Mosses on Geopolymers: Preliminary Durability Study and Chemical Characterization of Metakaolin-Based Geopolymers Filled with Wood Ash.

Burning wood is estimated to produce about 6-10% of ash. Despite the possibility of recycling wood ash (WA), approximately 70% of the wood ash generated is landfilled, causing costs as well as environmental pollution. This study aims to recycle WA in an alternative way by inserting it as filler in geopolymeric materials. Here, metakaolin, NaOH, sodium silicate, and WA are used to realize geopolymers. Geopolymers without and with 10, 20 and 30% of WA are synthesized and characterized after 7, 14, 28 and 56 days. The article's study methods are related to geopolymers' chemical, biological and mechanical properties. The geopolymers synthesized are compact and solid. The pH and conductivity tests and the integrity and weight loss tests have demonstrated the stability of materials. The FT-IR study and boiling water test have confirmed the successful geopolymerization in all samples. The antibacterial analysis, the moss growing test and the compressive strength test have given a first idea about the durability of the materials synthesized. Furthermore, the compressive strength test result has allowed the comparison from the literature of the specimens obtained with the Portland cement (PC). The results obtained bode well for the future of this material.

Antibacterial and Photocatalytic Activities of LDH-Based Sorbents of Different Compositions.

Layered double hydroxides (LDHs) play a fundamental role in the processes for the abatement of pollutants in water, with reference to heavy metal decontamination. The research on the topic is multiobjective target oriented, aiming at combining environmental remediation with the possibility of reusing a sorbent as many times as possible, turning it into a renewable resource. In this study, the antibacterial and catalytic properties of a ZnAl-SO4 LDH and its resulting product after being subjected to a Cr(VI) remediation process are compared. Both solid substrates have also been tested after undergoing a thermal annealing process. The sorbent (previously described and tested for remediation) has been investigated for its antibacterial activity in view of further surgery and drug delivery applications. Finally, its photocatalytic properties have been experimentally tested in the degradation of a model pollutant, i.e., Methyl Orange (MO), under solar-simulated light. Identifying the best recycling strategy for these materials requires an accurate knowledge of their physicochemical properties. The results show that both the antimicrobial activity and the photocatalytic performance may considerably improve after thermal annealing.

Antibacterial and Cytotoxic Silica-Polycaprolactone-Chlorogenic Acid Hybrids by Sol-Gel Route.

Organic-inorganic hybrid materials were synthesized by a sol-gel route, using silicon alkoxide together with low molecular weight polycaprolactone and caffetannic acid. The synthesized hybrids were characterized by scanning Fourier-transform infrared (FTIR) spectroscopy, and their surface morphology was acquired by scanning electron microscopy (SEM) analysis. The hybrids were investigated for their antiradical capacity using the DPPH and ABTS tests, while the Kirby-Bauer test was used to evaluate their effects on the growth of Escherichia coli and Enterococcus faecalis. Furthermore, a biologically active hydroxyapatite layer has been observed to form on the surface of intelligently synthesized materials. The MTT direct test showed that the hybrid materials are biocompatible with NIH-3T3 fibroblast cells, while they were cytotoxic towards colon, prostate, and brain tumor cell lines. These results shed new light on the suitability of the synthesized hybrids in the medical field, thus affording knowledge on the features of the bioactive silica-polycaprolactone-chlorogenic acid hybrids.

Thermal and Electrical Characterization of Polyester Resins Suitable for Electric Motor Insulation.

This paper undertakes the thermal and electrical characterization of three commercial unsaturated polyester imide resins (UPIR) to identify which among them could better perform the insulation function of electric motors (high-power induction motors fed by pulse-wide modulation (PWM) inverters). The process foreseen for the motor insulation using these resins is Vacuum Pressure Impregnation (VPI). The resin formulations were specially selected because they are one-component systems; hence, before the VPI process, they do not require mixing steps with external hardeners to activate the curing process. Furthermore, they are characterized by low viscosity and a thermal class higher than 180 °C and are Volatile Organic Compound (VOC)-free. Thermal investigations using Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) techniques prove their excellent thermal resistance up to 320 °C. Moreover, impedance spectroscopy in the frequency range of 100 Hz-1 MHz was analyzed to compare the electromagnetic performance of the considered formulations. They manifest an electrical conductivity starting from 10-10 S/m, a relative permittivity around 3, and a loss tangent value lower than 0.02, which appears almost stable in the analyzed frequency range. These values confirm their usefulness as impregnating resins in secondary insulation material applications.

Role of MWCNTs Loading in Designing Self-Sensing and Self-Heating Structural Elements.

This work proposes nanocomposites with carbon nanotubes characterized by self-sensing and self-heating properties. Recently, a growing interest in these two properties has been found in many industrial sectors, especially in the aerospace and automotive fields. While the self-sensing function allows diagnosing the presence of micro-damage in the material thanks to the detection of residual resistance, the self-heating function is exploited to properly tune the heating performance in terms of the heating rate and final temperature values. An electrical percolation value of around 0.5% by weight of carbon nanotubes was found by electrical characterization. The AC conductivity of the nanocomposites, in the range of 100 Hz to 1 MHz, evidences that beyond a CNTs amount of 0.5% wt/wt, they are characterized by a purely resistive behavior. The self-sensing analysis displayed a gauge factor value of 4.1. The solid thermal stability up to 300 °C makes the material suitable as a heating element at high temperatures. SEM investigations and temperature maps evidence a good dispersion of the conductive filler in the epoxy matrix and, consequently, good isotropy in heat distribution. As regards the trend of electrical resistance by varying the temperature, the electro-thermal investigation has shown the presence of both Positive Temperature Coefficient (PTC) and Negative Temperature Coefficient (NTC) behaviors with a predominance of NTC as soon as the temperature becomes closer to the glass transition temperature of the epoxy resin.

Entrapment of Acridine Orange in Metakaolin-Based Geopolymer: A Feasibility Study.

Few studies have explored the immobilization of organic macromolecules within the geopolymer matrix, and some have found their chemical instability in the highly alkaline geopolymerization media. The present work reports on the feasibility of encapsulating the potentially toxic acridine orange (AO) dye in a metakaolin based geopolymer while maintaining its structural integrity. The proper structural, chemical, and mechanical stabilities of the final products were ascertained using Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric (TGA/DTG), and mechanical analyses, whereas the dye integrity and its stability inside the geopolymer were investigated by the UV-Vis analysis. In addition, the antimicrobial activity was investigated. The FT-IR and XRD analyses confirmed the geopolymerization occurrence, whereas the TGA/DTG and mechanical (compressive and flexural) strength revealed that the addition of 0.31% (AO mg/ sodium silicate L) of AO to the fresh paste did not affect the thermal stability and the mechanical properties (above 6 MPa in flexural strength and above 20 MPa for compressive strength) of the hardened product. UV-Vis spectroscopy revealed that the dye did not undergo chemical degradation nor was it released from the geopolymer matrix. The results reported herein provide a useful approach for the safe removal of toxic macromolecules by means of encapsulation within the geopolymer matrix.

Characterisation of White Metakaolin-Based Geopolymers Doped with Synthetic Organic Dyes.

Over the years, many materials have been used to restore buildings, paintings, ceramics, and mosaic pieces exhibiting different types of dyes and colour hues. Recently, geopolymers have been used for restoration purposes owing to their high chemical and mechanical resistance. In this work, white metakaolin was used to obtain white geopolymers, cured at 25 and 40 °C, as bulk materials to be coloured with synthetic organic dyes, i.e., bromothymol blue, cresol red, phenolphthalein, and methyl orange. These dyes were added during the fresh paste preparation to obtain dyed geopolymeric solids. Ionic conductivity and pH measurement confirmed the chemical stability of the consolidated materials, while FT-IR analyses were used to follow the geopolymerisation occurrences at different ageing times (from 7 to 56 days). Finally, the colour hues and properties were assessed in the CIELAB colour space before and after immersion in water.

Recycling of Waste Corundum Abrasive Powder in MK-Based Geopolymers.

Recycling corundum abrasive powder in metakaolin-based geopolymer formulations is proposed to reduce the amount of waste to be treated or disposed of in landfills, allowing to decrease ecological damage as well as to reduce transport costs for removal. The addition of waste corundum, as an important source of Al2O3, has proved to increase the slight ionic conductivity of the leachate solution obtained after immersion in water of samples at 28 d of curing at room temperature. With the same curing conditions, the geopolymerization process has not been disturbed as evidenced by the FT-IR peak shift and XRD patterns. It was recorded a decrease in resistance to compression of the consolidated geopolymers of about 5% with 10 wt% addition and of about 77% with the addition of 20 wt% of waste corundum. In any case, the waste abrasive powder does not release heavy metals when added to a geopolymeric formulation based on MK, NaOH, and Na-silicate, and does not show relevant antibacterial properties, indicating the formation of a stable and safe final product with a ceramic-like appearance.

Chemical Compounds of Berry-Derived Polyphenols and Their Effects on Gut Microbiota, Inflammation, and Cancer.

Berry-derived polyphenols are bioactive compounds synthesized and secreted by several berry fruits. These polyphenols feature a diversity of chemical compounds, including phenolic acids and flavonoids. Here, we report the beneficial health effects of berry-derived polyphenols and their therapeutical application on gut-microbiota-related diseases, including inflammation and cancer. Pharmacokinetic investigations have confirmed the absorption, availability, and metabolism of berry-derived polyphenols. In vitro and in vivo tests, as well as clinical trials, showed that berry-derived polyphenols can positively modulate the gut microbiota, inhibiting inflammation and cancer development. Indeed, these compounds inhibit the growth of pathogenic bacteria and also promote beneficial bacteria. Moreover, berry-derived polyphenols exhibit therapeutic effects against different gut-microbiota-related disorders such as inflammation, cancer, and metabolic disorders. Moreover, these polyphenols can manage the inflammation via various mechanisms, in particular the inhibition of the transcriptional factor Nf-κB. Berry-derived polyphenols have also shown remarkable effects on different types of cancer, including colorectal, breast, esophageal, and prostate cancer. Moreover, certain metabolic disorders such as diabetes and atherosclerosis were also managed by berry-derived polyphenols through different mechanisms. These data showed that polyphenols from berries are a promising source of bioactive compounds capable of modulating the intestinal microbiota, and therefore managing cancer and associated metabolic diseases. However, further investigations should be carried out to determine the mechanisms of action of berry-derived polyphenol bioactive compounds to validate their safety and examinate their clinical uses.

Surface Interactions between Ketoprofen and Silica-Based Biomaterials as Drug Delivery System Synthesized via Sol-Gel: A Molecular Dynamics Study.

Biomaterial-based drug delivery systems for a controlled drug release are drawing increasing attention thanks to their possible pharmaceutical and biomedical applications. It is important to control the local administration of drugs, especially when the drug exhibits problems diffusing across biological barriers. Thus, in an appropriate concentration, it would be released in situ, reducing side effects due to interactions with the biological environment after implantation. A theoretical study based on Molecular Mechanics and Molecular Dynamics methods is performed to investigate possible surface interactions between the amorphous SiO2 surface and the ketoprofen molecules, an anti-inflammatory drug, considering the role of drug concentration. These theoretical results are compared with experimental data obtained by analyzing, through Fourier transform infrared spectroscopy (FT-IR), the interaction between the SiO2 amorphous surface and two percentages of the ketoprofen drug entrapped in a silica matrix obtained via the sol-gel method and dried materials. The loaded drug in these amorphous bioactive material forms hydrogen bonds with the silica surface, as found in this theoretical study. The surface interactions are essential to have a new generation of biomaterials not only important for biocompatibility, with specific structural and functional properties, but also able to incorporate anti-inflammatory agents for release into the human body.

Geopolymers-Design, Preparation, and Applications.

Concrete is the most commonly used construction material worldwide, and many efforts have been carried out in recent years to improve its functional properties while also trying to increase its sustainability [...].

Environmental and Biological Impact of Fly Ash and Metakaolin-Based Alkali-Activated Foams Obtained at 70°C and Fired at 1,000°C.

Alkali-activated foams (AAFs) are inorganic porous materials that can be obtained at temperatures well below 100°C with the use of inorganic wastes as aluminosilicate precursors. In this case, fly ash derived from a Slovenian power plant has been investigated. Despite the environmental benefits per se, due to saving of energy and virgin materials, when using waste materials, it is of extreme importance to also evaluate the potential leaching of heavy metal cations from the alkali-activated foams. This article presents an environmental study of a porous geopolymer derived from this particular fly ash, with respect to the leachability of potentially hazardous elements, its environmental toxicity as determined by biological testing, and the environmental impact of its production. In particular, attention was focused to investigate whether or not 1,000°C-fired alkali-activated fly ash and metakaolin-based foams, cured at 70°C, are environmentally friendlier options compared to unfired ones, and attempts to explain the rationale of the results were done. Eventually, the firing process at 1,000°C, apart from improving technical performance, could reinforce heavy metal cation entrapment within the aluminosilicate matrix. Since technical performance was also modified by addition of different types of activators (K-based or Na-based), as well as by partial replacement of fly ash with metakaolin, a life cycle assessment (LCA) analysis was performed to quantify the effect of these additions and processes (curing at 70°C and firing at 1,000°C) in terms of global warming potential. Selected samples were also evaluated in terms of leaching of potentially deleterious elements as well as for the immobilization effect of firing. The leaching test indicated that none of the alkali-activated material is classified as hazardous, not even the as-received fly ash as component of new AAF. All of the alkali-activated foams do meet the requirements for an inertness. The highest impact on bacterial colonies was found in samples that did not undergo firing procedures, i.e., those that were cured at 70°C, which induced the reduction of bacterial Enterococcus faecalis viability. The second family of bacteria tested, Escherichia coli, appeared more resistant to the alkaline environment (pH = 10-12) generated by the unfired AAMs. Cell viability recorded the lowest value for unfired alkali-activated materials produced from fly ash and K-based activators. Its reticulation is only partial, with the leachate solution appearing to be characterized with the most alkaline pH and with the highest ionic conductivity, i.e., highest number of soluble ions. By LCA, it has been shown that 1) changing K-based activators to Na-based activators increases environmental impact of the alkali-activated foams by 1%-4% in terms of most of the impact categories (taking into account the production stage). However, in terms of impact on abiotic depletion of elements and impact on ozone layer depletion, the increase is relatively more significant (11% and 18%, respectively); 2) replacing some parts of fly ash with metakaolin also results in relatively higher environmental footprint (increase of around 1%-4%, while the impact on abiotic depletion of elements increases by 14%); and finally, 3) firing at 1,000°C contributes significantly to the environmental footprint of alkali-activated foams. In such a case, the footprint increases by around one third, compared to the footprint of alkali-activated foams produced at 70°C. A combination of LCA and leaching/toxicity behavior analysis presents relevant combinations, which can provide information about long-term environmental impact of newly developed waste-based materials.

Antibacterial and Chemical Characterization of Silica-Quercetin-PEG Hybrid Materials Synthesized by Sol-Gel Route.

This paper aims to synthesize, via the sol-gel method, a biomaterial usable in the medical field. Here, the silica-PEG-quercetin system was evaluated in relation to the different concentrations of PEG (0, 6, 12, 24, 50 wt%) and quercetin (0, 5, 10, 15 wt%), respectively. In addition, Fourier Transform-Infrared spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Kirby-Bauer analyses were performed. FT-IR was used to evaluate the hybrid formation and the influence of both PEG and Quercetin in the hybrid synthesized materials, SEM was used to evaluate the morphological properties, while the Kirby-Bauer test was used to understand the ability of the materials to inhibit the growth of the assayed bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Enterococcus faecalis, and Staphylococcus aureus).

Pharmacological Effects of Grifolin: Focusing on Anticancer Mechanisms.

Grifolin is a volatile compound contained in essential oils of several medicinal plants. Several studies show that this substance has been the subject of numerous pharmacological investigations, which have yielded interesting results. Grifolin demonstrated beneficial effects for health via its multiple pharmacological activities. It has anti-microbial properties against bacteria, fungi, and parasites. In addition, grifolin exhibited remarkable anti-cancer effects on different human cancer cells. The anticancer action of this molecule is related to its ability to act at cellular and molecular levels on different checkpoints controlling the signaling pathways of human cancer cell lines. Grifolin can induce apoptosis, cell cycle arrest, autophagy, and senescence in these cells. Despite its major pharmacological properties, grifolin has only been investigated in vitro and in vivo. Therefore, further investigations concerning pharmacodynamic and pharmacokinetic tests are required for any possible pharmaceutical application of this substance. Moreover, toxicological tests and other investigations involving humans as a study model are required to validate the safety and clinical applications of grifolin.

Encapsulating Calendula arvensis (Vaill.) L. Florets: UHPLC-HRMS Insights into Bioactive Compounds Preservation and Oral Bioaccessibility.

Wild edible plants, once consumed in times of famine or for health purposes, today represent an interesting dietary supplement, aimed at enriching local dishes and/or formulating healthy nutraceutical products. In fact, the broad content of different, and diversely bioactive, specialized metabolites therein suggests new scenarios of use which, in order to be as functional as possible, must maximize the bioactivity of these compounds while preserving their chemistry. In this context, based on a recent investigation on the metabolic profile of the organs of Calendula arvensis that highlighted that florets are abundant in flavonol glycosides and triterpene saponins, the freeze-drying encapsulation of their alcoholic extract (FE) into maltodextrin (MD) was investigated. FE-MD chemical composition was evaluated using Fourier Transform InfraRed spectroscopy (FTIR), while ultra-high performance liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) techniques were employed to unravel FE compound preservation also during in vitro simulated digestion. The establishment of H-bonds between FE compounds and MD hydroxyl groups was in line with FE-MD biocompatibility in Caco-2 cells, while in vitro digestion mostly affected structural integrity and/or diversity. Flavonol compounds underwent deglycosylation and demethylation, while deacylation, beyond oxidation, involved triterpene saponins, which massively preserve their aglycone core.

FT-IR Study, Thermal Analysis, and Evaluation of the Antibacterial Activity of a MK-Geopolymer Mortar Using Glass Waste as Fine Aggregate.

Food containers made from glass are separately collected from urban solid waste at 76% in most parts of Europe. The cullet glass finds its way to re-melting, while the debris is often disposed of. With this contribution, we suggest an upcycling process where glass debris is simply ground without any washing operation and added to an alkali-activated paste. Metakaolin-based geopolymer mortar added with coarsely ground glass waste as fine aggregate has been prepared via alkali activation with NaOH and Na-silicate. After 7, 14 and 28 days of room temperature curing time, the 3D geopolymer network was investigated by Fourier-transform infrared spectroscopy (FT-IR). Vibrational spectra revealed the geopolymerization occurrences, results which have been supported by both FT-IR deconvoluted spectra and thermogravimetric analysis (TGA). Finally, the antibacterial properties were investigated against both gram-negative (E. coli) and gram-positive (E. faecalis) bacterial strains. The results suggest the ability of the 28 days cured geopolymers to inhibit the growth of the gram-negative bacterium assayed.

Efficient Addition of Waste Glass in MK-Based Geopolymers: Microstructure, Antibacterial and Cytotoxicity Investigation.

Reuse of waste glass can significantly decrease the quantity of waste to be treated or disposed of in landfills, allowing to both diminish the ecological damage and to reduce the costs of transportation for removal. Geopolymer mixes with diverse percentages (20, 50 and 60 wt%) and with different grain size ranges (37 µm < diam < 53 µm; 75 µm < diam < 105 µm) of waste glass and the residual part of pure metakaolin were prepared by addition of NaOH and sodium silicate as alkaline activator solutions. The effect of waste glass on the mechanical and microstructure of new geopolymers has been explored in this study. Fourier transform infrared spectroscopy (FTIR) evidenced the reactivity of waste glass in terms of Si-O and Si-O-Al bonds, more evident for the finer waste glass powder. The consolidation of the materials has been established by reduced weight loss in water and decreased pH and ionic conductivity of the eluate after 7, 14 and 28 days of curing at room temperature. The decrease of the mechanical properties with waste glass content was less evident for the finer glassy powders, yet the value of about 4-5 MPa indicates their potential use as non-structural materials. The consolidated final materials were tested for their effects on the microbial growth of Escherichia coli and Enterococcus faecalis after 24 and 48 h, respectively. The samples showed a very limited and absent inhibition zone, for fine and coarse grain size ranges, respectively. Finally, the cytotoxicity tests accomplished the ecological valuation of the final consolidated products.

Synthesis, Structural, Morphological and Thermal Characterization of Five Different Silica-Polyethylene Glycol-Chlorogenic Acid Hybrid Materials.

The present study investigated the structure, morphology, thermal behavior, and bacterial growth analysis of novel three-component hybrid materials synthesized by the sol-gel method. The inorganic silica matrix was weakly bonded to the network of two organic components: a well-known polymer such as polyethylene glycol (PEG, average molar mass of about 4000 g/mol), and an antioxidant constituted by chlorogenic acid (CGA). In particular, a first series was made by a 50 wt% PEG-based (CGA-free) silica hybrid along with two 50 wt% PEG-based hybrids containing 10 and 20 wt% of CGA (denoted as SP50, SP50C10 and SP50C20, respectively). A second series contained a fixed amount of CGA (20 wt%) in silica-based hybrids: one was the PEG-free material (SC20) and the other two contained 12 and 50 wt% of PEG, respectively (SP12C20 and SP50C20, respectively), being the latter already included in the first series. The X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) images of freshly prepared materials confirmed that all the materials were amorphous and homogeneous regardless of the content of PEG or CGA. The thermogravimetric (TG) analysis revealed a higher water content was adsorbed into the two component hybrids (SP50 and SC20) because of the availability of a larger number of H-bonds to be formed with water with respect to those of silica/PEG/CGA (SPC), where silica matrix was involved in these bonds with both organic components. Conversely, the PEG-rich materials (SP50C10 and SP50C20, both with 50 wt% of the polymer) retained a lower content of water. Decomposition of PEG and CGA occurred in almost the same temperature interval regardless of the content of each organic component. The antibacterial properties of the SiO2/PEG/CGA hybrid materials were studied in pellets using either Escherichia coli and Enterococcus faecalis, respectively. Excellent antibacterial activity was found against both bacteria regardless of the amount of polymer in the hybrids.

Characterization of Hybrid Materials Prepared by Sol-Gel Method for Biomedical Implementations. A Critical Review.

The interaction between tissues and biomaterials (BM) has the purpose of improving and replacing anatomical parts of the human body, avoiding the occurrence of adverse reactions in the host organism. Unfortunately, the early failure of implants cannot be currently avoided, since neither a good mixture of mechanical and chemical characteristics of materials nor their biocompatibility has been yet achieved. Bioactive glasses are recognized to be a fine class of bioactive substances for good repair and replacement. BM interact with living bones through the formation of a hydroxyapatite surface layer that is analogous to bones. Bioglasses' composition noticeably affects their biological properties, as does the synthesis method, with the best one being the versatile sol-gel technique, which includes the change of scheme from a 'sol' fluid into a 'gel'. This process is widely used to prepare many materials for biomedical implants (e.g., hip and knee prostheses, heart valves, and ceramic, glassy and hybrid materials to serve as carriers for drug release). Nanoparticles prepared by the sol-gel method are interesting systems for biomedical implementations, and particularly useful for cancer therapy. This review provides many examples concerning the synthesis and characterization of the above-mentioned materials either taken from literature and from recently prepared zirconia/polyethylene glycol (PEG) hybrids, and the corresponding results are extensively discussed.

(‒)-Cannabidiolic Acid, a Still Overlooked Bioactive Compound: An Introductory Review and Preliminary Research.

Cannabidiolic acid (CBDA) is the main phytocannabinoid in fiber and seed-oil hemp (Cannabis sativa L.) plants, but its potential health-related capabilities have been masked for years by a greater scientific interest towards its neutral derivative cannabidiol (CBD). This review aims to collect from the literature and critically discuss all the information about this molecule, starting from its biosynthesis, and focusing on its bioactivity, as an anti-inflammatory, anti-emetic, anti-convulsant, and anti-cancerogenic drug. Furthermore, in the awareness that, despite its multiple bioactive effects, currently poor efforts have been made to achieve its reliable purification, herein, we propose a relatively simple, fast, and inexpensive procedure for its recovery from pollen of industrial hemp cultivars. Spectroscopic and spectrometric techniques allowed us to unequivocally identify pure isolated CBDA and to distinguish it from the constitutional isomer tetrahydrocannabinolic acid (THCA-A).