Abstract
Ordering particles at the nanometre length scale is a challenging and active research area in materials science. Several approaches have so far been developed, ranging from the manipulation of individual particles1,2 to the exploitation of self-assembly in colloids3. Nanometre-scale ordering is well known to appear spontaneously when anisotropic organic moieties form liquid-crystalline phases; this behaviour is also observed for anisotropic mineral nanoparticles4,5 resulting in the formation of nematic4,5,6,7, smectic8 and hexagonal9,10 mesophases. Here we describe a lyotropic liquid-crystalline lamellar phase comprising an aqueous dispersion of planar solid-like sheets in which all the atoms involved in a layer are covalently bonded. The spacing of these phosphatoantimonate single layers can be increased 100-fold, resulting in one-dimensional structures whose periodicity can be tuned from 1.5 to 225 nanometres. These highly organized materials can be mechanically or magnetically aligned over large pH and temperature ranges, and this property can be used to measure residual dipolar couplings for the structure determination of biomolecules by liquid-state NMR. We also expect that our approach will result in the discovery of other classes of mineral lyotropic lamellar phases.
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Acknowledgements
We thank the LURE and ESRF synchrotron radiation facilities for the award of beamtime, C. Bourgaux, P. Panine and T. Narayanan for technical support at D24 (LURE) and ID2 (ESRF), Y. Piffard for supplying us with 1g of H3Sb3P2O14 powder at the start of this work, C. Chaudemanche and X. Leguevel for their participation in the synthesis of large amounts of H3Sb3P2O14, F. Alvarez for pH measurements, S. Grolleau for TGA measurements, P. Berthault and D. Jeannerat for their help in NMR measurements and processing of the spectra, P. Sinaÿ and Y. Zhang for the gift of the pentasaccharide and J. P. Simorre for giving us access to a 18.7 T magnet while we were performing our SAXS experiments at the ESRF. Financial support from the Ministry of Education (PhD fellowship for F.C.), the Ecole Normale Supérieure and the Ecole Nationale des Ponts et Chaussées (PhD fellowships for B.L.), the Région Pays de Loire and the GDR-CNRS 690 FORMES (for D2O) is gratefully acknowledged.
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Synthesis of H3Sb3P2O14 aqueous suspensions
A homogeneous mixture in stoichiometric proportions of NH4H2PO4 (ALFA, 23 mmol, 2.66g), Sb2O3 (MERCK, 17 mmol, 5.06g) and KNO3 (PROLABO, 34 mmol, 3.51g) was placed in a platinum crucible and heated in air, first at 300°C for 10 hrs to decompose NH4H2PO4, then at 1000°C for 24 hrs to yield high purity (checked by X-ray powder diffraction) K3Sb3P2O14 (9g, 12 mmol). The total amount of crude powder was thoroughly ground and stirred in a 1.0 L solution of 8.0 N nitric acid at 50 °C for 24 hrs. Along this process, the solid is filtered and the acid solution is renewed three times to ensure complete exchange of the alkali metal cations for protons to yield H3Sb3P2O14 (7.44g, 11 mmol) (over 98% potassium to proton exchange). This product is then rinsed in 18 MW water and retrieved by centrifugation (13000 rpm) three times. Usually, after the third rinse, the powder starts to significantly swell. In the last centrifugation, only the gel phase is collected and it is placed in a regenerated cellulose tubular membrane (Cellu Sep®, width 46mm, thickness 28 µm, pore size 10 Å) and subjected to dialysis in 18 MW water, replacing the water every 24 h, until the nitrate ion concentration decreases to less than 1 ppm (JBL, nitrate test). Along the progress of the dialysis, the lamellar, protonated phosphatoantimony acid, H3Sb3P2O14 continues to swell. The pH of the suspensions obtained varied from 1.5 to 2.5 depending upon their volume fraction. The suspension volume fraction was determined by thermogravimetric analysis (TGA) under N2 (PERKIN-ELMER TGS2) by heating to 500°C. Note that the material collected after TGA remained white indicating that the dialysis procedure did not lead to contamination of the gel with cellulose from the dialysis membranes.
The stability of the H3Sb3P2O14 versus pH has been studied by titration, 2H NMR spectroscopy and optical birefringence observations. Using bases with bulky counter-ions, since the titration curves are relatively smooth, any pH in the range 2.5-9.5 can easily be obtained at volume fractions f useful for NMR (0.1% to 1.5%). The liquid crystalline phase boundaries are almost insensitive to the pH. All liquid crystalline and alignment properties are kept in the whole pH range.
NMR measurements of the alignment induced by a H3Sb3P2O14 aqueous suspension on a pentasaccharide
1H-13C residual dipolar couplings (D) were measured on the same non-labeled pentasaccharide that was used in Ref. 23 for testing induced alignment in aqueous suspensions of vanadium pentoxide (V2O5). The measurements were performed in the same conditions, i.e. on a Bruker DRX800 spectrometer at 18.6 T and 293 K using a sample containing 0.8 mM of pentasaccharide dissolved in a H3Sb3P2O14 suspension of (f ~ 0.75 %) in D2O. The pulse sequence was a Heteronuclear Single Quantum Correlation pulse sequence with sensitivity enhanced by gradients29 and no decoupling during the acquisition. The high degree of deuteration of water was obtained by successive lyophilizations of the whole sample, previously diluted to f ~ 0.1 %, followed by re-dissolution in heavy water. The deuterium residual quadrupolar splitting was equal to 29 Hz. The D values were extracted from the observed splittings in the acquisition dimension (See Table).
A comparison of the D values found in this medium and those found in V2O5 suspensions shows the absence of correlation (See Figure), which proves that the alignment tensors induced by these two media are different. This illustrates how these two media complement each other24. This result was confirmed by the determination of the orientations of the two tensors determined on the LewisX motif (Gal 1, Fuc 2, Nag 3) known to be rigid. This result is further substantiated by the fact that the vanadium pentoxide ribbons orient parallel to the magnetic field23, whereas H3Sb3P2O14 planes are perpendicular to the field.
Figure
(GIF 9.3 KB)
Comparison of the residual dipolar couplings measured in V2O5 and H3Sb3P2O14 aqueous suspensions. The three pyranosid units of the LewisX (Gal 1, Fuc 2, Nag 3), known to form a rigid structural motif, are distinguished. No correlation between the two sets of data can be detected, showing that the two media induced different orientations of this pentasaccharide.
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Gabriel, JC., Camerel, F., Lemaire, B. et al. Swollen liquid-crystalline lamellar phase based on extended solid-like sheets. Nature 413, 504–508 (2001). https://doi.org/10.1038/35097046
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DOI: https://doi.org/10.1038/35097046
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