The preparation of ketene dithioacetals and thiophenes from chloropyridines containing an active methylene group

The base catalysed reaction of carbon disulphide with the active methylene groups of chloropyridines 4 and 7, followed by alkylation with reagents which also contain active methylene groups, lead to ketene dithioacetals. Further reaction with base afforded highly substituted thiophenes

Primary investigation into the occurrence of Hydroxymethylfurfural (HMF) in a range of smoked products

5-hydroxymethylfurfural (HMF) is produced in foods through many different pathways. Recently, studies have revealed its potential mutagenic and carcinogenic properties. Determination of HMF was originally used as an indicator of both the extent of thermal processing a food had undergone and food quality. It has been identified in a variety of food products such as bread, breakfast cereals, fruit juices, milk and honey. In addition to the thermal processes that lead to the formation of HMF during thermal treatment, food smoking also creates conditions that result in the formation of HMF. This can take place within the food due to the elevated temperatures associated with hot smoking, or by the proximity of the products of the pyrolysis of the wood matrix that is used for smoking (cold smoking). This may lead to further contamination of the product by HMF over and above that associated with the rest of the preparation process. Until now, there have been no studies examining the relation between the smoking procedure and HMF contamination in smoked food. This study is a primary investigation measuring HMF levels in three categories of smoked food products; cheese, processed meat, and fish using HPLC-UV. The amount of HMF found in all three product categories supports our hypothesis that HMF levels are due to both internal pathways during processing and external contamination from smoke generation matrix (wood) employed. The results ranged from 1 ppb (Metsovone traditional Greek smoked cheese) to 4ppm (Hot-smoked ready to eat mackerel). Subsequently for smoked cheese products, a correlation was found between HMF and phenolic compounds generated by the smoking procedures and identified by SPME-GCMS. It was observed that cheese samples that had higher concentrations of HMF were also found to have higher concentrations of syringol and cresols. It is important therefore to understand the smoking procedure’s effect on HMF formation. This will aid in the development of mitigation strategies to reduce HMF formation while retaining the flavour of the smoked products

Visualisation of fingermarks and grab impressions on fabrics. Part 1: gold/zinc vacuum metal deposition

Vacuum metal deposition (VMD) is a highly sensitive technique originally introduced for detecting latent fingermarks on smooth non-porous surfaces such as carrier bags, plastics and glass. The current study explores whether VMD can be used in the examination of clothing from physical and sexual assault cases in order to visualise identifiable fingermark ridge detail and/or palmar flexion crease detail, thus allowing potential areas to be indicated for DNA swabbing and/or to determine the sequence of events. Four different fabrics were utilised during this study – nylon, polyester, polycotton and cotton, along with 15 donors who ranged in their age and propensity to leave fingermarks, from good to medium to poor as determined by results obtained from test runs using paper and plastic carrier bags processed with VMD. Once samples were collected they were kept for a determined time (1, 2, 3, 4, 5, 6, 7, 14, 21 or 28 days) and then treated using the gold/zinc metal VMD process. From the results, it appears that greater ridge detail is visible on the smoother non-porous fabrics, such as nylon whereas on rougher porous fabrics, such as cotton, only empty prints and impressions, rather than any ridge details, were visible. All fabrics did however allow the development of touch marks that could be targeted for DNA taping thus potentially leading to a DNA profile and possible identification of a suspect

Visualisation of fingermarks and grab impressions on dark fabrics using silver vacuum metal deposition

Vacuum metal deposition (VMD) involves the thermal evaporation of metal (silver) in a vacuum, resulting in a uniform layer being deposited on the specimen being treated. This paper examines the use of silver on dark fabrics, thus offering a simpler operation and more obvious colouration to that of the traditional use of gold and zinc metals which must be evaporated separately. The aim of this study was to investigate the effect of fabric type, donor, mark age and method of fingermark deposition on the quality of marks visualised using silver VMD. This was achieved by collecting fingermark deposits from fifteen donors, of both sexes and various ages, by a grab or a press method. Four different fabrics: satin, polyester, polycotton and cotton were studied over a 10 day timeline of 1, 2, 3, 4, 5, 6, 7, 14, 21 and 28 + days. It was found that satin and polyester gave the most positive results, with polyester often producing excellent ridge detail. Cotton and polycotton were less successful with no ridge detail being observed. The donors also had an observable effect on the results obtained probably due to variations in secretions produced or pressures applied during specimen collection. The age of the mark or the method of mark deposition had little influence on the results obtained. Silver VMD is a viable process for visualising marks on certain dark fabrics and has the advantage over gold/zinc VMD in that the marks visualised are light in colour which contrasts well against the dark background

Three dimensional quantification of soil hydraulic properties using X-ray Computed Tomography and image based modelling

We demonstrate the application of a high-resolution X-ray Computed Tomography (CT) method to quantify water distribution in soil pores under successive reductive drying. We focus on the wet end of the water release characteristic (WRC) (0 to -75 kPa) to investigate changes in soil water distribution in contrasting soil textures (sand and clay) and structures (sieved and field structured), to determine the impact of soil structure on hydraulic behaviour. The 3D structure of each soil was obtained from the CT images (at a 10 µm resolution). Stokes equations for flow were solved computationally for each measured structure to estimate hydraulic conductivity. The simulated values obtained compared extremely well with the measured saturated hydraulic conductivity values. By considering different sample sizes we were able to identify that the smallest possible representative sample size which is required to determine a globally valid hydraulic conductivity

Evaluation of Salmon (<i>Salmo salar</i>) and Rainbow Trout (<i>Oncorhynchus mykiss</i>) pin bones using textural analysis and micro X-ray computational tomography

Industrially, common problems arise with the deboning pin bone process, where Atlantic Salmon (Salmo salar) and Rainbow Trout (Oncorhynchus mykiss) fillets, post rigor, are subjected to a pulling process to remove the pin bones from the fillet. This study measured the length of pin bones from two species of fish and two different industrial graded weights, and then used a texture analyser and lCT X-ray to measure the pulling force, break point and volume of the pin bones of both species of fish. Results showed that salmon pin bones required significantly higher pulling force to remove pin bones from the fish fillet when compared with Trout pin bones. Interestingly Trout pin bones were significantly longer and stronger than Salmon pin bones, but had significantly lower volume. This research has progressed the issues surrounding pin boning industrially, however, more studies are required in order to understand if these differences affect the overall deboning pin bone process

Using µX-Ray CT to observe postmortem diffusion from the stomach in a rat model

The stomach has long been recognised as a depot for postmortem diffusion. A better understanding of the phenomena of postmortem diffusion would aid forensic practitioners in their interpretation of toxicological results. A limitation of previous stomach diffusion studies was the lack of ability to visualise postmortem diffusion in real time, the use of μX-ray Computed Tomography (CT) could overcome this problem. We utilised CT to track the diffusion of the contrast medium caesium ions (Cs+) (administered by oral gavage) from the rat stomach over 6 days. We investigated the influence of temperature (4 °C and 20 °C) and body position (horizontal and vertical). The results show that the a) diffusion of Cs+ from the stomach can be visualised over 6 days, over which a significant amount (∼50 %) of the diffusion occurs in the first 24 h following administration; b) storing the rat at 4 °C reduces the distance of diffusion from the stomach by ∼ 66%; c) body position influences the route of diffusion and d) in 2 of the 16 rats studied Cs+ was found in the right lobe of the liver. Overall these results show that CT using Cs+ is a good model to visualise postmortem diffusion and that bodies show significant variation in postmortem diffusion.It is also clear that bodies should be refrigerated and postmortem samples should be taken as soon as possible to minimise the influences of postmortem diffusion from the stomach

Evaluation of the effect of berry extracts on carboxymethyllysine and lysine in ultra-high temperature treated milk

Both the Maillard reaction (MR) and thermal treatment influence the nutritional value of milk. In this paper, the capability of polyphenolic berry extract (PBE) to inhibit MR in an ultra-high temperature (UHT) treated milk was investigated. Total polyphenol content and antioxidant capacity of blueberry (BE) and raspberry extracts (RE) were also tested. A gas chromatography-mass spectrometry (GC-MS) method was developed to monitor the MR product N ε-(carboxymethyl)-L-lysine (CML) and L-lysine (LYS). PBE was added to milk at 0.05 and 0.1% w/v prior to UHT processing. Data revealed that formation of CML was significantly reduced (23.4 ± 5.1 %) by addition of 0.1% w/v BE. The final concentrations of LYS measured following the addition of PBE prior to thermal treatment were statistically similar to the control milk which was not subjected to thermal processing. Additionally, the metabolic profile of milk samples was investigated by GC-MS and visualised using ‘FancyTiles’

Acrylamide in industrial potato crisp manufacturing:a potential tool for its reduction

This paper considers the potential for identifying industrial manufacturing conditions that will lead to high acrylamide formation in potato crisp manufacture. Considering the available historical industrial processing data, initial tests were undertaken to identify the degree of variability and confidence in the data. Following data visualisation which indicated data ‘fingerprints’ characteristic of high acrylamide, Partial Least Squares (PLS) Discriminant Analysis (DA) was implemented to provide indications of the probability that high acrylamide product would be produced. It was determined that in a third of instances, high acrylamide could be predicted while maintaining a low level of false predictions. The predominance of fructose concentration in the prediction along with the need for asparagine were indicated and aligned well with prior literature mechanistic model indications. The ability to identify a third of high acrylamide occurrences provides the process operators with a good opportunity to make process modifications that would comply with increasingly stringent regulation