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Imidacloprid is the most widely used insecticide in agriculture and its intensive use over the last 30 years has caused a global concern due to its potentially toxic effects on the ecosystem. Considering the recent scientific interest in novel simple methods for imidacloprid analysis, we propose a label-free sensitive and specific localised surface plasmon resonance system for the detection of the insecticide based on 2D nanostructured metasurfaces with highly performing plasmonic properties. The specificity of the sensor proposed was achieved by covalent bio-functionalization of the metasurface using a smart and easy one-step procedure mediated by carbon disulphide. The biosensor produced was tested using a set of imidacloprid standard solutions showing a competitive limit of detection, lower than 1 ng mL

Thermoplastic, polysaccharide-based plastics are environmentally friendly. However, typical shortcomings include lack of water resistance and poor mechanical properties. Nanocomposite manufacturing using pure, highly linear, polysaccharides can overcome such limitations. Cast nanocomposites were fabricated with plant engineered pure amylose (AM), produced in bulk quantity in transgenic barley grain, and cellulose nanofibers (CNF), extracted from agrowaste sugar beet pulp. Morphology, crystallinity, chemical heterogeneity, mechanics, dynamic mechanical, gas and water permeability, and contact angle of the films were investigated. Blending CNF into the AM matrix significantly enhanced the crystallinity, mechanical properties and permeability, whereas glycerol increased elongation at break, mainly by plasticizing the AM. There was significant phase separation between AM and CNF. Dynamic plasticizing and anti-plasticizing effects of both CNF and glycerol were demonstrated by NMR demonstrating high molecular order, but also non-crystalline, and evenly distributed 20 nm-sized glycerol domains. This study demonstrates a new lead in functional polysaccharide-based bioplastic systems.

New bio-based polymers capable of either outperforming fossil-based alternatives or possessing new properties and functionalities are of relevant interest in the framework of the circular economy. In this work, a novel bio-based polycarvone acrylate di-epoxide (PCADE) was used as an additive in a one-step straightforward electrospinning process to endow the fibres with functionalisable epoxy groups at their surface. To demonstrate the feasibility of the approach, poly(vinylidene fluoride) (PVDF) fibres loaded with different amounts of PCADE were prepared. A thorough characterisation by TGA, DSC, DMTA and XPS showed that the two polymers are immiscible and that PCADE preferentially segregates at the fibre surface, thus developing a very simple one-step approach to the preparation of ready-to-use surface functionalisable fibres. We demonstrated this by exploiting the epoxy groups at the PVDF fibre surface in two very different applications, namely in epoxy-based carbon fibre reinforced composites and membranes for ω-transaminase enzyme immobilisation for heterogeneous catalysis.

Biocompatible and bio-based materials are an appealing resource for the pharmaceutical industry. Poly(glycerol-adipate) (PGA) is a biocompatible and biodegradable polymer that can be used to produce self-assembled nanoparticles (NPs) able to encapsulate active ingredients, with encouraging perspectives for drug delivery purposes. Starch is a versatile, inexpensive, and abundant polysaccharide that can be effectively applied as a bio-scaffold for other molecules in order to enrich it with new appealing properties. In this work, the combination of PGA NPs and starch films proved to be a suitable biopolymeric matrix carrier for the controlled release preparation of hydrophobic drugs. Dynamic Light Scattering (DLS) was used to determine the size of drug-loaded PGA NPs, while the improvement of the apparent drug water solubility was assessed by UV-vis spectroscopy. In vitro biological assays were performed against cancer cell lines and bacteria strains to confirm that drug-loaded PGA NPs maintained the effective activity of the therapeutic agents. Dye-conjugated PGA was then exploited to track the NP release profile during the starch/PGA nanocomposite film digestion, which was assessed using digestion models mimicking physiological conditions. The collected data provide a clear indication of the suitability of our biodegradable carrier system for oral drug delivery.

Interference in protein–starch interactions in barley by the expression of an exogenous high-affinity starch-binding factor (Carbohydrate-Binding Motif 20, CBM20) reveals a link between starch granule biosynthesis and the level of photosynthesis., The biosynthesis of starch granules in plant plastids is coordinated by the orchestrated action of transferases, hydrolases, and dikinases. These enzymes either contain starch-binding domain(s) themselves, or are dependent on direct interactions with co-factors containing starch-binding domains. As a means to competitively interfere with existing starch–protein interactions, we expressed the protein module Carbohydrate-Binding Motif 20 (CBM20), which has a very high affinity for starch, ectopically in barley plastids. This interference resulted in an increase in the number of starch granules in chloroplasts and in formation of compound starch granules in grain amyloplasts, which is unusual for barley. More importantly, we observed a photosystem-independent inhibition of CO2 fixation, with a subsequent reduced growth rate and lower accumulation of carbohydrates with effects throughout the metabolome, including lower accumulation of transient leaf starch. Our results demonstrate the importance of endogenous starch–protein interactions for controlling starch granule morphology and number, and plant growth, as substantiated by a metabolic link between starch–protein interactions and control of CO2 fixation in chloroplasts.

Possible inhibitory effects on wheat starch amylolysis of native and hydrolysed pea protein, in an extruded wheat snack matrix were investigated by using a combined in vitro dynamic gastric model (DGM) and a static duodenal digestion model (SDM). The matrix was prepared by blending wheat flour and pea proteins (12%, w/w) in their native or proteolyzed forms. Extruded snacks were ground, mixed with saliva and poured in the DGM-fundus. The slurry in the antrum was released simulating the in vivo emptying of the stomach and subsequently transferred to the SDM. Native pea protein did not influence the release of soluble glucans and glucose after complete gastric emptying into the vessel. However, the addition of hydrolysed pea protein significantly reduced starch amylolysis at the first 40 min of digestion. No inhibitory effect was observed at later digestion times. Fourier-Transform Infrared (FTIR) analysis of the extruded samples clearly indicated enhanced starch-protein interactions, where the magnitude of interaction found to be greatest in the blend with hydrolysed pea protein through hydrogen bonding. At our knowledge, this is the first study using DGM to determine the effect of exogenous protein on the digestibility of extruded wheat starch. The data suggested the possibility of using protease hydrolysed pea protein as an ingredient to formulate low glycemic food products.

In this study, we explored possibilities to develop low glycaemic-index foods from barley (Hordeum vulgare – Hv). Barley has a potential to suppress postprandial blood glucose levels, possibly because of its high content of β-glucan (BG). BG content is particularly high in Hordeum vulgare Subsp. spontaneum (Hs), which is the wild ancestor of cultivated barley. Increasing amylose content in starch is another way to decrease the glycaemic index of a starch-rich-food. Therefore, a recently developed Amylose-only barley grain (AO) containing a 99% amylose starch was included. Two in vitro gastro-intestinal models were used to predict glycaemic indices (pGIs). Grains and bread from Hs and AO showed lower pGIs as compared to Hv. The low pGI value of AO was due to the resistant starch. The low pGI of Hs barley grains was caused by increased viscosity of the digesta. A simulated colon was used to predict potential effects on microbiota.

There is significant potential for industrial use of renewables for a wide range of materials demanded by society. Plants, trees and algae are increasingly attracting attention as sustainable sources for functionalised and polymerizable building blocks. In particular, the outer bark of the birch tree (Betula pendula) is a side stream of the forestry industry with so far very little utilisation besides energy recovery. It is composed of a macromolecular network, suberin, that could provide a renewable, low cost and competitive resource. Within raw suberin is the potentially very useful multifunctional extract cis-9,10-epoxy-18-hydroxyoctadecanoic acid (CHA). Our drive has been to develop a green and sustainable synthetic strategy to CHA-based polyesters, by exploiting supercritical carbon dioxide (scCO2) as a reaction medium and leveraging the regio- and chemo-selective properties of the biocatalyst Novozym 435 (Lipase B). Low temperature (35–55 °C) polycondensation in scCO2 shows significant advantages compared to traditional polymerisation methods leading to reasonably high molecular weight polyesters. The mild synthetic conditions also preserve the valuable epoxy groups of the CHA which we show can be exploited by post-polymerisation functionalisation to create sustainable resins for bio-renewable coatings.

Isomaltooligosaccharides (IMOs) is a mixture of branched-maltooligosaccharides (MOSs), classified as a functional food ingredient with prebiotic potential. The objective of this study was to investigate alternative enzymatic methods to produce a sweetness/viscosity/degradability balance product containing soluble carbohydrate ranging from glucose, maltose, isomaltose and linear and branched MOS (IMOs), of different digestibility. The modified samples were produced using two main routes: 1. simultaneous catalysis by α-amylase and branching enzyme (BE) followed by α-transglucosidase (ABT) treatment, 2. simultaneous catalysis by α-amylase and BE followed by simultaneous β-amylase and α-transglucosidase (ABbT). For both routes, 30% or 50% (w v−1) cassava starch were used and a commercial IMO (comIMO) preparation was used as a positive control. The 30ABbT and 50ABbT showed the highest α-1,6 glucosidic linkages, panose and branched MOS (Degree of Polymerisation (DP) 4–7) compared to all other samples. All ABT and ABbT products showed decreased molecular weight and increased resistance to degradation by amylolytic enzymes as compared to cassava starch. The 50ABbT sample demonstrated the lowest digestion rate constant. Due to their high solubility and structural composition, containing-balanced-glucose, maltose, isomaltose and linear and branched MOS (IMOs), of different digestibility, these compositions can be suitable especially in soft drink- and sport drink formulations.

Starch is one of the most abundant polysaccharides on the earth and it is the most important source of energy intake for humans. Thermoplastic starch (TPS) is also widely used for new bio-based materials. The blending of starch with other molecules may lead to new interesting biodegradable scaffolds to be exploited in food, medical, and pharmaceutical fields. In this work, we used native starch films as biopolymeric matrix carriers of chemo enzymatically-synthesized poly (glycerol-adipate) (PGA) nanoparticles (NPs) to produce a novel and biocompatible material. The prototype films had a crystallinity ranging from 4% to 7%. The intrinsic and thermo-mechanical properties of the composite showed that the incorporation of NPs in the starch films decreases the glass transition temperature. The utilization of these film prototypes as the basis for new biocompatible material showed promise, particularly because they have a very low or even zero cytotoxicity. Coumarin was used to monitor the distribution of the PGA NPs in the films and demonstrated a possible interaction between the two polymers. These novel hybrid nanocomposite films show great promise and could be used in the future as biodegradable and biocompatible platforms for the controlled release of amphiphilic and hydrophobic active ingredients.

Adherence to a low-gluten diet has become increasingly common in parts of the general population. However, the effects of reducing gluten-rich food items including wheat, barley and rye cereals in healthy adults are unclear. Here, we undertook a randomised, controlled, cross-over trial involving 60 middle-aged Danish adults without known disorders with two 8-week interventions comparing a low-gluten diet (2 g gluten per day) and a high-gluten diet (18 g gluten per day), separated by a washout period of at least six weeks with habitual diet (12 g gluten per day). We find that, in comparison with a high-gluten diet, a low-gluten diet induces moderate changes in the intestinal microbiome, reduces fasting and postprandial hydrogen exhalation, and leads to improvements in self-reported bloating. These observations suggest that most of the effects of a low-gluten diet in non-coeliac adults may be driven by qualitative changes in dietary fibres., Gluten-free diets are increasingly common in the general population. Here, the authors report the results of a randomised cross-over trial involving middle-aged, healthy Danish adults, showing evidence that a low-gluten diet leads to gut microbiome changes, possibly due to variations in dietary fibres.

Starch provides our main dietary caloric intake and over-consumption of starch-containing foods results in escalating life-style disease including diabetes. By increasing the content of α-1,6 branch points in starch, digestibility by human amylolytic enzymes is expected to be retarded. Aiming at generating a soluble and slowly digestible starch by increasing the content and changing the relative positioning of the branch points in the starch molecules, we treated cassava starch with amylomaltase (AM) and branching enzyme (BE). We performed a detailed molecular analysis of the products including amylopectin chain length distribution, content of α-1,6 glucosidic linkages, absolute molecular weight distribution and digestibility. Step-by-step enzyme catalysis was the most efficient treatment, and it generated branch structures even more extreme than those of glycogen. All AM- and BE-treated samples showed increased resistance to degradation by porcine pancreatic α-amylase and glucoamylase as compared to cassava starch. The amylolytic products showed chain lengths and branching patterns similar to the products obtained from glycogen. Our data demonstrate that combinatorial enzyme catalysis provides a strategy to generate potential novel soluble α-glucan ingredients with low dietary digestibility assets.

Bio-plastics and bio-materials are composed of natural or biomass derived polymers, offering solutions to solve immediate environmental issues. Polysaccharide-based bio-plastics represent important alternatives to conventional plastic because of their intrinsic biodegradable nature. Amylose-only (AO), an engineered barley starch with 99% amylose, was tested to produce cross-linked all-natural bioplastic using normal barley starch as a control. Glycerol was used as plasticizer and citrate cross-linking was used to improve the mechanical properties of cross-linked AO starch extrudates. Extrusion converted the control starch from A-type to Vh- and B-type crystals, showing a complete melting of the starch crystals in the raw starch granules. The cross-linked AO and control starch specimens displayed an additional wide-angle diffraction reflection. Phospholipids complexed with Vh-type single helices constituted an integrated part of the AO starch specimens. Gas permeability tests of selected starch-based prototypes demonstrated properties comparable to that of commercial Mater-Bi© plastic. The cross-linked AO prototypes had composting characteristics not different from the control, indicating that the modified starch behaves the same as normal starch. The data shows the feasibility of producing all-natural bioplastic using designer starch as raw material.

International audience; Grain polysaccharides represent potential valuable raw materials for next-generation advanced and environmentally friendly plastics. Thermoplastic starch (TPS) is processed using conventional plastic technology, such as casting, extrusion, and molding. However, to adapt the starch to specific functionalities chemical modifications or blending with synthetic polymers, such as polycaprolactone are required (e.g. Mater-Bi). As an alternative, all-natural and compostable bio-plastics can be produced by blending starch with other polysaccharides. In this study, we used a maize starch (ST) and an oat beta-glucan (BG) composite system to produce bio-plastic prototype films. To optimize performing conditions, we investigated the full range of ST:BG ratios for the casting (100:0, 75:25, 50:50, 25:75 and 0:100 BG). The plasticizer used was glycerol. Electron Paramagnetic Resonance (EPR), using TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) as a spin probe, showed that the composite films with high BG content had a flexible chemical environment. They showed decreased brittleness and improved cohesiveness with high stress and strain values at the break. Wide-angle X-ray diffraction displayed a decrease in crystallinity at high BG content. Our data show that the blending of starch with other natural polysaccharides is a noteworthy path to improve the functionality of all-natural polysaccharide bio-plastics systems.

Corrigendum to “Plant-crafted starches for bioplastics production” [Carbohydr. Polym. 152 (2016) 398–408] http://doi.org/10.1016/j.carbpol.2016.10.077 The authors regret the affiliation of Eric Leroy. The correct affiliation is: LUNAM Université, CNRS, GEPEA, UMR 6144, CRTT, 37, Boulevard de l¹Université, 44606 St Nazaire Cedex, France.; Transgenically-produced amylose-only (AO) starch was used to manufacture bioplastic prototypes. Extruded starch samples were tested for crystal residues, elasticity, glass transition temperature, mechanical properties, molecular mass and microstructure. The AO starch granule crystallinity was both of the Band Vh-type, while the isogenic control starch was mainly A-type. The first of three endothermic transitions was attributed to gelatinization at about 60 • C. The second and third peaks were identified as melting of the starch and amylose-lipid complexes, respectively. After extrusion, the AO samples displayed Vh-and B-type crystalline structures, the B-type polymorph being the dominant one. The AO prototypes demonstrated a 6-fold higher mechanical stress at break and 2.5-fold higher strain at break compared to control starch. Dynamic mechanical analysis showed a significant increase in the storage modulus (E) for AO samples compared to the control. The data support the use of pure starch-based bioplastics devoid of non-polysaccharide fillers.

Thermostable branching enzyme (BE, EC 2.4.1.18) from Rhodothermus obamensis in combination with amylomaltase (AM, EC 2.4.1.25) from Thermus thermophilus was used to modify starch structure exploring potentials to extensively increase the number of branch points in starch. Amylose is an important constituent in starch and the effect of amylose on enzyme catalysis was investigated using amylose-only barley starch (AO) and waxy maize starch (WX) in well-defined ratios. All products were analysed for amylopectin chain length distribution, α-1,6 glucosidic linkages content, molar mass distribution and digestibility by using rat intestinal α-glucosidases. For each enzyme treatment series, increased AO content resulted in a higher rate of α-1,6 glucosidic linkage formation but as an effect of the very low initial branching of the AO, the final content of α-1,6 glucosidic linkages was slightly lower as compared to the high amylopectin substrates. However, an increase specifically in short chains was produced at high AO levels. The molar mass distribution for the enzyme treated samples was lower as compared with substrate WX and AO, indicating the presence of hydrolytic activity as well as cyclisation of the substrate. For all samples, increased amylose substrate showed decreased α- and β-amylolysis. Surprisingly, hydrolysis with rat intestinal α-glucosidases was higher with increasing α-1,6 glucosidic linkage content and decreasing M¯w indicating that steric hindrance towards the α-glucosidases was directed by the molar mass rather that the branching density of the glucan per se. Our data demonstrate that a higher amylose content in the substrate starch efficiently produces α-1,6 glucosidic linkages and that the present of amylose generates a higher M¯w and more resistant product than amylopectin. The combination of BE → AM → BE provided somewhat more resistant α-glucan products as compared to BE alone.

Plant starches regularly require extensive modification to permit subsequent applications. Such processing is usually done by the use of chemical and/or physical treatments. The use of recombinant enzymes produced by large-scale fermentation of GM microorganisms is increasingly used in starch processing and modification, sometimes as an alternative to chemical or physical treatments. However, as a means to impart the modifications as early as possible in the starch production chain, similar recombinant enzymes may also be expressed in planta in the developing starch storage organ such as in roots, tubers and cereal grains to provide a GM crop as an alternative to the use of enzymes from GM microorganisms. We here discuss these techniques in relation to important structural features and modifications of starches such as: starch phosphorylation, starch hydrolysis, chain transfer/branching and novel concepts of hybrid starch-based polysaccharides. In planta starch bioengineering is generally challenged by yield penalties and inefficient production of the desired product. However, in some situations, GM crops for starch bioengineering without deleterious effects have been achieved.

International audience; Piezoelectric thin films are widely used in MEMS and NEMS actuators and resonators, but also in mechanical sensors and energy harvesters for IoT applications and Wireless Sensors Networks. Nanotechnology involving piezoelectric materials is a key research direction, with benefits expected from nanostructuring and the replacement of toxic materials. Piezoelectric nanocomposites based on semiconducting nanowires (NWs) are an alternative to thin films with nanostructuration benefits, such as low temperature fabrication and higher flexibility than thin films. In addition, they exhibit larger piezoelectric coefficient than their thin films counterparts. In this work we study the piezoelectric performance of vertically grown ZnO NWs based on Finite Element simulations in the PFM (Piezoresponse Force Microscopy) configuration. In this AFM (Atomic Force Microscope) mode, the AFM tip is placed in contact with the top surface of the NW while applying a voltage, thus inducing a deformation of the structure by the reverse piezoelectric effect. Different parameters are assessed: the effect of the surrounding air, the NW size and geometry and the effect of the semiconducting properties, in particular the doping level and surface traps density. The results are compared to previous theoretical approaches and experimental findings.