New Enzymatically Produced Interpenetrating Starch-Cellulose Gels

Lead Research Organisation: University of Bath
Department Name: Chemistry

Abstract

The project aims to translate existing academic research to enable the production of interpenetrating network (IPN) gels of starch and nanocellulose fibres using side-by-side enzymatic and/or bacterial synthesis routes. These IPN gels will be produced with the end aim of use in the food and home care industries. The project will develop tandem enzymatic processes for the production of small fragments of starch, xyloglucan and cellulose, assembly of components into gels in the presence of water, and characterisation of the mechanical and physical properties of the gels. We will valorise waste, making new products, reducing costs and CO2 emissions for the companies we will support through this technology. Industrial input will guide development of the gels, targetting key industrial applications. No research has yet developed gels based on industrial biotechnology approaches to produce small molecules of starch combining them with cellulose fibrils.

Publications

10 25 50
 
Description We have developed methods of causing functionalised cellulose nanofibrils to interact with soluble starch to form interpenetrating networks that thicken aqueous suspensions of these components at low concentrations, and have evaluated their use in the presence of common formulation ingredients such as small alcohols, salts, surfactants and oils. We have also studied the effects of the aspect ratio of the fibrils, the magnitude and sign of their surface charge, and the presence of fillers of different sizes on the gel network formed and its rheological properties. These building blocks therefore provide a range of thickening agents which have tunable interactions based on the addition of salts and alcohols, and which can be utilised for the development of further soft materials systems. To this end, using our functionalised cellulose and starch components, we have developed emulsions stabilised using functionalised cellulose nanofibrils and demonstrated long term stability of the emulsions and slow release of actives from the emulsions. We have also developed methods to use partially oxidised cellulose nanofibrils in formation of capsules for enzyme entrapment, and produced and studied biodegradable clear flexible films produced from functionalised cellulose-starch mixtures. Ongoing work is applying these polysaccharide building blocks as components of microcapsules towards replacement of plastic microcapsules in aqueous formulations and in non-aqueous gels which are non-volatile and have high conductivity with potential application in biomedical sensors.
Exploitation Route The reported starch and modified cellulose rheology modifiers in interaction with surfactants, inorganic particles, salts, oils and alcohols could be used in many different forms of aqueous formulations including fast moving consumer goods such as sunscreens, insect repellant creams and sprays, hand sanitisers, shower gels and moisturising creams or in formulations such as paints, lubricants, foods, cosmetics, therapeutic creams and gels or pesticide and herbicide mixtures. They provide stable shear thinning formulations at low solids content, with good suspending power, using bio-derived, and biodegradable materials which can be prepared from waste (paper, sawdust etc) using relatively "green" synthesis methods, so if supply chains could be developed these materials could provide useful formulation components for the future. The modified cellulose and starch components can also be used for development of biodegradable materials such as thin films and microcapsules with tunable properties for replacement of petrochemically derived polymers in such applications and these are areas where we, and others are now moving in this research.
Sectors Agriculture, Food and Drink,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

 
Description Our findings have been used by our company partners to evaluate the use of functionalised cellulose nanofibrils and starches as aqueous rheology modifiers in various formulations for fast moving consumer goods. They are also evaluating modified cellulose/starch films as replacements for synthetic polymers in laundry capsules.
First Year Of Impact 2019
Sector Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description Member of STFC Science Board
Geographic Reach National 
Policy Influence Type Participation in a advisory committee
 
Description Polysaccharide based formulation ingredients for use in fast moving consumer goods
Amount £41,346 (GBP)
Organisation Unilever 
Sector Private
Country United Kingdom
Start 10/2019 
End 09/2023
 
Description Solution and Interfacial Properties of Biosourced Anionic Surfactants
Amount £132,696 (GBP)
Funding ID ICASE voucher 20000191 
Organisation Unilever 
Sector Private
Country United Kingdom
Start 10/2020 
End 09/2024
 
Title Dataset for "Alcohol induced gelation of TEMPO-oxidized cellulose nanofibril dispersions" 
Description The data set contains ASCII files (tab delimited) for the following: - Oscillatory frequency sweeps for OCNF dispersions in water/ethanol dispersions with alcohol content varying from 10 to 60 wt% at 10wt% steps. - Dependence of shear storage modulus and on the ethanol concentration. - Shear storage modulus values for OCNF hydrogels at 50 wt% of alcohol. - Dependence of tan delta with the alcohol content on OCNF dispersions. - Oscillatory frequency sweeps for OCNF dispersions in water/ethanol with OCNF content varying from 0.4 to 1.2 wt% at 0.2 wt% steps. - Dependence of tan delta on the OCNF concentration for methanol, ethanol, 1- and 2- propanol. - Dependence of storage modulus on the OCNF concentration for methanol, ethanol, 1- and 2- propanol. - Flow curves for OCNF dispersions in water/ethanol with alcohol content varying from 00 to 60 wt% at 10wt% steps. - SAXS curves and fits for OCNF dispersions in water/ethanol dispersions with alcohol content varying from 10 to 50 wt% at 10wt% steps. Parameters obtained from SAXS data fitting: - Dependence of Rmax and Rmin on ethanol concentration. - Dependence of ?RPA on ethanol concentration. - SEM images of 0.8 wt% OCNF dispersions freeze dried and supercritically dried from methanol and ethanol. 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Dataset for "Composite hydrogel spheroids based on cellulose nanofibrils and nanofibrous chiral coordination polymer by green synthesis" 
Description This dataset contains data combined SAXS/WAXS data, rheology data, optical microscopy data (extracted using ImageJ) and powder X-ray diffraction data for hydrogel spheroids based on TEMPO-oxidised cellulose nanofibrils and a nanofibrous copper(II) aspartate coordination polymer. The data are provided in the form of Excel files and relate to figures presented in the main text and supplementary information of the publication "Composite hydrogel spheroids based on cellulose nanofibrils and nanofibrous chiral coordination polymer by green synthesis". The file "Fig3B_data_SAXS-WAXS.xlsx" contains combined SAXS and WAXS data for the main text Figure 3B, which comprises combined SAXS and WAXS patterns for pure Cu-Asp as reference (prepared in water) and OCNF dispersions containing L-Asp at the following concentrations: a) 0 mM (control sample), b) 50 mM, c) 75 mM, d) 100 mM and e) 125 mM. The file "Fig4_data_rheology1.xlsx" contains rheology data for the main text Figure 4, which comprises plots of G* and tan(delta) for OCNF dispersions containing L-Asp as a function L-Asp concentration in the range 0-150 mM. The file "Fig6B_data_time-lapse-optical-microscopy.xlsx" contains data for the main text Figure 6B from time lapse optical microscopy, extracted using ImageJ as detailed in the manuscript. Relative image darkness (proportional to crystallite density), d, is plotted as a function of time for 100 microL of OCNF dispersions with the following ligand concentrations: a) 50 mM L-Asp only (measured in triplicate); b) 50 mM L-Asp + 15 mM D-Asp (measured in triplicate) and c) 50 mM L-Asp + 50 mM D-Asp (measured in duplicate). The file "FigS1_data_PXRD.xlsx" contains powder X-ray diffraction (PXRD) data for the supplementary information Figure S1, where PXRD patterns are presented for: a) [Cu(L-Aspartate)]n; b) Cu(D-Aspartate)]n as described by I. Imaz, M. Rubio-Martínez, W. J. Saletra, D. B. Amabilino, D. Maspoch, J. Am. Chem. Soc. 2009, 131, 18222 (diffraction data extracted from the cited paper) and c) Cu-Asp prepared in water as a reference sample as part of the present study, from copper nitrate and L-Asp. The file "FigS5_data_rheology2.xlsx" contains rheology data for the supplementary information Figure S5, which comprises plots of G* and tan(delta) for OCNF dispersions containing 50 mM L-Asp (with 100 mM NaOH) and doped with D-Asp at concentrations of 0 mM to 50 mM (with 0 to 100 mM NaOH, accordingly) showing no considerable changes as a function of D-Asp mole fraction. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://researchdata.bath.ac.uk/id/eprint/905
 
Title Dataset for "Core-shell spheroidal hydrogels produced via charge-driven interfacial complexation" 
Description The dataset for "Core-Shell spheroidal Hydrogels produced via charge-driven interfacial complexation" contains data, in the form of excel and txt files, for the figures shown in the main manuscript and the electronic supplementary information (ESI). The study focuses on the structure of the spheroidal hydrogels (SH) and their resilience in aqueous media. Furthermore, SH are used as microreactors for biocatalysis, providing a proof-of-concept for this material. The dataset contains data regarding the structural information of the spheroidal hydrogels (SH) (e.g. shell thickness, small angle X-rays scattering, Z-potential and oscillatory rheology) their stability in solvents with different osmotic pressure and ionic strength (e.g. swelling kinetic, swelling ratio) and the enzymatic activity to support a proof-of-concept of the SH. Specification of the materials and methods employed throughout the data collection are available in the main manuscript. Each excel sheet is specific for a set of data acquired utilising the same protocol. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact N/A 
 
Title Dataset for "Deep Eutectic Solvent in Water Pickering Emulsions Stabilised by Cellulose Nanofibrils" 
Description These files contain raw SAXS, rheology, and laser diffraction data associated with the paper titled "Deep Eutectic Solvent in Water Pickering Emulsions Stabilised by Cellulose Nanofibrils" in the form of .txt files. This includes information on menthol:dodecanoic acid in water emulsions stabilised with cellulose nanofibrils as well as starch, Tween-20, and SDS. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://researchdata.bath.ac.uk/id/eprint/920
 
Title Dataset for "Filler size effect in an attractive fibrillated network: a structural and rheological perspective" 
Description The dataset for "Filler size effect in an attractive fibrillated network: a structural and rheological perspective" contains data, in the form of excel and txt files, for the figures shown in the main manuscript and the electronic supplementary information (ESI). Each excel sheet is specific for a set of data acquired utilising the same protocol. Rheological and scattering data are provided and specifications regarding each dataset can be found in the dataset description. This study is conducted to unravel how the size of colloidal fillers modulates the structure-property relationship of hydrogels composed by a fibrillated network. Specification of the materials and methods employed throughout the data collection are available in the main manuscript. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
Impact N/A 
 
Title Dataset for "Impact of wormlike micelles on nano and macroscopic structure of TEMPO-oxidized cellulose nanofibrils hydrogels" 
Description The data set contains ASCII files (comma delimited) for the following: - Small-angle neutron scattering (SANS) curves and fits for cocamidopropyl betaine (CAPB), cocamidopropylamine oxide (CAPOx) and sodium lauroyl sarcosinate (SLS) as a function of the surfactant concentration in sodium chloride (NaCl) 1wt% in 100% heavy water (deuterium oxide, D2O). - SANS curves and fits for CAPB/sodium dodecyl sulphate (SDS), CAPOx/SDS and CAPB/SLS as a function of the surfactant concentration in NaCl 1wt% in 100% D2O. - Oscillatory shear frequency sweeps for CAPB/SDS and CAPOx/SDS solution at 60/60 mM of surfactant in aqueous NaCl 1wt%. - SANS curves and fits for CAPB, CAPOx and SLS mixtures as a function of the surfactant concentration in oxidized cellulose nanofibrils (OCNF) 1wt% in aqueous NaCl 1wt% in 100% D2O. - Oscillatory shear frequency sweeps for CAPB, CAPOx and SLS mixtures as a function of surfactant concentration in OCNF 1wt% in aqueous NaCl 1wt%. - Oscillatory shear frequency sweeps for CAPB/SDS, CAPOx/SDS and CAPB/SLS mixtures as a function of surfactant concentration in OCNF 1wt% in aqueous NaCl 1wt%. - Oscillatory shear amplitude sweeps CAPB/SDS, CAPOx/SDS and CAPB/SLS mixtures as a function of surfactant concentration in OCNF 1wt% in aqueous NaCl 1wt%. - SANS curves and fits for CAPB/SDS in 100wt% D2O, CAPOx/SDS in 100wt% D2O and CAPB/SDS in 15wt% D2O mixtures as function of the surfactant concentration in OCNF 1wt%/NaCl 1wt%. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://researchdata.bath.ac.uk/id/eprint/797
 
Title Dataset for "Microstructural, thermal, crystallization and water absorption properties of films prepared from never-dried and freeze-dried cellulose nanocrystals" 
Description Self-assembled cellulose film was prepared from a stable aqueous dispersion of ND CNCs using the air-drying process at room temperature. For comparison, another pure cellulose film was prepared from the FD CNCs (which also produced from the same ND CNC suspension after quickly freezing using liquid nitrogen followed by freeze-drying) via casting from their aqueous suspension. The dataset contains the raw data highlighting the influence of the microstructures created during the air and freeze-drying processes on nanoscale structure (measured by small-angle x-ray scattering (SAXS)), light transparency (UV-visible), chemical (FTIR), thermal (TGA, DSC), crystallization (XRD) and water contact angle properties of the cellulose nanocrystal films. 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://researchdata.bath.ac.uk/id/eprint/930
 
Title Dataset for "Non-Volatile Conductive Gels Made From Deep Eutectic Solvents and Oxidised Cellulose Nanofibrils". 
Description This dataset contain SAXS, rheology, and conductivity data associated with the paper titled "Non-Volatile Conductive Gels Made From Deep Eutectic Solvents and Oxidised Cellulose Nanofibrils" in the form of tab-separated value (TSV) .txt files. 
Type Of Material Database/Collection of data 
Year Produced 2021 
Provided To Others? Yes  
Impact too early to say 
 
Title Dataset for "Surfactant controlled zwitterionic cellulose nanofibril dispersions" 
Description Dataset for each figure appearing in the manuscript, "Surfactant controlled zwitterionic cellulose nanofibril dispersions". Fig. 2 shows the z-potential (mV) of ZCNF and OCNF dispersions as a function of pH. The average and standard deviation of values obtained for duplicate samples are reported. Fig. 3 shows the z-potential (mV) of ZCNF dispersions at 0.01 wt% upon addition of 25 mM SDS, 25 mM DTAB and 25 mM TW80 is presented as an average of measurements on duplicate samples. Fig. 4 shows the surface tension at the air-water interface (gamma-aw) of 0.001 wt% ZCNF dispersions upon addition of (a) 125 mMSDS,(b) 125 mM DTAB and (c) 2.5 mM TW80. The average of duplicate measurements is reported. Fig. 6 shows the relative viscosity (eta-r) as a function of shear rate (s-1) for 0.5 wt% ZCNF dispersions containing (a) SDS, (b) DTAB and (c) TW80. Fig. 7 shows the relative viscosity (eta-r) as a function of the shear rate (s-1) for 0.5 wt% ZCNF containing 50 mM SDS, 50 mM DTAB and 50 mM TW80. Fig. 8 shows the SANS data for 0.5 wt% ZCNF dispersions in the presence of 1 mM d-SDS and 5mMd-DTAB in D2O. The data were fitted with a model of cylinder with an elliptical cross section. The intensity (I) is given in arbitrary units (A.U.). 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Dataset for "TEMPO-oxidized cellulose nanofibrils; probing the mechanisms of gelation via Small Angle X-Ray Scattering" 
Description These data are associated with the study of oxidized cellulose nanofibril (OCNF) suspensions upon concentration and salt. The set includes TEM (transmission electron microscopy) and cryo-TEM micrographs, rheology files, SAXS (small-angle X-ray scattering) data and SAXS fits. 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Dataset for "Understanding heat driven gelation of anionic cellulose nanofibrils: Combining Saturation Transfer Difference (STD) NMR, Small Angle X-ray Scattering (SAXS) and rheology" 
Description This dataset contains the data underlying the figures in the paper "Understanding heat driven gelation of anionic cellulose nanofibrils: Combining Saturation Transfer Difference (STD) NMR, Small Angle X-ray Scattering (SAXS) and rheology". The data for figure 4 (SAXS) is given as four different data files: Figure 4(a) Oxidised cellulose nanofibrils (OCNF) at 25 °C and OCNF at 25°C after annealing at 80°C and Figure 4(b) cationic cellulose nanofibrils (CCNF) at 25 °C and CCNF at 25°C after annealing at 80°C as explained in the materials and methods of the main manuscript. In a similar fashion, the Fig. ESI3 and Fig. ESI6 files contain the data underlying figures 3 and 6 of the electronic supplementary information. 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Dataset for 'Cationic surfactants as a non-covalent linker for oxidised cellulose nanofibrils and starch-based hydrogels' 
Description Rheological properties of hydrogels composed of TEMPO-oxidised cellulose nanofibrils (OCNF)-starch in the presence of cationic surfactants were investigated in this study. The dataset includes rheology (oscillatory frequency and amplitude sweeps, viscosity), zeta-potential, starch-iodine test data of OCNF/starch hydrogels in presence of cationic surfactants, like dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB) surfactants. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
Impact N/A 
 
Title Dataset for Charge-driven interfacial gelation of cellulose nanofibrils across the water/oil interface 
Description The Dataset for Charge-driven interfacial gelation of cellulose nanofibrils across the water/oil interface contains data, in the form of Excel files, for the figures shown in the associated manuscript and the supplementary information. Each Excel file is specific for a set of data acquired utilising the same protocol. In the Excel file named "Data_rheology_Fig2_3_S4_S5", the rheological data presented in Figures 2 and 3 of the manuscript and Figures S4 and S5 from the supplementary information are shown. The data are subdivided in different spreadsheets in according to the concentration of oxidised cellulose nanofibrils (OCNF) and ionic strength employed (NaCl concentration in mM), as specified at the top of each spreadsheet. In the Excel file named "Data_rheology_Fig4", the rheological data presented in Figure 4 are shown. For all the rheological data, parameters as Gi* (N/m), tani(d) (-), Gi' (N/m) and Gi'' (N/m) are given as function of time (h) or strain amplitude (%) as shown in the relative figures. In the Excel file named "Data_surface tension_Fig_S1", the surface tension measured at the oil-air interface (gamma, mN/m) as a function of Oleylamine (OA) concentration (mM) is given as illustrated in Figure S1 from the supplementary material. Specification of the materials and methods employed throughout the data collection are available in the associated manuscript. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
Impact N/A 
 
Description Gelenz - New Enzymatically Produced Interpenetrating Starch-Cellulose Gels 
Organisation Croda International
Country United Kingdom 
Sector Private 
PI Contribution Bath researchers provide expertise in gelation of partially oxidised cellulose and starch materials and their characterisation by rheology and small angle scattering techniques.
Collaborator Contribution Bristol heads the Gelenz partnership, and provides expertise in cellulose nanocrystal materials, UEA brings expertise in advanced NMR techniques and solid state NMR, Manchester (formerly JIC) provides expertise in enzymatic modification of cellulose materials. Croda and Unilever provide advice on potential commercial interest of the work. Croda has tested some materials in their labs.
Impact please see publication list. The collaboration is multidisciplinary involving biologists, physical chemists and engineers (see above).
Start Year 2016
 
Description Gelenz - New Enzymatically Produced Interpenetrating Starch-Cellulose Gels 
Organisation Unilever
Country United Kingdom 
Sector Private 
PI Contribution Bath researchers provide expertise in gelation of partially oxidised cellulose and starch materials and their characterisation by rheology and small angle scattering techniques.
Collaborator Contribution Bristol heads the Gelenz partnership, and provides expertise in cellulose nanocrystal materials, UEA brings expertise in advanced NMR techniques and solid state NMR, Manchester (formerly JIC) provides expertise in enzymatic modification of cellulose materials. Croda and Unilever provide advice on potential commercial interest of the work. Croda has tested some materials in their labs.
Impact please see publication list. The collaboration is multidisciplinary involving biologists, physical chemists and engineers (see above).
Start Year 2016
 
Description Gelenz - New Enzymatically Produced Interpenetrating Starch-Cellulose Gels 
Organisation University of Bristol
Country United Kingdom 
Sector Academic/University 
PI Contribution Bath researchers provide expertise in gelation of partially oxidised cellulose and starch materials and their characterisation by rheology and small angle scattering techniques.
Collaborator Contribution Bristol heads the Gelenz partnership, and provides expertise in cellulose nanocrystal materials, UEA brings expertise in advanced NMR techniques and solid state NMR, Manchester (formerly JIC) provides expertise in enzymatic modification of cellulose materials. Croda and Unilever provide advice on potential commercial interest of the work. Croda has tested some materials in their labs.
Impact please see publication list. The collaboration is multidisciplinary involving biologists, physical chemists and engineers (see above).
Start Year 2016
 
Description Gelenz - New Enzymatically Produced Interpenetrating Starch-Cellulose Gels 
Organisation University of East Anglia
Country United Kingdom 
Sector Academic/University 
PI Contribution Bath researchers provide expertise in gelation of partially oxidised cellulose and starch materials and their characterisation by rheology and small angle scattering techniques.
Collaborator Contribution Bristol heads the Gelenz partnership, and provides expertise in cellulose nanocrystal materials, UEA brings expertise in advanced NMR techniques and solid state NMR, Manchester (formerly JIC) provides expertise in enzymatic modification of cellulose materials. Croda and Unilever provide advice on potential commercial interest of the work. Croda has tested some materials in their labs.
Impact please see publication list. The collaboration is multidisciplinary involving biologists, physical chemists and engineers (see above).
Start Year 2016
 
Description Gelenz - New Enzymatically Produced Interpenetrating Starch-Cellulose Gels 
Organisation University of Manchester
Country United Kingdom 
Sector Academic/University 
PI Contribution Bath researchers provide expertise in gelation of partially oxidised cellulose and starch materials and their characterisation by rheology and small angle scattering techniques.
Collaborator Contribution Bristol heads the Gelenz partnership, and provides expertise in cellulose nanocrystal materials, UEA brings expertise in advanced NMR techniques and solid state NMR, Manchester (formerly JIC) provides expertise in enzymatic modification of cellulose materials. Croda and Unilever provide advice on potential commercial interest of the work. Croda has tested some materials in their labs.
Impact please see publication list. The collaboration is multidisciplinary involving biologists, physical chemists and engineers (see above).
Start Year 2016