Influence of macromolecular structure of novel 2- and 4-armed polylactides on their physicochemical properties and in vitro degradation process

The objective of this study was to analyse how macromolecular structure of polylactides influences their properties and degradation rate. To achieve this, novel 2- and 4-armed PDLLA and PLLA (noted as 2b and 4b) were synthesized by ring-opening method. 1,4-butanediol and pentaerythritol were used as initiators and stannous octoate was used as catalyst. The obtained polymers were investigated in terms of molecular weight by size exclusion chromatography, thermal properties by differential scanning calorimetry and thermogravimetry, and hydrophilicity by the contact angle measurements. The in vitro degradation test was carried out in PBS solution at 37 °C by means of the mass loss, water uptake, molecular weight and thermal properties changes. The branched polylactides including 2bPDLLA, 4bPDLLA, 2bPLLA and 4bPLLA were successfully synthesized and the average molecular weights were around 40-45 kDa. The numbers of arms in each polymer just slightly influenced the thermal properties and the contact angle. The crystallinity of 4bPLLA was 23 %, whereas for 2bPLLA it was 41 %. The degradation rates of both 2b and 4bPLLA were similar and the degradation process was similar only during first 7 weeks. After this period, the degradation rate of 4bPDLLA increased. Consequently, thermal properties and degradation profiles of the branched polymers would depend on plural factors, such as chain length and crystallinity in branched structure.     

Modeling of the degradation kinetics of biodegradable scaffolds: The effects of the environmental conditions

The rate of hydrolytic degradation of tissue‐engineered scaffolds made from bioresorbable polyesters is dependent on several factors. Some are related to the properties of the degrading polymeric material, but others are related to the geometry of the porous structure and the operating environment. It is well known that the rate of hydrolytic degradation of a given object, porous or nonporous, is lower when it is exposed to dynamic conditions, a flowing medium, than when it operates in static conditions. The most likely reason is the more efficient removal of the acidic degradation products from the vicinity of the polymeric material when it is operating in a flowing medium. In this article, we present a new phenomenological reaction–diffusion model of aliphatic polymer degradation. The model can be used to predict the significance of various factors in in vitro degradation tests, with particular reference to the flow of the degradation medium, and the frequency of medium replacement in the case of static conditions. The developed model was used to simulate the degradation of poly(dl ‐lactide‐co‐glycolide) scaffolds with different porosities subjected to static and dynamic testing conditions. The results confirm that the porosity of the scaffold had a significant influence on the degradation rate. It was shown that the combination of dynamic conditions and high porosity effectively reduced the mass loss and molecular weight loss of the degrading polymer. However, the effect of changes in the velocity of the flowing medium had a negligible effect on the rate of degradation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40280.     

Sensitivity Analysis as a Tool for Estimating Numerical Modeling Results

Modeling of real physical processes by numerical methods is highly time-consuming and requires significant computational capacity. In some cases, tens or even hundreds of hours of high-power computing are needed to virtually model a real process that lasts one second. Processes that take many hours, such as drying, pose an even greater challenge. This problem can be solved in two ways: by using faster computers (such as computing clusters) or by significantly simplifying the modeled process (its geometry, physical phenomena, or the impact of individual factors). For this reason, all methods which speed up or minimize the number of simulations required to achieve the research objective should be analyzed. This article focuses on the latter approach, and it proposes a simple method for predicting the responses of a numerical model (values of any output parameter) to changes in input values (values of any input parameter). This method requires a base model, such as a numerical model which is qualitatively and quantitatively consistent with experimental observations, and a sensitivity analysis. This article discusses the mathematical and logical premises for the discussed model, and it proposes two methods for predicting numerical simulation results. Those methods are illustrated with examples which analyze the behavior of the Eulerian Multiphase Model and describe phase interactions based on Gidaspow's approach. The discussed example relies on data from a series of articles published by the authors in Drying Technology. This article was inspired by the observations made during a time-consuming process of modeling a spouted bed grain dryer, which was described in the above publications. The objective of this study was to discuss the advantages and possibilities created by sensitivity analyses of numerical models and to encourage their practical application.     

Heterogenicity within the LPS Structure in Relation to the Chosen Genomic and Physiological Features of the Plant Pathogen Pectobacterium parmentieri

Pectobacterium parmentieri is a pectinolytic plant pathogenic bacterium causing high economic losses of cultivated plants. The highly devastating potential of this phytopathogen results from the efficient production of plant cell wall-degrading enzymes, i.e., pectinases, cellulases and proteases, in addition to the impact of accessory virulence factors such as motility, siderophores, biofilm and lipopolysaccharide (LPS). LPS belongs to pathogen-associated molecular patterns (PAMPs) and plays an important role in plant colonization and interaction with the defense systems of the host. Therefore, we decided to investigate the heterogeneity of O-polysaccharides (OPS) of LPS of different strains of P. parmentieri, in search of an association between the selected genomic and phenotypic features of the strains that share an identical structure of the OPS molecule. In the current study, OPS were isolated from the LPS of two P. parmentieri strains obtained either in Finland in the 1980s (SCC3193) or in Poland in 2013 (IFB5432). The purified polysaccharides were analyzed by utilizing 1D and 2D NMR spectroscopy (¹H, DQF-COSY, TOCSY, ROESY, HSQC, HSQC-TOCSY and HMBC) in addition to chemical methods. Sugar and methylation analyses of native polysaccharides, absolute configuration assignment of constituent monosaccharides and NMR spectroscopy data revealed that these two P. parmentieri strains isolated in different countries possess the same structure of OPS with a very rare residue of 5,7-diamino-3,5,7,9-tetradeoxy-l-glycero-l-manno-non-2-ulosonic acid (pseudaminic acid) substituted in the position C-8: →3)-β-d-Galf-(1→3)-α-d-Galp-(1→8)-β-Pse4Ac5Ac7Ac-(2→6)-α-d-Glcp-(1→6)-β-d-Glcp-(1→. The previous study indicated that three other P. parmentieri strains, namely IFB5427, IFB5408 and IFB5443, exhibit a different OPS molecule than SCC3193 and IFB5432. The conducted biodiversity-oriented assays revealed that the P. parmentieri IFB5427 and IFB5408 strains possessing the same OPS structure yielded the highest genome-wide similarity, according to average nucleotide identity analyses, in addition to the greatest ability to macerate chicory tissue among the studied P. parmentieri strains. The current research demonstrated a novel OPS structure, characteristic of at least two P. parmentieri strains (SCC3193 and IFB5432), and discussed the observed heterogenicity in the OPS of P. parmentieri in a broad genomic and phenotype-related context.     

On the dynamic self-diffraction in methylene blue-sensitised gelatine

Dynamic self-diffraction processes have been observed and analysed for methylene blue-sensitised water-swollen gelatine (MBSG). A degenerate two-wave mixing experiment performed on thick samples of MBSG with 10 mW, 632.8 nm wavelength He Ne laser light allowed for the formation of phase- and amplitude-transient holographic gratings. Single-beam propagation characteristics through MBSG were measured with a Mach-Zehnder interferometer. The observed energy transfer between the writing beams in the two-beam coupling experiment and the considerable temporal oscillations of diffraction efficiency are explained by simple formulae. Two processes are considered: the time-dependent phase shift between the writing beams and the transverse self-phase modulation effects (self-focusing and interference ring formation).     

Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.     

Double-Headed Cationic Lipopeptides: An Emerging Class of Antimicrobials

Antimicrobial peptides (AMPs) constitute a promising tool in the development of novel therapeutic agents useful in a wide range of bacterial and fungal infections. Among the modifications improving pharmacokinetic and pharmacodynamic characteristics of natural AMPs, an important role is played by lipidation. This study focuses on the newly designed and synthesized lipopeptides containing multiple Lys residues or their shorter homologues with palmitic acid (C₁₆) attached to the side chain of a residue located in the center of the peptide sequence. The approach resulted in the development of lipopeptides representing a model of surfactants with two polar headgroups. The aim of this study is to explain how variations in the length of the peptide chain or the hydrocarbon side chain of an amino acid residue modified with C₁₆, affect biological functions of lipopeptides, their self-assembling propensity, and their mode of action.     

Fly ash as a sorbent for boron removal from aqueous solutions: Equilibrium and thermodynamic studies

ABSTRACT

This study presents the application of fly ash from brown coal and biomass burning power plant as a sorbent for the removal of boron ions from an aqueous solution. The adsorption process efficiency depended on the parameters, such as adsorbent dosage, pH, temperature, agitation time and initial boron concentration. The experimental data fitted well with the Freundlich isotherm model and the maximum capacity was found to be 16.14 mg g^?1. The adsorption kinetics followed the pseudo-second-order model. Also, the intra-particle diffusion model parameters were calculated. Thermodynamic parameters such as change in free energy (ΔG°), enthalpy (ΔH°), entropy (ΔS°) revealed on exothermic nature of boron adsorption onto the fly ash.     

Fully automatic AI-based leak detection system

This paper presents a fully automatic system intended to detect leaks of dielectric fluid in underground high-pressure, fluid-filled (HPFF) cables. The system combines a number of artificial intelligence (AI) and data processing techniques to achieve high detection capabilities for various rates of leaks, including leaks as small as 15 l per hour. The system achieves this level of precision mainly thanks to a novel auto-tuning procedure, enabling learning of the Bayesian network – the decision-making component of the system – using simulated leaks of various rates. Significant new developments extending the capabilities of the original leak detection system described in [1] and [2] form the basis of this paper. Tests conducted on the real-life HPFF cable system in New York City are also discussed.