Kinetics of hydroxymethyl phenols formation by in‐line FTIR spectroscopy

The kinetics of phenol–formaldehyde prepolymers catalyzed by sodium hydroxide at various temperatures was studied. Several reactions were conducted with different phenol to formaldehyde as well as phenol to sodium hydroxide molar ratios. The React‐IR system was used to monitor the reaction as well as to determine residual free phenol and formaldehyde. The changes in the concentrations of phenol and formaldehyde with the reaction time were determined. The value of the concentration of the hydroxide ion, [OH^?], was obtained by measuring the pH value of reaction mixture. The concentration of the hydroxide ion, [OH^?], expressed as a function of reaction time, was fitted by the six‐order polynomial to the experimental data. On the basis of the proposed reaction scheme the kinetic model was developed. The kinetic parameters were obtained by adjusting the experimental evolution of phenol and formaldehyde during the synthesis. Using this method the changes in the concentrations of five species of hydroxymethyl phenols with the reaction time was also been calculated. The activation energy and preexponential factor have been calculated for individual reactions. The accuracy of the kinetic model was confirmed by comparing experimental concentration profiles of formaldehyde and phenol with the calculated ones for different molar ratios. The experimental tendencies are in agreement with the results of the model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fast single domain–subdomain BEM algorithm for 3D incompressible fluid flow and heat transfer

In this paper acceleration and computer memory reduction of an algorithm for the simulation of laminar viscous flows and heat transfer is presented. The algorithm solves the velocity–vorticity formulation of the incompressible Navier–Stokes equations in 3D. It is based on a combination of a subdomain boundary element method (BEM) and single domain BEM. The CPU time and storage requirements of the single domain BEM are reduced by implementing a fast multipole expansion method. The Laplace fundamental solution, which is used as a special weighting function in BEM, is expanded in terms of spherical harmonics. The computational domain and its boundary are recursively cut up forming a tree of clusters of boundary elements and domain cells. Data sparse representation is used in parts of the matrix, which correspond to boundary‐domain clusters pairs that are admissible for expansion. Significant reduction of the complexity is achieved. The paper presents results of testing of the multipole expansion algorithm by exploring its effect on the accuracy of the solution and its influence on the non‐linear convergence properties of the solver. Two 3D benchmark numerical examples are used: the lid‐driven cavity and the onset of natural convection in a differentially heated enclosure. Copyright © 2008 John Wiley & Sons, Ltd.     

Filler-Enhanced Piezoelectricity of Poly-L-Lactide and Its Use as a Functional Ultrasound-Activated Biomaterial

Poly-L-lactide (PLLA) offers a unique possibility for processing into biocompatible, biodegradable, and implantable piezoelectric structures. With such properties, PLLA has potential to be used as an advanced tool for mimicking biophysical processes that naturally occur during the self-repair of wounds and damaged tissues, including electrostimulated regeneration. The piezoelectricity of PLLA strongly depends on the possibility of controlling its crystallinity and molecular orientation. Here, it is shown that modifying PLLA with a small amount (1 wt%) of crystalline filler particles with a high aspect ratio, which act as nucleating agents during drawing-induced crystallization, promotes the formation of highly crystalline and oriented PLLA structures. This increases their piezoelectricity, and the filler-modified PLLA films provide a 20-fold larger voltage output than nonmodified PLLA during ultrasound (US)-assisted activation. With 99% PLLA content, the ability of the films to produce reactive oxygen species (ROS) and increase the local temperature during interactions with US is shown to be very low. US-assisted piezostimulation of adherent cells directly attach to their surface (such as skin keratinocytes), stimulate cytoskeleton formation, and as a result cells elongate and orient themselves in a specific direction that align with the direction of PLLA film drawing and PLLA dipole orientation.     

Culturomics meets random fractal theory: insights into long-range correlations of social and natural phenomena over the past two centuries

Culturomics was recently introduced as the application of high-throughput data collection and analysis to the study of human culture. Here, we make use of these data by investigating fluctuations in yearly usage frequencies of specific words that describe social and natural phenomena, as derived from books that were published over the course of the past two centuries. We show that the determination of the Hurst parameter by means of fractal analysis provides fundamental insights into the nature of long-range correlations contained in the culturomic trajectories, and by doing so offers new interpretations as to what might be the main driving forces behind the examined phenomena. Quite remarkably, we find that social and natural phenomena are governed by fundamentally different processes. While natural phenomena have properties that are typical for processes with persistent long-range correlations, social phenomena are better described as non-stationary, on–off intermittent or Lévy walk processes.     

Three Important Points that Relate to Improving the Hot Workability of Ledeburitic Tool Steels

In this article, the importance of selecting the right process parameters for ledeburitic tool steels, i.e., casting temperature, cooling rate, and soaking temperature, which is needed to improve their intrinsic hot workability, is presented. The results were obtained from investigations in industrial practice and in the laboratory. It was found that inappropriate selection of these process parameters results in the occurrence of carbides that are not usually present in these types of steels, in terms of type, shape, fractions, and their distribution that decreases the steels?? hot workability. In particular, a casting temperature that is too high and cooling rates that are too low result in the additional precipitation of carbides, which are not common in these steels, leading to cracking, predominately along these carbide stringers and consequently to a deterioration of the hot workability and the properties of the final products. It was also found that by selecting the proper soaking conditions, it is possible to decrease the negative influence of previous processing parameters on the hot workability.     

Two robust long short-term memory frameworks for trading stocks

This paper aims to find a superior strategy for the daily trading on a portfolio of stocks for which traditional trading strategies perform poorly due to the low frequency of new information. The experimental work is divided into a set of traditional trading strategies and a set of long short-term memory networks. The networks incorporate general and specific trading patterns, where the former takes into account the universal decision factors for trading across many stocks, while the latter takes into account stock-specific decision factors. Our research shows that both long short-term memory networks, regardless of whether they are based on universal or stock-specific decision factors, significantly outperform traditional trading strategies. Interestingly, however, on average neither has the edge compared to the other, thus remaining ambivalent as to whether universality or specificality is to be preferred when it comes to designing long short-term memory networks for optimal trading.

     

When is it better not to look ahead?

In situations where one needs to make a sequence of decisions, it is often believed that looking ahead will help produce better decisions. However, it was shown 30 years ago that there are “pathological” situations in which looking ahead is counterproductive. Two long-standing open questions are (a) what combinations of factors have the biggest influence on whether lookahead pathology occurs, and (b) whether it occurs in real-world decision-making.This paper includes simulation results for several synthetic game-tree models, and experimental results for three well-known board games: two chess endgames, kalah (with some modifications to facilitate experimentation), and the 8-puzzle. The simulations show the interplay between lookahead pathology and several factors that affect it; and the experiments confirm the trends predicted by the simulation models. The experiments also show that lookahead pathology is more common than has been thought: all three games contain situations where it occurs.     

Discovery of Mono‐ and Disubstituted 1H‐Pyrazolo[3,4]pyrimidines and 9H‐Purines as Catalytic Inhibitors of Human DNA Topoisomerase IIα

Human DNA topoisomerase IIα (htIIα) is a validated target for the development of anticancer agents. Based on structural data regarding the binding mode of AMP‐PNP (5′‐adenylyl‐β,γ‐imidodiphosphate) to htIIα, we designed a two‐stage virtual screening campaign that combines structure‐based pharmacophores and molecular docking. In the first stage, we identified several monosubstituted 9H‐purine compounds and a novel class of 1H‐pyrazolo[3,4]pyrimidines as inhibitors of htIIα. In the second stage, disubstituted analogues with improved cellular activities were discovered. Compounds from both classes were shown to inhibit htIIα‐mediated DNA decatenation, and surface plasmon resonance (SPR) experiments confirmed binding of these two compounds on the htIIα ATPase domain. Proposed complexes and interaction patterns between both compounds and htIIα were further analyzed in molecular dynamics simulations. Two compounds identified in the second stage showed promising anticancer activities in hepatocellular carcinoma (HepG2) and breast cancer (MCF‐7) cell lines. The discovered compounds are suitable starting points for further hit‐to‐lead development in anticancer drug discovery.