Studies on factors relating to the development of defects in commercial cheese

Defects in commercial cheese result in a downgrading of the final cheese and a consequential economic loss to the cheese producer. Developments of defects in cheese are often not fully understood and therefore not controllable by the producer. This research investigated the underlying factors in the development of split and secondary fermentation defect and of pinking defects in commercial Irish cheeses. Split defect in Swiss-type cheese is a common defect associated with eye formation and manifests as slits and cracks visible in the cut cheese loaf (Reinbold, 1972; Daly et al., 2010). No consensus exists as to the definitive causes of the defect and possible factors which may contribute to the defect were reviewed. Models were derived to describe the relationship between moisture, pH, and salt levels and the distance from sample location to the closest external block surface during cheese ripening. Significant gradients within the cheese blocks were observed for all measured parameters in cheeses at 7 day post/after manufacture. No significant pH gradient was found within the blocks on exit from hot-room ripening and at three months post exit from the hot-room. Moisture content reached equilibrium within the blocks between exit from hot-room and 3 months after exit from hot-room while salt and salt-to-moisture levels had not reached equilibrium within the cheese blocks even at three months after exit from hot-room ripening. A characterisation of Swiss-type cheeses produced from a seasonal milk supply was undertaken. Cheeses were sampled on two days per month of the production year, at three different times during the manufacturing day, at internal and external regions of the cheese block and at four ripening time points (7 days post manufacture, post hot-room, 14 days post hot-room and 3 months in a cold room after exit from hot-room). Compositional, biochemical and microbial indices were determined, and the results were analysed as a splitplot with a factorial arrangement of treatments (season, time of day, area) on the main plot and ripening time on the sub-plot. Season (and interactions) had a significant effect on pH and salt-in-moisture levels (SM), mean viable counts of L. helveticus, propionic acid and non-starter lactic acid bacteria, levels of primary and secondary proteolysis and cheese firmness. Levels of proteolysis increased significantly during hot-room ripening but also during cold room storage, signifying continued development of cheese ripening during cold storage (> 8°C). Rheological parameters (e.g. springiness and cohesiveness) were significantly affected by interactions between ripening and location within cheese blocks. Time of day of manufacture significantly affected mean cheese calcium levels at 7 days post manufacture and mean levels of arginine and mean viable counts of NSLAB. Cheeses produced during the middle of the production day had the best grading scores and were more consistent compared to cheeses produced early or late during day of manufacture. Cheeses with low levels of S/M and low values of resilience were associated with poor grades at 7 days post manufacture. Chesses which had high elastic index values and low values of springiness in the external areas after exit from hot-room ripening also obtained good commercial grades. Development of a pink colour defect is an intermittent defect in ripened cheese which may or may not contain an added colourant, e.g., annatto. Factors associated with the defect were reviewed. Attempts at extraction and identification of the pink discolouration were unsuccessful. The pink colour partitioned with the water insoluble protein fraction. No significant difference was observed between ripened control and defect cheese for oxygen levels and redox potential or for the results of elemental analysis. A possible relationship between starter activity and defect development was established in cheeses with added coulourant, as lower levels of residual galactose and lactose were observed in defective cheese compared to control cheese free of the defect. Swiss-type cheese without added colourant had significantly higher levels of arginine and significantly lower lactate levels. Flow cell cytometry indicated that levels of bacterial cell viability and metabolic state differed between control and defect cheeses (without added colourant). Pyrosequencing analysis of cheese samples with and without the defect detected the previously unreported bacteria in cheese, Deinococcus thermus (a potential carotenoid producer). Defective Swiss-type cheeses had elevated levels of Deinococcus thermus compared to control cheeses, however the direct cause of pink was not linked to this bacterium alone. Overall, research was undertaken on underlying factors associated with the development of specific defects in commercial cheese, but also characterised the dynamic changes in key microbial and physicochemical parameters during cheese ripening and storage. This will enable the development of processing technologies to enable seasonal manipulation of manufacture protocols to minimise compositional and biochemical variability and to reduce and inhibit the occurrence of specific quality defects.

Contemporary pilgrimage in Ireland: a cultural geographic perspective

Using the lenses of contemporary cultural geography, this research develops an understanding of pilgrimage as a relational and reciprocal process that co-produces self and world. Drawing on the phenomenology of Merleau-Ponty, I argue that through the performances and experiences of contemporary pilgrimage in Ireland, participants and locations emerge as pilgrims and pilgrimage places. This approach unites different strands of cultural geography, including the mobilities field, more-than representational concerns, discussions of embodiment and practice, emotional and affective geographies, and religious and spiritual geographies. I explore how pilgrimage is an active process in which self and world, belief and practice, and the numinous and material entwine and merge. An autoethnographic methodology is enacted as an embodied, intersubjective, and reflexive research approach that incorporates the motivations, experiences, and beliefs of research participants, alongside my own descriptions and reflections. The methodology is focused on encountering and documenting pilgrimage practices as they occur in place and relating these embodied spatial practices to the accounts of pilgrims. The insights generated by engagements with research participants and through my own pilgrimages, offer new appreciations of the enduring appeal of pilgrimage in Ireland as a religious-spiritual and cultural activity that allows people to express personal intentions, to develop their faith, and to seek numinous encounters. Through the pilgrimages at Lough Derg, Croagh Patrick, and three holy wells, I produce a layered account of the empirical circumstances of the practices. The presentation of these places and events is enhanced by the use of evocative images and audiovisual recordings. By centring my study on the practices and experiences of different pilgrimages in present-day Ireland, and critically deploying strands of cultural geography and pilgrimage studies, this research produces new qualitative understandings of pilgrimage and contributes to discussions concerned with the relationships between self and world.

Studies in asymmetric and heterocyclic synthesis: I. chiral ketones II. Quinolones III. Trifluoromethylated pyrones

This thesis is split into three sections based on three different areas of research. In the first section, investigations into the α-alkylation of ketones using a novel chiral auxiliary is reported. This chiral auxiliary was synthesised containing a pyrrolidine ring in the chiral arm and was applied in the preparation of α-alkylated ketones which were obtained in up to 92% ee and up to 63% yield over two steps. Both 3-pentanone and propiophenone based ketones were used in the investigation with a variety of both alkyl and benzyl based electrophiles. The novel chiral auxiliary was also successful when applied to Michael and aldol reactions. A diamine precursor en route to the chiral auxiliary was also applied as an organocatalyst in a Michael reaction, with the product obtained in excellent enantioselectivity. In the second section, investigations into potential anti-quorum sensing molecules are reported. The bacteria Pseudomonas aeruginosa is an antibiotic-resistant pathogen that demonstrates cooperative behaviours and communicates using small chemical molecules in a process termed quorum sensing. A variety of C-3 analogues of the quorum sensing molecules used by P. aeruginosa were synthesised. Expanding upon previous research within the group, investigations were carried out into alternative protecting group strategies of 2-heptyl-4-(1H)- quinolone with the aim of improving the yields of products of cross-coupling reactions. In the third section, investigations into fluorination and trifluoromethylation of 2-pyrones, pyridones and quinolones is reported. The incorporation of a fluorine atom or a trifluoromethyl group into a molecule is important in pharmaceutical drug discovery programmes as it can lead to increased lipophilicity and bioavailability, however late-stage incorporation is rarely reported. Both direct fluorination and trifluoromethylation were attempted. Eight trifluoromethylated 2-pyrones, five trifluoromethylated 2-pyridones and a trifluoromethylated 2-quinolone were obtained in a late-stage synthesis from their respective iodinated precursors using methyl fluorosulfonyldifluoroacetate as a trifluoromethylating reagent.

Comparison between local anaesthetic agents, lidocaine and bupivacaine, in patients undergoing third molar extraction in terms of patient satisfaction.

AIMS: (1) To determine if anaesthetic agent bupivacaine, has a prolonged effect on the period of acute postoperative pain when compared to lidocaine, a shorter acting agent. (2) To determine patient’s post-operative satisfaction and preference with regard to anaesthetic choice. METHODS: This double blind, randomised, interventional clinical trial included 85 patients. All patients had bilateral impacted lower third molars of removed under general anaesthetic. All patients received 0.5% plain bupivacaine on one randomly allocated side, with 2% lidocaine (with adrenaline) administered on the opposite side. Pain was measured using visual analogue scales at 0, 30, 60 minutes and 3, 4, 6 and 8 hours post-surgery. Pain was analysed for 1 week following surgery. Psychological evaluations and patient reported outcomes, including patient satisfaction were evaluated. RESULTS: A significant difference in pain (P=0.001) was seen during the 3-8 hour post-operative period. The upper limit of the 95% confidence interval was 10.0 or above at 3hours and 4 hours post-surgery. Two-thirds of patients preferred bupivacaine. CONCLUSION: Longer lasting anaesthetics such as bupivacaine offer a longer period of analgesia, and improve overall patient satisfaction.

Interspecific competition between the potato cyst nematode species Globodera pallida and G. rostochiensis

The two potato cyst nematode species, Globodera pallida and G. rostochiensis, are among the most important pests of potato. PCN are difficult to manage, while the two species respond differently to the main control methods. An increase in the incidence of G. pallida had been reported and is generally attributed to greater effectiveness of control measures against G. rostochiensis. The status of PCN in Ireland was studied using PCR. The results demonstrated qPCR to be an efficient means of high-throughput PCN sampling, being able to accurately identify both species in mixed-species populations. Species discrimination using qPCR revealed an increase in the incidence of G. pallida in Ireland in the absence of G. pallida-selective control measures. The population dynamics of G. pallida and G. rostochiensis in Ireland were studied in mixed- and single-species competition assays in vivo. G. pallida proved to be the more successful species, with greater multiplication in mixed- than single-species populations, with G. rostochiensis showing the opposite. This effect was similarly observed in staggered inoculation trials and population proportion trials. It was hypothesised that the greater G. pallida competitiveness could be attributed to its later hatch. G. pallida exhibited a later peak in hatching activity and more prolonged hatch, relative to G. rostochiensis. G. rostochiensis hatch was significantly reduced in mixedspecies hatching assays. G. pallida hatch was significantly higher when hatch was induced in potato root leachates containing G. rostochiensis-specific compounds, indicating that G. pallida hatch is stimulated upon perception of G. rostochiensis–derived compounds. Rhizotron studies revealed that root damage, caused by feeding of the early-hatching G. rostochiensis, resulted in increased lateral root proliferation and significantly increased G. pallida multiplication. Split-root trials indicated a significant G. pallida-induced ISR effect. G. rostochiensis multiplication was significantly reduced in split-root rhizotrons when G. pallida colonised roots before or after G. rostochiensis infection.