Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

Experimental and numerical study of polymeric foam efficacy in portable water filled barriers

Portable, water filled road safety barriers are used to provide protection and reduce the potential hazard due to errant vehicles in areas where the road conditions change frequently (e.g. near road work sites). As part of an effort to reduce excessive working widths typical of these systems, a study was conducted to assess the effectiveness of introducing polymeric foam filled panels into the design. Surrogate impact tests of a design typical of such as barrier system were conducted utilising a pneumatically powered horizontal impact testing machine up to impact energies of 7.40 kJ. Results of these tests are utilised to examine the barrier behaviour, in addition to being used to validate a couple FE/SPH model of the barrier system. Once validated, the FE/SPH model it utilised as the basis for a parametric study into the efficacy and effects of the inclusion of polymeric foam filled panels on the performance of portable water filled road safety barriers. It was found that extruded polystyrene foam functioned well, with a greater thickness of the foam panel significantly reducing the impacting body velocity as the barrier began to translate.

A non-linear interface element model for thin layer high adhesive mortared masonry

A nonlinear interface element modelling method is formulated for the prediction of deformation and failure of high adhesive thin layer polymer mortared masonry exhibiting failure of units and mortar. Plastic flow vectors are explicitly integrated within the implicit finite element framework instead of relying on predictor–corrector like approaches. The method is calibrated using experimental data from uniaxial compression, shear triplet and flexural beam tests. The model is validated using a thin layer mortared masonry shear wall, whose experimental datasets are reported in the literature and is used to examine the behaviour of thin layer mortared masonry under biaxial loading.

Experimental and numerical studies of fire exposed lipped channel columns subject to distortional buckling

Cold-formed steel sections are commonly used in low-rise commercial and residential buildings. During fire events, cold-formed steel structural elements in these buildings are exposed to elevated temperatures. Hence after such events there is a need to determine the residual strength of these structural elements. However, only limited information is available in relation to the residual strength of fire exposed cold-formed steel members. This research is aimed at investigating the residual distortional buckling capacities of fire exposed cold-formed steel lipped channel sections. A series of compression tests of fire exposed, short lipped channel columns made of varying steel grades and thicknesses was undertaken in this research. Test columns were exposed to different elevated temperatures up to 800 oC. They were then allowed to cool down at ambient temperature before they were tested to failure. Suitable finite element models of tested columns were also developed and validated using test results. The residual compression capacities of tested columns were predicted using the ambient temperature cold-formed steel design rules (AS/NZS 4600, AISI S100 and Direct Strength Method). Post-fire mechanical properties obtained from a previous study were used in this study. Comparison of results showed that ambient temperature design rules for compression members can be used to predict the residual compression capacities of fire exposed short or laterally restrained cold-formed steel columns provided the maximum temperature experienced by the columns can be estimated after a fire event. Such residual capacity assessments will allow structural and fire engineers to make an accurate prediction of the safety of buildings after fire events. This paper presents the details of these experimental and numerical studies and the results.

Application of meshfree methods to numerically simulate microscale deformations of different plant food materials during drying

Plant food materials have a very high demand in the consumer market and therefore, improved food products and efficient processing techniques are concurrently being researched in food engineering. In this context, numerical modelling and simulation techniques have a very high potential to reveal fundamentals of the underlying mechanisms involved. However, numerical modelling of plant food materials during drying becomes quite challenging, mainly due to the complexity of the multiphase microstructure of the material, which undergoes excessive deformations during drying. In this regard, conventional grid-based modelling techniques have limited applicability due to their inflexible grid-based fundamental limitations. As a result, meshfree methods have recently been developed which offer a more adaptable approach to problem domains of this nature, due to their fundamental grid-free advantages. In this work, a recently developed meshfree based two-dimensional plant tissue model is used for a comparative study of microscale morphological changes of several food materials during drying. The model involves Smoothed Particle Hydrodynamics (SPH) and Discrete Element Method (DEM) to represent fluid and solid phases of the cellular structure. Simulation are conducted on apple, potato, carrot and grape tissues and the results are qualitatively and quantitatively compared and related with experimental findings obtained from the literature. The study revealed that cellular deformations are highly sensitive to cell dimensions, cell wall physical and mechanical properties, middle lamella properties and turgor pressure. In particular, the meshfree model is well capable of simulating critically dried tissues at lower moisture content and turgor pressure, which lead to cell wall wrinkling. The findings further highlighted the potential applicability of the meshfree approach to model large deformations of the plant tissue microstructure during drying, providing a distinct advantage over the state of the art grid-based approaches.

Experimental studies on web crippling behaviour of hollow flange channel beams under two flange load cases

This paper presents the details of an experimental study of a cold-formed steel hollow flange channel beam known as LiteSteel beam (LSB) subject to web crippling under End Two Flange (ETF) and Interior Two Flange (ITF) load cases. The LSB sections with two rectangular hollow flanges are made using a simultaneous cold-forming and electric resistance welding process. Due to the geometry of the LSB, and its unique residual stress characteristics and initial geometric imperfections, much of the existing research for common cold-formed steel sections is not directly applicable to LSB. Experimental and numerical studies have been carried out to evaluate the behaviour and design of LSBs subject to pure bending, predominant shear and combined actions. To date, however, no investigation has been conducted on the web crippling behaviour and strength of LSB sections. Hence an experimental study was conducted to investigate the web crippling behaviour and capacities of LSBs. Twenty-eight web crippling tests were conducted under ETF and ITF load cases, and the ultimate web crippling capacities were compared with the predictions from the design equations in AS/NZS 4600 and AISI S100. This comparison showed that AS/NZS 4600 and AISI S100 web crippling design equations are unconservative for LSB sections under ETF and ITF load cases. Hence new equations were proposed to determine the web crippling capacities of LSBs based on experimental results. Suitable design rules were also developed under the direct strength method (DSM) format.

Experimental investigation and design of lipped channel beams in shear

Cold-formed high strength steel members are increasingly used as primary load bearing components in low rise buildings. Lipped channel beam (LCB) is one of the most commonly used flexural members in these applications. In this research an experimental study was undertaken to investigate the shear behaviour and strengths of LCB sections. Simply supported test specimens of back to back LCBs with aspect ratios of 1.0 and 1.5 were loaded at mid-span until failure. Test specimens were chosen such that all three types of shear failure (shear yielding, inelastic and elastic shear buckling) occurred in the tests. The ultimate shear capacity results obtained from the tests were compared with the predictions from the current design rules in Australian/NewZealand and American cold-formed steel design standards. This comparison showed that these shear design rules are very conservative as they did not include the post-buckling strength observed in the shear tests and the higher shear buckling coefficient due to the additional fixity along the web-flange juncture. Improved shear design equations are proposed in this paper by including the above beneficial effects. Suitable lower bound design rules were also developed under the direct strength method format. This paper presents the details of this experimental study and the results including the improved design rules for the shear capacity of LCBs. It also includes the details of tests of LCBs subject to combined shear and flange distortion, and combined bending and shear actions, and proposes suitable design rules to predict the capacities in these cases.

Experimental colonization of the canine urinary tract with the asymptomatic bacteriuria Escherichia coli strain 83972

Establishment of asymptomatic bacteriuria (ABU) with Escherichia coli 83972 is a viable prophylactic alternative to antibiotic therapy for the prevention of recurrent bacterial urinary tract infection in humans. Approximately 2 x 108 viable E. coli 83972 cells were introduced into the bladder of six healthy female dogs via a sterile urinary catheter. The presence of pyuria, depression, stranguria, pollakiuria and haematuria was documented for 6 weeks and urinalysis and aerobic bacterial cultures were performed every 24–72 h. Pyuria was present in all dogs on day 1 post-inoculation and 4/6 dogs (67%) had a positive urine culture on this day. Duration of colonization ranged from 0 to 10 days (median 4 days). Four dogs were re-inoculated on day 20. Duration of colonization following the second inoculation ranged from 1 to 3 days. No dog suffered pyrexia or appeared systemically unwell but all dogs initially exhibited mild pollakiuria and a small number displayed gross haematuria and/or stranguria. By day 3 of each trial all clinical signs had resolved. Persistent bacteriuria was not achieved in any dog but two dogs were colonized for 10 days following a single inoculation. Further research is required to determine whether establishment of ABU in dogs with recurrent urinary tract infection is a viable alternative to repeated doses of antimicrobial agents.

Genetic susceptibility to environmental toxicants : the interface between human and experimental studies in the development of new toxicological concepts

The growing knowledge of the genetic polymorphisms of enzymes metabolising xenobiotics in humans and their connections with individual susceptibility towards toxicants has created new and important interfaces between human epidemiology and experimental toxicology. The results of molecular epidemiological studies may provide new hypotheses and concepts, which call for experimental verification, and experimental concepts may obtain further proof by molecular epidemiological studies. If applied diligently, these possibilities may be combined to lead to new strategies of human-oriented toxicological research. This overview will present some outstanding examples for such strategies taken from the practically very important field of occupational toxicology. The main focus is placed on the effects of enzyme polymorphisms of the xenobiotic metabolism in association with the induction of bladder cancer and renal cell cancer after exposure to occupational chemicals. Also, smoking and induction of head and neck squamous cell cancer are considered.

Species differences in acrylonitrile metabolism and toxicity between experimental animals and humans based on observations in human accidental poisonings

The high acute toxicity of acrylonitrile may be a result of its intrinsic biological reactivity or of its metabolite cyanide. Intravenous N-acetylcysteine has been recommended for treatment of accidental intoxications in acrylonitrile workers, but such recommendations vary internationally. Acrylonitrile is metabolized in humans and experimental animals via two competing pathways; the glutathione-dependent pathway is considered to represent an avenue of detoxication whilst the oxidative pathway leads to a genotoxic epoxide, cyanoethylene oxide, and to elimination of cyanide. Cases of acute acrylonitrile overexposure or intoxication have occurred within persons having industrial contact with acrylonitrile; the route of exposure was by inhalation and/or by skin contact. The combined observations lead to the conclusion of a much higher impact of the oxidative metabolism of acrylonitrile in humans than in rodents. This is confirmed by differences in the clinical picture of acute life-threatening intoxications in both species, as well as by differential efficacies of antidotes. A combination of N-acetylcysteine with sodium thiosulfate seems an appropriate measure for antidote therapy of acute acrylonitrile intoxications. Clinical observations also highlight the practical importance of human individual susceptibility differences. Furthermore, differential adduct monitoring, assessing protein adducts with different rates of decay, enables the development of more elaborated biological monitoring strategies for the surveillance of workers with potential acrylonitrile contact.