The effect of cellulose nanocrystals on latex and adhesive properties in emulsion- based polymer nanocomposites

Pressure sensitive adhesives (PSAs) adhere quickly and firmly to surfaces with the application of light pressure, and can be removed without leaving a residue. Their mechanical performance is measured by tack, peel strength and shear strength. A balanced combination between the three mechanical performance measurements depends on the specific end-use application and is challenging to achieve. This is particularly so when replacing solvent-based technologies with more sustainable, water-based (i.e., emulsion polymerization) technologies. PSAs synthesized using emulsion polymerization tend to have a lower shear strength due to poor gel network formation. As a result, conventional emulsion-based PSAs suffer from the inability to increase certain adhesive properties (e.g., tack and peel strength) while simultaneously increasing shear strength. Nanomaterials are often used in polymer composites to improve polymer properties (e.g., tensile strength). They are particularly effective in low quantities (e.g., \u3c2 \u3ewt.%) because of their high surface area. Cellulose nanocrystals (CNCs) are a “green alternative” to common nanomaterials and are isolated from natural cellulose. CNCs have been used more commonly, in the past, as rheological modifiers and interface stabilizers.[1] Because CNCs form colloidally stable dispersions in water, they can be incorporated/processed in water-based systems, eliminating the need for organic solvents.[2] The most common method to produce CNCs is through acid hydrolysis with sulfuric acid; this process preferentially degrades the disordered cellulose regions and leaves behind the crystalline CNCs with grafted anionic sulfate half ester groups.[1] The resulting nanoparticles are whisker-shaped and have a high aspect ratio.[3] CNCs provide composite material reinforcement in the range of other nanomaterials. In the past, CNCs have been blended with polymers and significant strength improvements were noted.[4] Our studies demonstrate how to incorporate CNCs in a nanocomposite using an in situ semi-batch emulsion polymerization protocol.[5] PSA nanocomposite films were generated for a broad variety of copolymer systems including monomers such as iso-butyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, styrene and vinyl acetate. In all cases, the monomer composition of the reaction formulations was manipulated to achieve a suitable range of polymer glass transition temperatures. CNC loadings were varied from 0 to 0.5 to 1 wt.% (based on monomer weight). The addition of CNC was shown to significantly and simultaneously increase tack, peel strength, and shear strength.[6] References [1] Dufresne, A., Nanocellulose, De Gruyter, Saint Martin D’Heres Cedex, France 2012. [2] Flauzino Neto, W. P., Mariano, M., da Silva, I. S. V., Silvério, H. A., Putaux, J.-L., Otaguro, H., Pasquini, D., Dufresne, A., Carbohydr. Polym. 2016, 153, 143. [3] Moon, R. J., Martini, A., Nairn, J., Simonsen, J., Youngblood, J., Chem. Soc. Rev., 2011, 40, 3941. [4] Rajisha, K. R., Maria, H. J., Pothan, L. A., Ahmad, Z., Thomas, S., Int. J. Biol. Macromol., 2014, 67, 147. [5] Dastjerdi, Z., Cranston, E. D., Dubé, M. A., Macromol. React. Eng., 2018, in press. [6] Dastjerdi, Z., Cranston, E. D., Dubé, M. A., Int. J. Adh. Adh. 2018, 81, 36-42

Transmission Electron Microscopy for the Characterization of Cellulose Nanocrystals

Cellulose nanocrystals (CNCs) are high aspect ratio nanomaterials readily obtained from cellulose microfibrils via strong acid hydrolysis. They feature unique properties stemming from their surface chemistry, their crystallinity, and their three-dimensional structure. CNCs have been exploited in a number of applications such as optically active coatings, nanocomposite materials, or aerogels. CNC size and shape determination is an important challenge and transmission electron microscopy (TEM) is one of the most powerful tools to achieve this goal. Because of the specifics of TEM imaging, CNCs require special attention. They have a low density, are highly susceptible to electron beam damage, and easily aggregate. Specific techniques for both imaging and sampling have been developed over the past decades. In this review, we describe the CNCs, their properties, their applications, and the need for a precise characterization of their morphology and size distribution. We also describe in detail the techniques used to record quality images of CNCs. Finally, we survey the literature to provide readers with specific examples of TEM images of CNCs

Pressure sensitive adhesives produced by in-situ emulsion polymerization of cellulose nanocrystal-poly(nBA-VAc)

Pressure sensitive adhesives (PSAs) are conventionally produced using a variety of polymerization methods such as emulsion, solution, or radiation curing. Environmental concerns favor the development of emulsion polymerization based PSAs.[1] However, maintaining and controlling the PSA properties achievable from solution polymerization in PSAs produced by emulsion polymerization remains challenging. Depending on the particular adhesive application, PSA properties are largely guided by the polymer glass transition temperature and the polymer microstructure. The latter is controlled in a variety of ways but typically via the addition of chain transfer agents and crosslinkers.[2] During the last decades, efforts in PSA property manipulation have included the preparation of nanocomposite latexes by introducing nanomaterials such as titanium dioxide, silica, and carbon nanotubes into the formulations.[3] On the other hand, utilizing cellulose nanocrystals (CNCs) as a sustainable source of reinforcement in polymers is emerging rapidly.[4] CNCs are the product of controlled hydrolysis of plant based tissues, through which crystalline domains of cellulose are isolated from the disordered parts of the raw material. High aspect ratio, surface activity and modulus, as well as non-toxic nature of CNCs make them ideal candidates for use in nanocomposite formulations. More recently, our group have prepared CNC nanocomposite PSAs which were revealed to significantly and simultaneously improve tack, peel strength and shear strength in the PSA films.[5] The ability to improve tack and peel strength without decreasing shear strength overcomes a major challenge in PSA formulation. We will present results from emulsion polymerization of n-butyl acrylate/vinyl acetate/CNC nanocomposite PSAs. We will identify the location of the CNCs relative to the latex particles and show their effect on latex viscosity, gel content, and PSA properties. The goal of these new results is to show how the manipulation of the reaction formulation (e.g., monomer feed ratio, surfactant type) will affect the distribution and relative location of the CNCs in the polymer latex and ultimately the PSA properties. [1] Jovanović, R., Dubé, M. A., J. Macromol. Sci., Part C, 44:1, 1-51, 2004. [2] Qie, L., Dubé, M. A., 46, 1225–1236, 2010. [3] Dastjerdi, Z., Cranston, E. D., Berry, R. Fraschini, C., Dubé, M. A., J. Matls. Sci., submitted January 2018. [4] Lee, K-Y., Aitomäki, Y., Berglund, L. A., Oksman, K., Bismarck, A., Compos. Sci. Technol. 105, 15–27, 2014. [5] Dastjerdi, Z., Cranston, E. D., Dubé, M. A., Macromol. React. Eng., 11, 1700013, 2017. [6] Dastjerdi, Z., Cranston, E. D., Dubé, M. A., Int. J. Adh. Adh., 81, 36-42, 201

Synthèse de maltooligosaccharides linéaires et cycliques régiosélectivement modifiés par voie chimique et/ou enzymatique

Le premier volet de ce travail décrit la synthèse de nouvelles cyclodextrines sélectivement oxydées solubles dans l'eau, grâce à l'utilisation du radical TEMPO en tant que médiateur chimique en présence d'hypochlorite de sodium. L'optimisation des conditions réactionnelles a été réalisée à l'aide d'un plan d'expériences et permet un contrôle optimal du taux d'oxydation des hydroxyles primaires. Les propriétés de complexation du monodérivé avec des composés modèles appartenant à la famille des aromatiques ont été étudiées par RMN du proton. Le deuxième volet concerne la synthèse, par voie chimio-enzymatique, de maltooligosaccharides sélectivement modifiés à partir de cyclodextrines monofonctionnalisées. Ces composés, difficiles d'accès par une approche purement "chimique", ont été obtenus avec d'excellents rendements. De cette étude, de nouvelles informations concernant les spécificités des sites actifs de la CGTase et de l'amyloglucosidase ont été obtenues.GRENOBLE1-BU Sciences (384212103) / SudocSudocFranceF

Modification of Nanocrystalline Cellulose for Bioactive Loaded Films

Despite the use of petrochemical derived packaging, many problems such as browning and food spoilage still happen in food after harvesting. There is an increasing consumers concern for food shelf life to be extended as much as possible along with a big interest in green and bioactive materials, that could be used in direct contact with aliments. In order to reach public demand, biopolymers coming from natural sources such as plants or animals have been used to replace synthetic materials. Even though natural polymers are biodegradable, they do not reach regulations required with respect to mechanical properties in commercial applications. However, the mechanical properties can be improved when reinforced with nanoparticles. Several reinforcing nanoparticules such as clays, silica or silver have been used for industrial applications, but cellulose nanocrystals (CNCs) are a better choice for food industry due to their biodegradable and biocompatible nature as well as their outstanding potential in improving mechanical and barrier properties of nanocomposites. CNCs consist of anhydroglucopyranose units (AGU) linked together and several functional hydroxyl groups found on its surface. Modifications of the CNC surface chemistry can give to cellulose new functionalities that open the way to the development of new bioactive reinforcement in food packaging. The present review will be focused on covalent and non covalent modifications that can be achieved on surface CNC with the aim of adding functionalities to be applied for food industry

Gamma-Irradiation of Cellulose Nanocrystal (CNS): Investigation ofPhysicochemical Properties for Irradiated CNC/ALGINATE Based Beads

Irradiation was performed in dispersed suspensions of cellulosenanocrystals (CNCs). A formation of carboxylic acid and aldehyde groups was observed when gamma irradiation doses were applied from 0 to 80 kGy. Changes in FTIR spectra confirmed the changes of CNC upon irradiation treatment at wavelengths of 1750 and 1650 cm-1of ketones and adsorbed water on CNC surface respectively. These new functional groups improved hydrophilic character of CNC, tested by the decrease of interaction angle between irradiated CNC films and droplet of water. Concerning the degree of polymerization (DP) of CNC, it was found by gel permeation chromatography that DP decreases from 135 (native) to 95 (80 kGy CNC). It was suggested that low molecular weight of CNC and high aldehyde content may enhance the antiradical properties observed in irradiated CNC compared to native CNC

Effect of the optimized selective enrichment medium on the expression of the p60 protein used as Listeria monocytogenes antigen in specific sandwich ELISA

International audienceThis paper presents the effects of the composition of different media (i.e., Tryptic soy broth (TSB), Brain heart infusion (BHI), Listeria enrichment broth (LEB), Fraser broth (FB) and University of Vermont medium (UVM)) on the detection of a short peptide fragment PepD specific to the p60 protein (p60) of L. monocytogenes by a monoclonal antibody (anti-PepD mAb). Expression of the p60 obtained was demonstrated to be proportional to the cellular growth of Listeria monocytogenes regardless of the tested growth medium. However, the early growth of L. monocytogenes and the expression of the p60 were negatively affected by the presence of selective agents present in LEB, FB and UVM. Among those three selective enrichment media commonly used for L. monocytogenes, LEB allowed a better expression of L. monocytogenes p60 after an incubation period of 18 h. Optimization of the LEB revealed that the dextrose concentration was the critical factor for improving the expression of p60 and promotes the early expression of p60. Moreover, an optimal dextrose concentration of 0.5% (w/v) in LEB, coupled with anti-PepD mAb immobilized to solid support, reduced the detection of p60 from 18 h to 9 h for an initial concentration of L. monocytogenes of 108 CFU/ml

Free radical grafting of gallic acid (GA) on cellulose nanocrystals (CNCS) and evaluation of antioxidant reinforced gellan gum films

International audienceAntiradical properties were introduced on cellulose nanocrystals (CNCs) by redox pair (RP) initiator and γ-radiation treatments. Different procedures were tested on CNC, first a 2 h reaction of hydrogen peroxide (H2O2)/ascorbic acid (AA) was performed on CNC solution. γ-Radiation treatment at 20 kGy dose was then applied and immediately after GA was reacted during 24 h with the pretreated CNCs, giving CNC-H2O2-AA-γ-GA. The formation of new carboxylic acids and carbonyl groups were characterized by FT-IR at 1650 and 1730 cm−1 respectively. Carboxylic acid functionalities were also analyzed by conductometric titration where an increase from 49 to 134 mmol COOH kg−1 was found from native to irradiated CNCs. A similar increase in the carboxylic acid content (132 mmol kg−1) was observed for CNC-H2O2-AA-γ-GA, showing the highest radical scavenging properties (8 mM Trolox eq/mg CNC). Thermogravimetric analysis confirmed the structural changes onto CNC. Film packaging containing 20% of CNC-H2O2-AA-γ-GA was then added to a gellan-based film packaging. A significant improvement (p<0.05) of the tensile strength (TS), the tensile modulus (TM) and the elongation at break (EB) and water vapor permeability reduction was observed when CNC-H2O2-AA-γ-GA was added to the film packaging formulation

Alginate based nanocomposite for microencapsulation of probiotic: Effect of cellulose nanocrystal (CNC) and lecithin.

International audienceProbiotic (Lactobacillus rhamnosus ATCC 9595) was encapsulated in alginate-CNC-lecithin microbeads to produce nutraceutical microcapsules. Addition of CNC and lecithin in alginate microbeads (ACL-1) improved the viability of L. rhamnosus during gastric passage and storage. The compression strength of the freeze-dried ACL-1 microbeads improved 40% compared to alginate microbeads alone. Swelling studies revealed that addition of CNC and lecithin in alginate microbeads decreased (around 47%) the gastric fluid absorption but increased the dissolution time by 20min compared to alginate microbeads (A-0). During transition through the gastric passage, the viability of L. rhamnosus in dried ACL-1 microbeads was increased 37% as compared to A-0 based beads. At 25 and 4°C storage conditions, the viability of L. rhamnosus encapsulated in ACL-1 microbeads decreased by 1.23 and 1.08 log respectively, whereas the encapsulation with A-0 microbeads exhibited a 3.17 and 1.93 log reduction respectively