5′-O-TBDMS-3′-O--(1H-Imidazole-1-Thiocarbonyl)thymidine: A Novel Intermediate for the Synthesis of 2,3′-Anhydrothymidine

Thermal or base-promoted conversion of 5′-O-TBDMS-3′-O-(1H-imidazole-1-thiocarbonyl)thymidine (1) afforded 5′-O-TBDMS-2,3′-anhydro-thymidine (2), a pivotal intermediate for the transformation of the 3′-hydroxy group of 2′-deoxyribonucleosides, in high yield.     

Self-assembled discotic nematic liquid crystals formed by simple hydrogen bonding between phenol and pyridine moieties

New discotic nematic liquid crystals have been prepared through intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene (phloroglucinol, PG) or 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) and the peripheral molecules of stilbazole derivatives. The various nematic phases formed by new hydrogen bonding building blocks were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The first discotic complexes of PG and trans-4-alkoxy-4′-stilbazoles exhibited nematic columnar (N_C) and hexagonal columnar phases depending on the length of alkyl chains, which were considered as the basic discotic structure. Several structural variations on the building blocks were attempted to examine their effects on the liquid crystalline properties of discotic complexes. The nematic lateral phase (N_L) with enhanced intercolumnar order was observed for the complexes of PG and trans-4-cyanoalkoxy-4′ stilbazoles due probably to the strong dipole interactions between cyano groups at the end of alkoxy chains. By introducing the nonlinear structure in three arms of supramolecular discotic mesogen, a discotic nematic phase (N_D) was observed for the complex of THPB and trans-4-octyloxy-4 -stilbazole. The single hydrogen bonding between phenol and pyridine moieties in this study provides a simple and effective method for preparing the rarely found discotic nematic liquid crystals.     

Substrate interaction effects on order to disorder transition behavior in block copolymer films

We present an overview of the recent progress on the phase transition in the block copolymer (BCP) films in terms of the interfacial interactions effects of the substrates and the χ (Flory-Huggins segmental interaction parameter) effects between the two blocks. For the BCP films thinner than a critical thickness (L_c) above which the transition is independent of film thickness, the order-to-disorder transition (ODT) increased or decreased with decreasing film thickness depending on the interfacial interaction types. The rapid and slow changes in the ODT were attributed to the relative magnitude of enthalpic contribution to χ between two blocks. Interestingly, a periodic amplification in the block composition for the BCP films suppressed the compositional fluctuation in the film geometry, resulting in the ODT shifts from the bulk ODTs above L_c. This effect of the BCP films was more illustrated by the ODT shift effects depending on the strength of the preferential interactions on the substrates. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Ni‐Catalyzed [4+3+2] Cycloaddition of Ethyl Cyclopropylideneacetate and Dienynes: Scope and Mechanistic Insights

A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes.     

A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine

The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]₂ ( 1 ; L =PhC(NtBu)₂) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe₂C₅H₄NSiMe₃]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ ₂( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)₃}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)₂C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography.     

Sieving properties of end group‐halogenated Pluronic polymer matrix in DNA separation under nondenaturing CE analysis

CE‐SSCP analysis is a well‐established DNA separation method that is based on variations in mobility caused by sequence‐induced differences in the conformation of single‐stranded DNA. The resolution of CE‐SSCP analysis was improved by using a Pluronic polymer matrix, and it has been successfully applied in various genetic analyses. Because the Pluronic polymer forms a micellar cubic structure in the capillary, it provides a stable internal structure for high‐resolution CE‐SSCP analysis. We hypothesized that formation of micellar cubic structure is influenced by the end hydroxyl group of the Pluronic polymer, which affords structural stability through hydrogen bonding. To test this hypothesis, the hydroxyl group was halogenated to eliminate the hydrogen bonding without disturbing the polarity of polymer matrix. CE‐SSCP resolution of two DNA fragments with a single base difference was significantly worse in the halogenated polymer matrices due to band broadening. The viscoelastic properties of control (which has hydroxyl group), chlorinated, and brominated F108 solution upon heating were also investigated by rheological experiments, and we found that gelation was significantly associated with resolution. In this series of experiments, the effect of the hydroxyl group in Pluronic polymer matrix on separation resolution of CE‐SSCP analysis was demonstrated.     

Development of an LC-MS/MS method for aromatase inhibitor screening

Aromatase (CYP 19A1) is a key steroidogenic enzyme that catalyzes the conversion of androgen to estrogen. In this study, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for aromatase inhibitor screening was developed and validated. The substrate androstenedione was incubated with human CYP 19A1 supersomes in the presence of NADPH for 30 min, and estrone formation was determined by LC-MS/MS analysis. Cortisone was used as internal standard. The incubation mixture was extracted using a liquid-liquid extraction method with ethyl acetate. Chromatographic separation was achieved using a C₁₈ column (3.0?×?50 mm, 2.7 μm) with a mobile phase consisting of 0.1 % formic acid/acetonitrile adopting gradient elution at a flow rate of 0.4 mL/min. The mass spectrometer was operated in positive electrospray ionization mode. The precursor-product ion pairs used for multiple reaction monitoring were m/z 287→97 (androstenedione), m/z 271?→?159 (estrone), and m/z 361?→?163 (IS, cortisone). The developed method met the required criteria for the validation of bioanalytical methods. The validated method was successfully applied to evaluate aromatase inhibitory activity of plants extracts of Simaroubaceae.

Chemical Composition of a Novel Distillate from Fermented Mixture of Nine Anti-Inflammatory Herbs and Its UVB-Protective Efficacy in Mouse Dorsal Skin via Attenuating Collagen Disruption and Inflammation

Since ancient times, various herbs have been used in Asia, including Korea, China, and Japan, for wound healing and antiaging of the skin. In this study, we manufactured and chemically analyzed a novel distillate obtained from a fermented mixture of nine anti-inflammatory herbs (Angelica gigas, Lonicera japonica, Dictamnus dasycarpus Turcz., D. opposita Thunb., Ulmus davidiana var. japonica, Hordeum vulgare var. hexastichon Aschers., Xanthium strumarium L., Cnidium officinale, and Houttuynia cordata Thunb.). The fermentation of natural plants possesses beneficial effects in living systems. These activities are attributed to the chemical conversion of the parent plants to functional constituents which show more potent biological activities. In our current study, the distillate has been manufactured after fermenting the nine oriental medical plants with Lactobacillus fermentum, followed by distilling. We analyzed the chemical ingredients involved in the distillate and evaluated the effects of topical application of the distillate on ultraviolet B (UVB)-induced skin damage in Institute of Cancer Research (ICR) mice. Topical application of the distillate significantly ameliorated the macroscopic and microscopic morphology of the dorsal skin against photodamage induced by UVB radiation. Additionally, our current results showed that topical application of the distillate alleviated collagen disruption and reduced levels of proinflammatory cytokines (tumor necrosis factor alpha and interleukin 1 β expressions) in the dorsal skin against UVB radiation. Taken together, our current findings suggest that the distillate has a potential to be used as a material to develop a photoprotective adjuvant.     

Neuroprotective Effect and Antioxidant Potency of Fermented Cultured Wild Ginseng Root Extracts of Panax ginseng C.A. Meyer in Mice

Wild ginseng has better pharmacological effects than cultivated ginseng. However, its industrialization is limited by the inability to grow wild ginseng on a large scale. Herein, we demonstrate how to optimize ginseng production through cultivation, and how to enhance the concentrations of specific ginsenosides through fermentation. In the study, we also evaluated the ability of fermented cultured wild ginseng root extract (HLJG0701-β) to inhibit acetylcholinesterase (AChE), as well as its neuroprotective effects and antioxidant activity. In in vitro tests, HLJG0701-β inhibited AChE activity and exerted neuroprotective and antioxidant effects (showing increased catalyst activity but decreased reactive oxygen species concentration). In in vivo tests, after HLJG0701-β was orally administered at doses of 0, 125, 250, and 500 mg/kg in an animal model of memory impairment, behavioral evaluation (Morris water maze test and Y-maze task test) was performed. The levels of AChE, acetylcholine (ACh), blood catalase (CAT), and malondialdehyde (MDA) in brain tissues were measured. The results showed that HLJG0701-β produced the best results at a dose of 250 mg/kg or more. The neuroprotective mechanism of HLJG0701-β was determined to involve the inhibition of AChE activity and a decrease in oxidative stress. In summary, both in vitro and in vivo tests confirmed that HJG0701-β administration can lead to memory improvement.