Determination of benzotrifluoride derivative compounds in groundwater

Two simple analytical methods for the simultaneous determination and quantification of benzotrifluoride and eight chlorinated, amino and nitro benzotrifluoride derivatives in groundwater are proposed. Benzotrifluoride, 4-chlorobenzotrifluoride, 2,4-dichlorobenzotrifluoride and 3,4-dichlorobenzotrifluoride, were extracted by Purge-and-Trap on the basis of their volatile properties, while 3-aminobenzotrifluoride, 4-nitrobenzotrifluoride, 3-amino-4-chlorobenzotrifluoride, 3-nitro-4-chlorobenzotrifluoride and 4-chloro-3,5-dinitrobenzotrifluoride extractions were done with an automated SPE system. The analytical separations and detections were performed with two different GC systems, both equipped with single quadrupole mass spectrometer as detector. The LOD ranges for the two methods were 0.002–0.005 μg L⁻¹ and 0.01–0.07 μg L⁻¹, respectively. Both extraction methods were developed using spiked Milli-Q water and were then demonstrated with groundwater samples collected during autumn 2008. The areas of groundwater collection were polluted due to an episode of improper industrial soil disposal and consequent leakage of aliphatic and aromatic, fluorinated chemicals into the groundwater. This work eventually revealed the presence of several benzotrifluoride compounds most of them, like dichloro- and amino-derivatives, never been reported as environmental contaminants.     

DIC Challenge 2.0: Developing Images and Guidelines for Evaluating Accuracy and Resolution of 2D Analyses

Experimental Mechanics - The DIC Challenge 2.0 follows on from the work accomplished in the first Digital Image Correlation (DIC) Challenge Reu et al. (Experimental Mechanics 58(7):1067, 1). The...     

Hydrogen bonding versus van der Waals interactions: competitive influence of noncovalent interactions on 2D self-assembly at the liquid-solid interface

The structures of the self-assembled monolayers of various 4-alkoxybenzoic acids physisorbed at the liquid-solid interface were established by employing scanning tunnelling microscopy (STM). This study has been essentially undertaken to explore the competitive influence of van der Waals and hydrogen-bonding interactions on the process of two-dimensional self-assembly. These acid derivatives form hydrogen-bonded dimers as expected; however, the dimers organise themselves in the form of relatively complex lamellae. The characteristic feature of these lamellae is the presence of regular discommensurations or kinks along the lamella propagation direction. The formation of kinked lamellae is discussed in light of the registry mechanism of the alkyl chains with the underlying graphite substrate. The location of the kinks along a lamella depends on the number (odd or even) of carbon atoms in the alkyl chain. This result indicates that concerted van der Waals interactions of the alkyl chain units introduce the odd/even chain-length effect on the surface-assembled supramolecular patterns. The odd/even effects are retained even upon complexation with a hydrogen-bond acceptor. However, as the solvent is changed from 1-phenyloctane to 1-octanoic acid, the kinked lamellae as well as the odd/even effects disappear. This solvent-induced convergence of supramolecular patterns is attained by means of co-crystallisation of octanoic acid molecules in the 2D crystal lattice, which is evident from high-resolution STM images. The solvent co-adsorption phenomenon is discussed in terms of competing van der Waals and hydrogen-bonding interactions.     

Error estimation in measuring strain fields with DIC on planar sheet metal specimens with a non-perpendicular camera alignment

The determination of strain fields based on displacement components obtained via 2D-DIC is subject to several errors that originate from various sources. In this contribution, we study the impact of a non-perpendicular camera alignment to a planar sheet metal specimen's surface. The errors are estimated in a numerical experiment. To this purpose, deformed images - that were obtained by imposing finite element (FE) displacement fields on an undeformed image - are numerically rotated for various Euler angles. It is shown that a 3D-DIC stereo configuration induces a substantial compensation for the introduced image-plane displacement gradients. However, higher strain accuracy and precision are obtained - up to the level of a perfect perpendicular alignment - in a proposed “rectified” 2D-DIC setup. This compensating technique gains benefit from both 2D-DIC (single camera view, basic amount of correlation runs, no cross-camera matching nor triangulation) and 3D-DIC (oblique angle compensation). Our conclusions are validated in a real experiment on SS304.     

Assessment of measuring errors in DIC using deformation fields generated by plastic FEA

In this article, systematic errors that arise from different implementations of digital image correlation (DIC) techniques are analyzed. In particular, we investigate the influence of the adopted correlation function, the interpolation order, the shape function and the subset size on the derived displacements. These errors are estimated using numerically deformed images that were obtained by imposing finite element (FE) displacement fields on an undeformed image yielding plastic deformation of the specimen. This FE procedure simulates realistic experimental heterogeneous deformations at various load steps. It is shown that DIC is able to reproduce these displacements up to a satisfactory level if conscious choices in the above-mentioned implementations are made.     

Stereo-DIC Calibration and Speckle Image Generator Based on FE Formulations

Stereo digital image correlation (stereo-DIC) is being accepted by the industry as a valid full-field measurement technique for measuring shape, motion and deformation, and it is therefore of utmost importance to provide uncertainties on the obtained measurements. However, the influences on a stereo-DIC measurement are not fully understood; indeed, stereo-DIC is a complex optical-numerical process and it is not always clear how errors are propagating throughout the measurement chain. In order to investigate the magnitude of the different error-sources a simulator for stereo-DIC is proposed. This simulator is able to generate realistic synthetic images as if they were made during a real set-up, so the error sources can be investigated separately and an optimal set-up can be chosen before any physical test is performed. We present in this paper the mathematical approach to the DIC simulator including details on how to convert FE displacement field results to stereo-DIC images. The simulator includes the ability to control the lighting and to create synthetic calibration images. The synthetic images are compared to simulations for a bulge test as a validation of the simulator. Synthetic calibration images are compared to experimental calibration studies to verify those. Finally a brief look at how the simulator could be used for looking at calibration quality is conducted.     

1,10-Phenanthrolinium ionic liquid crystals

The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10-phenanthroline were quaternized by reaction with 1,3-dibromopropane or 1,2-dibromoethane. The resulting cations were combined with dodecyl sulfate or dioctyl sulfosuccinate anions. The influence of both the cation and anion type on the thermal behavior was investigated. Several of the complexes exhibit mesomorphic behavior, with smectic E phases for the dodecyl sulfate salts and smectic A phases for the dioctyl sulfosuccinate salts. Structural models for the packing of the 1,10-phenanthrolinium and anionic moieties in the liquid-crystalline phases are presented. The ionic compounds show fluorescence in the solid state and in solution.     

Digital image correlation in the classroom: Determining stress concentration factors with webcams

Experimental Techniques - In this study, we introduce graduate students to an experiment with digital image correlation (DIC). From an educational point of view, the aim is to get students familiar...     

Reagent‐Based DOS: Developing a Diastereoselective Methodology to Access Spirocyclic‐ and Fused Heterocyclic Ring Systems

Herein, we report a diversity‐oriented‐synthesis (DOS) approach for the synthesis of biologically relevant molecular scaffolds. Our methodology enables the facile synthesis of fused N‐heterocycles, spirooxoindolones, tetrahydroquinolines, and fused N‐heterocycles. The two‐step sequence starts with a chiral‐bicyclic‐lactam‐directed enolate‐addition/substitution step. This step is followed by a ring‐closure onto the built‐in scaffold electrophile, thereby leading to stereoselective carbocycle‐ and spirocycle‐formation. We used in silico tools to calibrate our compounds with respect to chemical diversity and selected drug‐like properties. We evaluated the biological significance of our scaffolds by screening them in two cancer cell‐lines. In summary, our DOS methodology affords new, diverse scaffolds, thereby resulting in compounds that may have significance in medicinal chemistry.     

Implementation of Convergence in Adaptive Global Digital Image Correlation

In FE based global digital image correlation (DIC) a finite element mesh is used to describe the deformation of the region of interest (ROI). However, the identification of an optimal mesh is a difficult problem and is often obtained by using “mechanical” pre-knowledge of the solution. In Finite Element Analysis (FEA) an optimal mesh can be found without any pre-knowledge of the solution by using mesh adaptivity, where an initial (non optimal) mesh is refined until the optimal solution is obtained. Refinement of the mesh can be based on error and/or convergence estimators. Despite the fundamental differences between FEA and DIC, in the present article the convergence procedure is successfully used in a recently published global FE based DIC method. In the used global DIC method elements can receive higher order shape functions, also known as p-elements. Using the aforementioned algorithm, also called p-DIC, refinement to a non-uniform higher order mesh is possible. Using the non-uniform mesh, an optimal mesh can be obtained for each section of the ROI. The presented study shows that a convergence scheme can be used to automatically control the mesh refinement in a global DIC approach. The convergence boundary, in percentage, is a more intuitive boundary than the absolute error boundary used in the original p-DIC approach. The procedure is validated using numerical examples and the robustness to experimental variables is investigated. Finally, the complete procedure is tested against a wide range of practical examples.