Preparation of Amide-Containing Insecticidal Derivatives from the Renewable Natural Productβ-Pinene

The preparation of bioactive derivatives from the renewable natural product pinene is a hot research topic in the deep processing and utilization of pinene.In this study,β-pinene was used to develop novel molecules as a promising new precursor of insecticide.A series of amide-containing derivatives ofβ-pinene were synthesized and characterized.The insecticidal activities of these derivatives against Mythimna separate and Semiaphis heraclei were tested.The structure characterization results showed that the characterization data of amide-containing derivatives were in full agreement with their proposed structures.The insecticidal activities evaluation results indicated that amide-containing derivatives exhibited weak insecticidal activity against Mythimna separate,but exhibited moderate to good insecticidal activity against Semiaphis heraclei.After testing for 72 h,the corrected mortality against Semiaphis heraclei of compounds 5c,5e,5f,5 h,5j,and 5 m was 100%at 1000 mg/L.The structure-activity relationship analysis results showed that the introduction of an amide group into the structure of derivatives improved their insecticidal activity against Semiaphis heraclei.Meanwhile,the amide-containing derivatives containing the F and NO_(2) substituted benzene ring might improve their insecticidal activity against Semiaphis heraclei.This study will be helpful for the high value-added utilization of the natural renewable resourceβ-pinene and the development of novel insecticides.

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.

Vibrational spectroscopic identification of isoprene, pinenes and their mixture

Here we show a study of vibrational spectroscopic identification of a few typical organic compounds which are known as the main sources of organic aerosols（OAs） particle matter in air pollution. Raman and IR spectra of isoprene, terpenoids, pinenes and their mixture are meticulously examined, showing distinguishable intrinsic vibrational spectroscopic fingerprints for these chemicals, respectively. As a reference, first-principles calculations of Raman and infrared activities are also conducted. It is interestingly found that, the experimental spectra are peak-to-peak consistent with the DFT（Density Functional Theory）-calculated vibrational activities. Also found is that, in a certain case such as for bpinene, a dimer model, rather than an isolated single molecular model, reproduces the experimental results, indicating unneglected intermolecular interactions. Starting with this study, we are endeavoring to advocate a database of Raman/IR fingerprint spectra for OA haze identification.

Genomic and transcriptional changes in response to pinene tolerance and overproduction in evolved Escherichia coli

α-Pinene is an important monoterpene,which is widely used as a flavoring agent and in fragrances,pharmaceuticals and biofuels.Although an evolved strain Escherichia coli YZFP,which had higher tolerance to pinene and titer,has been successfully used to produce high levels of pinene,the pinene titer is much lower than that of hemiterpene(isoprene)and sesquiterpenes(farnesene)to date.Moreover,the overall cellular physiological and metabolic changes caused by higher tolerance to pinene and overproduction of pinene remains unclear.To reveal the mechanism of Escherichia coli YZFP with the higher tolerance to pinene and titer,a comparative genomics and transcriptional level analyses combining with CRISPR activation(CRISPRa)and interference(CRISPRi)were carried out.The results show that the tolerance to pinene and the overproduction of pinene in E.coli may be associated with:1)the mutations of the DXP pathway genes,the rpoA and some membrane protein genes,and their upregulations of transcription levels;and 2)the mutations of some genes and their downregulation of transcriptional levels.These comparative omics analyses provided some genetic modification strategies to further improve pinene production.Overexpression of the mutated cbpA,tabA,pitA,rpoA,sufBCDS,mutS,ispH,oppF,dusB,dnaK,dxs,dxr and flgFGH genes further improved pinene production.This study also demonstrated that combining comparative omics analysis with CRISPRa and CRISPRi is an efficient technology to quickly find a new metabolic engineering strategy.

Improved pinene production in a recombinant yeast by fusion linker optimization and chaperon coexpression

Pinene is an active natural monoterpene from plants and has important applications in favorings,fragrances,and pesticides.Especially,pinene dimers are regarded as renewable fuels with high density.However,the microbial pinene production was limited by the low activity pinene synthase.In this study,the pinene synthase activity was improved by fusion linker optimization and chaperon coexpression.To construct the pinene pathway in Saccharomyces cerevisiae,YPL062W gene was deleted to increase the MVA pathway precursor acetyl-CoA.Truncated 3-hydroxyl-3-methylglutaryl-CoA reductase(tHMG1),isopentenyl-diphosphate isomerase(IDI1),and farnesyl diphosphate synthase mutant(ERG20F96W−N127W)were then integrated to improve the GPP pool.Pinene synthase tPt1 was expressed in the constructed engineered yeast,and the titer of pinene reached 0.166 mg/L.GPP is the direct precursor of pinene,ERG20ww and tPt1 were fused by diferent linkers and orders to improve the accessibility of GPP.Pinene titer reached 9.94 mg/L by fusion these proteins in the order of ERG20ww and tPt1 and with a fexible linker(G)8.After that,several chaperons were coexpressed and the chaperon Sil1p improved the pinene titer to 10.2 mg/L with a yield of 1.63 mg/L·OD600.The results presented here provide novel information on the applications of protein fusion and protein chaperons in microbial pinene production.

室内空气中单萜类化合物检测方法的研究

Monoterpenoids are widely existing in indoor air.A GC-MS method was established for determination of monoterpenoids in the indoor air by using silonite coated canisters(SUMMA canisters),and preconcentrating low level samples utilizing three stages focuser.The method was suitable for the determination of trace VOCs in indoors air.The detection limits of method for α-pinene and β-pinene were both 0.71 μg/m3.

曲安奈德鼻喷雾剂联合桉柠蒎肠溶胶囊治疗分泌性中耳炎

分泌性中耳炎（secretory otitis media,SOM）主要以传导性聋及鼓室积液为主要特征的中耳炎症,儿童和成人发生率均较高,治疗方法 主要为药物和鼓膜穿刺、切开置管术等,如何尽量减少有创治疗一直是临床医师探讨的问题。本研究用曲安奈德鼻喷雾剂（triamcinolone acetonide nasal spray,TANS）喷鼻加桉柠蒎肠溶胶囊（eucalyptol,limonene and pinene enteric soft capsules,ELPESC）治疗SOM取得了较好的临床治疗效果,

Diversity in chemical compositions of essential oil of myrtle leaves from various natural habitats in south and southwest Iran

Myrtle, Myrtus communis L. （Myrtaceae）, an evergreen shrub also known as wild myrtle, has a history of use as a culinary and medicinal plant. To determine the diversity within the species, plant leaves of myrtle were collected in 12 natural habitats in Iran for investigation of chemical constituents in the essential oil. Extraction of the essential oils produced yields ranging from 0.7 to 1.5 mL per 100 g dry tissue. An analysis of the oils by GC and GC/MS revealed 40 compounds, constituting 90.1-99.9 % of the essential oils. Chemical constituents varied with the site of sample origin, although the principal essential oil compo- nents from all populations, were pinene （17.5-37.1%）, 1,8-cineole （9.9-29.8 %）, linalool （7.0-23.1%）, and a-ter- pineol （5.3-8.3 %）. Limonene （tr, 22.7 %） was a major constituent in three populations. Characterized chemotypes included Chemotype pinene/1,8-cineole/linalool, Chemotype II： a-pinene/linalool, Chemotype III： a-pinene/1,8- cineole, and Chemotype IV： pinene/1,8-cineole/limonene.The main source of variabifity in chemical composition and oil yield appeared to be differences in environmental conditions and chemotypes as plant populations collected from close geographical areas could be classified in a cluster.

Emissions of non-methane hydrocarbons from cars in China

This study investigated the exhaust emission of non-methane hydrocarbons(NMHCs) from cars in China at the Beijing driving cycle on the chassis dynamometer.The emission factor average of NMHCs was 0.9 g/km,which was over twice that from the Australian car fleet and 2-4 times that of the American car emission in the 1990s-2000s.The emission profile of Beijing cars showed higher fractions of aromatics and C4?C7 HCs,and lower percentages of C2?C3 HCs,compared with those of the US car fleet.The average ratio of benzene/toluene for cars tested was 0.5,the average benzene/toluene/ethyl benzene/xylenes(BTEX) ratios were 1/2.2/0.1/1.8,which were consistent with those of the Tanyugou tunnel located in the suburb of Beijing.α-pinene and β-pinene were detected from the exhaust gas on dynamometer for the first time,and had likely similar exhaust emission characteristics with C2?C3 HCs and styrene,giving an evidence that air pinenes may be related to human activities.Isoprene was also detected directly.These observations suggest that the procedure regarding pinenes and isoprene as coming from biologic sources of VOCs in the atmosphere should be applied with great care,especially in the core of the big city like Beijing.The specific reactivity of NMHCs was higher than that of cars of US,and the specific reactivity of volatile aromatic compounds was higher than that of the US SPECIATE database.