RESUMO
The organoleptic properties of plant-based meat alternatives do not meet consumer expectations due to the lack of characteristic flavors resembling meat. To address this challenge, a fermentation system utilizing Laetiporussulphureus was developed to generate a meat-like and fatty flavor from a vegetable source, onion. By means of multiple stir bar sorptive extraction and gas chromatography-mass spectrometry-olfactometry, an unsaturated aldehyde, (E,Z)-2,4-decadienal, which imparts a tallow-like and fatty odor, and a sulfurous compound benzothiazole, with a broth-like odor were identified, which well contributed to the characteristic odor of the supernatant. (E,Z)-2,4-Decadienal as the most important odorant (odor activity value = 206) was biosynthesized by transformation of linoleic acid with L.sulphureus, as revealed by isotopic tracing experiments. For the first time in Basidiomycota, the biogenetic pathway of (E,Z)-2,4-decadienal from linoleic acid was proposed.
Assuntos
Aldeídos , Fermentação , Cromatografia Gasosa-Espectrometria de Massas , Odorantes , Cebolas , Odorantes/análise , Cebolas/química , Aldeídos/análise , Aldeídos/metabolismo , Basidiomycota/metabolismo , Ácido Linoleico/metabolismo , Ácido Linoleico/análise , Alcadienos/metabolismo , OlfatometriaRESUMO
Dehydration is an effective method for the long-term storage and aroma retention of gonggan (Citrus sinensis Osb. 'Deqing Gonggan'), which is a Chinese variety of citrus, with unique and characteristic floral, fruity, and citrus flavors. However, the aroma profiles of gonggans prepared using oven- and freeze-drying, the most widely-used drying methods, remain unclear. In this study, a total of 911 volatile organic compounds (VOCs) were detected in dried gonggan. These were primarily composed of alcohols (7.69%), aldehydes (7.03%), esters (15.38%), ketones (7.58%), and terpenoids (23.19%). A total of 67 odorants contributed significantly to the overall aroma of dried gonggans, with the major odor qualities being detected as green, citrus, fruity, floral, and sweet. These were mainly attributed to the presence of aldehydes, esters, and terpenoids. Freeze-drying was more effective in maintaining the unique citrus and mandarin-like aromas attributed to compounds such as limonene, citrial, ß-myrcene, ß-pinene, and γ-terpinene. Moreover, (E,E)-2,4-decadienal had the highest relative odor activity value (rOAV) in freeze-dried gonggans, followed by (E)-2-nonenal, furaneol, (E, E)-2, 4-nonadienal, and E-2-undecenal. Oven-drying promoted the accumulation of terpenes such as octatriene, trans-ß-ocimene, cyclohexanone, copaene, and É-irone, imparting a soft aroma of flowers, fruits, and sweet. Increasing the temperature led to an increase in existing VOCs or the generation of new VOCs through phenylpropanoid, terpenoid, and fatty acid metabolism. The findings of this study offer insights into an optimized procedure for producing high-quality dried gonggans. These insights can be valuable for the fruit-drying industry, particularly for enhancing the quality of dried fruits.
Assuntos
Liofilização , Odorantes , Terpenos , Compostos Orgânicos Voláteis , Compostos Orgânicos Voláteis/análise , Odorantes/análise , Terpenos/análise , Frutas/química , Citrus sinensis/química , Dessecação/métodos , Aldeídos/análise , Cromatografia Gasosa-Espectrometria de Massas , Cetonas/análise , Monoterpenos Bicíclicos/análise , Ésteres/análise , Alcadienos/análise , Cicloexenos/análise , Manipulação de Alimentos/métodos , Monoterpenos Acíclicos , Monoterpenos Cicloexânicos , Alcenos , SesquiterpenosRESUMO
Diatoms are key primary producers across marine, freshwater, and terrestrial ecosystems. They are responsible for photosynthesis and secondary production that, in part, support complex food webs. Diatoms can produce phytochemicals that have transtrophic ecological effects which increase their competitive fitness. Polyunsaturated aldehydes (PUAs) are one class of diatom-derived phytochemicals that are known to have allelopathic and anti-herbivory properties. The anti-herbivory capability of PUAs results from their negative effect on grazer fecundity. Since their discovery, research has focused on their production by pelagic marine diatoms, and their effects on copepod egg production, hatching success, and juvenile survival and development. Few investigations have explored PUA production by the prolific suite of benthic marine diatoms, despite their importance to coastal trophic systems. In this study, we tested eight species of benthic diatoms for the production of the bioactive PUAs 2,4-heptadienal, 2,4-octadienal, and 2,4-decadienal. Benthic diatom species were isolated from the Salish Sea, an inland sea within the North Pacific ecosystem. All species were found to be producers of at least two PUAs in detectable concentrations, with five species producing all three PUAs in quantifiable concentrations. Our results indicate that production of PUAs from Salish Sea benthic diatoms may be widespread, and thus these compounds may contribute to benthic coastal food web dynamics through heretofore unrecognized pathways. Future studies should expand the geographic scope of investigations into benthic diatom PUA production and explore the effects of benthic diatoms on benthic consumer fecundity.
Assuntos
Aldeídos , Diatomáceas , Diatomáceas/metabolismo , Diatomáceas/química , Aldeídos/metabolismo , Aldeídos/análise , Oceano Pacífico , Animais , AlcadienosRESUMO
Sex pheromone analogs have high structural similarity to sex pheromone components. They also play a role in studying many agricultural pests. In our study, (Z, Z, Z)-3,6,9-nonadecadiene (Z3Z6Z9-19:Hy) was successfully synthesized, which is an analogue to 1 of 2 sex pheromone components of Ectropis grisescens Warren (Z, Z, Z)-3,6,9-octadecatriene (Z3Z6Z9-18:Hy), and it showed potential inhibition in experiments. In the electroantennogram test, Z3Z6Z9-19:Hy showed a dose-dependent response, and only measured half the response of Z3Z9-6,7-epo-18:Hy. However, the compound significantly reduced positive response of E. grisescens males by up to 70% in the Y-tube olfactometer. Furthermore, in the wind tunnel, it significantly inhibited all types of behavioral responses. The percentage of moths contacting the pheromone odor source was reduced even at the lowest dose tested. In silico study afterward, molecular docking results showed affinity between Z3Z6Z9-19:Hy and sensory neuron membrane protein 1. Our study revealed the potential of Z3Z6Z9-19:Hy as a sex pheromone inhibitor, which would provide new tools for monitoring and mating disruption of E. grisescens.
Assuntos
Antenas de Artrópodes , Mariposas , Atrativos Sexuais , Animais , Atrativos Sexuais/farmacologia , Mariposas/efeitos dos fármacos , Mariposas/fisiologia , Masculino , Antenas de Artrópodes/fisiologia , Antenas de Artrópodes/efeitos dos fármacos , Feminino , Alcadienos , Simulação de Acoplamento Molecular , Simulação por ComputadorRESUMO
Diarylpentanoids are synthesized to overcome curcumin's poor bioavailability and low stability to show enhanced anti-cancer effects. Little is known about the anti-cancer effects of diarylpentanoid MS17 (1,5-bis(2-hydroxyphenyl)-1,4-pentadiene-3-one) in colon cancer cells. This study aimed to elucidate molecular mechanisms and pathways modulated by MS17 in colon cancer based on proteomic profiling of primary SW480 and metastatic SW620 colon cancer cells. Cytotoxicity and apoptotic effects of MS17 were investigated using MTT assay, morphological studies, and Simple Western analysis. Proteomic profiling using LC/MS analysis identified differentially expressed proteins (DEPs) in MS17-treated cells, with further analysis in protein classification, gene ontology enrichment, protein-protein interaction network and Reactome pathway analysis. MS17 had lower EC50 values (SW480: 4.10 µM; SW620: 2.50 µM) than curcumin (SW480: 17.50 µM; SW620: 13.10 µM) with a greater anti-proliferative effect. MS17 treatment of 1× EC50 induced apoptotic changes in the morphology of SW480 and SW620 cells upon 24 h treatment. A total of 24 and 92 DEPs (fold change ≥ 1.50) were identified in SW480 and SW620 cells, respectively, upon MS17 treatment of 2× EC50 for 24 h. Pathway analysis showed that MS17 may induce its anti-cancer effects in both cells via selected DEPs associated with the top enriched molecular pathways. RPL and RPS ribosomal proteins, heat shock proteins (HSPs) and ubiquitin-protein ligases (UBB and UBC) were significantly associated with cellular responses to stress in SW480 and SW620 cells. Our findings suggest that MS17 may facilitate the anti-proliferative and apoptotic activities in primary (SW480) and metastatic (SW620) human colon cancer cells via the cellular responses to stress pathway. Further investigation is essential to determine the alternative apoptotic mechanisms of MS17 that are independent of caspase-3 activity and Bcl-2 protein expression in these cells. MS17 could be a potential anti-cancer agent in primary and metastatic colon cancer cells.
Assuntos
Alcadienos , Neoplasias do Colo , Curcumina , Humanos , Curcumina/farmacologia , Proteômica , Apoptose , Linhagem Celular Tumoral , Neoplasias do Colo/metabolismoRESUMO
"Intuition" is probably the most frequently used term in all Bion's writings. However, in order to understand its role in his thought it is essential to give it the clearest possible definition. The thesis of this article is that by intuition Bion means a "specific" psychoanalytic concept. It is thus possible to extract intuition from the vague and mystifying reading of it by some authors, whic runs the risk of falling into an empty "intuitionism". For Bion, intuition is a psychoanalytic function of the analyst, the principal factors of which are the various expressions of dream-thought and insight. Furthermore, within the frame of the post-Bionian theory of the analytic field, the author suggests adding to these factors the use of the "we" vertex (or we-ness), i.e. to regard virtually every fact of analysis as co-created. The aim is to make the very concept of "field" more accessible. Compared with the metaphor of the analytic field, the concept of we-ness has both greater clinical versatility and greater pregnancy on the metapsychological plane. Indeed, it more directly reflects a radically social conception of human subjectivity: what is known in contemporary speculative thought - in J-L. Nancy, for example - as the "ontology of we".
Assuntos
Alcadienos , Intuição , Feminino , Gravidez , Humanos , Metáfora , PolímerosRESUMO
Alkylidene cyclopropanes (ACPs) are valuable synthetic intermediates because of their constrained structure and opportunities for further diversification. Although routes to ACPs are known, preparations of ACPs with control of both the configuration of the cyclopropyl (R vs S) group and the geometry of the alkene (E vs Z) are unknown. We describe enzymatic cyclopropanation of allenes with ethyl diazoacetate (EDA) catalyzed by an iridium-containing cytochrome (Ir(Me)-CYP119) that controls both stereochemical elements. Two mutants of Ir(Me)-CYP119 identified by 6-codon (6c, VILAFG) saturation mutagenesis catalyze the formation of (E)-ACPs with -93% to >99% ee and >99:1 E/Z ratio with just three rounds of 96 mutants. By four additional rounds of mutagenesis, an enzyme variant was identified that forms (Z)-ACPs with up to 94% ee and a 28:72 E/Z ratio. Computational studies show that the orientation of the carbene unit dictated by the mutated positions accounts for the stereoselectivity.
Assuntos
Alcadienos , Irídio , Catálise , Alcenos/químicaRESUMO
1,5-Diaryl-3-Oxo-1,4-Pentadiene derivatives are intriguing organic compounds with a unique structure featuring a pentadiene core, aryl groups, and a ketone group. This study investigates the influence of fluorine atoms on the conformational features of these derivatives in deuterated chloroform (CDCl3) solution. Through nuclear magnetic resonance (NMR) spectroscopy and quantum chemical calculations, we discerned variations in interatomic distances and established predominant conformer proportions. The findings suggest that the non-fluorinated entity exhibits a uniform distribution across various conformer groups. The introduction of a fluorine atom induces substantial alterations, resulting in the predominance of a specific conformer group. This structural insight may hold the key to their diverse anticancer activities, previously reported in the literature.
Assuntos
Alcadienos , Flúor , Flúor/química , Conformação Molecular , Espectroscopia de Ressonância Magnética/métodosRESUMO
This paper explores how the allure of magical thinking and groupthink contrasts with intuition of emotional truth. Since truth can terrify, the author suggests that a longer learning curve is needed to apprehend what Bion (1970a) called the "evolving O" of the analytic session. Traumatized patients are described as dream weavers who spin webs of partial truths and lies around their true selves. For the analyst, untangling these webs involves what Bion (1970b) calls an "act of faith." Clinical material is presented to show how groupthink and other concretions of thought can, under favorable circumstances, be transformed on the wings of psychic truth. Alternatively, uncontained violent emotions can become calcified, creating a carapace over the chrysalis of the patient's true self. The author concludes that the analyst's desire for a particular treatment outcome can unwittingly lead to the formation of an adhesive web where healthy analytic culture becomes a cult. Paradoxically, it is only when there is equal attention to emotional truth and lies that a trajectory of growth is likely to evolve.
Assuntos
Alcadienos , Terapia Psicanalítica , Humanos , Teoria Psicanalítica , EmoçõesRESUMO
Enveloped viruses encased within a lipid bilayer membrane are highly contagious and can cause many infectious diseases like influenza and COVID-19, thus calling for effective prevention and inactivation strategies. Here, we develop a diatomic iron nanozyme with lipoxidase-like (LOX-like) activity for the inactivation of enveloped virus. The diatomic iron sites can destruct the viral envelope via lipid peroxidation, thus displaying non-specific virucidal property. In contrast, natural LOX exhibits low antiviral performance, manifesting the advantage of nanozyme over the natural enzyme. Theoretical studies suggest that the Fe-O-Fe motif can match well the energy levels of Fe2 minority ß-spin d orbitals and pentadiene moiety π* orbitals, and thus significantly lower the activation barrier of cis,cis-1,4-pentadiene moiety in the vesicle membrane. We showcase that the diatomic iron nanozyme can be incorporated into air purifier to disinfect airborne flu virus. The present strategy promises a future application in comprehensive biosecurity control.
Assuntos
Alcadienos , Influenza Humana , Vírus , Humanos , Antivirais , Lipoxigenase , FerroRESUMO
A regio- and stereoselective allylation of N-unsubstituted anilines has been developed that explores aryl allenes as masked allyl synthons and a combination of Mg(OTf)2/HFIP as an effective proton source. The protocol is operationally simple and scalable and offers high yields of diverse p-allyl anilines bearing an olefin motif with exclusive E-geometry. The methodology was also suitable for the regioselective allylation of indole and can be advanced in a three-component reaction mode using NIS activator. The alteration of the catalytic system with TfOH resulted in the regioselective difunctionalization of allenes, which follows an allylation/hydroarylation cascade.
Assuntos
Alcadienos , Estereoisomerismo , PropanóisRESUMO
We report an approach to the core of the manzamine alkaloid keramaphidin B that relies on the strain-promoted cycloaddition of an azacyclic allene with a pyrone trapping partner. The cycloaddition is tolerant of nitrile and primary amide functional groups and can be complemented with a subsequent retro-Diels-Alder step. These efforts demonstrate that strained cyclic allenes can be used to build significant structural complexity and should encourage further studies of these fleeting intermediates.
Assuntos
Alcadienos , Alcaloides , Alcadienos/química , Piridinas , Reação de Cicloadição , Nitrilas/químicaRESUMO
The terms unrepresented and unrepresented states are increasingly being referred to in psychoanalytic discourse, without our having established a generally agreed upon consensus about their definition, use or meaning. While these particular designations were never used by Freud, a careful reading of his work reveals them to be qualities that characterize the initial state of both the drive and perception. This paper attempts to place these terms in a clinically useful, metapsychological perspective by reviewing their conceptual origin in Freud and examining their elaboration and clinical relevance in the work of Bion, Winnicott, and Green. These concepts should prove especially useful for understanding and addressing problems presented by non-neurotic patients and psychic organizations and will help expand the reach and efficacy of psychoanalytic understanding and technique to increasing numbers of contemporary patients.
Assuntos
Alcadienos , Psicanálise , Humanos , Psicanálise/história , Relevância Clínica , Consenso , Confiabilidade dos Dados , Teoria PsicanalíticaRESUMO
In this review, the latest achievements in the field of multiply bonded organogermanium derivatives, mostly reported within the last two decades, are presented. The isolable Ge-containing analogues of alkenes, alkynes, 1,3-dienes, allenes, and vinylidenes are discussed, and for each class of unsaturated organogermanium compounds, the most representative examples are given. The synthetic approaches toward homonuclear multiply bonded combinations solely consisting of germanium atoms, and their heteronuclear variants containing germanium and other group 14 elements, both acyclic and cyclic, are discussed. The peculiar structural features and nonclassical bonding nature of the abovementioned compounds are discussed based on their spectroscopic and structural characteristics, in particular their crystallographic parameters (double bond length, trans-bending at the doubly bonded centers, and twisting about the double bond). The prospects for the practical use of the title compounds in synthetic and catalytic fields are also briefly discussed.
Assuntos
Alcadienos , Germânio , Alcenos/química , Alcinos/química , Germânio/químicaRESUMO
Twenty 1,4-pentadiene-3-one derivatives containing quinazolinone (W1-W20) were designed and synthesized. The bioactivity test results showed that some compounds had antifungal activities in vitro. W12 showed excellent bioactivity against Sclerotinia sclerotiorum (S. sclerotiorum) and Phomopsis sp., with EC50 values of 0.70 and 3.84 µg/mL, which are higher than those of the control drug azoxystrobin at 8.15 and 17.25 µg/mL. In vivo activity tests were carried out on oilseed rape and kiwifruit. The protective effect of W12 on oilseed rape infected with S. sclerotiorum (91.7 and 87.3%) was better than that of azoxystrobin (90.2 and 79.8%) at 100 and 50 µg/mL, respectively, and the protective effect on kiwifruit infected with Phomopsis sp. (96.2%) was better than that of azoxystrobin (94.6%) at 200 µg/mL. Scanning electron microscopy results showed the hyphae of S. sclerotiorum treated with compound W12 abnormally collapsed and shriveled, inhibiting the growth of mycelium and, thus, laying the inhibiting effect on S. sclerotiorum. The results of the mechanism research showed that the action of W12 changed the mycelial morphology of S. sclerotiorum, affected the permeability of cells, increased the leakage of cytoplasm and allowed the cell membrane to break down. This study shows that 1,4-pentadiene-3-one derivatives containing quinazolinone have good effects on plant fungi and the potential for becoming new fungicides.
Assuntos
Alcadienos , Brassica napus , Fungicidas Industriais , Antifúngicos/farmacologia , Doenças das Plantas/microbiologia , Fungicidas Industriais/farmacologia , Relação Estrutura-AtividadeRESUMO
Asymmetric organocatalysis is a growing method for the synthesis of axially chiral tetrasubstituted allenes, the most challenging one among allene syntheses. In this method, chiral organocatalysts such as phase-transfer catalysts, peptides, disulfonimides, and binaphthyl/bispiro phosphoric acids have displayed remote control of regio- and stereoselectivity. Highly functionalized enantiopure allenes including those with an adjacent tertiary or quaternary stereocenter have been efficiently prepared with high levels of regio-, diastereo-, and enantioselectivity using this method. Several mechanistic pathways, including electrophilic addition to cumulenolate or zwitterionic enolate intermediates, alkynylogous Mukaiyama aldol reaction, nucleophilic addition to quinone methides, and dearomative addition to imino esters, were proposed. The method is necessary for providing access to axially chiral tetrasubstituted allenes, which can be utilized for the preparation of novel ligands, natural products, and organic materials, particularly those having complex structures. This review covers the enantioselective organocatalytic synthesis of these tetrasubstituted allenes and the mechanistic insights into the formation of the chiral axis up to July 2022.
Assuntos
Alcadienos , Estereoisomerismo , Alcadienos/química , CatáliseRESUMO
The endocannabinoids anandamide and 2-arachidonoylglycerol are not only metabolized by serine hydrolases, such as fatty acid amide hydrolase, monoacylglycerol lipase, and α,ß-hydrolases 6 and 12, but they also serve as substrates for cyclooxygenases, cytochrome P450s, and lipoxygenases. These enzymes oxygenate the 1Z,4Z-pentadiene system of the arachidonic acid backbone of endocannabinoids, thereby giving rise to an entirely new array of bioactive lipids. Hereby, a protocol is provided for the enzymatic synthesis, purification, and characterization of various oxygenated metabolites of anandamide generated by lipoxygenases, which enables the biological study and detection of these metabolites.
Assuntos
Alcadienos , Endocanabinoides , Ácido Araquidônico , Ácidos Araquidônicos , Citocromos , Endocanabinoides/metabolismo , Lipoxigenases , Monoacilglicerol Lipases , Alcamidas Poli-Insaturadas , Prostaglandina-Endoperóxido Sintases/metabolismo , SerinaRESUMO
This article focuses on understanding and working with patients who have poorly developed symbolic capacity, or for whom symbolic capacity has been disrupted due to trauma, particularly as it pertains to the use of reverie and interpretation in the analytic process. Many patients who present for Jungian analysis will initially present with deficits in symbolic functioning. This situation results in necessary limitations or modifications in utilizing traditional Jungian techniques such as dream analysis, active imagination, sand tray and other expressive art techniques. The initial phase of analytic work with these patients requires a focus on developing their symbolic capacity before traditional Jungian techniques can be utilized effectively. During the paper Jung's concept of 'the symbolic attitude' will be examined as well as the conceptual models of Wilfred Bion and other post-Bionians who outline theories and method for cultivating symbolic capacity and reflective functioning in patients for whom these capacities are impaired or poorly developed.
Cet article se concentre sur la compréhension et le travail avec des patients dont la capacité symbolique est mal développée, ou pour qui la capacité symbolique a été perturbée par le traumatisme. Ceci concerne tout particulièrement l'utilisation de la rêverie et de l'interprétation dans le processus analytique. Beaucoup de patients qui viennent pour une analyse Jungienne montrent initialement des déficits dans le fonctionnement symbolique. Ceci a pour conséquence des limitations nécessaires ou des modifications dans l'utilisation de techniques traditionnelles Jungiennes telles l'analyse des rêves, l'imagination active, la thérapie par le jeu de sable et autres techniques d'expression par l'art. La phase initiale du travail analytique avec ces patients requiert de mettre l'accent sur le développement de leur capacité symbolique avant que les techniques Jungiennes traditionnelles puissent être utilisée de manière efficace. Dans l'article, le concept Jungien 'd'attitude symbolique' sera étudié ainsi que les modèles conceptuels de Wilfred Bion et d'autres post-Bioniens qui présentent des théories et une méthode pour cultiver la capacité symbolique et le fonctionnement réfléchi chez des patients pour qui ces capacités sont déficientes ou mal développées.
El presente artículo se focaliza en la comprensión y trabajo con pacientes que han tenido un desarrollo limitado de su capacidad simbólica, o para quienes, la capacidad simbólica se ha visto perturbada debido a un trauma, particularmente en lo que se refiere al uso del reverie y de la interpretación en el proceso analítico. Muchos pacientes que se presentan para un análisis Junguiano, presentan inicialmente deficitis en su funcionamiento simbólico. Esta situación tiene como resultado limitaciones necesarias o modificaciones en la utilización de técnicas Junguianas tradicionales como el análisis de sueños, la imaginación activa, la caja de arena y otras técnicas artísticas y expresivas. La fase inicial del trabajo analítico con estos pacientes requiere hacer foco en el desarrollo de su capacidad simbólica antes de que técnicas Junguianas tradicionales puedan utilizarse efectivamente. Durante el escrito se examina el concepto de Jung de `actitud simbólica`, así como los modelos conceptuales de Wilfred Bion y otros post-Bionianos quienes describen teorías y métodos para cultivar la capacidad simbólica y el funcionamiento reflexivo en pacientes para quienes estas capacidades se encuentran perturbadas o poco desarrolladas.
Assuntos
Alcadienos , Terapia Psicanalítica , Humanos , Terapia Psicanalítica/métodos , ImaginaçãoRESUMO
Herein, we disclose an unprecedented and robust Ru(II)-catalyzed non-oxidative [5+1] annulation of 2-hydroxystyrenes with allenyl acetates to access biologically relevant chromene skeletons. The heteroatom on allene plays a pivotal role in controlling the regioselectivity of migratory insertion, and the reaction proceeds through a Ru-σ-allyl pathway, which has been elusive so far in C-H activation reactions with allenes. The protocol is sustainable in nature as it proceeds at room temperature and avoids the use of any toxic metal oxidants. In addition, the synthetic utility of the protocol was also demonstrated by late stage functionalization and modular synthesis of various natural product conjugates.