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The lindenane dimeric sesquiterpenoids with versatile biological activities are accessible via biometric synthesis, in which the endo-selective Diels-Alder reaction plays an important role. To explore the endo-selectivity of the Diels-Alder reaction between lindenane sesquiterpenes promoted by pyridines, density functional theory (DFT) calculations were performed to explore the reaction mechanism between pyridines and D-A monomers. The calculations performed on the reaction pathways explain why pyridines can promote endo-selectivity via hydrogen bonding, and the hydrogen bond strength is a key factor driving the Diels-Alder reaction in major biochemical systems. These DFT-level insights will pave the way for designing better promoters for Diels-Alder reactions in biometric synthesis applications.
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A hydrogen atom transfer (HAT)-initiated Dowd-Beckwith rearrangement reaction was developed, which enables the efficient assembly of diversely functionalized polyquinane frameworks. By incorporation of an iridium-catalyzed regio- and enantioselective hydrogenation and a diastereocontrolled ODI-[5+2] cycloaddition/pinacol rearrangement cascade reaction, the asymmetric total syntheses of eight tetraquinane natural products, including (-)-crinipellins A-F and (-)-dihydrocrinipellins A and B, have been achieved in a concise and divergent manner.
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The first and asymmetric total syntheses of two C11-oxygenated hetisine-type diterpenoid alkaloids, namely, (+)-davisinol and (+)-18-benzoyldavisinol, is described. The concise synthetic approach features a HAT-initiated transannular redox radical cyclization, an ODI-Diels-Alder cycloaddition, and an acylative kinetic resolution. By incorporating an efficient late-stage assembly of the azabicycle, our strategy would streamline the synthetic design of C20-diterpenoid alkaloids and pave the way for their modular syntheses.
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Multicomponent reactions (MCRs) are powerful tool for the construction of polyfunctional molecules in an operationally simple and atom-economic manner, and the discovery of novel MCRs requests various building blocks. Herein, triazenyl alkynes were disclosed as versatile building blocks in a multicomponent reaction with carboxylic acids, aldehydes and anilines to furnish ß-amino amides with the achievement of high diastereoselectivity and structural diversity. In this process, triazenyl alkynes were bifunctional so that the alkyne moiety acts as C2 fragment and triazene serves as directing group to modulate the transition state thus achieving high diastereoselectivity, in consistence with DFT calculations. Furthermore, the triazenyl group also enables diverse late-stage transformation. This protocol opens a new vision for the discovery of building block and rational design of MCRs.
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Mixtures of ionic liquids (ILs) have shown their potential in both physical and chemical processes, regarded as alternatives to common ILs. In this work, four guanidinium-based ILs, 2-ethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([TMG(C2)][C2OSO3]) and bis(trifluoromethylsulfonyl)imide ([TMG(C2)][NTf2]), and 2,2-diethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([TMG(C2)2][C2OSO3]) and bis(trifluoromethylsulfonyl)imide ([TMG(C2)2][NTf2]), are employed to investigate the structures, interactions and properties of four systems of IL-IL binary mixtures, including [TMG(C2)][C2OSO3]x[NTf2]1-x, [TMG(C2)]x[TMG(C2)2]1-x[C2OSO3], [TMG(C2)]x[TMG(C2)2]1-x[NTf2] and [TMG(C2)2][NTf2]x[C2OSO3]1-x. Combining experiments with theory, the relationships among H-bond interactions, structures and volumetric properties have been revealed. 1H NMR characterizations show the changes of H-bond interactions in the IL-IL mixtures in relation to composition, and DFT calculations reveal significant cation-anion interactions through the active hydrogen atom (N+-H) and the methyl groups in the cations with the anions in the manner of HO and HF. The ethyl group in the [C2OSO3]- anion hardly forms interactions with other components. The size effect of the calculated system has been evaluated for the IL-IL clusters with 2, 4 and 8 ions. Different structures due to variation of cationic and anionic species have remarkable influence on the volumetric properties of the IL-IL mixtures. Negative excess molar volume (VEm) is found in [TMG(C2)]x[TMG(C2)2]1-x[C2OSO3], and it is caused by the close packing of ions. Positive VEm values indicate that interaction loss occurs in the other three systems, where a linear arrangement or square packing of ions with low space utilization is found.
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Palladium-catalyzed intramolecular dearomative reductive-Heck reaction of C2-substituted indoles is developed, which provides access to structurally diverse 3,2'-spiropyrrolidine oxindoles. By changing the hydride source to AcONa base, direct C3-arylation products [2,3-b]quinolinones are achieved in good yields. The reaction of C2-substituted benzofuran is also realized, delivering the desired spiro-product.
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BACKGROUND: In the production process of surimi, large quantities of wastewater are produced. Thus it would be interesting to develop an efficient protocol for the recovery of protein from hairtail surimi wash-water. RESULTS: A technique involving the use of immobilized chymotrypsin-trypsin (I-CT) was developed, providing a practical method for the preparation of protein-peptide nutritional material (PPNM). Under optimized reaction conditions, the recovery rate of nitrogen of surimi wash-water was measured as 98.3 ± 2.9%. Nutritional evaluation of the protein-peptide fraction demonstrated that it contained all essential amino acids (EAA) for humans, accounting for 44.1% of the total amino acid (TAA) content, which was determined to be 78.2 g per 100 g dry matter. The essential amino acid index (EAAI) and biological value (BV) were 101.7 (>95) and 76.7 respectively. A wide range of volatile flavor compounds (>50), including aldehydes, ketones, alcohols, hydrocarbons and heterocyclic compounds, were identified in PPNM by gas chromatography/mass spectrometry (GC/MS) analysis. CONCLUSION: An efficient and practical protocol for the recovery of protein from hairtail surimi wash-water has been developed. The PPNM prepared in this work could be used as a nutraceutical and as an ingredient of functional foods. © 2016 Society of Chemical Industry.
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Quimotripsina/química , Produtos Pesqueiros/análise , Proteínas de Peixes/química , Peptídeos/química , Tripsina/química , Águas Residuárias/química , Biocatálise , Enzimas Imobilizadas/química , Cromatografia Gasosa-Espectrometria de Massas , Compostos Orgânicos Voláteis/química , Resíduos/análiseRESUMO
The first enantioselective total synthesis of (+)-steenkrotinâ A has been achieved in 18â steps and 4.2 % overall yield. The key features of the strategy entail a Rh-catalyzed O-H bond insertion followed by an intramolecular carbonyl-ene reaction, two sequential SmI2 -mediated Ueno-Stork and ketyl-olefin cyclizations, and a cascade intramolecular aldol condensation/vinylogous retro-aldol/aldol process with inversion of the relative configuration at the C7 position. The absolute configuration of (+)-steenkrotin A was determined based on the stepwise construction of the stereocenters during the total synthesis.
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Produtos Biológicos/química , Produtos Biológicos/síntese química , Diterpenos/química , Diterpenos/síntese química , Catálise , Ciclização , EstereoisomerismoRESUMO
The visible-light-promoted diastereodivergent intramolecular oxyamination of alkenes is described to construct oxazolindinones, pyrrolidinones and imidazolidones via mild generation of primary amidyl radicals from functionalized hydroxylamines. A unique phenomenon of highly diastereoselective ring-opening of aziridines controlled by electron sacrifices was observed. Highly diastereoselective amino alcohols derivatives were obtained efficiently through this protocol in gram scales. The mechanistic studies suggested the isolatable anti-aziridine intermediates were generated quickly from primary amidyl radicals and the diastereoselectivities were controlled by pKa values of the electron sacrifices.
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The first nitro-group-initiated redox-neutral [3+2] cycloaddition of nitrocyclopropanes with alkenes by using visible-light-absorbing transition-metal complexes was reported. High diastereoselectivities were observed for two quaternary carbon centers on the ring and validated by DFT calculations. Spiro- or polycyclic structures can be constructed smoothly. Cyclic γ-amino acid derivatives and polysubstituted cyclic amino alcohols can be obtained easily through reduction of the nitro group.
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Mechanisms and reactivity differences for the cycloaddition of anhydride to alkyne catalyzed by the palladium and nickel catalysts have been investigated by extensive density functional theory (DFT) calculations. The predicted free energy profiles for the Pd- and Ni-catalyzed reactions have been used to evaluate possible mechanisms for the formation of different products. Calculations show that the formation of isocoumarin via the decarbonylative addition of anhydride to alkyne is kinetically more favorable than the channel to indenone in the Ni-catalyzed reaction. On the contrary, the preparation of naphthalene through sequential liberation of CO2 and CO is kinetically more favorable than that the formation of indenone in the Pd-catalyzed process. The bonding differences between Pd-C and Ni-C bonds, arising from the relativistic effect of late transition metals, play an important role in regulating their catalytic activity. The calculation results show good agreement with the experiments.
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The mechanisms and origins for the Pd- and Ni-catalyzed regioselective hydrosilylation of allene have been investigated by means of density functional theory (DFT) calculations. The free-energy profiles of Pd- and Ni-catalyzed reactions with small and bulky N-heterocyclic carbene (NHC) ligands are calculated to determine the mechanism for regioselectivities. The calculation results show that different metals (Ni vs Pd) lead to regiochemical reversals for the hydrosilylation of allene. The allylsilane is the major product via palladium catalysis with small NHC ligand, while the vinylsilane is the major product via nickel catalysis with bulky NHC ligand. Both electronic and steric factors play a key role in the regioselectivities for the hydrosilylation of allene via Pd and Ni catalysts. The calculation results are in good agreement with observed regioselectivities and could provide insights into the design of new catalysts for the regioselectivity of hydrosilylation reactions.
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Discovery of the isoform-selective histone deacetylases (HDACs) inhibitors is of great medical importance and still a challenge. The comparison studies on the structure-function relationship of the conserved residues, which are located in the linker binding channel among class I HDACs (including 4 isoforms: HDAC1/2/3/8), have been carried out by using ab initio QM/MM MD simulations, a state-of-the-art approach to simulate metallo-enzymes. We found that the conserved tyrosine (Y303/308/286/306 in HDAC1/2/3/8, respectively) could modulate the zinc-inhibitor chelation among all class I HDACs with different regulatory mechanisms. For HDAC1/2/3 selective-inhibitor benzamide, the conserved tyrosine could modulate the coordinative ability of the central atom (Zn(2+)), while for pan-inhibitor SAHA, the conserved tyrosine could increase the chelating ability of the ligand (SAHA). Moreover, it is first found that the conserved tyrosine is correlated with the intertransformation of π-π stacking styles (parallel shift vs T-shaped) by the aromatic ring in benzamide and the two conserved phenylalanine residues of HDACs. In addition, the catalytic roles of the conserved tyrosine in stabilizing the transition state and intermediate are further revealed. These findings provide useful molecular basis knowledge for further isoform-selective inhibitor design among class I HDACs.
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Inibidores de Histona Desacetilases/farmacologia , Histona Desacetilases/química , Histona Desacetilases/metabolismo , Simulação de Dinâmica Molecular , Tirosina , Acetilação , Benzamidas/química , Benzamidas/farmacologia , Biocatálise , Inibidores de Histona Desacetilases/química , Ligação de Hidrogênio , Ligantes , Conformação Proteica , Prótons , Teoria Quântica , Relação Estrutura-Atividade , TermodinâmicaRESUMO
A sorbent based on affinity ionic liquid (AIL), triazacyclononane-ionic liquid, was synthesized, characterized, and applied to the extraction of histidine (His)-tagged proteins from aqueous buffer to ionic liquid (IL) phase. The adsorbed His-tagged proteins could be back-extracted from the IL phase to the aqueous buffer with an imidazole solution. The specific binding of His-tagged proteins with AIL/IL could be affected by a few factors including the ionic strength and coordinated metal ions. In the case of His-tagged enhanced green fluorescent protein (EGFP), the maximum binding capacity of Cu(2+)-AIL/IL reached 2.58 µg/µmol under the optimized adsorption conditions. The eluted His-tagged EGFP kept fluorescent and remained active through the purification process. Moreover, a tandem extraction process successively using Cu(2+)-AIL/IL and Zn(2+)-AIL/IL systems was developed, which was proven very efficient to obtain the ultimate protein with a purity of about 90 %. An effective reclamation method for the AIL/IL extraction system was further established. The sorbent could be easily regenerated by removing metal ions with EDTA and the followed reimmobilization of metal ions. Easy handling of the presented M(2+)-AIL/IL system and highly specific ability to absorb His-tagged proteins make it attractive and potentially applicable in biomolecular separation.
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Extração Líquido-Líquido/métodos , Proteínas/isolamento & purificação , Adsorção , Compostos Aza/química , Líquidos Iônicos/química , Piperidinas/química , Proteínas/químicaRESUMO
Soluble dietary fibre (SDF) has gained growing interest because of its multiple functional and nutritional benefits. In the current study, the effect of SDF extracted from eucheuma seaweed on both the physicochemical properties and the released metabolites of yellow cakes was evaluated systematically. The results revealed that the addition of SDF induced increases in specific gravity, specific volume and water content of yellow cakes, and caused a decrease in weight loss and changes in texture and colour. In addition, sensory evaluation showed that up to 10 % substitution of flour with SDF was acceptable. In vitro digestion of cakes demonstrated that flour substitution with SDF at different levels (8 %-14 %) significantly reduced the release of glucose, ranging from 11.24 % to 29.12 %. In addition to the increased apparent viscosity of the cake digesta, the metabolite analysis based on nuclear magnetic resonance spectroscopy identified a total of 29 metabolites, including amino acids, fatty acids and sugars. Notably, the addition of SDF reduced the release of amino acids and fatty acids after digestion. These findings suggested that seaweed SDF was a potential substitute for some food components, which would provide functional benefits to the digestive characteristics.
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Fibras na Dieta , Digestão , Alga Marinha , Fibras na Dieta/metabolismo , Alga Marinha/química , Alga Marinha/metabolismo , Digestão/efeitos dos fármacos , Solubilidade , Viscosidade , Farinha/análise , Aminoácidos/metabolismo , Aminoácidos/análise , Humanos , Ácidos Graxos/metabolismoRESUMO
Aromatic metallacycles are of considerable current interest. Reported aromatic metallacycles are mainly those with carbon, nitrogen, oxygen and sulfur. In this work, we report the synthesis and characterization of aromatic chloroosmacyclopentatrienes, which represent the first structurally confirmed metallaaromatic with a chlorine atom in its framework. Single-crystal X-ray diffraction studies show that these planar chloroosmacyclopentatrienes possess a very short Os-ClC distance suggesting M=ClC bond character.
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Advanced glycation end-products (AGEs) are a group of heterogeneous compounds formed during the Maillard Reaction (MR) and have been proven to be detrimental to human health. In addition to thermally processed foods, the digestive tract may be an additional site for exogenous AGE formation since the MR would possibly occur between (oligo-)peptides, free amino acids, and reactive MR products (MRPs) such as α-dicarbonyl compounds (α-DCs) along the digestion. In this study, through establishing a simulated gastrointestinal (GI) model consisting of whey protein isolate (WPI) and two typical α-DCs, i.e., methylglyoxal (MGO) or glyoxal (GO), we first validated that co-digestion of WPI with α-DCs generated extra amounts of AGEs in a precursor-dependent manner, especially seen in the intestinal stage. At the end of GI digestion, the contents of total AGEs in WPI-MGO and WPI-GO systems were 4.3-242 and 2.5-73.6 times higher than those formed in the control system, respectively. Evaluation of the protein digestibility further showed that AGE formation along the digestion process slightly affected the digestibility of whey protein fractions. However, as sequenced and identified by high-resolution mass spectrometry, different types of AGE modifications were identified in peptides released from ß-lactoglobulin and α-lactalbumin in the final digests, as well as changes in peptide sequence motifs. This suggested that the glycated structures formed during co-digestion affected the action of digestive proteases toward whey proteins. Overall, these results highlight the GI tract as an additional source of exogenous AGEs and provide new insights into the biochemical consequences of MRPs in heat-processed foods.
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Óxido de Magnésio , Reação de Maillard , Humanos , Proteínas do Soro do Leite/metabolismo , Óxido de Magnésio/metabolismo , Glioxal/química , Aldeído Pirúvico/metabolismo , Peptídeos/metabolismo , Produtos Finais de Glicação Avançada/metabolismo , Trato Gastrointestinal/metabolismo , DigestãoRESUMO
To improve the viability of Lactobacillus plantarum (P) during digestion and storage, the probiotics were encapsulated by alginate (ALG) and alginate-gelatin (ALG-GE) hydrogels beads. ALG-P-GE showed much better physicochemical properties than ALG-P. The scanning electron microscopy (SEM) results validated the incorporation of bacterial cells into the beads. ALG-P-GE exhibited good encapsulation efficiency of 97.7 %, and the storage and thermal stability of probiotic were increased by 15 % and 8 %, respectively, when comparing with ALG-P. ALG-P-GE beads could protect the probiotics from inactivation in simulated gastric fluid and then release it in simulated intestinal fluid. The protective mechanism of ALG-GE for probiotics was further studied by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and found that ALG and GE can form gel network through hydrogen bonding and electrostatic interactions. In the mimic beverage systems, ALG-P-GE beads could protect the encapsulated probiotics and increase its viability. The storage, thermal, and digestion stability of encapsulated probiotic were significantly increased and showed high viability in the mimic beverage systems. ALG-P-GE beads have great potential for the protection and delivery of probiotics in food systems.
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Lactobacillus plantarum , Probióticos , Lactobacillus plantarum/fisiologia , Gelatina , Alginatos/química , Hidrogéis/química , Bebidas , Probióticos/química , Digestão , Viabilidade MicrobianaRESUMO
Novel nanoparticles (Z-R/H) were successfully fabricated by a resveratrol-grafted zein covalent conjugate (Z-R) combined with quaternary ammonium chitosan (HTCC), which were used as stabilizers to prepare peppermint oil (PO) Pickering emulsions with antioxidant activity. HTCC effectively adjusted wettability of Z-R conjugate, and three-phase contact angle of Z-R/H3:1 was moderate (95.01°). The influencing factors of Pickering emulsion formation, including volume fraction of PO, concentration of Z-R/H, and mass ratio of Z-R to HTCC, were evaluated by droplet size, ζ-potential, microscopic observation, and stability index analysis. Pickering emulsions stabilized by Z-R/H3:1 showed excellent physical stability under heat treatment. Z-R/H nanoparticles adsorbed on the oil-water interface yielded a dense filling layer as a physical barrier to improve the emulsion stability, which was validated by confocal laser-scanning microscopy. After 4 weeks of storage, retention rate of PO in Pickering emulsion stabilized by Z-R/H3:1 remained high (72.1 %). Electronic nose analysis showed that Z-R/H3:1-stabilized emulsion effectively prevented volatilization of PO aroma components. Additionally, PO and Z-R/H nanoparticles provided an additive antioxidant effect of Pickering emulsions against DPPH and ABTS free radicals. In summary, these novel Z-R/H nanoparticle offer promising applications as a stabilizer with great potential in preparing functional Pickering emulsions to improve essential oil delivery.
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Quitosana , Nanopartículas , Zeína , Emulsões , Antioxidantes/farmacologia , Resveratrol , Tamanho da PartículaRESUMO
Lipase-catalyzed transesterification of structured phospholipids (sPLs) is a hot topic, but the structural variation of the fatty acyl chains in intact phospholipids at the molecular level remains unclear to date. The present study explored the detailed characteristics of synthesized phospholipids through high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in precursor ion scan mode. The optimal conditions were in-depth inspected and determined for the reaction system, including phospholipase A1 as catalyst, 15% lipase loading, and 1% water content. The sPLs enriched with EPA/DHA were structurally and quantitatively characterized by focusing on the fragments of m/z 301.6 (eicosapentaenoic acid, EPA) and m/z 327.6 (docosahexaenoic acid, DHA), and the results were statistically analyzed using partial least squares discriminant analysis and clustered heatmap hierarchical clustering analysis. PC 38:6 (18:1/20:5), PC 38:7 (18:2/20:5), PC o-40:6 (o-18:0/22:6), and PE 40:8 (18:2/22:6) etc. were revealed as the main variables that were active in the reaction.