Synthesis of versatile TIPNO-based alkoxyamines

The versatile chloromethyl TIPNO-based alkoxyamine was efficiently transformed into other valuable functionalised TIPNO-based alkoxyamines such as amino alkoxyamines which are interesting initiators for block copolymers and bisalkoxyamines in good yield and in two steps at the most. One bisalkoxyamine has allowed to prepare well-defined polystyrene-b-poly(n-butyl acrylate)-b-polystyrene symmetrical triblock copolymer. The last representative example of such alkoxyamines is a styrenic alkoxyamine which was copolymerized with styrene to afford branched polystyrene. Finally, for the first time branched poly(n-butyl acrylate) by nitroxide mediated radical polymerization was obtained and was a efficient macroinitiator of styrene, which indicates that the radical polymerization mediated by this styrenic alkoxyamine is living.     

Mathematical modelling of mass transfer in the concentration polarisation layer of flat‐sheet membranes during clarification of pomegranate juice

Evaluation of membrane clarification of pomegranate juice showed that a cake layer is created at the beginning of the process. This evaluation was used as the basis for modelling the solute concentration in the concentration polarisation layer to control the fouling of the membrane. The model of changes in concentration as a function of time and distance (in its dimensionless form) was solved numerically using the Forward‐Time/Central‐Space (FTCS) method. Programming was performed using MATLAB software, and the predicted concentration on the membrane surface was compared with experimental data; the prediction fit well with the experimental data. The model showed that the solute concentration increased as distance to the membrane surface decreased, time increased, transmembrane pressure increased and velocity decreased. Also, the model matched the experimental data in that it showed the cake layer to be created in the early stages of the membrane clarification process.     

Optimization of the water-based road-marking paint by experimental design, mixture method

The main purpose of this research is formulating and optimizing a new road-marking paint which is an environmentally friendly product. This paint is produced with an emulsion of an acrylic copolymer and contains the least of the volatile organic compounds. The formulation and optimization procedure is carried out on the base of experimental design by the method of mixture in which the important paint properties are modeled by using special cubic model. The present method has the capability of investigation the effect of raw materials at different levels with fewer experiments than factorial and fractional factorial design.

In this research, the main parameters such as resin, pigment and filler were selected at different levels, and different samples were prepared by combination of additives and other required reagents. The properties of wet and dry films of the samples were determined using ASTM test methods. Different responses such as pigment volume concentration (PVC), latex critical pigment volume concentration (LCPVC), abrasion resistance, hardness, gloss, no pick up time and surface drying time, were selected as the objective functions of this study. By running DX6 software, using special cubic model and selection of desired range of end-use properties, the region of optimum paint formula was determined.

The accuracy of the model was examined by preparing a sample in optimized region and by determining its final properties, experimentally. The results exhibit a good agreement between the model and experimental measurements. This product was compared with commercial solvent based traffic paint and good quality was reported in end-use properties.     

Heat capacities of aluminium alloys

In the framework of the European COST 507 project the specific heat capacities of aluminium alloys and metal matrix composites based thereon have been measured between 20 and 520 °C by differential scanning calorimetry and stored in the databank THERSYST along with other thermophysical properties mainly drawn from literature. The curves show the influence of additional elements and reinforcements, of the fabrication process, thermomechanical treatment and scanning rate on the precipitation and dissolution kinetics of the various metastable phases and their relative amounts. The database may be used to select existing light alloys or elaborate new ones in view of specific technical applications.Dedicated to Professor Dr. Hans Löffler on the occasion of his 72nd birthday.     

Adult age differences in episodic memory: Further support for an associative-deficit hypothesis.

This study further tested an associative-deficit hypothesis (ADH; M. Naveh-Benjamin, 2000), which attributes a substantial part of older adults' deficient episodic memory performance to their difficulty in merging unrelated attributes-units of an episode into a cohesive unit. First, the results of 2 experiments replicate those observed by M. Naveh-Benjamin (2000) showing that older adults are particularly deficient in memory tests requiring associations. Second, the results extend the type of stimuli (pictures) under which older adults show this associative deficit. Third, the results support an ADH in that older adults show less of an associative deficit when the components of the episodes used are already connected in memory, thereby facilitating their encoding and retrieval. Finally, a group of younger adults who encoded the information under divided-attention conditions did not show this associative deficit. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Dosimetric characteristic of a new 125I brachytherapy source

A new brachytherapy (125)I source has been investigated at Iranian Agricultural, Medical and Industrial Research School. Dosimetric characteristics [dose-rate constant Λ, radial dose function g(l)(r) and anisotropy function F(r,)] of IRA-(125)I were theoretically determined in terms of the updated AAPM task group 43 (TG-43U1) recommendations. Versions 5 and 4C of the Monte Carlo radiation transport code were used to calculate the dosimetry parameters around the source. The Monte Carlo calculated dose-rate constant of the (125)I source in water was found to be 92×10(-4) Gy h(-1) U(-1) with an approximate uncertainty of ±3 %. Brachytherapy seed model, 6711-(125)I, carrying (125)I radionuclides, was modelled and benchmarked against previously published values. Finally, the calculated results were compared with the published results of those of other source manufacturers.     

Topical Capsaicin in Poly(lactic-co-glycolic)acid (PLGA) Nanoparticles Decreases Acute Itch and Heat Pain

Background: Capsaicin, the hot pepper agent, produces burning followed by desensitization. To treat localized itch or pain with minimal burning, low capsaicin concentrations can be repeatedly applied. We hypothesized that alternatively controlled release of capsaicin from poly(lactic-co-glycolic acid) (PLGA) nanoparticles desensitizes superficially terminating nociceptors, reducing burning. Methods: Capsaicin-loaded PLGA nanoparticles were prepared (single-emulsion solvent evaporation) and characterized (size, morphology, capsaicin loading, encapsulation efficiency, in vitro release profile). Capsaicin-PLGA nanoparticles were applied to murine skin and evaluated in healthy human participants (n = 21) for 4 days under blinded conditions, and itch and nociceptive sensations evoked by mechanical, heat stimuli and pruritogens cowhage, β-alanine, BAM8-22 and histamine were evaluated. Results: Nanoparticles (loading: 58 µg capsaicin/mg) released in vitro 23% capsaicin within the first hour and had complete release at 72 h. In mice, 24 h post-application Capsaicin-PLGA nanoparticles penetrated the dermis and led to decreased nociceptive behavioral responses to heat and mechanical stimulation (desensitization). Application in humans produced a weak to moderate burning, dissipating after 3 h. A loss of heat pain up to 2 weeks was observed. After capsaicin nanoparticles, itch and nociceptive sensations were reduced in response to pruritogens cowhage, β-alanine or BAM8-22, but were normal to histamine. Conclusions: Capsaicin nanoparticles could be useful in reducing pain and itch associated with pruritic diseases that are histamine-independent.     

Insight into the Impact of Oxidative Stress on the Barrier Properties of Lipid Bilayer Models

As a new field of oxidative stress-based therapy, cold physical plasma is a promising tool for several biomedical applications due to its potential to create a broad diversity of reactive oxygen and nitrogen species (RONS). Although proposed, the impact of plasma-derived RONS on the cell membrane lipids and properties is not fully understood. For this purpose, the changes in the lipid bilayer functionality under oxidative stress generated by an argon plasma jet (kINPen) were investigated by electrochemical techniques. In addition, liquid chromatography-tandem mass spectrometry was employed to analyze the plasma-induced modifications on the model lipids. Various asymmetric bilayers mimicking the structure and properties of the erythrocyte cell membrane were transferred onto a gold electrode surface by Langmuir-Blodgett/Langmuir-Schaefer deposition techniques. A strong impact of cholesterol on membrane permeabilization by plasma-derived species was revealed. Moreover, the maintenance of the barrier properties is influenced by the chemical composition of the head group. Mainly the head group size and its hydrogen bonding capacities are relevant, and phosphatidylcholines are significantly more susceptible than phosphatidylserines and other lipid classes, underlining the high relevance of this lipid class in membrane dynamics and cell physiology.     

Switching from Ethylene Trimerization to Ethylene Polymerization by Chromium Catalysts Bearing SNS Tridentate Ligands: Process Optimization Using Response Surface Methodology

Two types of chromium catalysts bearing pyridine and amine based SNS ligands under the title of (pyridine-SNS-alkyl/CrCl₃) and (amine-SNS-alkyl/CrCl₃) were synthesized. Different thiolates such as octyl, pentyl, butyl, cyclohexyl and cyclopentyl thiolates were reacted with 2,6-pyridine-dimethylene-ditosylate (PMT)/THF solution at room temperature. Then, the purified pyridine-based SNS ligands (1–5) were reacted with CrCl₃ (THF)₃ to obtain the pyridine-SNS-alkyl/CrCl₃ catalysts (6–10) in 50–70% yields. MMAO-activated pyridine-SNS-alkyl/CrCl₃ catalysts were capable of oligomerizing ethylene. Statistical experimental design was conducted using the central composite design method and surface methodology to study of the effect of important parameters such as ethylene pressure, Al/Cr ratio, catalyst concentration and the reaction temperature on 1-C₆ productivity of catalyst (7). A quadratic polynomial equation was developed to predict the 1-C₆ productivity. Ethylene oligomerization using the catalyst (7) was lead to a optimized reaction conditions, including the ethylene pressure of 19.5 bar, the temperature of 58.2 °C, the MMAO co-catalyst, Al/Cr?=?841 and the catalyst concentration of 8.7 µmol. The catalytic properties for ethylene oligomerization are strongly affected by reaction temperature. The experimental results indicated the reasonable agreement with the predicted values. The transformation from ethylene trimerization to ethylenev polymerization of catalyst system (7) was occurred by exchanging the reaction pressure. Influence of ligand structure with different substitutions on sulphur atom on productivity and selectivity was investigated. 1-C₆ with the high selectivity and productivity 4318 (g 1-C₆/g Cr h) was obtained for catalyst (7). In the second part, 1-C₆ was obtained with high selectivity and productivity around 141?×?10³ (g 1-C₆/g Cr h) for amine-based catalyst. All amine-based catalysts (14–16) showed considerably higher catalytic activities compared to pyridine-based catalysts. According to the TGA analysis the thermal stability of pyridine-based catalysts was found to be higher than the amine-based catalysts.

Graphical Abstract

Chromium complexes bearing pyridine and amine based SNS ligands have been synthesized and their catalytic performance in ethylene oligomerization has been investigated. A switching from ethylene trimerization to ethylene polymerization of the catalyst (7) was obtained utilizing exchanging of the ethylene pressure.

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