GC–MS analysis of oxysterols and their formation in cultivated liver cells (HepG2)

Oxysterols play a key role in many (patho)physiological processes and they are potential biomarkers for oxidative stress in several diseases. Here we developed a rapid gas chromatographic-mass spectrometry-based method for the separation and quantification of 11 biologically relevant oxysterols bearing hydroxy, epoxy, and dihydroxy groups. Efficient chromatographic separation (resolution ≥ 1.9) was achieved using a medium polarity 35%-diphenyl/65%-dimethyl polysiloxane stationary phase material (30 m × 0.25 mm inner diameter and 0.25 μm film thickness). Based on thorough analysis of the fragmentation during electron ionization we developed a strategy to deduce structural information of the oxysterols. Optimized sample preparation includes (i) extraction with a mixture of n-hexane/iso-propanol, (ii) removal of cholesterol by solid phase extraction with unmodified silica, and (iii) trimethylsilylation. The method was successfully applied on the analysis of brain samples, showing consistent results with previous studies and a good intra- and interday precision of ≤20%. Finally, we used the method for the investigation of oxysterol formation during oxidative stress in HepG2 cells. Incubation with tert-butyl hydroperoxide led to a massive increase in free radical formed oxysterols (7-keto-chol > 7β-OH-chol >> 7α-OH-chol), while 24 h incubation with the glutathione peroxidase 4 inhibitor RSL3 showed no increase in oxidative stress based on the oxysterol pattern. Overall, the new method described here enables the robust analysis of a biologically meaningful pattern of oxysterols with high sensitivity and precision allowing us to gain new insights in the biological formation and role of oxysterols.     

Characterization of the stress distribution and evolution inside a thermal barrier coating after initial thermal cycles

The residual stress introduced inside a thermal barrier coating (TBC) during manufacturing and service processes is one of the main causes of thermal barrier failure. The formation and evolution of internal stress in the TBC begin at the early stage of service, but studies on the mechanism of the distribution and evolution of the stress in the TBC during the initial thermal cycle are still lacking. To explore the evolution mechanism of the stress in the TBC interior, an experimental study on the regulation mechanism of the initial thermal cycle on the TBC internal stress was carried out in this paper. First, the internal stress of TBC specimens after thermal cycles was characterized based on photoluminescence spectroscopy (PL) and terahertz time-domain spectroscopy (THz-TDS) technologies, in which the homogenization of the near-interface stress field was observed during the initial thermal cycle. Then, the evolution of the microstructure and phase structure of the TBC specimens was characterized. Finally, the phenomenological model of the evolution of the TBC internal structure was established, revealing that the initial thermal cycle regulated the microstructure of the top coating (TC) through phase transformation to realize the homogenization of the near-interface stress field.     

Evaporation rate effect on starting point of shrinkage stress development during drying process in solvent cast polymer film

To reveal the effect of drying conditions on shrinkage stress existing between a film and a substrate, a polystyrene/toluene solution was coated on a glass substrate, and the volume fraction of toluene at the time when the stress starts to grow (?_S) was measured at various drying temperatures and evaporation rates. ?_S decreased with increase of drying temperature at a constant evaporation rate, while ?_S increased with increase of evaporation rate at a constant drying temperature. From these results, it was suggested that the dominant factors affecting the starting point of stress were both the chain mobility and the measurement time‐scale. Considering the two factors, the tendency of ?_S with the drying conditions is quite similar to that of the solvent content at glass transition point, and this fact indicates a strong correlation between the starting point of stress and the glass transition of coated solution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal stress–strain of self‐compacting concrete in compression

Self‐compacting concrete or self‐consolidation concrete (SCC) is being used in underground and other industrial structures that may be subjected to high temperatures during operation or in case of an accidental fire. The proper understanding of the effects of elevated temperatures on the stress–strain relationship of SCC is necessary in the assessment of structural safety. This paper presents the high temperature behavior from an experimental study carried out on SCC subjected to high temperatures. The effects of temperature, strength grade, and polypropylene (PP) fibers on the initial elastic modulus, strain at peak stress, and stress–strain curves of SCC are studied, which offered a test basis for estimating the deformation of SCC under high temperature. An empirical constitutive formula for the thermal stress–strain of SCC is developed on the basis of the deformation characteristics of PP fiber‐modified SCC. Copyright © 2012 John Wiley & Sons, Ltd.     

Modelling of Functionally Graded Adhesive Joints

Nowadays, there is a strong trend towards the use of functionally graded materials, with particular importance for the functionally graded joints. The main objective of this work was to study a functionally modified adhesive in order to have mechanical properties that vary gradually along the overlap of a joint, allowing a uniform stress distribution along the overlap. This allows for a stronger and more efficient adhesive joint and would permit to work with much smaller areas, reducing considerably the weight of the structure which is a key factor in the transport industry. In the proposed joint, the adhesive stiffness varies along the overlap, being maximum in the middle and minimum at the ends of the overlap. The functionally graded joint was found to have a higher joint strength compared to the cases where the adhesive has homogeneous properties along the overlap. A simple analytical model to study the performance of the functionally graded joints was developed. The differential equation of this model was solved by a power series. Numerical modelling by finite element analysis was performed to validate the analytical model developed.     

Stress Analysis of Adhesively Bonded Electroprimed Steel Lap Shear Joints

Structural applications for adhesive bonding have been increasing in recent years due to improvements in the types of adhesives available and in improved knowledge of bonding procedures. Consequently, there exists a demand for precise numerical modeling of adhesive joint behavior, particularly along bondline interfaces where low surface energy adhesives contact high surface energy metallic oxides. The purpose of the present study is to determine the effect of electrodeposited organic paint primer (ELPO) on the stress and strain distributions within an adhesively bonded single-lap-shear joint. Initial experimental studies have shown that bonding to ELPO-primed steel adherends has enhanced strength and durability characteristics compared to conventional bonds to unprimed steel surfaces. Recent studies based on finite element analysis of varied single-lap-shear joint moduli and thicknesses, and subsequent testing of joints with two different adhesive moduli, have indicated the mechanisms involved in this phenomenon. The presence of the ELPO-primer reduced peak peel and shear stresses and allowed for more uniform stress distribution throughout the joint.     

A Comparison of Linear with Nonlinear Viscoelastic Solutions for Shear Stress Concentration in Double Lap Joints

The correspondence principle based on the Maxwell model and a nonlinear viscoelastic solution involving an iterative scheme are used to describe the time dependent variation of the adhesive maximum shear stress in adhesively bonded double lap joints. The results indicate that if the correspondence principle is applied, the use of Maxwell chain is necessary to approximate the continuous change in the relaxation time and to coincide with the results calculated using the nonlinear viscoelastic theory.     

A Method for the Stress Analysis of Lap Joints

A theory is presented for the adhesive stresses in single and double lap joints under tensile loading, while subjected to thermal stress. The formulation includes the effects of bending, shearing, stretching and hygrothermal deformation in both the adherend and adhesive. All boundary conditions, including shear stress free surfaces, are satisfied. The method is general and therefore applicable to a range of material properties and joint configurations including metal-to-metal, metal-to-CFRP or CFRP-to-CFRP. The solution is numerical and is based on an equilibrium finite element approach. Through the use of an iterative procedure, the solution has been extended to cater for non-linear adhesive materials.     

Viscoelastic and Processing Effects on the Fiber-Matrix Interphase Strength. Part I. The Effects of Loading Rate,Test Temperature,Fiber Sizing and Global Strain Level

The effects of loading rate, fiber sizing, test temperature and global strain level on the adhesion strength between carbon fibers and a thermosetting epoxy (Epon 815) are studied using the single fiber fragmentation test procedure. Analytical methodology describing the viscoelastic behavior observed is also presented. The possibility of rate-temperature-interphase thickness superposition for the interfacial strength function is illustrated based on the analytical models discussed. Experimental data are discussed using Weibull statistics and also presented in the form of percent relative frequency histograms for the fiber fragments in a collective fashion. The use of histograms allows for interpretation of the skewness in the data population.     

Surface force arising from adsorbed graphene oxide in alumina suspensions with different shape and size

The effects of graphene oxide (GO) on the yield stress‐pH of α‐Al₂O₃ (alumina) suspensions were investigated. For micron‐sized platelet alumina suspensions, micron‐sized GO additive increased the maximum yield stress by as much as six‐folds. This was attributed to GO‐mediated bridging interactions between the platelet particles. This type of bridging interactions was much less effective with submicron‐sized, spherical, and irregular shape alumina. Adsorption of the anionic GO reflected by the shift of pH of zero zeta potential to a lower pH is particularly high for platelet alumina. The 1.0 dwb % GO concentration added is sufficient to reinforce each platelet particle–particle bond, assisted by a directed GO–platelet interaction configuration. This is, however, not true with submicron‐sized particles as the particle concentration increases sharply with the inverse of the particle diameter to power of 3. Moreover, a GO sheet can adsorb several submicron‐sized particles and this does not produce the right interaction configuration. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3633–3641, 2013