MICRON AND SUB-MICRON SIZED PARTICLES WITH REDUCED ENVIRONMENTAL INTERACTIONS AND METHODS FOR PRODUCING THESE PARTICLES

Description

This application claims the benefit of U.S. Provisional Application No. 63/654,883, filed 31 May 2024, the entirety of which are hereby incorporated herein by reference.

GOVERNMENT RIGHTS

This invention was made with government support under contract number 2328262 awarded by the National Science Foundation. The government has certain rights in the invention.

FIELD

Embodiments of the present disclosure relate generally to modification, stabilization and/or reduction of particles, and to modification, stabilization and/or reduction of particles using cannabinoids.

BACKGROUND

Various types of modern equipment (electronic circuit boards being one example) utilize materials (e.g., micro- and nano-sized particles) that interact with the environment. Example environments where unmodified materials may be placed and interact include the ambient atmosphere and living tissue, such as the human body where materials may be placed for medical reasons. Interaction between the materials (and particles of the materials) and their environment during manufacture, utilization and/or application can result in changes in the performance of the material, which can be apparent almost immediately, or over time. Some examples of these interactions are oxidation of the material (and particles of the materials) in the presence of gases, radicals, ions, heat and/or water. As an example, even small amounts of surface oxidation of electronic components such as printed circuit boards (PCBs) can have a substantially negative impact on the performance of the components. To prevent these interactions, some common approaches include sealing, coating and/or encapsulating the materials using non-reactive materials, such as noble metals (e.g., gold or platinum) or carbon-based materials.

However, it was realized by the inventors of the current disclosure that problems exist with current methods of preventing materials from reacting with the environment, such as oxidizing in moist or alkaline environments, and that improvements in the ability to create and utilize particles that do not interact with the environment are needed. For example, it was realized that many types of ligands are not natural and have detrimental or unknown effects on humans and the environment.

Certain preferred features of the present disclosure address these and other needs and provide other important advantages.

SUMMARY

Embodiments of the present disclosure provide improved apparatuses and methods for manufacturing particles with limited environmental interaction.

Various embodiments include cannabinoid-based capping of micron and sub-micron particles.

Additional embodiments of the present disclosure relate generally to the manufacture and/or use of particles that are modified to change how they interact with the environment, and to particles that are typically reactive with the environment that are modified using cannabinoids to reduce the tendency of the particle to react with the environment, such as to oxidize in the presence of moisture and/or oxygen.

Further embodiments of this disclosure relate generally to the manufacture, processing and/or application of particles whose performance can be degraded by oxidizers and/or corrosive media present in ambient or application specific environments. Particles may be modified, stabilized and/or reduced using cannabinoids to reduce detrimental impact to particle performance (i.e., electrical, thermal and/or functional performance) resulting from exposure to environments with oxidizers, corrosive agents and/or environmental conditions that accelerate degradation, such as the presence of moisture, oxygen, radicals, ions and/or heat.

Still further embodiments of the present disclosure create materials that are capped by cannabinoids, which may have uses in the manufacture of printed electronics, such as by producing a relatively inexpensive conductive ink that resists oxidation when exposed to corrosive environments. One advantage of these materials is that they may be readily substituted for the printed materials that are currently used in industry while requiring little or no equipment modification.

This summary is provided to introduce a selection of the concepts that are described in further detail in the detailed description and drawings contained herein. This summary is not intended to identify any primary or essential features of the claimed subject matter. Some or all of the described features may be present in the corresponding independent or dependent claims, but should not be construed to be a limitation unless expressly recited in a particular claim. Each embodiment described herein does not necessarily address every object described herein, and each embodiment does not necessarily include each feature described. Other forms, embodiments, objects, advantages, benefits, features, and aspects of the present disclosure will become apparent to one of skill in the art from the detailed description and drawings contained herein. Moreover, the various apparatuses and methods described in this summary section, as well as elsewhere in this application, can be expressed as a large number of different combinations and subcombinations. All such useful, novel, and inventive combinations and subcombinations are contemplated herein, it being recognized that the explicit expression of each of these combinations is unnecessary.

BRIEF DESCRIPTION OF THE DRAWINGS

Some of the figures shown herein may include dimensions or may have been created from scaled drawings. However, such dimensions, or the relative scaling within a figure, are by way of example, and not to be construed as limiting.

FIG. 1A depicts chemical structures of example cannabinoids according to embodiments of the present disclosure.

FIG. 1B depicts example chemical modifications to change the solubility in water according to at least one embodiment of the present disclosure.

FIG. 2A depicts a first step in the synthesis of capped metal particles through acid reduction of ions according to at least one embodiment of the present disclosure.

FIG. 2B depicts another step in the synthesis of capped metal particles through acid reduction of ions that may follow the step illustrated in FIG. 2A according to at least one embodiment of the present disclosure.

FIG. 2C depicts still another step in the synthesis of capped metal particles through acid reduction of ions that may follow the step illustrated in FIG. 2B according to at least one embodiment of the present disclosure.

FIG. 3 depicts four samples of copper particles, some of which have been treated according to embodiments of the present disclosure, suspended in water after a five hour period.

FIG. 4A depicts the corrosion rate of bare copper and copper with corrosion inhibitors (Cu—Cl) including the ligands cannabidiol, benzotriazole, polyvinylpyrrolidone and curcumin over a 24-period with measurements taken every hour according to embodiments of the present disclosure. The corrosion rate of copper in micrometers per year (um/yr) is plotted versus the time of measurement in hours.

FIG. 4B depicts the 24-hour maximum inhibitor efficiency in percentage of the corrosion rate analysis illustrated in FIG. 4A with bare copper as a reference for the ligands cannabidiol, benzotriazole, polyvinylpyrrolidone and curcumin according to embodiments of the present disclosure.

FIG. 5A depicts thermogravimetric analysis (TGA) of bare copper particles in air (oxidizing), cannabidiol-capped copper particles (CuP-CBD) in air, and CuP-CBD in nitrogen (inert) according embodiments of the present disclosure. The left plot compares the mass gain in percentage to the temperature from 50 to 600° C., and the right plot is an enhanced (blown up portions of a subset of the left plot) plot showing the mass gain in percentage to the temperature from 100 to 250° C.

FIG. 5B depicts a scanning electron microscopy (SEM) image of the CuP-CBD Air sample from FIG. 5A after TGA according to at least one embodiment of the present disclosure.

FIG. 5C depicts a scanning electron microscopy (SEM) image of the CuP-CBD Nitrogen sample from FIG. 5A after TGA according to at least one embodiment of the present disclosure.

FIG. 6 depicts the XRD spectra of CBD-coated copper particles as synthesized in FIG. 2. The natural log of the counts with arbitrary units is plotted vs. the 2-theta angle of measurement. The 2-theta angle from 30 to 80 degrees is reported. The crystal lattice values that correspond to zero-valent copper are labelled above the corresponding peaks.

FIG. 7 depicts FTIR spectra of CBD-coated copper particles and of CBD measured from 4000 to 600 wavenumber. The absorbance vs. the wavenumber is reported for each sample with independent axes for each with CuP-CBD ranging from 0.0 to 0.4 and CBD from −0.1 to 0.6 absorbance (for clarity). Some but not all shared peaks between CuP-CBD and CBD that are normally not present in copper particles are highlighted with vertical lines and approximate wavenumber.

FIG. 8 illustrates the type of arrangement that is expected of the CBD on the surface of a copper particles according to simulation and experimental results. CBD arrangement is exaggerated with the alkyl chain facing the copper particle directly which will vary in reality depending on coating conditions and the thickness of copper coating on the surface.

FIG. 9A depicts differential scanning calorimetry (DSC) of copper (I) oxide (CuO) particles in a composite with cannabidiol according to embodiments of the present disclosure. The heat flow in watts per gram (W/g) is plotted versus the temperature. The direction of temperature scan is indicated by arrows. Endothermic heat flow is in the positive direction and labelled with negative values (sample is absorbing heat).

FIG. 9B depicts a scintillation vial with copper (I) oxide (CuO), cannabidiol, and zero-valent copper that has been temperature treated in argon at 200° C. to demonstrate the reduction of CuO to copper (Cu) according to embodiments of the present disclosure.

FIG. 10A illustrates the processing of a conductive composite comprising cannabidiol-capped copper particles (CuP-CBD) and a polycannabinoid binder phase using a uniform applied load by a press or lamination while being heated according to at least one embodiment of the present disclosure.

FIG. 10B illustrates the formation of inter-particle necking as a result of the processing conditions in FIG. 10A according to at least one embodiment of the present disclosure.

FIG. 10C depicts a scanning electron microscopy (SEM) image of a fractured composite surface processed according to FIG. 10A using a hot press at 90° C. according to at least one embodiment of the present disclosure.

FIG. 11 depicts the conductivity of conductive copper traces processed according to FIG. 10A versus variable hot-press temperature ranging from 40-160 Celsius for 1 weight percent (wt %) cannabidiol content and from 40-200° C. for 2 wt % cannabidiol content according to at least one embodiment of the present disclosure. Positive and negative error represents the standard deviation of the sample set at each temperature for a given wt %. In FIG. 11, the behavior of the CBD with respect to the particle can be divided into temperature regions, for example: Region 1<90° C.; Region 2 90-120° C.; and Region 3>120° C. which is denoted with vertical lines. The functionality of the cannabidiol (CBD) in each of these regions can be classified as described in the callout titled “CBD Functionality in Temperature Regions” located above the legend in FIG. 11.

FIG. 12 depicts the electrolytic synthesis of alkali and alkaline earth metals in solution with cannabinoid-mediated capping according to embodiments of the present disclosure.

FIG. 13 is an illustration of cannabinoids shown passing through the barriers of cells and encapsulating contained microplastic particles according to embodiments of the present disclosure.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

For the purposes of promoting an understanding of the principles of the disclosure, reference will now be made to one or more embodiments, which may or may not be illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended; any alterations and further modifications of the described or illustrated embodiments, and any further applications of the principles of the disclosure as illustrated herein are contemplated as would normally occur to one skilled in the art to which the disclosure relates. At least one embodiment of the disclosure is shown in great detail, although it will be apparent to those skilled in the relevant art that some features or some combinations of features may not be shown for the sake of clarity.

Any reference to “invention” that may occur within this document is a reference to an embodiment of a family of inventions, with no single embodiment including features that are necessarily included in all embodiments, unless otherwise stated. Furthermore, although there may be references to benefits or advantages provided by some embodiments, other embodiments may not include those same benefits or advantages, or may include different benefits or advantages. Any benefits or advantages described herein are not to be construed as limiting to any of the claims.

Likewise, there may be discussion with regards to “objects” associated with some embodiments of the present invention, it is understood that yet other embodiments may not be associated with those same objects, or may include yet different objects. Any advantages, objects, or similar words used herein are not to be construed as limiting to any of the claims. The usage of words indicating preference, such as “preferably,” refers to features and aspects that are present in at least one embodiment, but which are optional for some embodiments.

Specific quantities (spatial dimensions, temperatures, pressures, times, force, resistance, current, voltage, concentrations, wavelengths, frequencies, heat transfer coefficients, dimensionless parameters, etc.) may be used explicitly or implicitly herein, such specific quantities are presented as examples only and are approximate values unless otherwise indicated. Discussions pertaining to specific compositions of matter, if present, are presented as examples only and do not limit the applicability of other compositions of matter, especially other compositions of matter with similar properties, unless otherwise indicated.

In order to prevent interactions with their environment, interactive materials and their particles can be processed to include surface coatings that can have several functions during synthesis, storage and/or device manufacturing. During synthesis for example, surface coatings can influence the particle size or particle shape. During storage, surface coatings can be used to reduce agglomeration or inhibit chemical changes of the particles such as oxidation. And, during manufacturing of some types of devices, it is sometimes desirable that particles come in physical contact or fuse together, such as through high temperature processing, to enable electrical or thermal conductivity of the resulting deposited material. During these manufacturing steps, some surface coatings can either inhibit or enhance the formation of desirable properties in composite materials.

Surface coatings can include organic molecules that associate with the surface of the interactive particles either through chemical bonds (chemisorption) or through other interactions such as physisorption or hydrophobic-hydrophilic interactions. A number of organic molecules have been investigated as surface coatings for particles. For example, U.S. Pat. No. 10,279,393 B2 investigates 19 organic ligands to determine their effectiveness for controlling the size of copper nanoparticles during synthesis and the stability of the resulting copper solutions to settling and oxidation. The ligands can be applied during the reduction step forming zero valent copper particles, or they can be applied after the reduction step after the reducing agents have been exhausted. However, U.S. Pat. No. 10,279,393 B2 focuses on synthetic ligands that form bonds with the copper particle surface to limit oxidation.

For oxidizable metals (silver, copper, aluminum, etc.), surface coatings can influence the oxidation stability of the particles. A number of organic species have been investigated for slowing the oxidation process, such as alkyl amines (see, e.g., US 2006/0254387 A1; U.S. Pat. No. 7,935,170 B2; U.S. Pat. No. 10,071,426 B2; and US 2008/0278181 A1), thiols (see, e.g., US 2006/0254387 A1; Dabera et al, Nature Communications, 2017, 8:1894; and U.S. Pat. No. 10,052,692 B2), azoles (see, e.g., US 2016/0346838 A1), and polymers such as polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA) (see, e.g., EP 2587899 B1). Zeng et al., Nanoscale, 2022, 14:16003-16032. DOI: 10.1039/D2NR03990G, is a recent review article that provides a comprehensive overview of ligands that have been used for copper particles. Many ligands that are effective for slowing oxidation (e.g., thiols and azoles) act by chemically bonding to the surface atoms of the material, which can be disadvantageous if the particles are intended to be used in electrically conductive or thermally conductive inks because the ligand must be removed with chemical or thermal treatments to enable electrical conduction between particles. For example, azoles are commonly used as ligands for copper because they are effective at limiting copper oxidation (see, e.g., US 2016/0346838 A1), but inks must then be treated at high temperatures to become conductive (see, e.g., U.S. Pat. No. 10,518,323 B2), typically to temperatures above 300° C. (see, e.g., EP 2587899 B1). In addition, azoles such as benzotriazole are likely to have detrimental effects in the environment.

Alternatively, some organic chemicals can influence the oxidation stability of particles without bonding to the surface by preferentially reacting with oxidizing species. These chemicals can be incorporated into the composition of a particle dispersion to reduce the rate of oxidation (see, e.g., U.S. Pat. No. 9,028,724 B2).

In addition to organic ligands, an alternative method for modifying the susceptibility of metal particles to oxidation includes coating the desired metal with a metal that is less susceptible to oxidation. For example, U.S. Pat. Nos. 7,611,644 B2 and 10,580,910 B2 disclose coating copper particles, which are susceptible to oxidation, with a layer of silver, which is less susceptible to oxidation. This process has disadvantages including, for example, the use of substantial amounts of silver, which is more expensive than copper.

The treatment of existing particles with surface treatment agents can also be used to modify the chemical structure of the particle surface. For example, treatment of oxidized surfaces of copper with thiols can reduce the surface from copper oxide to metallic copper (see, e.g., Wang et al., Thiol Adsorption on and Reduction of Copper Oxide Particles and Surfaces, Langmuir, 2016, 32:3848-3857. DOI: 10.1021/acs.langmuir.6b00651), which may be beneficial for composite materials used in electronic devices.

When fabricating devices or solutions that integrate micro-sized particles (e.g., particles from 0.1 to 1000 micrometers (μm) in diameter) and/or nano-sized particles (e.g., particles from 1 to 100 nanometers (nm) in diameter), the particles can be integrated into composites, inks or structures that are processed using heat or reactive environments (e.g., reducing environments such as H2 or formic acid), or are applied in environments where corrosion and oxidation are possible. Agents that reduce environmental interaction (typically in the form of antioxidants) may be added during processing. Agents that promote the fusion of particles (frequently referred to as sintering aids) can also be used. Sintering aids in the most simple cases are a low melting temperature material that increases mobility of particles and atoms. They frequently can also complex with or react with the material of the particles to increase the mobility of atoms to allow particle fusion at lower temperatures. For example, sodium alginate has been used as a sintering aid to reduce the sintering temperature of copper (see, e.g., Sarwar et al, Applied Surface Science, 2021, 542:148609. DOI: 10.1016/j.apsusc.2020.148609). Some agents can also act as both an antioxidant and a sintering aid.

One material of interest in a number of applications is copper, which can be in the form of copper particles, such as micro- or nano-sized particles of copper. The printed electronics industry primarily uses silver for conductive inks because silver oxidizes slowly and silver oxide is relatively conductive, so some oxidation of the silver oxide is still tolerable. However, silver exhibits electromigration and costs substantially more (about two orders of magnitude more) than copper. Consequently, there has a been interest in developing copper inks as a low-cost replacement for the conventional silver. However, limitations of using copper, such as the fast oxidation of copper during manufacturing and the highly resistive nature of copper oxide that adversely affects the flow of electricity when the copper oxidizes, has prevented the widespread use of copper for these purposes.

Embodiments of the present disclosure address the limited stability of metal micro- and nano-particles by utilizing cannabinoids, which can have inherent antioxidant properties.

Cannabinoids are a class of molecules that can be derived from plants of the Cannabis family (i.e. hemp). Many cannabinoids including cannabigerol (CBG), cannabidiol (CBD) and cannabinol (CBN) possess ring structures similar to terpenoids and hydroxyl groups similar to phenols such as bisphenol A, that provide antioxidant properties that exceed or match other known antioxidant materials such as vitamin E and olivetol. Raw cannabinoids and synthesized derivatives with enhanced surfactant properties or solvency are employed in the synthesis, capping, inhibition and/or reduction of particles that share desired properties of bulk materials with expanded lifetime according to embodiments of the present disclosure. Cannabinoid-capped nanoparticles and/or cannabinoid-mediated particle formulations according to embodiments of the present disclosure can be used in many applications ranging from electronics to biomedical and sustainable energy.

Embodiments of the present disclosure include micron and/or sub-micron sized particles that are capped with cannabinoids and/or cannabinoid derivatives. Embodiments are capable of leveraging various properties of cannabinoids and/or cannabinoid derivatives including (1) antioxidant properties, (2) degradability, (3) molecular structure, (4) mechanical properties, and/or (5) biological compatibility. The particles being capped can include corrodible metals (such as Cu, Fe, Mo, W and/or Zn), reactive alkali or alkaline earth metals (such as Ca, K, Li, Mg and/or Na), oxidizable (and/or toxic) inorganic compounds (such as quantum dots and/or MXenes), biologically active components (such as antibodies, enzymes and/or proteins) and/or microplastics.

Cannabinoids and/or Cannabinoid Derivatives as Capping Agents

Cannabinoids (including, for example, CBG, CBD, A9-tetrahydrocannabinol (THC) and CBN) can possess a nonpolar structure, making them only slightly soluble in water, which is the medium in which particles are often encapsulated. This limited solubility can lead to a narrow range of possible particle sizes for a given material. Derivatives created through chemical modification of cannabinoids, such as sulphonated CBD (which may have particular applicability in applications for pharmaceuticals and supplements), may be used to improve solubility (see, e.g., CN 112441952 A) but may increase the possible concentration and range of particles that can be capped as well.

Example cannabinoids and cannabinoid derivatives utilized in embodiments of the present disclosure are shown in FIGS. 1A and 1B. FIG. 1A depicts chemical structures of the example cannabinoids cannabidiol (CBD), cannabigerol (CBG), cannabinol (CBN) and A9-tetrahydrocannabinol (THC). FIG. 1B depicts example chemical modifications that may be used to change the solubility in water. In at least some embodiments of the present disclosure, these sulfonate and carboxylic acid groups replace the OH groups in the cannabinoids. In FIG. 1B, the “R” represents the cannabinoid.

In some embodiments the antioxidant cannabinoid is in the form of hemp oil. Compared to synthetic antioxidant ligands, hemp oil has the advantage of being natural and bio-sourced. And, when compared to organic antioxidant ligands such as curcumin, hemp oil has good stability and lower cost. Additional advantages include the ability to perform the synthesis process in environmentally friendly conditions that require few, if any, safety measures. By utilizing the antioxidant properties of the cannabinoids (for example, as supplied by help oil), materials that are sensitive to oxidation can be readily used in products that previously required expensive non-reactive materials (such as gold or platinum) to resist oxidation.

Capping of Synthesized Compounds

Corrodible Metals

Corrosion of non-noble metals (such as Mg, Fe, Zn, Mo, Cu and/or W) is largely a result of environmental oxidation, which is exacerbated by reduced size. Corrosion is especially pronounced for nanoparticles. As a result, commercially available particles are typically somewhat or fully oxidized, limiting their applications. Passivated particles are generally priced higher, lack variety of particle size, and may be ineffectively passivated. Particles can be synthesized through reduction of metal salts or oxides. For particles synthesized in solution, surfactants (also referred to as capping agents or ligands) such as polyvinylpyrrolidone (PVP) or dodecyl sulfate are commonly utilized to control size. Commercial surfactants are not always capable of preventing the oxidation of corrodible metals, resulting in diminished properties such as electrical or thermal conductivity.

Example 1—Wet Synthesis of Copper Particles in the Presence of Cannabinoids

FIGS. 2A, 2B and 2C illustrate a method of synthesizing pure copper particles from copper sulfate pentahydrate according to embodiments of the present disclosure. FIG. 2A depicts the salt being dissolved in water, mixed with a cannabinoid (e.g., cannabidiol), and having a gas (e.g., N2 gas) used to displace reactive dissolved gases. In at least one embodiment the cannabinoid (cannabidiol in this example) is supplied by adding cannabidiol to the solution after solvating in, for example, ethanol to improve solubility. When a reducing agent (e.g., ascorbic acid) is added as depicted in FIG. 2B, copper ions are reduced and precipitate out of solution as solid copper as depicted in FIG. 2C. The solid copper particles grow until they reach an equilibrium size due to the added cannabidiol. Additional embodiments utilize a similar strategy for other metal salts that can be precipitated in the presence of reducing agents. Compared to traditional ligands such as PVP, copper particles synthesized using CBD have a higher stability in aqueous environments, as illustrated qualitatively in FIG. 3.

Example 2—Qualitative Comparison of Oxidation Stability of Copper Particles

FIG. 3 is an image of four separate containers containing sample copper particles suspended in deionized (DI) water after a five hour exposure period. In some samples the copper particles have been synthesized according to FIG. 2 with cannabidiol ligands and PVP ligands. Other samples were procured from copper particle suppliers and used as received. These depictions help illustrate the varying degrees of stability of copper particles when synthesized using the different capping agents.

Sample 1 in FIG. 3 is a control sample and depicts 325 mesh atomized copper particles procured from Inoxia and suspended in DI water. Here it can be seen that the copper particles are interacting with the water resulting in the copper particles partially oxidizing and turning a dark, almost black, color. Note that there are few of the darker copper particles near the center of the container resulting in a lighter color near the container's center.

Sample 2 in FIG. 3 depicts copper particles synthesized with CBD ligands that have been suspended in water. Compared to the control samples (Samples 1, 3 and 4), the copper particles synthesized with CBD ligands maintain their copper color in water instead of exhibiting a darker patina color typical when copper is exposed to DI water, indicating that the copper particles are not interacting as strongly with reactive species in the DI water.

Sample 3 in FIG. 3 is another control sample and depicts copper particles synthesized using PVP in the same fashion as sample 2 and suspended in DI water. In this sample the copper is a dark burnt red color indicating that the copper is interacting with the water more than the copper particles synthesized with CBD ligands (Sample 2), but less than in the first control sample (Sample 1).

Sample 4 in FIG. 3 is yet another control sample and depicts −625 mesh copper particles procured from Thermo Fisher Scientific® and suspended in DI water. Here it can be seen that the copper particles are strongly interacting with the water with the entire sample appearing black in color.

Other types of particles, such as prefabricated metal particles, can also be used in this strategy by reducing surface oxides on the prefabricated metal particles then suspending the prefabricated metal particles in water (or another inert medium) along with dissolved cannabinoids (or cannabinoid derivatives).

FIGS. 4A and 4B depicts the corrosion rate and inhibitor efficiency of bare copper, cannabidiol, benzotriazole, polyvinylpyrrolidone, and curcumin over a 24-period with measurements every hour.

Example 3—Thermal Characterization of Oxidation Stability of Copper Particles

The oxidation stability of copper particles coated with cannabinoids were measured by thermogravimetric analysis (TGA) by starting at, e.g., 25° C. and heating samples at a rate of, e.g., 20° C./min. The CuP-CBD sample represented in FIG. 5A was produced using the process described in Example 1. TGA measurements were conducted both in air atmosphere and in inert nitrogen atmosphere. The two curves in FIG. 5A are similar up to a temperature of 190° C., indicating that the copper particles coated with cannabinoid (e.g., CBD) exhibit negligible oxidation up to that temperature. A control condition is created in which the CBD is removed from the particles by washing in solvent, dilute nitric acid, and then dilute formic acid before the TGA measurement, indicate by the Bare Air condition in FIG. 5A. The comparison of the copper particles coated with CBD and the bare particles indicate that the presence of CBD delays the onset temperature for increasing weight of particles that indicates oxidation.

Based on thermal characterization results in this example, the utilization of CBD is maximized in comparison to conventional ligands, whereby substantially all (e.g., ≥95%, and in some embodiments ≥98%) of the CBD is present in the resulting particles which is not the case for traditional capping approaches. Variations to process conditions such as capping agent, precursor, reducing agent concentrations can be utilized to generate particles of varying size and morphology. The resulting particles, according to X-ray diffraction (XRD) analysis (see, e.g., FIG. 6) are high purity copper with characteristic peaks shown for zero-valent copper. Notably, there are no peaks indicating a crystalline cannabidiol (CBD) structure despite the indication of the presence of CBD by Fourier transform infrared spectroscopy (FTIR) as shown in FIG. 7. The CBD therefore appears to be preferentially arranged in an orientation that resembles surfactants, where a hydrophilic end (terpene group in the case of CBD) is oriented towards the solution and a hydrophobic end (alkyl chain in the case of CBD) is oriented towards the particle. See, e.g., FIG. 8, depicting a schematic example arrangement of cannabinoids on a particle. This is the first case that this arrangement has been demonstrated which does not resemble a binary mixture of nano- and/or micro-structures and cannabinoids.

Example 4—Electrochemical Characterization of Anticorrosion Effects of Cannabinoids

Electrochemistry experiments were used to quantify the anti-corrosion effect of cannabinoid coatings on solid copper electrodes comprising primarily copper particles. A copper working electrode was coated with dilute solution of corrosion inhibitors (e.g., natural antioxidants) and polymers. In this example, the electrode was then dried, for example, at a low temperature (e.g., 4° C. for 20 minutes), then at a higher temperature (e.g., 60° C. for 5 minutes), then at a higher temperature (e.g., room temperature for 5 minutes). The electrode was replaced in the electrochemical cell with an Ag/AgCl reference electrode and a platinum counterelectrode. The potential of the electrode was swept at a scan rate of, e.g., 10 mV/min. The corrosion potential (Ecorr) was determined by finding the open circuit potential. Linear sweep voltammetry (LSV) was repeated at a regular rate (e.g., every hour) by sweeping a voltage (e.g., ±100 mV) around Ecorr with a given rate (e.g., 10 mV per minute). The current from the LSV was used to determine the corrosion current (Icorr), which was subsequently used to calculate the corrosion rate and inhibitor efficiency of bare copper, cannabidiol, benzotriazole, polyvinylpyrrolidone and curcumin. The results for CBD were compared with three conventional ligands. FIG. 4A displays the calculated corrosion rate and in FIG. 4B displays the calculated corrosion inhibition efficiency. The three conventional ligands were benzotriazole (which is commonly used in corrosion inhibition of metals), PVP (which is commonly used as a ligand for metal particle synthesis), and curcumin (which is a natural antioxidant). FIG. 4A indicates that the corrosion rate of copper coated with CBD is lower than copper coated with PVP or curcumin but higher than copper coated with benzotriazole. Curcumin is commonly recognized as a stronger antioxidant than CBD. The electrochemical results indicate that the antioxidant strength measured according to methods such as ORAC or DPPH assays does not directly correlate to the corrosion inhibition properties. Additionally, coatings such as PVP and BTA bond to the surface of the copper through nitrogen groups, resulting in anodic corrosion inhibition, whereby the active sites for oxidation are minimized. CBD, which has been demonstrated to act as a cathodic inhibitor by Example 4, does not bond to the surface and easily dissociates from the surface which is advantageous as a mobile phase as demonstrated in Example 5. Additionally, the improved corrosion resistance compared to, e.g., PVP indicates that the passive and active corrosion inhibition of CBD can outperform common capping agents where a capping agent is needed strictly as a corrosion inhibitor.

Example 5—Conductive Ink Incorporating Cannabinoid Coated Particles

In embodiments of the present disclosure, particles prepared using the process in Example 1 were incorporated into inks that included the copper particles coated with CBD, a polycannabinoid (U.S. Pat. No. 2021/0322365 A1) binder, and xylene as a solvent. The weight ratio of CBD to copper in the particles was in the range of 0.5:100 to 3:100. The ratio of copper particles to polycannabinoid polymers was in the range of 40-65 vol %. The solvent xylene was an inactive ingredient that was only added to reduce the viscosity of the ink for processing and was evaporated after ink deposition. The ratio of xylene to polycannabinoid used in the polymer was 50-60 percent of the binder phase weight. FIG. 7 depicts a cross-sectional image of a sample of ink after hot pressing at, for example, 90° C. Different samples were prepared by hot pressing at different temperatures and the conductivity of the ink was measured using four-point measurements, resulting in the data shown in FIG. 11. The process was repeated for samples that had a CBD content of 1 wt % and 2 wt %. The results in FIG. 11 indicate that the ink composition with 1 wt % of CBD reached a conductivity of >7×10⁶ S/m with a hot-pressing temperature of 90° C. The ink composition with 2 wt % of CBD had improved temperature stability and reached a maximum conductivity of 7×10⁶ S/m at a hot-pressing temperature of 200° C.

The conductivity of traces versus the hot-pressing temperatures is characterized by 3 regions which are denoted in FIG. 7 (mobile phase, oxidation g.t. corrosion inhibition, reducing agent) which indicates the myriad functionalities of cannabinoids as additives/capping in reactive metal composites. In all regions, the CBD promotes corrosion inhibition. In the first region (e.g., between room temperature and 90° C.), the CBD acts as a sintering aid (in the case of particles that can sinter at low temperature) or a mobile phase (in the case of particles that cannot sinter at low temperature) which allows the local migration of particles in a way that enables physical contact or connection (necking) between neighboring particles, which promotes conductivity. In this first region, conductivity follows a quasi-linear trend where increasing temperature results in a corollary increase in conductivity similar to noble metals. This trend can result from stimuli including temperature and pressure. In the second region (e.g., between 90° C. and 120° C.), the temperature and processing conditions lead to an environment where oxidative forces exceed the passive and/or active barrier and anticorrosion properties of the CBD and/or polymeric binder which results in a break from the linear conductivity vs. temperature trend where the conductivity plateaus or decreases as temperature is increased. In the third region (e.g., between 120° C. and 200° C.), the CBD acts as a reducing agent whereby the elevated temperature triggers a reduction process where the particle oxides that form are reduced back to the elemental copper.

Example 6—Application of Cannabinoids to Existing Copper Oxide Particles

Cannabinoids can be added to the surface of existing particles to protect them from oxidation or other change in the chemical composition of their surface according to embodiments of the present disclosure. In one example, CBD was mixed with copper (II) oxide (CuO) particles in a 1:1 volume ratio.

FIGS. 9A and 9B depict the differential scanning calorimetry (DSC) and demonstration of the reduction of copper (I) oxide (CuO) by cannabidiol according to embodiments of the present disclosure. FIG. 9A depicts a DSC thermogram where the temperature was varied from 0° C. to 450° C. and back to 0° C. at a temperature ramp rate of 10° C./min. During the increasing temperature sweep, exothermic peaks indicative of reduction of CuO to zero-valent copper (Cu) are seen similar to other approaches with antioxidant macromolecules (Zuo et al, Advanced Powder Technology, 2020, 31:4135-4144. DOI: 10.1016/j.apt.2020.08.019). FIG. 9B shows that the initially brownish CuO particles are converted to pinkish Cu particles after heat treatment at or above a predetermined temperature in the presence of CBD, and optionally in an inert atmosphere, which is apparent from the contrast difference in the two phases. In some embodiments the predetermined temperature is 100° C., in other embodiments the predetermined temperature is 120° C., in further embodiments the predetermined temperature is 200° C., in still other embodiments the predetermined temperature is the melting temperature of the antioxidant cannabinoid (which may be advantageous when the oxidation on the particle is minimal), in still further embodiments the predetermined temperature is the vaporization temperature of the antioxidant cannabinoid, in yet further embodiments that use polymers in the suspension of oxidized particles the predetermined temperature is between the glass transition temperature of the polymer and the melting temperature of the cannabinoid, and in still additional embodiments, and in still other embodiments the predetermined temperature is below the burn-off temperature of the cannabinoid. These reduced copper particles may be useful for applications including conductive copper inks and metal bed 3D printing. This indicates that particles or structures that either inherently have oxide layers, are entirely composed of oxides, or form oxides during processing can be reduced by CBD and other antioxidant cannabinoids and derivatives when the temperature is sufficiently high. The temperature for each oxide will likely vary.

Example 7—Conductive Ink Incorporating Existing Copper Particles with Cannabinoids Applied

In embodiments of the present disclosure, cannabinoids can be added to the surface of particles during the preparation of a composite or ink. This approach is highlighted by an example process for reusing copper particles from an existing composite. The initial composites were prepared according to the processes in Examples 1 and 5. Copper particles coated with 1 wt % CBD were prepared according to Example 1, and 65 vol % of the CBD-coated copper particles were mixed with 45 vol % of polycannabinoids according to Example 5. The results were hot-pressed at 90° C. to yield conductive composites according to Example 5, which is referred to herein as a synthesized composite in FIG. 12. To simulate the recycling of copper traces after use, the composites were dissolved in acetone with sonication and the copper particles were recovered by filtering the solution. The copper particles were washed with acetone and dried at 60° C. to recover bare copper particles. The bare particles were then combined with 1 wt % CBD and 45 vol % polycannabinoids. The ink was mixed, deposited, dried, and hot-pressed at 200° C., which we refer to as the recycled ink. The conductivity values for the initial conductive composites and the recycled composites are compared in FIG. 12. The recycled composite has higher conductivity than the original synthesized composite prepared at 90° C. and has similar conductivity to synthesized composites prepared at 200° C. This procedure can be used in applications where reuse or recycling of reactive or oxidizable materials is desired or where particles which are already oxidized will be used in new inks to reduce them during regular processing.

Reactive Metals

Most alkali and alkaline earth metals are highly reactive with water or moisture resulting in a limited number of applications when they are in their metallic state and expected to be exposed to the environment. These metals are typically synthesized through electrolytic processes from molten salts in dry conditions. In many cases the salts of these metals are used instead of the raw form of these metals due to volatility of the raw form of the metal.

FIG. 12 depicts a method of synthesis of reactive metals through which the reactive metals can be stabilized according to embodiments of the present disclosure. In at least one embodiment a salt solution containing metal ions is electrolyzed, which results in the formation of the reactive metal. Due to the volatility of the reactive metal in water, the reactive metal particles quickly react with the water and form hydrogen gas and hydroxides. By including cannabinoids in the solution according to embodiments of the present disclosure, the surface groups of the reactive metal particles can complex (interact) with the cannabinoids to provide stability and limit oxidation.

In other embodiments, prefabricated particles can be encapsulated in a non-reactive liquid medium to produce stabilized reactive metal particles. Although sodium particle dispersions have been formed using fatty acid chains in inert carrier liquids, environmental stability of the sodium particles has not been addressed. Conversely, the antioxidant properties of cannabinoids can suspend the reaction of the reactive metal with ambient moisture or dissolved reactive species.

FIGS. 10A-10C depict the formation of conductive composites comprising cannabinoid-capped copper particles and a polymer phase. The processing, resulting composite after processing, and microscopy images are illustrated.

Tables 1 and 2 show the results of experimental tests performed on different particle inks according to embodiments of the present disclosure. Table 1 shows the conductivities of three (3) ink types that are characterized by their particle type: CBD content, volume percent (vol %) copper, and hot-press temperature in the experimental conditions section. Table 2 shows the results summarizing the individual conductivities of traces along with statistics including the maximum conductivity, the average conductivity of the samples, and the standard deviation of the average conductivity.

TABLE 1
Experimental Conditions

Particle Type	Synthesized	Synthesized	Recycled
CBD Content	1 wt % CBD	2 wt % CBD	1 wt % CBD
Vol % Copper	65	65	65
Hot-Press Temperature (C.)	90	200	200

TABLE 2
Results

—	Sample 1	Sample 2	Sample 3
Test 1	7.09E+06	7.31E+06	3.21E+06
Test 2	6.46E+06	8.15E+06	6.35E+06
Test 3	5.39E+06	6.29E+06	5.87E+06
Test 4	5.06E+06	5.32E+06	7.34E+06
Test 5	6.42E+06	1.02E+07	—
Maximum Conductivity (S/m)	7.09E+06	1.02E+07	7.34E+06
Average Conductivity (S/m)	6.08E+06	7.45E+06	5.69E+06
Standard Deviation	8.36E+05	1.87E+06	1.76E+06

Oxidizable and Toxic Inorganic Materials

Many novel applications require the use of inorganic materials with specific properties, such as the use of quantum dots for optical applications or the use of MXenes for conductive networks using nanoscale particles. Many of these materials are susceptible to oxidation and a gradual decay of their desirable properties. However, suspending nanomaterials in a suitable solvent and using cannabinoids or modified cannabinoids (e.g., polycannabinoids or cannabinoid surfactants) to cap particles according to embodiments of the present disclosure will minimize, and potentially eliminate, oxidation reactions.

Biologically Active Components

Some biologically active components, such as enzymes, biocatalysts, and antibodies, can be susceptible to damage from the environment. Protecting these biologically active components can be useful for biosensing or therapeutic applications. Encapsulation of biologically active components in cannabinoids and their derivatives can assist in maintaining stability and enable non-toxic controlled release.

Microplastics

The presence of microplastics in many parts of the human body have been recently discovered. Their impact on human health is largely unknown, but it is suspected that many commercial plastics are endocrine disruptors or carcinogenic. Microplastics remediation using cannabinoids and their derivatives is possible due to the lipophilic nature of cannabinoids as well as their low molecular weight. The surfactant properties of the cannabinoids can be used to encapsulate microplastics and mitigate the leaching of toxic materials into the body. Cannabinoid derivatives that have been linked with proteins or other immunologically recognizable compounds can also be used to trigger immune responses and subsequent disposal depicted in FIG. 5. Similarly, encapsulation of microplastics can be done in the environment (e.g., ocean and soil) by employing surfactants in fertilizers to prevent the uptake of plastics by foodstuffs.

Competitive Advantages

Cannabinoid Capped Gold and Silver Nanoparticles

Cannabinoids have been realized as surfactants for synthesis of the noble metals silver and gold (see, e.g., Josiah et al., ACS Omega, 2021, 6:29078-29090. DOI: 10.1021/acsomega.1c04303). However, this prior work used the cannabinoids only to cap the surface of the particles and did not leverage the antioxidant capabilities of cannabinoids. An important demonstration is that that the cannabinoid ligands make the metal particles biocompatible when they come in contact with cells. However, embodiments of the present disclosure that use cannabinoids to cap oxidizable metals have additional benefits in that the cannabinoids protect metals that are typically difficult to stabilize.

Ligands for Metal Particles

Ligands (capping agents) for metal particle synthesis have historically included polymers such as polyvinylpyrrolidone (PVP) or polyvinylalcohol (PVA). However, for the past several decades researchers have explored ligands that provide better stability or tailored nanoparticle growth processes. One class of ligands, based on azo compounds, are used for their improved antioxidant properties compared to traditional ligands, but they can be damaging or irritating to biological systems. Biologically-derived stabilizing agents include antioxidants such as curcumin. However, while curcumin can be effective as a ligand for the synthesis of Cu particles, the oxidation stability of the particles over time does not appear to be acceptable. Compared to other natural antioxidants, for example, curcumin, cannabinoids are available in higher volumes and lower cost due to their high concentrations in and ease of extraction from the hemp plant.

Many conventional antioxidant ligands, such as thiols and azoles, act by chemically bonding to the surface atom of metals, which makes them difficult to remove to create composites that are electrically or thermally conductive. Typically these inks require high temperature processing steps to achieve conductivity. In contrast, cannabinoids protect against oxidation by preferentially reacting with oxidizing species and does not need to bind to the surface. This means they can be displaced from the particle surface with mild temperature or pressure to allow contact between particles and the formation of electrically or thermally conductive composites. Example 1 and Example 6 describe results indicating that copper particles coated with CBD can form highly conductive composites at processing temperatures as low as 90° C., which is lower than most other copper inks and is low enough to process on low cost substrates such as polyethylene terephthalate (PET).

The antioxidant ligands can contribute a significant portion of the cost of the prepared ink. In the process described in this patent, by changing the solubility of CBD during the particle synthesis process, nearly all of the CBD is condensed onto the surface of the particle, therefore maximizing the use of the material for the capping agent.

Ligands for Toxic Particles

While cannabinoids may be effective for isolating the surface of particles from the surrounding environment to make a particle, such as Ag no longer toxic to the surrounding cells as mentioned above embodiments of the present disclosure use of cannabinoids to protect other toxic materials, such as quantum dots, from surrounding cells.

As described herein, the use of particular cannabinoids (e.g., cannabigerol (CBG), cannabidiol (CBD) and/or cannabinol (CBN)) in example embodiments does not imply that other cannabinoids cannot be used in those example embodiments. Particular cannabinoids discussed in relation to particular embodiments disclosed herein may be substituted with other cannabinoids unless explicitly stated otherwise.

Various Aspects of Different Embodiments of the Present Disclosure are Expressed in the Following Paragraphs.

One embodiment of the present disclosure includes a method for reducing particles with oxidization, including: placing particles with oxidization into a suspension with an antioxidant cannabinoid; mixing the suspension of the particles with oxidization and antioxidant cannabinoid; and/or heating the mixture to above a predetermined temperature.

Another embodiment of the present disclosure includes a method for applying a particle surface assembly to an environmentally reactive nano- or micro-structure, including: selecting an environmentally reactive micro-structure; selecting a solvent (e.g., water or ethanol) that is less attractive to a cannabinoid (e.g., CBD) than the micro-structure in the end state (e.g., the final step in process); adding the cannabinoid to the solvent; distributing the cannabinoid throughout solvent (can be active or passive); adding the environmentally reactive nano- or micro-structure (e.g., copper, which may be prefabricated nano- or micro-structures (or optionally precursors and/or ions of prefabricated nano- or micro-structures to allow the nano- or micro-structures to form in the solution); optionally adjusting conditions (either actively or passively) to favor creation of particle surface assembly; wherein the cannabinoid is fully (or partially) depleted onto the surface of the nano- or micro-structures; optionally waiting a given period (wherein the conditions may passively adjust on their own, e.g., addition of the nano- or micro-particle may be enough for the assembly to occur; allowing assembly on surface of the nano- or micro-structure (which may be sufficiently long for complete depletion of the cannabinoid in the solution (or less time for partial depletion)); optionally driving assembly using active input from a user (e.g., changing pH or adding heat); optionally deprotonating the cannabinoid (e.g., adding heat to the cannabinoid before adding the cannabinoid to the solution); and optionally isolating the microstructures with the surface assemblies from the solution (e.g., using filtration (vacuum is an example), centrifugation, and/or gravity (allow to settle)).

Yet other embodiments include the features described in any of the previous statements combined with

• • (i) one or more of the previous statements,
  • (ii) one or more of the following aspects, or
  • (iii) one or more of the previous statements and one or more of the following aspects:
  • Wherein the predetermined temperature is the vaporization temperature of the antioxidant cannabinoid.
  • Wherein the predetermined temperature is 120 (maybe as low as 100) degrees C.
  • Heating to above the melting temperature of the cannabinoid.
  • Heating to between the glass transition temperature of the polymer and the melting temperature of the cannabinoid.
  • Adding solvent to polymer to, e.g., create an ink.
  • Wherein the suspension includes a polymer.
  • Wherein the method includes maintaining the temperature below the burn-off temperature.

A method for applying a particle surface assembly to an environmentally reactive nano- or micro-structure, comprising:

• • 1. selecting an environmentally reactive micro-structure;
  • 2. selecting a solvent (water or ethanol) that is less attractive to CBD than the micro-structure in the end state (final step in process);
  • 3. adding CBD to the solvent
  • 4. distribute CBD throughout solvent (active or passive)
  • 5. Adding Copper—(base source/element?)
    • a. add precursors/ions of desired microstructure and microstructures form in the solution; or
    • b. add prefabricated micro-structure to mixture of solvent and CBD (prefabricated or precipitation from synthesis)
  • 6. adjusting conditions (actively/passively) (solvent composition) to drive/favor assembly/creation of particle surface assembly
    • a. some of CBD is fully or partially depleted onto the surface
    • b. can include waiting a given period
      • i. conditions may passively adjust on their own, e.g., addition of microparticle might be enough for the assembly to occur
      • ii. initially for some assembly on surface (but there is still CBD in the solution)
      • iii. longer for aggregation/accumulation
        • 1. long enough for maximum (sometimes 100%) depletion of CBD from solution—equilibrium reached
    • c. drive assembly using pH, heat, etc. (can occur before “optional steps e” or during “adjusting conditions steps f”)
      • i. add base (increase solubility of cannabinoids, e.g., in water)
      • ii. add heat (increase solubility of cannabinoids, e.g., in water)
      • iii. sometimes these changes are a result of the natural process
    • d. adjust CBD (heat CBD before adding; deprotonate CBD)
  • 7. isolate the microstructures with the surface assemblies from the solution
    • a. filtration (vacuum is an example), centrifugation, gravity (allow to settle),
  • 8. before adding micro-structure: manipulate solvent to increase concentration of CBD in solvent
  • 9. after adding micro-structure: manipulate solvent to decrease concentration of CBD in solvent so that it assembles onto the microstructure
    • a. heat, agitation, chemical reactions, pH, etc.
  • 10. heat (or agitate) solvent (water/glycols, to increase solubility) selected to ______ to melting point of cannabinoid;
  • 11. add/mix cannabinoid to/with solvent;
  • 12. add/mix the nano- or micro-structure to/with the cannabinoid-solvent combination;
  • 13. add CBD in concentrations greater than
  • 14. forcing concentration of CBD to be higher than equilibrium of solution so it aggregates onto the surface of the nano/micro-structures
  • 15. corrosion inhibiting features
  • 16. synthesis: we go from basic to acidic environment (solubility change during process to induce CBD attaching to particle)
  • 17. add one or more bases (to increase solubility)
  • 18. use cannabinoid during solution synthesis of a particle where the CBD is soluble.
  • 19. cannabinoids as a ligand during synthesis of a particle

An environmentally stable particle, comprising:

• • 1. an environmentally reactive material (copper) with a cannabinoid on the surface of the reactive material acting as a cathodic/corrosion inhibitor.
  • 2. lipophilic groups of cannabinoid being preferentially oriented toward the surface of the particle;
  • 3. a reactive nano-/micro-structure with cannabinoids or derivatives that are physically adsorbed in a layer on the microstructure (the volume of CBD is up to 50% (in some applications 5%-30%) of the total volume of the combined particle+CBD).
  • 4. cannabinoids do not bond or complex with the atoms and are easily dissociated by solvents that dissolve cannabinoids (e.g. alcohols, acetone).
  • 5. Cannabinoids can diffuse into polymer or out of a polymer matrix onto or off the surface of the particle (e.g. the particles are already coated with cannabinoids, or the cannabinoids as an additive to another composition migrate to the surface of the particle)
  • 6. Particles can be partially oxidized, in which case at temperatures >120 C oxides can be reduced
  • 7. Cannabinoids might be combined with other capping agents such that cannabinoids are greater than 0.01% of the volume composition of the capping layers of the particle
  • 8. the cannabinoid doesn't actually bond to surface
    • a. doesn't bond, but it is oriented so that the chain is facing the surface and the big rings are facing outward
      • i. lipophilic groups are oriented to the surface of the particle (surfactant alignment; hydrophobic alignment; non-ionic surfactant)
    • b. CBD is in a non-crystalline structure (chain at end prefers to face particle)
  • 9. functional pathways formed
  • 10. a reactive nano-/micro-structure with cannabinoids or derivatives that are physically adsorbed in a layer (less than 5% of vol?) (3% wasn't enough).

Cannabinoids or derivatives thereof with terpenoid and/or phenolic antioxidant groups coating metal or metal oxide particles whereby coatings can

• • 11. prevent oxidation during storage (in air, water, high temperatures, etc.)
  • 12. mobile in composites above their melting points (>49 (need specific) C for CBD) (e.g., as an ink composition)(would apply heat or pressure until the CBD becomes mobile, and therefore acts as a sintering aid)
  • 13. reduce metal oxides (above ˜160° C. for copper) (the antioxidant groups would produce a hydrogen radical (which is the most effective reducing agent for metal oxides))

A method of coating nanoparticles or microparticles with cannabinoids to modify their interaction with their environment with the goal of reducing the oxidation of the particle or reducing the toxicity of the particle in biological environments, wherein, optionally:

• • 1. the material of the particle is an oxidizable metal, including copper, aluminum, iron, zinc, tungsten, molybdenum, or magnesium.
  • 2. the material of the particle is an alkali metal, including sodium and potassium.
  • 3, wherein the material of the particle is an oxidizable semiconductor such as cadmium sulfide, cadmium selenide, or other semiconductors commonly used in quantum dots.
  • 4, wherein the material of the particle is an oxidizable compound from the group commonly referred to as MXenes (e.g. Ti3C2Tx).
  • 5, wherein the material of the particle is a sensitive biological compound such as an enzyme or antibodies.

A process for producing metal particles coated with cannabinoids during the synthesis of the metal particles, the process comprising the steps of: dissolving a salt of a reactive metal in water; mixing the dissolved salt with a cannabinoid; introducing an inert gas; displacing the reactive dissolved gases with the inert gas; precipitating the reactive metal by adding a reducing agent to the dissolved salt, cannabinoid and inert gas solution; and permitting the reactive metal particles to grow until reaching equilibrium size, wherein, optionally:

• • 1. the salt is copper sulfate pentahydrate.
  • 2. the cannabinoid is cannabidiol.
  • 3. the cannabinoid is supplied by adding cannabidiol to the solution.
  • 4. the reducing agent is ascorbic acid.
  • 5. the inert gas is nitrogen gas (N2).
  • 6. the metal particles can be heat treated to form an electrically conductive composite at temperatures lower than 200° C.
  • 7. other useful components are added, such as additional types of ligands that may modulate the particle size or shape. The additional ligands could include but are not limited to polyvinyl pyrrolidone (PVP), carboxylic acids, alkyl amines, or thiols.
  • 8. coating cannabinoids onto existing particles, the process consisting the steps of mixing cannabinoids with the particles.
  • 9. heat treatment is used to induce a reaction between the particle and the
  • 10. a solvent is used during the mixing process.
  • 11. a reducing agent is used to change the particle chemistry before or during exposure to the cannabinoids. Reducing agents could include hydrazine, formic acid, or ascorbic acid.

An ink composition that comprises: particles coated with cannabinoids; a polymer binder to adjust the rheology; and a solvent.

• • 1, wherein the total content of cannabinoids in the ink can range from 0.01 wt % to 20 wt %, with a preferred content in the range from 0.2 wt % to 3 wt %.
  • 2, wherein the polymer binder includes one or more of polycannabinoids (U.S. Pat. No. 2021/0322365 A1), polycaprolactone, polyethylene glycol, poly(methyl methacrylate), or polylactic acid.
  • 3, wherein a heat treatment step is used to induce a redox reaction between the particle and the cannabinoid.

An ink composition that comprises: particles coated with cannabinoids and a thermoset polymer binder that cures with covalent chemical bonds

• • 1, wherein the total content of cannabinoids in the ink can range from 0.01 wt % to 20 wt %, with a preferred content in the range from 0.2 wt % to 3 wt %.
  • 2, wherein the thermoset polymer forms covalent chemical bonds through the reaction of epoxy groups, urethane groups, or acrylate groups.

Reference systems that may be used herein can refer generally to various directions (e.g., upper, lower, forward and rearward), which are merely offered to assist the reader in understanding the various embodiments of the disclosure and are not to be interpreted as limiting.

To clarify the use of and to hereby provide notice to the public, the phrases “at least one of A, B, . . . and N” or “at least one of A, B, . . . N, or combinations thereof” or “A, B, . . . and/or N” are defined by the Applicant in the broadest sense, superseding any other implied definitions hereinbefore or hereinafter unless expressly asserted by the Applicant to the contrary, to mean one or more elements selected from the group comprising A, B, . . . and N. In other words, the phrases mean any combination of one or more of the elements A, B, . . . or N including any one element alone or the one element in combination with one or more of the other elements which may also include, in combination, additional elements not listed. As one example, “A, B and/or C” indicates that all of the following are contemplated: “A alone,” “B alone,” “C alone,” “A and B together,” “A and C together,” “B and C together,” and “A, B and C together.” If the order of the items matters, then the term “and/or” combines items that can be taken separately or together in any order. For example, “A, B and/or C” indicates that all of the following are contemplated: “A alone,” “B alone,” “C alone,” “A and B together,” “B and A together,” “A and C together,” “C and A together,” “B and C together,” “C and B together,” “A, B and C together,” “A, C and B together,” “B, A and C together,” “B, C and A together,” “C, A and B together,” and “C, B and A together.”

While examples, one or more representative embodiments and specific forms of the disclosure have been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive or limiting. The description of particular features in one embodiment does not imply that those particular features are necessarily limited to that one embodiment. Some or all of the features of one embodiment can be used or applied in combination with some or all of the features of other embodiments unless otherwise indicated. One or more exemplary embodiments have been shown and described, and all changes and modifications that come within the spirit of the disclosure are desired to be protected.