Exploring the physicochemical basis of cheese texture, rheology and functionality, with emphasis on cation-casein interactions

The physicochemical properties of cheese and milk gels are greatly influenced by molecular interactions between the casein proteins involving calcium. Novel experiments were designed to investigate the relationship between insoluble caseinbound cations and rheological properties of Cheddar cheese and rennet-induced milk gels. Cheddar cheese and rennet-induced milk gels were supplemented with Mg2+ or Sr2+ to compare their effects on their rheological properties to those previously reported in literature for Ca2+ supplementation. Sr2+ displayed behaviour similar to Ca2+ as observed by its ability to increase the rigidity of cheese and rennet milk gels and also decrease cheese meltability. Mg+2 had no influence on cheese rheological properties and was greatly inferior to Ca2+ and Sr2+ in its ability to increase rennet milk gel elasticity. Cheddar cheese was supplemented with the calcium-chelating salts trisodium citrate, disodium hydrogen phosphate or disodium EDTA, in an attempt to reduce the CCP content of cheese and thereby modify its rheological and functional properties. TSC and EDTA were successful in decreasing cheese CCP, whereas DSP caused an initial increase in CCP content. Cheddar cheese was supplemented with chlorides of iron, copper and zinc at salting to investigate the effects of concentrations of these elements in excess of those found innately or commonly in fortification studies, with emphasis on mineral equilibria changes and resultant alteration of rheological properties. Zinc addition was the only added metal that significantly influenced cheese rheological properties, leading to an increase in cheese rigidity and decreased cheese melt at elevated temperatures. Gum tragacanth was used as a fat-replacer in the manufacture of reduced-fat Cheddar cheese, in an attempt to improve the rheological, functional and sensory properties of reduced-fat Cheddar. Overall, the experimental work reported in this thesis generated new knowledge and theories about how casein-mineral interactions influence rheological properties of casein systems.

Studies on the texture, functionality, rheology and sensory properties of Cheddar and Mozzarella cheeses

The effect of fortification of skim milk powder and sodium caseinate on Cheddar cheeses was investigated. SMP fortification led to decreased moisture, increased yield, higher numbers of NSLAB and reduced proteolysis. The functional and texture properties were also affected by SMP addition and formed a harder, less meltable cheese than the control. NaCn fortification led to increased moisture, increased yield, decreased proteolysis and higher numbers of NSLAB. The functional and textural properties were affected by fortification with NaCn and formed a softer cheese that had similar or less melt than the control. Reducing the lactose:casein ratio of Mozzarella cheese by using ultrafiltration led to higher pH, lower insoluble calcium, lower lactose, galactose and lactic acid levels in the cheese. The texture and functional properties of the cheese was affected by varying the lactose:casein ratio and formed a harder cheese that had similar melt to the control later in ripening. The flavour and bake properties were also affected by decreased lactose:casein ratio; the cheeses had lower acid flavour and blister colour than the control cheese. Varying the ratio of αs1:β-casein in Cheddar cheese affected the texture and functionality of the cheese but did not affect insoluble calcium, proteolysis or pH. Increasing the ratio of αs1:β-casein led to cheese with lower meltability and higher hardness without adverse effects on flavour. Using camel chymosin in Mozzarella cheese instead of calf chymosin resulted in cheese with lower proteolysis, higher softening point, higher hardness and lower blister quantity. The texture and functional properties that determine the shelf life of Mozzarella were maintained for a longer ripening period than when using calf chymosin therefore increasing the window of functionality of Mozzarella. In summary, the results of the trials in this thesis show means of altering the texture, functional, rheology and sensory properties of Mozzarella and Cheddar cheeses.

Bioengineering of nisin to enhance functionality against dairy pathogens

The bacteriocin class of antimicrobial peptides have emerged as a viable alternative to at least partially fill the void created by the end of the golden age of antibiotic discovery. Along with this potential use in a clinical setting, bacteriocins also play an important role as bio-preservatives in the food industry. This thesis focuses on a specific bacteriocin group, the lantibiotics (Lanthionine-containing antibiotics). Their numerous methods of appliance in a food setting and how their gene-encoded nature can be modified to improve on overall bioactivity and functionality are explored here. The use of a lantibiotic (lacticin 3147) producing starter culture to control the Crohn’s disease-linked pathogen Mycobacterium paratuberculosis was assessed in a raw milk cheese. Although lacticin 3147 production did not effectively control the pathogen, the study provided an impetus to employ a variety of PCR-based mutagenesis techniques with a view to the creation of enhanced lantibiotic derivatives. Through the use of these techniques, a number of enhanced derivatives were generated from the ‘hinge’ region of the nisin peptide. Furthermore, a derivative in which the three hinge amino acids were replaced with three alanines represents the first enhanced derivative of nisin to have been designed through a rational process. This derivative also formed the backbone for the creation of an active, trypsin resistant, variant. Through the employment of further mutagenesis methods a derivative was created with potential use as an oral anti-bacterial in the future. Finally a number of lead nisin derivatives were investigated to assess their anti- Streptococcus agalactiae ability, a mastitis associated pathogen. Also a system was developed to facilitate the large scale production of these candidates, or other nisin derivatives, from dairy substrates.

The synthesis of novel isoindoline nitroxides bearing water-solubilising functionality

A range of novel tetramethyl- and tetraethylisoindolinenitroxides, possessing aryl-linked carboxylic acids, amines, alcohols and phosphonic acids were prepared. Notably, the chemistry established for the aromatic dibromination of the tetramethylisoindolines was not easily transferred to the corresponding tetraethylisoindoline system. Instead, various tetraethylisoindoline analogues were accessed by the oxidation of methyl groups attached to the aromatic ring to give the carboxylic acids. The increased steric bulk of the tetraethyl structures should limit bio-reduction and these compounds may have potential as antioxidants.

Effect of poly(acrylic acid) end-group functionality on inhibition of calcium oxalate crystal growth

A number of series of poly(acrylic acids) (PAA) of differing end-groups and molecular weights prepared using atom transfer radical polymerization were used as inhibitors for the crystallization of calcium oxalate at 23 and 80°C. As measured by turbidimetry and conductivity and as expected from previous reports, all PAA series were most effective for inhibition of crystallization at molecular weights of 1500–4000. However, the extent of inhibition was in general strongly dependent on the hydrophobicity and molecular weight of the end-group. These results may be explicable in terms of adsorption/desorption of PAA to growth sites on crystallites. The overall effectiveness of the series didn't follow a simple trend with end-group hydrophobicity, suggesting self-assembly behavior or a balance between adsorption and desorption rates to crystallite surfaces may be critical in the mechanism of inhibition of calcium oxalate crystallization.

Effect of poly(acrylic acid) molecular mass and end-group functionality on calcium oxalate crystal morphology and growth

A number of series of poly(acrylic acids) (PAA) of differing end-groups and molecular mass were used to study the inhibition of calcium oxalate crystallization. The effects of the end-group on crystal speciation and morphology were significant and dramatic, with hexyl-isobutyrate end groups giving preferential formation of calcium oxalate dihydrate (COD) rather than the more stable calcium oxalate monohydrate (COM), while both more hydrophobic end-groups and less-hydrophobic end groups led predominantly to formation of the least thermodynamically stable form of calcium oxalate, calcium oxalate trihydrate. Conversely, molecular mass had little impact on calcium oxalate speciation or crystal morphology. It is probable that the observed effects are related to the rate of desorption of the PAA moiety from the crystal (lite) surfaces and that the results point to a major role for end-group as well as molecular mass in controlling desorption rate.

Content and functionality of alcohol and other drug websites : results of an online survey

Background: There is a growing trend for individuals to seek health information from online sources. Alcohol and other drug (AOD) use is a significant health problem worldwide, but access and use of AOD websites is poorly understood. ----- ----- Objective: To investigate content and functionality preferences for AOD and other health websites. Methods: An anonymous online survey examined general Internet and AOD-specific usage and search behaviors, valued features of AOD and health-related websites (general and interactive website features), indicators of website trustworthiness, valued AOD website tools or functions, and treatment modality preferences. ----- ----- Results: Surveys were obtained from 1214 drug (n = 766) and alcohol website users (n = 448) (mean age 26.2 years, range 16-70). There were no significant differences between alcohol and drug groups on demographic variables, Internet usage, indicators of website trustworthiness, or on preferences for AOD website functionality. A robust website design/navigation, open access, and validated content provision were highly valued by both groups. While attractiveness and pictures or graphics were also valued, high-cost features (videos, animations, games) were minority preferences. Almost half of respondents in both groups were unable to readily access the information they sought. Alcohol website users placed greater importance on several AOD website tools and functions than did those accessing other drug websites: online screening tools (χ²2 = 15.8, P < .001, n = 985); prevention programs (χ²2 = 27.5, P < .001, n = 981); tracking functions (χ²2 = 11.5, P = .003, n = 983); self help treatment programs (χ²2 = 8.3, P = .02, n = 984); downloadable fact sheets for friends (χ²2 = 11.6, P = .003, n = 981); or family (χ²2 = 12.7, P = .002, n = 983). The most preferred online treatment option for both the user groups was an Internet site with email therapist support. Explorations of demographic differences were also performed. While gender did not affect survey responses, younger respondents were more likely to value interactive and social networking features, whereas downloading of credible information was most highly valued by older respondents. ----- ----- Conclusions: Significant deficiencies in the provision of accessible information on AOD websites were identified, an important problem since information seeking was the most common reason for accessing these websites, and, therefore, may be a key avenue for engaging website users in behaviour change. The few differences between AOD website users suggested that both types of websites may have similar features, although alcohol website users may more readily be engaged in screening, prevention and self-help programs, tracking change, and may value fact sheets more highly. While the sociodemographic differences require replication and clarification, these differences support the notion that the design and features of AOD websites should target specific audiences to have maximal impact.

Representative learning design and functionality of research and practice in sport

Egon Brunswik proposed the concept of “representative design” for psychological experimentation, which has historically been overlooked or confused with another of Brunswik’s terms, ecological validity. In this article, we reiterate the distinc­tion between these two important concepts and highlight the relevance of the term representative design for sports psychology, practice, and experimental design. We draw links with ideas on learning design in the constraints-led approach to motor learning and nonlinear pedagogy. We propose the adoption of a new term, repre­sentative learning design, to help sport scientists, experimental psychologists, and pedagogues recognize the potential application of Brunswik’s original concepts, and to ensure functionality and action fidelity in training and learning environments.

“Modeling with tools is easier, believe me” : the effects of tool functionality on modeling grammar usage beliefs

Increasingly, studies are reported that examine how conceptual modeling is conducted in practice. Yet, typically the studies to date have examined in isolation how modeling grammars can be, or are, used to develop models of information systems or organizational processes, without considering that such modeling is typically done by means of a modeling tool that extends the modeling functionality offered by a grammar through complementary features. This paper extends the literature by examining how the use of seven different features of modeling tools affects usage beliefs users develop when using modeling grammars for process modeling. We show that five distinct tool features positively affect usefulness, ease of use and satisfaction beliefs of users. We offer a number of interpretations about the findings. We also describe how the results inform decisions of relevance to developers of modeling tools as well as managers in charge for making modeling-related investment decisions.

Electronic functionality in graphene-based nanoarchitectures : discovery and design via first-principles modeling

Graphene has promised many novel applications in nanoscale electronics and sustainable energy due to its novel electronic properties. Computational exploration of electronic functionality and how it varies with architecture and doping presently runs ahead of experimental synthesis yet provides insights into types of structures that may prove profitable for targeted experimental synthesis and characterization. We present here a summary of our understanding on the important aspects of dimension, band gap, defect, and interfacial engineering of graphene based on state-of-the-art ab initio approaches. Some most recent experimental achievements relevant for future theoretical exploration are also covered.