Functional properties of cream and butter oil from milk of Holstein cows abomasally infused with increasing amounts of high-oleic sunflower fatty acids.

This research paper addresses the hypothesis that there is an optimal amount of intestinally available oleic acid (provided via abomasal infusion) to produce higher-oleic acid milk fat with satisfactory functional characteristics of cream and butter oil. A control and four increasing doses of free fatty acids from high oleic sunflower oil (HOSFA) were infused into the abomasum of four lactating dairy cows in a crossover experimental design with 7-d periods. Treatments were: (1) control (no HOSFA infused), (2) HOSFA (250 g/d), (3) HOSFA (500 g/d), (4) HOSFA (750 g/d), and (5) HOSFA (1000 g/d). All treatments included meat solubles and Tween 80 as emulsifiers. Viscosity, overrun and whipping time as well as foam firmness and stability were evaluated in whipping creams (33% fat). Solid fat content (from 0 to 40°C), melting point and firmness were determined in butter oil. Whipping time of cream increased linearly and viscosity decreased linearly as infusion of HOSFA increased. Overrun displayed a quadratic response, decreasing when 500 g/d or more was infused. Foam firmness and stability were not affected significantly by HOSFA. For butter oil, melting point, firmness, and solid fat content decreased as HOSFA infusion increased. Changes in 21 TG fractions were statistically correlated to functional properties, with 6-10 fractions showing the highest correlations consistently. Decisions on the optimal amount of HOSFA were dependent on the dairy product to which milk fat is applied. For products handled at commercial refrigeration temperatures, such as whipping cream and butter oil, the 250 g/d level was the limit to maintain satisfactory functional qualities. Palmitic acid needed to be present in at least 20% in milk fat to keep the functional properties for the products.

Safety and Antitumor Activity of α-PD-L1 Antibody as Monotherapy or in Combination with α-TIM-3 Antibody in Patients with Microsatellite Instability-High/Mismatch Repair-Deficient Tumors.

PURPOSE: Immune checkpoint inhibitors show high response rates and durable clinical benefit in microsatellite instability-high/mismatch repair-deficient (MSI-H/dMMR) tumors. However, 50%-60% do not respond to single-agent anti-programmed death-1/programmed death ligand 1 (PD-1/PD-L1) antibodies, and approximately 50% of responders relapse within 6-12 months. This phase Ib trial evaluated safety and antitumor activity of anti-PD-L1 antibody LY3300054 monotherapy or in combination with anti-TIM-3 antibody LY3321367 in patients with MSI-H/dMMR advanced solid tumors. PATIENTS AND METHODS: Eligible patients ≥18 years without prior anti-PD-1/PD-L1 therapy received LY3300054 monotherapy (N = 40) or combination (N = 20); patients with PD-1/PD-L1 inhibitor-resistant/refractory tumors received the combination (N = 22). LY3300054 (700 mg) and anti-TIM-3 antibody (cycles 1-2: 1,200 mg, cycle 3 onward: 600 mg) were administered intravenously every 2 weeks. Primary endpoints were safety and tolerability. RESULTS: Eighty-two patients were enrolled. Most had colorectal (n = 39, 47.6%) or endometrial (n = 14, 17.1%) tumors. More than 70% of patients in the PD-1/PD-L1 inhibitor-resistant/refractory combination cohort had received ≥3 treatment lines. Treatment-related adverse events (TRAE) occurred in 22 patients (55.0%) receiving monotherapy, 13 (65.0%) in the PD-1/PD-L1 inhibitor-naïve combination cohort, and 6 (27.3%) in the PD-1/PD-L1 inhibitor-resistant/refractory combination cohort. A total of 2 patients (5.0%) receiving monotherapy and 3 (7.1%) receiving the combination experienced grade ≥3 TRAEs. Objective responses occurred in 13 patients (32.5%) with monotherapy, 9 (45.0%) in the PD-1/PD-L1 inhibitor-naïve combination cohort, and 1 patient (4.5%) in the PD-1/PD-L1 inhibitor-resistant/refractory combination cohort. CONCLUSIONS: LY3300054 monotherapy and combined LY3300054/anti-TIM-3 had manageable safety profiles. Both regimens showed promising clinical activity against PD-1/PD-L1 inhibitor-naïve MSI-H/dMMR tumors. The combination had limited clinical benefit in patients with PD-1/PD-L1 inhibitor-resistant/refractory MSI-H/dMMR tumors.

Characterization and categorization of commercial confectionary gels through napping-ultra flash profile (UFP) and hierarchical clustering analysis.

The use of high-solid gels (HSGs) in the confectionary and dietary supplement industries is rapidly expanding, increasing the interest in studying the relationships across their composition, sensory characteristics, thermal behavior, and texture. Thus, the objectives of this study were to characterize HSG product categories based on sensory characteristics and analytical parameters, and correlate analytical parameters with sensory descriptors generated through napping-ultra flash profile (napping-UFP). In one 90-min session, 15 panelists performed two napping-UFP exercises, categorizing and describing 13 confectionary HSGs by their overall degree of similarity and by their texture. Multiple factor analysis and hierarchical clustering were conducted on the napping-UFP data. The products were also characterized by their moisture content, water activity (aw ), thermal behavior, and texture profile. Principal component analysis and hierarchical clustering analysis were conducted on the analytical parameters; additionally, the analytical parameters were related to the sensory descriptors using Spearman's correlation. The panelists predominantly focused on texture to categorize the samples. The clustering of the samples across the napping-UFP exercises resulted in two categories-gelatin and nongelatin-containing products. Sensory descriptors generated by panelists during the napping-UFP were significantly correlated to the measured analytical parameters. The difference in texture between the two clusters, associated with the presence of a small (3 J/g) gelatin triple-helix structure as determined by differential scanning calorimetry (DSC), was significant enough to be perceived by panelists. These findings indicate that modified starch and pectin, impart different sensory characteristics than gelatin and have important implications for developing new formulations for HSGs in which gelatin-like texture is desirable. PRACTICAL APPLICATION: Increased consumer demands for nonanimal-derived ingredients have fueled the food and pharmaceutical industries interest in both finding an economical replacement material for gelatin and gaining a deeper understanding of gelatin's textural and thermal properties. The results of this research have important implications for finding suitable ingredients to replace gelatin in high-solid confectionary gels, as well as enhancing the quality of current gelatin-containing HSGs. The triple-helix is a powerful structural element that determined the textural properties perceived by panelists in HSGs. Consequently, the search for a replacement material for gelatin should focus on identifying materials that impart similar properties as the triple-helix structure, helping to create products with gelatin-like texture. Additionally, these findings begin to provide a better understanding of the thermal behavior of gelatin for enhancing the functionality, stability, and product integrity of HSG systems throughout shipping, storage, and consumption. Additional research is underway to explore in detail the thermal behavior of gelatin in commercial and model gummy systems.

Safety and Clinical Activity of a New Anti-PD-L1 Antibody as Monotherapy or Combined with Targeted Therapy in Advanced Solid Tumors: The PACT Phase Ia/Ib Trial.

PURPOSE: This phase Ia/Ib PACT study evaluated the safety, pharmacokinetics, pharmacodynamics, and antitumor activity of a new programmed cell death ligand 1 (PD-L1) inhibitor, LY3300054, as monotherapy or in combination with ramucirumab, abemaciclib, or merestinib (a type II MET kinase inhibitor) in patients with advanced, refractory solid tumors (NCT02791334). PATIENTS AND METHODS: Patients were enrolled into cohorts of escalating LY3300054 dose (phase Ia) as monotherapy (N = 15) or combined with ramucirumab (N = 10), abemaciclib (N = 24), or merestinib (N = 12). The phase Ib dose expansion enrolled 8 patients with melanoma in the monotherapy arm and 12 patients with pancreatic cancer in the merestinib combination arm. Combination treatments were administered concurrently from day 1 of each cycle. A 14-day lead-in abemaciclib arm was also explored. Primary endpoints were dose-limiting toxicity (DLT) and safety. RESULTS: Treatment-related adverse events included fatigue and nausea in the monotherapy arm (13% for each), hypothyroidism (30%) in the ramucirumab arm, diarrhea (54%) in the abemaciclib arm, and nausea (25%) in the merestinib arm. DLTs associated with hepatoxicity were observed in 3 of 4 patients in the abemaciclib lead-in cohorts. No DLTs or grade 3 or 4 hepatoxicity were reported in the concurrent abemaciclib arm. Pharmacokinetic characteristics were comparable with other PD-L1 inhibitors. One patient in each arm experienced a partial response per RECIST v1.1 lasting ≥7 months. CONCLUSIONS: LY3300054 was well tolerated without unexpected safety concerns when administered alone or concurrently with ramucirumab, abemaciclib, or merestinib. Lead-in abemaciclib before combining with LY3300054 was not feasible due to hepatotoxicity. Durable clinical benefits were seen in all regimens.

Temporal Texture Profile and Identification of Glass Transition Temperature as an Instrumental Predictor of Stickiness in a Caramel System.

Stickiness is an important texture attribute in many food systems, but its meaning can vary by person, product, and throughout mastication. This variability and complexity makes it difficult to devise analytical tests that accurately and consistently predict sensory stickiness. Glass transition temperature (Tg ) is a promising candidate for texture prediction. Our objective is to elucidate the temporal profile of stickiness in order to probe the relationship between Tg and dynamic stickiness perception. Nine caramel samples with diverse texture and thermal profiles were produced for sensory testing and differential scanning calorimetry. Sixteen trained panelists generated stickiness-relevant terms to be used in a subsequent temporal dominance of sensation (TDS) test with the same panelists. Following the TDS study, these panelists also rated samples for overall tactile and oral stickiness. Stickiness ratings were then correlated to TDS dominance parameters across the full evaluation period and within the first, middle, and final thirds of the evaluation period. Samples with temporal texture profiles dominated by tacky, stringy, and enveloping attributes consistently received the highest stickiness scores, although the correlation strength varied by time period. Tg was found to correlate well with trained panelist and consumer ratings of oral (R2trained = 0.85; R2consumer = 0.96) and tactile (R2trained = 0.78; R2consumer = 0.79) stickiness intensity, and stickiness intensity ratings decreased with Tg of completely amorphous samples. Further, glassy samples followed a different texture trajectory (brittle-cohesive-toothpacking) than rubbery samples (deformable-tacky-enveloping). These results illuminate the dynamic perception of stickiness and support the potential of Tg to predict both stickiness intensity and texture trajectory in caramel systems.

Sensory and Physical Effects of Sugar Reduction in a Caramel Coating System.

Sugar reduction in processed foods is a pressing and complex problem, as sugars contribute important sensory and physical properties to foods. Composed of sugars and lipids, caramel coating systems, like the coating in caramel popcorns, exemplify this challenge. In order to probe the feasibility and consequences of sugar reduction, both sensory and physical properties were measured for 3 types of caramel coating systems. Four commonly used sugar alcohols, isomalt, maltitol, mannitol, and sorbitol, with different thermal properties and relative sweetness values were chosen to replace sugar in the caramel coating systems at 25% and 50% sugar reduction levels. Full sugar (control) and reduced sugar caramel coating samples were prepared in duplicate. Ten trained panelists participated in a 6-wk descriptive analysis panel to define and quantify the intensity of important sensory characteristics. All 24 sensory terms generated by the panel differed significantly across caramel type and sugar replacer. Thermal properties were measured through differential scanning calorimetry, and textural properties were measured through texture profile analysis. Replacement of sugar with sugar alcohols was found to decrease the glass transition temperature and systematically alter the hardness and resilience of caramel samples. Principal component analysis of sensory and physical data revealed that caramel coating type dictates caramel aroma, aroma by mouth, taste, and aftertaste, while sugar replacer and replacement level dictate texture. This research represents the first comprehensive study of the effects of sugar reduction in a caramel coating system and suggests successful strategies for sugar reduction and key parameters to control in reduced sugar systems.

Napping-Ultra Flash Profile as a Tool for Category Identification and Subsequent Model System Formulation of Caramel Corn Products.

In a novel approach to formulation, the flash descriptive profiling technique Napping-Ultra Flash Profile (Napping-UFP) was used to characterize a wide range of commercial caramel corn products. The objectives were to identify product categories, develop model systems based on product categories, and correlate analytical parameters with sensory terms generated through the Napping-UFP exercise. In one 2 h session, 12 panelists participated in 4 Napping-UFP exercises, describing and grouping, on a 43×56 cm paper sheet, 12 commercial caramel corn samples by degree of similarity, globally and in terms of aroma-by-mouth, texture, and taste. The coordinates of each sample's placement on the paper sheet and descriptive terms generated by the panelists were used to conduct Multiple Factor Analysis (MFA) and hierarchical clustering of the samples. Strong trends in the clustering of samples across the 4 Napping-UFP exercises resulted in the determination of 3 overarching types of commercial caramel corn: "small-scale dark" (typified by burnt, rich caramel corn), "large-scale light" (typified by light and buttery caramel corn), and "large-scale dark" (typified by sweet and molasses-like caramel corn). Representative samples that best exemplified the properties of each category were used as guides in the formulation of 3 model systems that represent the spread of commercial caramel corn products. Analytical testing of the commercial products, including aw measurement, moisture content determination, and thermal characterization via differential scanning calorimetry, were conducted and results related to sensory descriptors using Spearman's correlation.

Does information about sugar source influence consumer liking of products made with beet and cane sugars?

Beet sugar contains an off-aroma, which was hypothesized to generate expectations on the acceptability of a product made with beet sugar. Thus, the objective of this study was to assess the impact of information about the sugar source (beet vs. cane) on the overall liking of an orange-flavored beverage. One hundred panelists evaluated an orange-flavored powdered beverage mix and beverage made with beet and cane sugars using a 5-phase testing protocol involving a tetrad test and hedonic ratings performed under blind and informed conditions. Tetrad test results indicated that there was a significant difference (P < 0.05) between the beverage mix made with beet sugar and cane sugar; however, no difference was found between the beverage made with beet sugar and cane sugar. Hedonic ratings revealed the significance of information conditions on the panelists evaluation of sugar (F = 24.67, P < 0.001); however, no difference in the liking was identified for the beverage mix or beverage. Average hedonic scores were higher under informed condition compared to blind condition for all products, possibly because labels tend to reduce uncertainty about a product. Results from this study are representative of the responses from the general population and suggest that they are not affected by sugar source information in a beverage product. Based on concerns with the use of beet sugar expressed in the popular press, there may be a subgroup of the population that has a preconceived bias about sugar sources due to their prior experiences and knowledge and, thus, would be influenced by labels indicating the sugar source used in a product.

Sensory differences between product matrices made with beet and cane sugar sources.

Although beet and cane sugar sources have nearly identical chemical compositions, the sugars differ in their volatile profiles, thermal behaviors, and minor chemical components. Scientific evidence characterizing the impact of these differences on product quality is lacking. The objective of this research was to determine whether panelists could identify a sensory difference between product matrices made with beet and cane sugar sources. Sixty-two panelists used the R-index by ranking method to discern whether there was a difference between 2 brands of beet and 2 brands of cane sugars in regard to their aroma and flavor, along with a difference in pavlova, simple syrup, sugar cookies, pudding, whipped cream, and iced tea made with beet and cane sugars. R-index values and Friedman's rank sum tests showed differences (P < 0.05) between beet and cane sugars in regard to their aroma and flavor. Significant differences between the sugar sources were also identified when incorporated into the pavlova and simple syrup. No difference was observed in the sugar cookies, pudding, whipped cream, and iced tea. Possible explanations for the lack of difference in these products include: (1) masking of beet and cane sensory differences by the flavor and complexity of the product matrix, (2) the relatively small quantity of sugar in these products, and (3) variation within these products being more influential than the sugar source. The findings from this research are relevant to sugar manufacturers and the food industry as a whole, because it identifies differences between beet and cane sugars and product matrices in which beet and cane sugars are not directly interchangeable.

Determining the mechanism and parameters of hydrate formation and loss in glucose.

Water-solid interactions are known to play a major role in the chemical and physical stability of food materials. Despite its extensive use throughout the food industry, the mechanism and parameters of hydrate formation and loss in glucose are not well characterized. Hydrate formation in alpha-anhydrous glucose (α-AG) and hydrate loss in glucose monohydrate (GM) were studied under equilibrium conditions at various relative humidity (RH) values using saturated salt slurries for 1 y. The mechanism of hydrate formation and hydrate loss were determined through mathematical modeling of Dynamic Vapor Sorption data and Raman spectroscopy was used to confirm the mechanisms. The critical temperature for hydrate loss in GM was determined using thermogravimetric analysis (TGA). The moisture sorption profiles of α-AG and GM were also studied under dynamic conditions using an AquaSorp Isotherm Generator. Hydrate formation was observed at and above 68% RH at 25 °C and the conversion of α-AG to GM can best be described as following a nucleation mechanism, however, diffusion and/or geometric contraction mechanisms were also observed by Raman spectroscopy subsequent to the coalescence of initial nucleation sites. Hydrate loss was observed to occur at and below 11% RH at 25 °C during RH storage and at 70 °C during TGA. The conversion of GM to α-AG follows nucleation and diffusion mechanisms. Hydrate formation was evident under dynamic conditions in α-AG and GM prior to deliquescence. This research is the first to report hydrate formation and loss parameters for crystalline α-AG and GM during extended storage at 25 ˚C.

Sensory differences between beet and cane sugar sources.

Research concerning the sensory properties of beet and cane sugars is lacking in the scientific literature. Therefore, the objectives of this research were to determine whether a sensory difference was perceivable between beet and cane sugar sources in regard to their (1) aroma-only, (2) aroma and taste without nose clips, and (3) taste-only with nose clips, and to characterize the difference between the sugar sources using descriptive analysis. One hundred panelists evaluated sugar samples using a tetrad test. A significant difference (P < 0.05) was identified between beet and cane sugar sources when evaluated by aroma-only and taste and aroma without nose clips. However, there was no difference when tasted with nose clips. To characterize the observed differences, ten trained panelists identified and quantified key sensory attributes of beet and cane sugars using descriptive analysis. Analysis of variance indicated significant differences (P < 0.05) between sugar samples for 8 of the 10 attributes including: off-dairy, oxidized, earthy, and barnyard aroma, fruity and burnt sugar aroma-by-mouth, sweet aftertaste, and burnt sugar aftertaste. The sensory profile of beet sugar was characterized by off-dairy, oxidized, earthy, and barnyard aromas and by a burnt sugar aroma-by-mouth and aftertaste, whereas cane sugar was characterized by a fruity aroma-by-mouth and sweet aftertaste. This study shows that beet and cane sugar sources can be differentiated by their aroma and provides a sensory profile characterizing the differences. As sugar is used extensively as a food ingredient, sensory differences between beet and cane sugar sources once incorporated into different product matrices should be studied as a next step.

Effect of temperature on the deliquescence properties of food ingredients and blends.

Deliquescence is a first-order phase transformation of a crystalline solid to a saturated solution that is triggered at a defined relative humidity (RH), RH0. Previous studies demonstrated that the RH0 of an inorganic substance with a positive heat of solution (ΔH) will decrease with increases in temperature. In this study, the relationships between ΔH, solubility, and deliquescence RH for single-ingredient and multicomponent systems were investigated. The deliquescence RHs of inorganic and organic crystalline solids and their mixtures were measured at temperatures ranging from 20 to 40 °C using a water activity meter and various gravimetric moisture sorption analyzers. The deliquescence behavior as a function of temperature for organic food ingredients was thermodynamically modeled and followed similar trends to those of the previously investigated inorganic ingredients. Furthermore, the models can be used as a predictive approach to determine physical stability and deliquescence RHs of deliquescent ingredients and blends if the storage temperature and ingredient ΔH and solubility are known.

Safety and pharmacokinetics of the antisense oligonucleotide (ASO) LY2181308 as a single-agent or in combination with idarubicin and cytarabine in patients with refractory or relapsed acute myeloid leukemia (AML).

Survivin is expressed in tumor cells, including acute myeloid leukemia (AML), regulates mitosis, and prevents tumor cell death. The antisense oligonucleotide sodium LY2181308 (LY2181308) inhibits survivin expression and may cause cell cycle arrest and restore apoptosis in AML. In this study, the safety, pharmacokinetics, and pharmacodynamics/efficacy of LY2181308 was examined in AML patients, first in a cohort with monotherapy (n = 8) and then post-amendment in a cohort with the combination of cytarabine and idarubicin treatment (n = 16). LY2181308 was administered with a loading dosage of three consecutive daily infusions of 750 mg followed by weekly intravenous (IV) maintenance doses of 750 mg. Cytarabine 1.5 g/m(2) was administered as a 4-hour IV infusion on Days 3, 4, and 5 of Cycle 1, and idarubicin 12 mg/m(2) was administered as a 30-minute IV infusion on Days 3, 4, and 5 of Cycle 1. Cytarabine and idarubicin were administered on Days 1, 2, and 3 of each subsequent 28-day cycle. Reduction of survivin was evaluated in peripheral blasts and bone marrow. Single-agent LY2181308 was well tolerated and survivin was reduced only in patients with a high survivin expression. In combination with chemotherapy, 4/16 patients had complete responses, 1/16 patients had incomplete responses, and 4/16 patients had cytoreduction. Nine patients died on study: 6 (monotherapy), 3 (combination). LY2181308 alone is well tolerated in patients with AML. In combination with cytarabine and idarubicin, LY2181308 does not appear to cause additional toxicity, and has shown some clinical benefit needing confirmation in future clinical trials.

Use of ramping and equilibrium water vapor sorption methods to determine the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose.

Recent research has demonstrated that the critical relative humidity (RHc) values, obtained using automatic water vapor sorption instruments, can be used to detect the glassy to rubbery transition. However, reported time dependency of these RHc values suggests that additional research be carried out using equilibrium water vapor sorption methods. Thus, the objectives of this study were to: (1) determine the RHc for amorphous polydextrose at various temperatures using both instrumental (Dynamic Vapor Sorption [DVS] ramping and equilibrium) and saturated salt slurry methods, and (2) compare the RHc values obtained via sorption methods to the glass transition temperature (Tg) values obtained via differential scanning calorimetry (DSC). When plotted as a "glass curve" on a state diagram, the RHc values (plotted as a function of temperature) were found to be similar to the Tg values (plotted as a function of relative humidity). Of the 3 sorption methods employed, at 25 °C, the saturated salt slurry exhibited the lowest RHc value (34.3%), followed by the DVS equilibrium method (41.7%), and the DVS ramping method (49.9%). The RHc DVS equilibrium method was closest to the calculated DSC Tg onset RHc value (41.6% at 25 °C). These water sorption methods show promise as practical tools for predicting the quality and stability attributes of amorphous materials by being able to routinely determine the location of the glassy to rubbery transition. Future research applying these sorption methods to more complex amorphous food systems is suggested. Practical Application: Despite its extreme usefulness, the Tg, a key element of the Food Polymer Science approach, remains a challenging parameter to routinely measure in amorphous food materials. Recent research has demonstrated that the RHc values can be used to detect the glassy to rubbery transition. However, reported time dependency of these RHc values suggests that additional research be carried out using equilibrium water vapor sorption methods. Therefore, in this research 2 instrumental (DVS ramping and equilibrium) methods and the traditional saturated salt slurry method were used to obtain RHc values, comparing them to DSC obtained Tg values. The water sorption methods show promise as practical tools for predicting the quality and stability attributes of amorphous materials by being able to routinely determine the location of the glassy to rubbery transition. Future research applying these sorption methods to more complex amorphous food systems is suggested.

Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.

Similar to an increase in temperature at constant moisture content, water vapor sorption by an amorphous glassy material at constant temperature causes the material to transition into the rubbery state. However, comparatively little research has investigated the measurement of the critical relative humidity (RHc) at which the glass transition occurs at constant temperature. Thus, the central objective of this study was to investigate the relationship between the glass transition temperature (Tg), determined using thermal methods, and the RHc obtained using an automatic water vapor sorption instrument. Dynamic dewpoint isotherms were obtained for amorphous polydextrose from 15 to 40 °C. RHc was determined using an optimized 2nd-derivative method; however, 2 simpler RHc determination methods were also tested as a secondary objective. No statistical difference was found between the 3 RHc methods. Differential scanning calorimetry (DSC) Tg values were determined using polydextrose equilibrated from 11.3% to 57.6% RH. Both standard DSC and modulated DSC (MDSC) methods were employed, since some of the polydextrose thermograms exhibited a physical aging peak. Thus, a tertiary objective was to compare Tg values obtained using 3 different methods (DSC first scan, DSC rescan, and MDSC), to determine which method(s) yielded the most accurate Tg values. In general, onset and midpoint DSC first scan and MDSC Tg values were similar, whereas onset and midpoint DSC rescan values were different. State diagrams of RHc and experimental temperature and Tg and %RH were compared. These state diagrams, though obtained via very different methods, showed relatively good agreement, confirming our hypothesis that water vapor sorption isotherms can be used to directly detect the glassy to rubbery transition. Practical Application: The food polymer science (FPS) approach, pioneered by Slade and Levine, is being successfully applied in the food industry for understanding, improving, and developing food processes and products. However, despite its extreme usefulness, the Tg, a key element of the FPS approach, remains a challenging parameter to routinely measure in amorphous food materials, especially complex materials. This research demonstrates that RHc values, obtained at constant temperature using an automatic water vapor sorption instrument, can be used to detect the glassy to rubbery transition and are similar to the Tg values obtained at constant %RH, especially considering the very different approaches of these 2 methods--a transition from surface adsorption to bulk absorption (water vapor sorption) versus a step change in the heat capacity (DSC thermal method).

Effects of heating conditions on the glass transition parameters of amorphous sucrose produced by melt-quenching.

This research investigates the effects of heating conditions used to produce amorphous sucrose on its glass transition (T(g)) parameters, because the loss of crystalline structure in sucrose is caused by the kinetic process of thermal decomposition. Amorphous sucrose samples were prepared by heating at three different scan rates (1, 10, and 25 °C/min) using a standard differential scanning calorimetry (SDSC) method and by holding at three different isothermal temperatures (120, 132, and 138 °C) using a quasi-isothermal modulated DSC (MDSC) method. In general, the quasi-isothermal MDSC method (lower temperatures for longer times) exhibited lower T(g) values, larger ΔC(p) values, and broader glass transition ranges (i.e., T(g end) minus T(g onset)) than the SDSC method (higher temperatures for shorter times), except at a heating rate of 1 °C/min, which exhibited the lowest T(g) values, the highest ΔC(p), and the broadest glass transition range. This research showed that, depending on the heating conditions employed, a different amount and variety of sucrose thermal decomposition components may be formed, giving rise to wide variation in the amorphous sucrose T(g) values. Thus, the variation observed in the literature T(g) values for amorphous sucrose produced by thermal methods is, in part, due to differences in the heating conditions employed.

Can the thermodynamic melting temperature of sucrose, glucose, and fructose be measured using rapid-scanning differential scanning calorimetry (DSC)?

The loss of crystalline structure in sucrose, glucose, and fructose has been shown to be due to the kinetic process of thermal decomposition (termed apparent melting), rather than thermodynamic melting. The purpose of this research was to investigate whether or not it is possible to scan quickly enough to suppress the kinetic process of thermal decomposition and reach the thermodynamic melting temperature of these sugars using a new rapid-scanning DSC. Indium, a thermodynamic melting material, and sucrose, glucose, and fructose were analyzed at three heating rates from 1 to 25 °C/min using standard DSC and at seven heating rates from 50 to 2000 °C/min using rapid-scanning DSC. Thermodynamic melting was achieved when the onset temperature (T(m onset)) of the endothermic peak leveled off to a constant value independent of heating rate. The T(m onset) for indium was constant (156.74 ± 0.42 °C) at all heating rates. In the case of fructose, the T(m onset) increased considerably until a heating rate of approximately 698 °C/min, after which the average T(m onset) for the remaining three heating rates was constant at 135.83 ± 1.14 °C. Thus, 135.83 °C is proposed to be the thermodynamic melting temperature of fructose. It is important to note that the heating rate at which this thermodynamic melting temperature is achieved is most likely influenced by the type and amount of trace components (e.g., water and salts) contained in the fructose, which are known to vary widely in sugars. In the case of sucrose and glucose, thermodynamic melting temperatures were not able to be obtained, because the upper limit heating rate used was not fast enough to suppress thermal decomposition and achieve thermodynamic melting, perhaps due to the higher apparent T(m onset) for sucrose and glucose compared to that for fructose.