Genetically Modified Starch as an Industrial Raw Material

Abstract

Starch is an important raw material for industrial applications, both for food and nonfood purposes. Of particular interest is the use of starch as a nonpetroleum chemical stock for the manufacture of biodegradable polymers. Annual EC starch production is nearing 10 million tons, with 80% from cereals and 20% from potatoes, and grows at 4?5% annually. The potential for genetically modified starch is considered very high. Such starch offers significant advantages: 1) chemical modifications, which are expensive and environmentally hazardous, are replaced; 2) novel carbohydrates can be produced.     

Polysaccharide functionality through extrusion processing

Extrusion processing is a technology applied in the food and pharmaceutical industry for affecting product microstructure, product chemistry or the macroscopic shape of products. Starch based products are often extruded to break down the starch granule to render it digestible and to produce a shaped product. Encapsulation of flavors, nutrients and drugs is another frequent application of extrusion processing. This short review article is concerned with the use of extrusion processes to modify polysaccharide functionality. Extrusion processes are applied to polysaccharides for specific purposes such as physical modification or chemical modification (reactive extrusion), manufacture of confectionary gels and encapsulation of flavors or drugs. Non-starch polysaccharides and confectionary gels have also been extruded. Another application area is in the field of dietary fibers, obtained through extrusion processing of by- or waste-products of the food industry. The focus of this article is on extruding starch and other polysaccharides as an ingredient rather than as part of a final food product obtained by extrusion processing. It concludes with a discussion on extrusion as microstructure generating process and the relevance of this application to taste perception in semi-liquid foods.     

Structural and mechanical properties of edible films from composite mixtures of starch,dextrin and different types of chemically modified starch

Abstract

Recent regulations restricting the use of one-use-plastics open the possibility to develop starch-based edible packaging material. The objective of this work was to determine the effect of three different modified starches on starch and dextrin composite edible films by a mixture design approach on edible films’ mechanical properties. The amylose content of chemically modified starches influenced their swelling capacities, where higher amylose content was inversely related to water-power uptake and directly related to film thickness. CMS3 Nifrastarch-TS edible films, with higher amylose content, presented higher puncture force and tensile strength, but lower puncture deformation and elongation, related to a less smooth surface, according to atomic force micrographs. The use of CMS1 Gelamil-100, with lower amylose content, decreased stiffness but increased films’ stretching, presenting higher surface smoothness film topography. The use of commercial chemical modified starches in combination with starch and dextrin will allow to control of edible film thickness and hence, mechanical properties, depending on food covering necessities.     

Surface activity of commercial food grade modified starches

An attempt to quantitative evaluation of the functionality of food grade chemically modified starches in the emulsion systems by estimation of their surface activity as well as the capability of thickening food products was the main purpose of this present work. It was stated that chemically modified starches reveal higher surface activity at air/water and toluene/water interfaces in comparison to the native starch. The increase of the degree of substitution of polar carboxyl groups as well as rather non-polar acetyl ones results in an enhance of surface activity. Starch sodium octenylsuccinate stands out from other investigated starches, in its excellent capability of lowering surface and interfacial tension. Cross-linked starches reveal excellent stabilisation activity at a pH range of 5.5–7.0 but their surface activity is lower than those of other modified starches. Acetylated starch as well as starch sodium octenylsuccinate reveal satisfactory thickening capability up to pH 4.5 and moreover their surface activity (especially of E 1450) allows us to recommend them as functional constituents of food emulsions. Low thickening capability of oxidised starches rather excluded these derivatives from the group of potential functional additives for food emulsions.     

Retrogradation characteristics of high hydrostatic pressure processed corn and wheat starch

High hydrostatic pressure (HHP) has been investigated as an alternative to thermal processing for food preservation. HHP has been known to affect high molecular weight polymers causing phase change. Starch is gelatinized at a pressure on the order of 600–700 MPa, at 25 °C. Gelatinized starch recrystallizes during storage affecting the texture and shelf life of food products. The effect of HHP processing on the crystallization of starches from different botanical origins during storage at 4 and 23 °C was investigated. Crystallization kinetics of HHP treated wheat and corn starch gels were compared using DSC. The effect of crystallization on structure was evaluated in terms of storage modulus. The rate of retrogradation depended on the storage temperature (23 °C and 4 °C) and the botanical origin of the starch. The least crystallization was observed in HHP treated wheat starch stored at 23 °C. The storage modulus increased with crystallization of starch.     

Graft copolymerization of acrylamide onto carboxymethyl starch

Water absorption resins of carboxymethyl starch graft acrylamide (CMS-g-AM) were synthesized by copolymerization based on a free radical reaction. At first, CMS was prepared with starch and chloroacetic acid in an alkali-methanol media. Then, AM was grafted onto CMS by using ceric ammonium nitrate as an initiator. The resulting graft products were identified by infrared spectra. The effects of the preparation conditions on the substituent degree (SD) of starch and the water absorption capacities of CMS-g-AM were investigated. The results showed that SD of starch first increased remarkably and then decreased gradually with increased addition of sodium hydroxide, and the water absorption capacity of CMS-g-AM depended greatly on the SD of CMS and its maximum with 0.75 of SD of starch was 350 g/g.     

Eine Frage der richtigen Stärke

Starch plays an important role in a broad range of industrial applications. The major part is gained from potatoes that usually include two starch components: Amylose and Amylopectin. Amylopectin is clearly superior in several applications due to its molecular structure. Therefore, a potato that does only build Amylopectin is important for the industry. “Amflora” is a genetically enhanced potato that is designed for this purpose.     

Thermoplastic starch films with vegetable oils of Brazilian Cerrado

Starch is one of the most promising natural polymers to be abundant, cheap and biodegradable. To get thermoplastic starch (TPS) is necessary mechanical shake, high temperature and use of plasticizers. In this work, TPS films were prepared by casting from cassava starch and three different vegetable oils of Brazilian Cerrado as plasticizer: buriti, macauba and pequi. The materials were analyzed by TG, DSC and TMA. Thermal properties of oils depend on their chemical structures. Starch and vegetable oils are natural resources that can be used how alternative to producing materials that cause minor environmental impact.     

高岭土／羧甲基淀粉复合颗粒的制备及其协同电流变效应

通过二次插层取代法，以二甲基亚砜为前驱体，羧甲基淀粉二次插层取代制备 了高岭土/羧甲基淀粉纳米复合材料。结合XRD，FTIR，SEM和EDS等测试手段对复合 材料的结构进行了表征。研究结果发现，羧甲基淀粉经过二次插层取代引起了高岭 土片层之间的剥离，形成剥离型纳米复合材料。该复合材料制备成电流变液出现了 较大的协同效应，具有很好的电流变行为，并发现电流变性能与复合物中羧甲基淀 粉的含量有密切关系。     

Electrospinning of carboxymethyl starch/poly(L‐lactide acid) composite nanofiber

Carboxymethyl starch (CMS) is a natural polymer derived from sago starch that is obtained from sago palm (Metroxylon spp.). Herein, CMS was used as a polysaccharide source in preparations of composite nanofibers with poly(L‐lactide acid) (PLLA). The incorporation of CMS with PLLA in nanofiber form has great potential to be used in biomedical applications. The composite PLLA/CMS nanofibers were fabricated by electrospinning technique at various ratios of CMS, which were 5, 10, 15, and 20% vol/vol. The composite nanofibers were characterized according to their physical morphology, chemical interaction, wettability, water uptake, and thermal and mechanical behaviors. The result showed that uniform and bead‐free nanofibers were produced at the low ratio of CMS while fractal and discontinuing fiber was observed at a high ratio of CMS. A better mechanical strength was obtained at low CMS ratio as compared with higher one. Fourier transform infrared results showed that there was an interaction between CMS and PLLA after electrospinning. The surface hydrophilicity and water uptake increased with increasing ratio of CMS. The results from the differential scanning calorimeter analysis showed the decrease of the glass transition (T_g) and cold crystallization temperature (T_cc) of the nanofiber after addition of CMS in PLLA.     

Clustering and percolation effects in microcrystalline starch-reinforced thermoplastic

The use of starch microcrystals as biodegradable particulate filler is evaluated by processing composite materials with a weight fraction of starch ranging from 0 to 60%. In a previous work [Macromolecules, 29, 7624] the preparation technique of a colloidal suspension of hydrolyzed starch and the processing of composite materials by freeze drying and molding a mixture of aqueous suspensions of starch microcrystals and synthetic polymer matrix were presented. Starch microcrystals with dimensions of a few nanometers were obtained from potatoes' starch granules, and it was found that this filler produces a great reinforcing effect, especially at a temperature higher than T_g of the synthetic matrix. Classical models for polymers containing nearly spherical particles based on a mean field approach could not explain this reinforcing effect. The morphology of these nanocomposite systems is discussed in light of aggregate formation and percolation concepts. The sorption behavior of these materials is also performed. Starch is a hygroscopic material, and it is found that the composites absorb more water, as the starch content is higher. The diffusion coefficient of the penetrant is predicted from modified mechanical three branch series-parallel model based on a percolation approach. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2211–2224, 1998     

Starch biosynthesis and modification of starch structure in transgenic plants

Starch is synthesised through the ADP-glucose pathway, involving the three enzymes ADP-glucose pyrophosphorylase, starch synthase and starch branching enzyme. ADP-glucose pyrophosphorylase is the key enzyme of the pathway, determining the flux of carbon into starch. It generates ADP-glucose, which is the substrate for the starch synthases, from glucose-1-phosphate and ATP releasing pyrophosphate. The enzyme is stimulated by 3-phosphoglycerate and inhibited through inorganic phosphate. The starch synthases, which catalyse the transfer of glucose from ADP-glucose to the nonreducing end of a growing α-1,4-glucan, are divided into two classes, the granule-bound starch synthases (GBSS) and the soluble starch synthases (SS). In both classes several isoforms have been described from many different plant species. The branching enzyme, which introduces branchpoints into the amylopectin, can also occur in different isoforms. Other enzymes present in plants, which also act on α-1,4-glucans, such as the starch phosphorylases, disproportionating enzyme and different starch hydrolases, might also be important for dertermining the starch structure and, therefore, its processibility. Many aspects of starch synthesis are not fully understood to date. Starch metabolism can be manipulated through genetic engineering, either by the ectopic expression of different heterologous genes, or through the repression of the expression of endogenous genes using antisense RNA technology. This not only allows the functional analysis of starch biosynthetic proteins, but also the manipulation of starch structure in order to widen its industrial applications. In this way many different potato lines have been generated, containing either different amounts of starch, or which synthesize a structurally modified starch. These structural changes relate to the amylose content, the phosphate content, or the gelatinisation and gelation characteristics of the starch.     

In situ 13C solid-state polarization transfer NMR to follow starch transformations in food

Convenience food products tend to alter their quality and texture while stored. Texture-giving food components are often starch-rich ingredients, such as pasta or rice. Starch transforms depending on time, temperature and water content, which alters the properties of products. Monitoring these transformations, which are associated with a change in mobility of the starch chain segments, could optimize the quality of food products containing multiple ingredients. In order to do so, we applied a simple and efficient in situ ¹³C solid-state magic angle spinning (MAS) NMR approach, based on two different polarization transfer schemes, cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT). The efficiency of the CP and INEPT transfer depends strongly on the mobility of chain segments—the time scale of reorientation of the CH-bond and the order parameter. Rigid crystalline or amorphous starch chains give rise to CP peaks, whereas mobile gelatinized starch chains appear as INEPT peaks. Comparing ¹³C solid-state MAS NMR experiments based on CP and INEPT allows insight into the progress of gelatinization, and other starch transformations, by reporting on both rigid and mobile starch chains simultaneously with atomic resolution by the ¹³C chemical shift. In conjunction with ¹H solid-state MAS NMR, complementary information about other food components present at low concentration, such as lipids and protein, can be obtained. We demonstrate our approach on starch-based products and commercial pasta as a function of temperature and storage.     

Preparation and study of carboxymethylstarch

It has been shown that when a mixture of starch with sodium hydroxide and monochloroacetic acid is irradiated, the carboxymethylstarch (CMS) obtained consists of fractions with high levels of carboxymethyl groups and fractions with a predominant content of carbonyl groups, and when this mixture is subjected to mechanical treatment a far-reaching rearrangement of the structure of the starch takes place with its homogeneous interaction with the reagents to form CMS.     

Flow-injection determination of starch and total carbohydrate with an immobilized glucoamylase reactor and pulsed amperometric detection

Starch and total carbohydrate are determined by using a flow-injection system comprised of an immobilized glucoamylase reactor followed by pulsed amperometric detection of the glucose produced. Glucoamylase, immobilized onto porous silica and packed into a short stainless steel column, is capable of nearly quantitative (98%) conversion of the starch to glucose. The sensitivity of pulsed amperoemtric detection for soluble starch is increased 26-fold by first passing the starch through the immobilized glucoamylase reactor. This system is successfully used to determine total carbohydrate in beer samples. The method is simple, rapid and sensitive for starch.     

Preparation of starch and soluble sugars of plant material for the analysis of carbon isotope composition: a comparison of methods

Starch and soluble sugars are the major photosynthetic products, and their carbon isotope signatures reflect external versus internal limitations of CO₂ fixation. There has been recent renewed interest in the isotope composition of carbohydrates, mainly for use in CO₂ flux partitioning studies at the ecosystem level. The major obstacle to the use of carbohydrates in such studies has been the lack of an acknowledged method to isolate starch and soluble sugars for isotopic measurements. We here report on the comparison and evaluation of existing methods (acid and enzymatic hydrolysis for starch; ion‐exchange purification and compound‐specific analysis for sugars). The selectivity and reproducibility of the methods were tested using three approaches: (i) an artificial leaf composed of a mixture of isotopically defined compounds, (ii) a C₄ leaf spiked with C₃ starch, and (iii) two natural plant samples (root, leaf). Starch preparation methods based on enzymatic or acid hydrolysis did not yield similar results and exhibited contaminations by non‐starch compounds. The specificity of the acidic hydrolysis method was especially low, and we therefore suggest terming these preparations as HCl‐hydrolysable carbon, rather than starch. Despite being more specific, enzyme‐based methods to isolate starch also need to be further optimized to increase specificity. The analysis of sugars by ion‐exchange methods (bulk preparations) was fast but produced more variable isotope compositions than compound‐specific methods. Compound‐specific approaches did not in all cases correctly reproduce the target values, mainly due to unsatisfactory separation of sugars and background contamination. Our study demonstrates that, despite their wide application, methods for the preparation of starch and soluble sugars for the analysis of carbon isotope composition are not (yet) reliable enough to be routinely applied and further research is urgently needed to resolve the identified problems. Copyright © 2009 John Wiley & Sons, Ltd.     

Crystalline starch based nanoparticles

Starch is an abundant, natural, renewable, and biodegradable polymer produced by many plants as a source of stored energy. Because of the multiscale structure of starch granules consisting of alternating crystalline and amorphous concentric layers, the controlled acid hydrolysis treatment of starch disrupts this organization and releases crystalline platelet-like particles with nanoscale dimensions. This paper intends to provide a comprehensive overview of their preparation, characterization, properties, and applications.     

淀粉基高分子材料的研究进展

概述了近5年国内外在淀粉的化学、物理改性及其作为一种材料使用方面取得的最新研究进展.淀粉的化学改性主要介绍了淀粉的酯化、醚化、氧化、交联、接枝共聚等,而物理改性主要介绍了淀粉分别与黏土、脂肪族聚酯、聚乙烯醇以及纤维素等天然大分子的共混改性,同时还介绍了通过酸化制备淀粉纳米晶.淀粉基材料除了用于制备可生物降解塑料、吸附材...     

Relation of Certain Infrared Bands to Starch Crystallinity

Starch is a homoglycan composed of but a single type of sugar unit. Nature has chosen the starch granule as an almost universal from for packaging and sturing carbohydrate in green plants. In granule form, starch is quasi-crystalline, water-insoluble, and dense. In structure of amylose, a hydrogen bond exists between the hydroxyl group at C-2 of one α-D-glucopyranosyl unit and the C-3 hydroxyl group of the adjacent ct-D-glucopyranosyl unit with the C-3 hydroxyl group donating the hydrogen atom in the hydrogen bond. The starch chains within the amorphous region are presumable available for reaction. With extensive chemical derivatization of starch in which the granule crystal structure is maintained essentially inact.     

Adsorption behavior of carboxymethyl starch on titanium dioxide surfaces

The adsorption of carboxymethyl starch (CMS) on titanium dioxide surface from aqueous solution of electrolyte was investigated by adsorption and electrokinetics mobility measurements. Zeta potential measurements showed that the addition of CMS resulted in a shift of isoelectric point to the more acidic region, indicating the adsorption of CMS from the aqueous solution onto titanium dioxide surface. The positively charged and hydrophilic surface sites of titanium dioxide favor the adsorption of CMS molecules. The adsorption capacity of CMS on titanium dioxide surface was found to be controlled by the number of functional group on CMS that promotes surface charge CMS adsorption in agreement with Langmuir isotherm. For the adsorption of CMS, the pseudo-second-order kinetics of chemical reaction provides the best correlation of the experimental data.