First Nitroxide‐Mediated Controlled/Living Free Radical Polymerization in an Ionic Liquid

Summary: The controlled/living radical polymerizations of methyl acrylate in 50% v/v of an ionic liquid initiated by the alkoxyamine generated in situ from 4‐oxo‐2,2,6,6‐tetramethyl‐1‐piperidinyl‐N‐oxyl (4‐oxo‐TEMPO) and 2,2′‐azoisobutyronitrile (AIBN) at 140–155 °C are reported. The number‐average molecular weights increased linearly with conversion, and polydispersity indices are approximately 1.4 in the best case. The rates of polymerization were greater than in anisole, and similar to the rate of spontaneous polymerization in the ionic liquid.

(filled symbols) and (open symbols) vs. conversion for the MA polymerization in the presence of [4‐oxo‐TEMPO]/[AIBN] (2.8:1) in 50% v/v anisole with 0.03 M AIBN (squares) and 50% v/v [hmim][PF₆] with 0.03 M AIBN (circles), and 0.06 M AIBN (triangles).     

Noncovalent inhibition of the serine proteases, alpha-chymotrypsin and trypsin by trifluoro(organo)borates

A series of potassium organotrifluoroborates were synthesized. Their stability to hydrolysis was determined in D2O, TRIS and phosphate buffer. It was found that in both D2O and TRIS buffers, these compounds are quite stable, whereas in phosphate buffer rapid hydrolysis occurs. Based on these results, a study was undertaken to determine whether potassium organotrifluoroborates can serve as protease inhibitors. It was found that potassium organotrifluoroborates increased inhibition by at least an order of magnitude over the corresponding boronates. Dixon plots showed that these compounds are reversible competitive inhibitors of alpha-chymotrypsin and trypsin. Based on 19F NMR, we speculate that they inactivate the enzymes as a result of the formation of hydrogen-bonds between fluorine atoms of the inhibitors and the serine protease.     

Two results in metric fixed point theory

We establish two fixed point theorems for certain mappings of contractive type. The first result is concerned with the case where such mappings take a nonempty, closed subset of a complete metric space X into X, and the second with an application of the continuation method to the case where they satisfy the Leray–Schauder boundary condition in Banach spaces.     

Complete dynamical analysis of a neuron under magnetic flow effect

In the last decades, many studies have been done about nervous system from the mathematical and computational point of view. Many mathematical models have been proposed to describe neuron. Most of them have described the membrane potential of a neuron in terms of the leakage current and the synaptic inputs. Very recently, according to the Maxwell electromagnetic induction theorem, researchers proposed a new neuron model which considers inner magnetic fluctuation and external electromagnetic radiation as a significant missing part that can participate in neural activity. In this paper, dynamical properties of this new model, such as equilibria and its stability, phase portraits, bifurcation diagram, Lyapunov exponents, and basin of attraction, are investigated. Moreover, an implementation of electronic circuit and FPGA is also done to verify the feasibility of the theoretical model.     

Adsorption modeling and mechanistic insight of hazardous chromium on para toluene sulfonic acid immobilized-polyaniline@CNTs nanocomposites

The development of highly efficient adsorbents materials for the purification of wastewater has caught a considerable deal of attention these days. Conducting polymers functionalized adsorbents has become a favorable route for enhancing their adsorption capability due to their ease of synthesis at laboratory scale. In this study, functionalized multiwalled carbon nanotube (CNT)-polyaniline (Pani) composites were fabricated using an oxidation polymerization methodology and later doped with para toluene sulfonic acid (pTSA). The CNTs provided an adequate substrate for the adhesion of Pani as well as a large surface area due to its nano size, and pTSA provided additional functionality for the adsorption of differently charged moieties through strong or weak interactions. The as-synthesized pTSA-Pani@CNT nanocomposite was analyzed by the scanning electron microscopy, transmission electron microscopy for the morphological studies and the structural analysis were done by the X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The characterization results confirmed that the Pani was adhered to the CNTs as well as its successful functionalization with pTSA. The pTSA-Pani@CNT composite was then applied to the adsorptive removal of hexavalent chromium (Cr(VI)) and the composite showed higher adsorption for Cr(VI) than pTSA-CNT and pTSA-Pani, and the maximum removal level was detected at acidic pH. The analyses of the equilibrium isotherms and adsorption kinetics were performed to elucidate the adsorption mechanism. The XPS analysis indicated that Cr(VI) was strongly bounded to the adsorbent and it further indicated that the amine, imine, and hydroxyl functional groups were involved in the adsorption process. This study presents a new insight for the fabrication of highly functional polymer-carbonaceous nanocomposites for the scavenging of heavy metals from water bodies.     

Modeling of Neurodegenerative Diseases Using Discrete Chaotic Systems

Parkinson's and Huntington's diseases are two of the most common neurodegenerative disorders.Tremor, muscle stiffness, and slowness of movement are symptoms of Parkinson's disease. The symptoms of Huntington's disease are severe reduction in muscle control, emotional disturbance, and pathological disorders in brain cells.These diseases are caused by destruction of the cells that secrete a substance called dopamine. In this paper,a new discrete chaotic system is introduced,which can mimic the brain's behavior for neurodegenerative diseases such as Parkinson,Huntington, and Hypokinesia. This system is described based on the similarity between the brain's behavior in normal and abnormal conditions and the chaotic systems. Bifurcation analysis is carried out with respect to different parameters, providing full spectrum of the behavior for different parameter values.Our results can be used to mathematically study the mechanisms behind these diseases.     

Radiobiological Implications of Nanoparticles Following Radiation Treatment

Materials with a high atomic number (Z) are shown to cause an increase in the level of cell kill by ionizing radiation when introduced into tumor cells. This study uses in vitro experiments to investigate the differences in radiosensitization between two cell lines (MCF-7 and U87) and three commercially available nanoparticles (gold, gadolinium, and iron oxide) irradiated by 6 MV X-rays. To assess cell survival, clonogenic assays are carried out for all variables considered, with a concentration of 0.5 mg mL⁻¹ for each nanoparticle material used. This study demonstrates differences in cell survival between nanoparticles and cell line. U87 shows the greatest enhancement with gadolinium nanoparticles (2.02 ± 0.36), whereas MCF-7 cells have higher enhancement with gold nanoparticles (1.74 ± 0.08). Mass spectrometry, however, shows highest elemental uptake with iron oxide and U87 cells with 4.95 ± 0.82 pg of iron oxide per cell. A complex relationship between cellular elemental uptake is demonstrated, highlighting an inverse correlation with the enhancement, but a positive relation with DNA damage when comparing the same nanoparticle between the two cell lines.     

Prevalence of odometers in cellular automata

We consider left permutive cellular automata  with no memory and positive anticipation, defined on the space of all doubly infinite sequences with entries from a finite alphabet. For each such automaton that is not one-to-one, there is a dense set of points  such that is topologically conjugate to an odometer, the ``' map on the countable product of finite cyclic groups. This set is a dense subset of an appropriate subspace. We identify the odometer in several cases.

     

Chain transfer to solvent in the radical polymerization of N‐isopropylacrylamide

Chain transfer to solvent has been investigated in the conventional radical polymerization and nitroxide‐mediated radical polymerization (NMP) of N‐isopropylacrylamide (NIPAM) in N,N‐dimethylformamide (DMF) at 120 °C. The extent of chain transfer to DMF can significantly impact the maximum attainable molecular weight in both systems. Based on a theoretical treatment, it has been shown that the same value of chain transfer to solvent constant, C_tr,S, in DMF at 120 °C (within experimental error) can account for experimental molecular weight data for both conventional radical polymerization and NMP under conditions where chain transfer to solvent is a significant end‐forming event. In NMP (and other controlled/living radical polymerization systems), chain transfer to solvent is manifested as the number‐average molecular weight (M_n) going through a maximum value with increasing monomer conversion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Investigation of porous graphitic carbon at high-temperature liquid chromatography with evaporative light scattering detection for the analysis of the drug combination artesunate—Azithromycin for the treatment of severe malaria

Artesunate combined therapies represent the best option for the treatment of malaria and require the development of new methods of analysis. Retention, selectivity and detection with high-temperature liquid chromatography-porous graphitic carbon-evaporative light scattering detection was studied for artesunate and azithromycin separation. Organic solvent, concentration of organic modifiers, temperature and flow rate were all relevant parameters to optimize this separation. The behaviour of artesunate in the tested conditions appeared close to a neutral compound. In CH₃OH, only azithromycin retention was dramatically altered depending on the [triethylamine]/[formic acid] ratio and on the temperature, whereas in CH₃CN, azithromycin, artesunate, artemisinin and dihydroartemisinin retentions decreased with the temperature increase whatever the organic modifier ratio. The best efficiency was obtained with CH₃CN. 25% variation of the concentration values of the organic modifiers did not significantly influenced the retention. The sensitivity of ELSD increased with the flow rate decrease. Peak area and S/N ratio dramatically decreased with the flow rate increase by 10- and 5-fold for artesunate and azithromycin, respectively. Non-linear calibration curves were obtained for both artesunate and azithromycin.