Jens Risbo

Transparent Films Based on PLA and Montmorillonite with Tunable Oxygen Barrier Properties

Polylactide (PLA) is viewed as a potential material to replace synthetic plastics (e.g., poly(ethylene terephthalate) (PET)) in food packaging, and there have been a number of developments in this direction. However, for PLA to be competitive in more demanding uses such as the packaging of oxygen-sensitive foods, the oxygen permeability coefficient (OP) needs to be reduced by a factor of ~10. To achieve this, a layer-by-layer (Lbl) approach was used to assemble alternating layers of montmorillonite clay and chitosan on extruded PLA film surfaces. When 70 bilayers were applied, the OP was reduced by 99 and 96%, respectively, at 20 and 50% RH. These are, to our knowledge, the best improvements in oxygen barrier properties ever reported for a PLA/clay-based film. The process of assembling such multilayer structures was characterized using a quartz crystal microbalance with dissipation monitoring. Transmission electron microscopy revealed a well-ordered laminar structure in the deposited multilayer coatings, and light transmittance results demonstrated the high optical clarity of the coated PLA films.

Molecular Gastronomy: A New Emerging Scientific Discipline

The science of domestic and restaurant cooking has recently moved from the playground of a few interested amateurs into the realm of serious scientific endeavor. A number of restaurants around the world have started to adopt a more scientific approach in their kitchens,1–3 and perhaps partly as a result, several of these have become acclaimed as being among the best in the world.4,5 Today, many food writers and chefs, as well as most gourmets, agree that chemistry lies at the heart of the very finest food available in some of the world’s finest restaurants. At least in the world of gourmet food, chemistry has managed to replace its often tarnished image with a growing respect as the application of basic chemistry in the kitchen has provided the starting point for a whole new cuisine. The application of chemistry and other sciences to restaurant and domestic cooking is thus making a positive impact in a very public arena which inevitably gives credence to the subject as a whole. As yet, however, this activity has been largely in the form of small collaborations between scientists and chefs. To date, little “new science” has emerged, but many novel applications of existing science have been made, assisting chefs to produce new dishes and extend the range of techniques available in their kitchens. Little of this work has appeared in the scientific literature,2,3,6–9 but the work has received an enormous amount of media attention. A quick Google search will reveal thousands of news articles over the past few years; a very few recent examples can be found in China,(10) the United States,11,12 and Australia.(13) In this review we bring together the many strands of chemistry that have been and are increasingly being used in the kitchen to provide a sound basis for further developments in the area. We also attempt throughout to show using relevant illustrative examples how knowledge and understanding of chemistry can be applied to good effect in the domestic and restaurant kitchen. Our basic premise is that the application of chemical and physical techniques in some restaurant kitchens to produce novel textures and flavor combinations has not only revolutionized the restaurant experience but also led to new enjoyment and appreciation of food. Examples include El Bulli (in Spain) and the Fat Duck (in the United Kingdom), two restaurants that since adopting a scientific approach to cooking have become widely regarded as among the finest in the world. All this begs the fundamental question: why should these novel textures and flavors provide so much real pleasure for the diners? Such questions are at the heart of the new science of Molecular Gastronomy. The term Molecular Gastronomy has gained a lot of publicity over the past few years, largely because some chefs have started to label their cooking style as Molecular Gastronomy (MG) and claimed to be bringing the use of scientific principles into the kitchen. However, we should note that three of the first chefs whose food was “labeled” as MG have recently written a new manifesto protesting against this label.(14) They rightly contend that what is important is the finest food prepared using the best available ingredients and using the most appropriate methods (which naturally includes the use of “new” ingredients, for example, gelling agents such as gellan or carageenan, and processes, such as vacuum distillation, etc.). We take a broad view of Molecular Gastronomy and argue it should be considered as the scientific study of why some food tastes terrible, some is mediocre, some good, and occasionally some absolutely delicious. We want to understand what it is that makes one dish delicious and another not, whether it be the choice of ingredients and how they were grown, the manner in which the food was cooked and presented, or the environment in which it was served. All will play their own roles, and there are valid scientific enquiries to be made to elucidate the extent to which they each affect the final result, but chemistry lies at the heart of all these diverse disciplines. The judgment of the quality of a dish is a highly personal matter as is the extent to which a particular meal is enjoyed or not. Nevertheless, we hypothesize that there are a number of conditions that must be met before food becomes truly enjoyable. These include many aspects of the flavor. Clearly, the food should have flavor; but what conditions are truly important? Does it matter, for example, how much flavor a dish has; is the concentration of the flavor molecules important? How important is the order in which the flavor molecules are released? How does the texture affect the flavor? The long-term aims of the science of MG are not only to provide chefs with tools to assist them in producing the finest dishes but also to elucidate the minimum set of conditions that are required for a dish to be described by a representative group of individuals as enjoyable or delicious, to find ways in which these conditions can be met (through the production of raw materials, in the cooking process, and in the way in which the food is presented), and hence to be able to predict reasonably well whether a particular dish or meal would be delicious. It may even become possible to give some quantitative measure of just how delicious a particular dish will be to a particular individual. Clearly, this is an immense task involving many different aspects of the chemical sciences: from the way in which food is produced through the harvesting, packaging, and transport to market via the processing and cooking to the presentation on the plate and how the body and brain react to the various stimuli presented. MG is distinct from traditional Food Science as it is concerned principally with the science behind any conceivable food preparation technique that may be used in a restaurant environment or even in domestic cooking from readily available ingredients to produce the best possible result. Conversely, Food Science is concerned, in large measure, with food production on an industrial scale and nutrition and food safety. A further distinction is that although Molecular Gastronomy includes the science behind gastronomic food, to understand gastronomy it is sometimes also necessary to appreciate its wider background. Thus, investigations of food history and culture may be subjects for investigation within the overall umbrella of Molecular Gastronomy. Further, gastronomy is characterized by the fact that strong, even passionate feelings can be involved. Leading chefs express their own emotions and visions through the dishes they produce. Some chefs stick closely to tradition, while others can be highly innovative and even provocative. In this sense gastronomy can be considered as an art form similar to painting and music. In this review we begin with a short description of our senses of taste and aroma and how we use these and other senses to provide the sensation of flavor. We will show that flavor is not simply the sum of the individual stimuli from the receptors in the tongue and nose but far more complex. In fact, the best we can say is that flavor is constructed in the mind using cues taken from all the senses including, but not limited to, the chemical senses of taste and smell. It is necessary to bear this background in mind throughout the whole review so we do not forget that even if we fully understand the complete chemical composition, physical state, and morphological complexity of a dish, this alone will not tell us whether it will provide an enjoyable eating experience. In subsequent sections we will take a walk through the preparation of a meal, starting with the raw ingredients to see how the chemical make up of even the apparently simplest ingredients such as carrots or tomatoes is greatly affected by all the different agricultural processes they may be subjected to before arriving in the kitchen. Once we have ingredients in the kitchen and start to cut, mix, and cook them, a vast range of chemical reactions come into play, destroying some and creating new flavor compounds. We devote a considerable portion of the review to the summary of some of these reactions. However, we must note that complete textbooks have failed to capture the complexity of many of these, so all we can do here is to provide a general overview of some important aspects that commonly affect flavor in domestic and restaurant kitchens. In nearly all cooking, the texture of the food is as important as its flavor: the flavor of roast chicken is pretty constant, but the texture varies from the wonderfully tender meat that melts in the mouth to the awful rubber chicken of so many conference dinners. Understanding and controlling texture not only of meats but also of sauces, souffles, breads, cakes, and pastries, etc., will take us on a tour through a range of chemical and physical disciplines as we look, for example, at the spinning of glassy sugars to produce candy-floss. Finally, after a discussion of those factors in our food that seem to contribute to making it delicious, we enter the world of brain chemistry, and much of that is speculative. We will end up with a list of areas of potential new research offering all chemists the opportunity to join us in the exciting new adventures of Molecular Gastronomy and the possibility of collaborating with chefs to create new and better food in their own local neighborhoods. Who ever said there is no such thing as a free lunch?

Impact of Water Activity, Temperature, and Physical State on the Storage Stability of Lactobacillus paracasei ssp. paracasei Freeze‐Dried in a Lactose Matrix

The aim of this study was to determine whether the combined effect of water activity and temperature on inactivation rates of freeze‐dried microorganisms in a lactose matrix could be explained in terms of the glass transition theory. The stabilized glass transition temperature, Tg, of the freeze‐dried products was determined by differential scanning calorimetry at two different temperatures, T (20 and 37 °C), and different water activities (0.07–0.48). This information served as a basis for defining conditions of T and water activity, which led to storage of the bacteria in the glassy (T< Tg) and nonglassy (T> Tg) states. The rates of inactivation of the dry microorganisms subjected to different storage conditions were determined by plate counts and could be described by first‐order kinetics. Rates were analyzed as a function of water activity, storage temperature, and the difference between Tg and T. Inactivation below Tg was low; however, Tg could not be regarded as an absolute threshold of bacteria stability during storage. When the cells were stored in the nonglassy state (T> Tg), inactivation proceeded faster, however, not as rapid as suggested by the temperature dependence of the viscosity above the glass transition temperature. Furthermore, the first‐order rate constant, k, was dependent on the storage temperature per se rather than on the temperature difference between the glass transition temperature and the storage temperature (T – Tg).

Lag-burst kinetics in phospholipase A2 hydrolysis of DPPC bilayers visualized by atomic force microscopy

The lag-burst phenomenon in the phospholipase A(2) mediated hydrolysis of phospholipid bilayers is for the first time demonstrated in an atomic force microscopy (AFM) study. Simultaneous AFM measurements of the degree of bilayer degradation and the physical-chemical state of the membrane reveals growing nanoscale indentations in the membrane during the lag phase. It is argued that these indentations are domains of hydrolysis products (lysoPC/PC) which eventually trigger the burst. The rate of the rapid hydrolysis following the burst is found to be proportional to the length of the edge between membrane adsorbed and desorbed to the mica base. The observed maximal rate of membrane degradation is approx. 0.2 mmol lipid/min/mol lipase in solution.

Oxygen permeation through an oil-encapsulating glassy food matrix studied by ESR line broadening using a nitroxyl spin probe

Abstract A non-invasive method based on the broadening of electron spin resonance (ESR) lines in the presence of oxygen (oximetry) has been developed to determine the rate of permeation of oxygen from head space into oil, encapsulated in a glassy matrix (a food model made from sucrose, maltodextrin and gelatine by freeze-drying). The lipophilic nitroxide 16-doxylstearic acid, 16-DSA, was used as a spin-probe, and it was found to be concentrated mainly in the oil phase in the glassy matrix. The concentrations of oxygen in the freshly made glasses were found to be similar to the concentration in atmospheric air, and the process of freeze-drying is apparently not able to remove oxygen before the glassy system solidifies. Storing the oil-encapsulating glasses under oxygen increased the oxygen concentration inside the matrices, and the rate of permeation was found to increase with temperature. A kinetic model for the oxygen permeation was established, based on the rate data obtained up to full saturation of the oil with oxygen below the glass transition temperature (T g =65°C ), and on data for partial oxygen saturation above the glass transition temperature. The kinetic model includes a temperature independent master curve and allows for structural heterogeneity. The energy of activation for oxygen permeation was found to be 74±6 kJ/mol for the glassy matrix, and the large value is in favour of the molecular model for oxygen diffusion rather than the free volume model, and accords with the zeroth-order kinetics for oxidation of lipids encapsulated in a glassy matrix, which has previously been observed to be associated with oxygen permeation as the rate-determining step.

Water activity-temperature state diagrams of freeze-dried Lactobacillus acidophilus (La-5): influence of physical state on bacterial survival during storage.

Water activity‐temperature state diagrams for Lactobacillus acidophilus freeze‐dried in a sucrose or a lactose matrix were established based on determination of stabilized glass transition temperatures by differential scanning calorimetry during equilibration with respect to water activity at fixed temperatures. The bacteria in the lactose matrix had higher stabilized glass transition temperatures for all aw investigated. The survival of Lactobacillus acidophilus determined as colony forming units for up to 10 weeks of storage at 20°C for (i) aw = 0.11 with both freeze‐dried matrices in the glassy state, (ii) aw = 0.23 with the bacteria in the lactose matrix in a glassy state but with the bacteria in sucrose matrix in the nonglassy state, and (iii) aw = 0.43 with both freeze‐dried matrices in a nonglassy state showed that the nature of the sugar was more important for storage stability than the physical state of the matrix with the nonreducing sucrose providing better stability than the reducing lactose.

Cellulose nanofiber/nanocrystal reinforced capsules: a fast and facile approach toward assembly of liquid-core capsules with high mechanical stability.

Liquid-core capsules of high mechanical stability open up for many solid state-like applications where functionality depending on liquid mobility is vital. Herein, a novel concept for fast and facile improvement of the mechanical properties of walls of liquid-core capsules is reported. By imitating natures own way of enhancing the mechanical properties in liquid-core capsules, the parenchyma plant cells found in fruits and vegetables, a blend of short cellulose nanofibers (<1 μm, NFC) and nanocrystals (CNC) was exploited in the creation of the capsule walls. The NFC/CNC blend was prepared from a new version of the classical wood pulp hydrolysis. The capsule shell consisted of a covalently (by aromatic diisocyanate) cross-linked NFC/CNC structure at the outer capsule wall and an inner layer dominated by aromatic polyurea. The mechanical properties revealed an effective capsule elastic modulus of 4.8 GPa at 17 wt % NFC/CNC loading, about six times higher compared to a neat aromatic polyurea capsule (0.79 GPa) and 3 orders of magnitude higher than previously reported capsules from regenerated cellulose (0.0074 GPa). The outstanding mechanical properties are ascribed to the dense nanofiber structure, present in the outer part of the capsule wall, that is formed by oriented NFC/CNC of high average aspect ratio (L/d ∼ 70) and held together by both covalent (urethane bonds) and physical bonds (hydrogen bonds).

Relationship between meat toughness and properties of connective tissue from cows and young bulls heat treated at low temperatures for prolonged times

The aim of the current study was to elucidate whether cows and young bulls require different combinations of heating temperature and heating time to reduce toughness of the meat. The combined effect of heating temperature and time on toughness of semitendinosus muscle from the two categories of beef was investigated and the relationship to properties of connective tissue was examined. Measurements of toughness, collagen solubility, cathepsin activity and protein denaturation of beef semitendinosus heated at temperatures between 53°C and 63°C for up to 19 1/2 h were conducted. The results revealed that slightly higher temperatures and prolonged heating times were required to reduce toughness of semitendinosus from cows to the same level as in young bulls. Reduced toughness of semitendinosus as a result of low temperature for prolonged time is suggested to result from weakening of the connective tissue, caused partly by denaturation or conformational changes of the proteins and/or by solubilization of collagen.

The dynamics of moisture migration in packaged multi-component food systems I: shelf life predictions for a cereal–raisin system

Abstract A theory is developed for the kinetics of moisture migration in packaged multi-component food mixtures, such as cereal–fruit mixtures, mixed candy or freeze dried instant meals. The theory assumes the individual food components to be characterised by their initial water activities, isotherm slopes and a function describing the time course of moisture uptake under constant humidity conditions; the step-response functions. When specifying the product properties compositions and net weight and package parameters such as area and water vapour permeability, the time development of internal moisture redistribution and water uptake into the package can be calculated. Calculations on realistic packages containing a cereal–raisin mixture show that the headspace water activity attains the water activity of the cereal flakes within one minute. On a timescale of one year the processes of moisture transfer from raisins to cereals and permeations through the package film take place. For the raisin–cereal mixtures under consideration the product moisture transfer from raisin to cereals limits quality. Shelf life calculations based on the kinetic theory show that product composition and package permeability optimal for the overall product quality can be identified. The calculations demonstrate that information from focused experiments on individual food components can be used to predict storage stability on a number of mixtures and under different conditions.

Effect of Time and Temperature on Sensory Properties in Low-Temperature Long-Time Sous-Vide Cooking of Beef

Slices of beef eye of round were sous-vide cooked for 3, 6, 9, and 12 hours at 56, 58, and 60°C. The results showed that descriptors from a sensory descriptive analysis were divided into two groups based on response to heat treatment. In one group (12 descriptors including juiciness), the intensity of the descriptors increased (or decreased) with both time and temperature. In the other (6 descriptors including tenderness), the intensity increased with temperature but decreased with time (or decreased with temperature but increased with time). The sensory properties of the cooked beef corresponding to the descriptors in the two groups can consequently not be optimized simultaneously, and a compromise between, for example, tenderness and juiciness, is necessary.