Attractive π-Interaction as an Efficient Control Element for Acyclic Stereocontrol

During the course of our synthetic studies of a natural product, an indium-mediated allylation reaction in aqueous media has been developed as the key step for the assembly of the advanced intermediate 2 (Scheme 1) in our strategy. The reaction proceeds with very high diastereoselectivity (>99% de), a result rare for acyclic molecules in the absence of obvious steric interaction or intramolecular chelation.¹ The interlocking physical, chemical and computational studies undertaken supported a π-stacking effect between the phenyl ring with the ketone.     

关于Hirota-Satsuma系统初值问题的局部和整体适定性

本文利用ＫＤＶ方程所对应的线性方程解所具有的光滑效应及压缩映像原理,得到了Ｈｉｒｏｔａ－Ｓａｔｓｕｍａ系统初值问题的局部和整体适定性结果．     

Study of Antibacterial and Anticancer Properties of bioAgNPs Synthesized Using Streptomyces sp. PBD-311B and the Application of bioAgNP-CNC/Alg as an Antibacterial Hydrogel Film against P. aeruginosa USM-AR2 and MRSA

Here, we report the extracellular biosynthesis of silver nanoparticles (AgNPs) and determination of their antibacterial and anticancer properties. We also explore the efficacy of bioAgNPs incorporated in cellulose nanocrystals (CNCs) and alginate (Alg) for the formation of an antibacterial hydrogel film. Streptomyces sp. PBD-311B was used for the biosynthesis of AgNPs. The synthesized bioAgNPs were characterized using UV-Vis spectroscopy, TEM, XRD, and FTIR analysis. Then, the bioAgNPs’ antibacterial and anticancer properties were determined using TEMA and cytotoxicity analysis. To form the antibacterial hydrogel film, bioAgNPs were mixed with a CNC and Alg solution and further characterized using FTIR analysis and a disc diffusion test. The average size of the synthesized bioAgNPs is around 69 ± 2 nm with a spherical shape. XRD analysis confirmed the formation of silver nanocrystals. FTIR analysis showed the presence of protein capping at the bioAgNP surface and could be attributed to the extracellular protein binding to bioAgNPs. The MIC value of bioAgNPs against P. aeruginosa USM-AR2 and MRSA was 6.25 mg/mL and 3.13 mg/mL, respectively. In addition, the bioAgNPs displayed cytotoxicity effects against cancer cells (DBTRG-0.5MG and MCF-7) and showed minimal effects against normal cells (SVG-p12 and MCF-10A), conferring selective toxicity. Interestingly, the bioAgNPs still exhibited inhibition activity when incorporated into CNC/Alg, which implies that the hydrogel film has antibacterial properties. It was also found that bioAgNP-CNC/Alg displayed a minimal or slow release of bioAgNPs owing to the intermolecular interaction and the hydrogel’s properties. Overall, bioAgNP-CNC/Alg is a promising antibacterial hydrogel film that showed inhibition against the pathogenic bacteria P. aeruginosa and MRSA and its application can be further evaluated for the inhibition of cancer cells. It showed benefits for surgical resection of a tumor to avoid post-operative wound infection and tumor recurrence at the surgical site.     

Nanoporous asymmetric polyaniline films for filtration of organic solvents

A new family of functional materials is reported for organic solvent nanofiltration, with excellent chemical stability and high retention of solute molecules. Integrally skinned asymmetric polyaniline (PANI) membranes were fabricated from concentrated solutions of doped PANI by phase inversion. Doped PANI solutions were prepared by adding organic acids directly to PANI dissolved in a mixture of NMP and 4-methyl piperidine before casting. Among the organic acids investigated, maleic acid, phthalic acid, sulfosalicylic acid and camphorsulfonic acid were able to dope PANI without causing gelation. These acids acted as soft templates, creating nanoporosity in the thin skin layer of the asymmetric PANI film. Their removal by alkaline extraction created membranes through which small solvent molecules can pass. After extracting the organic acids, the membranes were thermally crosslinked which conferred excellent solvent stability. These membranes had a molecular weight cut-off (MWCO) in the range of 150–250 g mol⁻¹ in methanol, making them the tightest OSN membranes reported to date. It was found that an increase in crosslinking temperature or time led to a decrease in solvent flux. PANI membranes were found to be resistant to a variety of organic solvents such as ethyl acetate, acetonitrile and acetone. These remarkable membranes have the potential to be used in OSN operations at high temperatures (up to 150 °C), and gave increasing fluxes with increasing temperature while maintaining a high solute rejection.     

High-efficiency solution processable electrophosphorescent iridium complexes bearing polyphenylphenyl dendron ligands

We report the synthesis and electrophosphorescent behavior of a series of novel iridium complex materials (Complexes A–F), which are composed of ligands bearing polyphenylphenyl dendron groups and acetylacetonate. Yellow to saturated red organic light-emitting diodes (OLEDs) based on these newly developed Ir complexes were fabricated through solution process by doping the complex materials into polyvinyl carbazole (PVK)/2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) matrices. The emission wavelengths of the materials could be effectively tuned from 549 nm to 640 nm by changing the conjugation of the ligands either through incorporating additional aromatic segment (e.g. phenyl or fluorenyl group) onto the basic dendron ligand or fusing two of the phenyl rings on the polyphenylphenyl dendron group. High performance devices with the configuration of ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) (50 nm)/PVK:PBD (40%):Ir complex (6%) (70 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (12 nm)/Alq₃ (20 nm)/Mg:Ag (150 nm) have been demonstrated. For example, when Complex B was used as the emissive layer, maximum current efficiency of 34.0 cd/A and external quantum efficiency of 10.3% have been achieved. When 1,3,5-tris(N-phenylbenzimidazol-2-yl) benzene (TPBI) was used as the block layer, the efficiencies can be further improved to 46.3 cd/A and 13.9%, respectively. These solution processed OLED devices demonstrated quite stable EL efficiencies over a large range of current density, which indicated that triplet–triplet annihilation in electrophosphorescence could be effectively suppressed by incorporation of the polyphenylphenyl dendron structure into iridium complexes.     

Merging organocatalysis and gold catalysis-a critical evaluation of the underlying concepts

While both organocatalysis and gold catalysis have their roots deeply entrenched in the landscape of modern organic chemistry, an exciting trend in the complementary merging of organocatalysis and especially Au(I) catalysis has emerged in the last four years. This niche area has been developing rapidly and this minireview serves to pin-point the fundamental concepts guiding reaction design in these binary catalytic systems. Moreover, the proven synthetic utility of organo/Au(I) multicatalytic systems in accessing molecular frameworks, previously a challenge to single catalytic systems, has resulted in this new concept permeating numerous areas of organocatalysis, such as primary/secondary amine, Br?nsted acid, hydrogen-bonding as well as N-heterocyclic carbene (NHC) catalysis. The first detailed account of these recent developments is systematically presented.     

Organocatalytic, asymmetric synthesis of 3-sulfenylated N-boc-protected oxindoles

Sulfenylated oxindoles: The first asymmetric sulfenylation of N-Boc-protected oxindoles has been developed to provide products containing a tetrasubstituted stereogenic center in high to excellent yields (86-98?%) and, in most cases, excellent enantioselectivities (up to 96?%?ee; see scheme).