Head Space Research Articles

Volatiles extracted from Melaleuca Rugulosa (Link) Craven leaves: comparative profiling, bioactivity screening, and metabolomic analysis

Abstract Background Melaleuca species (family Myrtaceae) are characterized by their wide-ranging applications as antimicrobials and in skin-related conditions. Herein, we estimated the volatile profile and biological significance of M. rugulosa (Link) leaves for the first time supported by a dereplication protocol. Materials and methods Volatile components were extracted using hydrodistillation (HD), supercritical fluid (SF), and headspace (HS) techniques and identified using GC/MS. The variations among the three extracts were assessed using principal component analysis and orthogonal partial least square discriminant analysis (OPLS-DA). The extracted volatiles were tested for radical scavenging activity, anti-aging, and anti-hyperpigmentation potential. Finally, disc diffusion and broth microdilution assays were implemented to explore the antibacterial capacity against Streptococcus pyogenes, Staphylococcus aureus, Clostridium perfringens, and Pseudomonas aeruginosa. Results The yield of the SF technique (0.8%) was three times higher than HD. GC/MS analysis revealed that the oxygenated compounds are the most proponents in the three extracts being 95.93% (HD), 80.94% (HS), and 48.4% (SF). Moreover, eucalyptol (1,8-cineol) represents the major component in the HD-EO (89.60%) and HS (73.13%) volatiles, while dl-α-tocopherol (16.27%) and α-terpineol (11.89%) represent the highest percentage in SF extract. Regarding the bioactivity profile, the HD-EO and SF-extract showed antioxidant potential in terms of oxygen radical absorbance capacity, and β- carotene assays, while exerting weak activity towards DPPH. In addition, they displayed potent anti-elastase and moderate anti-collagenase activities. The HD-EO exhibited potent anti-tyrosinase activity, while the SF extract showed a moderate level compared to tested controls. OPLS-DA and dereplication studies predicted that the selective antibacterial activity of HD-EO to S. aureus was related to eucalyptol, while SF extract to C. perfringens was related to α-tocopherol. Conclusions M. rugulosa leaves are considered a vital source of bioactive volatile components that are promoted for controlling skin aging and infection. However, further safety and clinical studies are recommended.

Comparative volatiles profiling of two marjoram products via GC-MS analysis in relation to the antioxidant and antibacterial effects

AbstractMarjoram (Origanum majorana L.), also known as “sweet marjoram” or “sweet oregano” is a Mediterranean herbaceous perennial herb cultivated in Egypt and widely consumed as an herbal supplement for treatment of several ailments. The main goal of this study was to assess volatiles’ variation in marjoram samples collected from two different widely consumed commercial products using two different extraction techniques viz. head space solid phase microextraction (HS-SPME) and petroleum ether using gas chromatography mass spectrometry (GC-MS) analysis and multivariate data analysis. A total of 20 major aroma compounds were identified in samples extracted with HS-SPME found enriched in monoterpene hydrocarbons and oxygenated compounds. The major volatiles included β-phellandrene (20.1 and 14.2%), γ-terpinene (13.4 and 11.7%), 2-bornene (12.3 and 11.5%), p-cymene (9.8 and 4.6%) terpenen-4-ol (16.4 and 7.5%), sabinene hydrate (16.02 and 8.8%) and terpineol (4.2 and 3.2%) in MR and MI, respectively. Compared with HS-SPME, 51 aroma compounds were identified in marjoram samples extracted with petroleum ether, found more enriched in aliphatic hydrocarbons (42.8 and 73.8%) in MR and MI, respectively. While a higher identification score was observed in the case of solvent extraction, SPME appeared to be more selective in the recovery of oxygenated terpenes to account more for marjoram aroma. Multivariate data analysis using principal component analysis (PCA) revealed distinct discrimination between volatile composition of both marjoram samples. The total phenolic and flavonoid contents in marjoram samples were at (111.9, 109.1 µg GA/mg) and (18.3, 19.5 µg rutin eq/mg) in MR and MI, respectively. Stronger antioxidant effects were observed in MR and MI samples with IC50 at 45.5 and 56.8 µg/mL respectively compared to IC50 6.57 µg/mL for Trolox as assayed using DPPH assay. Moderate anti-bacterial effect was observed in MR and MI samples and expressed as a zone of inhibition mostly against Bacillus subtilis (16.03 and 15.9 mm), B. cereus (12.9 and 13.7 mm), Enterococcus faecalis (14.03 and 13.97 mm), and Enterobacter cloacae (11.6 and 11.6 mm) respectively.

Sustainability assessment in food analysis: the application of Green Analytical Chemistry tools to phthalate residue analysis in edible oils

Edible oils are essential in daily diet due to their high contribution of fatty acids, fat-soluble vitamins, and triglycerides. During the processes of growing, processing, storage, transport, or packaging, they can be contaminated by ubiquitous phthalate esters, considered endocrine disruptors. Thus, analytical methodologies to allow tight control of their presence are mandatory. Several sample treatments have been considered in this study: microwave-assisted extraction (MAE), liquid-liquid extraction (LLE), dispersive solid phase extraction (DSPE), magnetic SPE (MSPE), solid phase microextraction (SPME), Surface-enhanced Raman spectroscopy (SERS) or its combinations. However, the selection of an analytical procedure is usually performed from an Analytical Chemistry perspective, without considering factors such as the sustainability of the selected methodology and/or its impact on the environment. In this sense, the Green Analytical Chemistry strategy can play an important role. To demonstrate this fact, six different analytical procedures have been evaluated in terms of sustainability by using several greenness evaluation tools. Procedures from MAE-gel permeation chromatography (GPC)-SPE till SERS, showing adequate analytical characteristics, have been selected. The application of Analytical GREEnness calculator (AGREE), AGREE preparation (AGREE prep), and blue applicability grade index (BAGI) tools showed that MAE-GPC-SPE was the less green analytical procedure while SERS was the greener one. The BAGI evaluation showed that headspace (HS) and SERS were the most applicable procedures.

A General Strategy to Rapid and Sensitive Determination of Five High Boiling Point Solvents in Pharmaceuticals by RP-HPLC Combined with Precipitation Method

Abstract The difficulty on determination of high boiling point solvents, always exist due to their low vapor pressure in headspace (HS) vial. What’s worse, the commonly used GC diluents, such as N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N, N-dimethylformamide and N-methylpyrrolidone are often remained in HS instrument after frequent injection into HS, thus would result in terrible positive interference problem. In this work, a fast and sensitive HPLC method in combination with a sample precipitation method, was proposed for the determination of above five high boiling point solvents in drug substances within 14.5 min. The final method was validated with regard to limit of detection and limit of quantitation, precision, linearity and accuracy in accordance with ICH Q2 (R1). Finally, the proposed strategy was successfully applied for the analysis of high boiling point solvents used in three active pharmaceutical ingredients. The established generic strategy would provide another choice for the determination of high boiling point solvents in pharmaceuticals.

Chemical analysis, antibacterial and anti-inflammatory effect of Achillea fragrantissima essential oil growing wild in Egypt

BackgroundAchillea fragrantissima (F. Asteraceae) is traditionally used to treat skin infections and inflammation. The present work intended to prepare essential oils (EOs) from A. fragrantissima aerial parts growing widely in Egypt and investigate its antibacterial activity against skin-related pathogens and in vitro cell-based anti-inflammatory activity.MethodsEOs of the fresh aerial parts were extracted by hydrodistillation (HD), microwave-assisted hydrodistillation (MAHD), and head-space (HS), while those of the dried ones were prepared by supercritical fluid (SF). The result EOs were analyzed using GC/MS. The antibacterial activity was evaluated alongside Pseudomonas aeruginosa ATCC 9027, Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, Streptococcus pyogenes ATCC 12344, Clostridium perfringens ATCC 13124 by agar diffusion, microwell dilution, and biofilm formation tests. The anti-inflammatory activity was evaluated by measuring tumor necrosis factor-alpha (TNF-α), interleukin 2 (IL-2), and 6 (IL-6) in lipopolysaccharides (LPS)- stimulated RAW 264.7 cells using ELISA assays in addition, expression of nitric oxide synthase (iNOS) was measured via western blot.ResultsThe SF method gave the highest EO yield (1.50 mL v/w). Oxygenated components constituted the highest percentage in the four methods, 84.14, 79.21, 73.29 and 33.57% in the HS, HD, MAHD, and SF, respectively. Moreover, variation in the amount of identified compounds was apparent; in HS EO α-thujone (29.37%), artemisia ketone (19.59%), and santolina alcohol (14.66%) are major components, while α-thujone (20.38%) and piperatone (12.09%) were significant in HD. Moreover, ( +)-spathulenol (12.22%) and piperatone (10.48%) were significant in MAHD, while piperatone (14.83%) and β-sitosterol (11.07%) were significant in SF EO. HD, MAHD, and SF EOs exhibited susceptibility against P. aeruginosa (IZ = 9–14 mm), E. coli (11–13 mm), and C. perfringens (IZ = 10–14 mm) in agar diffusion assay. MAHD EOs demonstrated potent growth inhibition (MICs = 0.25–2 mg/mL), followed by HD EOs (MICs = 13–52 mg/mL) to all tested microorganisms in well microdilution assay. Also, they exert MBC values equal to or higher than the MICs. Furthermore, SF EOs inhibited the biofilm formation of all tested microorganisms by 65.12—80.84%. Specifically, MAHD and HD EOs efficiently suppress the biofilm of S. pyogenes (77.87%) and P. aeruginosa (60. 29%), respectively. Ultimately, HD and SF EOs showed anti-inflammatory activity by suppressing the TNF-α, IL-2, and IL-6 release and iNOS expression in LPS-stimulated RAW 264.7 macrophages.ConclusionA. fragrantissima EO is rich in oxygenated volatile compounds with antibacterial and anti-inflammatory activities. It is encouraged as a bioactive agent for adjusting skin infections, though additional studies are essential for their safety in clinical settings.

Identifying viral infections through analysis of head space volatile organic compounds

Volatile organic compounds (VOCs) produced by human respiratory cells reflect metabolic and pathophysiological processes which can be detected with the use of modern technology. Analysis of exhaled breath or indoor air may potentially play an important role in screening of upper respiratory tract infections such as COVID-19 or influenza in the future. In this experimental study, air samples were collected and analyzed from the headspace of anin vitrocell culture infected by selected pathogens (influenza A H1N1 and seasonal coronaviruses OC43 and NL63). VOCs were measured with a real-time proton-transfer-reaction time-of-flight mass spectrometer and a differential mobility spectrometer. Measurements were performed every 12 h for 7 d. Non-infected cells and cell culture media served as references. In H1N1 and OC43 we observed four different VOCs which peaked during the infection. Different, individual VOCs were also observed in both infections. Activity began to clearly increase after 2 d in all analyses. We did not see increased VOC production in cells infected with NL63. VOC analysis seems to be suitable to differentiate the infected cells from those which are not infected as well as different viruses, from another. In the future, this could have practical value in both individual diagnostics and indoor environment screening.

Head Space GC-MS/MS Method for Quantification of Five Nitrosoamine-Genotoxic Impurities in Metformin HCl

Background: N-nitrosamines have recently been discovered in metformin hydrochloride and other generic drugs. To quantify the five N-nitrosamines in metformin hydrochloride, we devised sensitive and reliable multiple reactions monitoring mode-based GCMS/ MS technique, particularly, N-nitrosodiethy amine (NDEA), N-nitroso ethyl isopropylamine (NEIPA), N-nitrosodiisopropylamine (NDIPA), N-nitrosodipropylamine (NDPA), as well as N-nitrosodibutylamine (NDBA). Objective: To develop a sensitive, precise, and accurate MRM mode based GC-MS/MS method for the quantification of five N-nitrosamines in metformin hydrochloride and valídate as per ICH guidelines. Methods: The settings for mass spectrometry and gas chromatography were optimized. With the linearity, sensitivity, specificity, accuracy, and precision of the parameter, the procedure was as per the recommendation of ICH: International Council for Harmonization guidelines. Results: N-nitrosamines in metformin hydrochloride had detection and quantification limits of 0.001 ppm and 0.004 ppm, correspondingly. The obtained results were within the sensitivity limitations issued by the US Food and Drug Administration. The calibration curve's regression coefficients for five N-nitrosamines were over 0.99, demonstrating the process's good linearity. The retrievals of N-nitrosamines in metformin hydrochloride between 97.1 – 127.4 %. The RSD (Relative Standard Deviation) was lower than 10 % for both inter-day and intra-day precision studies. Conclusion: The proposed method exhibited a rapid analysis capability, high accuracy, sensitivity, and precision, making it a trustworthy method for monitoring N-nitrosamines in metformin hydrochloride.

Regarding Bioanalysis Lasting a Few Minutes: Automated Cooling-SPME and Fast-GC for Urinary 2-Phenyl-2-Propanol Monitoring.

An innovative SPME head space GC-MS method, in cooling mode, using a fully automated routine, was developed to detect 2-phenyl-2-propanol, a representative urinary metabolite of cumene. Following an acid hydrolysis and derivatization step with lowered quantities of reagents, acetic anhydride and pyridine, a 30 μm polydimethylsiloxane SPME fiber was used to sample derivatized 2-phenyl-2-propanol, such as benzenemethanol,α,α-dimethyl-acetate, from the headspace. Performances of the method, optimized through experimental design, provide an LOD of 0.034 mg/L and an LOQ 0.10 mg/L, with a short sampling time necessary per sample. The method, developed on standard solutions, will be applied to both occupationally exposed and non-exposed populations.

Mapping soil VOCs using three green sample extraction techniques and GC–MS

Sample preparation is a very crucial step prior to sample analysis. Three green adsorptive sample preparation micro-extraction techniques were investigated (smart solid-phase microextraction (SPME), high-capacity sorptive extraction (HiSorb), and stir bar sorptive extraction (SBSE)) for the determination of volatile organic compounds (VOCs) emitted from vineyard soil samples after method optimization. More specifically, the 95 μm Carbon Wide Range/Polydimethylsiloxane (CWR/PDMS) smart SPME fiber, CWR/PDMS HiSorb, and PDMS Twister micro-extraction tools were compared for their extraction capabilities. The headspace (HS)-SPME-gas chromatography-mass spectrometry (GC–MS) method was proved better for the extraction of VOCs from the vineyard soils due to shorter exposure time (45 min), its automation (use of a fully automated system compared to the other two), and the high sample throughput analysis. The validation of the HS-SPME-GC–MS method showed good linearity (R2 ≥ 0.9951) and limit of detection (LOD), whereas the limit of quantitation (LOQ) ranged from 0.04-3.65 μg/kg. Also, the repeatability and reproducibility of the results showed a relative standard deviation (RSD) lower than 4.73 %. A total number of 47 soil-derived VOCs were identified through the validated HS-SPME-GC–MS method, and 9 targeted VOCs were quantified with total average concentrations ranging from 0.14-28.07 µg/kg. Smart SPME fiber proved beneficial over the two other tools, highlighting the aspects of green chemistry.

Feasibility of polylactic acid and essential oil composite with insecticidal properties for prevention of Sitophilus oryzae and Oryzophilus surinamensis in Sorghum and Pearl millet

Current study provides insight on the feasibility of polylactic acid (PLA) integrated with (1:1 ratio) of essential oils belonging to Ocimum gratissimum (OG) and Mentha spicata (MS) for prevention of major stored insect pests (Sitophilus oryzae and Oryzophilus surinamensis) in Sorghum and Pearl millet. A combination of OG and MS essential oils (1:1) was incorporated into the PLA polymer matrix. Further, SPME analysis of synthesized PLA showed the presence of volatiles corresponding to carvone (6.44 %) and thymol (6.22 %). Synthesized PLA composites were tested against S. oryzae and O. surinamensis using Sorghum and Pearl millets, and insect mortality was equivalent to commercial super bags (CSB). The head space oxygen decreased significantly in CSB and slightly in PLA bags. Thickness of EO blended PLA composite was increased (99 μm), tensile strength (23.94 MPa), WVTR (1.42 g/m2.hr) analysis, significant folding ability, and swelling capacity (0.24 %) showed slight reduction in composite film. TGA showed good thermal stability (334˚C) and XRD displayed the increased crystallinity (38.35 %) in PLAOM films, SEM and FTIR analysis of the synthesized composite films revealed complete homogenization of EO and PLA matrix. In addition, SEM analysis of insects (control & treated) revealed less topology changes in the elytra. Biodegradability study confirmed the weight loss in PLA films. Hence, current approach of using composite EO's with PLA offers sustainable solution for prevention of infestation during storage of millets.

Development of an Untargeted Method for the Analysis of the Volatile Profile of Onions via Solid-Phase Microextraction Arrow-Headspace-Gas Chromatography-Mass Spectrometry Using Design of Experiments.

The distinctive aroma of onions, consisting primarily of sulfur-containing compounds, is one of the reasons for the popularity of the vegetable. The rapid enzymatic and chemical reactions that occur after the destruction of onion bulb tissue render the analysis of the volatile profile challenging. Therefore, sample preparation is a crucial step in the analysis of the onion volatilome, but it often does not receive the necessary attention in the literature. In this work, we focused on two aspects: Firstly, we compared different sample preparation approaches to maximize the volatile yield and to enable the description of the onion volatile profile as it would emerge after a solid-phase microextraction (SPME) Arrow sampling procedure. For headspace (HS)-gas chromatography-mass spectrometry analysis, onion juice with the addition of an ammonium sulfate solution proved to be the best option. Secondly, we optimized the HS sampling and desorption parameters (enrichment time, enrichment temperature, agitator speed, desorption time) for onion volatiles using the efficient design of experiments (DoE) approach. The optimal conditions for the analysis with HS-SPME Arrow were an enrichment time of 75min at 60°C with an agitator speed of 713rpm and a desorption time of 120s.

Factors to Male-Female Sex Approaches and the Identification of Volatiles and Compounds from the Terminalia of Proholopterus chilensis (Blanchard) (Coleoptera: Cerambycidae) Females in Nothofagus obliqua (Mirb.) Oerst. (Nothofagaceae) Forests in Chile.

During the spring-summer seasons between 2019 and 2023, in the localities of Maquehue (La Araucanía Region) and Llifén (Los Ríos Region), we collected 262 virgin Proholopterus chilensis (1 female/2.3 males) specimens emerging from the live trunks of N. obliqua trees, an atypical sex ratio in Cerambycidae, suggesting high male competition for females. Virgin specimens of both sexes were individually placed in panel traps in the field, capturing only males (n = 184) over the field study seasons and only in traps baited with females. This fact preliminarily suggests the P. chilensis females emit possible "volatile or airborne" pheromones (eventually being a long-range sex pheromone), something unusual in Cerambycinae, the subfamily to which it currently belongs, although the taxonomic status of the species is under debate. In Llifén and Santiago (Metropolitan Region), behavioral observations were conducted, which allowed us to define the conditions necessary for male-female encounters that were replicated when carrying out volatile captures (Head Space Dynamic = HSD) and collections of compounds from terminalias excised from females. In field trials, virgin females less than ten days old were more attractive than older ones and attracted males during the night, i.e., between 23:00 and 5:00 AM, when the ambient temperature exceeded 11.6 °C. The aeration of females under the conditions described above and subsequent analysis of extracts by GC-MS allowed the identification of compounds absent in males and the control, including two oxygenated sesquiterpenes, a nitrogenous compound (C20), and a long-chain hydrocarbon (C26). From the terminalia extracts, hentriacontane, heptacosane, and heneicosyl, heptacosyl and docosyl acetates were identified by GC-MS, and their roles are unknown in the development of short-distance sexual behaviors, but they could serve to mark a trail leading the male towards the female in the final stage of approach for courtship/mating. Thus, we proposed the hypothesis that P. chilensis females emit both a long-range and a trail-pheromone, which, if confirmed, would be a rare case in this family. The specific identity of the compounds obtained by HSD, as well as the activities of these chemicals and those obtained from the terminalias, should be evaluated in future behavioral studies, as well as regarding their potential to attract males under field conditions. The current document is the first report on volatiles obtained from aerations and compounds extracted from female terminalia in P. chilensis.

Stimulated C2C12 Myotube Headspace Volatile Organic Compound Analysis.

Understanding exercise metabolism and the relationship with volatile organic compounds (VOCs) holds potential in both health care and sports performance. Exercise metabolism can be investigated using whole body exercise testing (in vivo) or through the culture and subsequent electrical pulse stimulation (EPS) of myotubes (in vitro). This research investigates the novel headspace (HS) analysis of EPS skeletal muscle myotubes. An in vitro system was built to investigate the effect of EPS on the volatile constituents in the HS above EPS skeletal muscle. The C2C12 immortalised cell line was chosen. EPS was applied to the system to induce myotube contraction. The in vitro system was applied to the analysis of VOCs using thermal desorption (TD) sampling. Samples were collected under four conditions: environmental samples (enviro), acellular media HS samples (blank), skeletal muscle myotubes without stimulation HS samples (baseline) and EPS of skeletal muscle myotube HS samples (stim). TD sampling combined with gas-chromatography mass spectrometry (GC-MS) detected two compounds that, after multivariate and univariate statistical analysis, were identified as changing due to EPS (p < 0.05). These compounds were tentatively assigned as 1,4-Dioxane-2,5-dione, 3,6-dimethyl- and 1-pentene. The former is a known lactide and the latter has been reported as a marker of oxidative stress. Further research should focus on improvements to the EPS system, including the use of more relevant cell lines, quantification of myotube contractions, and the application of targeted analysis, metabolic assays and media analysis.

Separation of benzene and cyclohexane azeotrope mixture using 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid using extractive distillation

Most of the cyclohexane used for various industrial applications is largely produced through catalytic hydrogenation of benzene and the separation of cyclohexane from the unreacted benzene is industrially significant. However, it is tough to separate cyclohexane from benzene by conventional distillation processes since these components have close boiling points and form an azeotrope mixture. Currently, extractive distillation is commercially used for the separation of cyclohexane from benzene using conventional solvents (entrainers) such as sulfolane, dimethyl sulfoxide, N-formylmorpholine, and N-methylpyrrolidone. However, separating benzene and cyclohexane with extractive distillation with these solvents makes the process complex and consumes high energy. On the other hand, ionic liquids are considered green and potentially environmentally friendly, hence have been attracting attention in replacing conventional solvents (entrainers) in extractive distillation because of their unique properties. In this work, 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO4]) was used for the separation of cyclohexane from benzene using extractive distillation. The performance of [EMIM][EtSO4] was evaluated by measuring the isothermal vapour-liquid equilibrium (VLE) for benzene, cyclohexane, and [EMIM][EtSO4] ternary mixture at 353.15 K. The isothermal VLE was measured using Head Space Gas Chromatography (HS-GC). Moreover, the VLE data was also predicted using COSMO-RS and compared with the experimental values. The addition of [EMIM][EtSO4] eliminated the azeotrope and increased the relative volatilities of benzene and cyclohexane resulting in their separation. The performance of [EMIM][EtSO4] on the benzene and cyclohexane system was compared with dimethyl sulfoxide. The current ionic liquid shows higher relative volatility compared to dimethyl sulfoxide showing this ionic liquid can be used for the separation of benzene and cyclohexane using extractive distillation.

Identification of gamma irradiated polycarbonate-polybutylene terephthalate stiff polymer blend products using HS-GC/MS, FTIR and UV/Vis spectroscopy

In this study, the fragmentation products of Makro-blend stiff polymer due to gamma exposure were identified using Head space (HS), Gas Chromatography, and Mass Spectrometry (HS-GC/MS) techniques and Fourier Transform Infra-Red (FTIR) spectroscopy. As well the electronic transitions due to gamma exposure were examined using UV/Vis spectroscopy. For the un-irradiated and 10 kGy irradiated samples, one product was detected by (HS-GC/MS) method with a clear peak of Dimethoxyethane (MW = 90), which has a peak area percentage of 98.58% and 97.13%, respectively. With increasing gamma doses the number of identified components was increased. At 1200 kGy, ten components were detected: Biethylene (MW = 54), Dimethoxyethane (MW = 90), 1,1-Dimethoxy-2-propanone (MW = 118), 1,1-Dimethoxy-2-propanol (MW = 120), 1,1-Dimethoxycyclopentane (MW = 130), 1,1-Dimethoxyheptane (MW = 160), 1,1-Dimethoxyoctane (MW = 174), Dimethyl terephthalate (MW = 194), 4-(Diethoxymethyl) benzaldehyde (MW = 208), and Terephthalate dihexyl (MW = 334), which have peaks area percentages of 4.22, 2.98, 25.84, 2.2, 10.65, 38.86, 1.57, 5.91, 1.22, and 6.48, respectively. The recorded mass spectrum of each component confirms the molecular ion peak. The FTIR measurements demonstrate the decrease in the detected band intensities following gamma radiation. Accordingly, a chain scission occurs, which causes the carbonate bond to scission, resulting in the creation of a hydroxyl group and the (–H) abstraction from the backbone of the irradiation blend samples. The absorbance edge of the gamma-exposed samples shifted towards a higher wavelength. This pattern shows that the band gap energy is declining. The use of FTIR and HS-GC/MS in mass spectrometry analysis will be useful tools for examining radiation-induced polymeric fragments and advancing our understanding of the process underlying the creation of these fragments in polymers.

Analysis of phthalate esters from vegetable oils by gas chromatography-mass spectrometry coupled with headspace solid-phase microextraction using cyclodextrin-based hypercrosslinked polymer coated fiber

Phthalate esters (PAEs) are used as additives to enhance the pliability and malleability of plastics. These substances frequently migrate from packaging materials to vegetable oils because of the absence of covalent bonds. Over time, this migration could result in the accumulation of PAEs in the human body through ingestion, contributing to various diseases. Therefore, accurate qualitative and quantitative analyses of PAEs in vegetable oils are imperative to assess the origins of contamination and investigate their toxicity, degradation, migration, and transformation patterns. However, the concentration of PAEs in most samples is low, and the composition of vegetable oils is complex. Thus, PAEs must be enriched and purified using appropriate sample pretreatment procedures before analysis. Common methods for pretreating PAEs in oil include solid-phase extraction (SPE), dispersive SPE, and magnetic SPE. These techniques require time-consuming and labor-intensive procedures such as oil dissolution, solvent extraction, and degreasing. These approaches also require numerous solvents and containers, increasing the risk of sample cross-contamination. Solid-phase microextraction (SPME) integrates sampling, extraction, purification, concentration, and injection into a single process, significantly accelerating analytical testing and reducing the potential for sample cross-contamination. In headspace (HS) mode, the analytes achieve equilibrium on the coating and are extracted in the gas phase. The fibers are shielded from nonvolatile and high-relative molecular mass substances in the sample matrix. Thus, SPME is an ideal method for extracting volatile compounds in vegetable oils. When HS-SPME coupled with gas chromatography-mass spectrometry (GC-MS), it can achieve the rapid screening of PAEs in vegetable oil. In this study, an SPME with cyclodextrin-based hypercrosslinked polymers (BnCD-HCP) coated on stainless steel fibers was employed to extract PAEs from vegetable oil. The structure and morphology of the polymers were characterized using Fourier-transform infrared spectroscopy, nuclear magnetic spectroscopy, and scanning electron microscopy. BnCD-HCP exhibited high stability and diverse interactions, including π-π, hydrophobic, and host-guest interactions. The oil samples were incubated with methanol, and the PAEs were extracted from the headspace using the probe. The optimal extraction parameters included an extraction time of 20 min, extraction temperature of 50 ℃, desorption time of 4 min, and desorption temperature of 275 ℃. The BnCD-HCP/HS-SPME method was evaluated under optimized experimental conditions. The limits of detection (LODs) and quantification (LOQs) were determined by applying signal-to-noise ratios (S/N) of 3 and 10, respectively. Method accuracy was evaluated using relative standard deviations (RSDs). Single-needle precision was evaluated by conducting three consecutive analyses at 3 h intervals within a day. Inter-needle precision was assessed by conducting the same analyses (three replicates) with differently coated fibers. The 12 PAE compounds exhibited good linearity with correlation coefficients (R2) of at least 0.99. The LODs and LOQs ranged from 0.21 to 3.74 μg/kg and from 0.69 to 12.34 μg/kg, respectively. The RSDs were in the range of 1.8%-11.4% and 5.1%-13.9% for the single-needle and needle-to-needle methods, respectively. The proposed method was applied to soybean, peanut, and sunflower oils, and two PAEs were found in all three oils. Moreover, the method demonstrated good precision (RSD=1.17%-11.73%) and recoveries (72.49%-124.43%). Compared with other methods, the developed method was able to extract many target analytes and had a low or comparable LOD and high recovery. More importantly, this method does not require tedious operations such as solvent extraction and purification. Consequently, the developed method can be used to extract not only PAEs in oils but also other substances with a high lipid content.

Comparative Study of Mechanical Properties and Microstructure Between Conventional and Infinite z-Axis Fused Deposition Modeling Printers

Additive Manufacturing (AM) has emerged as a critical technology in shaping manufacturing strategies, offering versatility and efficiency in designing complex structural components. Extensive literature exists on small- to mid-sized product production. However, a significant knowledge gap exists in manufacturing elongated products, such as wind turbine blades and constructional beams. Current AM technology faces limitations in this context, primarily due to the constraints imposed by the conventional 90-degree nozzle head and limited bed space. This study introduces an innovative AM approach called Infinite z-Axis Printing. This novel technique utilizes a belt-driven heated bed and a 45-degree nozzle head to 3D print objects of infinite length. The study compares this groundbreaking approach and the traditional 90-degree nozzle head Fused Deposition Modeling (FDM) method and the associated results. The findings of this research demonstrate that the Infinite z-Axis Printing methodology yields a significant improvement of up to 20% in tensile and compressive strength compared to the currently used FDM process. This advancement can potentially revolutionize on-site operations by enabling the efficient production of elongated structural components, thus contributing significantly to the construction and renewable energy sectors.

Impact of adding high-concentration neutron poisons to reactor moderator system for guaranteed shutdown

To ensure a reliable shutdown of the proposed advanced heavy water reactor (AHWR) of Indian origin during emergency conditions, it is imperative to use an increased concentration of liquid neutron poison for injection into the moderator system due to its higher reactivity. The sudden injection of this liquid poison may cause a surge in radiolytic product (H2O2 and H2) yield, posing safety risks. If H2/D2 yield exceeds 4 % (v/v), a combustible mixture with oxygen can be formed and presence of oxidizing H2O2 can enhance corrosion. Hence, accurate estimation of H2O2 and H2 is imperative from the reactor safety point of view. We investigated gadolinium and boron (two liquid neutron poisons) at varying concentrations through high energy electron beam and gamma radiolysis. The radiolytic yields from both the liquid neutron poisons of equivalent concentrations at a constant dose and operating moderator conditions in electron beam and gamma radiolysis were compared. The molecular product yield was observed to be concentration and dose-rate-dependent for both the neutron poisons. Electron radiolysis exhibited a higher yield of H2O2, whereas gamma radiolysis resulted in a greater H2 yield. In electron radiolysis, the H2O2 yield decreased with increasing B concentration. These results give an overall estimation of radiolytic products for a particular dose rate, total dose and effect of head space volume over liquid irradiation zone from these two liquid poisons of a particular concentration. These insights will aid in selecting suitable poisons and managing their effects effectively to avoid hydrogen deflagrations after emergency shutdown.

Volatilome changes during black truffle (Tuber melanosporum) ontogeny

The aroma is critical in the reproductive biology of truffles and in their commercial quality. However, previous research has almost exclusively focused on characterizing ripe ascocarps. We characterized the volatilome of the highly-prized black truffle (Tuber melanosporum) ascocarps from July, in an early development stage, to March, in the late harvesting season, and investigated the relationships among aroma, ascocarp growth and morphogenetic development. The aroma profile was analyzed using a head space gas chromatography technique coupled with mass spectrometer. Seventy-one volatile compounds were identified and three development stages were clearly distinguished according to the volatile profile. In unripe ascocarps of July-September, the profile was dominated by methanethiol (19 %), 4-penten-2-ol (11 %) and acetone (11 %), the monthly mean weight of ascocarps ranged 2–20 g, and morphogenetic stages 4-6a were prevalent. In unripe ascocarps of October-December, the most abundant volatiles were 4-penten-2-ol (21 %), methanethiol (20 %) and ethanol (13 %), the monthly mean ascocarp weight ranged 28–43 g, and morphogenetic stages 6a, 6b-c were prevalent. In ripe ascocarps (December-March), the most abundant volatiles were 4-penten-2-ol (17 %), dimethyl sulfide (16 %) and ethanol (10 %), ascocarp weight did not increase significantly, and 6b-c was practically the sole morphogenetic stage. Thirty volatiles were associated to one of these three development stages. Amongst those with higher occurrence, 4-penten-2-ol, dimethyl sulfide, ethyl acetate, 2-pentanol and 2-butanone were associated to ripe truffles, whereas methanethiol, isobutyl isobutyrate, butanedione and 3-methylanisole were associated to unripe truffles.

Characterization of Volatile Organic Compounds and Essential Oil Profile of Pittosporum tobira (Thunb.) W.T. Aiton Cultivated in Tunisia.

The chemical compositions of the essential oils (EOs) of roots, young and old leaves and stems, and flowers of Pittosporum tobira (Thunb.) W.T. Aiton cultivated in Tunisia and of the volatile organic compounds (VOCs) emitted by the powder of each organ were identified. The EOs are extracted from fresh material by hydrodistillation, whereas the VOCs are obtained by head space solid-phase microextraction (HS-SPME) from the powdered dry tissues. Fifty-eight VOCs are identified, while, 105 components are detected for the EOs. The main EOs compounds are α-neoclovene, β-caryophyllene and limonene in roots (22.56, 12.52, and 8.59 %, respectively), viridiflorol in young stems, flowers and young leaves (34.90, 31.60, and 24.60 %, respectively), α-cadinol in young stems and leaves, and flowers (13.80, 10.40, and 9.10 %, respectively), (E)-nerolidol in flowers (13.30 %), and germacrene D in old stems (9.06 %). The major detected VOCs are n-undecane, mainly in young and old leaves (71.40 and 40.90 %, respectively), n-nonane in young leaves and flowers (31.80 and 27.10 %, respectively), α-cubebene in old stems and flowers (22.60 and 15.50 %, respectively), and α-gurjunene and β-gurjunene in roots (14.20 and 12.20 %, respectively). Principal Component Analysis (PCA) carried out on the 26 main volatile compounds (relative content exceeding 6 %) identified both by HS and in the EOs allowed their classification into two groups; compounds specific to roots and those specific to aerial parts. The later are subdivided in to two subgroups; old leaves and stems compounds subgroup, and young leaves and stems, and flowers one. We can notice that the two methods used to extract P. tobira volatile compounds and identify them are complementary. This study defines and differentiates, for the first time, the specific aroma profile of P. tobira from Tunisia. In addition to its ornamental value, all the organs of this species, could be valued as a source of volatile compounds useful in perfume, cosmetics and as food flavoring products.