K. E. Kolb

Bio: K. E. Kolb is an academic researcher. The author has contributed to research in topics: Degree of unsaturation & Double bond. The author has an hindex of 1, co-authored 1 publications receiving 107 citations.

Differential scanning calorimetry of single acid triglycerides: Effect of chain length and unsaturation

Abstract: The polymorphism of 13 single acid triglycerides with acyl group chain lengths ranging from 16–22 was studied by differential scanning calorimetry. In contrast to the singleβ′-form generally attributed to such triglycerides, at least two intermediate endotherms were found for most samples between the least stable (α) and most stable (β) polymorphs. For saturated triglycerides, two versions of the familiar “tuning fork” model meet theβ′-form requirement of alternate fatty acid chains in planes perpendicular to each other. The detection of three intermediate endotherms for triolein, tri-cis-1 1-octadecenoin and trierucin (and possibly also trilinolein) may be rationalized by assuming that the segments of polymethylene chains on either side of double bonds may zigzag in different planes. Four exceptions for which no evidence was found forβ′-forms are tri-cis-6-octadecenoin, tri-cis-6-hexadecenoin, tri-trans-6-octadecenoin and trielaidin. Three of these exceptions contain Δ6-acyl groups and have in common segments with even numbers of methylene groups on either side of the double bonds. These same three triglycerides also have a shorter than usual polymethylene segment between the ester linkages and the double bonds and a longer than usual distance from the double bonds to the terminal methyl groups. Tri-trans-6-octadecenoin and trielaidin are exceptional in still another way. Only they and are exceptional in still another way. Only they and trierucin exhibited significant nonconformity with an empirical relationship between melting points and heats of fusion ofβ-forms. Otherwise, all points in a plot of the former physical constants vs. the latter closely fit a smooth curve, the positive slope of which gets larger as the X-axis values, i.e., melting points, increase.

A Comprehensive Evaluation of the Melting Points of Fatty Acids and Esters Determined by Differential Scanning Calorimetry

Abstract: The melting point is one of the most important physical properties of a chemical compound and it plays a significant role in determining possible applications. For fatty acid esters the melting point is essential for a variety of food and non-food applications, the latter including biodiesel and its cold-flow properties. In this work, the melting points of fatty acids and esters (methyl, ethyl, propyl, butyl) in the C8–C24 range were determined by differential scanning calorimetry (DSC), many of which for the first time. Data for triacylglycerols as well as ricinoleic acid and its methyl and ethyl esters were also acquired. For some compounds whose melting points have been previously reported, data discrepancies exist and a comprehensive determination by DSC has not been available. Variations in the present data up to several °C compared to data in prior literature were observed. The melting points of some methyl-branched iso- and anteiso-acids and esters were also determined. Previously unreported systematic effects of compound structure on melting point are presented, including those for ω-9 monounsaturated fatty acids and esters as well as for methyl-branched iso and anteiso fatty acids and esters. The melting point of a pure fatty acid or ester as determined by DSC can vary up to approximately 1 °C. Other thermal data, including heat flow and melting onset temperatures are briefly discussed.

The many roles of fats in overwintering insects.

Abstract: Temperate, polar and alpine insects generally do not feed over winter and hence must manage their energy stores to fuel their metabolism over winter and to meet the energetic demands of development and reproduction in the spring. In this Review, we give an overview of the accumulation, use and conservation of fat reserves in overwintering insects and discuss the ways insects modify fats to facilitate their selective consumption or conservation. Many insects are in diapause and have depressed metabolic rates over winter; together with low temperatures, this means that lipid stores are likely to be consumed predominantly in the autumn and spring, when temperatures are higher but insects remain dormant. Although there is ample evidence for a shift towards less-saturated lipids in overwintering insects, switches between the use of carbohydrate and lipid stores during winter have not been well-explored. Insects usually accumulate cryoprotectants over winter, and the resulting increase in haemolymph viscosity is likely to reduce lipid transport. For freeze-tolerant insects (which withstand internal ice), we speculate that impaired oxygen delivery limits lipid oxidation when frozen. Acetylated triacylglycerols remain liquid at low temperatures and interact with water molecules, providing intriguing possibilities for a role in cryoprotection. Similarly, antifreeze glycolipids may play an important role in structuring water and ice during overwintering. We also touch on the uncertain role of non-esterified fatty acids in insect overwintering. In conclusion, lipids are an important component of insect overwintering energetics, but there remain many uncertainties ripe for detailed exploration.