software package.
Ultimately, the model of the micelle adopted here is that of
a charged particle with an elliptical core–shell morphology and
therefore, the intensity of scattered radiation, I(Q), as a function
of the wave-vector, Q, is given by;
5,13-Bis-(2-hydroxydodecyl)-2,16-dimethyl-7,11-dihydroxy-2,5,13,16-
tetraaza-9-oxa-heptadecane (4a). To a solution of diglycidyl ether
(0.65 g, 5 mmol) in ethanol was added 40 (3.40 g, 12.5 mmol, 2.5
equivalents). The reaction mixture was allowed to stand at room
temperature for 14 days. The solvent was removed using a rotary
evaporator and the excess starting material was separated by
bulb-to-bulb distillation (oven temp 170 ꢄC, 0.05 mmHg) to
afford the desired product as a highly viscous pale yellow oil in
quantitative yield. 1H NMR (400 MHz, CDCl3): d ¼ 0.86 (t, 6H,
7.0 Hz, -CH3), 1.18–1.56 (m, 36H, C-CH2-C), 2.23 (s, 12H,
N-CH3), 2.15–2.82 (br m, 20H), 3.12–4.10 (m, 8H). HR-MS
(ESI, MeCN–H2O) (m/z): calculated for C38H83N4O5 + H+
(M + H+) 675.6358, found 675.6358.
2
2
I(Q) ¼ nm[S(Q)hF(Q)i + h|F(Q)|2i ꢃ hF(Q)i ] + Binc
(1)
where nm is the number of micelles per unit volume, S(Q) is the
structure factor and Binc is the incoherent background.
For an elliptical micelle, both F(Q) and F(Q)2 require numer-
ical integration over an angle g between Q and the axis of the
ellipsoid to account for the random distribution of orientations
of the ellipse. For clarity, we omit this.
5,16-Bis-(2-hydroxydodecyl)-2,19-dimethyl-7,14-dihydroxy-2,5,16,19-
tetraazaicosane (4b). This material was prepared by using the
method for 4a using rac/meso-1,2;9,10-diepoxydecane (0.850 g,
5 mmol) and 40 (3.40 g, 5 mmol, 2.5 equivalents). The yield was
F(Q) ¼ V1(r1 ꢃ r2)F0(QR1) + V2(r2 ꢃ rsolvent)F0(QR2) (2)
1
quantitative. H NMR (400 MHz, CDCl3): d ¼ 0.89 (t, 6H, 6.6
The first term in eqn (2) represents the scattering from the core
Hz, -CH3), 1.18–1.56 (m, 48H, C-CH2-C), 1.88 (br m, 4H, OH),
2.22 (s, 12H, N-CH3), 2.03–2.80 (8H, N-CH2), 3.15–3.55
(m, 8H), 3.77 (m, 4H, CHOH). HR-MS (ESI, MeCN–H2O)
(m/z): calculated for C42H91N4O4 + H+ (M + H+) 715.7035,
found 715.7054.
with radius R (subscript 1) and the second, the polar shell
4
3jiðQRiÞ
(subscript 2). Vi ¼ pR3i and F0ðQRiÞ ¼
(ji is the first-
3
QRi
order spherical Bessel function of the first kind). S(Q) represents
the spatial arrangement of the micelles in solution and n the
micelle number density.
Metallosurfactant formation and coordination
determination
r is the neutron scattering length density of the micellar core
(subscript 1), the polar shell (subscript 2) and the solvent
(subscript 0). These constants are combined into a single fittable
parameter used to ‘‘scale’’ the model intensity to the absolute
value. Post-fitting, this scalar is recalculated using the parameters
II
II
Ni and Cu complexes of 1, 2, 3, 4a and 4b were prepared by the
addition of 1.05 (or as stated explicitly) equivalents of the
appropriate divalent metal salt to a suspension of the ligand in
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Soft Matter, 2010, 6, 1981–1989 | 1987