Synthesis of bicyclo[2.2.2]octane-2,3,5,6,7,8 hexols (Bishomoinositols) as glycosidase inhibitors

For the construction of the bicyclo[2.2.2]octane skeleton, 2,2-dimethyl-3a,7a-dihydro-1,3-benzodioxole was reacted with vinylene carbonate to give two isomeric cycloadditon products having the bicyclo[2.2.2]octane skeleton. Hydrolysis of the ketal ring and the opening of the carbonate functionality, followed by hydroxylation of the remaining double bond resulted in the formation of a symmetrical hexol. Epoxidation of the double bond in the cycloaddition products and the subsequent ring-opening reactions produce two additional hexol derivatives. One of the synthesized molecules exhibited enzyme-specific inhibition against alpha-glycosidase.     

Substituent effects on the ring-opening mechanism of lithium bromocyclopropylidenoids to allenes

The ring-opening reactions of lithium bromocyclopropylidenoids to allenes have been investigated computationally at the B3LYP/6-31G(d) level of theory. Formally, two pathways can be considered: the reaction may either proceed in a concerted fashion or stepwise with the intermediacy of a free cyclopropylidene. In both cases, the loss of the bromide ion determines the kinetic of the reaction. The stability of the reactive intermediate, i.e., the carbene, is dependent on the substituent. Cyclopropylidenes bearing an electron-donating group (+M) are extremely unstable and ring-open readily to the allene. In contrast, bromocyclopropylidenoids with electron-withdrawing groups are particularly stable species. Here, a high energy barrier needs to be overcome in order to split off bromide and to generate the corresponding carbene or allene. Still, for most of the monosubstituted cyclopropylidenes investigated during this study, the activation energy for the cyclopropylidene to allene rearrangement is lower than the energy required for parent compound (X = H) except for X = -SiH3 and -CF3.     

Physics of transparent conductors

Transparent conductors (TCs) are materials, which are characterized by high transmission of light and simultaneously very high electrical DC conductivity. These materials play a crucial role, and made possible numerous applications in the fields of electro-optics, plasmonics, biosensing, medicine, and “green energy”. Modern applications, for example in the field of touchscreen and flexible displays, require that TCs are also mechanically strong and flexible. TC can be broadly classified into two categories: uniform and non-uniform TC. The uniform TC can be viewed as conventional metals (or electron plasmas) with plasma frequency located in the infrared frequency range (e.g. transparent conducting oxides), or ultra-thin metals with large plasma frequency (e.g. graphen). The physics of the nonuniform TC is much more complex, and could involve transmission enhancement due to refraction (including plasmonic), and exotic effects of electron transport, including percolation and fractal effects. This review ties the TC performance to the underlying physical phenomena. We begin with the theoretical basis for studying the various phenomena encountered in TC. Next, we consider the uniform TC, and discuss first the conventional conducting oxides (such as indium tin oxide), reviewing advantages and limitations of these classic uniform electron plasmas. Next, we discuss the potential of single- and multiple-layer graphene as uniform TC. In the part of the paper dealing with non-uniform metallic films, we begin with the review of random metallic networks. The transparency of these networks could be enhanced beyond the classical shading limit by the plasmonic refractive effects. The electrical conduction strongly depends on the network type, and we review first networks made of individual metallic nanowires, where conductivity depends on the inter-wire contact, and the percolation effects. Next, we review the uniform metallic film networks, which are free of the percolation effects and contact problems. In applications that require high-quality electric contact of a TC to an active substrate (such as LED or solar cells), the network performance can be optimized by employing a quasi-fractal structure of the network. We also consider the periodic metallic networks, where active plasmonic refraction leads to the phenomenon of the extraordinary optical transmission. We review the relevant literature on this topic, and demonstrate networks, which take advantage of this strategy (the bio-inspired leaf venation (LV) network, hybrid networks, etc.). Finally, we review “smart” TCs, with an added functionality, such as light interference, metamaterial effects, built-in semiconductors, and their junctions.     

Organic/inorganic interfaced field-effect transistor properties with a novel organic semiconducting material

A novel 1,3,4-oxadiazole-substituted benzo[b]triphenylene was synthesized by three-step synthetic procedure and OFET device design was successfully designed after theoretical calculations made using Gaussian software. For investigating the field-effect properties of designed organic electronic device, a SiO₂ (300 nm) was thermally grown on p-Si wafer at 1000 °C as a dielectric layer and gate, source and drain contacts have been deposited using Au metal with physical vapour deposition. 1,3,4-Oxadiazole-substituted benzo[b]triphenylene was spin coated on the source and drain electrodes of our device, forming organic/inorganic interfaced field-effect transistors. Surface morphology and thin film properties were investigated using AFM. All electrical measurements were done in air ambient. The device showed a typical p-type channel behaviour with increasing negative gate bias voltage values. Our results have surprisingly shown that the saturation regime of this device has high mobility (μ_FET), excellent on/off ratio (I_on/I_off), high transconductance (g_m) and a small threshold voltage (V_Th). The values of μ_FET, I_on/I_off, g_m and V_Th were found as 5.02 cm²/Vs, 0.7 × 10³, 5.64 μS/mm and 1.37 V, respectively. These values show that our novel organic material could be a potential candidate for organic electronic device applications in the future.     

Adhesion of biologically inspired vertical and angled polymer microfiber arrays

This paper proposes an approximate adhesion model for fibrillar adhesives for developing a fibrillar adhesive design methodology and compares numerical simulation adhesion results with macroscale adhesion data from polymer microfiber array experiments. A technique for fabricating microfibers with a controlled angle is described for the first time. Polyurethane microfibers with different hardnesses, angles, and aspect ratios are fabricated using optical lithography and polymer micromolding techniques and tested with a custom tensile adhesion measurement setup. Macroscale adhesion and overall work of adhesion of the microfiber arrays are measured and compared with the models to observe the effect of fiber geometry and preload. The adhesion strength and work of adhesion behavior of short and long vertical and long angled fiber arrays have similar trends with the numerical simulations. A scheme is also proposed to aid in optimized fiber adhesive design.     

An Improved Method to Determine Particle Dispersion Width for Efficient Modeling of Turbulent Two‐Phase Flows

An improved approach is presented for the hybrid Eulerian‐Lagrangian modeling of turbulent two‐phase flows. The hybrid model consists of a nonlinear k–ε model for the fluid flow and an efficient Lagrangian trajectory model for the particulate flow. The improved approach avoids an empirical correlation required to determine the dispersion width for the existing Stochastic‐Probabilistic Efficiency Enhanced Dispersion (SPEED) model. The improved SPEED model is validated using experimental data for a poly‐dispersed water spray interacting with a turbulent annular air jet behind a bluff‐body. Numerical results for the number‐mean and Sauter‐mean droplet diameters, as well as mean and fluctuating droplet velocities are compared with the experimental data and with the predictions of other dispersion models. It is demonstrated that higher computational efficiency and smoother profiles of Sauter‐mean diameter can be obtained with the improved stochastic‐probabilistic model than with the eddy‐interaction model.     

(2‐Hydroxy­ethyl)­hydrazinium(2+) dichloride

The crystal structure of the title compound, C₂H₁₀N₂O²⁺·2Cl⁻, is built up from one 2‐hydroxy­ethyl­hydrazinium(2+) cation and two Cl⁻ anions. The mol­ecular structure is stabilized by O—H⋯Cl and N—H⋯Cl hydrogen bonds. The crystal structure is stabilized by one N—H⋯O and three N—H⋯Cl inter­actions, and the three‐dimensional network of hydrogen bonds stabilizes the crystal packing. All five hydrazinium H atoms are involved in hydrogen bonds to Cl⁻ anions. The Cl⋯H contact distances range from 2.122 (15) to 2.809 (14) Å.     

Segmental dynamics in poly(methyl acrylate) on silica: molecular-mass effects

The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the polymer-air interface and the less-mobile species near the polymer-silica interface. The mobility of the adsorbed 77 kDa PMA sample was the lowest among the four different molecular-mass samples studied. Samples studied with masses both larger and smaller than 77 kDa had larger mobile-component fractions in the adsorbed polymer. The additional mobility was attributed to the presence of either longer tail and loop conformations in the higher molecular-mass samples or the inherent mobility of the tails in the lower molecular-mass samples on the surface.     

Characterization of N-Succinylation of L-Lysylphosphatidylglycerol in <Emphasis Type="Italic">Bacillus subtilis</Emphasis> Using Tandem Mass Spectrometry

Phospholipids generally dominate in bacterial lipids. The negatively charged nature of phospholipids renders bacteria susceptible to cationic antibiotic peptides. In comparison with Gram-negative bacteria, Gram-positive bacteria in general have much less zwitterionic phosphatidylethanolamine. However, they are known for producing aminoacylated phosphatidylglycerol (PG), especially positively charged l-lysyl-PG, which is catalyzed by lysyl-PG synthase MprF, which appears to have a broad range of specificity for l-aminoacyl transfer RNAs. In addition, many Gram-positive bacteria also have a dlt-gene-coded d-alanylation pathway for lipoteichoic acids and wall teichoic acids covalently attached to a glycolipid or peptidoglycan. d-Alanylation also masks the dominant negative charge of the phosphate-rich polymers of teichoic acids. Using mass spectrometry, we have recently observed that precursor scans in negative mode for deprotonated amino acid fragments were most sensitive for ester-linked amino acids. Such a scan for precursors generating an m/z 145 lysyl anion revealed lysyl-PG as well as an additional species 100?m/z units greater than lysyl-PG. This unexpected species corresponded precisely to the expected mass of N-succinylated lysyl-PG. Tandem mass spectrometry revealed a precise match to the fragmentation pattern of this putative new species. PG, lysyl-PG, and N-succinyl-lysyl-PG may form a complete loop of charge reversal from -1 to +1 and then back to -1. Analogous charge reversal by N-succinylation of lysine residues in the bacterial as well as eukaryotic proteomes has been recently discovered as a major posttranslational modification. Such modification in bacterial lipids is possibly catalyzed by an enzyme homologous to the enzymes that modify lysine residues in proteins.

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