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Optically active polymers are of great interest as materials for dense enantioselective membranes, as well as chiral stationary phases for gas and liquid chromatography. Combining the versatility of norbornene chemistry and the advantages of chiral natural terpenes in one molecule will open up a facile route toward the synthesis of diverse optically active polymers. Herein, we prepared a set of new chiral monomers from cis-5-norbornene-2,3-dicarboxylic anhydride and chiral alcohols of various natures. Alcohols based on cyclic terpenes ((-)-menthol, (-)-borneol and pinanol), as well as commercially available alcohols (S-(-)-2-methylbutanol-1, S-(+)-3-octanol), were used. All the synthesized monomers were successfully involved in ring-opening metathesis polymerization, affording polymers in high yields (up to 96%) and with molecular weights in the range of 1.9 × 105–5.8 × 105 (Mw). The properties of the metathesis polymers obtained were studied by TGA and DSC analysis, WAXD, and circular dichroism spectroscopy. The polymers exhibited high thermal stability and good film-forming properties. Glass transition temperatures for the prepared polymers varied from −30 °C to +139 °C and, therefore, the state of the polymers changed from rubbery to glassy. The prepared polymers represent a new attractive platform of chiral polymeric materials for enantioselective membrane separation and chiral stationary phases for chromatography.

The supported Ni-B/KIT-6 amorphous alloy catalyst was prepared by chemical reduction method for the hydrogenation reaction of α-pinene. The catalyst was characterized by XRD, BET, SEM–EDS, TEM, XPS, ICP and DLS, the influences of single factor of catalyst on its structure, morphology and performance were investigated and analyzed. It was found that the amount of Ni loading, preparation pH and B/Ni molar ratio had great effects on the reduction amount, dispersion and specific surface area of the catalyst, resulted in affecting the catalytic performance of the catalyst. The optimum synthesis conditions were at m(Ni2+)/m(KIT-6) = 1:3, pH 13 and n(B)/n(Ni) = 1.5, obtaining a 90.62% conversion of α-pinene and 97.67% selectivity of cis-pinane. In addition, the catalysts also exhibited better repeatability and stability.

The presented work describes the autoxidation of alpha-pinene for the first time using a catalyst based on activated carbon from biomass with introduced Fe. The raw material for the preparation of the carbon material was waste orange peel, which was activated with a KOH solution. The following instrumental methods characterized the obtained catalyst (Fe/O_AC):N2 adsorption at 77 K, XRD, UV, SEM, TEM, X-ray microanalysis, and catalytic studies. It was shown that the Fe/O_AC catalyst was very active in the autoxidation of alpha-pinene. The main reaction products were: alpha-pinene oxide, verbenone, verbenol, and campholenic aldehyde.

Turpentine is a renewable resource, has good combustion performance, and is considered to be a fuel or promising additive to diesel fuel. This is very important for the investigation of thermal stability and energy oxidation characteristics, because evaluation of energy or fuel quality assurance and use safety are necessary. The main components of turpentine are α-pinene and β-pinene, which have unsaturated double bonds and high chemical activity. By investigating their thermal stability and oxidation reaction characteristics, we know the chemical thermal properties and thermal explosion hazard of turpentine. In this present study, the thermal stability and oxidation characteristics of α-pinene, β-pinene and α-pinene/β-pinene mixture were investigated using a high sensitivity accelerating rate calorimeter (ARC) and C80 calorimeter. The important parameters of oxidation reaction and thermal stability were obtained from the temperature, pressure and exothermic behavior in chemical reaction. The results show that α-pinene and β-pinene are thermally stable without chemical reaction under a nitrogen atmosphere even when the temperature reaches 473 K. The initial exothermic temperature of the two pinenes and their mixture is 333–338 K, and the heat release (−ΔH) of their oxidation is 2745–2973 J g−1. The oxidation activation energy (Ea) of α-pinene, β-pinene and α-pinene/β-pinene mixture is 116.25 kJ mol−1, 121.85 kJ mol−1, and 115.95 kJ mol−1, respectively. There are three steps in the oxidation of pinenes: the first is the induction period of the oxidation reaction; the second is the main oxidation stage, and the pressure is reduced; the third is thermal decomposition to produce gas.

α-Pinene, an important biologically active natural monoterpene, has been widely used in fragrances, medicines, and fine chemicals, especially, in high-density renewable fuels such as jet fuel. The development of an α-pinene production platform in a highly modifiable microbe from renewable substitute feedstocks could lead to a green, economical avenue, and sustainable biotechnological process for the biosynthesis of α-pinene. Here, we report engineering of an orthogonal biosynthetic pathway for efficient production of α-pinene in oleaginous yeast Yarrowia lipolytica that resulted in an α-pinene titer of 19.6 mg/L when using glucose as the sole carbon source, a significant 218-fold improvement than the initial titer. In addition, the potential of using waste cooking oil and lignocellulosic hydrolysate as carbon sources for α-pinene production from the engineered Y. lipolytica strains was analyzed. The results indicated that α-pinene titers of 33.8 and 36.1 mg/L were successfully obtained in waste cooking oil and lignocellulosic hydrolysate medium, thereby representing the highest titer reported to date in yeast. To our knowledge, this is also the first report related to microbial production of α-pinene from waste cooking oil and lignocellulosic hydrolysate.

Optically active cyclobutanediyl- and cyclopropanediylbisalkylidene dihydrazides of isonicotinic and salicylic acids were synthesized when the peroxide products of ozonolysis of (–)-α-pinene and (+)-Δ3-carene were reduced with isonicotinic and salicylic acid hydrazides in methanol, methylene chloride or tetrahydrofuran. Using QSAR models, high antituberculosis activity in combination with low values ​​of acute toxicity and minimal inhibitory concentration was predicted for the obtained compounds.

Highly stereoselective hydrogenation of α-pinene under mild conditions in the utilization of natural products is important but challenging. Here, we report a facile strategy for the size-controlled...

The experimental vapor–liquid equilibrium (VLE) data for a ternary system of β-caryophyllene + dipentene + α-pinene and two binary systems composed of β-caryophyllene (1) + dipentene (2) and dipent...

Isothermal vapor–liquid equilibrium (VLE) data for expensive and thermosensitive Litsea cubeba oil systems, citral + linalool, citral + α-pinene, and linalool + α-pinene, were measured at 333.15, 3...

Gulcin, ilhami/0000-0001-5993-1668; KARAKAYA, Songul/0000-0002-3268-721X, WOS: 000524099800001, The oxidant, cholinesterase, and carbonic anhydrase inhibitions of essential oils and their major compounds of Leiotulus dasyanthus and molecular docking studies of alpha-pinene and (TM)-3-carene were evaluated in this study. Phenolic constituents and antioxidant activity of samples were determined by Folin-Ciocalteu's, DPPH, and TBA processes. Cholinesterase inhibition effect was evaluated through Ellman's method. GC-FID and GC/MS were used for analysing of essential oils. the root oil got the highest total phenolic content (898.87 mg/g). the utmost activity was shown flower oil (29.31 mu g/mL) in the DPPH test. the root oil indicated considerable inhibition towards acetylcholinesterase (21.92%) and butyrylcholinesterase (91.33%) enzymes, respectively. alpha-pinene and delta-3-carene indicated high acetylcholinesterase inhibitory activity (66.44 and 48.71%, respectively). Cytosolic hCA I and II isoenzymes were influentially inhibited by flower and aerial part oils with 1.694 and 1.677 mu M IC50 values, respectively. 1-Dodecanol (7.8%); beta-pinene (63.3%), alpha-pinene (20.5%); octyl acetate (14.7%); hexyl octanoate (55.1%) were characterized as principle compounds of aerial parts, roots, flowers, and fruits respectively., Ataturk UniversityAtaturk University [TAB-2018-6432], This work was assisted by the Scientific Research Projects of Ataturk University (TAB-2018-6432).Scientific Research Projects of Ataturk University (TAB-2018-6432).

International audience; This paper presents the successful use of ruthenium nanoparticles, stabilized in water by ammonium surfactants, in the selective hydrogenation of a-pinene and the first industrially reported scale-up of this catalyst on a multigram-scale. After designing the nanocatalyst at the lab scale, operational parameters (substrate/metal ratio, pressure, and temperature) were identified and optimized in the scale-up. The alpha-pinene hydrogenation process was operated with a 200 g batch, under 30 bar H-2 and at 110 degrees C, with a complete conversion and a selectivity of 98% into cis-pinane within 4 h. The catalyst was easily recycled through a liquid-liquid biphasic approach for 5 reaction cycles to achieve a total turnover number (TTON) of 14000.

Reduction of the peroxide ozonolysis products of (–)-α-pinene and (+)-3-carene by capric and benzoic acid hydrazides in CH2Cl2 or THF produced diacylhydrazones either pure or mixed with the corresponding ketoacids. The capric acid diacylhydrazone formed primarily in CH2Cl2; benzoic acid diacylhydrazone, in THF. The only reaction products formed in MeOH were the corresponding ketoesters.

The physicochemical properties and the synthesis of four α-pinene oxidation products, terebic acid, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), diaterpenylic acid acetate (DTAA), and pinanediol, are presented in this study. The physicochemical properties encompass thermal properties, solubility in water, and dissociation constant (pKa) for the investigated compounds. It was found that terebic acid exhibits a relatively high melting temperature of 449.29 K, whereas pinanediol revealed a low melting temperature of 329.26 K. The solubility in water was determined with the dynamic method and the experimental results were correlated using three different mathematical models: Wilson, NRTL, and UNIQUAC equations. The results of the correlation indicate that the Wilson equation appears to work the best for terebic acid and pinanediol. The calculated standard deviation was for 3.79 for terebic acid and 1.25 for pinanediol. In contrast, UNIQUAC was the best mathematical model for DTAA and MBTCA. The calculated standard deviation was 0.57 for DTAA and 2.21 for MBTCA. The measured water solubility increased in the following order: pinanediol > DTAA ≥ MBTCA > terebic acid, which affects their multiphase aging chemistry in the atmosphere. Moreover, acidity constants (pKa) at 298, 303, and 308 K were determined for DTAA with the Bates–Schwarzenbach spectrophotometric method. The pKa values obtained at 298, 303, and 308 K were found to be 3.76, 3.85, and 3.88, respectively.

α-Pinene is an important monoterpene that is widely used as a pharmaceutical product, biofuel, and so forth. We first established a cell-free system with modular cocatalysis for the production of pinene from glucose. After optimization of the compositions of the cell-free reaction mixture using the Plackett-Burman experimental design and the path of steepest ascent, the production of pinene increased by 57%. It was found that ammonium acetate, NAD+, and NADPH are the three most important parameters for the production of pinene. Mix-and-match experiments showed that the simultaneous addition of the lysate of Escherichia coli overexpressing native 4-hydroxy-3-methylbut-2-enyl diphosphate reductase, SufBCD Fe-S cluster assembly protein, isopentenyl-diphosphate isomerase, and Pinus taeda pinene synthase improved the production of pinene. Increasing the enzyme concentration of the extract further enhanced the production of pinene to 1256.31 ± 46.12 mg/L with a productivity of 104.7 mg/L h, almost 1.2-fold faster than any system reported thus far. This study demonstrates that a cell-free system is a powerful and robust platform for biomanufacture.

Headspace volatiles (HS) and hydrodistilled essential oils (EO) of fresh aerial parts of Artemisia annua L. and A. scoparia Waldst. et Kit., were analyzed by GC-MS/FID. Artemisia ketone was found to be the most abundant component among the EO volatiles (55.8 %), as well as among HS (52.1 %) of A. annua . Additionally, in both A. annua samples, EO and HS, α -pinene (12.7 and 24.2 %, respectively) was found in high percentage. On the other hand, it has been determined that the dominant components of A. scoparia EO and HS were different; in the essential oil capillene (63.8 %) was found as the main constituent, while β -pinene (26.1 %), ( Z )- β -ocimene (23.8 %) and limonene (10.7 %) were the major components among the HS. This is the first report on the composition of HS volatiles of the A. annua and A. scoparia obtained by direct static headspace.

Titanate nanotubes, prepared by the hydrothermal reconstitution and modification with hydrochloric acid, were tested as solid acid catalysts in the isomerization of α-pinene under solvent free conditions. The results showed that titanate nanotubes have better catalytic properties than titanium dioxide nanoparticles, and the camphene was the main product for α-pinene isomerization. The effects of several reaction variables, such as reaction temperature, catalyst dosage, and reaction time, on the conversion of α-pinene and the selectivity to camphene were examined. The highest conversion was up to 97.8% with selectivity to camphene of 78.5% under the mild reaction conditions, and the catalyst also showed outstanding reusability after four runs. It is proposed that appropriate surface acidic sites and opened nanotubular structures are mainly responsible for the excellent catalytic performance of titanate nanotubes materials.

Producción Científica, Biotechnologies have emerged as a promising solution for indoor air purification with the potential to overcome the inherent limitations of indoor air treatment. These limitations include the low concentrations and variability of pollutants and mass-transfer problems caused by pollutant hydrophobicity. A new latex-based biocoating was herein optimized for the abatement of the volatile organic compounds (VOCs) toluene, trichloroethylene, n-hexane, and α-pinene using acclimated activated sludge dominated by members of the phylum Patescibacteria. The influence of the water content, the presence of water absorbing compounds, the latex pretreatment, the biomass concentration, and the pollutant load was tested on VOC removal efficiency (RE) by varying the formulation of the mixtures. Overall, hexane and trichloroethylene removal was low (90%) were consistently recorded for toluene and pinene. The assays demonstrated the benefits of operating at high water content in the biocoating, either by including mineral medium or water absorbing compounds in the latex-biomass mixtures. The performance of the latex-based biocoating was likely limited by VOC mass-transfer rather than by biomass concentration in the biocoating. The latex-based biocoating supported a superior toluene and pinene removal than biomass in suspension when VOC loading rate was increased by a factor of 4., Ministerio de Ciencia, Innovación y Universidades (project RTI2018-0-096441-B-I00], Junta de Castilla y León (grant CLU 2017-09)

The chemical compositions of essential oils (EOs) prepared from six spices including cinnamon, amomum tsao-ko, cardamom, amomum, black pepper and white pepper were analyzed by gas chromatography-mass spectrometry (GC-MS), which led to identify almost 200 volatile compounds. All EOs of spices showed cholinesterase inhibitory activity. Among them, pepper EO showed most potent acetylcholinesterase (AChE) inhibitory activity with IC 50 values of 8.54 μg/mL (black pepper EO) and 5.02 µg/mL (white pepper EO). Molecular docking and in vitro validation suggested that 3-carene, α -pinene and β -pinene with IC 50 value of 1.73, 2.66, and 14.75 μg/mL, respectively, might be active constituents of spices oil in inhibiting AChE. Furthermore, amomum tsao-ko EO and amomum EO can improve behavioral disorder in dementia zebrafish induced by aluminum trichloride (AlCl 3 ).

The chemical composition and in vitro biological activities of the essential oil (EO) of Micromeria macrosiphon Coss. and M. arganietorum (J. Emb.) R. Morales, two Lamiaceae endemic to south Morocco, were investigated. GC/MS analysis resulted in the identification of 36 metabolites from the EO of M. macrosiphon, 45 from M. arganietorum. Borneol was the major metabolite in both oils and together with related derivatives such as camphor, accounted for 2/3 of the EO of M. macrosiphon, 1/3 of those of M. arganietorum. Pinene and terpinene derivatives were also present in high proportions. From a chemotaxonomic point of view, the composition of the examined samples may be related to those of other species endemic to Macaronesia. Both EOs showed significant toxicity towards liver HepG2 and melanoma B16 4A5 tumor cell lines at 100 mu g/mL; however, they were also cytotoxic towards S17 normal cell lines, with a selectivity index

The effect of light intensity (LI) and water availability (WA) on rosemary (Rosmarinus officinalis L.) plant growth, essential oil (EO) production and composition was investigated by a two-factorial field experiment, where the first factor was LI (100%, 50% or 25% of natural sunlight) and the second factor was WA (irrigation set at 85%, 70% or 55% of field capacity during plant growing). The EO obtained by steam distillation of the dried aerial part of the plant was analysed by GC/MS. Reduction of LI from 100 to 25% of natural sunlight markedly lowered plant biomass production, whereas reduction of WA from 85 to 55% had a smaller lowering effect on plant growth. High shading (25% of LI) markedly reduced EO yield on a plant basis (− 43%), whereas intermediate shading (50% of LI) increased EO yield as % content of the fresh biomass (+ 29%) when compared to full solar radiation. WA markedly influenced EO yield, as expressed on a plant basis, but only in plants exposed to 100% LI. Moreover, changes in LI and WA seemed to have an opposite effect on the relative abundance of EO constituents that are formed through the activity of two groups of enzymes, pinene synthases (α- and β-pinene, camphene and myrcene) and, respectively, bornyl diphosphate synthases (borneol, camphor and bornyl acetate). Accurate management of light conditions and water availability, in greenhouse as well as open field conditions, may allow to optimize rosemary EO yield and modulate EO profile in view of different potential uses.

A carbonaceous solid acid catalyst was prepared from Kraft lignin through the approach of incomplete carbonization and subsequent sulfonation in which Kraft lignin is activated by potassium hydroxi...

An oxidant-initiated, substitution process for dihapto-coordinated ligands is described for the {MoTp(NO)(DMAP)} system. Complexes of the form MoTp(NO)(DMAP)(η2-alkene), MoTp(NO)(DMAP)(η2-ketone), ...

Selective aerobic oxidation of α-pinene to high-value products is a major challenge in chemistry. Metalloporphyrins are proved to be selective catalysts for aerobic oxidation of simple hydrocarbons. Herein, we extend this method to more complex substrates using metallodeuteroporphyrins as model catalysts. It was found that the oxidation occurs mainly on the C=C and allylic C–H bonds of α-pinene influenced by the reaction temperature, reaction time, catalyst concentration, and oxygen flow rate. Allylic C–H oxidation products are obtained with a maximum selectivity value of 78.4% using the following reaction conditions: 105°C, 7 h, 5 ppm, and 60 mL/min. The influence of the metal nuclei of the metallodeuteroporphyrins on this reaction is also investigated. It was found that metallodeuteroporphyrins with Fe3+ as the metal nucleus exhibit the highest catalytic activity.

Six optically active macroheterocycles bearing ester and dihydrazide moieties were synthesized from available natural (-)-α-pinene through the intermediate keto acid, (31R,33R)- 1-hydroxy-32,32-dimethyl-1,4-dioxopentaphane, using the [2+1] reaction of this keto acid with di- or triethylene glycols and the [1+1] condensation of the resulting α,ω-diketo diesters with dicarboxylic acid dihydrazides in the key steps.

Ketol–acid reductoisomerase catalyzes the second step reaction in the biosynthesis of essential branched-chain amino acid, and is an important target enzyme to design the safe herbicides and fungic...

The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst (Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Brӧnsted acid and Lewis acid. Brӧnsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.

International audience; Mixing of anthropogenic gaseous pollutants and biogenic volatile organic compounds impacts the formation of secondary aerosols, but still in an unclear manner. The present study explores secondary aerosol formation via the interactions between β-pinene, O3, NO2, SO2, and NH3 under dark conditions. Results showed that aerosol yield can be largely enhanced by more than 330% by NO2 or SO2 but slightly enhanced by NH3 by 39% when the ratio of inorganic gases to β-pinene ranged from 0 to 1.3. Joint effects of NO2 and SO2 and SO2 and NH3 existed as aerosol yields increased with NO2 but decreased with NH3 when SO2 was kept constant. Infrared spectra showed nitrogen-containing aerosol components derived from NO2 and NH3 and sulfur-containing species derived from SO2. Several particulate organic nitrates (MW 215, 229, 231, 245), organosulfates (MW 250, 264, 280, 282, 284), and nitrooxy organosulfates (MW 295, 311, 325, 327, and 343) were identified using high-resolution orbitrap mass spectrometry in NO2 and SO2 experiments, and their formation mechanism is discussed. Most of these nitrogen- and sulfur-containing species have been reported in ambient particles. Our results suggest that the complex interactions among β-pinene, O3, NO2, SO2, and NH3 during the night might serve as a potential pathway for the formation of particulate nitrogen- and sulfur-containing organics, especially in polluted regions with both anthropogenic and biogenic influences.

The reactions of biogenic volatile organic compounds (BVOC) with the nitrate radicals (NO3) are major night-time sources of organic nitrates and secondary organic aerosols (SOA) in regions influenced by BVOC and anthropogenic emissions. In this study, the formation of gas-phase highly oxygenated organic molecules-organic nitrates (HOM-ON) from NO3-initiated oxidation of a representative monoterpene, β-pinene, was investigated in the SAPHIR chamber (Simulation of Atmosphere PHotochemistry In a large Reaction chamber). Six monomer (C = 7-10, N = 1-2, O = 6-16) and five accretion product (C = 17-20, N = 2-4, O = 9-22) families were identified and further classified into first- or second-generation products based on their temporal behavior. The time lag observed in the peak concentrations between peroxy radicals containing odd and even number of oxygen atoms, as well as between radicals and their corresponding termination products, provided constraints on the HOM-ON formation mechanism. The HOM-ON formation can be explained by unimolecular or bimolecular reactions of peroxy radicals. A dominant portion of carbonylnitrates in HOM-ON was detected, highlighting the significance of unimolecular termination reactions by intramolecular H-shift for the formation of HOM-ON. A mean molar yield of HOM-ON was estimated to be 4.8% (-2.6%/+5.6%), suggesting significant HOM-ON contributions to the SOA formation.

Liquid chromatography/negative electrospray ionization mass spectrometry [LC/(−)ESI-MS] is routinely employed to characterize the identity and abundance of molecular products in secondary organic aerosol (SOA) derived from monoterpene oxidation. Due to a lack of authentic standards, however, commercial terpenoic acids (e.g., cis-pinonic acid) are typically used as surrogates to quantify both monomeric and dimeric SOA constituents. Here, we synthesize a series of enantiopure, pinene-derived carboxylic acid and dimer ester homologues. We find that the (−)ESI efficiencies of the dimer esters are 19–36 times higher than that of cis-pinonic acid, demonstrating that the mass contribution of dimers to monoterpene SOA has been significantly overestimated in past studies. Using the measured (−)ESI efficiencies of the carboxylic acids and dimer esters as more representative surrogates, we determine that molecular products measureable by LC/(−)ESI-MS account for only 21.8 ± 2.6% and 18.9 ± 3.2% of the mass of SOA formed from ozonolysis of α-pinene and β-pinene, respectively. The 28–36 identified monomers (C₇₋₁₀H₁₀₋₁₈O₃₋₆) constitute 15.6–20.5% of total SOA mass, whereas only 1.3–3.3% of the SOA mass is attributable to the 46–62 identified dimers (C₁₅₋₁₉H₂₄₋₃₂O₄₋₁₁). The distribution of identified α-pinene and β-pinene SOA molecular products is examined as a function of carbon number (n_C), average carbon oxidation state (OS_C), and volatility (C*). The observed order-of-magnitude difference in (−)ESI efficiency between monomers and dimers is expected to be broadly applicable to other biogenic and anthropogenic SOA systems analyzed via (−) or (+) LC/ESI-MS under various LC conditions, and demonstrates that the use of unrepresentative surrogates can lead to substantial systematic errors in quantitative LC/ESI-MS analyses of SOA.

Epoxidation of monoterpenes, α-pinene, β-pinene, limonene, α-terpinene, and (R)-carvone was carried out by the in situ production of a peroxyacid rather than direct addition of such an expensive and difficult to handle chemical. Previous reports showed use of metal catalysts with high yields, while methodologies without catalysts at high temperature showed yields lower than 30%. The authors report a methodology that produces peroxyacetic acid in situ yielding up to 75% pure epoxide at room temperature avoiding the use of catalysts. The products were analyzed by gas chromatography mass spectrometry (GC-MS), and structures were characterized by 1H and 13C nuclear magnetic resonance (NMR).

The effect of furocoumarins on terpene photo-oxidation under UV-A light was investigated. For this purpose, four furocoumarins (8-methoxypsoralen, bergapten, bergaptol, bergamottin) each at a level of 5%, was added to solutions of the terpenes β-pinene, R-(+)-limonene and γ-terpinene in ethanol followed by UV irradiation at 366 nm. Bergaptol and bergamottin were synthesized and fully elucidated by NMR spectroscopy. UV-induced transformation of all terpenes was substantially reduced in the presence of furocoumarins. Best photo-protection was observed for γ-terpinene with the addition of bergaptol, i.e. degradation was reduced by 73% compared to the neat substance over a time period of ten days. Bergamottin (50.2%), bergapten (39.8%) and 8-methoxypsoralen (39.6%) also reduced degradation substantially. The protective effect of bergaptol was even noticeable at low concentrations of 0.1%. The main oxidation product of γ-terpinene was p-cymene. Limonene and β-pinene showed a predominated hydroperoxide formation under UV light which could almost completely prevented in the presence of furocoumarins. The protective effect of furocoumarins was presumably due to energy dissipation as a result of the conversion of high energetic radiation (UV-A) into visible light via fluorescence. Phosphorescence or self-quenching within the triplet state were further mechanisms avoiding reactions of excited furocoumarins with the terpenes under investigation. Hence, the photo-stability of the furocoumarins themselves correlated with the extent of their protective effect on all three terpenes.

The study describes the composition of volatile oils obtained by steam distillation of water fir (Abies alba), pine (Pinus sylvestris), juniper (Juniperus communis), rosemary (Rosmarinus officinalis), sage (Salvia officinalis), and coriander (Coriandrum sativum) using the gas chromatography technique coupled with mass spectrometry (GC-MS). Chromatographic profile revealed the presence of specific components for each studied volatile oil. It noted the presence of a and b- pinene in all volatile oils studied at different concentrations. Volatile oils studied, from green sources and rich in a, b-pinene will be used as raw materials for creating products with anti-inflammatory, antiseptic, bronchodilators properties.

PM2.5 samples were collected simultaneously at three urban sites including Beijing (BJ), Tianjin (TJ), Shijiazhuang (SJZ) and one background site Xinglong (XL) from June 2014 till April 2015. Typical polar organic aerosol tracers including 2-methylglyceric acid, 2-methyltetrols, 3-hydroxyglutaric acid, anhydrous saccharides and phthalic acid were analyzed by gas chromatography-mass spectrometry. Both Isoprene secondary organic aerosol (SOA) tracers and pinene SOA tracers had higher mass concentrations at background site than those at urban sites. But they showed different seasonal variations. The former had the highest mass concentration in summer while the latter had the highest mass concentration in spring. Anhydrous saccharides and phthalic acids at urban sites had higher mass concentrations than those at background site and showed higher mass concentration in autumn and winter, respectively. Corresponding estimated secondary organic carbons (SOCs) showed similar variation trends with tracers. In general, biogenic sources had more influence on background site while urban sites were more affected by anthropogenic sources.

alpha-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C-19 and C-20 accretion products from alpha-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C-10-RO2 radicals from alpha-pinene ozonolysis were O,O-C10H15(O-2)(x)O-2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O-2)(alpha)O-2 with alpha = 0, 1, 2. All detected C 20 accretion products can be explained via the accretion reaction RO2 + R'O-2 -> ROOR' + O-2 starting from the measured C-10-RO2 radicals. We speculate that C-19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C-5-RO2 radicals, leads to C-15 accretion products formed via cross-reactions with C-10-RO2 radicals. This process is competing with the formation of C-19/C-20 products from the pure alpha-pinene oxidation. A similar behavior has been observed for ethylene additives that form C-12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C-19/C-20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over alpha-pinene, respectively, as present in different forested areas.

The conditions for isomerization of α-pinene epoxide (2,3-epoxypinane) on modified clays that gave comparatively high contents (33.0%) of fencholenic (iso-campholenic) aldehyde in the product mixture were determined. An effective method for isolating it was proposed. The structure of iso-campholenic aldehyde was confirmed by analyzing 2D NOESY and HMBC NMR spectra.

The effect of different surface OH's groups on the amount of anchored Mo complex: Mo(VI)Cl2O2Bipy (Bipy = 4,4′-dicaboxylato-2,2′-bipyridine) grafted on TiO2 (Mo(VI)Cl2O2Bipy/TiO2) and its effect on the photocatalytic Oxygen Atom Transfer (OAT) activity to α-pinene with O2 was studied. The amount of supported complex on TiO2 nanotubes is 5 times the amount of the grafted complex on TiO2 P-25 and OAT activity increase of 25%, may be associated to the physicochemical properties of TiO2 nanotubes. High selectivity was preserved toward the epoxide formation (>90%). The amount of Mo complex covalently anchored on TiO2 depends on the concentration, distribution and accessibility of the Ti-OH surface groups, which depend on the TiO2 preparation method. The different OH's groups, namely: Bridged, geminal and isolated were identified by FT-IR Photoacoustic Spectroscopy. Surface OH's concentration was determined by TGA methods, silylation reactions and XPS analysis.

A sustainable lactam, which is derived from the renewable terpene β-pinene, is converted to polyamides via a convenient anionic ring-opening polymerization (ROP), which can be easily handled without the use of a costly catalyst. The resulting polyamides have prosperous thermal properties, which enable their future use as high-performance polymers.

A new supported Ni/AlPO4 catalyst was synthesized and studied for the selective hydrogenation of α-pinene to prepare cis-pinane. The support was flaky morphology with orthorhombic phase and Ni was well dispersed. The surface area of the catalyst was 37.62 m2·g−1 with a pore size of 2.83 nm. For the hydrogenation reaction, the performance of the catalyst was positively correlated with the surface area of support and loading content of Ni. Effects of hydrogenation condition were determined and the process was optimized by response surface methodology. The result suggested that the conversion was positively correlated to hydrogenation temperature, duration and catalyst dosage, while the selectivity showed a negative correlation to temperature and catalyst dosage. After optimization, 95.1% of selectivity was obtained under 94.8% of conversion at 405 K, 81 min and 2.28 wt% of catalyst.

CST (Crude Sulfated Turpentine) is an upcycled, biomass raw material derived from pinewood; obtained as a waste product of the Kraft process from the pulp and paper industry. The current report provides an overview of the major perfumery ingredients obtained from CST-derived alpha- and beta-pinene to-date and part of the Firmenich manufacturing portfolio, post DRT acquisition.

The selective synthesis of fine chemicals from wasted derived biomass is one of the main challenges for the industry for valorizing and transforming these products into valuable substances. In this work, several materials based on zeolites, titanium dioxide, titanates and molybdenum were tested in the isomerization reaction of biomass derived α- and β-pinene for obtaining camphene, a very high-added value chemical. Liquid phase reaction of α- and β-pinene revealed that zeolites and titanates materials are capable to isomerize both monoterpenes at benign conditions (1 h, 90 °C, cyclohexane as solvent); nevertheless, the catalyst based on titanates is suitable for obtaining camphene in the highest yield from both terpenes (77% from α-pinene and 67% from β-pinene). Density of acid sites, Bronsted acid sites and the typical architecture of each catalyst gave significant differences in the catalytic activity. An increase of the Bronsted sites with medium strength favored the yield to camphene. An excess of acidity respect to other materials (e.g. zeolites) increases the formation of secondary products (limonene, pinenes, β-phellandrene, among others) over camphene, in comparison with titanate catalyst, which shape and acidity is considerably lower. Catalytic isomerization was also explored in essential oils extracted from crude biomass. Camphene weight composition increased in turpentine and Rosmarinus essential oils from 3% to 61% and from 7% to 31%, respectively, in presence of titanates-based material. In addition, this material was also capable to isomerize camphene and limonene into added value chemicals in good to excellent yields. Finally, titanate-based material was reused until 5 times for the selective synthesis of camphene from α- and β-pinene.

Viscosity index improver (VII) and Pour point depressant (PPD) performances of the β-pinene based newly developed greener additives were tested in base oil in terms of viscosity index (VI) ...