Synthesis of Novel 1‐(Benzo[d]thiazol‐2‐yl)‐1H‐pyrrol‐2(5H)‐ones

The titled products comprising of two mutually merged bioactive nucleuses, 2‐aminobenzo[d]thiazole and 2,5‐dihydropyrrole rings, were obtained from the reaction between dialkyl acetylenedicarboxylates and alkyl 2‐(benzo[d]thiazol‐2‐yl)amino‐2‐oxoacetates in the presence of triphenylphosphine at RT.     

Small-scale effect on the vibration of thin nanoplates subjected to a moving nanoparticle via nonlocal continuum theory

The vibration of elastic thin nanoplates traversed by a moving nanoparticle involving Coulomb friction is investigated using the nonlocal continuum theory of Eringen. The eigen function technique and the Laplace transform method are employed to solve the governing equations of the nanoplate. The explicit expressions of the in-plane and transverse displacements are obtained when the moving nanoparticle traverses the nanoplate on an arbitrary straight line. In a special case, the obtained results are also compared with those of other researchers and a reasonably good agreement is achieved. The effects of small-scale parameters and velocity of the moving nanoparticle on the dynamic response as well as the dynamic amplitude factors (DAFs) of the in-plane and transverse displacements are then explored in some detail. The results indicate that the magnitude of DAF of the transverse displacement of the nanoplate (i.e., DAF_w) increases with the first small-scale effect parameter, irrespective of the values of the second small-scale effect parameter and the velocity of the moving nanoparticle. As the first small-scale effect parameter grows, the maximum values of DAF_w as a function of the moving nanoparticle velocity increase and generally occur in the lower levels of the moving nanoparticle velocity.     

Boronic acid hydrogen bonding in encapsulation complexes

Hydrogen bonding is a key determinant of much macromolecular structure in nature, but individual donor and acceptor pairs are rarely observed in solution. Their weak interactions result in nanosecond lifetimes and rapid exchange of partners. Reversible encapsulation isolates molecules in very small spaces for milliseconds to hours and allows their characterization by NMR methods. Here we report a competitive study of hydrogen-bonding functions--carboxylic acids, primary amides, and boronic acids--within a multicomponent capsular assembly. The pairwise co-encapsulation of these molecules allows the direct observation of homodimeric boronic acids and their heterodimeric complexes with carboxylic acids and primary amides. The efficiency of boronic acids as hydrogen-bonding partners derives from their adaptable structures rather than from their intrinsic acid/base properties.     

Investigating the interactions of the first 17 amino acid residues of Huntingtin with lipid vesicles using mass spectrometry and molecular dynamics

The first 17 amino acid residues of Huntingtin protein (Nt17 of htt) are thought to play an important role in the protein's function; Nt17 is one of two membrane binding domains in htt. In this study the binding ability of Nt17 peptide with vesicles comprised of two subclasses of phospholipids is studied using electrospray ionization ‐ mass spectrometry (ESI‐MS) and molecular dynamics (MD) simulations. Overall, the peptide is shown to have a greater propensity to interact with vesicles of phosphatidylcholine (PC) rather than phosphatidylethanolamine (PE) lipids. Mass spectra show an increase in lipid‐bound peptide adducts where the ordering of the number of such specie is 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC) > 1‐palmitoyl‐2‐oleoyl‐glycero‐3‐phosphocholine (POPC) > 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3 phosphoethanolamine (POPE). MD simulations suggest that the compactness of the bilayer plays a role in governing peptide interactions. The peptide shows greater disruption of the DOPC bilayer order at the surface and interacts with the hydrophobic tails of lipid molecules via hydrophobic residues. Conversely, the POPE vesicle remains ordered and lipids display transient interactions with the peptide through the formation of hydrogen bonds with hydrophilic residues. The POPC system displays intermediate behavior with regard to the degree of peptide‐membrane interaction. Finally, the simulations suggest a helix stabilizing effect resulting from the interactions between hydrophobic residues and the lipid tails of the DOPC bilayer.     

A nickel hydride complex in the active site of methyl-coenzyme m reductase: implications for the catalytic cycle

Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes the key step in the process, namely methyl-coenzyme M (CH3-S-CoM) plus coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. The active site of MCR contains the nickel porphinoid F430. We report here on the coordinated ligands of the two paramagnetic MCR red2 states, induced when HS-CoM (a reversible competitive inhibitor) and the second substrate HS-CoB or its analogue CH3-S-CoB are added to the enzyme in the active MCR red1 state (Ni(I)F430). Continuous wave and pulse EPR spectroscopy are used to show that the MCR red2a state exhibits a very large proton hyperfine interaction with principal values A((1)H) = [-43,-42,-5] MHz and thus represents formally a Ni(III)F430 hydride complex formed by oxidative addition to Ni(I). In view of the known ability of nickel hydrides to activate methane, and the growing body of evidence for the involvement of MCR in "reverse" methanogenesis (anaerobic oxidation of methane), we believe that the nickel hydride complex reported here could play a key role in helping to understand both the mechanism of "reverse" and "forward" methanogenesis.     

Structural paradigms in macropolyhedral boranes

Macropolyhedral borane clusters are concave polyhedra constituting fused convex simple polyhedra. They are formally obtained by condensation of simple polyhedral boranes under elimination of between one and four BH(3) or isoelectronic units. The number of eliminated vertexes from simple polyhedra equals the number of shared vertexes in macropolyhedral boranes. For each of the eight classes with general formulae ranging from B(n)H(n-4) to B(n)H(n+10), more than one structure type is possible, differing in the number of shared vertexes and in the types of the two combined cluster fragments. However, only one type of "potential structures" is represented by experimentally known examples and is found to be favored by theoretical calculations. A sophisticated system exists among the favored macropolyhedral borane structures. For each class of macropolyhedral boranes, the number of skeletal electron pairs is directly related to the general formula, the number of shared vertexes and the type of fused cluster fragments. In order to predict the distribution of vertexes among the fused fragments, we propose the concept of preferred fragments. Preferred fragments are those usually present in the thermodynamically most stable structure of a given class of macropolyhedral boranes and are also frequently observed in the experimentally known structures. This allows us to completely predict the cluster framework of the thermodynamically most stable macropolyhedral borane isomers.     

Investigation of turbulent flow past a flagged short finite circular cylinder

This study was conducted to investigate the flow structures of turbulent flow passing over a short finite cylinder in which a rigid flag is attached to the rear of the cylinder, in wake region. The length-to-diameter ratio of the cylinder was chosen to be L/D = 2, whereas the rigid flag had a width-to-diameter ratio of W/D = 1.5. Wall-adapted large-eddy simulation (LES-WALE) was used to resolve unsteady turbulent flow structures. The far field Reynolds number based on cylinder diameter was chosen to be 20,000. The results were compared with the regular case wherein no flag was attached to the cylinder. Results revealed that the flow pattern behind the cylinder with flag was totally different in comparison with the regular case one. However, top free end of the cylinder was not influenced by the flag in contrast with the wake region. At far downstream from the cylinder, most of the flow structures in both cases appeared the same. The horseshoe vortices in both cases appeared to be an unsteady phenomenon, with slightly different patterns. Moreover, in the case of flag attachment, the pressure coefficient was smaller than that of with no flag. Finally, it was shown that the main and secondary Strouhal numbers locations were different in both cases.     

Exploring the Loading Capacity of Generation Six to Eight Dendronized Polymers in Aqueous Solution

Aspects of size, structural (im)perfection, inner density, and guest molecule loading capacity of dendronized polymers (DPs) of high generation (6≤g≤8) in aqueous solution are studied using electron paramagnetic resonance spectroscopy on amphiphilic, spin‐labeled guest molecules. The results show that the interior of the charged DPs is strongly polar, especially in comparison to their lower generation (1–4) analogues. This is a direct sign that large amounts of water penetrate the DP surface, reflecting the structural (im)perfections of these high‐generation DPs and much lower segmental densities than theoretically achievable. Images obtained with atomic force microscopy reveal that the high‐generation DPs do not aggregate and give further insights into the structural imperfections. Electron paramagnetic resonance spectroscopic data further show that despite their structural imperfections, these DPs can bind and release large numbers of amphiphilic molecules. It is concluded that attention should be paid to their synthesis, for which a protocol needs to be developed that avoids the relatively large amount of defects generated in the direct conversion of a generation g=4 DP to a generation g=6 DP, which had to be used here.     

The effect of electrospinning parameters on the compliance behavior of electrospun polyurethane tube for artificial common bile duct

The present research introduced a method to produce an artificial common bile duct using electrospinning technique. Also, the effect of electrospinning variables on the mechanical properties of produced prostheses is investigated. Using electrospinning of polyurethane nanofibres, cylindrical prostheses were produced on a rotating mandrel considering the different controllable factors such as the mandrel rotational speed, the applied voltage, and the flow rate of polymer solution. Taguchi method was used to investigate the effect of mentioned factors on the compliance of circular prostheses. MTT assay was performed to study the cytotoxicity of prostheses. The results of the signal-to-noise analysis showed that the mandrel rotational speed factor has the strongest effect on the compliance values. The flow rate was the second factor and it was followed by electrospinning voltage. In addition, the optimum conditions to reach the highest compliance value were determined. The results of MTT assay indicated no cytotoxic effects of prostheses on the cells. The compliance of optimum prosthesis was found close to the compliance value of a native common bile duct.