Functionalization Methods of Starch and Its Derivatives: From Old Limitations to New Possibilities.

It has long been known that starch as a raw material is of strategic importance for meeting primarily the nutritional needs of people around the world. Year by year, the demand not only for traditional but also for functional food based on starch and its derivatives is growing. Problems with the availability of petrochemical raw materials, as well as environmental problems with the recycling of post-production waste, make non-food industries also increasingly interested in this biopolymer. Its supporters will point out countless advantages such as wide availability, renewability, and biodegradability. Opponents, in turn, will argue that they will not balance the problems with its processing and storage and poor functional properties. Hence, the race to find new methods to improve starch properties towards multifunctionality is still ongoing. For these reasons, in the presented review, referring to the structure and physicochemical properties of starch, attempts were made to highlight not only the current limitations in its processing but also new possibilities. Attention was paid to progress in the non-selective and selective functionalization of starch to obtain materials with the greatest application potential in the food (resistant starch, dextrins, and maltodextrins) and/or in the non-food industries (hydrophobic and oxidized starch).

Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry.

Blends of poly(lactic acid) (PLA) with poly(propylene carbonate) (PPC) are currently in the phase of intensive study due to their promising properties and environmentally friendly features. Intensive study and further commercialization of PPC-based polymers or their blends, as usual, will soon face the problem of their waste occurring in the environment, including soil. For this reason, it is worth comprehensively studying the degradation rate of these polymers over a long period of time in soil and, for comparison, in phosphate buffer to understand the difference in this process and evaluate the potential application of such materials toward agrochemical and agricultural purposes. The degradation rate of the samples was generally accompanied by weight loss and a decrease in molecular weight, which was facilitated by the presence of PPC. The incubation of the samples in the aqueous media yielded greater surface erosions compared to the degradation in soil, which was attributed to the leaching of the low molecular degradation species out of the foils. The phytotoxicity study confirmed the no toxic impact of the PPC on tested plants, indicating it as a "green" material, which is crucial information for further, more comprehensive study of this polymer toward any type of sustainable application.

Review of the Most Important Methods of Improving the Processing Properties of Starch toward Non-Food Applications.

Starch is the second most abundantly available natural polymer in the world, after cellulose. If we add its biodegradability and non-toxicity to the natural environment, it becomes a raw material very attractive for the food and non-food industries. However, in the latter case, mainly due to the high hydrophilicity of starch, it is necessary to carry out many more or less complex operations and processes. One of the fastest growing industries in the last decade is the processing of biodegradable materials for packaging purposes. This is mainly due to awareness of producers and consumers about the dangers of unlimited production and the use of non-degradable petroleum polymers. Therefore, in the present review, an attempt was made to show the possibilities and limitations of using starch as a packaging material. The most important physicochemical features of this biopolymer are discussed, and special attention is paid to more or less environmentally friendly methods of improving its processing properties.

The Importance of Ionic Liquids in the Modification of Starch and Processing of Starch-Based Materials.

The main applications of ionic liquids in chemistry and material research on one of the most important natural polymers-starch-are presented in this review. A brief characterization of ionic liquids and the advantages and disadvantages of using them in the modification and processing of polysaccharides is presented. The latest reports on the use of various ionic liquids as solvents or co-solvents; as media for synthesizing starch derivatives in oxidation, etherification, esterification, and transesterification, with particular emphasis on biocatalyzed reactions; and as plasticizers or compatibilizers in the processing of starch-based polymers have been investigated. The current trends, possibilities, and limitations of using this type of compound for the production of functional starch-based materials are presented.

From high oleic vegetable oils to hydrophobic starch derivatives: II. Physicochemical, processing and environmental properties.

Medium-substituted esters of starch and higher fatty acids, structurally identified in the first part of paper were subjected to further analyses, mainly to check application potential. In order to determine the possibility of using the esters in the packaging industry, the glycerol-plasticized starch esters were extruded on a single screw extruder in the form of a film. The mechanical properties tests consisted of tensile and tear strength. Hydrophobicity, water absorption and oil absorption were checked as the processing and functional properties. Environmental tests, such as phytotoxicity on monocotyledonous and dicotyledonous plants and biodegradability in soil under strictly controlled conditions of the vegetation hall were carried out. Esterification increased the hydrophobicity of the starch and the tensile and tear strength, without losing important environmental features such as biodegradability and non-toxicity. The obtained polymer materials give hope for their use in the production of new ecofriendly and biodegradable packaging.

From high oleic vegetable oils to hydrophobic starch derivatives: I. Development and structural studies.

Hydrophobic starch derivatives were obtained by biocatalysed esterification with hydrolysates from high oleic vegetable oils. First, the pure rapeseed oil or waste rapeseed oil, was hydrolysed with a Thermomyces lanuginosus lipase in the buffer solution form. Next, purified hydrolysates were used as donors of the acyl group for the esterification of potato starch after being pregelatinised in ionic liquid - 1-buthyl-3-methylimidazolium chloride. The esterification was catalysed by the same fungal lipase but immobilised on a polymer carrier and conducted in the anhydrous ternary reaction system: hydrophilic ionic liquid - non-ionic surfactant - hydrophobic higher fatty acids. The products have been identified and characterised using the following methods: degree of substitution (DS) by volumetric and elemental analysis method, FTIR and NMR spectroscopies, XRD and SEM. The proposed method can lead to the synthesis of more water-resistant starch derivatives as well as provide a possibility for recycling waste oils from the food industry.

Esterification of potato starch by a biocatalysed reaction in an ionic liquid.

In this study, potato starch was esterified with oleic acid, using 1-butyl-3-methylimidazolium chloride as a reaction medium and an immobilised lipase from Thermomyces lanuginosus as a catalyst. The degree of substitution (DS) of the products was determined by the volumetric method; and the best esterified product (with the highest DS) was determined by an elemental analysis. The effect of the reaction parameters on the DS, such as the time and the temperature, were also studied. The product with the highest DS (0.22) was found in the reaction carried out at 60 °C for 4h. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) analyses confirmed the esterification of the potato starch. Furthermore, the results of X-ray diffraction (XRD) and a scanning electron microscopy (SEM) revealed that the crystallinity and the morphology of the native potato starch was slightly changed during its partial gelatinisation in the ionic liquid, and was completely destroyed as a result of the formation of the esters. The thermal stability of the starch oleate decreased, when compared to the unmodified starch, as was indicated by a thermal gravimetric analysis (TGA).