Entropy and melt fracture

The onset of a well-known flow instability commonly called “melt fracture” has remained one of the fundamental unsolved problems of polymer rheology. This work attempts to explain this phenomenon via a criterion based upon limitations to configurational entropy as dicated by the second law of thermodynamics. It is shown that the molecular orientation resulting from a sustained stress-deformation rate field may be sufficient to affect the entropy balance of the system to the point of violation of the second law. The flow field then spontaneously changes, producing the condition called melt fracture, in a manner such as to prevent the violation of this law. Other theories on the mechanism of melt fracture are discussed in the context of the above criterion.     

ENTROPY AND AGING IN BIOLOGICAL SYSTEMS

The Second Law of Thermodynamics (which is often referred to as “times arrow” because it dictates the direction of increasing chronological time), should have a direct bearing on the aging process in biological systems. Basic aging related phenomena are discussed from the point of view of an entropy rate balance, and the known effects of body temperature, metabolic rate and food consumption rate on lifespan are considered. The problems of quantifying the rate of internal entropy production of complex systems is investigated using the fundamentals of non-equilibrium thermodynamics. Entropy rate balance data over the lifespan of the annual fish Nothobranchius guentheri are used to illustrate basic aging phenomena.     

The fate of chlorine in recirculating cooling towers Field results

Chlorine and chloramines are volatile compounds which are stripped (“flashed off”) from recirculating cooling water systems by the large volumes of air which flow through the water in the cooling tower. The fraction of a volatile gas, such as hypochlorous acid (HOCl), which is removed by stripping is determined by Henry's constant H for that gas: H = X_G/X_L, where X_G is the mole fraction of the gas in the air and X_L is the mole fraction of the gas in the water. We have measured H for HOCl, OCl⁻, NH₃, NH₂Cl, NHCl₂ and NCl₃ at 20 and 40°C. We found H = 0.076 for HOCl, compared to 0.71 for NH₃, at 20°C. At 40°C, H was about 2.5-fold larger for HOCl. This means that 10–15% of the HOCl is stripped from cooling water on each passage through a typical cooling tower. The measured flashoff of free available chlorine (HOCl + OCl⁻) was markedly pH-sensitive with a pK of 7.5, exactly as expected if HOCl is volatile but OCl⁻ is not. The data permit a quantitative understanding of the fate of chlorine in cooling systems. The values of H at 40°C for NH₂Cl, NHCl₂ and NCl₃ were 1.28, 3.76 and 1067. This means that all of the chloramines are quickly stripped in a cooling tower.     

Efficient procedures for the optimization of defects in photonic crystal structures

Seven different stochastic binary optimizers--based on the concepts of genetic algorithms and evolutionary strategies--are developed, applied to determine defect locations in several photonic crystal structures that serve as test cases, and compared by extensive statistical analysis. In addition to the stochastic optimizers, a quasi-deterministic optimizer based on an algorithm inspired by hill-climbing algorithms was implemented. The test cases include the prominent 90 degrees photonic crystal waveguide bend and a photonic crystal power divider. The analysis of the results shows that many different photonic crystal structures with high transmission may be found for any operating frequency. All of the eight optimizers outperform standard codes-because they maintain an incomplete fitness table-and find the global optima with a high probability even when the number of fitness evaluations is much smaller than the number of potential solutions contained in the discrete search space. Based on the incomplete fitness table, an algorithm to estimate bit-fitness values is presented. The bit-fitness values are then used to improve the performance of some algorithms. The four best algorithms-an extended microgenetic algorithm, two mutation-based algorithms, and the quasi-deterministic algorithm inspired by hill-climbing algorithms-are considered to be of high value for the optimization of defects in photonic crystals and for similar binary optimization problems.     

Development of a Metabolically Stable Neurotensin Receptor 2 (NTS2) Ligand

Subtype‐selective neurotensin receptor 2 (NTS2) ligands can be used as molecular probes to investigate the physiological role of neurotensinergic systems and serve as lead compounds to initiate the development of drugs for the treatment of tonic pain. Starting from our recently described NTS2 ligand 1 , structural variants of type 2 were synthesized to further improve binding affinity and selectivity to gain metabolic stability. The peptide–peptoid hybrid 2 b showed excellent NTS2 binding affinity (K_i=2.8 nM ) and 22 000‐fold selectivity over NTS1, as well as metabolic stability over 32 h in a serum degradation assay. Employing a MAPK‐driven luciferase reporter gene assay and an IP accumulation assay, the neurotensin mimetic 2 b displayed respective inhibitions of constitutive activity exceeding 4.3‐ and 3.9‐fold that of the inverse agonist activity of the endogenous ligand neurotensin.     

Development of lightweight high‐performance polymeric composites with functionalized nanotubes

In this article, we highlight the various properties of an ultralightweight poly(ether ketone) (PEK) composite. In this study, special emphases were laid on the preparation of low‐density, high‐performance polymeric foams with foaming agents and activators. PEK, foamed PEK, and carbon nanotube (CNT)–reinforced foamed PEK composites were considered for this study. The density of the polymer decreased with the reinforcement of the foaming agent. We also noted that with the reinforcement of the modified CNT in the foamed PEK, there were marginal increases in the density and hardness of the composites. We also noted that the mechanical properties of the CNT‐reinforced foamed PEK was on par with those of basic PEK. Thermogravimetric analysis gave us a clear indication that the thermal stability of the composites was not affected by the reinforcing foaming agent and nanoparticles. Scanning electron microscopy and transmission electron microscopy clearly indicated the formation of foams and also the dispersion of nanoparticles in the composite structure. We also observed that because of the reinforcement of multiwalled CNTs in the composite, there was an improvement in the hardness of the composite. An increase in the specific strength was observed in the foamed PEK composites. The CNT‐reinforced foamed PEK showed a marginal decrease in the specific strength without a compromise in the impact strength. The impact strength of the CNT‐reinforced foamed PEK composite was found to be similar to that of the basic PEK. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43471.     

Novel polyurethane dispersions based on renewable raw materials—Stability studies by variations of DMPA content and degree of neutralisation

Renewable resources, especially natural oils, have received increasing attention as raw materials for polymers. The synthesis and characterisation of novel aqueous polyurethane dispersions derived from rapeseed oil are investigated. The applied renewable polyol is high-hydrophobic due to the triglyceride backbone. Dimethylolpropionic acid (DMPA) as internal emulsifier was used to incorporate hydrophilic groups into the polymer chain to achieve stable self-emulsifying dispersions. By neutralisation of the carboxyl groups with triethylamine a predominately electrostatic stabilisation was generated. A weak steric stabilisation by pending chain ends exists beside the predominant electrostatic stabilisation. Outgoing from a DMPA content of 5.6 wt% related to the polymer, the content was decreased successively with the objective being to analyse the influence of ionic concentration and stability. Furthermore, the influence of the degree of neutralisation with respect to the stabilisation of these novel dispersions was investigated.     

Self-consistent algorithm for calibrating spectrometers to picometer accuracy over the entire wavelength range

Spectrometer calibration accuracies are of high importance for a wide range of applications. Typically, one calibrates the spectrometer with a calibration lamp, providing distinct and well-defined calibration lines. However, for small spectral ranges, where only two calibration lines are present, the calibration becomes inaccurate. We present a high-precision nonlinear wavelength calibration method, which is based on two or more reference lines from a calibration lamp. The additional key element introduced is a Fabry-Perot multilayer structure that yields multiple sharp transmission maxima of similar intensity over the full spectrometer range under broad-band illumination (e.g., white-light source). An iterative algorithm is put forward to obtain a self-consistent calibration of picometer precision over the full spectrometer range. In regions distant from calibration lines the accuracy is enhanced by at least a factor of two compared to conventional methods.     

Chemical Validation of DegS As a Target for the Development of Antibiotics with a Novel Mode of Action

Despite the availability of hundreds of antibiotic drugs, infectious diseases continue to remain one of the most notorious health issues. In addition, the disparity between the spread of multidrug-resistant pathogens and the development of novel classes of antibiotics exemplify an important unmet medical need that can only be addressed by identifying novel targets. Herein we demonstrate, by the development of the first in vivo active DegS inhibitors based on a pyrazolo[1,5-a]-1,3,5-triazine scaffold, that the serine protease DegS and the cell envelope stress-response pathway σE represent a target for generating antibiotics with a novel mode of action. Moreover, DegS inhibition is synergistic with well-established membrane-perturbing antibiotics, thereby opening promising avenues for rational antibiotic drug design.