Reduction in internal friction in silica glass with high OH content

The aim of this article was to investigate processes occurring during annealing of silica glass classified as being of type III (J Non Cryst Solids. 1970;5(2):123-75). This is an inexpensive silica glass produced by many manufacturers across the globe. However, it can be successfully used for fabrication of high-Q mechanical resonators. The relationship between residual internal stress and internal friction is elucidated. Quantitative analysis of the structural relaxation kinetics is presented. The influence of the cooling process for structural transformation is also discussed. On the basis of our results, we suggest optimal annealing conditions for minimizing internal friction type III silica glass. The results will be useful for further improvement of the Q-factor of mechanical resonators, including the test masses of the next generation of gravitational wave detectors. Our approach might, in addition, be used for studying the modification of atomic structure in multicomponent glasses.     

Cell-Based Optimization of Covalent Reversible Ketoamide Inhibitors Bridging the Unprimed to the Primed Site of the Proteasome β5 Subunit

The ubiquitin-proteasome system (UPS) is an established therapeutic target for approved drugs to treat selected hematologic malignancies. While drug discovery targeting the UPS focuses on irreversibly binding epoxyketones and slowly-reversibly binding boronates, optimization of novel covalent-reversibly binding warheads remains largely unattended. We previously reported α-ketoamides to be a promising reversible lead motif, yet the cytotoxic activity required further optimization. This work focuses on the lead optimization of phenoxy-substituted α-ketoamides combining the structure-activity relationships from the primed and the non-primed site of the proteasome β5 subunit. Our optimization strategy is accompanied by molecular modeling, suggesting occupation of P1′ by a 3-phenoxy group to increase β5 inhibition and cytotoxic activity in leukemia cell lines. Key compounds were further profiled for time-dependent inhibition of cellular substrate conversion. Furthermore, the α-ketoamide lead structure 27 does not affect escape response behavior in Danio rerio embryos, in contrast to bortezomib, which suggests increased target specificity.     

Synthesis of cross‐linked polyethylene oxide‐acetal macrocycles for solid superbase catalysts

A novel long‐chain divinyl ether of tris(diethyleneglycol)‐bisacetal, has been synthesized by electrophilic addition of one molecule of diethylene glycol to two molecules of divinyl ether of diethylene glycol (DVDEG) in the presence of CF₃COOH in quantitative yield. The monomer was cationically polymerized (BF₃·OEt₂, or complex LiBF₄·MeO(CH₂)₂OMe) and copolymerized with DVDEG to deliver solid polymers the yields being 80–100%. The polymers represent the cross‐linked polyether‐polyacetal structures comprising macrocycles. The polymers were treated with 3% solution of KOH or CsOH in methanol to afford solid superbase complexes of KOH (CsOH) with cross‐linked polyether‐polyacetal macrocyclic networks. Preliminary tests have shown the complexes to be active catalysts for ethynylation of acetones and prototropic isomerization of methyl propargyl ethers to allenyl methyl ethers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Catalysis of an Essential Step in Vitamin B2 Biosynthesis by a Consortium of Broad Spectrum Hydrolases

An enzyme catalysing the essential dephosphorylation of the riboflavin precursor, 5‐amino‐6‐ribitylamino‐2,4(1H,3H)‐pyrimidinedione 5′‐phosphate ( 6 ), was purified about 800‐fold from a riboflavin‐producing Bacillus subtilis strain, and was assigned as the translation product of the ycsE gene by mass spectrometry. YcsE is a member of the large haloacid dehalogenase (HAD) superfamily. The recombinant protein was expressed in Escherichia coli. It catalyses the hydrolysis of 6 (v_max, 12 μmol mg^?1 min^?1; K_M, 54 μm ) and of FMN (v_max, 25 μmol mg^?1 min^?1; K_M, 135 μm ). A ycsE deletion mutant of B. subtilis was not riboflavin dependent. Two additional proteins (YwtE, YitU) that catalyse the hydrolysis of 6 at appreciable rates were identified by screening 13 putative HAD superfamily members from B. subtilis. The evolutionary processes that have resulted in the handling of an essential step in the biosynthesis of an essential cofactor by a consortium of promiscuous enzymes require further analysis.     

Synthesis and gas permeation parameters of metathesis polytricyclononenes with pendant Me3E‐groups (E = C,Si, Ge)

Metathesis polytricyclononenes were synthesized via ROMP polymerization in the presence of the 1‐st generation Grubbs catalyst and their gas‐transport properties were studied for the first time. The aim of this work was to evaluate the influence of Me₃E‐groups (E = C, Si, Ge) on gas permeation parameters of ROMP materials. New metathesis poly(3‐tert‐butyltricyclononene‐7) and poly(3‐trimethylgermyltricyclononene‐7) were obtained with high yields (up to 95%) and high‐molecular weights (M_w～3–7×10⁵ g mol^?1). The glass transition temperatures of the ROMP polytricyclononenes with Me₃E‐groups decreased when E was changed from C to Si and then to Ge. It was shown that the polytricyclononene containing Me₃Si‐groups has the highest gas permeability while the polytricyclononene containing Me₃C‐substituents has the lowest gas permeability. In addition, the gas permeation parameters were estimated for ROMP Me₃Si‐ and Me₃Ge‐substituted polytricyclonona‐3,7‐dienes. So the influence of the second double bond in the monomer units on the permeability of the polymers obtained was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41395.     

Development and Application of a Label-Free Fluorescence Method for Determining the Composition of Gold Nanoparticle–Protein Conjugates

A method was developed for determining the composition of the conjugates between gold nanoparticles and proteins based on the intrinsic fluorescence of unbound protein molecules. The fluorescence was evaluated after separation of the conjugates from the reaction mixture by centrifugation. Gold nanoparticles obtained using the citrate technique (average diameter 24 nm) were conjugated at pH 5.4 with the following four proteins: human immunoglobulin G (IgG), bovine serum albumin (BSA), recombinant streptococcal protein G (protein G), and Kunitz-type soybean trypsin inhibitor (STI). The compositions of these conjugates were determined using the developed method. The conjugate compositions were dependent on the concentration of the added protein, and in all cases reached saturation. The equilibrium dissociation constants of the gold nanoparticle conjugates with IgG, BSA, protein G, STI in the initial section of the concentration dependence curve were 4, 6, 10, and 15 nM, respectively. Close to saturation, the corresponding values were 25, 76, 175, and 100 nM, respectively. The maximal binding capacities of a single gold nanoparticle for IgG, BSA, Protein G, and STI were 52, 90, 500, and 550, respectively, which agrees well with the hypothesis of monolayer immobilization.     

Absorption and reflection of infrared radiation by polymers in fire‐like environments

In large‐scale fires, the input of energy to burning materials occurs predominantly by radiative transfer. The in‐depth (rather than just surface) absorption of radiant energy by a polymer influences its ignition time and burning rate. The present investigation examines two methods for obtaining the absorption coefficient of polymers for infrared radiation from high‐temperature sources: a broadband method and a spectral method. Data on the total average broadband transmittance for 11 thermoplastics are presented (as are reflectance data), and the absorption coefficient is found to vary with thickness. Implications for modeling of mass loss experiments are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

The collision efficiency in a shear flow

Fluid flows with cohesive particles are present in oil industry (e.g. natural gas/oil with hydrates, wax or asphaltenes), medicine (e.g. blood cells), nano- and ferro-fluidic applications (e.g. fluids with nanoparticles subject to the van der Waals and electrostatic interactions) and even in astrophysics (e.g. grains in planetary rings). Such flows may lead to formation of agglomerates that, for example in pipelines, may result in unwanted phenomena such as formation of deposits. The main process parameter governing this is the “collision efficiency”, which is the ratio of the number of collisions resulting in agglomeration to the total number of collisions. This is commonly considered to depend on the relativemagnitudes of attractive and repulsive interactions during a collision. The effect of the particles' mechanical properties on the agglomeration efficiency has, however, not yet been studied. In this paper the agglomeration efficiency is studied as a function of inter-particle friction, stiffness, density and volume fraction by numerical simulation. By running direct numerical simulations (DNS) with Lagrangian particle tracking of a shear flow laden with solid particles, the parameters influencing the agglomeration efficiency are demonstrated and their effects quantified. Finally, an expression that relates the collision efficiency to the salient dimensionless physical parameters is proposed.     

Switching azonaphthols containing a side chain with limited flexibility. Part 1. Synthesis and tautomeric properties

A series of azo dyes, possessing amide fragments with restricted flexibility tethered to 4-(phenyldiazenyl)naphthalen-1-ol, was obtained from 1-hydroxy-2-naphthoic acid by subsequent conversion to amides and diazo coupling. It was shown that the position of the tautomeric equilibrium in solution strongly depends on the solvent in both UV and NMR concentration scale. The compounds exist as pure enol forms in chloroform and hydrocarbons, while in polar solvents (acetone, acetonitrile, alcohols) a tautomeric mixture is observed. According to the quantum-chemical calculations the aggregation of the keto tautomer is the possible reason for this shift in the position of the tautomeric equilibrium. To support the theoretical predictions, it was found that from acetone the keto form crystallizes as a dimer with hydrogen bonding between N₁-H in the one molecule and amide CO in the other forming a three-dimensional structure. The importance of the side-chain nitrogen atom on the dimer formation was confirmed by solution and solid state study of 4-(phenyldiazenyl)-2-acetylnaphthalen-1-ol. The results indicate that the new azo-dyes obtained could be suitable candidates for switching and sensing applications in non-polar solvents.