Stereocontrolled formation of beta-glucosides and related linkages in the absence of neighboring group participation: influence of a trans-fused 2,3-O-carbonate group

[reaction: see text] Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is alpha-selective and the 3,4-O-carbonate is beta-selective.     

A polymer electrolyte containing ionic liquid for possible applications in photoelectrochemical solar cells

Various iodide ion conducting polymer electrolytes have been studied as candidate materials for fabricating photoelectrochemical (PEC) solar cells and energy storage devices. In this study, enhanced ionic conductivity values were obtained for the ionic liquid tetrahexylammonium iodide containing polyethylene oxide (PEO)-based plasticized electrolytes. The analysis of thermal properties revealed the existence of two phases in the electrolyte, and the conductivity measurements showed a marked conductivity enhancement during the melting of the plasticizer-rich phase of the electrolyte. Annealed electrolyte samples showed better conductivity than nonannealed samples, revealing the existence of hysteresis. The optimum conductivity was shown for the electrolytes with PEO:salt = 100:15 mass ratio, and this sample exhibited the minimum glass transition temperature of 72.2 °C. For this optimum PEO to salt ratio, the conductivity of nonannealed electrolyte was 4.4 × 10⁻⁴ S cm⁻¹ and that of the annealed sample was 4.6 × 10⁻⁴ S cm⁻¹ at 30 °C. An all solid PEC solar cell was fabricated using this annealed electrolyte. The short circuit current density (I _SC), the open circuit voltage (V _OC), and the power conversion efficiency of the cell are 0.63 mA cm⁻², 0.76 V, and 0.47% under the irradiation of 600 W m⁻² light.     

Simultaneous Visualization of Mitochondria and Lysosome by a Single Cyanine Dye: The Impact of the Donor Group (-NR2) Towards Organelle Selectivity

Journal of Fluorescence - A benzothiazolium-based hemicyanine dye (probe 3) has been synthesized by attaching a morpholine group into a phenyl benzothiazolium skeleton. Probe 3 exhibited...     

Analysis of means approach in advanced designs

Analysis of means (ANOM), similar to Shewhart control chart that exhibits individual mean effects on a graphical display, is an attractive alternative mean testing procedure for the analysis of variance (ANOVA). The procedure is primarily used to analyze experimental data from designs with only fixed effects. Recently introduced, the ANOM procedure based on the q‐distribution (ANOMQ procedure) generalizes the ANOM approach to random effects models. This article reveals that the application of ANOM and ANOMQ procedures in advanced designs such as hierarchically nested and split‐plot designs with fixed, random, and mixed effects enhances the data visualization aspect in graphical testing. Data from two real‐world experiments are used to illustrate the proposed procedure; furthermore, these experiments exhibit the ANOM procedures' visualization ability compared with ANOVA from the point of view of the practitioner.     

Strong and electromagnetic mass splittings in heavy mesons

The contributions to heavy meson mass differences by the strong hyperfine interaction, the light quark masses and the electromagnetic interaction are obtained from the empirical values of the D  , D^∗$D^{\ast }$, B   and B^∗$B^{\ast }$ masses by means of a mass formula based on the heavy quark mass expansion. The three different types of contributions are determined with significant accuracy to next to leading order in that expansion.     

Enhanced diastereoselectivity in beta-mannopyranosylation through the use of sterically minimal propargyl ether protecting groups

[reaction: see text] 2-O-Propargyl ethers are shown to be advantageous in the 4,6-O-benzylidene acetal directed beta-mannosylation reaction. The effect is most pronounced when the O3 protecting group is a bulky silyl ether or a glycosidic bond; however, even with a 3-O-benzyl ether, the use of a 2-O-propargyl ether results in a significant increase in diastereoselectivity. The beneficial effect of the propargyl ether is thought to be a combination of its minimal steric bulk, as determined by a measurement of the steric A-value and of its moderately disarming nature, as reflected in the pKa of propargyl alcohol. Conversely, the application of a 3-O-propargyl ether in the benzylidene acetal directed mannosylation has a detrimental effect on stereoselectivity, for which no explanation is at present available. Deprotection is achieved by base-catalyzed isomerization of the propargyl ether group to the corresponding allenyl ether, followed by oxidative cleavage with N-methylmorpholine N-oxide and catalytic osmium tetroxide.     

Convergent synthesis of a beta-(1-->3)-mannohexaose

An as yet unknown beta-(1-->3)-mannohexaose has been synthesized by a block route involving the coupling of two trisaccharides. Comparison of three closely related attempted mannohexaose syntheses reinforces the influence of subtle matching and/or mismatching interactions on the outcome of convergent oligosaccharide synthesis.     

Nucleobase and ribose modifications control immunostimulation by a microRNA-122-mimetic RNA

Immune stimulation is a significant hurdle in the development of effective and safe RNA interference therapeutics. Here, we address this problem in the context of a mimic of microRNA-122 by employing novel nucleobase and known 2'-ribose modifications. The nucleobase modifications are analogues of adenosine and guanosine that contain cyclopentyl and propyl minor-groove projections. Via a site-by-site chemical modification analysis, we identify several immunostimulatory 'hot spots' within the miRNA guide strand at which single base modifications significantly reduce immune stimulation. A duplex containing one base modification on each strand proved to be most effective in preventing immune stimulation.     

Influence Cascades: Entropy-Based Characterization of Behavioral Influence Patterns in Social Media

Influence cascades are typically analyzed using a single metric approach, i.e., all influence is measured using one number. However, social influence is not monolithic; different users exercise different influences in different ways, and influence is correlated with the user and content-specific attributes. One such attribute could be whether the action is an initiation of a new post, a contribution to a post, or a sharing of an existing post. In this paper, we present a novel method for tracking these influence relationships over time, which we call influence cascades, and present a visualization technique to better understand these cascades. We investigate these influence patterns within and across online social media platforms using empirical data and comparing to a scale-free network as a null model. Our results show that characteristics of influence cascades and patterns of influence are, in fact, affected by the platform and the community of the users.     

2-O-propargyl ethers: readily cleavable, minimally intrusive protecting groups for beta-mannosyl donors

[reaction: see text]. The use of 2-O-propargyl ethers as protecting groups in 4,6-O-benzylidene-protected mannopyranosyl donors bearing either bulky silyl groups or glycosidic linkages on O3 overcomes the poor stereoselectivity achieved with the corresponding 2-O-benzyl ethers, due to a reduction of steric buttressing. Deprotection is conducted by treatment with potassium tert-butoxide followed by catalytic osmium tetroxide and N-methylmorpholine N-oxide.