Activated Carbon Modification towards Efficient Catalyst for High Value-Added Products Synthesis from Alpha-Pinene

DT0-activated carbons modified with HCl and HNO3 acids, which were used for the first time in the catalytic process of alpha-pinene isomerization, are presented in this study. The carbon materials DT0, DT0_HCl, DT0_HNO3, and DT0_HCl_HNO3 were examined with the following methods: XRF, SEM, EDX, XPS, FT-IR, XRD, and N2 adsorption at −196 °C. It was shown that DT0_HCl_HNO3-activated carbon was the most active material in the alpha-pinene isomerization process. Detailed studies of alpha-pinene isomerization were carried out over this carbon by changing the reaction parameters such as time (5–180 min) and temperature (60–175 °C). The 100% conversion of alpha-pinene was achieved at the temperature of 160 °C and catalyst content of 5 wt% after 3 h over the DT0_HCl_HNO3 catalyst. Camphene and limonene were the main products of the alpha-pinene isomerization reaction.

FeCl3-Modified Carbonaceous Catalysts from Orange Peel for Solvent-Free Alpha-Pinene Oxidation

The work presents the synthesis of FeCl3-modified carbonaceous catalysts obtained from waste orange peel and their application in the oxidation of alpha-pinene in solvent-free reaction conditions. The use of waste orange peel as presented here (not described in the literature) is an effective and cheap way of managing this valuable and renewable biomass. FeCl3-modified carbonaceous materials were obtained by a two-stage method: in the first stage, activated carbon was obtained, and in the second stage, it was modified by FeCl3 in the presence of H3PO4 (three different molar ratios of these two compounds were used in the studies). The obtained FeCl3-modified carbon materials were subjected to detailed instrumental studies using the methods FT-IR (Fourier-transform Infrared Spectroscopy), XRD (X-ray Diffraction), SEM (Scanning Electron Microscope), EDXRF (Energy Dispersive X-ray Fluorescence) and XPS (X-ray Photoelectron Spectroscopy), while the textural properties of these materials were also studied, such as the specific surface area and total pore volume. Catalytic tests with the three modified activated carbons showed that the catalyst obtained with the participation of 6 M of FeCl3 and 3 M aqueous solutions of H3PO4 was the most active in the oxidation of alpha-pinene. Further tests (influence of temperature, amount of catalyst, and reaction time) with this catalyst made it possible to determine the most favorable conditions for conducting oxidation on this type of catalyst, and allowed study of the kinetics of this process. The most favorable conditions for the process were: temperature of 100 °C, catalyst content of 0.5 wt% and reaction time 120 min (very mild process conditions). The conversion of the organic raw material obtained under these conditions was 40 mol%, and the selectivity of the transformation to alpha-pinene oxide reached the value of 35 mol%. In addition to the epoxy compound, other valuable products, such as verbenone and verbenol, were formed while carrying out the process.

Determination of Terpenoid Profile in Dry Cannabis Flowers and Extracts Obtained from Different Cannabis Varietes

Aim: The aim of this study was to determine the terpenoid profile in dried cannabis flowers obtained from different varieties of cannabis plant and in cannabis extracts in order to investigate quantity of terpenes lost during extraction and purification process. Methods: GC/MS method for determination of terpenes was verified. The concentration of terpenes was determined in dry flowers as raw material and in decarboxylated and distillated cannabis extracts, using the same GC/MS analytical method. The extraction was performed using 96% ethanol as a solvent. Results: The obtained results indicate that dry cannabis flowers from different cannabis plant can be distinguished only by their terpenoid profile. The use of standardized cannabis-based extracts can be confirmed by determination of terpenoid profile. The purification process of the cannabis extracts removes terpenes. The percentage of major terpen beta-Myrcene decreased from 68% in dry flower to 15% in decarboxylated and, 1.9% in distillated cannabis oil after purification. The percentage of second major terpene alpha-Pinene decreased from 15% in dry flower to 5% in decarboxylated and, 0.7% in distillated cannabis oil after purification. Conclusion: Terpenes act synergistically with cannabinoids. Following the monograph for quality testing of cannabis extracts in the German Pharmacopoeia, the purification process is necessary to achieve a final concentration of cannabinoids (Tetrahydrocannabinol) of more than 95% in the final active pharmaceutical ingredient. The purification process removes terpenes that have proven synergistically pharmacological effects with cannabinoids.

Activated Carbons Obtained from Orange Peels, Coffee Grounds, and Sunflower Husks—Comparison of Physicochemical Properties and Activity in the Alpha-Pinene Isomerization Process

This work presents studies on the preparation of porous carbon materials from waste biomass in the form of orange peels, coffee grounds, and sunflower seed husks. The preparation of activated carbons from these three waste materials involved activation with KOH followed by carbonization at 800 °C in an N2 atmosphere. This way of obtaining the activated carbons is very simple and requires the application of only two reactants. Thus, this method is cheap, and it does not generate much chemical waste. The obtained activated carbons were characterized by XRD, SEM, XPS, and XRF methods. Moreover, the textural properties, acidity, and catalytic activity of these materials were descried. During catalytic tests carried out in the alpha-pinene isomerization process (the use of the activated carbons thus obtained in the process of alpha-pinene isomerization has not been described so far), the most active were activated carbons obtained from coffee grounds and orange peels. Generally, the catalytic activity of the obtained materials depended on the pore size, and the most active activated carbons had more pores with sizes of 0.7–1.0 and 1.1–1.4 nm. Moreover, the presence of potassium and chlorine ions in the pores may also be of key importance for the alpha-pinene isomerization process. On the other hand, the acidity of the surface of the tested active carbons did not affect their catalytic activity. The most favorable conditions for carrying out the alpha-pinene isomerization process were the same for the three tested activated carbons: temperature 160 °C, amount of the catalyst 5 wt.%, and reaction time 3 h. Kinetic studies were also carried out for the three tested catalysts. These studies showed that the isomerization over activated carbons from orange peels, coffee grounds, and sunflower seed husks is a first-order reaction.

GC-MS/FID analysis, antibacterial activity and modes of action of essential oils from three Aframomum species found in Cameroon against foodborne pathogenic bacteria

Background: The current study examined the chemical profile and in vitro antibacterial activity of essential oils (EOs) extracted from Aframomum danielli (leaves and seeds), Aframomum chlamydentum (leaves), and Aframomum melegueta (leaves) against foodborne pathogenic bacteria. Methods: The hydro-distillation technique using a Clevenger-type apparatus was used to extract EOs, whereas the Gas Chromatography-Mass Spectrometry (GC-MS) and GC coupled to Flame Ionization Detector (GC-FID) allowed the chemical characterization of oil constituents. The broth micro-dilution method was applied for the determination of the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). Besides, some modes of action were studied on the cell membrane integrity and biofilm formation of Salmonella typhi. Results: The major compounds identified from EOs of A. danielli seeds were eucalyptol (48.707%), limonene (11.368%), beta pinene (10.342-10.335%), and alpha terpineol (8.785-9.049%), whereas EOs from A. danielli leaves were dominated by sabinene (42.87%), beta pinene, (11.22%), caryophyllene (7.84%), terpinen-4-ol (5.68%), linalool (3.48%) and gamma terpinene (2.02%). Major volatile markers from EOs of A. chlamydentum leaves comprised beta pinene (49.72%), caryophyllene (10.62%), alpha pinene (6.21%) and linalool (2.96%), while those of EOs from A. melegueta included beta pinene (37.15%), caryophyllene (17.64%), caryophyllene oxide (8.72%) and alpha pinene (8.26%). This study is the first to report on the chemical constituents of EOs from A. chlamydentum. Test oils displayed significant antibacterial activity with the MIC ranging from 0.0625 to 0.5% (v/v). EOs from A. melegueta (leaves) appeared to be the most active, acting against all tested bacteria. All EOs identified displayed bactericidal effects against Citrobacter freundii, a bacterium known to cause a broad range of infections associated with a higher rate of in-hospital mortality. The EOs from A. melegueta may act through perturbation of cell membrane integrity and permeability as well as the inhibition of bacterial biofilm formation. Conclusion: Our findings suggest the possible application of essential oils in agricultural food products for the control of bacterial diseases.

Pistacia integerrima (Shringi)- A Plant with Significant Pharmacological Activities

Pistacia integerrima is an important medicinal plant belongs to the family Anacardiacea. It is commonly called as Crab’s claw in English and Shani/Shringi in Hindi. It is a single-stemmed, dioecious tree widely distributed in countries like Nepal, China, Afghanistan, Pakistan, Armenia, North-west and West Himalayas. The plant has significant applications in the traditional systems of medications such as Ayurveda, Unani and Siddha. In addition, the plant is also used in many folkloric cultures around the world to treat a vast array of human ailments such as diarrhoea, dysentery, fever, vomiting, skin diseases, respiratory ailments and psoriasis appetizer, hepatitis and liver related disorders. The characteristic feature of the plant is its essential oil content comprised of many important phytochemical constituents such as alpha-pinene, camphene, di-limonene, 1:8-cineol, caprylic acid, alpha-terpineol and aromadendrene. However, the plant contains many other important secondary metabolites such as steroids, flavonoids, tannins, saponins and phenols which are associated with important pharmacological activities such as anti-bacterial, anti-oxidant, anti-inflammatory, cardio-protective, anti-cancer, antidiarrhoeal, anticonvulsant and muscle relaxant. The aim of the present study is to summarize the recent pharmacological activities of Pistacia integerrima along with its utilization in traditional medication systems

The nitrate radical (NO₃) oxidation of alpha-pinene is a significant source of secondary organic aerosol and organic nitrogen under simulated ambient nighttime conditions

The reaction of α-pinene with NO3 is an important sink of both α-pinene and NO3 at night in regions with mixed biogenic and anthropogenic emissions; however, there is debate on its importance for secondary organic aerosol (SOA) and reactive nitrogen budgets in the atmosphere. Previous experimental studies have generally observed low or zero SOA formation, often due to excessive [NO3] conditions. Here, we characterize the SOA and organic nitrogen formation from α-pinene + NO3 as a function of nitrooxy peroxy (nRO2) radical fates with HO2, NO, NO3, and RO2 in an atmospheric chamber. We show that SOA yields are not small when the nRO2 fate distribution in the chamber mimics that in the atmosphere, and the formation of pinene nitrooxy hydroperoxide (PNP) and related organonitrates in the ambient can be reproduced. Nearly all SOA from α-pinene + NO3 chemistry derives from the nRO2 + nRO2 pathway, which alone has an SOA mass yield of 65 (±9) %. Molecular composition analysis shows that particulate nitrates are a large (60–70 %) portion of the SOA, and that dimer formation is the primary mechanism of SOA production from α-pinene + NO3 under simulated nighttime conditions. We estimate an average nRO2 + nRO2 → ROOR branching ratio of ~18 %. Synergistic dimerization between nRO2 and RO2 derived from ozonolysis and OH oxidation also contribute to SOA formation, and should be considered in models. We report a 58 (±20) % molar yield of PNP from the nRO2 + HO2 pathway. Applying these laboratory constraints to model simulations of summertime conditions observed in the Southeast United States (where 80 % of α-pinene is lost via NO3 oxidation, leading to 20 % nRO2 + nRO2 and 45 % nRO2 + HO2) , we estimate yields of 13% SOA and 9% particulate nitrate by mass, and 26 % PNP by mole, from α-pinene + NO3 in the ambient. These results suggest that α-pinene + NO3 significantly contributes to the SOA budget, and likely constitutes a major removal pathway of reactive nitrogen from the nighttime boundary layer in mixed biogenic/anthropogenic areas.