Experimental and theoretical characterization of 5,10- diminoporphodimethenes: Dearomatized porphyrinoids from palladium-catalyzed hydrazinations of 5,10-diarylporphyrins

A new dearomatized porphyrinoid, 5,10-diiminoporphodimethene (5,10-DIPD), has been prepared by palladium-catalyzed hydrazination of 5,10-dibromo-15,20-bis(3,5-di-tert-butylphenyl)porphyrin and its nickel(II) complex, by using ethyl and 4-methoxybenzyl carbazates. The oxidative dearomatization of the porphyrin ring occurs in high yield. Further oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone forms the corresponding 5,10-bis(azocarboxylates), thereby restoring the porphyrin aromaticity. The UV/visible spectra of the NiII DIPDs exhibit remarkable redshifts of the lowest-energy bands to 780 nm, and differential pulse voltammetry reveals a contracted electrochemical HOMO–LUMO gap of 1.44 V. Density functional theory (DFT) was used to calculate the optimized geometries and frontier molecular orbitals of model 5,10-DIPD Ni7c and 5,10-bis(azocarboxylate) Ni8c. The conformations of the carbamate groups and the configurations of the CNZ unit were considered in conjunction with the NOESY spectra, to generate the global minimum geometry and two other structures with slightly higher energies. In the absence of solution data regarding conformations, ten possible local minimum conformations were considered for Ni8c. Partition of the porphyrin macrocycle into tri- and monopyrrole fragments in Ni7c and the inclusion of terminal conjugating functional groups generate unique frontier molecular orbital distributions and a HOMO–LUMO transition with a strong element of charge transfer from the monopyrrole ring. Time-dependent DFT calculations were performed for the three lowest-energy structures of Ni7c and Ni8c, and weighting according to their energies allowed the prediction of the electronic spectra. The calculations reproduce the lower-energy regions of the spectra and the overall forms of the spectra with high accuracy, but agreement is not as good in the Soret region below 450 nm.

A comparison of road traffic crashes along mountainous and non-mountainous roads in Sabah, Malaysia

Constrained topography and complex road geometry along rural mountainous roads often represent a demanding driving situation. As a result, traffic crashes along mountainous roads are likely to have different characteristics to crashes on roads in flatter areas; however, there is little research on this topic. The objective of this study is to examine the characteristics of road traffic crashes on rural mountainous roads and to compare these with the characteristics of crashes on non-mountainous roads. This paper explores and compares general crash characteristics including crash type, crash severity, roadway geometric features and environmental factors, and road user/vehicle characteristics. Five years of road traffic crash data (2008-2012) for Sabah were obtained from the Malaysian Institute of Road Safety Research. During this period, a total of 25,439 crashes occurred along federal roads in Sabah, of which 4,875 crashes occurred in mountainous areas. Categorical data analysis techniques were used to examine the differences between mountainous and non-mountainous crashes. Results show that the odds ratio of ‘out-of-control’ crashes and the crash involvement due to speeding are respectively about 4.2 times and 2.8 times higher on mountainous than non-mountainous roads. Other factors and crash characteristics that increase the odds of crashes along mountainous roads compared with non-mountainous roads include horizontal curved sections compared with straight sections, single-vehicle crashes compared with multi-vehicle crashes and weekend crashes compared with weekday crashes. This paper identifies some of the basic characteristics of crashes along rural mountainous roads to aid future research on traffic safety along mountainous roads.

A comparison of road traffic crashes along mountainous and non-mountainous roads in Sabah, Malaysia

Constrained topography and complex road geometry along rural mountainous roads often represent a demanding driving situation. As a result, traffic crashes along mountainous roads are likely to have different characteristics to crashes on roads in flatter areas; however, there is little research on this topic. The objective of this study is to examine the characteristics of road traffic crashes on rural mountainous roads and to compare these with the characteristics of crashes on non-mountainous roads. This paper explores and compares general crash characteristics including crash type, crash severity, roadway geometric features and environmental factors, and road user/vehicle characteristics. Five years of road traffic crash data (2008-2012) for Sabah were obtained from the Malaysian Institute of Road Safety Research. During this period, a total of 25,439 crashes occurred along federal roads in Sabah, of which 4,875 crashes occurred in mountainous areas. Categorical data analysis techniques were used to examine the differences between mountainous and non-mountainous crashes. Results show that the odds ratio of ‘out-of-control’ crashes and the crash involvement due to speeding are respectively about 4.2 times and 2.8 times higher on mountainous than non-mountainous roads. Other factors and crash characteristics that increase the odds of crashes along mountainous roads compared with non-mountainous roads include horizontal curved sections compared with straight sections, single-vehicle crashes compared with multi-vehicle crashes and weekend crashes compared with weekday crashes. This paper identifies some of the basic characteristics of crashes along rural mountainous roads to aid future research on traffic safety along mountainous roads.

In situ investigation of explosive crystallization in a-Ge: Experimental determination of the interface response function using dynamic transmission electron microscopy

The crystallization of amorphous semiconductors is a strongly exothermic process. Once initiated the release of latent heat can be sufficient to drive a self-sustaining crystallization front through the material in a manner that has been described as explosive. Here, we perform a quantitative in situ study of explosive crystallization in amorphous germanium using dynamic transmission electron microscopy. Direct observations of the speed of the explosive crystallization front as it evolves along a laser-imprinted temperature gradient are used to experimentally determine the complete interface response function (i.e., the temperature-dependent front propagation speed) for this process, which reaches a peak of 16 m/s. Fitting to the Frenkel-Wilson kinetic law demonstrates that the diffusivity of the material locally/immediately in advance of the explosive crystallization front is inconsistent with those of a liquid phase. This result suggests a modification to the liquid-mediated mechanism commonly used to describe this process that replaces the phase change at the leading amorphous-liquid interface with a change in bonding character (from covalent to metallic) occurring in the hot amorphous material.

Experimental people

From Kurt Vonnegut to Stephen King, many novelists use metanarrative techniques to insert fictional versions of themselves in the stories they tell. The function of deploying such techniques is often to draw attention to the liminal space between the fictional constructs inherent in the novel as a form, and the real world from which the constructs draw inspiration, and indeed, are read by an audience. For emerging writers working in short form narratives, however, the structural demands of the short story or flash fiction make the use of similar techniques problematic in the level of depth to which they can be deployed. Experimental People, the third in series of short stories, works to overcome the structural limitations of a succinct form by developing a fractured fictional version of the author over a number of pieces and published across a range of sites. The accumulative affect is a richer metanarrative textual arrangement that also allows for the individual short stories to function independently.

An experimental study on anisotropic mechanical properties of porcine thoracic aorta

Objective: To study the anisotropic mechanical properties of the thoracic aorta in porcine. Methods: Twenty-one porcine thoracic aortas were collected and categorized into three groups. The aortas were then cut through in their axial directions and expanded into two-dimensional planes. Then, by setting the length direction of the planar aortas (i.e., axial directions of the aortas) as 0°, each planar aorta was counterclockwisely cut into 8 samples with orientation of 30°, 45°, 60°, 90°, 120°, 135°, 150° and 180°, respectively. Finally, the uniaxial tensile tests were applied on three groups of samples at the loading rates of 1, 5 and 10 mm/min, respectively, to obtain the elastic modulus and ultimate stress of the aorta in different directions and at different loading rates. Results: The stress-strain curves exhibited different viscoelastic behaviors. With the increase of sample orientations, the elastic modulus gradually increased from 30°, reached the maximum value at 90°, and then gradually decreased till 180°. The variation trend of ultimate stress was similar to that of elastic modulus. Moreover, different loading rates showed a significant influence on the results of elastic modulus and ultimate stress, but a weak influence on the anisotropic degree. Conclusions: The porcine thoracic aorta is highly anisotropic. This research finding provides parameter references for assignment of material properties in finite element modeling, and is significant for understanding biomechanical properties of the arteries.

Experimental measurement of the mechanical properties of carotid atherothrombotic plaque fibrous cap

Eleven carotid atherothrombotic plaque samples were harvested from patients. Three samples that were highly calcified were discarded, while eight yielded results. The elastic properties of the material were estimated by fitting the measured indentation response to finite element simulations. The methodology was refined and its accuracy quantified using a synthetic rubber. The neo-Hookean form of the material model gave a good fit to the measured response of the tissue. The inferred shear modulus μ was found to be in the range 7-100 kPa, with a median value of 11 kPa. A review of published materials data showed a wide range of material properties for human atherothrombotic tissue. The effects of anisotropy and time dependency in these published results were highlighted. The present measurements were comparable to the static radial compression tests of Lee et al, 1991 [Structure-dependent dynamic behaviour of fibrous caps from human atherosclerotic plaques. Circulation 83, 1764-1770].

Nonlinear mechanical property of tracheal cartilage: A theoretical and experimental study

Background: Despite being the stiffest airway of the bronchial tree, the trachea undergoes significant deformation due to intrathoracic pressure during breathing. The mechanical properties of the trachea affect the flow in the airway and may contribute to the biological function of the lung. Method: A Fung-type strain energy density function was used to investigate the nonlinear mechanical behavior of tracheal cartilage. A bending test on pig tracheal cartilage was performed and a mathematical model for analyzing the deformation of tracheal cartilage was developed. The constants included in the strain energy density function were determined by fitting the experimental data. Result: The experimental data show that tracheal cartilage is a nonlinear material displaying higher strength in compression than in tension. When the compression forces varied from -0.02 to -0.03 N and from -0.03 to -0.04 N, the deformation ratios were 11.03±2.18% and 7.27±1.59%, respectively. Both were much smaller than the deformation ratios (20.01±4.49%) under tension forces of 0.02 to 0.01 N. The Fung-type strain energy density function can capture this nonlinear behavior very well, whilst the linear stress-strain relation cannot. It underestimates the stability of trachea by exaggerating the displacement in compression. This study may improve our understanding of the nonlinear behavior of tracheal cartilage and it may be useful for the future study on tracheal collapse behavior under physiological and pathological conditions.

Pulse-echo ultrasound transit time spectroscopy: A comparison of experimental measurements and simulation prediction

Considering ultrasound propagation through complex composite media as an array of parallel sonic rays, a comparison of computer simulated prediction with experimental data has previously been reported for transmission mode (where one transducer serves as transmitter, the other as receiver) in a series of ten acrylic step-wedge samples, immersed in water, exhibiting varying degrees of transit time inhomogeneity. In this study, the same samples were used but in pulse-echo mode, where the same ultrasound transducer served as both transmitter and receiver, detecting both ‘primary’ (internal sample interface) and ‘secondary’ (external sample interface) echoes. A transit time spectrum (TTS) was derived, describing the proportion of sonic rays with a particular transit time. A computer simulation was performed to predict the transit time and amplitude of various echoes created, and compared with experimental data. Applying an amplitude-tolerance analysis, 91.7±3.7% of the simulated data was within ±1 standard deviation (STD) of the experimentally measured amplitude-time data. Correlation of predicted and experimental transit time spectra provided coefficients of determination (R2) ranging from 100.0% to 96.8% for the various samples tested. The results acquired from this study provide good evidence for the concept of parallel sonic rays. Further, deconvolution of experimental input and output signals has been shown to provide an effective method to identify echoes otherwise lost due to phase cancellation. Potential applications of pulse-echo ultrasound transit time spectroscopy (PE-UTTS) include improvement of ultrasound image fidelity by improving spatial resolution and reducing phase interference artefacts.

Development of a novel experimental model to investigate the influence of mechanics on bone healing

This dissertation proposed a novel experimental model combining a defect configuration with an active instrumented fixation device to investigate the influence of mechanics on bone healing. The proposed defect configuration aimed to minimise physiological loading within an experimental fracture gap and the instrumented fixator was used for the application of controlled displacements and in vivo stiffness monitoring of the healing process. This thesis has provided a novel approach to advance current knowledge and understanding of mechanobiology, which has been limited in previous experimental models.

An experimental analysis of information acquisition in prediction markets

We study which factors in terms of trading environment and trader characteristics determine individual information acquisition in experimental asset markets. Traders with larger endowments, existing inconclusive information, lower risk aversion, and less experience in financial markets tend to acquire more information. Overall, we find that traders overacquire information, so that informed traders on average obtain negative profits net of information costs. Information acquisition and the associated losses do not diminish over time. This overacquisition phenomenon is inconsistent with predictions of rational expectations equilibrium, and we argue it resembles the overdissipation results from the contest literature. We find that more acquired information in the market leads to smaller differences between fundamental asset values and prices. Thus, the overacquisition phenomenon is a novel explanation for the high forecasting accuracy of prediction markets.

Plasma-enhanced synthesis of bioactive polymeric coatings from monoterpene alcohols: A combined experimental and theoretical study

This paper describes the synthesis and characterization of a novel organic polymer coating for the prevention of the growth of Pseudomonas aeruginosa on the solid surface of three-dimensional objects. Substrata were encapsulated with polyterpenol thin films prepared from terpinen-4-ol using radio frequency plasma enhanced chemical vapor deposition. Terpinen-4-ol is a constituent of tea tree oil with known antibacterial properties. The influence of deposition power on the chemical structure, surface composition, and ultimately the antibacterial inhibitory activity of the resulting polyterpenol thin films was studied using X-ray photoelectron spectroscopy (XPS), water contact angle measurement, atomic force microscopy (AFM), and 3-D interactive visualization and statistical approximation of the topographic profiles. The experimental results were consistent with those predicted by molecular simulations. The extent of bacterial attachment and extracellular polymeric substances (EPS) production was analyzed using scanning electron microscopy (SEM) and confocal scanning laser microscopy (CSLM). Polyterpenol films deposited at lower power were particularly effective against P. aeruginosa due to the preservation of original terpinen-4-ol molecules in the film structure. The proposed antimicrobial and antifouling coating can be potentially integrated into medical and other clinically relevant devices to prevent bacterial growth and to minimize bacteria-associated adverse host responses.

Experimental investigation of the effects of oxygenated fuels on exhaust emissions in a heavy duty diesel engine

Physical and chemical properties of biofuels vary among various feedstocks and their subsequent conversions to fuels. The biofuels contain various amounts of oxygen, and this has a significant influence on exhaust emission. This oxygen content has been considered in order to investigate its effect on diesel engine exhaust emissions. The experiments have been conducted with a heavy duty diesel engine and various oxygenated fuels. It is found that the amount of oxygen in the fuel has a high level of influence on its exhaust emissions, and this provides agreement with diesel emissions results such as PN reduction. By increasing the amount of oxygen in the blend (by adding more biofuel), the particulate number (PN) is reduced and NOx increases gradually. However, the variation of PN and NOx are not similar for waste cooking biodiesel (WCBD) and butanol blend, even though their oxygen content are the same in the blends. This is due to the source of the biofuel and their internal chemistry.

Experimental and numerical investigation of the behaviour of CFRP strengthened CHS beams subjected to bending

This paper presents the results of an experimental and numerical program to investigate the circular hollow section (CHS) beams, strengthened using Carbon Fibre Reinforced Polymer (CFRP) sheets. The circular hollow shaped steel beams bonded with different CFRP layer orientations were tested under four-point bending. The mid-span deflection, service load and failure load were recorded. The LHL (where L, first inner longitudinal layer, H, second hoop layer and L, third outer longitudinal layer) and LLH (where L, first inner longitudinal layer, L, second longitudinal layer and H, third outer hoop layer) layer oriented strengthened beams perform slightly better than HHL (where H, first inner hoop layer, H, second hoop layer and L, third outer longitudinal layer) layer oriented strengthened beams. The LHL and LLH layer oriented treated beams showed very similar structural behaviour. Numerical analyses were then conducted on the CFRP strengthened steel CHS beams. The validity of the models has been assessed by comparing the failure loads and mid-span deflections. The effects of various parameters such as bond length, section types, tensile modulus of CFRP, adhesive layer thickness and adhesive types have been studied.

Experimental and numerical investigation of strain-rate-dependent behavior of kangaroo shoulder cartilage

This thesis introduces a new animal model, kangaroo, to biomechanical investigations of shoulder cartilage research. It examines the effect of cartilage structure and constituents on tissue behavior and its adaptation to mechanical loading. In doing so, the study explains the relationship of tissue's functional behaviors to its structure and constituents which has important implications for tissue engineering strategies catering joint specific cartilage tissue generation.