the present invention is directed toward a laser system for producing stable nanoparticle colloidal suspensions from organic materials using an ultrafast pulsed laser ablation process . fig1 schematically illustrates a laser - based system for producing organic nanoparticles in a liquid in accordance with the present invention . in one embodiment a laser beam 1 is received from a ultrafast pulse source , not shown , and focused by a lens 2 . the source of the laser beam 1 can be any suitable ultrafast pulsed laser source capable of providing a pulse duration , repetition rate and / or power level as discussed below . the focused laser beam 1 then passes from the lens 2 to a guide mechanism 3 for controlling movement of the laser beam 1 . the guide mechanism 3 can be any of those known in the art including , by way of example only , piezo - mirrors , acousto - optic deflectors , rotating polygons , vibrating mirror , and prisms . preferably the guide mechanism 3 is a vibrating mirror 3 to enable controlled and rapid movement of the focused laser beam 1 . the guide mechanism 3 directs the focused laser beam 1 at a target 4 . in one embodiment , the target 4 is a compressed pellet of an organic compound that is being converted into nanoparticles . the compressed pellet can be formed from a variety of powder sources of the organic material . it is preferred to begin with a powdered source of the organic compound that has an average particle size of from submicron to millimeter ( mm ) size depending on the softness of the starting powder , preferably from submicron to submillimeter size . the powdered source material can then be compressed into a pellet using a mold and pressure . the pressures used depend on the starting material , but the target 4 pellet must be self sustaining and able to maintain integrity in a container 7 with a flow of a liquid 5 as described below . the size of the compressed target 4 is larger than 1 mm in at least one dimension . alternatively , the target 4 can be another source of the organic compound material such as : a film of the organic compound that has been deposited onto a substrate ; a bulk material of an organic compound with at least one dimension that is larger than 5 mm ; a stream of the bulk organic compound which has been ejected from a nozzle into the liquid 5 ; or a paste of the bulk organic compound that has been introduced into the liquid 5 . any of these can serve as the target 4 material in the present invention . at least a portion of the target 4 is in contact with the liquid 5 , preferably the target 4 is submerged a distance of from several millimeters to preferably less than 1 centimeter below the surface of a liquid 5 . preferably , the target 4 is positioned in a container 7 having a removable glass window 6 on top of the container 7 . an o - ring type of seal 8 is placed between the glass window 6 and the top of the container 7 to prevent the liquid 5 from leaking out of the container 7 . the container 7 includes an inlet 12 and an outlet 14 so the liquid 5 can be passed over the target 4 and so that it can be re - circulated . the container 7 is optionally placed on a motion stage 9 that can produce translational motion of the container 7 and movement of the liquid 5 . flow of the liquid 5 is used to carry generated nanoparticles 10 out of the container 7 to be collected elsewhere . the flow of liquid s over the target 4 also cools the laser focal volume . the flow rate and volume of liquid s should be sufficient to fill the gap between the target 4 and the glass window 6 as shown . in addition , it must be sufficient to prevent any gas bubbles generated during the laser ablation from staying on the glass window 6 . the liquid 5 can be any liquid that is largely transparent to the wavelength of the laser beam 1 and that preferably is a poor solvent for the target material 4 . in one embodiment , the liquid 5 is deionized water , preferably having a resistivity of greater than 0 . 05 mohm · cm , and more preferably greater than 1 mohm · cm . the ultrafast pulsed laser beam 1 preferably has a pulse duration of 500 picoseconds or less , preferably from about 10 femtoseconds to 500 picoseconds , more preferably from 10 femtoseconds to 200 picoseconds , and most preferably from 100 femtoseconds to 10 picoseconds . the pulse repetition rate is preferably from 1 hz to 100 mhz , more preferably from 10 khz to 10 mhz , and most preferably from 100 khz to 5 mhz . a preferred wavelength is about 1045 nanometers , however any suitable wavelength of from about 400 nanometers to 4000 nanometers may be used . at a wavelength of 1045 nanometers a layer of water of a few millimeters in thickness over the target 4 has a negligible absorption at this wavelength . preferably the laser beam 1 has a pulse energy in the range of about 1 nano - joules to 10 mili - joules , more preferably in the range from 100 nano - joules to 10 micro - joules for generation of nanoparticles 10 . preferably the laser beam 1 has a laser fluence at the focus spot on the surface of target 4 in the range of from about 100 micro - joules / cm 2 to 100 joules / cm 2 , more preferably from 10 milli - joules / cm 2 to 5 joules / cm 2 . in one embodiment the guide mechanism 3 is a vibrating mirror 3 that is configured for fast rastering or other movement of the laser beam 1 on the surface of the target 4 . the vibration frequency of mirror 3 is preferably 10 hz or greater and preferably it has an angular amplitude of 0 . 1 mrad or greater and more preferably of 1 . 0 mrad or greater , such that a rastering speed on the surface of the target 4 is 0 . 01 meters per second or greater and most preferably 0 . 1 meters per second or greater . such a mirror 3 can be a piezo - driven mirror , a galvanometer mirror , or other suitable apparatus for movement of the laser beam 1 . in one embodiment , flow of the liquid 5 through the container 7 is carried out by a circulation system , with a flow speed preferably of 1 . 0 milliliter per second or greater and more preferably of 10 . 0 milliliter per second or greater . flow of liquid 5 is necessary to uniformly distribute the generated nanoparticles 10 in the liquid 5 and to remove them from the container 7 . it is preferred to maintain a sufficient volume of the liquid 5 to avoid any fluctuations in the thickness of liquid 5 above the target 4 . if the liquid 5 thickness varies it can change the optical path properties of the laser beam 1 and cause a broader distribution of sizes of the generated nanoparticles 10 . the optical window 6 above the flowing liquid 5 helps to keep a constant thickness of liquid 5 above the target 4 . when a circulation system is not available , introducing lateral vibration movement , for example perpendicular to the laser beam 1 , as indicated in fig1 , to the motion stage 9 can also cause liquid 5 flow locally across the ablation spot . the motion stage 9 preferably has a vibration frequency of several hz and an amplitude of several millimeters . a shaker can also be used to circulate the liquid 5 , wherein the circular movement of the shaker causes the liquid 5 in the container 7 to have a circular movement too , therefore the organic nanoparticles 10 can distribute evenly in the liquid 5 . with either of these two methods of circulating the liquid 5 , the glass window 6 is not necessary ; however , the use of either will introduce non - uniformity into the thickness of the liquid 5 above the target 4 and will cause a broader size distribution of the nanoparticles 10 . the present invention provides a system and method for formation of stable and chemically pure nanoparticle colloidal suspensions from organic compounds . by stable it is meant that the hydro colloidal , if produced in water , or colloidal suspension if produced in another liquid is stable with no aggregation of the particles after storage at 25 ° c . for at least 7 days and more preferably stable for at least 2 months under these conditions . by chemically pure it is meant that the colloidal suspension is composed only of the organic materials found in the target 4 and the liquid 5 from which the colloidal suspension is derived . there is no need for added stabilizing agents or surface active agents to maintain the colloid in a stable state . the present inventors have discovered that through proper control of laser parameters including pulse duration , pulse energy , pulse repetition rate , and movement of the laser beam 1 over the target 4 such stable nanoparticle colloidal suspensions can be produced . both the laser beam 1 movement rate and the liquid 5 flow rate can be used to aid the process by controlling heat accumulation derived from the preferred high pulse repetition rates used in the present invention . in the present invention ultrashort pulse widths are preferred . it is preferred that the pulse width or pulse duration range from 10 femtoseconds to 200 picoseconds and more preferably from 100 femtoseconds to 10 picoseconds . these short duration pulses are believed to enhance ablation efficiency because of a very high peak power and a small heat - affected zone at the ablation site . previous studies of laser ablation to produce nanoparticles from metal and metal oxides have found that low pulse energy , more precisely a low laser fluence at or near the ablation threshold is preferred for nanoparticle generation from these inorganic target materials . see for example , b . liu , z . d . hu , y . che , “ ultrafast sources : ultrafast lasers produce nanoparticles ”, laser focus world , vol . 43 , 74 ( 2007 ) and b . liu , z . d . hu , y . che , y . b . chen , x . q . pan , “ nanoparticle generation in ultrafast pulsed laser ablation of nickel ”, applied physics letters , vol . 90 , 044103 ( 2007 ). in these studies from metal substrates it was found that the ablated material existed predominantly in the form of nanoparticles with a narrow size distribution . a u . s . patent application ser . no . 11 / 712 , 924 filed on mar . 2 , 2007 and published on jan . 10 , 2008 as us publication no . 2008 / 0006524 also teaches a method of generating nanoparticles from metals and metal oxides in a vacuum and ambient gas and depositing them on a substrate . the inventors have found that a low pulse energy near the ablation threshold is also preferred for formation of organic nanoparticle colloids . it is preferred for the present invention that the pulses have a pulse energy of from 1 nano - joules to 10 mili - joules , more preferably from 100 nano - joules to 10 micro - joules . the present inventors have discovered that a high pulse repetition rate is very beneficial for producing nanoparticles according to the present invention from organic source material . a preferred pulse repetition rate is in the range of from 1 hz to 100 mhz , more preferably 10 khz to 10 mhz and most preferably 100 khz to 5 mhz . these high repetition rates are beneficial for at least three reasons . first , these rates produce a multiple pulse effect in high repetition rate pulsed laser ablation . with a repetition rate of 100 khz or greater , for example , the pulse separation is 10 microseconds or less . this period of time is short enough that the ablated material , before drifting away from the laser focal volume , will receive multiple laser pulses and become highly charged . the inventors discovered stable nanoparticle colloids can be made at such high repetition rates without adding additional stabilizing chemical agents because of this charging . second , when the ablation process comprises multiple pulses of the ablated material , fragmentation of initially larger particles can occur , resulting in a final size distribution predominated by nanoparticles . finally , the high repetition rate leads to a high production rate of nanoparticles . the inventors have also discovered that fast rastering of the laser beam 1 during the ablation process is beneficial in conjunction with the high repetition rate to produce nanoparticles from organic sources . a preferred rastering rate is 0 . 01 meters per second or greater and more preferred is a rastering rate of 0 . 1 meters per second or greater . without such fast rastering of the laser beam 1 , the stream of nanoparticles 10 produced by the leading laser pulses will eventually block the subsequent laser pulses by scattering and absorption of the laser beam 1 . more importantly , accumulated heating of the liquid 5 due to the high repetition rate can also induce coagulation of the nanoparticles 10 . in addition to the laser parameters described above , the inventors have found that movement of the liquid 5 is also useful in making stable nanoparticle colloids . this is primarily because a dispersed colloidal suspension of nanoparticles 10 in a liquid 5 such as water is essentially in a metastable state , i . e ., a kinetically stable state and not a thermodynamically stable state . flow of the liquid 5 during production helps to reduce a nanoparticle &# 39 ; s 10 thermal movement , which may overcome the kinetic barrier to coagulation . preferably the liquid 5 flow rate is 1 milliliter per second or greater , more preferably 10 milliliter per second or greater . a fast rastering of the laser beam 1 is also beneficial in reducing a nanoparticle &# 39 ; s 10 thermal motion . fig2 schematically illustrates an alternative laser - based system for producing organic nanoparticles in a liquid in accordance with the present invention . in this embodiment the laser beam 1 is received from a ultrafast pulse source , not shown , and focused by the lens 2 . the source of the laser beam 1 can be any suitable pulsed laser source capable of providing a pulse duration , repetition rate and / or power level as discussed above . the focused laser beam 1 then passes from the lens 2 to the guide mechanism 3 for controlling movement of the laser beam 1 . the guide mechanism 3 can be any of those known in the art including by way of example piezo - mirrors , acousto - optic deflectors , rotating polygons , vibrating mirror , and prisms . preferably the guide mechanism 3 is a vibrating minor 3 to enable controlled and rapid movement of the focused laser beam 1 . the guide mechanism 3 directs the focused laser beam 1 at the target 4 . preferably the target 4 is a compressed pellet of the organic compound that is being converted into nanoparticles . the compressed pellet can be formed from a variety of powder sources of the organic material . the powdered source material is then compressed into a pellet using a mold and pressure . the bottom of the container 7 serves as glass window 6 to allow the focused laser beam 1 pass through to ablate the organic compound target 4 . the target can be submerged into the liquid 5 , or the bottom of target 4 can just touch a top surface of the liquid 5 . the distance between the bottom of target 4 and glass window 6 can be from several millimeters to preferably less than 1 centimeter . the container 7 includes the inlet 12 and the outlet 14 so the liquid 5 can be passed over the target 4 and so that it can be re - circulated . flow of the liquid 5 is used to carry generated nanoparticles 10 out of the container 7 to be collected elsewhere . the flow of liquid 5 over the target 4 also cools the laser focal volume . the liquid 5 can be any liquid that is largely transparent to the wavelength of the laser beam 1 and that preferably is a poor solvent for the target material 4 . in one embodiment the target 4 can be mounted on a rotating mechanism and spin during the ablation with the spin speed from several revolutions per minute to a several hundred revolutions per minute as shown by the arrow in the figure . as the target 4 rotates , some of the liquid described as the hydrodynamic boundary layer is dragged by the spinning . liquid flows up , perpendicular to the target 4 , from the bottom to replace the boundary layer . the sum results are a laminar flow of liquid 5 towards and across the target 4 , and distribution of the generated nanoparticles 10 into liquid 5 . this also prevents any gas bubbles generated during the laser ablation from staying on the target 4 . fig3 schematically illustrates another alternative laser - based system for producing organic nanoparticles in a liquid in accordance with the present invention . in this embodiment the laser beam 1 is received from a ultrafast pulse source , not shown , and focused by the lens 2 . the source of the laser beam 1 can be any suitable pulsed laser source capable of providing a pulse duration , repetition rate and / or power level as discussed above . the focused laser beam 1 then passes from the lens 2 to the guide mechanism 3 for controlling movement of the laser beam 1 . the guide mechanism 3 can be any of those known in the art including by way of example piezo - mirrors , acousto - optic deflectors , rotating polygons , vibrating mirror , and prisms . preferably the guide mechanism 3 is a vibrating mirror 3 to enable controlled and rapid movement of the focused laser beam 1 . the guide mechanism 3 directs the focused laser beam 1 at the target 4 . preferably the target 4 is a compressed cylinder of the organic compound that is being converted into nanoparticles . the compressed cylinder can be formed from a variety of powder sources of the organic material . the powdered source material is then compressed into a cylinder using a mold and pressure . the bottom of the container 7 serves as glass . window 6 to allow the focused laser beam 1 to pass through and to ablate the organic compound target 4 . the target 4 can be submerged into liquid 5 , or the side surface of target 4 can just touch the top surface of liquid 5 . the distance between the side surface of target 4 and glass window 6 can be from several millimeters to preferably less than 1 centimeter . the container 7 includes the inlet 12 and the outlet 14 so the liquid 5 can be passed over the target 4 and so that it can be re - circulated . flow of the liquid 5 is used to carry generated nanoparticles 10 out of the container 7 to be collected elsewhere . the flow of liquid 5 over the target 4 also cools the laser focal volume . the liquid 5 can be any liquid that is largely transparent to the wavelength of the laser beam 1 and that preferably is a poor solvent for the target material 4 . in one embodiment the target 4 is mounted on a rotating mechanism and rotates during the ablation with the rotation speed from several revolutions per minute to a several hundred revolutions per minute as shown by the arrow in the figure . in this layout , the nanoparticles 10 are generated at the side surface of the cylindrical organic compound target 4 instead of at the end surface of the cylindrical target . as the target 4 rotates , it will help to distribute generated nanoparticles 10 into liquid 5 , and prevent any gas bubbles generated during the laser ablation from staying on the target 4 . in a first experiment curcumin powder , purchased from sigma aldrich , was used as the organic source material . the curcumin powder was formed into a pellet of target material by compression in a 0 . 5 inch in diameter mold using three tons of pressure . the curcumin pellet was then ablated according to the present invention using deionized water as the liquid . the flow rate of the liquid in the container was about 80 milliliters per second . the curcumin pellet was ablated using an ultrafast pulsed laser having a wavelength of 1045 nanometers , using a pulse duration of 500 femtoseconds , a pulse energy of 1 microjoules , a power of 1 w and a pulse repetition rate of 1 mhz . the laser focus spot size was about 30 micrometers in diameter and the fluence is calculated at about 0 . 14 joules / cm 2 . the frequency of the vibrating mirror was 50 hz with a 4 millimeter trace for 0 . 4 meters per second . the obtained curcumin nanoparticle hydrocolloidal suspension had a yellow color . fig4 shows an absorption spectrum of the curcumin nanoparticle hydrocolloidal which is represented by an absorption peak centered at about 420 nanometers . the hydrocolloidal contains some large particles as evidenced by the spread of the peak and the background absorbance of the curve . the y - axis is the absorption and the x - axis is the wavelength . because curcumin does not dissolve in water there is no curcumin in water spectrum that can be used as a reference to compare to the hydrocolloidal curcumin nanoparticles . curcumin is dissolvable in methanol , thus the starting curcumin powder was dissolved in methanol at a concentration of 2 . 5 × 10 − 5 m to serve as a standard . in addition , 0 . 1 milliliters of the curcumin nanoparticle hydrocolloidal prepared according to the present invention was mixed with 1 . 0 milliliters of methanol . the mixture of prepared nanoparticle hydrocolloidal and methanol was a clear yellow colored solution as was the solution of curcumin powder dissolved in methanol . fig5 shows the absorption spectra of each curcumin methanol solution . the solid line trace is the hydrocolloidal sample prepared according to the present invention . the dotted line trace is the curcumin standard . as can be seen the two spectra are virtually identical with a major peak at 420 nanometers indicating the existence of curcumin in the hydrocolloidal sample . the trace with the slightly higher peak at 420 nanometers is from the hydrocolloidal sample prepared according to the present invention . the identical nature of the spectra indicates that ablation of a curcumin pellet in water using a low energy ultrafast pulsed laser according to the present invention does not destroy the curcumin structure , instead curcumin nanoparticles are generated and disperse into water forming a stable curcumin nanoparticle hydrocolloidal suspension . it was found that ablation of the curcumin pellet target in water using higher pulse energies generated larger particles and these larger particles tended to precipitate from the hydrocolloidal suspension . thus , as the pulse energy is increased the number of larger particles increases . these large particles can be easily separated from the hydrocolloidal suspension either by filtration or by centrifugal separation at 2000 rpm for 3 to 5 minutes . using filter paper to retain the large curcumin aggregates enables them to be separated from the curcumin hydrocolloid . the filter paper is then washed with methanol to dissolve the retained aggregates . for example , fisher p8 paper with a particle retention size of 25 microns can be used . using the pure curcumin powder dissolved in methanol an absorbance at 420 nm standard curve can be generated . then the curcumin level can be determined in both the nanoparticle hydrocolloid and in the filtrate washed off of the filter . then the efficiency of using laser ablation to generate curcumin nanoparticles can be determined . it was found that the efficiency of production of nanoparticles increased as the laser pulse energy was decreased . fig8 shows the efficiency of producing nanoparticles versus the laser repletion rate . the total power of the laser was fixed at 1 watt ; therefore , an increase of repetition rate represents a decrease of pulse energy . the efficiency was calculated from the amount of nanoparticles in colloidal solution and the amount of particles retained on the filter paper as a percentage of the total . the amounts in each were determined from the absorbance at 420 nanometers of uv - vis absorption curves for colloid / meoh and filter paper retained particles dissolved in methanol as described above . if the laser pulse energy is decreased too much , then the production rate is too slow . it is possible to compensate for some of the low production rate at low pulse energies by raising the repetition rate . fig6 is a transmission electron microscope ( tem ) image of curcumin nanoparticles generated from a pellet of curcumin in deionized water according to the present invention . the average power of the laser used was 0 . 9 w with a repetition rate of 100 khz , pulse energy of 9 micro - joules , wavelength of 1045 nanometers , pulse duration of 500 femtoseconds . the laser beam had a focal spot diameter of 50 microns and the raster rate was as described above . the generated nanoparticle hydrocolloidal suspension was filtered through fisher scientific &# 39 ; s p8 filter paper which has a retention size of 25 microns . a drop of the filtrate was transferred to a tem sampling grid and dried . although the curcumin nanoparticles aggregate during the drying process , the original nanoparticles are still recognizable and it can be seen that most have a size of less than 100 nanometers . fig7 a is the mass spectrum ( ms ) of pure curcumin starting powder and fig7 b is the ms of a curcumin hydrocolloidal sample prepared according to the present invention . the curcumin hydrocolloidal sample was prepared using ultrafast laser ablation according to the present invention in a container with the following laser parameters : 1 watt of power , repetition rate of 1 mhz , wavelength of 1045 nanometers , 500 femtosecond pulse duration , and the same raster rate as described above . the liquid was deionized water . it is observed that the most intense peaks in both ms tracings are at a mass of 391 for both standard curcumin and the hydrocolloidal sample , which indicates that the curcumin molecules are unchanged during the laser ablation according to the present invention . the major peak at mass 391 can be assigned to the complex of curcumin , mass 368 , and sodium , mass 23 . the starting curcumin powder was examined using energy dispersed spectroscopy and no existence of sodium in the curcumin powder was found . this indicates that the sodium is introduced into both samples during the ms process . despite the appearance of sodium on the ms for both standard curcumin and the hydrocolloidal sample , this does not change the fact that laser ablation of the curcumin pellet in water to form the nanoparticle hydrocolloidal did not destroy the molecular structure of the curcumin . while the present invention has been illustrated using curcumin as the organic target material and deionized water as the liquid it is much more broadly applicable . any other organic material that can be formed into a target pellet could be used as the target material . alternatively , as discussed above , the target can be another source of the organic compound material such as : a film of the organic compound that has been deposited onto a substrate ; a bulk material of an organic compound with at least one dimension that is larger than 5 mm ; a stream of the bulk organic compound which has been ejected from a nozzle into the liquid ; or a paste of the bulk organic compound that has been introduced into the liquid . any of these can serve as the target material in the present invention . in addition , liquids other than deionized water could be used depending on the desired colloidal suspension . the foregoing invention has been described in accordance with the relevant legal standards , thus the description is exemplary rather than limiting in nature . variations and modifications to the disclosed embodiment may become apparent to those skilled in the art and do come within the scope of the invention . accordingly , the scope of legal protection afforded this invention can only be determined by studying the following claims .
disclosed is a method of producing a chemically pure and stably dispersed organic nanoparticle colloidal suspension using an ultrafast pulsed laser ablation process . the method comprises irradiating a target of an organic compound material in contact with a poor solvent with ultrashort laser pulses at a high repetition rate and collecting the nanoparticles of the organic compound produced . the method may be implemented with a high repetition rate ultrafast pulsed laser source , an optical system for focusing and moving the pulsed laser beam , an organic compound target in contact with a poor solvent , and a solvent circulating system to cool the laser focal volume and collect the produced nanoparticle products . by controlling various laser parameters , and with optional poor solvent flow movement , the method provides stable colloids of dispersed organic nanoparticles in the poor solvent in the absence of any stabilizing agents .