WO2017011877A1 - Détection de nanoparticules d'or - Google Patents

Détection de nanoparticules d'or Download PDF

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WO2017011877A1
WO2017011877A1 PCT/AU2016/050649 AU2016050649W WO2017011877A1 WO 2017011877 A1 WO2017011877 A1 WO 2017011877A1 AU 2016050649 W AU2016050649 W AU 2016050649W WO 2017011877 A1 WO2017011877 A1 WO 2017011877A1
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gold
bodipy
fluorescent
concentration
nanoparticles
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PCT/AU2016/050649
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English (en)
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Agnieszka ZUBER
Heike Ebendorff-Heidepriem
Malcolm Stuart PURDEY
Andrew David Abell
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Deep Exploration Technologies Crc Limited
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Priority claimed from AU2015902890A external-priority patent/AU2015902890A0/en
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Publication of WO2017011877A1 publication Critical patent/WO2017011877A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/648—Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence

Definitions

  • the present invention relates to methods for the detection and measurement of low concentrations of gold nanoparticles utilising fluorescence spectroscopy. It is envisaged that the methods of the present invention will find use in a wide variety of technical areas from mineral exploration through to biomedical and environmental research and to medical diagnosis and gene therapy.
  • Gold is utilised in everyday life from jewellery, through electronics, to drug delivery.
  • Global consumer demand for this precious metal is increasing, and in 2013 it reached above 4000t per year.
  • the major consumers are China and India, demanding 1275 ton and 975 ton in 2013 respectively.
  • the global discovery rate of gold deposits is rapidly declining, which is primarily a function of mineral deposits exposed at the Earth's surface already being found, and undiscovered deposits being buried by younger rock sequences.
  • an alternative method for gold exploration is to analyse the concentration of gold in the regolith, as well as in the leaves and twigs of trees growing in the area of gold deposits.
  • gold is first transported in an ionic (Au 3+ ), water soluble form from roots to leaves, and then reduces to gold nanoparticles (in a non-oxidised state, represented as Au°) and accumulates within plant cells.
  • Au° gold nanoparticles
  • the subsequent analysis of such plant samples to determine the concentration of gold nanoparticles in the samples can avoid the need for traditional exploratory drilling to recognise the signature of a nearby gold deposit.
  • Plants are not the only living organisms capable of accumulating gold nanoparticles. Bacteria such as Cupriavidus metallidurans can also take up gold ions (Au 3+ ) and convert them into gold nanoparticles (Au°), which contribute to the formation of gold grains in soil. The ability to detect low concentrations of gold nanoparticles in soil can also potentially reduce the cost of searching for new gold deposits.
  • Gold nanoparticles conjugated with antibodies are used for drug delivery and sensing applications, and gold nanoparticles are also employed for gene therapy and gene specific sequence sensing.
  • Sensitive methods for the detection of gold nanoparticles would thus facilitate tracking a potentially dangerous accumulation of gold nanoparticles in these cells.
  • detection at concentration levels in the parts per billion (ppb) range is required, noting that the accumulation of gold nanoparticles in rat organs after administration of 0.56mg of nanoparticles per gram of animal are known to range from 0.08ppb in brain, through 20ppb in muscle and 30ppb in bone, to 260ppb in blood.
  • Similar detection limits as for medical diagnosis can be beneficial for gold exploration purposes.
  • the average crustal abundance of gold is about 1 .3ppb, while anomalous gold concentrations can be between 0.5 and 8ppm. Therefore, detecting anomalous levels of gold also requires instrumentation with low detection limits, again in the ppb range.
  • nanoparticles according to the American Society for Testing and Materials (ASTM) standard definition, are particles with lengths that range from 1 to 100 nm in two or three dimensions, and that a "ppb range” is a range from 1 to 1000 pg/kg (or 1 to 1000 pg/L).
  • the present invention provides a method for detecting gold nanoparticles present in an aqueous sample containing gold nanoparticles, the method including: a) mixing a fluorophore with the aqueous sample containing gold nanoparticles to form a fluorescent gold solution, the fluorophore being a boron-dipyrromethane (BODIPY) dye, the fluorescent gold solution having a BODIPY concentration in a range of from 1 .0 nM to 500.0 nM;
  • BODIPY boron-dipyrromethane
  • the fluorescent gold solution has a BODIPY concentration in a range of from 5.0 nM to 300.0 nM. In another form, the fluorescent gold solution has a BODIPY concentration in a range of from 10.0 nM to 150.0 nM. In another form, the fluorescent gold solution has a BODIPY concentration of about 60.0 nM.
  • the BODIPY fluorophore may be any of the fluorescent dyes composed of dipyrromethane complexed with a disubstituted boron atom, typically a BF 2 unit, and having a core of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene as below:
  • the method of the present invention will utilise a BODIPY fluorophore in the form of a bisiodinated derivative of BOBIPY, preferably one obtained by the introduction of iodine at the 2,6-positions of the BODIPY, and more preferably being one synthesised by the reaction of a fluorescent H-BODIPY with iodine to form a non-fluorescent l-BODIPY.
  • l-BODIPY shows specific and desirable reactivity towards gold nanoparticles, with fluorescence being observed as a result of a catalytical change of the non-fluorescent l-BODIPY to the fluorescent H-BODIPY upon excitation of the fluorescent gold solution.
  • the synthesis of a suitable l-BODIPY is conducted via the addition of l 2 to H-BODIPY, while HIO 3 is added dropwise, ideally while stirring, until it turns a deep fluorescent red/brown colour.
  • the compound may then be eluted through a column to provide an l-BODIPY fluorophore as a dark red solid.
  • the solid l-BODIPY fluorophore can then be dissolved in a polar aprotic solvent, being a solvent that dissolves salts but lacks an acidic hydrogen, and has both high dielectric constants and high dipole moments.
  • a polar aprotic solvent being a solvent that dissolves salts but lacks an acidic hydrogen, and has both high dielectric constants and high dipole moments.
  • suitable solvents are the organosulfur compound dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and hexarnethylphosphoric amide (HMPA), with DMSO being the preferred solvent.
  • the dissolved l-BODIPY fluorophore is then preferably diluted in an aqueous solution prior to being mixed with the aqueous sample to form the fluorescent gold solution.
  • the preparation of the fluorescent gold solution in this manner is thus ideally conducted in the presence of a 100% water solvent, rather than an alcohol-based solvent, as diluting the l-BODIPY in water instead of alcohol broadens the range of potential applications, especially the biological applications, where cells die and proteins denaturate in the presence of alcohol.
  • the l-BODIPY fluorophore is preferably in the form of:
  • the method of the present invention thus includes the step of mixing a fluorophore with the aqueous sample to form a fluorescent gold solution, the fluorophore being an l-BODIPY dye of Formula B dissolved with a polar aprotic solvent and water, the fluorescent gold solution having an l-BODIPY concentration in the range of 1 .0 nM to 500.0 nM, or in a range of from 5.0 nM to 300.0 nM, or in a range of from 10.0 nM to 150.0 nM, or of about 60.0 nM.
  • the method of the present invention includes the addition of the fluorescent gold solution to an optical chamber.
  • the optical chamber can be any suitable form of optical chamber, suitable for holding samples for spectroscopic experiments, such as a cuvette or an optical fibre sensor.
  • Suitable cuvettes include optical glass cuvettes, plastic cuvettes, fused quartz cuvettes, or UV, visible or IR quartz cuvettes.
  • Suitable optical fibre sensors include sensors that utilize evanescent field based sensing, such as tapered fibre sensors, D- shaped fibre sensors, microstructured optical fibres, photonic crystal fibres, and nanowires, and also include sensors that do not rely on the use of an evanescent field, such as capillary tubes, fibre tip sensors and hollow core photonic bandgap fibres.
  • evanescent field based sensing such as tapered fibre sensors, D- shaped fibre sensors, microstructured optical fibres, photonic crystal fibres, and nanowires
  • sensors that do not rely on the use of an evanescent field such as capillary tubes, fibre tip sensors and hollow core photonic bandgap fibres.
  • One particular form of optical fibre sensor envisaged to be beneficial for use with the method of the present invention is the optical fibre sensor described in International patent publication WO2009/012528A1 , the full content is herein incorporate by reference in order to include a description of one suitable form of optical fibre sensor.
  • an optical chamber for use in the method of the present invention would be such an optical fibre sensor, and would include an elongate central core for propagating incident light, an interaction region capable of receiving the fluorescent gold solution for excitation by the incident light to produce emitted fluorescent light, and an interface region (at least one elongate chamber) located between the elongate core and the interaction region.
  • the interface region can be provided by three elongate chambers configured symmetrically along the fibre sensor about the elongate core.
  • the method of the present invention includes the excitation of the fluorescent gold solution in the optical chamber with incident light to produce emitted fluorescent light, and the subsequent collection of the emitted fluorescent light and the determination of the concentration of the gold nanoparticles in the fluorescent gold solution and thus in the aqueous sample, all being steps based upon fluorescence spectroscopy, a measurement technique reliant on the analysis of fluorescence from a sample.
  • fluorescence spectroscopy utilises the excitation of a fluorescent sample (containing a fluorophore) with incident light to produce emitted fluorescent light, and the subsequent collection of the emitted fluorescent light to permit the determination of the concentration of the fluorophore in the sample.
  • Fluorescence occurs when a fluorescent capable material (the fluorophore) is excited into a higher electronic state by absorbing an incident photon and cannot return to the ground state except by emitting a photon.
  • the emission usually occurs from the ground vibrational level of the excited electronic state and goes to an excited vibrational state of the ground electronic state.
  • the energies and relative intensities of the fluorescence signals give information about structure and environments of the fluorophores.
  • the fluorescent gold solution is allowed to incubate in the optical chamber during excitation with incident light for a period of between 40 and 60 minutes before the emitted fluorescent light is collected for the determination of the concentration of the gold nanoparticles.
  • this incubation period is about 50 minutes.
  • the peak fluorescence intensity increases during this incubation time and then becomes saturated, indicating that after the incubation time, equilibrium for the transformation of l-BODIPY into H-BODIPY is reached, with further incubation being unlikely to further improve the fluorescence intensity.
  • the method additionally includes a pre-treatment step where the concentration of the nanoparticles in the aqueous sample is increased without altering the concentration of the gold in the aqueous sample.
  • the pre-treatment step includes reducing the size of the nanoparticles without reducing the gold concentration, such as by known filtration or separation steps, including density gradient centrifugation, magnetic fields, chromatography, electrophoresis, selective precipitation, membrane filtration or extraction.
  • the detection limit of the method of the present invention improves with decreasing nanoparticle size, which is believed to be due to the larger number of nanoparticles present in a sample of smaller nanoparticles with the same gold concentration, noting that, for example, for the same gold concentration of 74ppb, the nanoparticle concentration is higher for 5nm nanoparticles (97.3pM) compared to 50nm nanoparticles (0.97pM).
  • the catalytic effect of the gold nanoparticles increases with the increasing amount of the nanoparticles in a certain sample volume as more gold nanoparticles are then available to react with the BODIPY fluorophore.
  • the need for such an additional pre-treatment step is more likely in applications where the range of sizes of nanoparticles in the aqueous sample is broader and somewhat random, as might be expected in mineral exploration applications.
  • the component parts typically necessary for fluorescence spectroscopy are a sample holder (referred to above as the optical chamber) and a spectrometer, an incident photon source, monochromators used for selecting particular incident wavelengths, focussing optics, a photon-collecting detector (single, or preferably multiple channel, and usually set at 90 degrees to the light source) and finally a control software unit.
  • An emission monochromator or cutoff filters may also be employed.
  • a method for determining the gold concentration of an ore body including preparing from the ore body an aqueous sample containing gold nanoparticles, and thereafter conducting on the aqueous sample the detecting method as described above.
  • Figure 1 shows the optical set-up for the measurement of BODIPY in the presence of gold nanoparticles in a cuvette, for the purpose of the following experimental work for preferred embodiments of the method of the present invention.
  • Figure 2 shows the optical set-up for the measurement of BODIPY in the presence of gold nanoparticles in an optical fibre sensor, for the purpose of the following experimental work for preferred embodiments of the method of the present invention.
  • Figure 3A shows a cross-sectional image of the optical fibre sensor used in Figure 2 (with the inset showing a magnified image of the fibre core).
  • Figure 3B shows an example of a fibre core for the optical fibre sensor used in Figure 2, indicating the intensity of the evanescent field in the holes surrounding the fibre core with high intensity marked red and low intensity marked blue.
  • Figure 4 shows a fluorescence spectrum measured in the cuvette set-up of Figure 1 using a laboratory spectrometer at a 50m in incubation period for different concentrations of 5nm gold nanoparticles in water with a 60.0 nM l-BODIPY fluorophore.
  • Figure 5 shows the impact of incubation time on the fluorescence intensity for a range of gold concentrations measured in the cuvette set-up of Figure 1 , again using a laboratory spectrometer and 5nm (A), 20nm (B) and 50nm (C) gold nanoparticles mixed with a 60.0 nM l-BODIPY fluorophore.
  • Figure 6 shows fluorescence spectra for a range of concentrations of an I- BODIPY fluorophore with 197ppb of 5nm gold nanoparticles measured in the cuvette set-up of Figure 1 .
  • Figures 7A and 7B show the dependence of the fluorescence intensity at 510nm on gold concentration for 5nm, 20nm and 50nm gold nanoparticles with 50 minutes of incubation with a 60.0 nM l-BODIPY fluorophore, again measured in the cuvette set-up of Figure 1 , with Figure 7A using a laboratory spectrometer and Figure 7B using a portable spectrometer.
  • Figure 8 shows the detection limit for different sized gold nanoparticles in the cuvette set-up of Figure 1 , based on fluorescence measurements using a 50 minute incubation time and a 60.0 nM l-BODIPY fluorophore for both a laboratory spectrometer and a portable spectrometer.
  • Figure 9 shows the fluorescence spectra obtained with the optical fibre sensor set-up of Figure 2, again with a 60.0 nM l-BODIPY fluorophore and different gold concentrations of 5nm gold nanoparticles after a 50 minute incubation time using a high resolution laboratory spectrometer.
  • Figures 10A and 10B show the detection limit for three different sizes of gold nanoparticles (A-5nm, B-20nm, C-50nm) measured with the optical fibre sensor set-up of Figure 2 using a laboratory spectrometer ( Figure 10A) and a portable spectrometer ( Figure 10B).
  • Figure 10A a laboratory spectrometer
  • Figure 10B a portable spectrometer
  • Nanocomposix Commercially available, monodispersed gold nanoparticles in three different sizes (4.8 ⁇ 0.7nm, 20 ⁇ 2.5nm and 51 ⁇ 6.1 nm diameter, hereafter referred to as 5nm, 20nm and 50nm NPs) were acquired from Nanocomposix.
  • the initial concentration of the nanoparticles in 2mM sodium citrate solution was 0.25mM.
  • a range of concentrations was prepared by adding nanoparticulate solution to water with a final volume of 2ml.
  • the concentration of gold nanoparticles was calculated using: where c s is the molar concentration of gold NPs, c Au is the molar concentration of gold atoms/ions, M Au is the molecular weight of gold, p Au is the density of gold, D s is the diameter of the gold NPs, and N A is the Avogadro constant.
  • the fluorophore l-BODIPY was synthesized by reaction of H-BODIPY with iodine. Specifically, H-BODIPY (25mg, 0.08 mmol) was suspended in methanol (10 ml_), and l 2 (54 mg, 0.20 mmol) was added whilst stirring. A solution of HIO3 (30 mg, 0.16 mmol) in water (200 ⁇ _) was added dropwise over 5 min. The reaction mixture was stirred at 25 °C for 30 min and the solution turned a deep fluorescent red/brown colour.
  • l-BODIPY was first dissolved in dimethyl sulfoxide (DMSO) and then diluted in water as a solvent, for subsequent use in forming fluorescent gold solutions with the required l-BODIPY concentration.
  • DMSO dimethyl sulfoxide
  • the SCF was an optical fibre sensor of the type described in International patent publication WO2009/012528A1 , the whole content of which is incorporated by reference for the purpose of describing suitable optical fibre sensors.
  • the SCF included an elongate central core for propagating incident light, an interaction region capable of receiving the fluorescent gold solution for excitation by the incident light to produce emitted fluorescent light, and an interface region located between the elongate core and the interaction region.
  • the interface region in the SCF was provided by three elongate chambers configured symmetrically along the fibre sensor about the elongate core.
  • part of the light guided along its fibre core is located outside of the core, in the elongate chambers, commonly referred to as its evanescent field.
  • the portion of the light located in the elongate chambers can be used for light- matter-interaction, and hence sensing of an analyte situated in the elongate d chambers.
  • Such SCFs offer a range of advantages for sensing applications, including that the analysis in such a SCF requires only small samples (nanoliter volumes), and that sensing with a SCF can be made highly specific by binding specific functional groups on the surface of the fibre core. Also, due to their compact size, such an SCF is particularly suitable for portable devices such that SCFs are useful for remote measurements, such as might be required for mineral exploration.
  • silica is made in ultrahigh purity, enabling low fibre loss and thus the use of long fibre length. Also, the high thermal, mechanical and corrosion stability of silica allows use in harsh environments, and the relatively low refractive index of silica (1 .45 in the visible) leads to a larger fraction of light being located in the air holes, enabling higher sensitivity.
  • the power fraction of light in the elongate chambers of the SCF increases with decreasing core size, and hence the sensitivity of the SCF increases with decreasing core size. Therefore, a SCF was used with a small core diameter of 1 .5pm with a cross-sectional structure shown in Figure 3a. Additionally, the fraction of light being guided in the elongate chambers for sensing is schematically shown in Figure 3b.
  • the fibre core is surrounded by three elongate chambers of 60 pm diameter, such that the large chamber size prevents blockage by particles present in a liquid, as well as reducing the required time to fill the SCF.
  • the fibre was mounted on a 3- axis stage and light was coupled into the core until maximal power at the end of the fibre was measured with a power meter. Approximately 50 cm lengths of fibre were used for the experiment.
  • the fluorescence was measured using a 473nm laser with 8mW output power and an exposure time of 4 seconds.
  • the laser power was decreased to yield similar signal intensity to that of the cuvette results.
  • l-BODIPY was added in a 1 : 1 ratio into the aqueous samples containing gold nanoparticles to form the fluorescent gold solution referred to above.
  • the spectrum of a blank sample (a solution of l-BODIPY with no gold nanoparticles) was subtracted from all spectra measured for samples containing gold nanoparticles.
  • LOQ limit of quantification
  • the experimental detection limit is the lowest gold concentration used for which the fluorescence intensity is higher than the LOQ value.
  • the theoretical detection limit is the gold concentration value at which the corresponding fluorescence intensity is equal to the LOQ value.
  • the gold concentration is calculated using the linear regression of the concentration dependence of the fluorescence intensity.
  • the l-BODIPY fluorophore in the fluorescent gold solution when tested in the cuvette set-up of Figure 1 , resulted in a fluorescence peak at 510nm (the vertical black line in Figure 4) in the presence of the gold nanoparticles, whereby the intensity of the peak increased with increasing concentration of gold nanoparticles in the solution.
  • a laboratory spectrometer and these cuvette measurements the impact of the incubation time of the fluorescent gold solution, and of the l-BODIPY concentration, on the fluorescence intensity and detection limit of 5nm, 20nm and 50nm gold nanoparticles was assessed.
  • Figure 5 shows the impact of incubation time on the fluorescence intensity.
  • the peak fluorescence intensity increased until approximately 50 minutes and then became saturated, indicating that after an incubation time of 50 minutes, equilibrium for the transformation of l-BODIPY into H-BODIPY was reached.
  • the reaction rate for small nanoparticles (5nm) is slower than than for the larger nanoparticles (20nm, 50nm).
  • the fluorescence intensity of the samples is measured at the same incubation time regardless of nanoparticle size, which is preferably after an incubation time between about 40 and 60 minutes, but more preferably after an incubation time of about 50 minutes.
  • the detection limit of cuvette measurements using the portable spectrometer was found to be identical to that using the laboratory spectrometer: namely, 74ppb for the 5nm gold nanoparticles and 1230ppb for the 50nm gold nanoparticles; and slightly different for the 20nm gold nanoparticles (392ppb and 492ppb).
  • the similar detection limits achieved using two different spectrometers confirms consistency across the same optical set up, and the same amount of laser light coupled into the sample, and the same method of collection of fluorescent light measured, confirming the applicability of the method of the present invention to a portable, off-site, use, such as would be required for remote mineral exploration efforts.
  • the consistent detection limit is also reflected in a similar LOQ being obtained (using Eq (2) above) for both spectrometers (being 0.015 for the laboratory spectrometer and 0.032 for the portable spectrometer). These values are of course usually higher than the theoretical detection limit values presented in Table 1 (below) due to the range of analysed concentrations. In this respect, it will be appreciated that these theoretical detection limit values represent a concentration in the range between the detection limit (the LOQ value) and the lowest experimentally detected signal above the detection limit.
  • the theoretical detection limit is the gold nanoparticle concentration that yields a fluorescence intensity that equals the LOQ value. This concentration was determined using a line between the lowest experimentally used gold concentration yielding a fluorescence intensity above LOQ and the highest experimentally used concentration yielding a fluorescence intensity below LOQ.
  • the experimental detection limits for these measurements are: laboratory spectrometer (see Figure 10A) - 74ppb for 5nm gold nanoparticles, 492ppb for 20nm gold nanoparticles, 738ppb for 50nm gold nanoparticles; portable spectrometer (see Figure 10B) - 74ppb for 5nm gold nanoparticles, 246ppb for 20nm gold nanoparticles and 492ppb for 50nm gold nanoparticles.
  • a similar detection limit regardless of the type of spectrometer used is related, at least in part, to the use of the same optical set up for the measurements, and is reflected in similar values of LOQ (0.059 for the laboratory spectrometer and 0.025 for the portable spectrometer).
  • the catalytic effect of the gold nanoparticles increases with the increasing amount of the nanoparticles in a certain sample volume as more gold nanoparticles are available to react with the l-BODIPY fluorophore. Additionally, for all nanoparticle sizes, the molar nanoparticle concentration at detection limits is considerably smaller than that of the l-BODIPY fluorophore, which is consistent with the gold nanoparticles acting as catalyser for the reaction of the l-BODIPY to H-BODIPY.
  • the lower detection limit for the 50nm nanoparticles measured in the SCF compared to the cuvette measurement is attributed to the interactions between gold nanoparticles and the silica core of the fibre of the SCF.
  • the repulsion forces are stronger than for bigger nanoparticles.
  • the 50nm nanoparticles thus attach to the fibre core of the SCF and interact with light longer than the 5nm nanoparticles do, resulting in a decreased detection limit in the SCF fibre in contrast to the cuvette.
  • gold nanoparticles conjugated with ligand, such as antibody, which binds specifically to a target such as a cancer cell or protein could be quickly analysed without the need for time consuming analysis by ICP-MP, ICP-AES or TEM, leading to faster diagnosis of carcinogenesis or proteopathies.

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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

L'invention concerne un procédé de détection de nanoparticules d'or présentes dans un échantillon aqueux contenant des nanoparticules d'or, le procédé consistant : a. à mélanger un fluorophore à l'échantillon aqueux contenant des nanoparticules d'or pour former une solution d'or fluorescente, le fluorophore étant un colorant bore-dipyrrométhane (BODIPY), la concentration en BODIPY de la solution d'or fluorescente étant comprise entre 1,0 nM et 500,0 nM; et b. à exciter la solution d'or fluorescente dans une chambre optique avec de la lumière incidente pour produire une lumière fluorescente émise, à collecter la lumière fluorescente émise, et à déterminer la concentration de nanoparticules d'or dans la solution d'or fluorescente et ainsi dans l'échantillon aqueux.
PCT/AU2016/050649 2015-07-21 2016-07-21 Détection de nanoparticules d'or WO2017011877A1 (fr)

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CN113646630A (zh) * 2019-03-29 2021-11-12 百时美施贵宝公司 测量色谱树脂的疏水性的方法

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