Search Results (23)

Bumblebees are important pollinating insects in crop pollination. Chemical attractants can effectively improve the flower-visiting efficiency of bumblebees, thereby increasing blueberry yields. To identify volatile compounds that attract bumblebees, we collected volatile compounds from blueberry flowers using headspace extraction. Gas chromatography– mass spectrometry (GC–MS) identified 32 volatile compounds, with Linalool and Styrene being the primary substances that accounted for 25.93% and 14.28%, respectively. The olfactory threshold of bumblebee antennae was assessed using electroantennography (EAG), and the behavioral responses from bumblebees were investigated using a Y-tube olfactometer. Results indicate that among the six classes of volatiles—alcohols, aldehydes, esters, ketones, aromatic compounds, and olefins—alcohols constituted the predominant proportion. Among these, six compounds—benzaldehyde, phenylpropylaldehyde, citral, linalool, α-terpineol, and geraniol—induced significant antennal responses in bumblebees. Our assays showed that geraniol, linalool, and α-terpineol at concentrations of 0.1 μg/μL, 1 μg/μL, and 10 μg/μL elicited attraction, whereas higher concentrations of benzaldehyde, benzenepropanal, and citral had repellent effects. Full article

Polystyrene microfragments are among the most common plastic pollutants globally. They significantly affect aquatic life, harming various organs and tissues. In this study, we examined the effects of 3 µm polystyrene beads (MPs, 20 µg/L) on development and yolk resorption in pre-feeding nauplii of Artemia salina, a lecithotrophic crustacean used in toxicity testing. Results showed a reduced hatching rate, slower growth, and the onset of oxidative stress. Histological analysis revealed no significant morphological alteration; however, yolk platelets lost N-acetyl galactosamine (galNAc), and resorption was delayed. Lectin staining also showed a reduction in N-acetyl glucosamine (glcNAc) in the gut brush border, indicating impaired gut function. Gas chromatography detected the release of nanogram amounts of toxic volatile compounds (VOCs, ethylbenzene, xylene, benzaldehyde, and styrene) into the culture medium. In conclusion, the data demonstrate a delay in larval yolk resorption that can likely be attributed to the release of VOCs, which induce oxidative stress. Further research is urgently needed, given the potential biological and ecological implications of this finding. Full article

Chemical pollution is an increasing worldwide concern, with children being especially vulnerable to the harmful effects of air pollution. This study aimed to characterize the mixture of volatile organic compounds (VOCs) present in indoor air across residential, educational, and recreational settings. It analyzed data on VOC concentrations from previous sampling campaigns conducted in households with children, primary schools, and indoor swimming pools (70 buildings, 151 indoor spaces) in northern Portugal. The findings reveal the co-occurrence of 16 VOCs (1,2,4-trimethylbenzene, benzene, ethylbenzene, m/o/p-xylenes, styrene, toluene, tetrachloroethylene, 2-ethylhexanol, butanol, acetophenone, ethyl acetate, benzaldehyde, decanal, nonanal, 1-methoxy-2-propanol and limonene) across all three settings, primarily associated to emissions from building materials and detergents. However, distinct patterns were also observed in the VOCs detected across the three indoor environments: in homes, the predominant VOCs were primarily released from cleaning and fragranced products; in schools, from ammonia-based cleaners and occupant activities; and in swimming pools, the predominant airborne chemicals were disinfection by-products resulting from the chemical dynamics associated with water disinfection. Overall, the findings highlight the need for additional research to deepen our understanding of the risks posed by combined exposure to multiple indoor air chemicals for children. These results also underscore the importance of developing and enforcing regulations to monitor VOC levels in environments frequented by children and implementing preventive measures to minimize their exposure to harmful chemicals. Full article

Transition-metal-catalyzed nitrene transfer reactions are typically performed in organic solvents under inert and anhydrous conditions due to the involved air and water-sensitive nature of reactive intermediates. Overall, this study provides insights into the iron-based ([Fe^II(PBI)₃](CF₃SO₃)₂ (1), where PBI = 2-(2-pyridyl)benzimidazole), catalytic and stoichiometric aziridination of styrenes using PhINTs ([(N-tosylimino)iodo]benzene), highlighting the importance of reaction conditions including the effects of the solvent, co-ligands (para-substituted pyridines), and substrate substituents on the product yields, selectivity, and reaction kinetics. The aziridination reactions with 1/PhINTs showed higher conversion than epoxidation with 1/PhIO (iodosobenzene). However, the reaction with PhINTs was less selective and yielded more products, including styrene oxide, benzaldehyde, and 2-phenyl-1-tosylaziridine. Therefore, the main aim of this study was to investigate the potential role of water in the formation of oxygen-containing by-products during radical-type nitrene transfer catalysis. During the catalytic tests, a lower yield was obtained in a protic solvent (trifluoroethanol) than in acetonitrile. In the case of the catalytic oxidation of para-substituted styrenes containing electron-donating groups, higher yield, TON, and TOF were achieved than those with electron-withdrawing groups. Pseudo-first-order kinetics were observed for the stoichiometric oxidation, and the second-order rate constants (k₂ = 7.16 × 10⁻³ M⁻¹ s⁻¹ in MeCN, 2.58 × 10⁻³ M⁻¹ s⁻¹ in CF₃CH₂OH) of the reaction were determined. The linear free energy relationships between the relative reaction rates (logk_rel) and the total substituent effect (TE, 4R-PhCHCH₂) parameters with slopes of 1.48 (MeCN) and 1.89 (CF₃CH₂OH) suggest that the stoichiometric aziridination of styrenes can be described through the formation of a radical intermediate in the rate-determining step. Styrene oxide formation during aqueous styrene aziridination most likely results from oxygen atom transfer via in situ iron oxo/oxyl radical complexes, which are formed through the hydrolysis of [Fe^III(N•Ts)] under experimental conditions. Full article

Volatile organic compounds (VOCs), particularly monoaromatic hydrocarbon compounds (MACHs), pose a potential risk to the atmospheric environment and human health. Therefore, the progressive development of efficient detection methodologies is a pertinent need, which is still a challenge at present. In this study, we present a rapid and sensitive method to detect trace amounts of MACHs using a bifunctional SERS composite substrate. We prepared an Au/SiO₂ enhanced layer and a porous Cu(OH)₂ adsorption layer via microfluidic-assisted gas-liquid interface self-assembly. The composite substrate effectively monitored changes in benzaldehyde using time-varying SERS spectra, and track-specifically identified various VOCs such as benzene, xylene, styrene, and nitrobenzene. In general, the substrate exhibited a rapid response time of 20 s to gaseous benzaldehyde, with a minimum detection concentration of less than 500 ppt. Further experimental assessments revealed an optimum Cu(OH)₂ thickness of the surrounding adsorption layer of 150 nm, which can achieve an efficient SERS response to MACHs. Furthermore, the recoverable and reusable property of the composite substrate highlights its practicality. This study presents a straightforward and efficient approach for detecting trace gaseous VOCs using SERS, with significant implications in the designing of SERS substrates for detecting other VOCs. Full article

Chemical recycling is considered one of the most sustainable solutions to limit the environmental issues related to plastic waste pollution, whereby plastic is converted into more valuable compounds when mechanical recycling is not feasible. Among the most critical fast-growing components of municipal solid waste, polystyrene represents 1/3 of the filling materials in landfills. In this work, the chemical recycling of polystyrene via two main thermochemical processes is investigated: pyrolysis and hydrothermal liquefaction (HTL). The influence of temperature (HTL: 300–360 °C and pyrolysis: 400–600 °C) and reaction time (HTL: 1–4 h; pyrolysis: 30 min) on the products obtained was studied. The obtained liquid and solid products were analyzed by using gas chromatography-mass spectrometry (GC-MS), an elemental analysis (EA), Fourier-transform infrared spectroscopy (FT-IR) and a thermogravimetric analysis (TGA). During HTL, a temperature of 360 °C and reaction time of 4 h were needed to completely decompose the polystyrene into mainly oil (83%) and water-soluble compounds (10%). The former was mainly composed of aromatics while the water phase was mainly composed of aromatics and oxygenated compounds (benzaldehyde and acetophenone). The pyrolysis led to the formation of 45% gas and 55% oil at 500 °C, and the oil was 40% styrene. Pyrolysis was thus more selective towards the recovery of the styrene monomer while the HTL can be an effective process to produce renewable aromatics. Full article

Selective oxidation of organics over an efficient heterogeneous catalyst under mild liquid phase conditions is a very demanding chemical reaction. Herein, we first report the modification of the surface of mesoporous silica MCM-41 material by phosphate for the efficient incorporation of Ti(IV) in the silica framework to obtain highly ordered 2D hexagonal mesoporous material STP-1. STP-1 has been synthesized by using tetraethyl orthosilicate, triethyl phosphate, and titanium isopropoxide as Si, P, and Ti precursors, respectively, in the presence of cationic surfactant cetyltrimethylammonium bromide (CTAB) under hydrothermal conditions. The observed specific surface area and pore volume of STP-1 were 878 m²g⁻¹ and 0.75 ccg⁻¹, respectively. Mesoporous STP-1 has been thoroughly characterized by XRD, FT-IR, Raman spectroscopy, SEM, and TEM analyses. Titanium incorporation (Ti/Si = 0.006) was confirmed from the EDX analysis. This mesoporous STP-1 was used as a heterogeneous catalyst for the selective oxidation of styrene into benzaldehye in the presence of dilute aqueous H₂O₂ as an oxidizing agent. Various reaction parameters such as the reaction time, the reaction temperature, and the styrene/H₂O₂ molar ratio were systematically studied in this article. Under optimized reaction conditions, the selectivity of benzaldehyde could reach up to 93.8% from styrene over STP-1. Further, the importance of both titanium and phosphate in the synthesis of STP-1 for selective styrene oxidation was examined by comparing the catalytic result with only a phosphate-modified mesoporous silica material, and it suggests that both titanium and phosphate synergistically play an important role in the high selectivity of benzaldehyde in the liquid phase oxidation of styrene. Full article

Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fire-retardant moieties through co- or ter-polymerization reactions of styrene with diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl-p-vinylbenzyl phosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methylamino]ethyl ester (ADEPMAE) and maleimide (MI). In the present study, the condensed-phase and the gaseous-phase activities of the abovementioned fire retardants within the prepared co- and ter-polymers were evaluated for the first time. Pyrolysis–Gas Chromatography/Mass Spectrometry was employed to identify the volatile products formed during the thermal decomposition of the modified polymers. Benzaldehyde, α-methylstyrene, acetophenone, triethyl phosphate and styrene (monomer, dimer and trimer) were detected in the gaseous phase following the thermal cracking of fire-retardant groups and through main chain scissions. In the case of PS modified with ADEPMAE, the evolution of pyrolysis gases was suppressed by possible inhibitory actions of triethyl phosphate in the gaseous phase. The reactive modification of PS by simultaneously incorporating P- (DEAMP or DEpVBP) and N- (MI) monomeric units, in the chains of ter-polymers, resulted in a predominantly condensed-phase mode of action owing to synergistic P and N interactions. The solid-state ³¹P NMR spectroscopy, Scanning Electron Microscopy/Energy Dispersive Spectroscopy, Inductively-Coupled Plasma/Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy of char residues, obtained from ter-polymers, confirmed the retention of the phosphorus species in their structures. Full article

Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L₁NHC)₂](PF₆)₂; 3, [Ni-(L₂NHC)₂](PF₆)₂; 4, [Ni-(L₃NHC)](PF₆)₂; 7 and [Ni-(L₄NHC)](PF₆)₂; 8, (where L₁NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L₂NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L₃NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L₄NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle. Full article

The tea green leafhopper, Empoasca flavescens, is a major pest of tea Camellia sinensis (L.) Kuntze. Until recently, it has mainly been controlled by pesticides, but their use has led to high levels of toxic residues in plants, which threaten both the environment and human health. Therefore, a safer biological control approach is needed. Tea plants produce many volatile compounds, and different tea clones differ in their resistance to the pest. We explored the possibility that volatile compounds influence the resistance of tea. Here, we assessed the resistance of 15 clones of tea plants to the pest, the volatile compounds produced by the clones, and the effects of the compounds on E. flavescens behavior. Six clones were classified as resistant, eight as moderately susceptible, and one as susceptible. Fresh leaf samples from resistant and susceptible clones were analyzed using HS–SPME–GC–MS. Sesquiterpenes and monoterpenes were two major groups characterized, representing 30.15% and 26.98% of the total compounds, respectively. From our analysis, we conclude that 3-hexen-1-ol, 2,6-dimethyleneoct-7-en-3-one, humulene, β-bourbonene, styrene, and benzaldehyde were important for the resistance and susceptibility of the clones. In a bioassay, E. flavescens were attracted to β-ocimene and methyl salicylate, but avoided linalool compounds. Full article

Currently, the effect of exposure to indoor air contaminants and the presence of dampness at home on respiratory/atopic health is of particular concern to physicians. The measurement of volatile organic compounds (VOCs) in exhaled breath is a useful approach for monitoring environmental exposures. A great advantage of this strategy is that it allows the study of the impact of pollutants on the metabolism through a non-invasive method. In this paper, the levels of nine VOCs (acetone, isoprene, toluene, p/m-xylene, o-xylene, styrene, benzaldehyde, naphthalene, and 2-ethyl-1-hexanol) in the exhaled breath of subjects exposed and not exposed to home dampness were assessed. Exhaled breath samples were collected from 337 mother–child pairs of a birth cohort and analysed by gas-chromatography–mass-spectrometry. It was observed that the levels of 2-ethyl-1-hexanol in the exhaled breath of the mothers were significantly influenced by exposure to household humidity. In the case of the infants, differences in some of the VOC levels related to home dampness exposure; however, they did not reach statistical significance. In addition, it was also found that the eosinophil counts of the mothers exposed to home dampness were significantly elevated compared to those of the non-exposed mothers. To our knowledge, these findings show, for the first time, that exposure to home dampness may influence VOC patterns in exhaled breath. Full article

The selective oxidation of styrene with highly efficient, environmentally benign, and cost-effective catalysts are of great importance for sustainable chemical processes. Here, we develop an in situ self-assembly strategy to decorate Cu-based metal-organic framework (MOF) Cu-BDC-NH₂ nanocrystals on Cu₂O octahedra to construct a series of Cu₂O@Cu-BDC-NH₂ catalysts for selective oxidation of styrene. Using H₂O₂ as green oxidants, the optimized sample of Cu₂O@Cu-BDC-NH₂-8h could achieve 85% styrene conversion with 76% selectivity of benzaldehyde under a mild condition of 40 °C. The high performance of the as-prepared heterogeneous catalysts was attributed to the well-designed Cu⁺/Cu²⁺ interface between Cu₂O and Cu-BDC-NH₂ as well as the porous MOF shells composed of the uniformly dispersed Cu-BDC-NH₂ nanocrystals. The alkaline properties of Cu₂O and the –NH₂ modification of MOFs enable the reaction to be carried out in a base-free condition, which simplifies the separation process and makes the catalytic system more environmentally friendly. Besides the Cu₂O octahedra (od-Cu₂O), the Cu₂O cuboctahedrons (cod-Cu₂O) were synthesized by adjusting the added polyvinyl pyrrolidone, and the obtained cod-Cu₂O@Cu-BDC-NH₂ composite also showed good catalytic performance. This work provides a useful strategy for developing highly efficient and environmentally benign heterogeneous catalysts for the selective oxidation of styrene. Full article

In this work, we explored how solvents can affect olefin oxidation reactions catalyzed by MCM-bpy-Mo catalysts and whether their control can be made with those players. The results of this study demonstrated that polar and apolar aprotic solvents modulated the reactions in different ways. Experimental data showed that acetonitrile (aprotic polar) could largely hinder the reaction rate, whereas toluene (aprotic apolar) did not. In both cases, product selectivity at isoconversion was not affected. Further insights were obtained by means of neutron diffraction experiments, which confirmed the kinetic data and allowed for the proposal of a model based on substrate–solvent crosstalk by means of hydrogen bonding. In addition, the model was also validated in the ring-opening reaction (overoxidation) of styrene oxide to benzaldehyde, which progressed when toluene was the solvent (reaching 31% styrene oxide conversion) but was strongly hindered when acetonitrile was used instead (reaching only 7% conversion) due to the establishment of H-bonds in the latter. Although this model was confirmed and validated for olefin oxidation reactions, it can be envisaged that it may also be applied to other catalytic reaction systems where reaction control is critical, thereby widening its use. Full article

Biomass-derived materials are put forward as eco-friendly alternatives to design heterogeneous catalysts. To contribute in this field, we explored the potential of mesoporous biogenic silica (RH-Silica) obtained from lignocellulosic waste, in particular from rice husk, as an inorganic support to prepare heterogenized iron oxide-based catalysts. Mechanochemistry, considered as a green and sustainable technique, was employed to synthetize iron oxide nanoparticles in pure hematite phase onto the biosilica (α-Fe₂O₃/RH-Silica), making this material a good candidate to perform catalyzed organic reactions. The obtained material was characterized by different techniques, and its catalytic activity was tested in the selective oxidation of styrene under microwave irradiation. α-Fe₂O₃/RH-Silica displayed a good catalytic performance, achieving a conversion of 45% under optimized conditions, and more importantly, with a total selectivity to benzaldehyde. Furthermore, a good reusability was achieved without decreasing its activity after multiple catalytic cycles. This work represents a good example of using sustainable approaches and green materials as alternatives to conventional methods in the production of high-added value products. Full article

The selective oxidation of styrene under heterogeneous catalyzed conditions delivers environmentally friendly paths for the production of benzaldehyde, an important intermediate for the synthesis of several products. The present review explores heterogeneous catalysts for styrene oxidation using a variety of metal catalysts over the last decade. The use of several classes of supports is discussed, including metal–organic frameworks, zeolites, carbon materials and silicas, among others. The studied catalytic systems propose as most used oxidants tert-butyl hydroperoxide, and hydrogen peroxide and mild reaction conditions. The reaction mechanism proceeds through the generation of an intermediate reactive metal–oxygen species by catalyst-oxidant interactions. Overall, most of the studies highlight the synergetic effects among the metal and support for the activity and selectivity enhancement. Full article