Distribution of 35 Polycyclic Aromatic Hydrocarbons in Pine Needle Samples from Selected Locations in the Republic of Korea.

Polycyclic aromatic hydrocarbons (PAHs), dust, and wax were measured in pine needles, and PAHs were also measured in surface soil. Pearson correlation analysis was performed between the analytical values. The main compounds responsible for the increase in total PAHs were non-carcinogenic phenanthrene and fluoranthene. Therefore, the % content of carcinogenic PAHs decreased with a slope = -0.037 (r = 0.47, p < 0.01), as the total PAH concentration in pine needles increased. Correlations between individual PAHs in pine needles and surface soil were very high when only low-number ring PAHs (2R- and 3R-PAHs) were statistically analyzed and significant when only high-number ring PAHs were statistically analyzed. Low-number ring PAH mainly moves in the gas phase and diffuses into the wax layer, so it was found to be statistically significant with the wax content of pine needles. High-number ring PAHs showed a high correlation with the amount of dust in pine needles because they mainly attached to dust particles and accumulated on the surface of pine needles. The ratios of fluoranthene/pyrene and methylphenanthrene/phenanthrene for predicting the origin of atmospheric PAHs have also been proven valid for pine needles.

A novel seawater hydrothermal-deep eutectic solvent pretreatment enhances the production of fermentable sugars and tailored lignin nanospheres from Pinus massoniana.

Lignocellulose biorefinery depended on effective pretreatment strategies is of great significance for solving the current global crisis of ecosystem and energy security. This study proposes a novel approach combining seawater hydrothermal pretreatment (SHP) and microwave-assisted deep eutectic solvent (MD) pretreatment to achieve an effective fractionation of Pinus massoniana into high value-added products. The results indicated that complex ions (Mg2+, Ca2+, and Cl-) in natural seawater served as Lewis acids and dramatically promoted the depolymerization of mannose and xylan into oligosaccharides with 40.17 % and 75.43 % yields, respectively. Subsequent MD treatment realized a rapid and effective lignin fractionation (~90 %) while retaining cellulose. As a result, the integrated pretreatment yielded ~85 % of enzymatic glucose, indicating an eightfold increase compared with untreated pine. Because of the increased hydrophobicity induced by the formation of acyl groups during MD treatment, uniform lignin nanospheres were successfully recovered from the DES. It exhibited low dispersibility (PDI = 2.23), small molecular weight (1889 g/mol), and excellent oxidation resistance (RSI = 5.94), demonstrating promising applications in functional materials. The mechanism of lignin depolymerization was comprehensively elucidated via FTIR, 2D-HSQC NMR, and GPC analyses. Overall, this study provides a novel and environmentally friendly strategy for lignocellulose biorefinery and lignin valorization.

UV blocking edible films based on corn starch/moringa gum incorporated with pine cone extract for sustainable food packaging.

Corn starch (CS) is a good alternative to synthetic polymers due to its sustainability; nevertheless, because of its weak tensile strength, the matrix requires another polymer. Therefore, 0.5 % (w/v) moringa gum (MG) was added. The purpose of this study was to assess how pine cone extract (PCE) affected the physiochemical and mechanical properties of corn starch and moringa gum (CS/MG) films and their use as UV-blocking composites. The findings suggest that the PCE improved the elongation at break from 3.27 % to 35.2 % while greatly reducing the tensile strength. The hydrogen bonding between CS/MG and PCE was visible in the FTIR spectra. The XRD graph indicated that the films were amorphous. In comparison to CS/MG films, PCE-incorporated edible films demonstrated significant UV-blocking ability indicating their potential as sustainable packaging material for light-sensitive food products.

Promotion of levoglucosan production from biomass pyrolysis by hydrogen peroxide pre-oxidation.

Due to the complexity of biomass structures, the conversion of raw biomass into value-added chemicals is challenging and often requires efficient pretreatment of the biomass. In this paper, a simple and green pre-oxidation method, which was conducted under the conditions of 2 wt% H2O2, 80 min, and 150 °C, was reported to significantly increase the production of levoglucosan (LG) from biomass pyrolysis. The result showed that the LG yield significantly increased from 2.3 wt% (without pre-oxidation) to 23.1 wt% when pine wood was employed as a sample for pyrolysis at 400 °C, resulting from the removal of hemicellulose fraction and the in-situ acid catalysis of lignin carboxyl groups formed during the pre-oxidation. When the conditions for pre-oxidation became harsher than the above, the LG yield reduced because the decomposition of cellulose fraction in biomass. The study supplies an effective method for utilization of biomass as chemicals.

Residues of Deltamethrin in Pine Needles and Pine Nuts of Catalonia (Spain).

In recent years, recurrent droughts have weakened stone pine (Pinus pinea) forests and facilitated the emergence of harmful pests and diseases, including the Leptoglossus occidentalis. The production of stone pine nuts has declined over the past five years. To control this hemipteran pest, a synthetic pyrethroid insecticide called deltamethrin is being tested. However, it is necessary to estimate the residue left by these treatments in forest stands. Therefore, a fast and robust analytical procedure was developed based on QuEChERS clean-up extraction, followed by gas chromatography coupled with an electron capture detector. This optimized method can detect residual concentrations of deltamethrin in pine nuts and pine needles up to 0.1 and 6 µg kg-1, respectively, with a limit of quantification of 0.4 and 20 µg kg-1. Great recoveries (between 84 and 102%) were obtained for both matrices, and no matrix effect was observed. The results showed that two weeks after spraying, the deltamethrin content in the needles of stone pines decreased by up to 75%, and after nine months, its presence was like that of nontreated trees.

Water-extractable polysaccharide fraction PNE-P1 from Pinus koraiensis pine nut: Structural features and immunostimulatory activity.

The polysaccharide fraction PNE-P1 was isolated from hot water extract (PNE) of the defatted meal of pine nuts (Pinus koraiensis) using DEAE-cellulose column chromatography. This fraction had three components of molecular masses 1251, 616, and 303 g/mol consisting mainly of arabinose, xylose, and galacturonic acid at a molar ratio of 2:1.6:1. Structural analysis with FTIR/Raman, methylation and GC-MS, and NMR revealed that PNE-P1 is a cell wall polysaccharide complex including arabinan, heteroxylan, homogalacturonan (HM) and rhamnogalacturonan I (RG-I) parts. Being nontoxic to RAW 264.7 macrophages in the concentration range of 10-200 µg/mL, PNE-P1 promoted proliferation of these cells, significantly induced the secretion of proinflammatory cytokines (TNF-α and IL-6) and chemokines (RANTES and MIP-1α) and enhanced the expression of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2) and nitric oxide (NO). PNE-P1 also markedly induced macrophage-mediated phagocytosis of apoptotic Jurkat T cells. These results demonstrate that pine nuts Pinus koraiensis contain a complex of water-soluble plant cell wall polysaccharides, which can stimulate innate immunity by potentiating macrophage function.

Anti-Aging Constituents from Pinus morrisonicola Leaves.

Pinus morrisonicola Hayata is a unique plant species found in Taiwan. Previous studies have identified its anti-hypertensive, anti-oxidative, and anti-inflammatory effects. In this study, a bioactivity-guided approach was employed to extract 20 compounds from the ethyl acetate fraction of the ethanol extract of Pinus morrisonicola Hayata's pine needles. The anti-aging effects of these compounds were investigated using HT-1080 cells. The structures of the purified compounds were confirmed through NMR and LC-MS analysis, revealing the presence of nine flavonoids, two lignans, one coumarin, one benzofuran, one phenylic acid, and six diterpenoids. Among them, PML18, PML19, and PML20 were identified as novel diterpene. Compounds 3, 4, and 5 exhibited remarkable inhibitory effects against MMP-2 and showed no significant cell toxicity at 25 µM. Although the purified compounds showed lower activity against Pro MMP-2 and Pro MMP-9 compared to the ethyl acetate fraction, we speculate that this is the result of synergistic effects.

Optimized extraction of polysaccharide from Pinus elliottii: Characterization, antioxidant, and moisture-preserving activities.

The study on the extraction conditions, purification, and biological activity of slash pine (Pinus elliottii.) is important for the development of slash pine resources. The optimal process conditions for the extraction of slash pine polysaccharide (SPP) were determined, resulting in a liquid-solid ratio of 66.94 mL/g, extraction temperature of 83.74 °C and extraction time of 2.56 h by using the response surface methodology, and the yield of SPP was 5.99% under the optimized conditions. Following the purification of SPP, the SPP-2 component was obtained and its physicochemical properties, functional group composition, antioxidant capacity, and moisturizing capacity were determined. Structural analysis suggested that SPP-2 has a molecular weight of 118.407 kDa, and was composed of rhamnose, arabinose, fucose, xylose, mannose, glucose, and galactose in a ratio of 5.98: 14.34: 1: 1.75: 13.50: 3.43: 15.79. The antioxidant activity analysis showed that SPP-2 has good free radical scavenging activity, and it was also found to have in vitro moisturizing activity and low irritation. These results suggest that SPP-2 has the potential for applications in the pharmaceutical, food, and cosmetic industries.

Toxicity evaluation of Pinus radiata D.Don bark wax for potential cosmetic application.

Radiata pine bark is a widely available organic waste, requiring alternative uses due to its environmental impact on soil, fauna, and forest fires. Pine bark waxes could be used as cosmetic substitutes, but their toxicity requires evaluation since pine bark may contain toxic substances or xenobiotics, depending on the extraction process. This study evaluates the toxicity of radiata pine bark waxes obtained through various extraction methods on human skin cells grown in vitro. The assessment includes using XTT to evaluate mitochondrial activity, violet crystal dye to assess cell membrane integrity, and ApoTox-Glo triple assay to measure cytotoxicity, viability, and apoptosis signals. Pine bark waxes extracted via T3 (acid hydrolysis and petroleum ether incubation) and T9 (saturated steam cycle, alkaline hydrolysis, and petroleum ether incubation) exhibit non-toxicity up to 2% concentration, making them a potential substitute for petroleum-based cosmetic materials. Integrating the forestry and cosmetic industries through pine bark wax production under circular economy principles could promote development while replacing petroleum-based materials. Extraction methodology affects pine bark wax toxicity in human skin cells due to the retention of xenobiotic compounds including methyl 4-ketohex-5-enoate; 1-naphthalenol; dioctyl adipate; eicosanebioic acid dimethyl ester; among others. Future research will investigate whether the extraction methodology alters the molecular structure of the bark, affecting the release of toxic compounds in the wax mixture.

Toumeyella parvicornis versus endotherapic abamectin: three techniques, 1 year after.

BACKGROUND: Toumeyella parvicornis is an invasive soft scale insect native to North America that is rapidly spreading in Italy and France, provoking severe infestations on Pinus pinea L. To date, the control of this pest is entrusted to three endotherapic techniques whose short-term efficacy is partially known. No information on long-term efficacy is currently available, although fundamental. This work aims to report on the long-term effect that abamectin-based insecticides, injected with the three different techniques, have on adult female populations. RESULTS: The study was carried out in an infested P. pinea forest in the area of Rome, Italy. Results showed that the tested methods had a similar long-term effect, and only in one case there were differences with the untreated control. Multiresidue analysis reported a zero level of abamectin in plant tissues 14 months apart from injection, except for one treatment where pesticide concentration was just above the limit of quantification. CONCLUSIONS: This study represents the first long-term evaluation about endotherapic control strategy against T. parvicornis. In fact, the pest may quickly bring the death and fall of the stone pines, representing a concerning risk for citizens, however, control actions to manage it are still partially known and deserve more in-depth investigations. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Combination of biological pretreatment with deep eutectic solvent pretreatment for enhanced enzymatic saccharification of Pinus massoniana.

Lignocellulosic biorefineries depended on effective pretreatment strategies to improve the conversion efficiency of the enzymatic hydrolysis. Here, this study coupled brown rot fungi and deep eutectic solvent (DES) to pretreat Pinus massoniana. The results showed that compared to fungal pretreatment and DES pretreatment alone, the combined ChCl-Lac/fungal pretreatments could effectively improve enzymatic saccharification of Pinus massoniana. The highest content of releasing reducing sugar reached 510.3 mg/g substrate. Environmental scanning electron micrograph (ESEM) showed that the surface structure of Pinus massoniana was almost completely torn and loose and FT-IR spectra and component analysis revealed that most of hemicellulose and lignin were selected removed and cellulose was enriched after ChCl-Lac/fungal pretreatments, which could account for the enhanced hydrolysis efficiency. The combination of biological pretreatment with DES pretreatment could be a mild and promising pretreatment approach for enzymatic saccharification of lignocellulose and had an extensive application prospect in the field of biorefinery.

Dynamic structural evolution of lignin macromolecules and hemicelluloses during Chinese pine growth.

To comprehend the biosynthesis processes of conifers, it is essential to investigate the disparity between the cell wall shape and the interior chemical structures of polymers throughout the development of Chinese pine. In this study, branches of mature Chinese pine were separated according to their growth time (2, 4, 6, 8 and 10 years). The variation of cell wall morphology and lignin distribution was comprehensively monitored by scanning electron microscopy (SEM) and confocal Raman microscopy (CRM), respectively. Moreover, the chemical structures of lignin and alkali-extracted hemicelluloses were extensively characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The thickness of latewood cell walls increased steadily from 1.29 µm to 3.38 µm, and the structure of the cell wall components became more complicated as the growth time increased. Based on the structural analysis, it was found that the content of ß-O-4 (39.88-45.44/100 Ar), ß-ß (3.20-10.02/100 Ar) and ß-5 (8.09-15.35/100 Ar) linkages as well as the degree of polymerization of lignin increased with the growth time. The complication propensity increased significantly over 6 years before slowing to a trickle over 8 and 10 years. Furthermore, alkali-extracted hemicelluloses of Chinese pine mainly consist of galactoglucomannans and arabinoglucuronxylan, in which the relative content of galactoglucomannans increased with the growth of the pine, especially from 6 to 10 years.

Aleppo pine seeds (Pinus halepensis Mill.) as a promising novel green coagulant for the removal of Congo red dye: Optimization via machine learning algorithm.

Consideration is now being given to the use of metal coagulants to remove turbidity from drinking water and wastewater. Concerns about the long-term impact of non-biodegradable sludge on human health and the potential contamination of aquatic systems are gaining popularity. Recently, alternative biocoagulants have been suggested to address these concerns. In this study, using a 1 M sodium chloride (NaCl) solution, the active coagulating agent was extracted from Pinus halepensis Mill. Seed, and used for the first time to remove Congo red dye, the influence of numerous factors on dye removal was evaluated in order to make comparisons with conventional coagulants. The application of biocoagulant was shown to be very successful, with coagulant dosages ranging from 3 to 12 mL L-1 achieving up to 80% dye removal and yielding 28 mL L-1 of sludge. It was also found that biocoagulant is extremely pH sensitive with an optimum operating pH of 3. Ferric chloride, on the other hand, achieved similar removal rate with higher sludge production (46 mL L-1) under the same conditions. A Fourier Transform Infrared Spectroscopy and proximate composition analysis were undertaken to determine qualitatively the potential active coagulant ingredient in the seeds and suggested the involvement of proteins in the coagulation-flocculation mechanism. The evaluation criteria of the Support vector machine_Gray wolf optimizer model in terms of statistical coefficients and errors reveals quite interesting results and demonstrates the performance of the model, with statistical coefficients close to 1 (R = 0.9998, R2 = 0.9995 and R2 adj = 0.9995) and minimal statistical errors (RMSE = 0.5813, MSE = 0.3379, EPM = 0 0.9808, ESP = 0.9677 and MAE = 0.2382). The study findings demonstrate that Pinus halepensis Mill. Seed extract might be a novel, environmentally friendly, and easily available coagulant for water and wastewater treatment.

COX-2 and iNOS inhibitory abietane diterpenoids from Pinus yunnanensis exudates.

Pinuskesiols A-F (1-6), six new structurally diverse abietane diterpenoids were isolated from Pinus yunnanensis resins. Their structures including absolute configurations were characterized by using spectroscopic and computational methods. All the compounds bear a carbonyl functionality at C-4 with 1 and 2 behaving as a lactone thereof. The isopropyl group is attached to C-13 via O-atom in 3. In addition, the presence of a Δ5(6) double bond and a ketone at C-7 makes 2 a large conjugated system. Biological evaluation revealed that 1, 2, and 4 could concentration-dependently inhibit iNOS and COX-2 expression in lipopolysaccharide-induced RAW 264.7 cells with 2 to be the most active toward COX-2 inhibition.

Essential oil composition and biological activities of Aleppo pine (Pinus halepensis Miller) needles collected from different Tunisian regions.

The aim of this research was to investigate the variation regarding the chemical composition and biological activities of needles essential oils (EOs) of P. halepensis. Chemical profiles demonstrated a significant (P < 0.05) variability among the different EOs. The main identified compounds were caryophyllene (48.77 ± 2.26), phenyl isovalerate (22.22 ± 2.26), ß-myrcene (15.55 ± 5.65) and α-pinene (14.52 ± 2.26). Further, it was shown that EO from Tabouba (Tab) displayed the highest DPPH scavenging (IC50 = 73.03 mg/mL), anti-inflammatory (IC50 = 23.29 µg/mL) and α-glucosidase inhibition activities (IC50 = 254.45 µg/mL). While Elmahres (Elm) exhibited the most potent ABTS radical's inhibition (IC50 = 197.87 mg/mL). For the cytotoxic capacities, Kettana (Ket) was the most efficient against breast cancer MCF-7 cell line with IC50 value better than doxorubicin used as positive control. Obtained results suggest that EO of P. halepensis could be used as a source of bioactive compounds.

Optimization of the ultrasound-assisted aqueous enzymatic extraction of Pinus koraiensis nuts oil by response surface methodology.

Response surfaces methodology was established in order to optimize ultrasound-assisted aqueous alkaline protease extraction parameters of Pinus koraiensis nuts oil (PNO) in this short communication. On the oil yield, the impacts of single factors were studied. The solid-liquid ratio, enzyme concentration, enzyme hydrolysis temperature, and enzyme hydrolysis duration were chosen for further optimization of the extraction process utilizing a Box-Behnken design based on statistical significance analysis. Under ideal extraction conditions, a maximum oil recovery of 68.35% was achieved: solid-liquid ratio, enzyme concentration, enzyme hydrolysis temperature, and enzyme hydrolysis duration were 1:5 (g/mL), 3.23 mg/g, 44 °C, and 2.84 h, respectively. Furthermore, physicochemical properties testing revealed that the oil was of higher quality than other approaches. Meanwhile, the DPPH radical-scavenging activities increased with increased content compared to olive oil, with an IC50 value of 0.082 mg/mL. The method has a lot of potential when it comes to extracting oils from plants.

Pinus massoniana needle extracts attenuate oxidative stress injury in cerebral ischemia reperfusion rats by regulating JNK3/caspase-3 signal transduction.

OBJECTIVE: To investigate the effect and mechanism of Pinus massoniana needle extracts (PNE) on oxidative stress injury in cerebral ischemia reperfusion rats. METHODS: The SD male rats were randomly divided into sham group, model control group, Edaravone (3 mg/kg) group, PNE low-dose (200 mg/kg), medium-dose (400 mg/kg) and high-dose (800 mg/kg) groups. PNE was administered by gavage for 7 d before modeling and 6 h after modeling in PNE treatment groups; Edaravone was given by intraperitoneal injection 7 d before modeling and 6 h after reperfusion. The rat model of cerebral ischemia reperfusion injury was established by middle cerebral artery occlusion method. After 24 h of reperfusion, the neurological deficit score, brain water content and cerebral infarction volume of rats were measured. The pathological changes of cerebral cortex and hippocampus were observed by HE staining, and the number of normal nerve cells was counted. The apoptosis rate of neurons in cerebral cortex was detected by TUNEL method. The content of nitric oxide (NO), malondialdehyde (MDA) and superoxide dismutase (SOD) activity in ischemic brain tissue were detected. The protein expression of c-Jun N-terminal kinase (JNK) 3, phosphorylated JNK3 (p-JNK3), B-cell lymphoma protein(Bcl) -2, Bcl-2 associated X (Bax), cytochrome C and caspase-3 in cerebral cortex were detected by Western blotting method. RESULTS: Compared with the model control group, the behavioral score, brain water content and cerebral infarction volume in PNE groups were significantly reduced (all P<0.05), the pathological damage of cerebral cortex and hippocampal CA1 area was significantly alleviated, and the number of normal nerve cells in ischemic cortex and hippocampal CA1 area was increased (all P<0.05). The medium-dose PNE group had the best effect. Compared with the model control group, the apoptosis rate of cortical neurons, the content of NO and MDA in cerebral cortex, the ratio of p-JNK3/JNK3, the expression level of cytochrome C and caspase-3 protein in PNE medium-dose group were significantly reduced , and the activity of SOD, the Bcl-2/Bax ratio were significantly improved (all P<0.05). CONCLUSION: PNE ameliorates brain injury after cerebral ischemia reperfusion in rats, which may be related to scavenging NO and MDA, inhibiting oxidative stress-mediated JNK3/caspase-3 signsal transduction to inhibit neuronal apoptosis.

Hydroxypropylation of Polyphenol-Rich Alkaline Extracts from Pinus radiata Bark and Their Physicochemical Properties.

Pinus radiata bark is a rich source of polyphenols, which are mainly composed of proanthocyanidins. This study aimed to utilize P. radiata bark as a polyol source for bio-foam production in the future. Polyphenol-rich alkaline extracts (AEs) from P. radiata bark were prepared by mild alkaline treatment and then derivatized with propylene oxide (PO). Hydroxypropylated alkaline extracts (HAEs) with varying molar substitutions (MS 0.4-8.0) were characterized by FT-IR, NMR, GPC, TGA, and DSC. The hydroxyl value and solubility in commercial polyols were also determined. The molecular weights of the acetylated HAEs (Ac-HAEs) were found to be 4000 to 4900 Da. Analyses of FT-IR of HAEs and 1H NMR of Ac-HAEs indicated that the aromatic hydroxyl groups were hydroxypropylated and showed an increase in aliphatic hydroxyl group content. The glass transition temperature (Tg) of AE and HAEs were 58 to 60 °C, showing little difference. The hydroxyl value increased as the hydroxypropylation proceeded. Although salts were produced upon neutralization after hydroxypropylation, HAEs still showed suitable solubility in polyether and polyester polyols; HAEs dissolved well in polyether polyol, PEG#400, and solubility reached about 50% (w/w). This indicated that neutralized HAEs could be directly applied to bio-foam production even without removing salts.

Chemical Diversity and α-Glucosidase Inhibitory Activity in Needles Essential Oils of Four Pinus Species from Northwestern Himalaya, India.

This work describes the study of the chemical profiling and α-glucosidase inhibitory activity of essential oils (EOs) from four Pinus species (P. wallichiana, P. patula, P. roxburghii and P. gerardiana). The identification and quantification of EOs metabolites were performed by GC/MS, GC-FID and 13 C-NMR. The needles of P. wallichiana and P. gerardiana presented the highest oil yields (0.35 % and 0.36 %, respectively). Twenty-four constituents were characterized in among samples exhibiting 93.8-97.7 % of the total EOs. The components and yields of the targeted samples were varied according to the species. Major components of the oils were α-pinene (20.5-34.1 %), ß-pinene (1.4-53.0 %), δ-3-carene (0.2-47.0 %), limonene (1.7-13.4 %), ß-phellandrene (0.2-23.4 %), ß-myrcene (1.8-7.2 %) and α-terpinolene (0.6-7.9 %). The extracted EOs showed strong α-glucosidase inhibitory activity, which was close to the positive control, acarbose. This study showed that the EOs of Pinus species may be used as natural antidiabetic.