A case of Z/E-isomers elution order inversion caused by cosolvent percentage change in supercritical fluid chromatography.

A case of elution order inversion caused by cosolvent percentage change in supercritical fluid chromatography was observed and investigated in some detail. Z- and E-isomers of phenylisobutylketone oxime experience an elution order reversal on most columns if the mobile phase consists of CO2 and alcohol. At lower percentages of alcohol Z-oxime is retained less, somewhere at 2-5% coelution occurs and at larger cosolvent volume elution order reverses - Z-oxime is eluted later than E-oxime. We suppose inversion with CO2-ROH phases happens due to a shift in balance between two main interactions governing retention. At low ROH percentages stationary phase surface is only slightly covered by ROH molecules so oximes primarily interact with adsorption sites via hydrogen bond formation. Due to intramolecular sterical hindrance Z-oxime is less able to form hydrogen bonds and consequently is eluted first. At higher percentages alcohols occupy most of strong hydrogen bonding sites on silica surface thus leaving non-specific electrostatic interactions predominantly responsible for Z/E selectivity. Z-oxime has a much larger dipole moment than E-oxime and at these conditions it is eluted later. Additional experimental data with CO2-CH3CN, hexane-iPrOH and CHF3-ROH mobile phases supporting this explanation are presented.

Laser radiation effect on chondrocytes and intercellular matrix of costal and articular cartilage impregnated with magnetite nanoparticles.

BACKGROUND AND OBJECTIVE: Magnetic nanoparticles with the ability to absorb laser radiation are the perspective agents for the early diagnostics and laser therapy of degenerative cartilage. The effect of starch stabilized magnetite nanoparticles (SSNPs) on the cartilage structure components has never been studied before. The aim of the work is to establish the Erbium:glass laser effect on costal and articular cartilage impregnated with SSNPs. MATERIALS AND METHODS: Porcine articular and costal cartilage disks (2.0 mm in diameter and 1.5-2 mm in thickness) were impregnated with SSNPs and irradiated using a 1.56 µm laser in therapeutic laser setting. The one sample group underwent the second irradiation after the SSNPs impregnation. The samples were analyzed by the means of histology, histochemistry and transmission electron microscopy (TEM) to reveal the alterations of cells, glycosaminoglycans and collagen network. RESULTS: The irradiated cartilage demonstrates the higher content of cell alterations than the intact one due to the heat and mechanical affection in the course of laser irradiation. However the alterations are localized at the areas near the irradiated surfaces and not dramatic. The impregnation of SSNPs does not cause any additional cell alterations. For both costal and articular cartilage the matrix alterations of irradiated samples are not critical: there is the slight decrease in acid proteoglycan content at the irradiated areas while the collagen network is not altered. Distribution and localization of impregnated SSNPs is described: agglomerates of 150-230 nm are observed located at the borders between matrix and cell lacunas of articular cartilage; SSNPs of 15-45 nm are found in the collagen network of costal cartilage. CONCLUSIONS: It was shown that SSNPs do not appreciably affect the structural components of both articular and costal cartilage and can be safely used for the laser diagnostics and therapy. The area of structural alterations is diffuse and local as the result of the mechanical and heat effect of laser impact. SSNPs reveal the areas of the structural alterations of cartilage matrix and give information about the size of the pores and defects.

Laser reshaping of costal cartilage for transplantation.

BACKGROUND AND OBJECTIVE: Laser reshaping of cartilage is a new effective and safe technique for correction of nasal septum and ear deformities. Costal cartilage is a most suitable natural material for transplantation. The problem is to obtain stable proper shape of cartilage implants. The objective of this article is to study reshaping of porcine costal cartilage for larynx stenosis surgery using Erbium glass fiber laser. MATERIALS AND METHODS: Porcine cartilage plates 3 mm in thickness were mechanically curved and irradiated (1) on one side (stretched or compressed) and (2) on both sides with different sequence. Irradiation was performed using a 1.56 µm laser with power varied from 1 to 2.5 W, exposure time from 5 to 20 seconds, spot diameter of 2.5 mm, pulse duration of 500 milliseconds, pulse repetition rate of 1.4 Hz. For each laser setting, stable curvature radius was measured during 24 hours after the experiment. Irradiated samples were analyzed by means of differential scanning calorimerty (DSC) to reveal the collagen denaturation degree. RESULTS: The optimum laser setting for stable reshaping of costal cartilage without visual thermal damage of cartilage matrix was established: laser power of 2.2 W, exposure time of 6 seconds. Nonlinear thermomechanical behavior of cartilage in the course of its laser reshaping is experimentally revealed. The influence of irradiation sequence on the curvature radius of cartilage implant is found for the first time. It is shown that (1) it is possible to use laser reshaping technique for making stable proper shape of costal cartilage, and (2) primary irradiation of compressed side followed with an irradiation of stretched side is more effective than reverse sequence of laser treatment. DSC analysis showed that thermal effect of irradiated specimens (2.58-3.79 J/g) was slightly lower that that for intact cartilage specimens and considerably lower than that for denaturation of collagen (65 ± 5 J/g). CONCLUSIONS: It is possible to use laser reshaping technique for preparation of stable cartilage implants. Nonlinear thermomechanical behavior of cartilage is experimentally revealed. The influence of irradiation sequence on curvature radius of cartilage grafts is established for the first time.