Search Results (38)

As population growth and climate change intensify pressures on agriculture, innovative strategies are vital for ensuring food security, optimizing resources, and protecting the environment. This study introduces a novel approach to predictive agriculture by utilizing the unique properties of terpenes, specifically S(-)-limonene, emitted by plants under stress. Advanced sensors capable of detecting subtle limonene variations offer the potential for early stress diagnosis and precise crop interventions. This research marks a significant leap in sensor technology, introducing an innovative active sensing material that combines molecularly imprinted polymer (MIP) technology with electrospinning. S(-)-limonene-selective MIP nanoparticles, engineered using methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA), were synthesized with an average diameter of ~160 nm and integrated into polyvinylpyrrolidone (PVP) nanofibers reinforced with multiwall carbon nanotubes (MWCNTs). This design produced a conductive and highly responsive sensing layer. The sensor exhibited rapid stabilization (200 s), a detection limit (LOD) of 190 ppb, and a selectivity index of 73% against similar monoterpenes. Optimal performance was achieved at 55% relative humidity, highlighting environmental conditions’ importance. This pioneering use of polymeric MIP membranes in chemiresistive sensors for limonene detection opens new possibilities for monitoring VOCs, with applications in agricultural stress biomarkers, contaminant detection, and air quality monitoring, advancing precision agriculture and environmental protection. Full article

(R)-3,3,6-trimethyl-3,3a,4,5-tetrahydro-1H-cyclopenta[c]furan was obtained by the acid cyclization of the alcohol (S)-(2-methyl-5-(prop-1-en-2-yl)cyclopent-1-en-1-yl)methanol, which, in turn, is obtained from (R)-limonene. The structure of the new compound was established using NMR spectroscopy (¹H, ¹³C, COSY, HSQC, and HMBC spectra) and high-resolution mass spectrometry. The chemical shifts of the proton and carbon atoms were calculated at the DFT level with a high correlation between the calculated and experimental values. Full article

In this study, headspace–bar adsorptive microextraction (HS-BAµE) combined with gas chromatography–mass spectrometry (GC-MS) was employed to screen the major biogenic volatile organic compounds (BVOCs) emitted by six different Portuguese shrub species (Erica scoparia L., Cistus ladanifer L., Cistus monspeliensis L., Lavandula stoechas L., Thymus villosus L., and Thymus camphoratus). The HS-BAµE/GC-MS methodology was developed, optimized, and validated using five common monoterpenoids (α-pinene, β-pinene, limonene, 1,8-cineole, and thymol) and one sesquiterpenoid (caryophyllene oxide). Under optimized experimental conditions (microextraction-sorbent phase: activated carbon (CN1), 3 h (35 °C); back-extraction: n-C₆ (1 h)), good efficiencies (>45%), low analytical thresholds (5.0–15.0 µg/L) and suitable linear dynamic ranges (20.0–120.0 µg/L, r² > 0.9872) were achieved, as well as acceptable intra and inter-day precisions (RSD ≤ 30.1%). Benchmarking the proposed methodology, HS-BAµE(CN1), against the reference methodology, HS-SPME(PDMS/DVB), revealed comparable analytical responses and demonstrated excellent reproducibility. Among the six shrub species studied, Thymus camphoratus exhibited the highest emissions of BVOCs from its leaves, notably, 1,8-cineole (4136.9 ± 6.3 µg/g), α-pinene (763.9 ± 0.5 µg/g), and β-pinene (259.3 ± 0.5 µg/g). It was also the only species found to release caryophyllene oxide (411.4 ± 0.3 µg/g). The observed levels suggest that these shrub species could potentially serve as fuel sources in the event of forest fires occurring under extreme conditions. In summary, the proposed methodology proved to be a favorable analytical alternative for screening BVOCs in plants. It not only exhibited remarkable performance but also demonstrated user- and eco-friendliness, cost-effectiveness, and ease of implementation. Full article

A liquid–liquid extraction pretreatment method using n-hexane as the extractant was developed for the analysis of volatile aroma substances in three flavors (six cola samples, six lemon samples, and six orange samples) of carbonated beverages by gas chromatography–mass spectrometry (GC-MS). Quantitative analysis was conducted using the external standard method. The spiked recovery rate of α-terpineol was used as the evaluation criterion. Single-factor and response surface experiments were conducted to investigate the effects of extraction temperature, extraction time, and solvent-to-sample ratio. The results indicated that the maximum spiked recovery rate of α-terpineol, 81.00%, was achieved at an extraction temperature of 45 °C, extraction time of 30 min, and a solvent-to-sample ratio of 1 mL:15 mL. Thirty-four components were identified by GC-MS on the pretreated samples via the internal standard method. 1,4-Cineole, fenchyl alcohol, borneol, and α-terpineol are covered aroma substances in cola beverages. Two aromatic substances, D-limonene and α-terpineol, were detected in orange juices. α-Terpineol was detected in each lemon-flavor carbonated beverage sample. Going a step further, α-terpineol was detected in all 18 carbonated beverage samples and had high response values. The principal component analysis by functional group classification led to the conclusion that acids, phenols, hydrocarbons, alcohols, and ethers played a major contribution to the aroma of these 18 beverages. Increased separation of target compounds was found using the new pre-treatment methods, resulting in improved analytical resolution and selectivity. Full article

Volatile organic compounds (VOCs) pose significant risks to human health and environmental quality, prompting stringent regulations on their emissions from various industrial processes. Among VOCs, d-limonene stands out due to its low threshold and contribution to malodorous emissions. While biofiltration presents a promising approach for VOC removal, including d-limonene, a comprehensive understanding of its performance and kinetics is lacking. This study aims to comprehensively assess the performance of a lab-scale biotrickling filter in treating gas-phase d-limonene. The experimental results indicate that the biotrickling filter efficiently removed d-limonene, achieving a critical loading rate of 19.4 g m⁻³ h⁻¹ and a maximum elimination capacity of 31.8 g m⁻³ h⁻¹ (correspondingly, up to 85% removal) at the condition of 94.2 s of EBRT. Microbial activity played a significant role in biotrickling filter performance, with a strong linear correlation being observed between CO₂ production and substrate consumption. The Michaelis–Menten model was employed to represent enzyme-catalyzed reactions, suggesting no inhibition during biotrickling filter operation. Full article

Detecting volatile organic compounds (VOCs) emitted from different plant species and their organs can provide valuable information about plant health and environmental factors that affect them. For example, limonene emission can be a biomarker to monitor plant health and detect stress. Traditional methods for VOC detection encounter challenges, prompting the proposal of novel approaches. In this study, we proposed integrating electrospinning, molecular imprinting, and conductive nanofibers to fabricate limonene sensors. In detail, polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) served here as fiber and cavity formers, respectively, with multiwalled carbon nanotubes (MWCNT) enhancing conductivity. We developed one-step monolithic molecularly imprinted fibers, where S(−)-limonene was the target molecule, using an electrospinning technique. The functional cavities were fixed using the UV curing method, followed by a target molecule washing. This procedure enabled the creation of recognition sites for limonene within the nanofiber matrix, enhancing sensor performance and streamlining manufacturing. Humidity was crucial for sensor working, with optimal conditions at about 50% RH. The sensors rapidly responded to S(−)-limonene, reaching a plateau within 200 s. Enhancing fiber density improved sensor performance, resulting in a lower limit of detection (LOD) of 137 ppb. However, excessive fiber density decreased accessibility to active sites, thus reducing sensitivity. Remarkably, the thinnest mat on the fibrous sensors created provided the highest selectivity to limonene (Selectivity Index: 72%) compared with other VOCs, such as EtOH (used as a solvent in nanofiber development), aromatic compounds (toluene), and two other monoterpenes (α-pinene and linalool) with similar structures. These findings underscored the potential of the proposed integrated approach for selective VOC detection in applications such as precision agriculture and environmental monitoring. Full article

Among the Moscato grapes, Moscato Giallo is a winegrape variety characterised by a high content of free and glycosylated monoterpenoids, which gives wines very intense notes of ripe fruit and flowers. The aromatic bouquet of Moscato Giallo is strongly influenced by the high concentration of linalool, geraniol, linalool oxides, limonene, α-terpineol, citronellol, hotrienol, diendiols, trans/cis-8-hydroxy linalool, geranic acid and myrcene, that give citrus, rose, and peach notes. Except for quali-quantitative analysis, no investigations regarding the isotopic values of the target volatile compounds in grapes and wines are documented in the literature. Nevertheless, the analysis of the stable isotope ratio represents a modern and powerful tool used by the laboratories responsible for official consumer protection, for food quality and genuineness assessment. To this aim, the aromatic compounds extracted from grapes and wine were analysed both by GC-MS/MS, to define the aroma profiles, and by GC-C/Py-IRMS, for a preliminary isotope compound-specific investigation. Seventeen samples of Moscato Giallo grapes were collected during the harvest season in 2021 from two Italian regions renowned for the cultivation of this aromatic variety, Trentino Alto Adige and Veneto, and the corresponding wines were produced at micro-winery scale. The GC-MS/MS analysis confirmed the presence of the typical terpenoids both in glycosylated and free forms, responsible for the characteristic aroma of the Moscato Giallo variety, while the compound-specific isotope ratio analysis allowed us to determine the carbon (δ¹³C) and hydrogen (δ²H) isotopic signatures of the major volatile compounds for the first time. Full article

Nowadays, the effective processing of natural monoterpenes that constitute renewable biomass found in post-production waste into products that are starting materials for the synthesis of valuable compounds is a way to ensure independence from non-renewable fossil fuels and can contribute to reducing global carbon dioxide emissions. The presented research aims to determine, based on DFT calculations, the activity and reactivity of limonene, an organic substrate used in previous preparative analyses, in comparison to selected monoterpenes such as cymene, pinene, thymol, and menthol. The influence of the solvent model was also checked, and the bonds most susceptible to reaction were determined in the examined compounds. With regard to E_HOMO, it was found that limonene reacts more easily than cymene or menthol but with more difficultly than thymol and pienene. The analysis of the global chemical reactivity descriptors “locates” the reactivity of limonene in the middle of the studied monoterpenes. It was observed that, among the tested compounds, the most reactive compound is thymol, while the least reactive is menthol. The demonstrated results can be a reference point for experimental work carried out using the discussed compounds, to focus research on those with the highest reactivity. Full article

This study explored the design of an innovative stereoselective S-(-)-limonene sensor according to the molecular imprinting polymer (MIP) strategy using UV light to generate in situ polymer cross-linking. A conductive composite nanofibrous fabric of polyvinylpyrrolidone (PVP), polyacrylic acid (PAA) and carbon nanotubes (MWCNTs) was deposited on purpose in a single step by electrospinning onto interdigital microelectrodes. The nanostructured layer was investigated by microscopy (SEM, TEM, AFM) and infrared transmission measurements (FTIR). The resulting sensing features (carried out in environmental air) seemed to be mainly dependent on the peculiarity of the nanostructure and the phenomena occurring at the interfaces between the cross-linked PVP–PAA/cavity shape and MWCNTs. Furthermore, the specificity of the host–guest interaction was proven by the sensitivity, selectivity and stereoselectivity of the sensor when exposed to similar monoterpenes ((±)-α-pinene and (±)-linalool) and the enantiomer of limonene (R(+)), respectively. Full article

Terpenes are high-value chemicals which can be produced by engineered cyanobacteria from sustainable resources, solar energy, water and CO₂. We previously reported that the euryhaline unicellular cyanobacteria Synechocystis sp. PCC 6803 (S.6803) and Synechococcus sp. PCC 7002 (S.7002) produce farnesene and limonene, respectively, more efficiently than other terpenes. In the present study, we attempted to enhance farnesene production in S.6803 and limonene production in S.7002. Practically, we tested the influence of key cyanobacterial enzymes acting in carbon fixation (RubisCO, PRK, CcmK3 and CcmK4), utilization (CrtE, CrtR and CruF) and storage (PhaA and PhaB) on terpene production in S.6803, and we compared some of the findings with the data obtained in S.7002. We report that the overproduction of RubisCO from S.7002 and PRK from Cyanothece sp. PCC 7425 increased farnesene production in S.6803, but not limonene production in S.7002. The overexpression of the crtE genes (synthesis of terpene precursors) from S.6803 or S.7002 did not increase farnesene production in S.6803. In contrast, the overexpression of the crtE gene from S.6803, but not S.7002, increased farnesene production in S.7002, emphasizing the physiological difference between these two model cyanobacteria. Furthermore, the deletion of the crtR and cruF genes (carotenoid synthesis) and phaAB genes (carbon storage) did not increase the production of farnesene in S.6803. Finally, as a containment strategy of genetically modified strains of S.6803, we report that the deletion of the ccmK3K4 genes (carboxysome for CO₂ fixation) did not affect the production of limonene, but decreased the production of farnesene in S.6803. Full article

This study proposes a two-step process to design a chiral sensor combining MIP (molecularly imprinted polymer) and electrospinning technologies. First, stereoselective S(-)-limonene molecularly imprinted polymer nanoparticles (MINPs) were fabricated and dispersed into polyvinylpyrrolidone–carbon nanotube (PVP-MWCNT) conductive nanofibers to cover resistive interdigitated electrodes (IDEs). The electrical and sensing performances of the resulting sensor confirmed its capacity to discriminate and quantify the two limonene enantiomers. The sensor’s response to terpene gases appeared completely reversible, probably due to the peculiarity of the nanostructure. The sensor characteristics were influenced by the polymer matrix’s composition ratio, the cavity shape and the interfaces with carbon nanotubes. The morphological properties of the nanofibers were investigated by microscopy (optical, SEM, TEM and AFM). Full article

Edible fungi are renowned for producing biologically active secondary metabolites that possess anti-tumor activity, protect the liver and have other benefits. The cultivation of truffle mycelia through submerged fermentation has gained interest in the production of metabolites for bio-medicinal purposes. In the present study, Tuber borchii was cultivated by submerged fermentation to produce both biomass and triterpenoids. Various additives, including palmitic acid, stearic acid, linoleic acid, chitosan, CaCl₂ and limonene, were investigated to enhance triterpenoid production. It was observed that increasing the medium’s linoleic acid concentration to 1 g/L increased the production of triterpenoids to 129.29 ± 6.5 mg/L, which was 2.94 times higher than the control. A number of variables, including potassium and magnesium ion concentrations and carbon and nitrogen sources and concentrations, were considered to ascertain the ideal conditions for T. borchii growth in submerged fermentation. The best concentrations for glucose, yeast extract, peptone, malt extract, KH₂PO₄ and MgSO₄·7H₂O in submerged fermentation were 19.45, 4.58, 7.91, 5.3, 0.58 and 0.82 g/L, respectively, according to response surface methodology. Validation analysis revealed that the experimental values and the predicted values were in good agreement. Under ideal circumstances, the maximum dry cell weight (2.980.18 g/L), which was 1.39 times greater than the control, was attained. Finally, the addition of 1.5 g/L linoleic acid on day 14 to the optimal medium elevated the triterpenoid production to 212.63 ± 16.58 mg/L, which was a 4.84-fold increase compared to the control. Full article

Zanthoxylum armatum DC. is a plant that has been homologated for medicine and food by the Chinese for three thousand years. In this study, the essential oils of fresh leaves and fruits were extracted by hydrodistillation, the aromas of fresh leaves and fruits were extracted by headspace solid-phase microextraction and their chemical compositions were analyzed by gas chromatography mass spectrometry. The main components of the leaf essential oils were linalool (62.01%), 2-undecanone (9.83%) and 2-tridecanone (5.47%); the fruit essential oils were linalool (72.17%), limonene (8.05%) and sabinene (6.77%); the leaf aromas were limonene (39.15%), β-myrcene (15.8%), sabinene (8.17%) and linalool (5.25%); the fruit aromas were limonene (28.43%), sabinene (13.56%), linalool (11.47%) and β-myrcene (8.64%). By comparison, it was found that the composition of leaf essential oils and fruit essential oils were dominated by oxygenated monoterpenes, while the composition of their aromas were both dominated by monoterpenes; the relative content of non-terpene components in leaf essential oil and leaf aroma is second only to oxygenated monoterpenes, while their content in fruits is low; the chemical composition of leaf aromas and fruit aromas were richer than those of essential oils. In this study, we reported for the first time that the antitumor, tyrosinase inhibition, HMGR inhibition and nitric oxide production inhibition activity of leaf essential oils were stronger than those of fruit essential oils in in vitro tests. The results of the study can provide a reference for the recycling and green low-carbon transformation of the leaves, and also help to deepen the understanding of the value of the volatile chemical constituents of this plant in “forest medicine” or “aromatherapy”, and provide new ideas for the transformation of the value of the plant in the secondary and tertiary industry chain. Full article

Tire wear particles (TWPs), as a type of thermosetting microplastic (MP), accumulate in aquatic environments due to their wide application in road traffic globally. The increase in temperature because of friction heat may cause aging of tire materials, inducing water evaporation, additive volatilization, polymer decomposition, and may pose serious potential risks to aquatic and terrestrial ecosystems. However, research on real-time pyrolysis dynamics of thermally aged tire MPs is very limited. In this study, a thermogravimetric analyzer coupled with Fourier transform infrared spectrometry and gas chromatography-mass spectrometry (TG-FTIR-GC/MS) was used to investigate pyrolysis behaviors and products of thermally aged tire MPs. FTIR analysis indicated that the main pyrolysis gases included carbon dioxide, carbon monoxide, aliphatic compounds, aromatic compounds and carbonyl compounds. The GC/MS analysis further determined the main pyrolytic products, including methylbenzene, styrene, m-xylene and D-limonene. These data combined with TG analysis revealed that the main pyrolytic products of TWPs were released at 400–600 °C. Moreover, the results showed that the number of aliphatic/aromatic compounds released increased in short-term thermo-oxidative aging but decreased in long-term thermo-oxidative aging. Moreover, the aged TWPs presented higher released amounts of styrene and methylbenzene but lower amounts of D-limonene compared to the original TWPs. These results can provide new insights into the evaluation method of TWP aging and a better understanding on TWP fate in aquatic and terrestrial environments. Full article

Salen, Salan, and Salalen chromium (III) chloride complexes have been investigated as catalysts for the ring-opening copolymerization reactions of cyclohexene oxide (CHO) with CO₂ and of phthalic anhydride (PA) with limonene oxide (LO) or cyclohexene oxide (CHO). In the production of polycarbonates, the more flexible skeleton of salalen and salan ancillary ligands favors high activity. Differently, in the copolymerization of phthalic anhydride with the epoxides, the salen complex showed the best performance. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures from mixtures of CO₂, cyclohexene oxide, and phthalic anhydride with all complexes. In addition, all chromium complexes were revealed to be very active in the chemical depolymerization of polycyclohexene carbonate producing cyclohexene oxide with high selectivity, thus offering the opportunity to close the loop on the life of these materials. Full article