Superparamagnetic colloidal photonic structures

Abstract

Monodisperse colloidal nanocrystal clusters of magnetite (Fe.sub.3O.sub.4) with tunable sizes from about thirty to about three hundred nanometers have been synthesized using a high-temperature hydrolysis process. The colloidal nanocrystal clusters are capped with polyelectrolytes, and highly water soluble. Each cluster is composed of many single magnetite crystallites, thus retaining the superparamagnetic behavior at room temperature. The combination of superparamagnetic property, high magnetization, and high water dispersibility makes the colloidal nanocrystal clusters ideal candidates for various important biomedical applications such as drug delivery and bioseparation. The present invention is further directed to methods for forming colloidal photonic crystals from both aqueous and nonaqueous solutions of the superparamagnetic colloidal nanocrystal clusters with an external magnetic field applied thereto. The diffraction of the photonic crystals can be tuned from near infrared to visible and further ultraviolet spectral region by varying the external magnetic field.

Claims

1. A method of forming chain-like colloidal assemblies that diffract light, consisting of: mixing an iron salt precursor, a polar solvent, and a surfactant to form a first mixture; introducing a precipitation agent into the first mixture to initiate a hydrolysis reaction, wherein the precipitation agent is a base; controlling the hydrolysis reaction to occur at a temperature ranging from about 100 C. to about 320 C.; obtaining monodisperse superparamagnetic magnetite colloidal particles from the hydrolysis reaction, wherein each of the superparamagnetic magnetite colloidal particles is formed from a plurality of nanocrystals; controlling a size of the monodisperse superparamagnetic magnetite colloidal particles from about 30 nanometers to about 300 nanometers based on a concentration of the base; dispersing the monodisperse superparamagnetic magnetite colloidal particles in a polar solution; and applying an external magnetic field on the monodisperse superparamagnetic magnetite colloidal particles so as to assemble the magnetite colloidal particles in chain-like structures that diffract light in the polar solution, wherein the colloidal particles within the chain-like structures are periodically arranged, with tunable periodicity and diffraction frequency by varying the external magnetic field.

2. The method of claim 1, wherein the polar solution is chosen from the group comprising: water and solutions of other polar solvents wherein the superparamagnetic magnetite colloidal particles are dispersed.

3. The method of claim 1, wherein the diffraction frequency of the chain-like colloidal assemblies under varying the external magnetic field covers the entire visible region, the near-ultraviolet region, and the infrared region of the light spectrum.

4. The method of claim 1, wherein when the external magnetic field is oscillating, the optical response of the chain-like colloidal assemblies follows the oscillation.

5. A method of forming chain-like colloidal assemblies, consisting of: mixing an iron salt precursor, a polar solvent, and a surfactant to form a first mixture; introducing a precipitation agent into the first mixture to initiate a hydrolysis reaction, wherein the precipitation agent is a base; controlling the hydrolysis reaction to occur at a temperature ranging from about 100 C. to about 320 C.; obtaining monodisperse superparamagnetic magnetite colloidal particles from the hydrolysis reaction, wherein each of the superparamagnetic magnetite colloidal particles is formed from a plurality of nanocrystals; controlling a size of the superparamagnetic magnetite colloidal particles from about 30 nanometers to about 300 nanometers based on a concentration of the base; rendering a surface of the superparamagnetic magnetite colloidal particles to be dispersible in nonaqueous solvents; dispersing the superparamagnetic magnetite colloidal particles in a nonaqueous polar solution; and applying an external magnetic field on the superparamagnetic magnetite colloidal particles so as to assemble the magnetite colloidal particles in chain-like structures that diffract light in the nonaqueous solution, wherein the colloidal particles within the chain-like structures are periodically arranged, with tunable periodicity and diffraction frequency under varying the external magnetic field.

6. The method of claim 5, wherein the nonaqueous polar solution is chosen from a group consisting of alcohol solvents.

7. The method of claim 5, wherein rendering the surface of the monodisperse superparamagnetic magnetite colloidal particles includes coating the monodisperse superparamagnetic magnetite colloidal particles with a layer of silica.

8. The method of claim 7, further comprising the step of tuning a thickness of the silica layer for further tuning the diffraction frequency under the external magnetic field.

9. The method of claim 5, wherein the diffraction frequency of the chain-like colloidal assemblies under varying the external magnetic field covers the entire visible region, the far-ultraviolet region, and the infrared region of the light spectrum.

10. The method of claim 1, wherein the surfactant is chosen from the group consisting of polyelectrolytes.

11. The method of claim 1, wherein the obtaining of the superparamagnetic magnetite colloidal particles comprises: coating the particles with a layer of silica or polymer; and linking a ligand to the surface of the coated colloidal particles.

12. The method of claim 5, wherein the surfactant is chosen from the group consisting of polyelectrolytes.

13. The method of claim 5, wherein the obtaining of the superparamagnetic magnetite colloidal particles comprises: coating the colloidal particles with a layer of silica or polymer; and linking a ligand to the surface of the coated colloidal particles.

14. The method of claim 1, wherein each nanocrystal of the plurality of the nanocrystals is approximately 10 nanometers in size.

15. The method of claim 5, wherein each nanocrystal of the plurality of the nanocrystals is approximately 10 nanometers in size.

16. The method of claim 1, wherein upon removing the external magnetic field, the chain-like colloidal assemblies disassemble from the chain-like structures.

17. The method of claim 1, wherein the base is sodium hydroxide (NaOH).

18. The method of claim 1, wherein the surfactant is polyacrylic acid (PAA), the precursor is Iron (III) chloride (FeCl.sub.3), the polar solvent is diethylene glycol, and the base is sodium hydroxide (NaOH).

19. The method of claim 1, comprising: controlling the size of the monodisperse superparamagnetic magnetite colloidal particles by modulating the concentration of the base while keeping all other parameters fixed.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1a-1f are transmission electron microscopy (TEM) images of Fe.sub.3O.sub.4 nanocrystal clusters in the present invention.

(2) FIGS. 2a-2c are high-resolution and high magnification TEM images of secondary structures for isolated colloidal nanocrystal clusters in the present invention.

(3) FIG. 2d is the selected area diffraction of an isolated colloidal nanocrystal cluster.

(4) FIG. 3 shows X-ray diffraction patterns confirming the secondary structure of magnetite colloidal nanocrystal clusters of the present invention and magnetite nanodots as a reference.

(5) FIG. 4 is a XAS spectrum at Fe L edge of Fe.sub.3O.sub.4 colloidal nanocrystal clusters and referential spectra for Fe.sub.3O.sub.4, -Fe.sub.2O.sub.3, -Fe.sub.2O.sub.3.

(6) FIGS. 5a-5c show hysteresis loops of colloidal nanocrystal clusters of the present invention, wherein mass magnetization (M) is plotted as a function of applied external field.

(7) FIGS. 6a-6c show the aqueous dispersion of colloidal nanocrystal clusters of the present invention on a glass substrate.

(8) FIGS. 6d-6f show photos of a CNC aqueous dispersion in a vial with or without magnetic field applied.

(9) FIGS. 7a-7b show the digital photos and reflectance spectra, respectively, of an aqueous solution of CNCs made in the present invention in response to a varying magnetic field at normal incidence.

(10) FIG. 8 shows the dependence of the tuning range of diffraction spectra of the colloidal photonic crystals, represented by the vertical bars, and the wavelength of maximum diffraction intensity, represented by the solid squares, on the size of CNCs.

(11) FIGS. 9a-9c show modulated optical responses of Fe.sub.3O.sub.4 colloidal photonic crystals in a periodic magnetic field of different frequencies.

(12) FIGS. 10a-10e show TEM images of Fe.sub.3O.sub.4 colloidal nanocrystal clusters coated with silica layers of various thickness (Fe.sub.3O.sub.4@SiO.sub.2).

(13) FIG. 11 shows reflection spectra of Fe.sub.3O.sub.4@SiO.sub.2 in ethanol solution in response to an external magnetic field with varying strength.

(14) FIG. 12 shows reflection spectra of Fe.sub.3O.sub.4@SiO.sub.2 colloids in various alkanol solvents in response to a defined magnetic field.

(15) FIG. 13a shows fabrication procedure of a field-responsive PDMS composite embedded with droplets of EG solution of Fe.sub.3O.sub.4@SiO.sub.2 colloid.

(16) FIG. 13b shows magnetically induced color change of a flexible PDMS film with EG solution of Fe.sub.3O.sub.4@SiO.sub.2 colloids.

DETAILED DESCRIPTION OF THE INVENTION

(17) The present invention is directed to superparamagnetic magnetite colloidal nanocrystal clusters (CNC) and methods of their production. Highly water soluble magnetite (Fe.sub.3O.sub.4) CNCs are synthesized by a high temperature hydrolysis reaction using a precursor, a surfactant, a precipitation agent and a polar solvent. A NaOH/DEG stock solution was prepared by dissolving NaOH (50 mmol) in DEG (20 ml); this solution was heated at 120 C. for one hour under nitrogen, and cooled down and kept at 70 C. In a typical synthesis, a mixture of PAA (4 mmol), FeCl.sub.3 (0.4 mmol) and DEG (17 ml) was heated to 220 C. in a nitrogen atmosphere for at least 30 min under vigorous stirring, forming a transparent light-yellow solution. A NaOH/DEG stock solution (1.75 ml) was injected rapidly into the above hot mixture, and the temperature dropped to about 210 C. instantly. The reaction solution slowly turned black after about two minutes and eventually slightly turbid. The resulting mixture' was further heated for 1 h to yield 93-nm magnetite clusters. The amount of NaOH/DEG solution determines the size of the CNCs. For example, 1.6, 1.65, 1.7, 1.8, 1.85 ml of stock solutions lead to the formation of CNCs with average sizes of 31, 53, 71, 141, 174 nm, respectively. The final products were washed with the mixture of de-ionized (DI) water and ethanol several times and then dispersed in DI water.

(18) The method of the present invention for forming colloidal nanocrystal clusters includes precursors chosen from iron salts including, but not limited to, iron (II) chloride, iron (III) chloride, iron (II) sulfate, iron (III) sulfate, iron (II) nitrate, iron (III) nitrate, iron (II) fluoride, iron (III) fluoride, iron (II) bromide, iron (III) bromide, iron (II) iodide, iron (III) iodide, iron (II) sulfide, iron (III) sulfide, iron (II) selenide, iron (III) selenide, iron (II) telluride, iron (III) telluride, iron (II) acetate, iron (III) acetate, iron (II) oxalate, iron (III) oxalate, iron (II) citrate, iron (III) citrate, iron (II) phosphate, iron (III) phosphate. Other transition metals such as cobalt, nickel, and manganese can be incorporated into the synthesis by adding the corresponding salts so that the final products are iron based complex oxides. Suitable surfactants for use in the method of the present invention can be chosen from a wide range of polyelectrolytes such as, but not limited to those containing carboxylic acid groups including polyacrylic acid and polymethacrylic acid. Suitable polar solvents for use in the method of the present invention include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycols.

(19) In the method of the present invention, the precipitation of the colloidal nanocrystal clusters can be initiated by adding bases such as hydroxides, carbonates, bicarbonates, phosphates, hydrogen phosphate, dihydrogen phosphates of group 1 and 2, ammonium (for example, NaOH, KOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3), ammonia, as well as group 1 salts of carbanions, amides and hydrides. The reaction to form the colloidal nanocrystal clusters of the present invention can be carried out at a temperature between room temperature and the boiling point of the solvents. In one embodiment, the temperature for synthesis is controlled between about 100 C. to about 320 C. In accordance with the present invention, the size of the clusters can be controlled from approximately thirty (30) nm to approximately three hundred (300) nm.

(20) In one embodiment of the present invention, highly water soluble magnetite (Fe.sub.3O.sub.4) CNCs are synthesized by using a high temperature hydrolysis reaction with polyacrylic acid (PAA) as the surfactant. Iron (III) chloride (FeCl.sub.3) is used as a precursor, and diethylene glycol, (DEG, a polyhydric alcohol with a boiling point of 244-245 C.) is used as a polar solvent. PAA was selected as the surfactant for the strong coordination of carboxylate groups with iron cations on the magnetite surface. An additional advantage of using PAA is that the uncoordinated carboxylate groups on the polymer chains extend to aqueous solution, conferring upon the particles a high degree of dispersibility in water. Introduction of sodium hydroxide (NaOH) into the hot mixture of DEG, FeCl.sub.3 and PAA produces water molecules and also increases the alkalinity of the reaction system, with both results favoring the hydrolysis of Fe.sup.3+. Under the reductive atmosphere provided by DEG at high temperature, Fe(OH).sub.3 partially transforms to Fe(OH).sub.2, finally leading to the formation of Fe.sub.3O.sub.4 particles through dehydration. These Fe.sub.3O.sub.4 nanocrystals spontaneously aggregate to form flower-like three-dimensional clusters, as shown in the representative transmission electron microscopy (TEM) images in FIGS. 1a-1f. The average sizes of the CNCs in FIGS. 1a-1f, obtained by measuring about 150 clusters for each sample, are 31 nm, 53 nm, 71 nm, 93 nm, 141 nm, and 174 nm respectively, wherein all scale bars are 200 nm. Close inspection of these images confirms that these monodisperse colloids are consisted of small subunits.

(21) The size of the CNCs can be precisely controlled from 30 nm to 300 nm by simply increasing the amount of NaOH while keeping all other parameters fixed (FIG. 1). This size tunability might be the result of slight differences in H.sub.2O concentration and alkalinity caused by varying NaOH additions. Higher H.sub.2O concentration and relatively stronger alkalinity could accelerate the hydrolysis of Fe.sup.3+, promoting the formation of larger oxide clusters. The growth of CNCs follows the well-documented two-stage growth model where primary nanocrystals nucleate first in a supersaturated solution and then aggregate into larger secondary particles.

(22) The secondary structure of CNCs can be observed more clearly in FIGS. 2a-2c for isolated clusters of 31 nm, 93 nm, and 174 nm, respectively. Lattice fringes were recorded for a small cluster with diameter of 31 nm, as shown in the high-resolution TEM (HRTEM) image in FIG. 2a. It's clear that the cluster is composed of small subcrystals of 6-8 nm size and of the same crystal orientation. Measuring the distance between two adjacent planes in a specific direction gives a value of 0.482 nm, which corresponds to the lattice spacing of (111) planes of cubic magnetite. The fact that subcrystals crystallographically align with adjacent ones can be understood as the result of oriented attachment and subsequent high temperature sintering during the synthesis. FIGS. 2b and 2c show the secondary structures of CNCs of much larger size. FIG. 2d shows selected-area electron diffraction (SAED) pattern recorded on an isolated cluster of 174 nm, which reveals a single-crystal-like diffraction where diffraction spots are seen to have widened into narrow arcs, indicating slight misalignments among the subcrystals.

(23) XRD measurements also confirm the secondary structure of magnetite CNCs. FIG. 3 shows the diffraction patterns with almost identical broadenings for clusters of different sizes of 53-nm, 93-nm, and 174-nm and 8-nm magnetite nanodots, wherein peak positions and intensities recorded in the literature for bulk magnetite samples are indicated by the vertical bars. Calculations using Debye-Scherrer formula for the strongest peak (311) give grain sizes of 9.73, 9.65 and 10.83 nm for CNCs of size 53, 93 and 174 nm, respectively, implying that the subcrystals do not grow significantly with the increasing size of CNCs. Consistently, the peak shape and broadening in XRD patterns of CNCs are comparable to that of 8-nm isolated nanodots. We also confirmed the composition of iron oxide being magnetite by combining the XRD results with the X-ray absorption spectroscopy (XAS) measurements in FIG. 4.

(24) The unique and complex structure allows CNCs to retain superparamagnetic behavior at room temperature even though their size exceeds 30 nm. FIGS. 5a and 5b show hysteresis loops of 93-nm CNCs measured at 300 K. and 2 K., respectively. FIG. 5c is a comparison of hysteresis loops of 53-nm, 93-nm, 174-nm CNCs and a reference sample of 8-nm nanodots and the insert depicts the magnetic moment () per cluster (or dot) plotted in a logarithmic graph. The clusters show no remanence or coercivity at 300 K., corresponding to superparamagnetic behavior. At 2 K., thermal energy is insufficient to induce moment randomization so that the clusters show typical ferromagnetic hysteresis loops with a remanence of 12.6 emu/g and a coercivity of 140 Oe.

(25) To evaluate the magnetic response of CNCs to an external field, the mass magnetization () was measured at 300 K. by cycling the field between 20 kOe and 20 kOe. FIG. 5c shows that all the CNCs, as the reference sample of 8-nm Fe.sub.3O.sub.4 nanodots, are superparamagnetic at room temperature, i.e., 300 K. The saturation magnetization (.sub.s) was determined to be 63.5 emu/g, 56.7 emu/g, 30.9 emu/g, 21.2 emu/g for 174-nm, 93-nm, 53-nm CNCs and 8-nm particles, respectively. The values for large clusters are close but decrease noticeably for small particles, which may be attributed to a surface related effect such as surface disorder or surface spin canting. The magnetic moment of an individual grain () can be determined by the Langevin paramagnetic function: M(x)=N(cothx(1/x)).

(26) The CNCs are highly water soluble even after washing with the mixture of ethanol and water for three times, thanks to the robust surface coating of PAA. The method of the present invention included the ability to visualize their magnetic responses in an optical microscope by observing a thin layer of aqueous dispersion of CNCs on a glass substrate.

(27) FIGS. 6a-6c show optical dark-field images of a thin layer of CNC aqueous dispersion on a glass substrate, without magnetic field, with magnetic field, and after the applied magnetic field is removed, respectively. The bright region at the lower-left corner in each image represents the dried CNCs.

(28) As shown in FIG. 6b, the initially well-dispersed CNCs shown in FIG. 6a forms chain-line structures when a magnetic field was applied. The chain-like structures are disassembled immediately upon removing the external field, as seen in FIG. 6c, displaying a typical superparamagnetic behavior. FIGS. 6d-6f show photos of a CNC aqueous dispersion in a vial without magnetic field, with magnetic field, and after the applied magnetic field is removed, respectively. If a CNC solution is subjected to a strong magnetic field, the particles can be completely separated from the solution within minutes, as shown in FIGS. 6d and 6e. A slight agitation will bring the CNCs back into the original solution if the magnetic field is removed as shown in FIG. 6f.

(29) The present invention is further directed to a method for constructing colloidal photonic crystals out of the polyacrylate capped superparamagnetic magnetite (Fe.sub.3O.sub.4) colloidal nanocrystal clusters (CNCs) with tunable size from about thirty to about three hundred nm using a high-temperature hydrolysis process. The colloidal photonic crystals show highly tunable diffractions covering the whole visible region owing to the highly charged polyacrylate covered surfaces and the strong magnetic responses of the magnetite CNCs. Such a system, with the advantages of simple and inexpensive to synthesize, wide and reversible tunability, and instant response to external magnetic field, opens the door to many critical applications including as active components in optical micro-electromechanical (MEMS) systems.

(30) Uniform magnetite CNC building blocks were synthesized by hydrolyzing FeCl.sub.3 with NaOH at about 220 C. in a diethylene glycol (DEG) solution containing the surfactant of polyacrylic acid (FAA), which is described in the last section. These CNCs retain the superparamagnetic behavior at room temperature and show much stronger response to the external magnetic field than individual nanodots. Polyacrylate binds to the particle surface through the strong coordination of carboxylate groups with iron cations, while the uncoordinated carboxylate groups on the polymer chains extend to aqueous solution and render the particles highly charged surfaces.

(31) These Fe.sub.3O.sub.4 CNCs can readily self-assemble into colloidal crystals in deionized water upon application of a magnetic field; after removing the extra surfactants and decreasing the ionic strength through repeated centrifugation. FIGS. 7a and 7b show the digital photos and reflectance spectra, respectively, of an aqueous solution of CNCs (approximately 10.2 mg/ml) in response to a varying magnetic field at normal incidence. The colloidal photonic crystals, shown in FIG. 7a, with magnetically tunable diffractions covering the whole visible spectra have been fabricated from superparamagnetic magnetite 120-nm CNCs. The magnetic field has been increased from 87.8 to 352 Gauss by moving a NdFeB magnet towards the sample (3.7-2.0 cm) with step size of 0.1 cm. As shown in FIG. 7a, the color of the aqueous solution of CNCs changes from red (in the vial 710) to blue (in the vial 720) as the magnetic filed increases. As shown in FIG. 7b, the diffraction peak resulting from the close pack (111) planes accordingly blue shifts under increasing magnetic filed as, for example, the peak 730 shifts to the peak 740. The peak frequency gradually shifts from about 750 nm to below 450 nm. As the magnet moves away from the sample, the diffraction peak reversibly red shifts. A rapid response (<<1 s) of the diffraction to the change in the magnetic field is observed. The interplanar spacing decreases from 274 to 169 nm as the strength of magnetic field increases, as estimated by using the Bragg's Law (=2nd sin ), where is the diffraction wavelength, n is the refractive index of water, d is the lattice plane spacing, and =90 is the Bragg angle.

(32) The three-dimensional order of the formed colloidal crystals is the result of the balance between the interparticle electrostatic repulsive force and the magnetic forces. The as synthesized CNCs without cleaning show no diffractions even when the magnetic field is so strong that they are separated from the solution. Their optical response to the magnetic field increases with the number of cleaning cycles which reduce the ionic strength of the solution and increases the Debye-Hiickel screening length and therefore the electrostatic repulsion -potential measurement of a sample cleaned five times gave a typical value of 51 mV, demonstrating their highly charged surface characteristics. Unlike the previously reported case for superparamagnetic polystyrene spheres, the CNCs do not form colloidal crystal in the absence of a magnetic field.

(33) Since CNCs are composed of pure Fe.sub.3O.sub.4, their response to the external magnetic field is much stronger than that of the similarly sized polystyrene beads doped with iron oxide nanoparticles. The application of magnetic field results in additional magnetic packing forces, magnetic dipole-dipole repulsive and attractive forces. The magnetic packing force is exerted on every cluster and attracts them towards the maximum of local magnetic gradient. The repulsive and attractive forces are perpendicular and parallel to the magnetic field, respectively. For example, a 120-nm cluster shows a magnetic moment about 6.31910.sup.14 emu in a 235 Gauss magnetic field, and experiences a magnetic packing force(F.sub.m=(B)) of 1.2610.sup.11 dyn in a 200 Gauss.Math.cm.sup.1 gradient. With a 197.4 nm nearest-neighbor spacing d derived from the diffraction peak position, the interparticle repulsive force F.sub.mr=3(.sup.2/d.sup.4) and the attractive force F.sub.ma=6(.sup.2/d.sup.4) are estimated to be 9.9110.sup.7 and 1.9810.sup.6 dyn respectively. These values, which are negligible when the magnetic moment per particle is small, are now comparable to that of the interparticle electrostatic repulsive forces. It is also worth noting that the magnetic field required for inducing the ordering of the particles in the current system is ten times less than the previously reported value due to the much stronger magnetic moment of the Fe.sub.3O.sub.4 CNCs. The broad tunability and rapid responses of the current system may benefit from the large contribution of the magnetic forces in determining the crystal structure and the lattice constant.

(34) The tuning range of the diffraction wavelength is found to relate to the average size of the CNCs. In general, crystals of large-size clusters (160-180 nm) preferably diffract red light in a relatively weak magnetic field, and their ordered structures become unstable when the magnetic field is too strong. Small-size clusters (60-100 nm) form ordered structures only when the magnetic field is sufficiently strong and the crystals preferably diffract blue light. As demonstrated by the example in FIG. 7b, the medium-size clusters can form stable colloidal crystals in a magnetic field with tunable diffractions covering the whole visible spectrum. To clearly reveal such size dependence, FIG. 8 plots the tuning range of colloidal photonic crystals, represented by the vertical bars, and the wavelength of maximum diffraction intensity, represented by the solid squares, against the size of CNCs. For each sample, the position of maximum diffraction intensity is determined by the polynomial fitting of the curve consisted of all peak values of the reflectance spectra, and the tuning range is obtained by including all the diffractions whose intensity is above 30% of the maximum value. FIG. 8 indicates that the diffraction with maximum intensity red-shifts as the size increases approximately in a linear fashion, which agrees with our visual observations.

(35) The optical responses of these photonic crystals are rapid and fully reversible. To characterize the response time, we recorded changes in the reflection spectrum of a magnetic colloidal photonic crystal in the presence of a periodically on-off magnetic field with a controllable switching frequency. FIG. 9a shows the reflection spectra of a 70 nm Fe.sub.3O.sub.4 colloidal photonic crystals in a periodic magnetic field with a frequency of 0.5 Hz with spectra integration time of 200 msec. They demonstrate that the switch of diffraction at 470 nm between on and off states can be achieved with the same frequency as the external field. FIGS. 9b and 9c show the variation of peak intensity at 470 nm in response to electromagnetic fields at higher frequencies such as 1 and 2 Hz with integration time of 100 msec. As shown in FIGS. 9b and 9c, the diffraction intensity shows periodic modulations which closely match the profile of external field, displaying clear on/off states with the corresponding frequency. No gradual transition from longer wavelengths to the final shorter wavelength was observed during the development of the spectra, indicating that the ordered structures form within the first 200 msec upon the application of magnetic field. During the rest of the on stage, the order of the crystals further improves as the remaining particles rearrange their positions. The diffraction peak disappears completely within 100-200 msec after the magnetic field is off, which is much faster than the time needed for development of translational order under a magnetic field.

(36) Further modifications and improvements may additionally be made to the superparamagnetic magnetite colloidal nanocrystal clusters and methods of production disclosed herein without departing from the scope of the present invention. Accordingly, it is not intended that the invention be limited by the embodiments disclosed herein.

(37) The present invention is further directed to a method of fabricating magnetically responsive photonic structures that can operate in nonaqueous solutions. Unlike the previously reported polyelectrolyte-grafted CNCs which are only dispersible in water, the modification of the particle surface with a layer of silica allows their dispersion in various nonaqueous organic solvents such as alkanols. Interestingly, upon application of an external magnetic field, the modified particles in these nonaqueous solvents can also assemble into ordered structures and diffract light. Given the expected diminished role for electrostatic forces for silica coated particles in alkanols, it is natural to suspect that other repulsive forces must be present to counter the magnetic attractive force and yield the observed persistence of ordering. The photonic response of the solutions to external fields suggests a rough range for this force and allows us to identify it with effects already observed in the literature. As well as allowing us to study fundamental details of interparticle forces, forming tunable photonic structures in nonaqueous solvents provides a number of advantages over the water-based approach for practical applications. For example, solvents with low volatility can now be used as dispersion media for improved long-term stability and ease of processing. The use of nonaqueous solvents also addresses the issue in the previous system where trace amount of ions released from environment such as glass containers may gradually alter the system's photonic response. While maintaining the merits of our earlier work with aqueous colloids such as a fast and reversible response, the modification with silica layer also provides a convenient method for extending the diffraction wavelength beyond the visible range. Our synthetic procedure currently can produce Fe.sub.3O.sub.4 CNCs with sizes below 300 nm, which limit the maximum diffraction wavelength to below 800 nm. The size limitation can be conveniently overcome by coating a layer of silica whose thickness can be precisely controlled by using the facile sol-gel processes. The silica coating also makes it possible to link a large variety of ligands to the particle surface through the well-developed silane chemistry for further enhancing the compatibility between the particles and solvents.

(38) FIGS. 10a-10e show TEM images of Fe.sub.3O.sub.4 colloidal nanocrystal clusters coated with silica layers of various thickness of 16.5, 25, 37, 56, and 70.5 nm, respectively, where the CNCs have a similar core size of 110 nm. Fe.sub.3O.sub.4@SiO.sub.2 colloids were synthesized as follows. Fe.sub.3O.sub.4 CNCs were synthesized using a high-temperature hydrolysis reaction reported previously. Fe.sub.3O.sub.4@SiO.sub.2 core/shell colloids were prepared through a modified Stber process. Typically, an aqueous solution (3 mL) containing Fe.sub.3O.sub.4 CNCs (25 mg) was mixed with ethyl alcohol (20 mL), ammonium hydroxide (28%, 1 mL) aqueous solution by vigorous stirring using mechanical stirrer. TEOS (0.1 mL) was injected to the solution in every 20 min till the total amount of TEOS reaches 0.9 mL. At the end of every cycle, reflection spectra of reaction solution were measured under magnetic field (622 Gauss) to monitor the thickness of silica layer. After obtaining the desired size, the Fe.sub.3O.sub.4@SiO.sub.2 colloids were collected by magnetic separation, washed by ethanol for three times, and finally dispersed in ethanol (3 mL).

(39) Fe.sub.3O.sub.4@SiO.sub.2 core-shell particles can be dispersed in a number of alkanol solvents and show a tunable optical response in the presence of an external magnetic field. The diffraction peak blue-shifts as the distance decreases from 4.3 to 1.9 cm with step size of 0.2 cm.

(40) FIG. 11 shows the typical reflection spectra of an ethanol solution of 170-nm (overall diameter with 114 nm in core size and 28 nm in shell thickness) Fe.sub.3O.sub.4@SiO.sub.2 as a function of the external magnetic field strength, achieved by changing the magnet-sample distance. The diffraction intensity increases steadily with increasing external field strength until reaching a saturation value. Further increasing the strength of the magnetic field does not significantly change the peak position and the peak intensity drops only slightly. The contour of the peaks therefore shows a skewed profile. From the reflection spectra, one can estimate an average value for interparticle spacings along the magnetic field using Bragg's law, =2nd sin , as well as a surface-to-surface distance, d.sub.s-s, by subtracting the colloid diameter.

(41) For the Fe.sub.3O.sub.4@SiO.sub.2 dispersions in ethanol, besides the electrostatic force, another repulsive force, solvation force, must be considered besides the reduced electrostatic force when discussing the interactions in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. It has been widely accepted that for an ethanol dispersion of silica, a wetting film of solvent formed on the silica surface through the hydrogen bonds can significantly stabilize the system. When the solvation layers of two nearby particles overlap, a strong disjoining pressure appears to prevent the particles from coming together. While the electrostatic force still remains effective at larger separations, the solvation force may dominate the interparticle repulsions at small separations, making it possible to counter the induced magnetic attractive force and assemble the particles into ordered structures. The combined effect of these two repulsive forces leads to the skewed dependence profile of the diffraction to the changes in the strength of magnetic field. By calculating the spacing from the shortest diffraction wavelength, we estimate the thickness of the solvation layer to be 20.4 nm which is close to the value reported in literature. The solvation force is also present in aqueous systems, however, its contribution to the overall repulsive interaction might be negligible in comparison to the strong electrostatic force resulted from high surface charges.

(42) Alkanol solutions of Fe.sub.3O.sub.4@SiO.sub.2 colloids show significant long-term stability in photonic activity. In the previous aqueous Fe.sub.3O.sub.4 CNC system, slow release of ions from the environment or from the particles into the solution may eventually alter the photonic properties including both diffraction intensity and wavelength. The system reported here was able to display consistent photonic response after storage for several months, owing to the lower ionic strength of the alkanol solutions and the predominantly non-electrostatic contribution to interparticle repulsion.

(43) The diffraction spectra of the Fe.sub.3O.sub.4@SiO.sub.2 colloids can be modified by changing the thickness of the silica shell. To avoid the homogeneous nucleation of small silica particles, TEOS was added to the reaction slowly and continuously during the synthesis. Interestingly, the Fe.sub.3O.sub.4@SiO.sub.2 colloids show an optical response to external magnetic field even in the original reaction solution (12.5% water, 4.2% NH.sub.4OH solution, and 83.3% ethanol), providing a convenient way to monitor the growth of silica layers around the Fe.sub.3O.sub.4 cores. The detection method is fast in comparison to other measurement techniques such as dynamic light scattering or TEM imaging. FIGS. 10a-10e show TEM measurements which confirm the increasing thickness of the silica shell from 16 to 70 nm. While the average diameter of the Fe.sub.3O.sub.4 CNCs is below 180 nm as limited by the synthesis procedure, silica coating allows to increasing the effective particle size in a controlled manner so that the diffraction wavelength of the photonic crystals can be extended into the near-IR region.

(44) Silanol surface makes the Fe.sub.3O.sub.4@SiO.sub.2 colloids compatible with many alkanol solvents besides ethanol. FIG. 12 shows the reflection spectra of 170-nm Fe.sub.3O.sub.4@SiO.sub.2 colloids in various alkanol solvents in response to a same magnetic field of 622 Gauss. The applied magnetic field is strong enough to drive the neighboring particles close to hard contact so that the intensity of the diffraction is around the maximum value. In this case, the thickness of solvation layer (d=(dd.sub.colloid)/2) in each solvent can be estimated from the calculated lattice spacing (d)

(45) The ability to assemble magnetic colloids into ordered structures in nonaqueous solvents represents a significant step towards the practical applications of these tunable photonic structures. The method of the present invention provides the ability to embed alkanol solutions of Fe.sub.3O.sub.4@SiO.sub.2 colloids in a polydimethylsiloxane (PDMS) matrix in the form of liquid droplets, thus producing solid composite materials with field responsive optical properties. Similar operations have been extremely difficult using aqueous solutions due to the high polarity of water. In a typical process, Fe.sub.3O.sub.4@SiO.sub.2 colloids are dispersed in a nonvolatile alkanol solvent such as EG, DEG, and glycerol, and then mixed with PDMS prepolymer and curing agent using mechanical stirring. Thanks to the high viscosity of prepolymer (3900 cp), EG solution of Fe.sub.3O.sub.4@SiO.sub.2 forms very stable emulsion-like droplets with an average diameter of 5 m. The stability of droplets is also believed to benefit from the close match between the densities of the glycol and the PDMS matrix. Curing the mixture at room temperature for 24 hours (or at 60 C. for 2 hours) produces a dark brown silicone gel, which displays color change property when placed under a varying magnetic field.

(46) EG droplets remain intact during the curing process. Direct observation of the droplets using optical microscope has been difficult due to the close match between the refractive indices of EG (1.431) and PDMS (1.430). FIG. 13a shows fabrication procedure of s field-responsive PDMS composite embedded with droplets of EG solution of Fe.sub.3O.sub.4@SiO.sub.2 colloids and an optical microscopy graph of the droplets under a vertically aligned external magnetic field. The assembly of Fe.sub.3O.sub.4@SiO.sub.2 colloids in the droplets under the magnetic field leads to the diffraction of green light. As shown in FIG. 13a, the droplets change color and show significantly increased contrast against the PDMS matrix under a vertically aligned magnetic field, and therefore can be easily observed and imaged. Careful inspection reveals that the droplets contain many bright spots, each of which represents a chain of Fe.sub.3O.sub.4@SiO.sub.2 particles assembled along the magnetic field. FIG. 13b shows magnetically induced color change of a flexible PDMS film with EG solution of Fe.sub.3O.sub.4@SiO.sub.2 colloids. As shown in FIG. 13b, the composite film retains the flexibility of the PDMS matrix and can be folded into various shapes while still displaying magnetically induced colors. The material is also very stable, wherein no apparent degradations in optical or mechanical properties were observed after storing the samples for month.