Addition reactions to chiral aziridine-2-carboxaldimine toward various enantiopure nitrogen-containing heterocycles

Chiral (2R,1′R)-(1′-phenylethyl)aziridine-2-carboxaldimine was utilized as a nitrogen-containing starting substrate for the preparation of various enantiopure nitrogen-containing heterocycles. The additions of nucleophiles including organomagnesium reagents, cyanotrimethylsilane and ketene acetal to the chiral (2R,1′R)-(1′-phenylethyl)aziridine-2-carboxaldimine proceeded in highly stereoselective manner via chelation controlled transition states. Subsequent treatment of adducts with triphosgene and NaH yielded 5-substituted-4-chloromethylimidazolidin-2-ones. This imine was also served as either aza-diene or aza-dienophile with olefin or diene to provide hetero-Diels-Alder adducts 2-aziridinylpiperidines or 1,2,3,4-tetrahydroquinolines.     

Effect of plant matrix and fluid ethanol concentration on supercritical fluid extraction efficiency of schisandrin derivatives

An investigation of the effect of plant matrix on the supercritical fluid extraction efficiency of five schisandrin derivatives is reported, exhibiting a great difference with respect to extraction efficiency depending on the matrix. Pure supercritical CO2 at 60 degrees C and 34.0 MPa cannot fully recover schisandrin derivatives from the leaves as much as from the other matrices. Only 36.9% of these compounds are extracted from leaves of Schisandra chinensis by supercritical CO2 in comparison with organic solvent extraction. However, more than 80% of schisandrin derivatives are obtained from both stem and fruit parts. Ethanol addition also shows a different effect depending on plant matrix; that is, CO2 modified with 10% ethanol could enhance the yield of schisandrin derivatives from leaves by four times when compared with that of pure CO2, but it has little effect on both stems and fruits.     

Evaluation of planarity and aromaticity in sapphyrin and inverted sapphyrin using a bidirectional NICS (Nucleus-Independent Chemical Shift) scan method?

Using the bidirectional NICS scan method in conjunction with two-photon absorption (TPA) measurements, it has proved possible to determine the relationship between pi-conjugation and aromaticity in two structurally related expanded porphyrin systems, sapphyrin and inverted sapphyrin, and establish that differences in these defining factors depend on the presence or absence of a key sp3 hybrid molecular orbital within the macrocyclic periphery.     

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.     

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π–π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm⁻¹ after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.     

HGLM modelling of dropout process using a frailty model

Summary  We introduce a shared random-effect model, derived from frailty models to account for informative dropout. We extend the iterative weighted least squares algorithm for hierarchical generalized linear models to shared random-effect models. Monte-Carlo simulations are carried out to illustrate that the proposed method works well whether the random-effect distribution is correctly specified or not. This study was supported by a grant of the Korea Health 21 R & D Project, Ministry of Health & Welfare, Republic of Korea. (01-PJ1-PG3-51200-0002).     

REML estimation for binary data in GLMMs

The restricted maximum likelihood (REML) procedure is useful for inferences about variance components in mixed linear models. However, its extension to hierarchical generalized linear models (HGLMs) is often hampered by analytically intractable integrals. Numerical integration such as Gauss-Hermite quadrature (GHQ) is generally not recommended when the dimensionality of the integral is high. With binary data various extensions of the REML method have been suggested, but they have had unsatisfactory biases in estimation. In this paper we propose a statistically and computationally efficient REML procedure for the analysis of binary data, which is applicable over a wide class of models and design structures. We propose a bias-correction method for models such as binary matched pairs and discuss how the REML estimating equations for mixed linear models can be modified to implement more general models.     

Valuation ideals of order one in 2-dimensional regular local rings

Let υ be a prime divisor of a 2-dimensional regular local ring (R m) with algebraically closed residue field k. Zariski showed that a prime divisor υ of R is uniquely associated to a simple m-primary integrally closed ideal I of R, there exist finitely many simple υ-ideals including I, and all the other υ-ideals can be uniquely factored into products of simple υ-ideals. It is known that such an m-primary ideal I of R can be minimally generated by o(I) + 1 elements.Given a simple integrally closed ideal I of order one with arbitrary rank and its associated prime divisor υ, we find minimal generating sets of all the simple υ-ideals and describe factorizations of all the composite υ-ideals in terms of power products of simple υideals as explicitly as possible.     

Bonding modes of nitrite and nitrate in palladium(II) and platinum(II) complexes

The crystal structures of the well-known complexes, [(Me₄en)M(II)X₂] (Me₄en?=?N,N,N??,N??-tetramethylethylenediamine; M(II)?=?Pd(II) or Pt(II); X ^??=?NO₂ ^? or NO₃ ^?) have been determined. For [(Me₄en)Pd(NO₂)₂] and [(Me₄en)Pt(NO₂)₂], the nitrite anion acts as a monodentate N-donor ligand in the solid state. In contrast, for [(Me₄en)Pd(ONO₂)(O₂NO)], the two nitrate anions act as a monodentate O-donor (ONO₂) and a bidentate O,O??-donor (O₂NO). Recrystallization of [(Me₄en)Pt(NO₃)₂] from Me₂SO yields the Me₂SO adduct with a monodentate O-donor nitrate and a counteranionic nitrate, [(Me₄en)Pt(ONO₂)(S-Me₂SO)](NO₃). The solution behavior of these complexes, including the equilibrium between coordinated and free Me₂SO, has been investigated.