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MICROCHEMICAL JOURNAL · 2022 · IF 5.304

Early identification of fungal leaf blight disease (Alternaria alternate) on Platycladus orientalis plants by using gas chromatography-ion mobility spectrometry

Chengyu Zheng,Qin'an Zhou,Wenqing Shao,Jing Zhang,Jun Wang

Platycladus orientalis (L.) is a typical urban greening tree in Asia, but the young leaves of P. orientalis are   vulnerable to pathogenic fungi with hidden early   signs. In this study, we investigated the volatile organic compounds (VOCs) emissions of the Alternaria alternate infected P. orientalis plants, for the first time, using the gas chromatography-ion mobility spectrometry (GC-IMS) combined with chemometric approaches. Results showed that the A. alternate infection could reduce the VOCs release of P. orientalis leaves. The α-pinene and β-pinene emissions were down to 70% and 55% of controls on day 10, respectively. The destructive inoculated plants responded more to the A. alternate , both   in the VOCs emissions and the fungal growth. The (Z)-3-hexenol, n-hexanol, α-pinene, and β-pinene can serve as potential markers for infection discrimination, and their IMS signal intensities were calibrated with corresponding volume concentrations ranging from 0 to 250 μg/L. The PLS-DA model based on GC-IMS fingerprints can correctly classify at least 83% of samples in infection durations after fungal inoculation for the first 10 days. The PLSR model can predict the fungal colony counts in the P. orientalis needles (R c 2 >0.97 and R p 2 >0.92) with good robustness, whose RMSEP was lower than 0.68 (×10 6 CFU g −1 ) in predict set. In a word, the GC-IMS-based approach had the potential to evaluate A. alternate infection in P. orientalis , and the variation of potential markers can provide reference to its fungal infection monitor with   millisecond response in the forest.

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TREES-STRUCTURE AND FUNCTION · 2021 ·Vol. 36 ·期 2 ·711-721 · IF 2.529

Monoterpene emissions and their protection effects on adult Cinnamomum camphora against high temperature

Xu Chenyi,Ma Yuandan,Tian Zhengfeng,Luo Qingyun,Zheng Tiefeng,Wang Bin,Zuo Zhaojiang

Key message The four chemotypes of adult C. camphora released different monoterpenes which protected these plants against high temperature by lowering ROS levels and maintaining photosynthetic abilities. Abstract High temperature seriously impacts plant growth and development, and terpenes are believed to improve plant thermotolerance through indoor experiments using seedlings. To uncover the actual protection effects of monoterpenes on outdoor adult plants, we investigated the monoterpene emissions, reactive oxygen species (ROS) metabolism, and photosynthetic abilities in four chemotypes of adult Cinnamomum camphora that were blocked monoterpene synthesis by fosmidomycin (Fos) under high temperature in summer (the mean highest temperature at about 38.2 °C). Eucalyptol (EuL), linalool (Lnl), borneol (BeL), and camphor (CmR) chemotypes of C. camphora released an abundance of monoterpenes, with eucalyptol, linalool, endo-borneol, and camphor as the typical monoterpene, respectively. When the four chemotypes of C. camphora were treated with Fos, their monoterpene emission was inhibited remarkably, with disappearance of some monoterpenes. In that case, the content of O 2 − , H 2 O 2 , and thiobarbituric acid reactive substance (TBARS) in the four chemotypes of C. camphora significantly increased although antioxidant enzyme activities remarkably increased, and the photosynthetic abilities significantly decreased by declining the quantum production and electron transport in photosystem II and increasing the dissipation of absorbed light energy. Among the four chemotypes, monoterpenes might play the maximum roles in CmR lowering ROS levels and in EuL maintaining photosynthesis. It can be speculated that monoterpenes can protect adult C. camphora against high temperature by lowering ROS levels and maintaining photosynthetic abilities.

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INDUSTRIAL CROPS AND PRODUCTS · 2021 · IF 5.645

Seasonal emission of monoterpenes from four chemotypes of Cinnamomum camphora

Zhengfeng Tian,Qingyun Luo,Zhaojiang Zuo

Plant terpenes are the main functional agents in forest bathing and have great value in several industries. To uncover the seasonal variation of Cinnamomum camphora monoterpene emission and the difference among the chemotypes for promoting the development of forest bathing and exploitation of monoterpenes using the species, the emission of monoterpenes and related gene expression in the camphor chemotype, eucalyptol chemotype, linalool chemotype and borneol chemotype of C. camphora were analyzed in May (spring), July (summer) and November (autumn), and the stored monoterpenes and storage structure were investigated. Eleocytes were the storage structure of monoterpenes in C. camphora , which widely existed in the leaf palisade tissue and spongy tissue, as well as around the glands and vascular bundles. The 4 chemotypes of C. camphora released different monoterpene components which mainly derived from the immediate emission after synthesis. Camphor, eucalyptol, linalool and endo-borneol showed the uppermost emission rate and were the typical monoterpenes in the corresponding chemotype, respectively, due to the high expression of the genes encoding bornyl diphosphate synthase ( E5.5.1.8 ), linalool synthase ( TSP14 ) and (+)-neomenthol dehydrogenase ( E1.1.1.208 ) for the biosynthesis of camphor, linalool and endo-borneol, respectively, and only expression of the gene encoding 1,8-cineole synthase ( TSP-cin ) for eucalyptol biosynthesis. Among the 4 chemotypes, the linalool chemotype showed the highest emission rate of monoterpenes in the same month (without significant difference with the eucalyptol chemotype in November), due to the high expression of the genes ( dxs , dxr , ispF , gcpE , and GGPS ) in methylerythritol-4-phosphate (MEP) pathway, α-terpineol synthase gene ( E4.2.3.111 ) and TSP14 . Among the 3 months, temperature was the remarkably varied meteorological condition. The highest monoterpene emission rate from the 4 chemotypes of C. camphora was detected in July, which should result from the up-regulated expression of related genes in monoterpene biosynthesis and improved vaporization and diffusion of stored monoterpenes under high temperature, with the former providing a major contribution.

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INDUSTRIAL CROPS AND PRODUCTS · 2021 · IF 5.645

Insecticidal activities of Salvia hispanica L. essential oil and combinations of their main compounds against the beet armyworm Spodoptera exigua

Yijuan Chen,Jiaxuan Luo,Nan Zhang,Wenjuan Yu,Jiexian Jiang,Guanghui Dai

Plant essential oils are the powerful candidates to develop natural insect management agents. Their chemical compounds along with their biological activity are often affected by many factors. However, the relationships between the composition and bioactivity of the compounds are not well understood. In this study, eight plant essential oils were screened, and the main compounds from the most effective oil showing insecticidal properties against third-instar larvae of the beet armyworm ( Spodoptera exigua Hübner) were evaluated for comparative and synergistic interactions by topical application. The results indicated that Salvia hispanica L. essential oil showed significant insecticidal activity against S. exigua compared with the other seven essential oils. Fifteen major compounds were identified from S. hispanica via gas chromatography-mass spectrometry, with the most abundant compound (α-thujone) possessing the highest insecticidal activity. Several combinations of the four major compounds (α-thujone, (+)-camphor, 1,8-cineole, and α-caryophyllene) from S. hispanica exhibited synergistic insecticidal activities. This study demonstrates the potential of S. hispanica essential oil and α-thujone as effective botanical insecticides in the control of beet armyworm and provides a better understanding of essential oil compound-pest interactions.

CAS / MDL: 18172-67-3
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FOOD CONTROL · 2021 · IF 5.548

Varietal differences in the phytochemical components’ accumulation and aroma profile of three Humulus lupulus cultivars

Kai Hong,Zhenzhen Xu,Limin Wang,Agbaka Johnpaul,Yongqiang Cheng,Chenyan Lv,Changwei Ma

Humulus lupulus (hop) cone is a key ingredient in beer, which determines its taste and aroma. The impact of ripening on the bitter acids, aroma compounds, and polyphenols of hops has been reported separately, there is no systematic study on all three components. Here, three hop varieties (‘TP1’, ‘TP2’, and ‘QTF’) in China were sampled to investigate the correlation between the harvest maturity and these three components, which indicated that polyphenols synthesized earlier than hop bitter acids, followed by the aroma compounds. Variety differences of the hop cultivars prompted the obvious separation in the partial least-squares discriminant analysis (PLS-DA). Among three hop cultivars. ‘TP1’ with the highest contents of aroma compounds contributed to flower aroma, and with higher contents of bitter acids which contributed to bitter taste. In contrast, ‘TP2’ has been reported to be rich in caffeic acid, salicylic acid, syringaldehyde, (+)-catechin, and (−)-epicatechin. To analyze the hop aroma characteristics, two matrices of hop tea and late-hopped beer were prepared and used for sensory evaluation. Compared to ‘TP2’ and ‘QTF’, the hop tea with ‘TP1’ scored best for ‘strong’ (P < 0.01), ‘herbal’ (P < 0.05) and ‘citrus’ (P < 0.01). While the ‘strong’ and ‘herbal’ characteristics from terpene compounds receded in the late-hopped beer, the ‘citrus’ and ‘fruity’ notes from terpenol compounds remained noticeable.

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TALANTA · 2020 · IF 5.339

Covalent coupling fabrication of microporous organic network bonded capillary columns for gas chromatographic separation

Xue Li,Yuan-Yuan Cui,Cheng-Xiong Yang

Microporous organic networks (MONs) have shown great promise in separation science recently. Exploring novel, simple and convenient strategy to fabricate MONs coated capillary columns for gas chromatography (GC) still remains challenging but desirable for the development of MONs in chromatographic separation. To extend the potential application of MONs in separation science and to further develop novel method for the fabrication of MONs-based capillary columns, here we demonstrate a novel covalent coupling strategy to fabricate uniform MONs bonded capillary columns for GC separation of position isomers and hydrocarbons. The bare capillary column was firstly modified with (3-bromopropyl)trimethoxysilane to provide bromine sites for coupling with alkynyl monomers . The amino- and hydroxyl-functionalized MONs (MON-NH 2 and MON-OH) were then directly grown onto the inner wall of the brominated capillary columns via the covalent coupling between bromine and alkynyl groups. The uniform MON-NH 2 and MON-OH bonded capillary columns were obtained and showed good resolution for GC separation of dichlorobenzene , chlorotoluene, bromotoluene, and propylbenzene position isomers and many other hydrocarbons including linear alkanes, alkylbenzenes , pinene isomers, cyclohexane and benzene, ketones and aldehydes. The MONs bonded capillary columns also owned good lifetime and precision for dichlorobenzene isomers with the relative standard deviations (RSDs) of 0.2–0.3%, 1.2–2.1%, and 1.7–2.5% for retention time, peak height and peak area, respectively. In addition, the fabricated MON-NH 2 and MON-OH bonded capillary columns offered better resolution than commercial InertCap-1, InertCap-5, InertCap-1701 and InertCap-WAX capillary columns for the separation of chlorotoluene and bromotoluene position isomers. These results revealed the feasibility of covalent coupling strategy to fabricate MONs-based stationary phases in GC, highlighting the potential of MONs in separation science.

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LANGMUIR · 2021 · IF 3.882

Synthesis and Shape-Selective Catalytic Application of Ordered Cubic Ia3̅d Supermicroporous Materials Templated by Rosin-Derived Quaternary Ammonium Salt with a Hydroxyl Radical in the Headgroup

Shiyu Wu,Yufu Yi,Shengliang Liao,Hongyan Si,Yuling Yang,Guorong Fan,Peng Wang

We described the comprehensive synthesis, characterization, and catalytic performance of a novel type of the ordered cubic Ia3̅d supermicroporous silicas by using tetraethyl orthosilicate as a silicon source and a hydroxyl-functionalized quaternary ammonium salt as a template under alkali conditions. The effects of various reaction conditions on the pore structure and morphology of the silica materials were thoroughly investigated. Our results showed that under a wide range of reaction conditions, supermicroporous silicas with a highly ordered cubic Ia3̅d structure can be produced with a large BET specific surface area of 1741 m2/g, high pore volume of 0.91 cm3/g, concentrated pore size at 19.1 Å, and crystalline morphology. After Al doping, the obtained aluminosilicates preserved a highly ordered cubic supermicroporous structure. By using the H-form aluminosilicates as catalysts, we selectively dimerized β-pinene. The catalysts exhibited an excellent catalytic activity for β-pinene dimerization with a conversion yield up to 100%. Compared with conventional mesoporous H-form Al-MCM-48 catalysts, the prepared supermicroporous catalysts exhibited superior catalytic performance due to their excellent shape-selective properties, producing the β-pinene dimer in a yield up to 72.4% with dimer/oligomer ratios in the range of 7.5–10.1. This study featured a detailed preparation and characterization of supermicroporous silica with novel microstructures and showed its utility in catalytic dimerization.

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COMPUTERS AND ELECTRONICS IN AGRICULTURE · 2020 · IF 3.858

Discrimination of wood-boring beetles infested Platycladus orientalis plants by using gas chromatography-ion mobility spectrometry

Chengyu Zheng,Zhenhe Wang,Jing Zhang,Jun Wang,Jianli Zhong,Yongwei Wang

Platycladus orientalis plants in China are experiencing a serious problem with wood-boring beetles, but conventional physical detection methods cannot perform well due to hidden larvae and less obvious symptoms in the early infestation. In this study, the volatile organic compounds (VOCs) of P. orientalis were investigated using gas chromatography-ion mobility spectrometry (GC-IMS) to identify its internal infestation. An image-based evaluation method of the degree of internal wood damage was proposed, the principal component analysis (PCA) based on specific markers was applied for natural clustering of samples, and unsupervised learning approaches based on specific markers and automatically located peaks were used to create predictive models for sample classification. The results showed that the herbivore-induced plant volatiles (HIPVs) of P. orientalis samples had two main characteristics compared with undamaged plants. One was the emergence of several compounds such as C 3 -C 6 ketones, aldehydes, and alcohols, while the other was the obvious content variation of several monoterpenes and their derivatives. The classification models based on specific markers and automatically located peaks could correctly classify at least 89.5% and 87.9% of the samples, respectively. In a word, these results proved that GC-IMS based approaches combined with different feature extraction methods have the potential to identify the internal infestation of wood-boring beetles in P. orientalis .

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FUEL · 2021 · IF 6.609

Synthesis and performance of cyclopropanated pinanes with high density and high specific impulse

Yakun Liu,Chengxiang Shi,Lun Pan,Xiangwen Zhang,Ji-Jun Zou

With the rapid development of aerospace industry, it is significantly necessary to develop advanced rocket fuels with high density, high specific impulse and good combustion performance. In this work, we report the synthesis of cyclopropanated pinanes through cyclopropanation of pinene. The reaction conditions including reaction time, solvent type, halohydrocarbon and molar ratio of zinc carbenoid to pinene were optimized. The basic physical properties of fuel, including density, kinematic viscosity, freezing point, calorific value, and combustion performance were tested, and the specific impulses of cyclopropanated pinanes were also calculated. Importantly, the cyclopropanated α- and β-pinane possess high density of 0.90 and 0.91 g/mL, specific impulse of 330.58 and 330.39 s, which results in higher volumetric specific impulse than reported rocket fuels. They also show good low-temperature performance and better ignition and combustion performance than JP-10. These excellent performances indicate that the cyclopropanated α- and β-pinane have great application prospect as high-energy rocket fuel.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2021 ·Vol. 413 ·期 23 ·5789-5798 · IF 4.157

Behavioral responses of Platycladus orientalis plant volatiles to Phloeosinus aubei by GC-MS and HS-GC-IMS for discrimination of different invasive severity

Zheng Chengyu,Zhou Qinan,Wang Zhenhe,Wang Jun

In recent years, the invasive cypress bark beetle ( Phloeosinus aubei ) has caused extensive damage to Platycladus orientalis plants in China, but its infestation is hard to monitor in the early stages. In this study, gas chromatography-mass spectrometry (GC-MS) was initially employed to investigate the volatile organic compound (VOC) emissions of P. aubei- infested P. orientalis saplings. The emissions of total sesquiterpenes were dominating (84−86% of total VOCs) and increased by 3.09-fold in P. aubei- damaged P. orientalis samples compared to undamaged samples, and the monoterpenes, aromatic compounds, and ketone emissions also had varying degrees of increase between 1.39-fold and 5.65-fold. Based on this variation, gas chromatography-ion mobility spectrometry (GC-IMS) was applied, as an untargeted analytical approach, to discriminate P. orientalis samples with different invasive severity. Two different features derived from GC-IMS data were adopted as the input information for classification and prediction models. Results showed that grid search support vector machine (GS-SVM) combined with multilinear principal component analysis (MPCA) based on spectral fingerprint achieved the best classification performances (> 88.98%), and partial least squares discriminant analysis (PLSR) method can accurately predict the pest numbers ( R 2 > 0.9423 and RMSE < 0.9827). In a word, the VOC profiling-based approach had the potential for evaluating P. aubei invasive severity and pest management.

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EUROPEAN POLYMER JOURNAL · 2019 · IF 3.621

Renewable sulfur- and monoterpenes-derived polysulfides as functional crosslinker for epoxy thermosets

Longfeng Sun,Shuxi Gao,Xuefeng Gui,Lingli Liu,Kai Xu,Huan Liu

Polymer materials, with sulfur as the major part of the backbone structure, are gaining increasing importance because of the large abundance of sulfur and the unique features of polysulfide linkages for modifying material properties. Herein, we introduce polysulfides, which are synthesized from sulfur and monoterpenes, as poly-thiols platform for the crosslinking of epoxy, allowing flexible sulfur constituents incorporate into covalently linked networks. This synthesis can be conducted in a simple, mild, and practical one-pot procedure proceed smoothly in a solvent-free manner with high sulfur utilization to afford sulfur–monoterpene polysulfides (PST) with high sulfur content (up to 58%) and good solubility. The epoxy was cured with PST with imidazole as the catalyst, producing highly sulfur crosslinked thermosets, which is supposed to proceed via a thiol-epoxy reaction mechanism. The resulting thermoset perform good toughness, high transmittance and potential self-healing ability.

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GREEN CHEMISTRY · 2019 ·Vol. 21 ·期 21 ·5886-5895 · IF 9.405

Photoinduced cycloaddition of biomass derivatives to obtain high-performance spiro-fuel

Junjian Xie,Lun Pan,Genkuo Nie,Jiawei Xie,Yakun Liu,Chi Ma,Xiangwen Zhang,Ji-Jun Zou

The photoinduced conversion of biomass-derived chemicals to high value chemicals and advanced fuels is of great significance but still challenging. Herein, a green and efficient self-sensitized [2 + 2] cycloaddition process is developed to convert biomass-derived β-pinene and isophorone to spirocyclic molecules, which cannot be achieved by thermal catalytic conversion. The photoreaction can take place with isophorone as the self-sensitizer, with high selectivity and a yield of up to 91.1%. A triplet sensitization mechanism is disclosed by a combination of triplet quenching, phosphorescence quenching, Stern–Volmer kinetic analysis, DFT calculations and photochemical kinetic studies. When combined with hydrodeoxygenation, spiro-fuel is obtained with an overall yield of 85.0% showing a high density of 0.911 g mL−1 which is 16.8% higher than that of conventional aviation kerosene (ca. 0.78 g mL−1), along with excellent cryogenic properties. Notably the self-sensitized cycloaddition strategy can be extended to a wide range of biomass derived α,β-unsaturated ketones and alkenes. Thus, this work provides a promising ring-increasing route to upgrade low-density bio-derived feedstocks to high-density hydrocarbons.

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