RESUMO
We report here a homo-Mannich reaction of cyclopropanol with an iminium ion, generated by an asymmetric allylic dearomatization of indole, to construct a tricyclic hydrocarbazole core, which is shared by a variety of monoterpenoid indole alkaloids across families. Through this approach, an all-carbon quaternary stereogenic center as well as an allyl and a ketone group were installed. Using this functionalized hydrocarbazole as the structural platform, D ring and E rings of different sizes (i.e., five-, six-, and seven-membered) were successively or simultaneously assembled, leading to a collective asymmetric synthesis of seven alkaloids belonging to the ibophyllidine, Aspidosperma, Kopsia, and Melodinus alkaloid families.
Assuntos
Apocynaceae , Aspidosperma , Alcaloides de Triptamina e Secologanina , Humanos , Aspidosperma/química , Apocynaceae/química , Alcaloides Indólicos/química , Estrutura MolecularRESUMO
Experimental and numerical experiments were carried out to study the coffee rings or coffee splats formed by droplet evaporation with micro or nano polystyrene sphere particles (Dp = 10 µm or 100 nm). Particle image velocimetry (PIV) and a high-resolution camera were used in this experiment, along with a temperature-controlled heater and a data-acquisition computer. The results showed that a nano particle could form a homogeneous coffee splat, instead of the common coffee ring formed when using micro particles. In order to account for this phenomenon, this paper developed a complex multiphase model, one which included the smooth particle hydrodynamics (SPH) fluid model coupled with the van der Waals equation of state for droplet evaporation, the rigid particle model of finite-size micro particles, and the point-particle model of the nanometer particles. The numerical simulation was operated on a GPU-based algorithm and tested by four validation cases. A GPU could calculate 533 times the speed of a single-core CPU for about 300,000 particles. The results showed that, for rigid solid particles, the forms emerged spontaneously on the wall, and their structure was mainly affected by the boundary wettability, and less affected by the fluid flow and thermal condition. When the wall temperature was low, it was easier for the particles to be deposited on the contact line. At high wall temperature, the coffee ring effect would be weakened, and the particles were more likely to be deposited in the droplet center. The hydrophilic surface produced a larger coffee ring compared to the hydrophobic surface. The experimental and numerical results proved that particle size could play a significant role during the particle deposition, which may be a possible route for producing uniform-distributed and nano-structure coatings.
RESUMO
A Fe(NO3)3-mediated ring-opening arylation of cyclopropanol with the electron-rich pyrrole has been developed, which might proceed through oxidative radical ring opening of cyclopropanol followed by cyclization to the pyrrole motif and then aromatization. This method enables direct arylation of cyclopropanol without prefunctionalization and thus allows rapid access to a diverse array of chiral 5,6,7,8-tetrahydroindolizines from easily available chiral amino acid esters. The synthetic utility has been demonstrated by the asymmetric synthesis of alklaoids (-)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, and a natural product analogue.
RESUMO
Breast cancer is one of the most common types of cancers which results in a high mortality rate for patients worldwide. In this study, we performed systematical experiments including tissue analysis (immunohistochemistry etc.) and cell functional experiments (cell counting assay, MTT assay, cell colony formation, cell migration assay, cell invasion assay etc.). We demonstrated that the expression level of RNA binding motif protein 3 (RBM3) was higher in human breast cancer tissues compared with adjacent nontumor tissues. A high level of RBM3 was associated with worse postoperative relapsefree survival (RFS) and overall survival (OS) rates in patients with breast cancer. Among the patients with breast cancer, the expression of RBM3 was associated with patient lymph node metastasis and a high tumor grade. The knockdown of RBM3 markedly decreased the proliferation and metastasis of human breast cancer cells. In downstream pathway analysis, actin related protein 2/3 complex subunit 2 (ARPC2) was determined to be positively regulated by RBM3 through a posttranscriptional 3'UTRbinding manner. ARPC2 also played an oncogenic role and mediated the promoting role of RBM3 in the proliferation and metastasis of human breast cancer cells. Thus, on the whole, the findings of this study demonstrate that RBM3 acts as an oncogene in human breast cancer cells and that the functional depletion of RBM3 may be considered as a potential method for breast cancer therapy.
Assuntos
Complexo 2-3 de Proteínas Relacionadas à Actina/genética , Neoplasias da Mama/metabolismo , Proteínas de Ligação a RNA/metabolismo , Regulação para Cima , Regiões 3' não Traduzidas , Complexo 2-3 de Proteínas Relacionadas à Actina/metabolismo , Neoplasias da Mama/genética , Neoplasias da Mama/patologia , Linhagem Celular Tumoral , Proliferação de Células , Progressão da Doença , Feminino , Regulação Neoplásica da Expressão Gênica , Humanos , Células MCF-7 , Gradação de Tumores , Metástase Neoplásica , Análise de SobrevidaRESUMO
Liquid atomization is applied in nanostructure dense coating technology to inject suspended nano-size powder materials into a suspension plasma spray (SPS) torch. This paper presents the effects of the atomization parameters on the nanoparticle processing. A numerical model was developed to simulate the dynamic behaviors of the suspension droplets, the solid nanoparticles or agglomerates, as well as the interactions between them and the plasma gas. The plasma gas was calculated as compressible, multi-component, turbulent jet flow in Eulerian scheme. The droplets and the solid particles were calculated as discrete Lagrangian entities, being tracked through the spray process. The motion and thermal histories of the particles were given in this paper and their release and melting status were observed. The key parameters of atomization, including droplet size, injection angle and velocity were also analyzed. The study revealed that the nanoparticle processing in SPS preferred small droplets with better atomization and less aggregation from suspension preparation. The injection angle and velocity influenced the nanoparticle release percentage. Small angle and low initial velocity might have more nanoparticles released. Besides, the melting percentage of nanoparticles and agglomerates were studied, and the critical droplet diameter to ensure solid melting was drawn. Results showed that most released nanoparticles were well melted, but the agglomerates might be totally melted, partially melted, or even not melted at all, mainly depending on the agglomerate size. For better coating quality, the suspension droplet size should be limited to a critical droplet diameter, which was inversely proportional to the cubic root of weight content, for given critical agglomerate diameter of being totally melted.