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1.
J Sci Food Agric ; 102(1): 291-298, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34096061

RESUMO

BACKGROUND: 'Gold Finger' is a grape cultivar with a finger-like shape and a milk flavor. The process by which its aroma profile evolves during ripening is unclear. Thus, changes in the free and bound volatile compounds present in 'Gold Finger' grapes during ripening were investigated using headspace sampling-solid-phase microextraction-gas chromatography-mass spectroscopy (HS-SPME-GC-MS). RESULTS: A total of 83 volatile aroma components were identified in the grapes, with aldehydes, esters, acids, and alcohols being the main components. The total aroma compound content exhibited significant differences between the bound and free forms. The total content of bound volatile compounds did not change significantly during fruit development, although the free aroma compound content was significantly higher than the bound content. The total content of free aldehydes, free alcohols, bound norisoprenoids, and ketones gradually increased for up to 70 days after flowering (DAF), while the total free ester, terpene, and acid content decreased. The characteristic aroma compounds of 'Gold Finger' grapes were identified as hexanal, (E)-2-hexenal, and ethyl hexanoate. CONCLUSIONS: These results give a foundation for the further development of 'Gold Finger' grapes and provide a theoretical basis for the selection and breeding of novel aromatic grape varieties. © 2021 Society of Chemical Industry.


Assuntos
Frutas/química , Odorantes/análise , Vitis/crescimento & desenvolvimento , Compostos Orgânicos Voláteis/química , Álcoois/química , Álcoois/isolamento & purificação , Aldeídos/química , Aldeídos/isolamento & purificação , Aromatizantes/química , Aromatizantes/isolamento & purificação , Frutas/crescimento & desenvolvimento , Cromatografia Gasosa-Espectrometria de Massas , Microextração em Fase Sólida , Vitis/química , Compostos Orgânicos Voláteis/isolamento & purificação
2.
Molecules ; 26(23)2021 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-34885990

RESUMO

(1) Background: Solid phase microextraction (SPME)-Arrow is a new extraction technology recently employed in the analysis of volatiles in food materials. Grape volatile organic compounds (VOC) have a crucial role in the winemaking industry due to their sensory characteristics of wine.; (2) Methods: Box-Behnken experimental design and response surface methodology were used to optimise SPME-Arrow conditions (extraction temperature, incubation time, exposure time, desorption time). Analyzed VOCs were free VOCs directly from grape skins and bound VOCs released from grape skins by acid hydrolysis.; (3) Results: The most significant factors were extraction temperature and exposure time for both free and bound VOCs. For both factors, an increase in their values positively affected the extraction efficiency for almost all classes of VOCs. For free VOCs, the optimum extraction conditions are: extraction temperature 60 °C, incubation time 20 min, exposure time 49 min, and desorption time 7 min, while for the bound VOCs are: extraction temperature 60 °C, incubation time 20 min, exposure time 60 min, desorption time 7 min.; (4) Conclusions: Application of the optimized method provides a powerful tool in the analysis of major classes of volatile organic compounds from grape skins, which can be applied to a large number of samples.


Assuntos
Produtos Agrícolas/química , Cromatografia Gasosa-Espectrometria de Massas/normas , Extratos Vegetais/análise , Microextração em Fase Sólida/normas , Vitis/química , Compostos Orgânicos Voláteis/análise , Ácidos/análise , Ácidos/isolamento & purificação , Álcoois/análise , Álcoois/isolamento & purificação , Temperatura Alta , Monoterpenos/análise , Monoterpenos/isolamento & purificação , Norisoprenoides/análise , Norisoprenoides/isolamento & purificação , Extratos Vegetais/isolamento & purificação , Compostos Orgânicos Voláteis/isolamento & purificação , Vinho/análise
3.
Molecules ; 26(4)2021 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-33562181

RESUMO

The African weaver ant, Oecophylla longinoda, is used as a biological control agent for the management of pests. The ant has several exocrine glands in the abdomen, including Dufour's, poison, rectal, and sternal glands, which are associated with pheromone secretions for intra-specific communication. Previous studies have analyzed the gland secretions of Dufour's and poison glands. The chemistry of the rectal and sternal glands is unknown. We re-analyzed the secretions from Dufour's and poison glands plus the rectal and sternal glands to compare their chemistries and identify additional components. We used the solid-phase microextraction (SPME) technique to collect gland headspace volatiles and solvent extraction for the secretions. Coupled gas chromatography-mass spectrometry (GC-MS) analysis detected a total of 78 components, of which 62 were being reported for the first time. These additional components included 32 hydrocarbons, 12 carboxylic acids, 5 aldehydes, 3 alcohols, 2 ketones, 4 terpenes, 3 sterols, and 1 benzenoid. The chemistry of Dufour's and poison glands showed a strong overlap and was distinct from that of the rectal and sternal glands. The different gland mixtures may contribute to the different physiological and behavioral functions in this ant species.


Assuntos
Formigas/química , Glândulas Exócrinas/química , Controle Biológico de Vetores , Abdome , Álcoois/química , Álcoois/isolamento & purificação , Aldeídos/química , Aldeídos/isolamento & purificação , Animais , Formigas/metabolismo , Ácidos Carboxílicos/química , Ácidos Carboxílicos/isolamento & purificação , Cromatografia Gasosa-Espectrometria de Massas , Hidrocarbonetos/química , Hidrocarbonetos/isolamento & purificação , Cetonas/química , Cetonas/isolamento & purificação , Feromônios/biossíntese , Feromônios/química , Feromônios/isolamento & purificação , Microextração em Fase Sólida , Esteróis/química , Esteróis/isolamento & purificação , Terpenos/química , Terpenos/isolamento & purificação
4.
Chem Biodivers ; 17(10): e2000526, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32652902

RESUMO

The present study was aimed at analyzing the chemical components of the essential oil from six Pyrrosia species by GC/MS and evaluating their in vitro antibacterial activities. Seventy volatile compounds were identified in the essential oil of six Pyrrosia samples. The identified volatile components were divided into following nine categories: aldehydes, terpenoids, fatty acids, ketones, furans, hydrocarbons, alcohols, esters, and phenols. The major components of the essential oil were 2,4-pentadienal, phytol and nonanal. The antimicrobial assays showed that the essential oils from Pyrrosia samples exhibited a broad-spectrum antimicrobial activity. However, P. lingua had the highest antibacterial activity against Staphylococcus aureus (ATCC 25923) with a minimum inhibitory concentration (MIC) of 2.5 µL/mL. This article is the first report of the chemical components and antimicrobial activity of the essential oil from six Pyrrosia species, which will lay the foundation for developing medicinal resources from Pyrrosia fronds.


Assuntos
Antibacterianos/farmacologia , Óleos Voláteis/farmacologia , Polypodiaceae/química , Staphylococcus aureus/efeitos dos fármacos , Álcoois/química , Álcoois/isolamento & purificação , Álcoois/farmacologia , Aldeídos/química , Aldeídos/isolamento & purificação , Aldeídos/farmacologia , Antibacterianos/química , Antibacterianos/isolamento & purificação , Ésteres/química , Ésteres/isolamento & purificação , Ésteres/farmacologia , Ácidos Graxos/química , Ácidos Graxos/isolamento & purificação , Ácidos Graxos/farmacologia , Furanos/química , Furanos/isolamento & purificação , Furanos/farmacologia , Hidrocarbonetos/química , Hidrocarbonetos/isolamento & purificação , Hidrocarbonetos/farmacologia , Cetonas/química , Cetonas/isolamento & purificação , Cetonas/farmacologia , Testes de Sensibilidade Microbiana , Óleos Voláteis/química , Óleos Voláteis/isolamento & purificação , Fenóis/química , Fenóis/isolamento & purificação , Fenóis/farmacologia , Especificidade da Espécie , Terpenos/química , Terpenos/isolamento & purificação , Terpenos/farmacologia
5.
Molecules ; 25(10)2020 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-32423117

RESUMO

The aim of this study was to evaluate the development of volatile compounds in yogurt samples obtained from goats fed a dietary supplementation with olive leaves (OL). For this purpose, thirty Saanen goats were divided into two homogeneous groups of 15 goats each: a control group that received a standard diet (CG) and an experimental group whose diet was supplemented with olive leaves (OLG). The trial lasted 28 days, at the end of which the milk of each group was collected and used for yogurt production. Immediately after production, and after 7 days of storage at 4 °C in the absence of light, the yogurt samples were characterized in terms of fatty acid profile, oxidative stability and volatile compounds by the solid-phase microextraction (SPME)-GC/MS technique. Dietary OL supplementation positively affected the fatty acid composition, inducing a significant increase in the relative proportion of unsaturated fatty acids, mainly oleic acid (C18:1 cis9) and linolenic acid (C18:3). With regard to the volatile profile, both in fresh and yogurt samples stored for 7 days, the OL supplementation induced an increase in free fatty acids, probably due to an increase in lipolysis carried out by microbial and endogenous milk enzymes. Specifically, the largest variations were found for C6, C7, C8 and C10 free fatty acids. In the same samples, a significant decrease in aldehydes, mainly heptanal and nonanal, was also detected, supporting-at least in part-an improvement in the oxidative stability. Moreover, alcohols, esters and ketones appeared lower in OLG samples, while no significant variations were observed for lactones. These findings suggest the positive role of dietary OL supplementation in the production of goats' milk yogurt, with characteristics potentially indicative of an improvement in nutritional properties and flavor.


Assuntos
Ração Animal , Ácidos Graxos não Esterificados/isolamento & purificação , Ácidos Graxos Insaturados/isolamento & purificação , Olea/química , Compostos Orgânicos Voláteis/isolamento & purificação , Iogurte/análise , Álcoois/classificação , Álcoois/isolamento & purificação , Aldeídos/isolamento & purificação , Animais , Ésteres/classificação , Ésteres/isolamento & purificação , Ácidos Graxos não Esterificados/classificação , Ácidos Graxos Insaturados/classificação , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Cabras , Cetonas/classificação , Cetonas/isolamento & purificação , Lactonas/classificação , Lactonas/isolamento & purificação , Leite/química , Folhas de Planta/química , Microextração em Fase Sólida/métodos , Compostos Orgânicos Voláteis/classificação
6.
Sensors (Basel) ; 19(10)2019 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-31137611

RESUMO

Transdermal alcohol biosensors have the ability to detect the alcohol that emanates from the bloodstream and diffuses through the skin. However, previous biosensors have suffered from long-term fouling of the sensor element and drift in the resulting sensor readings over time. Here, we report a wearable alcohol sensor platform that solves the problem of sensor fouling by enabling drift-free signals in vivo for up to 24 h and an interchangeable cartridge connection that enables consecutive days of measurement. We demonstrate how alcohol oxidase enzyme and Prussian Blue can be combined to prevent baseline drift above 25 nA, enabling sensitive detection of transdermal alcohol. Laboratory characterization of the enzymatic alcohol sensor demonstrates that the sensor is mass-transfer-limited by a diffusion-limiting membrane of lower permeability than human skin and a linear sensor range between 0 mM and 50 mM. Further, we show continuous transdermal alcohol data recorded with a human subject for two consecutive days. The non-invasive sensor presented here is an objective alternative to the self-reports used commonly to quantify alcohol consumption in research studies.


Assuntos
Oxirredutases do Álcool/química , Álcoois/isolamento & purificação , Técnicas Biossensoriais , Etanol/isolamento & purificação , Álcoois/química , Etanol/química , Ferrocianetos/química , Humanos , Dispositivos Eletrônicos Vestíveis
7.
Molecules ; 24(17)2019 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-31454898

RESUMO

A reliable Headspace-Solid Phase Microextraction (HS-SPME) method was developed for the determination of polar volatile components of commercial nut-based milk alternative drinks prior to Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Under the optimum extraction conditions, a divinylbenzene (DVB)/Carboxen™ CAR)/polydimethylsiloxane (PDMS) fiber was used and 2 mL of sample was heated at 60 °C for 40 min under stirring, without salt addition. Ten compounds from different chemical classes (heptane, a-pinene, toluene, 2-methylpyrazine, 3-heptanone, heptanal, 2-octanone, 1-heptanol, benzaldehyde and 1-octanol) were chosen as model analytes for quantification. Limits of detection and limits of quantification were found to be 0.33-1.67 ng g-1 and 1-5 ng g-1, accordingly. Good linearity, precision and accuracy were obtained as well as a wide linear range. The proposed method was successfully applied to various beverages including almond milk, walnut milk, peanut milk and almond chocolate milk. More than 70 volatile compounds were detected in the different samples. Most of the detected volatiles were aldehydes, ketones and alcohols. This technique can be used for the determination of volatile compounds in nut-based beverages, to detect compositional changes during storage and technological treatment used for their production.


Assuntos
Bebidas/análise , Nozes/química , Compostos Orgânicos Voláteis/análise , Álcoois/isolamento & purificação , Aldeídos/isolamento & purificação , Cromatografia Gasosa-Espectrometria de Massas , Cetonas/isolamento & purificação , Limite de Detecção , Microextração em Fase Sólida , Compostos Orgânicos Voláteis/isolamento & purificação
8.
Molecules ; 24(16)2019 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-31426356

RESUMO

Halitosis and submandibular abscesses are examples of mouth-related diseases with the possible bacterial origin. Salivary volatile organic compounds (VOCs) are potential biomarkers of them, once they can be addressed as metabolites of bacterial activity. Healthy patients (n = 15), subjects with submandibular abscesses located in fascial deep space (n = 10), and subjects with halitosis (n = 5) were enrolled in the study. Saliva samples were subjected to headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC/MS) analysis. A total number of 164 VOCs was detected by the developed methodology, 23 specific for halitosis and 41 for abscess. Halitosis' profiles were characterized by a larger number of sulfur compounds, while for abscess they had a higher variety of alcohols, aldehydes, and hydrocarbons-biomarkers of inflammatory processes. Principal components analysis allowed visualization of clusters formed according to the evaluated conditions. Kruskal-Wallis test indicated that 39 VOCs presented differentiated responses between the studied groups, with statistical relevance (p < 0.05). Random forest was applied, and a prediction model based on eight VOCs (2-butanone, methyl thioacetate, 2-methylbutanoic acid, S-methyl pentanethioate, dimethyl tetrasulfide, indolizine, pentadecane, and octadecanal) provided 100% of sensitivity, 82% of specificity, and 91% of balanced accuracy, indicating the specific presence of submandibular abscess.


Assuntos
Abscesso/diagnóstico , Álcoois/isolamento & purificação , Aldeídos/isolamento & purificação , Halitose/diagnóstico , Hidrocarbonetos/isolamento & purificação , Compostos de Enxofre/isolamento & purificação , Abscesso/metabolismo , Abscesso/patologia , Adulto , Idoso , Álcoois/classificação , Aldeídos/classificação , Biomarcadores/análise , Estudos de Casos e Controles , Giro Denteado/metabolismo , Giro Denteado/patologia , Diagnóstico Diferencial , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Halitose/metabolismo , Halitose/patologia , Humanos , Hidrocarbonetos/classificação , Masculino , Mandíbula/metabolismo , Mandíbula/patologia , Pessoa de Meia-Idade , Análise de Componente Principal , Saliva/química , Sensibilidade e Especificidade , Microextração em Fase Sólida/métodos , Compostos de Enxofre/classificação , Compostos Orgânicos Voláteis
9.
Anal Chem ; 90(22): 13212-13216, 2018 11 20.
Artigo em Inglês | MEDLINE | ID: mdl-30352501

RESUMO

The absolute-configuration determination of natural products and synthetic compounds with stereogenic centers is very important because stereoisomers dramatically and differentially affect many crucial properties, such as physical behaviors and biological functions. Despite several established methods for determining the absolute configuration, significant unmet needs for new methods still exist owing to the specific limitations of established methodologies. Here, we present a simple, optimized, new chemical-derivative method that utilizes competing enantioselective acylation followed by LC/MS analysis, and we demonstrate its successful application in determining the absolute configuration of a secondary alcohol in natural products with multiple reactive functional groups. This new development relies on the enantiomeric pair of homobenzotetramisole (HBTM) catalysts exhibiting adequate kinetic resolution for acylation of the secondary alcohol, and then the fast reaction was quantitatively confirmed via LC/MS as the characterization technique for the enantioselective transformations. Our new approach was successfully applied to determine the absolute configuration of one secondary alcohol in compound 1, which has other hydroxyl groups to be reacted. The identified stereocenter of 1 was verified by previously established methods including quantum chemical electronic-circular-dichroism (ECD) calculations, computational NMR-chemical-shift calculations followed by DP4+ calculations, and modified Mosher's method. In addition, our method was applied to five known naturally occurring compounds, which led to the successful verification of their absolute configurations. Our newly developed method using the HBTM catalyst provides a highly sensitive, simple, and cost- and time-effective approach and an applicable and convenient analytical method for determining the absolute configuration of one secondary alcohol in natural products.


Assuntos
Álcoois/química , Cromatografia Líquida/métodos , Espectrometria de Massas/métodos , Aceraceae/química , Acilação , Álcoois/isolamento & purificação , Produtos Biológicos/química , Catálise , Catequina/química , Cinética , Lauratos/química , Estrutura Molecular , Monoglicerídeos/química , Estereoisomerismo , Tricotecenos/química
10.
Electrophoresis ; 39(7): 924-932, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29314158

RESUMO

In this work, an organic-inorganic hybrid boronate affinity monolithic column was prepared via "one-pot" process using 4-vinylphenylboronic acid as organic monomer and divinylbenzene as cross-linker. The effects of reaction temperature, solvents and composition of organic monomers on the column properties (e.g. morphology, permeability, and mechanical stability) were investigated. A series of test compounds including small neutral molecules, aromatic amines, and cis-diol compounds were used to evaluate the retention behaviors of the prepared hybrid monolithic column. The results demonstrated that the prepared hybrid monolith exhibited mixed-interactions including hydrophilicity, cation exchange, and boronate affinity interaction. The run-to-run, day-to-day and batch-to-batch reproducibilities of the prepared hybrid monolith for thiourea's retention time were satisfactory with the relative standard deviations (RSDs) less than 0.09, 1.45 and 4.05% (n = 3), respectively, indicating the effectiveness and practicability of the proposed method.


Assuntos
Álcoois/química , Ácidos Borônicos/química , Compostos de Vinila/química , Álcoois/isolamento & purificação , Aminas/química , Eletrocromatografia Capilar , Cromatografia de Afinidade , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Isomerismo , Estrutura Molecular , Polimerização , Dióxido de Silício/química , Relação Estrutura-Atividade
11.
J Chem Ecol ; 44(6): 534-546, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29752680

RESUMO

Termite colonies are almost always founded by a pair of winged dispersers, in spite of the high costs and low success rates inherent in independent colony foundation. The dispersal flights of imagoes from natal colonies are followed by mate search, mediated by sex-pairing pheromones. Here, we studied the chemistry of sex-pairing pheromones and the related aspects of mate search in winged imagoes of two facultatively parthenogenetic species, Embiratermes neotenicus and Silvestritermes minutus, and an additional species from the same subfamily, Silvestritermes heyeri. All three species are widespread in the Neotropics, including the rainforests of French Guiana. After the dispersal flight and spontaneous loss of wings, females expose their hypertrophied tergal glands situated under abdominal tergites VIII - X. The females are attractive to males and, upon direct contact, the two sexes form characteristic tandems. Chemical analyses indicated that the females secrete species-specific combinations of unbranched, unsaturated C12 primary alcohols from the tergal glands, (3Z,6Z,8E)-dodeca-3,6,8-trien-1-ol (approx. 200 pg per female) and (3Z)-dodec-3-enol (185 pg) in E. neotenicus, (3Z,6Z)-dodeca-3,6-dien-1-ol (3500 pg) in S. heyeri, and (3Z,6Z)-dodeca-3,6-dien-1-ol (300 pg) and (3Z)-dodec-3-enol (50 pg) in S. minutus. (3Z,6Z,8E)-Dodeca-3,6,8-trien-1-ol and (3Z,6Z)-dodeca-3,6-dien-1-ol act as major pheromone components in the respective species and mimic the function of female tergal gland extracts in electrophysiological and behavioral experiments. Biologically relevant amounts of the third compound, (3Z)-dodec-3-enol, elicited non-significant reactions in males of E. neotenicus and S. minutus, and slight synergistic effects in males of S. minutus when tested in combination with the major component.


Assuntos
Isópteros/fisiologia , Atrativos Sexuais/química , Comportamento Sexual Animal/fisiologia , Álcoois/química , Álcoois/isolamento & purificação , Animais , Glândulas Exócrinas/metabolismo , Glândulas Exócrinas/patologia , Feminino , Cromatografia Gasosa-Espectrometria de Massas/métodos , Masculino , Atrativos Sexuais/análise , Atrativos Sexuais/isolamento & purificação , Microextração em Fase Sólida , Especificidade da Espécie , Estereoisomerismo
12.
Molecules ; 23(2)2018 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-29439462

RESUMO

Milled Roselle (Hibiscus sabdariffa L.) seeds of the UMKL cultivar were analyzed for proximate composition, water and oil absorption capacity, and the influence of storage conditions on storage stability. The storage stability was determined under four types of conditions: light/oxygen (air) (LO), light/nitrogen (LN), darkness/oxygen (air) (DO), and darkness/nitrogen (DN) while monitoring for seven consecutive months. During the storage period, the formation of volatiles was determined using dynamic headspace sampling and Gas Chromatography-Mass Spectrometry (GC-MS) analysis. In total, 85 volatiles were identified, mainly aldehydes, alcohols, ketones, furans, and acids indicating lipid oxidation. It is recommended that milled Roselle seeds should be flushed with nitrogen and stored in darkness. Under these conditions, the seeds can be stored for at least three months without changes in volatile profile. This is important to ensure the good quality of milled Roselle seeds for further commercialization.


Assuntos
Armazenamento de Alimentos/métodos , Hibiscus/química , Sementes/química , Compostos Orgânicos Voláteis/química , Álcoois/química , Álcoois/isolamento & purificação , Álcoois/metabolismo , Aldeídos/química , Aldeídos/isolamento & purificação , Aldeídos/metabolismo , Furanos/química , Furanos/isolamento & purificação , Furanos/metabolismo , Cromatografia Gasosa-Espectrometria de Massas , Hibiscus/efeitos dos fármacos , Hibiscus/metabolismo , Cetonas/química , Cetonas/isolamento & purificação , Cetonas/metabolismo , Luz , Nitrogênio/farmacologia , Oxirredução , Oxigênio/farmacologia , Sementes/efeitos dos fármacos , Sementes/metabolismo , Compostos Orgânicos Voláteis/isolamento & purificação , Compostos Orgânicos Voláteis/metabolismo
13.
Metab Eng ; 39: 102-109, 2017 01.
Artigo em Inglês | MEDLINE | ID: mdl-27816771

RESUMO

Monolignols are important plant metabolites involved in lignin biosynthesis. Their derivatives exhibit various physiological and pharmaceutical functions. Here, efficient enzymes were selected to construct p-coumaryl alcohol biosynthetic pathway and the titer reached 501.8±41.4mg/L under optimized conditions. The pathway was further extended to produce caffeyl alcohol and coniferyl alcohol by introducing a hydroxylase and methyltransferases. However, the promiscuity of the hydroxylase HpaBC led to the formation of an instable intermediate L-dopa from tyrosine, causing loss of the carbon sources. To solve this problem, microbial co-cultures were designed to minimize the accessibility of HpaBC to tyrosine. With the optimal inoculation ratio, 401.0±15.3mg/L of caffeyl alcohol was produced, which is nearly 12 times higher than that of the mono-culture. The titer reached 854.1±44.6mg/L in scale-up production. The same strategy was used for coniferyl alcohol production. Limited by the activity of methyltransferases, the highest titer was 124.9±5.1mg/L with 232.9±15.1mg/L of caffeyl alcohol accumulated. To the best of our knowledge, this is the first report about microbial production of caffeyl alcohol and coniferyl alcohol. This work also demonstrated the promising potential of microbial co-cultures for prevention of side-reactions.


Assuntos
Álcoois/metabolismo , Vias Biossintéticas/fisiologia , Proteínas de Escherichia coli/metabolismo , Escherichia coli/fisiologia , Engenharia Metabólica/métodos , Fenóis/metabolismo , Álcoois/isolamento & purificação , Proteínas de Escherichia coli/genética , Melhoramento Genético/métodos , Redes e Vias Metabólicas/fisiologia , Fenóis/isolamento & purificação
14.
Electrophoresis ; 38(19): 2513-2520, 2017 10.
Artigo em Inglês | MEDLINE | ID: mdl-28678407

RESUMO

Natural amino acids are well known to form coordination polymers with transition metal ions. In this study, six homochiral metal-organic frameworks constructed from Zn2+ or Co2+ ions and various enantiopure amino acid (L-tyrosine, L-histidine, L-tryptophan and L-glutamic acid), namely [Zn(L-tyr)]n (L-tyrZn), [Zn4 (btc)2 (Hbtc)(L-His)2 (H2 O)4 ]·1.5H2 O, {[Zn2 (L-trp)2 (bpe)2 (H2 O)2 ]·2H2 O·2NO3 }n , [Co2 (L-Trp)(INT)2 (H2 O)2 (ClO4 )], [Co2 (sdba)((L-Trp)2 ] and [Co(L-Glu)(H2 O)·H2 O]∞ , were synthesized according to the methods previously reported in the literature. The six homochiral MOFs were explored as the chiral stationary phases for high-performance liquid chromatographic separation of enantiomers using hexane/isopropanol or hexane/dichloromethane as mobile phase. Various types of enantiomers such as alcohols, amines, ketones, ethers, organic acids, etc. can be resolved on these homochiral MOF columns. The results revealed that the enantioseletivities of homochiral MOFs based on amino acids as chiral bridging ligands used as stationary phases are practical in HPLC.


Assuntos
Aminoácidos/química , Cromatografia Líquida de Alta Pressão/métodos , Estruturas Metalorgânicas/química , Polímeros/química , 2-Propanol/química , Álcoois/isolamento & purificação , Aminas/isolamento & purificação , Cromatografia Líquida de Alta Pressão/instrumentação , Éteres/isolamento & purificação , Hexanos/química , Cetonas/isolamento & purificação , Cloreto de Metileno/química , Estereoisomerismo
15.
Biotechnol Bioeng ; 114(9): 1946-1958, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28464284

RESUMO

Biosynthesis of advanced biofuels by engineered non-natural microorganisms has been proposed to be the most promising approach for the replacement of dwindling fossil fuel resources. Brevibacterium flavum (Bf) is a model brevibacterium aerobe which lacks basic and applied research that could enable this species to produce biofuels. There are no reports regarding engineering this microorganism to produce advanced alcohols before. Here, for the first time, we developed the bacterium as a novel biosynthetic platform for advanced alcohols production via the mutagenesis and engineering to produce 2-ketoacids derived alcohols. In order to enhance the strain's capability of producing advanced alcohols, we preferentially improved intrinsic metabolism ability of the strain to obtain improved expression host (IEH) via generating mutagenesis libraries by whole cell mutagenesis (WCM). The IEH was determined via screening out the mutant strain with the highest production of branched-chain organic acids (BCOA) using high throughput screening method.. Subsequently, a novel vector system for Bf was established, and the corresponding biosynthetic pathway of directing carbon flux into the target advanced alcohols was recruited to make the bacterium possess the capability of producing advanced alcohols and further enhance the production using the IEH. Specifically, we generated bioengineered strains that were able to synthesize up to the highest 5362 and 4976 mg/L isobutanol, 1945 and 1747 mg/L 2-methyl-1-butanol (2 MB), and 785.34 and 781 mg/L 3-methyl-1-butanol (3 MB) from pure glucose and duckweed substrates, respectively. Our findings confirmed the feasibility and potential of using Bf as a novel biosynthetic platform to generate advanced biofuels with glucose and inexpensive renewable feedstock-duckweed as a fermentation substrate. Biotechnol. Bioeng. 2017;114: 1946-1958. © 2017 Wiley Periodicals, Inc.


Assuntos
Álcoois/metabolismo , Biocombustíveis/microbiologia , Vias Biossintéticas/fisiologia , Brevibacterium flavum/fisiologia , Cetoácidos/metabolismo , Engenharia Metabólica/métodos , Energia Renovável , Álcoois/isolamento & purificação , Melhoramento Genético/métodos
16.
Molecules ; 22(5)2017 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-28468275

RESUMO

This study investigated the composition of volatile compounds in two pummelo cultivars, including 'Shatian' and 'Guanxi', cultivated in different regions of China with the aim of studying the effect of cultivar and cultivation condition on biosynthesis of volatile compounds in pummelo. Volatile compounds were extracted from pummelo juice using head-space microextraction and then analyzed using gas chromatography coupled with mass spectrometry. Results showed that a total of 49 volatile compounds was detected in the study, including 11 aldehydes, 7 alcohols, 3 ketones, 7 esters, 19 terpenes and 2 other volatiles. The 'Guanxi' pummelo cultivar possessed a more complex composition of volatile compounds compared with the 'Shatian' cultivar. Meanwhile, the volatile compounds appeared to exhibit a higher concentration in the 'Guanxi' cultivar samples than the 'Shatian' cultivar. Cluster analysis revealed that the 'Guanxi' cultivar samples from the different regions were grouped together, whereas the 'Shatian' cultivar samples were assembled. Principal component analysis showed that an obvious separation was observed between the 'Guanxi' and 'Shatian' cultivar. However, the 'Shatian-SC15' was significantly separated from the other 'Shatian' cultivar samples. These indicated that cultivar genotype was the primary factor that determined the volatile profile of the pummelo cultivar. Cultivation region might affect the biosynthesis of volatile compounds, resulting in the differentiation of the volatile composition in each pummelo cultivar.


Assuntos
Citrus/química , Frutas/química , Terpenos/isolamento & purificação , Álcoois/química , Álcoois/isolamento & purificação , Aldeídos/química , Aldeídos/isolamento & purificação , China , Análise por Conglomerados , Cetonas/química , Cetonas/isolamento & purificação , Análise de Componente Principal , Terpenos/química , Compostos Orgânicos Voláteis/química , Compostos Orgânicos Voláteis/isolamento & purificação
17.
Molecules ; 22(9)2017 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-28885582

RESUMO

Viticultural practices influence both grape and wine quality. The influence of training systems on volatile composition was investigated for Albariño wine from Rías Baixas AOC in Northwest Spain. The odoriferous contribution of the compounds to the wine aroma was also studied. Volatile compounds belonging to ten groups (alcohols, C6-compounds, ethyl esters, acetates, terpenols, C13-norisoprenoids, volatile phenols, volatile fatty acids, lactones and carbonyl compounds) were determined in Albariño wines from different training systems, Vertical Shoot-Positioned (VSP), Scott-Henry (SH), Geneva Double-Curtain (GDC), Arch-Cane (AC), and Parral (P) during 2010 and 2011 vintages. Wines from GDC showed the highest total volatile composition with the highest concentrations of alcohols, ethyl esters, fatty acids, and lactones families. However, the highest levels of terpenes and C13-norisoprenoids were quantified in the SH system. A fruitier aroma was observed in Albariño wines from GDC when odor activity values were calculated.


Assuntos
Agricultura/métodos , Frutas/metabolismo , Odorantes/análise , Compostos Orgânicos Voláteis/metabolismo , Vinho/análise , Álcoois/química , Álcoois/isolamento & purificação , Álcoois/metabolismo , Ácidos Graxos/química , Ácidos Graxos/isolamento & purificação , Ácidos Graxos/metabolismo , Frutas/química , Frutas/crescimento & desenvolvimento , Cromatografia Gasosa-Espectrometria de Massas , Norisoprenoides/química , Norisoprenoides/isolamento & purificação , Norisoprenoides/metabolismo , Fenóis/química , Fenóis/isolamento & purificação , Fenóis/metabolismo , Espanha , Terpenos/química , Terpenos/isolamento & purificação , Terpenos/metabolismo , Vitis/crescimento & desenvolvimento , Vitis/metabolismo , Compostos Orgânicos Voláteis/química , Compostos Orgânicos Voláteis/isolamento & purificação
18.
Metab Eng ; 38: 98-104, 2016 11.
Artigo em Inglês | MEDLINE | ID: mdl-27424209

RESUMO

Industrial gas-to-liquid (GTL) technologies are well developed. They generally employ syngas, require complex infrastructure, and need high capital investment to be economically viable. Alternatively, biological conversion has the potential to be more efficient, and easily deployed to remote areas on relatively small scales for the utilization of otherwise stranded resources. The present study demonstrates a novel biological GTL process in which engineered Escherichia coli converts C2-C4 gaseous alkenes into liquid diols. Diols are versatile industrially important chemicals, used routinely as antifreeze agents, polymer precursors amongst many other applications. Heterologous co-expression of a monooxygenase and an epoxide hydrolase in E. coli allows whole cell conversion of C2-C4 alkenes for the formation of ethylene glycol, 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol at ambient temperature and pressure in one pot. Increasing intracellular NADH supply via addition of formate and a formate dehydrogenase increases ethylene glycol production titers, resulting in an improved productivity of 9mg/L/h and a final titer of 250mg/L. This represents a novel biological method for GTL conversion of alkenes to industrially valuable diols.


Assuntos
Álcoois/metabolismo , Alcenos/metabolismo , Epóxido Hidrolases/genética , Escherichia coli/fisiologia , Gases/metabolismo , Engenharia Metabólica/métodos , Oxigenases de Função Mista/genética , Álcoois/isolamento & purificação , Epóxido Hidrolases/metabolismo , Proteínas de Escherichia coli/genética , Proteínas de Escherichia coli/metabolismo , Melhoramento Genético , Redes e Vias Metabólicas/genética , Oxigenases de Função Mista/metabolismo , Transição de Fase , Soluções/isolamento & purificação , Soluções/metabolismo
19.
Prev Sci ; 17(6): 689-99, 2016 08.
Artigo em Inglês | MEDLINE | ID: mdl-27167074

RESUMO

Despite the evidence base, alcohol screening and brief intervention (ASBI) have rarely been integrated into routine clinical practice. The aim of this study is to identify strategies that could tackle barriers to ASBI implementation in general practice by involving primary healthcare professionals and addiction prevention experts. A three-round online Delphi study was carried out in the Netherlands. The first-round questionnaire consisted of open-ended questions to generate ideas about strategies to overcome barriers. In the second round, participants were asked to indicate how applicable they found each strategy. Items without consensus were systematically fed back with group median ratings and interquartile range (IQR) scores in the third-round questionnaire. In total, 39 out of 69 (57 %) invited participants enrolled in the first round, 214 participants completed the second round, and 144 of these (67 %) completed the third-round questionnaire. Results show that participants reached consensus on 59 of 81 strategies, such as the following: (1) use of E-learning technology, (2) symptom-specific screening by general practitioners (GPs) and/or universal screening by practice nurses, (3) reimbursement incentives, (4) supportive materials, (5) clear guidelines, (6) service provision of addiction care centers, and (7) more publicity in the media. This exploratory study identified a broad set of strategies that could potentially be used for overcoming barriers to ASBI implementation in general practice and paves the way for future research to experimentally test the identified implementation strategies using multifaceted approaches.


Assuntos
Alcoolismo/diagnóstico , Alcoolismo/prevenção & controle , Álcoois/isolamento & purificação , Atenção à Saúde/métodos , Difusão de Inovações , Medicina Geral , Técnica Delphi , Humanos , Países Baixos , Inquéritos e Questionários
20.
Chem Pharm Bull (Tokyo) ; 64(6): 638-43, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27250798

RESUMO

Chemical study of the leaves of Meliosma pinnata spp. arnottiana afforded five sulfated glucosides of oct-1-en-3-ol (1) and cyclic linalool derivatives (2-5), and two megastigmanes (6, 7). Their structures were elucidated by extensive investigation of one- and two-dimensional NMR spectroscopic data, and the absolute structures of the megastigmanes were determined by the modified Mosher's method.


Assuntos
Álcoois/química , Glucosídeos/química , Magnoliopsida/química , Monoterpenos/química , Norisoprenoides/química , Sulfatos/química , Álcoois/isolamento & purificação , Conformação Molecular , Monoterpenos/isolamento & purificação , Norisoprenoides/isolamento & purificação , Folhas de Planta/química
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