A novel approach to bar adsorptive microextraction: Cork as extractor phase for determination of benzophenone,triclocarban and parabens in aqueous samples

This study describes the use of cork as a new coating for bar adsorptive microextraction (BAμE) and its application in determining benzophenone, triclocarban and parabens in aqueous samples by HPLC–DAD. In this study bars with 7.5 and 15 mm of length were used. The extraction and liquid desorption steps for BAμE were optimized employing multivariate and univariate procedures. The desorption time and solvent used for liquid desorption were optimized by univariate and multivariate studies, respectively. For the extraction step the sample pH was optimized by univariate experiments while the parameters extraction time and ionic strength were evaluated using the Doehlert design. The optimum extraction conditions were sample pH 5.5, NaCl concentration 25% and extraction time 90 min. Liquid desorption was carried out for 30 min with 250 μL (bar length of 15 mm) or 100 μL (bar length of 7.5 mm) of ACN:MeOH (50:50, v/v). The quantification limits varied between 1.6 and 20 μg L⁻¹ (bar length of 15 mm) and 0.64 and 8 μg L⁻¹ (bar length of 7.5 mm). The linear correlation coefficients were higher than 0.98 for both bars. The method with 7.5 mm bar length showed recovery values between 65 and 123%. The bar-to-bar reproducibility and the repeatability were lower than 13% (n = 2) and 14% (n = 3), respectively.     

Analysis of trace‐level nitrated polycyclic aromatic hydrocarbons in water samples by solid‐phase microextraction with gas chromatography and mass spectrometry

A solid‐phase microextraction coupled with gas chromatography and mass spectrometry method has been developed for the determination of ten nitrated polycyclic aromatic hydrocarbons in water samples. Five different kinds of commerical fibers were used to compare the extraction efficiency, including 65 μm polydimethylsiloxane/divinylbenzene, 100 μm polydimethylsiloxane, 30 μm polydimethylsiloxane, 7 μm polydimethylsiloxane, and 85 μm polyacrylate fibers. Five factors were also selected to optimize conditions, including extraction temperature, time, stirring speed, salt concentration, and headspace volume. Taguchi design was applied to design the experiments and obtain the best parameters. The results show that 65 μm polydimethylsiloxane/divinylbenzene fiber directly immersed into aqueous solution for 35 min at 55°C with a constant stirring rate of 1150 rpm were the optimal conditions. Under these conditions, the limits of quantification were 0.007–0.063 μg/L, and the relative standard deviation based on six replicates ranged from 2.8 to 9.5%. The spiked recoveries ranged from 69.1 to 110.1%. Intra‐ and inter day relative standard deviations at three concentration levels were less than 12%, and the recoveries were 66.4–111.5%. The proposed method is reliable for analyzing nitrated polycyclic aromatic hydrocarbons in different water samples.     

Dynamic uniaxial extension of elastomers at constant true strain rate

Elastomers are widely used for damping components in various industrial contexts because of their remarkable dissipative properties: they can bear severe mechanical loading conditions, i.e., high strain rates and large strains. Depending on the strain rate, the mechanical response of these materials can vary from purely rubber-like to glassy. In the intermediate strain rate range (1-100/s), uniaxial extension experiments are classically conducted at constant nominal strain rate. We present here a new experimental methodology to investigate the mechanical response of soft materials at constant true strain rate in the intermediate strain rate range. For this purpose, the displacement imposed on the specimen by the tensile machine is an exponential function of time. A high speed servo-hydraulic machine is used to perform experiments at strain rates ranging from 0.01 to 100/s. A specific specimen is designed in order to achieve a uniform strain field (and thus a uniform stress field). Furthermore, an instrumented aluminium bar is used to measure the applied force; which overcomes the difficulties due to dynamic effects. Simultaneously, a high speed camera enables the measurement of strain in the sample using a point tracking technique. Finally, the method is applied to determine the stress-strain curve of an elastomer for both loading and unloading responses up to a stretch ratio λ = 2.5; the influence of the true strain rate on both stiffness and dissipation of the material is then discussed.     

A new method to study the fiber-matrix interface in unidirectional composite materials: Application for carbon fiber-epoxy composites

Numerous studies have been done on the nature of the fiber-matrix interface and on the role of this interface in mechanical properties of epoxy-carbon fiber composite materials. In this study, we describe a new test to study the fiber-matrix interface in unidirectional composites by dynamic shear testing along the fiber axis. This method, based on three scans with increased dynamic displacement amplitude, enables us to study the recovery of mechanical properties and appearance of damage in the material. For carbon fiber-epoxy unidirectional composite materials, it is possible to distinguish two ranges in the amplitude of dynamic displacement: a first for which a recovery for G′ and tan σ is observed and a second for which permanent damage appears. The influences of fiber surface treatments such as oxidation and/or sizing on dynamic behavior are clearly displayed by this test.     

Mechanical Properties of 1.5 wt.% TiB2-added Hypoeutectic Al-Mg- Si Alloys Processed by Equal Channel Angular Pressing

In order to improve the mechanical properties and to optimize grain refinement of Al-Mg-Si alloy, ECAP processing with an addition of hard particle TiB₂ is applied in this work. Mechanical property and microstructural evolution of Al-0.3Mg-7Si+1.5 wt.% TiB₂ specimen were investigated by using hardness-testing, optical micrograph observation and electron-backscattering diffraction (EBSD). ECAP processing was done through B_A route for 4 passes at room temperature. Hardness test results show that the ECAP process doubled the hardness of the specimen compared to annealed specimen, and from EBSD/OIM analysis, the ECAP processing refined grains from an average grain size of 35 μm to 0.79 μm and led to producing grains having high misorientation angle (≥15).     

Core–shell column Tanaka characterization and additional tests using active pharmaceutical ingredients

In the last decade, core–shell particles have gained more and more attention in fast liquid chromatography separations due to their comparable performance with fully porous sub‐2 μm particles and their significantly lower back pressure. Core–shell particles are made of a solid core surrounded by a shell of classic fully porous material. To embrace the developed core–shell column market and use these columns in pharmaceutical analytical applications, 17 core–shell C₁₈ columns purchased from various vendors with various dimensions (50 mm × 2.1 mm to 100 mm × 3 mm) and particle sizes (1.6–2.7 μm) were characterized using Tanaka test protocols. Furthermore, four selected active pharmaceutical ingredients were chosen as test probes to investigate the batch to batch reproducibility for core–shell columns of particle size 2.6–2.7 μm, with dimension of 100 × 3 mm and columns of particle size 1.6 μm, with dimension 100 × 2.1 mm under isocratic elution. Columns of particle size 2.6–2.7 μm were also tested under gradient elution conditions. To confirm the claimed comparable efficiency of 2.6 μm core–shell particles as sub‐2 μm fully porous particles, column performances of the selected core–shell columns were compared with BEH C₁₈, 1.7 μm, a fully porous column material as well.     

Porous electrospun polycaprolactone fibers: Effect of process parameters

The effect of electrospinning process parameters (solution flow rate, applied voltage, spinning distance) on the size and surface morphology of porous electrospun poly(ε‐caprolactone) was investigated in this study. Response surface methodology was implemented for the design and conduction of electrospinning experiments. The feed solution was a 12.5% w/v poly(ε‐caprolactone) (PCL) solution in a binary solvent mixture of 90%v/v chloroform/dimethyl sulfoxide. Spinning distance of 10–25 cm, applied voltage of 10–25 kV and feed flow rate of 0.5–5 mL/h were the range of limiting values of the independent variables used for the development of a central composite design. Second‐order polynomial equations, correlating electrospinning process parameters to relative pore coverage, and fiber average diameter were developed and validated. An increase in any of the investigated parameters (solution flow rate, applied voltage, spinning distance) resulted in the increase of both, pore formation on electrospun fibers, and produced fiber average diameter. Under the experimental conditions investigated, the relative pore surface coverage was 15.8–31.9% and the average fiber diameter was in the range of 1.6–3.3 μm. Applied voltage was proven to be the parameter with the strongest impact on both, fiber diameter and surface morphology. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1878–1888     

Stage-frit: A straightforward sub-2 μm nano-liquid chromatography column fabrication for proteomic analysis

In this work we demonstrated a facile method for the fabrication of C18 coordination polymer gel in a capillary, called stage-frit, which was efficiently applied to pack sub-2 μm C18 beads into the capillary by a high pressure bomb for the online separation of proteolytic peptides. The back pressure of the column with 10 cm × 75 μm i.d. is regularly lower than 170 bar at a flow rate of 300 nl/min, which could be operated on a common nanoLC system instead of nanoUPLC system due to the good permeability, low back pressure and high mechanical stress of the frit that will totally reduce the cost for the purchase of instrument. The stage-frit allows long-term continuous flow of the solvent and no significant beads loss or pressure instability was observed during the period. The repeatability of retention time for fifteen BSA tryptic peaks was found to be less than 1.08% (RSD) in six time nanoLC-ESI-MS/MS experiments. The average full width at half maximum (FWHM) of peptide peaks is 5.87 s. The sub-2 μm stage-frit nanoLC column showed better sensitivity than the commercial available for large scale proteomic analysis of total tissue proteins from human spleen. The number of identified peptides is approximately 0.4-fold and 0.2-fold higher than that obtained by utilizing commercial columns packed with 3 μm and 1.8 μm C18 materials, respectively. In the field of analytical chemistry, particularly the use of nanoLC systems, stage-frit nanoLC column offers a great potential for the separation of complex mixtures.     

A microtubular all CNT gas diffusion electrode

We report a microtubular gas diffusion electrodes made of multi-walled carbon nanotubes (MWCNT). The electrodes were prepared by inside-out cake filtration of an aqueous MWCNT suspension onto a microfiltration hollow fiber (HF) membrane, followed by washing out the surfactant, drying and removal of the all CNT microtube from the HF membrane. Length, outer diameter, and wall thickness of the tubular electrodes are: up to 44 cm, ~ 1.7 mm and 275 μm, respectively. The BET surface area is 200 m²/g with a porosity of 48–67% and an electrical conductivity of ~ 20 S/cm. Application of this microtubular Gas Diffusion Electrodes (GDE) was studied for the oxygen reduction reaction (ORR) in divided and undivided electrochemical cells. Oxygen supply into the lumen of the tubular electrodes resulted in much higher current densities for ORR than in experiments where the electrolyte was saturated by bubbling with pure oxygen. Within the 0.25–1.0 bar pressure (gauge) region, higher ORR rates were achieved at lower pressure. We also show that H₂O₂ production is possible using the new GDE. We propose to use such novel electrodes for the fabrication of tubular electrochemical reactors, e.g. fuel cells, H₂O₂ generators, CO₂ reduction and other processes that involve GDE application.     

Variations in fiber length within a first-thinning Scots pine (Pinus sylvestris) stem

Variations in average fiber length and fiber length distribution both in the longitudinal and horizontal directions of a first-thinning Scots pine (Pinus sylvestris) stem and between six stems of similar age (26–30 years) and height (10.7–12.8 m) were studied. As a general trend, fiber length increased from the pith (0.8–1.3 mm) to the outer part of the stem (1.9–2.9 mm) maximizing at the relative stem height of 20–40%. Variations in fiber length between stems were smaller than those within a stem. The average fiber length of different stems of the same age (28 years) or diameter at breast height (11 cm) depended typically on wood growth rate. Finally, kraft cooking experiments on different parts of the stem (i.e., butt and top as well as inner and outer parts of the stem) indicated clear differences in their pulp properties. It was concluded that due to the acceptable properties of these pulps, first-thinning wood material as such or after the suitable fractionation may offer a potential source of fiber for a variety of different purposes.     

Measurement of the dynamic fracture toughness with notched PMMA specimen under impact loading

In the present study three-point-bend impact experiments were conducted using an instrumented Charpy pendulum with a laser displacement measurement to better understand the correlation between impact velocity and the dynamic effects observed on the load-time curves. The experiments were performed at impact velocities ranging from 1 to 4 m/s.The aim of this work is to measure the dynamic fracture toughness at high impact velocities where the classical method is limited by the inertial effects. The direct measurements of the specimen deflection are successfully used for the toughness evaluation. The results obtained with this method, which are compared to other studies, indicate that this approach seems promising for brittle materials such as PMMA.     

Development and validation of a stability‐indicating HPLC method for topiramate using a mixed‐mode column and charged aerosol detector

The analysis of topiramate in the presence of its main degradation products is challenging due to the absence of chromophore moieties and their wide range of polarity. Mixed‐mode chromatography has been used in such cases because it combines two or more modes of separation. Charged aerosol detector is also an alternative since its detection is independent of optical properties and analyte ionization. This study is aimed to develop and validate two new stability‐indicating methods by high‐performance liquid chromatography for the main degradation products of topiramate using mixed‐mode chromatography and a charged aerosol detector. Method 1 employed an Acclaim Trinity P1® column (3.0 mm × 150 mm, 2.7 μm) with a mobile phase comprising of 80% ammonium acetate buffer (20 mM, pH 4.0) and 20% methanol at a flow rate of 0.5 mL/min at 35°C. Method 2 utilized a C18 Acclaim 120® column (4.6 mm × 250 mm; 5 μm) with ACN/water (50:50) at a flow rate of 0.6 mL/min at 50°C. Validation of the two methods demonstrated excellent performance with respect to linearity, precision, accuracy, and selectivity. The limits of detection for topiramate, fructose, sulfate, sulfamate, and compound A were 2.97, 12.08, 4.02, 13.91, and 3.94 μg/mL, respectively.     

Properties Investigation of novel nitrile rubber composites with rockwool fibers

Rockwool is an inorganic fiber with interesting properties obtained from basaltic rocks. It can possibly be used in rubber technical products which work under critical conditions in several industries. This study aims to investigate properties of three short rockwool fibers/nitrile rubber composites. Ten formulations were prepared with 10, 25 and 40 phr of rockwool fibers with different length and modification. The composites were assessed on its morphological aspects, thermal, rheological, and mechanical behaviors. The results remarked that the rockwool fiber with chemical modification had better interfacial interaction with the polymer enhancing modulus at 100% of deformation, Shore A hardness, tear strength, Payne effect and stress relaxation under a compressive regime. An outstanding result was observed for the composite with 10 phr of fiber with chemical modification that had less stress relaxation when compared with the unfilled NBR indicating an excellent possibility of use of this fiber in materials that work under compressive forces. The difference in length of the rockwool fibers (125 μm–300 μm) did not interfere significantly on most of the results.     

Preparation and properties of dynamically cured poly(vinylidene fluoride)/silicone rubber blends

Blends of poly(vinylidene fluoride) (PVDF) and silicone rubber (SR) were prepared through dynamic vulcanization. The effects of SR content on crystallization behavior, rheology, dynamic mechanical properties and morphology of the blends were investigated. Morphology characterization shows that the crosslinked spherical SR particles with an average diameter of 2-4 μm form a “network” in the PVDF continuous phase. The dynamic mechanical properties indicate the interface adhesion between PVDF and rubber phase is improved by the dynamic vulcanization. The rheology study shows that with the increase of rubber content the blends pseudoplastic nature is retained, while the viscosity increases, and hence the processability is less good. The incorporation of SR phase promotes the nucleation process of PVDF, leading to increased polymer crystallization rate and crystallization temperature. However, a higher content of SR seems to show a negative effect on the crystallinity of the PVDF component.     

Novel experimental design paradigm for development of eco-friendly gradient chromatographic method for simultaneous determination of metronidazole and spiramycin

This work describes the innovative experimental design-assisted development of a green gradient chromatographic method for concomitant analysis of metronidazole (MTR) and spiramycin (SPR). Two different designs including fractional factorial and Box-Behnken designs were implemented for screening and optimization steps, respectively. The optimum chromatographic conditions involved a mobile phase consisting of ethanol and 20 mM sodium dihydrogen phosphate solution (pH adjusted to 2.5) in the ratio 2:98 (v/v) for 2 min then the ratio changed to 30:70 (v/v). The flow rate was 1.3 mL/minute. Separation and analysis were performed on X-bridge C18 (150 mm × 4.6 mm × 3.5 μm) column with diode array detector set at 230 nm. Column oven temperature was 40°C. A linear response was acquired over the range of 5–125 μg/mL for both drugs. Detection and quantitation limits were 0.86 and 2.62 μg/mL for MTR and 0.92 and 2.83 μg/mL for SPR, respectively. The method was implemented for determination of both drugs in three tablet formulations. The method was proved to be green as evaluated by three assessment tools. The application of experimental designs assists in development of a robust green chromatographic method in gradient elution mode for determination of both drugs within reasonable time.     

Rapid screening of amitraz and its metabolite residues in honey using a quick,easy, cheap,effective, rugged,and safe extraction method coupled with UHPLC and Q Exactive

A method for determining amitraz and 2,4‐dimethylaniline in honey was established by using ultra‐high‐performance liquid chromatoghaphy and Q Exactive after applying quick, easy, cheap, effective, rugged, and safe extracting process. A suitable extraction method was designed to extract the amitraz and 2,4‐dimethylaniline after a suitable amount of honey samples was dissolved. A Thermo Syncronis C₁₈ column (100 × 2.1 mm, 1.7 μm) was used for chromatographic separation of the samples. Then the two compounds were quantitatively analyzed via a program of Q Exactive. The linearity of amitraz and 2,4‐dimethylaniline was good in the concentration range of 0.5–100 μg/L, and the correlation coefficient R² was >0.99. The average recovery and relative standard deviation of each component were 81.3–90.0% and 5.1–7.2%. The 24‐ and 48‐h test results showed that the sample needed to be tested within 24 h. The limit of detection was 0.1 μg/kg for amitraz and 2,4‐dimethylaniline, whereas for both the limit of quantitation was 0.3 μg/kg.     

Dielectric investigation of interphase formation in composite materials. I. Ionic conductivity and permittivity exploration

The aim of this study was to demonstrate the application of dielectric spectroscopy to composite material characterization during processing. Therefore, the microdroplet pullout test was used to follow the mechanical interfacial properties during processing. The results showed that interfacial shear stress strongly depends on the pressure, temperature, and process time at resin deposition. These observations were understood with dielectric spectroscopy. Literature data were first applied to our system. Results based on the ionic conductivity signal showed the existence of a mutual diffusion mechanism at the interface The mechanism rate constant depends strongly on the temperature, pressure, and process time. In a second part, we developed a way to follow the penetration depth with the permittivity signal. This approach is based on electric field line exploitation. The results highlighted the same observations. In conclusion, it appears that the adhesion of matrix–fiber is increased by composite processing at the monomeric state of the resin. Moreover, this study shows that this improvement is a consequence of a mutual diffusion mechanism at the interface. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2154–2161, 2000     

Improvement of solid phase microextraction fiber assembly and interface for liquid chromatography

Modifications were made on commercial SPME fiber assembly and SPME–LC interface to improve the applicability of SPME for LC. Polyacrylonitrile (PAN)/C18 bonded fuse silica was used as the fiber coating for LC applications because the fiber coating was not swollen in common LC solvents at room temperature. The inner tubing of SPME fiber assembly was replaced with a 457 μm outside diameter (o.d.) solid nitinol rod. And the coated fiber (o.d. 290 μm) was installed onto the nitinol rod. The inner diameter (i.d.) of the through hole of the ferrule in the SPME–LC interface was enlarged to 508 μm to accommodate the nitinol rod. The much larger inner rod protected the fiber coating from being stripped when the fiber was withdrawn from the SPME–LC interface. The system was evaluated in term of pressure test, desorption optimization, peak shape, carryovers, linear range, precision, and limit of detection (LOD) with polycyclic aromatic hydrocarbons (PAHs) as the test analytes. The results demonstrated that the improved system was robust and reliable. It overcame the drawbacks, such as leak of solvents and damage of fiber coatings, associated with current SPME fibers and SPME–LC interface. Another sealing mechanism was proposed by sealing the nitinol rod with a specially designed poly(ether ether ketone) (PEEK) fitting. The device was fabricated and tested for manual use.     

Quantification of rosiglitazone in rat plasma and tissues via LC–MS/MS: Method development,validation, and application in pharmacokinetic and tissue distribution studies

A bioanalytical method for the quantification of rosiglitazone in rat plasma and tissues (adipose tissue, heart, brain, bone, and kidney) using LC–MS/MS was developed and validated. Chromatographic separation was achieved on a Gemini C₁₈ column (50 × 4.6 mm, 3 μm) using a mobile phase consisting of 10 mM ammonium formate (pH 4.0) and acetonitrile (10:90, v/v) at a flow rate of 0.8 mL/min and injection volume of 10 μL (internal standard: pioglitazone). LC–MS detection was performed with multiple reaction monitoring mode using target ions at m/z → 358.0 and m/z → 357.67 for rosiglitazone and pioglitazone (internal standard), respectively. The calibration curve showed a good correlation coefficient (r²) over the concentration range of 1–10,000 ng/mL. The mean percentage recoveries of rosiglitazone were found to be over the range of 92.54–96.64%, with detection and lower quantification limit of 0.6 and 1.0 ng/mL, respectively. The developed method was validated per U.S. Food and Drug Administration guidelines and successfully utilized to measure rosiglitazone in plasma and tissue samples. Further, the developed method can be utilized for validating specific organ-targeting delivery systems of rosiglitazone in addition to conventional dosage forms.     

Development of the split-Hopkinson pressure bar technique for viscous fluid characterization

The split Hopkinson pressure bar (SHPB) technique has been employed to evaluate the dynamic squeeze flow behavior of viscous Newtonian fluids. In this paper, the conditions under which classic Hopkinson bar data analysis is applicable for fluid specimens are discussed in detail. Requirements include the development of a parabolic flow profile and associated pressure distribution across the specimen. The times required for these processes to occur are calculated and compared with the experimental timescale in order to establish a specimen design criterion for valid SHPB testing. To evaluate this design criterion, an isothermal squeeze flow model describing the behavior of a cylindrical fluid specimen which includes inertial forces is used to predict the experimental results for a model Newtonian fluid. Good agreement between the theory and the experiment is obtained for thin specimens (1.0 mm) across a wide range of shear strain rates (over 10⁵ s⁻¹). As a result of this study, the conditions under which valid SHPB experimental results may be obtained for a Newtonian fluid specimen are identified.