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Three types of starch with different amylose content were esterified and blended with polybutylene succinate (PBS) to obtain esterified manioc starch/PBS (EMS/PBS), esterified corn starch/PBS (ECS/PBS), and esterified waxy corn starch/PBS (EWS/PBS) composites. The EMS/PBS and ECS/PBS composites with high amylose content displayed typical V-type crystal structures. The original crystals of EWS, which had low amylose content, were disrupted during the esterification process. EWS exhibited the strongest interaction with PBS and the most favorable interface compatibility. The pyrolysis temperature was in order of EMS/PBS < ECS/PBS < EWS/PBS. The elongation at break of the three blends was higher than that of pure PBS. The esterification and plasticization of the EWS/PBS composite were the most comprehensive. The EWS/PBS composite showed the lowest storage modulus (G') and complex viscosity (η*). The interfacial bonding force of the composite materials increased with more amylopectin, decreasing intermolecular forces and destroying crystal structures, which decreased G' and η* and increased toughness. The EWS/PBS composite, with the least amylose content, had the best hydrophobicity and degradation performance.
Assuntos
Amilose , Amilose/química , Esterificação , Amido/química , Polímeros/química , Viscosidade , Polienos/química , Zea mays/química , Butileno Glicóis/químicaRESUMO
Ganoderma capense is a precious medicinal fungus in China. In this study, a novel fungal immunomodulatory protein gene, named as FIP-gca, was cloned from G. capense by homologous cloning. Sequencing analysis indicated that FIP-gca was composed of 336 bp, which encoded a polypeptide of 110 amino acids. Protein sequence blasting and phylogenetic analysis showed that FIP-gca shared homology with other Ganoderma FIPs. FIP-gca was effectively expressed in Pichia pastoris GS115 at an expression level of 166.8 mg/L and purified using HisTrap™ fast-flow prepack columns. The immunomodulation capacity of rFIP-gca was demonstrated by that rFIP-gca could obviously stimulate cell proliferation and increase IL-2 secretion of murine spleen lymphocytes. Besides, antitumor activity of rFIP-gca towards human stomach cancer AGS cell line was evaluated in vitro. Cell wound scratch assay proved that rFIP-gca could inhibit migration of AGS cells. And flow cytometry assay revealed that rFIP-gca could significantly induce apoptosis of AGS cells. rFIP-gca was able to induce 18.12% and 22.29% cell apoptosis at 0.3 µM and 0.6 µM, respectively. Conclusively, the novel FIP-gca gene from G. capense has been functionally expressed in Pichia and rFIP-gca exhibited ideal immunomodulation and anti-tumour activities, which implies its potential application and study in future.
Assuntos
Ganoderma , Saccharomycetales , Animais , Camundongos , Humanos , Filogenia , Ganoderma/genética , Ganoderma/química , Pichia/genética , Pichia/metabolismo , Proteínas Fúngicas/metabolismoRESUMO
A highly selective and divergent synthesis which enabled access to various complex compounds is highly attractive in organic synthesis and medicinal chemistry. Herein, we developed an effective method for divergent synthesis of highly substituted tetrahydroquinolines via Lewis base catalyzed switchable annulations of Morita-Baylis-Hillman carbonates with activated olefins. The reaction displayed switchable [4 + 2] or [3 + 2] annulations via catalyst or substrate control, providing a diverse range of architectures which contained highly substituted tetrahydroquinolines or cyclopentenes with three contiguous stereocenters bearing a quaternary carbon center in high yields with excellent diastereoselectivities and regioselectivities. Furthermore, synthetic utility of this strategy was further highlighted by gram-scale experiments and simple transformations of the products.
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Daytime atmospheric pollution has received wide attention, while the vertical structures of atmospheric pollutants at night play a crucial role in the photochemical process on the following day, which is still less reported. Focusing on Guangzhou, a megacity of South China, we established an unmanned aerial vehicle (UAV) equipped with micro detectors to collect consecutive high-resolution samples of fine particle (PM2.5), submicron particle (PM1.0), black carbon (BC) and ozone (O3) concentrations in the atmosphere, as well as the air temperature (AT) and relative humidity (RH) within a 500 m altitude during nighttime from Oct. 24th to Nov. 6th, 2018. The measurements showed that PM2.5, PM1.0, and BC decreased with altitude and were influenced by the nighttime shallow planetary boundary layer (PBL) where BC was more accumulated and fluctuated. In contrast, O3 was positively correlated with altitude. Backward trajectory clustering and Pasquill stability classification showed that advection and convection significantly influenced the vertical distribution of all pollutants, particularly particulate matter. External air masses carrying high concentrations of pollutants increased PM1.0 and PM2.5 levels by 145% and 455%, respectively, compared to unaffected periods. The ratio of BC to PM2.5 indicated that local emissions had a minor role in nighttime particulate matter. Vertical transport caused by atmospheric instability reduced the differences in pollutant concentrations at various heights. Geodetector and generalized additive model showed that RH and BC accumulation in the PBL were significant factors influencing vertical changes of the secondary aerosol intensity as indicated by the ratio of PM1.0 to PM2.5. The joint explanation of RH and atmospheric stability with other variables such as BC is essential to understand the generation of secondary aerosols. These findings provide insights into regional and local measures to prevent and control night-time particulate matter pollution.
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In the present study, we report that a GFP fusion tag facilitated the soluble expression of a pea actin isoform (PEAc1) in E. coli. To investigate the influence of a GFP fusion tag on PEAc1 structure and activity, PEAc1, His-tagged PEAc1 (His-PEAc1), His-tagged GFP (His-GFP), and His-tagged PEAc1 fusion with GFP (His-PEAc1-GFP) were expressed in E. coli. SDS-PAGE and western blot analyses reveal that the solubility of His-PEAc1-GFP was higher than that of PEAc1 and His-PEAc1. The His-PEAc1-GFP and His-GFP fusion proteins were purified from the supernatant of cell homogenate on a Ni-affinity column, and PEAc1 and His-PEAc1 were purified from inclusion bodies. CD spectrum analysis of the four purified proteins indicated that the proportion of α-helix and ß-sheet in PEAc1 was closest to the predicted data in His-PEAc1-GFP (compared with His-PEAc1 or PEAc1). In addition, the actin-associated activities of His-PEAc1-GFP, including polymerization to microfilaments under specific ionic conditions and DNase I inhibition by monomers, were more similar to those of muscle actin (compared with PEAc1 and His-PEAc1). These improvements in PEAc1 solubility and activity are likely the result of correct PEAc1 folding mediated by GFP fusion.
Assuntos
Proteínas de Escherichia coli , Escherichia coli , Escherichia coli/metabolismo , Actinas/metabolismo , Pisum sativum , Proteínas de Escherichia coli/química , Isoformas de Proteínas/metabolismo , Solubilidade , Proteínas Recombinantes de Fusão/metabolismoRESUMO
To prevent the spread of COVID-19, China enacted a series of strict policies, which reduced anthropogenic activities to a near standstill. This provided a precious window to explore its effects on the spatio-temporal distribution of air pollution in Beijing, China. In this study, continuous wavelet transforms and spatial interpolation methods were used to explore the spatiotemporal variations in air pollutants and their lockdown effects. The results indicate that except O3, the annual average concentration of NO2, PM2.5 and SO2 showed a decreasing trend during 2016 and 2019; NO2, PM2.5 and SO2 show a trend of "low in summer and high in winter"; the diurnal variation of NO2 concentration was mainly related to the rush hours of traffic volume, with the first peak at the morning peak (7:00), and then accumulating gradually to second peak (22:00). The continuous wavelet analysis shows that PM2.5, SO2 and NO2 had four primary periods, while O3 only had two primary periods. The high NO2 concentration areas were mainly in Dongcheng, Xicheng, Chaoyang and Fengtai, while the low concentration areas were located in the northern areas, such as Miyun and Huairou; the PM2.5 concentration decreased from south to north; this characteristic presented more obviously in winter. Compared to the pre-lockdown, NO2 and SO2 decreased considerably during lockdown, whereas PM2.5 and O3 increased dramatically. The contribution rates of transportation activities to the NO2, O3, PM2.5 and SO2 were estimated be 9.4 % â¼ 17.2 %, -76.4 % â¼ -42.9 %, -39.5 % â¼ -22.8 % and 5.7 % â¼ 43.7 %, respectively; the contribution rates of industrial activities were 19.9 % â¼ 26.7 %, 7.8 % â¼ 30.9 %, 1.6 % â¼ 36.2 % and -10.5 % â¼ 15.9 %, respectively. Considering meteorological factors, we inferred that pauses in anthropogenic activities indeed help improving air pollution, but it is difficult to offset the impact of extreme weather. These findings can enhance our understanding on the sources of air pollution, and can therefore provide insights on urban air pollution mitigation.
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The additive-free [3 + 2] annulation from isatins, amino acids with 2-styrylbenzoxazoles, was described, providing a series of functional and structurally complex 3,3'-pyrrolidinyl-spirooxindole derivatives containing four contiguous and two quaternary stereogenic centers in high yields (up to 95%) and excellent diastereoselectivities (up to >25:1 dr). Interestingly, the reaction exhibits switchable regioselectivity depending on the substrate of amino acids. With proline or thioproline as the substrate, the reaction afforded α-regioselective spirooxindole skeletons. In contrast, when piperidine acid is the substrate, the reaction provided γ-regioselective spirooxindole skeletons.
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Compostos de Espiro , Aminoácidos , Catálise , Indóis/química , Compostos de Espiro/química , EstereoisomerismoRESUMO
NHC-alcohol adduct-mediated deoxygenation of alcohols under photocatalytic conditions is described. This process provides various alkyl radicals, which can react with 2-isocyanobiaryls to afford 6-substituted phenanthridine derivatives in moderate to good yields. This method offered the first example of directly using alcohols as radical sources for 6-phenanthridine synthesis.
Assuntos
Etanol , FenantridinasRESUMO
An efficient, three-component reaction of aldehydes and benzofuran-3-ones was developed. This process provides a new approach for the preparation of synthetically and biologically important spirobenzofuran-3-one derivatives with moderate-to-good yields under mild conditions. A switch of intramolecular to intermolecular domino Michael-aldol-lactonization leading to differential product formation was achieved by different NHCs catalysis.
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Benzofuranos , Compostos Heterocíclicos , Aldeídos , Catálise , Lactonas , Estrutura Molecular , Compostos de Espiro , EstereoisomerismoRESUMO
A CuI-catalyzed coupling reaction of benzofuran-3(2H)-ones with amines has been well established for the direct synthesis of α-ketoamides. This process involves C-O bond cleavage and C[double bond, length as m-dash]O/C-N bond formation. Mechanism studies indicated that this α-ketoamide formation reaction may involve a free radical process.
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A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.
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A novel tetrabutylammonium iodide (TBAI)-promoted three-component reaction of carboxylic acid with alkene and alcohol has been developed, which represents facile and straightforward access to polysubstituted γ-lactone skeletons in moderate-to-good yields. This methodology is distinguished by the use of a commercial catalyst and readily available starting materials, wide substrate scope, and operational simplicity. Mechanistic studies suggested that this transformation went through a radical process.
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A cross 1,3-dipolar cycloaddition of two different ylides between C,N-cyclic azomethine imines with an in situ-generated nonstabilized azomethine ylide from an N-benzyl precursor was realized. The reactions afforded a clean and facile access to diverse fused tricyclic 1,2,4-hexahydrotriazines in high yields (up to 96%). The chemical structures of the typical compounds were confirmed by X-ray single-crystal structure analysis.
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The cooperative chiral N-heterocyclic carbene and Lewis acid catalyzed reactions between 2-aroylvinylcinnamaldehydes and various aromatic aldehydes produced multifunctional tetrahydroindeno[1,2-c]furan-1-ones with excellent enantioselectivity. This work developed a versatile and efficient method for highly enantioselective construction of chiral tetrahydroindeno[1,2-c]furan-1-one, which are not easily prepared by other synthetic methods.
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The chiral triazole carbene and Ti(OPr-i)4 cocatalyzed reaction between α,ß-unsaturated aldehydes and 2-(aroylvinyl)benzaldehydes was systematically studied. A divergence in reaction pathways was observed under different reaction conditions. In benzene solvent and at ambient temperature, the reaction produced 4,5-dihydro-1,4-methanobenzo[c]oxepin-3-ones, the bridged caprolactones, as the major products in moderate yields with excellent enantioselectivity. The same reaction in dichloroethane and at 50 °C, however, gave 2,8-dihydrocyclopenta[a]indenes as the major products in most cases. The application of the method developed was demonstrated by the transformation of the bridged lactone products into enantiopure 4-hydroxy-1,2,3,4-tetrahydronaphthalene-2-carboxylic acids.
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MOTIVATION: Given a set of biallelic molecular markers, such as SNPs, with genotype values on a collection of plant, animal or human samples, the goal of quantitative genetic trait prediction is to predict the quantitative trait values by simultaneously modeling all marker effects. Quantitative genetic trait prediction is usually represented as linear regression models which require quantitative encodings for the genotypes: the three distinct genotype values, corresponding to one heterozygous and two homozygous alleles, are usually coded as integers, and manipulated algebraically in the model. Further, epistasis between multiple markers is modeled as multiplication between the markers: it is unclear that the regression model continues to be effective under this. In this work we investigate the effects of encodings to the quantitative genetic trait prediction problem. RESULTS: We first showed that different encodings lead to different prediction accuracies, in many test cases. We then proposed a data-driven encoding strategy, where we encode the genotypes according to their distribution in the phenotypes and we allow each marker to have different encodings. We show in our experiments that this encoding strategy is able to improve the performance of the genetic trait prediction method and it is more helpful for the oligogenic traits, whose values rely on a relatively small set of markers. To the best of our knowledge, this is the first paper that discusses the effects of encodings to the genetic trait prediction problem.
Assuntos
Modelos Genéticos , Alelos , Animais , Marcadores Genéticos , Genótipo , Heterozigoto , Homozigoto , Humanos , Modelos Lineares , Fenótipo , Plantas/genética , Polimorfismo de Nucleotídeo Único , Característica Quantitativa HerdávelRESUMO
Highly diastereoselective and enantioselective reactions between 2-aroylvinylcinnamaldehydes and α,ß-unsaturated imines were achieved under asymmetric catalysis of chiral triazole carbene catalysts. In the presence of N-anisylindeno[2,1-b]triazolo[4,3-d][1,4]oxazinium salt, the reaction of 2-aroylvinylcinnamaldehydes with α,ß-unsaturated imines afforded indeno[2,1-c]pyran-1-one derivatives 4 with 90%-99% ee, while enantiopure indenocyclopentan-1-ones 5 (>99% ee) were obtained under the catalysis of N-mesitylindeno[2,1-b]triazolo[4,3-d][1,4]oxazinium salt. A slight variation of an N-substituent on triazole carbenes was found to switch completely the diastereoselectivity of the reaction for the formation of indeno[2,1-c]pyran-1-ones.
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A novel and efficient method for the highly enantioselective synthesis of chiral 4,5-dihydropyridazin-3-one derivatives has been developed based on the chiral N-heterocyclic carbene-catalyzed oxidative annulation between α,ß-unsaturated aldehydes and hydrazones. Meanwhile, the selective synthesis of either 4,5-dihydropyridazin-3-ones or pyridazin-3-one derivatives from the same reactants has been achieved by simply varying catalytic and reaction conditions.
Assuntos
Aldeídos/química , Compostos Heterocíclicos/síntese química , Metano/análogos & derivados , Piridazinas/síntese química , Catálise , Compostos Heterocíclicos/química , Hidrazonas , Metano/química , Estrutura Molecular , Oxirredução , Piridazinas/químicaRESUMO
We optimized the culture medium for 3-hydroxycarboxylic acid production by Pseudomonas mendocina DS-04-T-biodegraded polyhydroxybutyrate (PHB) using the Plackett-Burman design, steepest ascent method, and Box-Behnken design. The optimized concentrations of the constituents of the culture medium were as follows: PHB (7.57 g/L), NH4 Cl (5.0 g/L), KH2 PO4 (2.64 g/L), Na2 HPO4 ·12H2 O (12 g/L), MgSO4 ·7H2 O (0.5 g/L), and CaCl2 ·2H2 O (5 mg/L). The yield of 3-hydroxycarboxylic acid obtained using the optimized culture medium was 56.8 ± 1.64%, which was 2.5-fold higher than that obtained when the unoptimized culture medium was used.
Assuntos
Plásticos Biodegradáveis/metabolismo , Ácidos Carboxílicos/metabolismo , Meios de Cultura/química , Meios de Cultura/metabolismo , Hidroxibutiratos/metabolismo , Poliésteres/metabolismo , Pseudomonas mendocina/metabolismo , Reatores Biológicos/microbiologia , Hidroxibutiratos/química , Poliésteres/química , Pseudomonas mendocina/crescimento & desenvolvimentoRESUMO
Abrasives are one of key influencing factors on surface quality during chemical mechanical polishing (CMP). Silica sol, a widely used abrasive in CMP slurries for sapphire substrates, often causes lower material removal rate (MRRs). In the present paper, Fe-doped colloidal SiO2 composite abrasives were prepared by a seed-induced growth method in order to improve the MRR of sapphire substrates. The CMP performance of Fe-doped colloidal SiO2 abrasives on sapphire substrates was investigated using UNIPOL-1502 CMP equipment. Experimental results indicate that the Fe-doped colloidal SiO2 composite abrasives exhibit lower surface roughness and higher MRR than pure colloidal SiO2 abrasives for sapphire substrates under the same testing conditions. Furthermore, the acting mechanism of Fe-doped colloidal SiO2 composite abrasives in sapphire CMP was analyzed by x-ray photoelectron spectroscopy. Analytical results show that the Fe in the composite abrasives can react with the sapphire substrates to form aluminum ferrite (AlFeO3) during CMP, which promotes the chemical effect in CMP and leads to improvement of MRR.