Post-modification of Cellulose Nanocrystal Aerogels with Thiol–Ene Click Chemistry

Aalbers, Guus J.W.; Boott, Charlotte E.; D’Acierno, Francesco; Lewis, Lev; Ho, Joseph Khoa; Michal, Carl A.; Hamad, Wadood Y.; MacLachlan, Mark J.

doi:10.1021/acs.biomac.9b00533

Cited by 30 publications

(20 citation statements)

References 47 publications

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“…Whenever mentioned in this study, E053, E092, and E152 represent cellulose esters with a DS of 0.53, 0.92, and 1.52, respectively. The characteristic peaks at 3423, 2890, 1643, 1421, and 1062 cm -1 in the neat cellulose samples reflected O-H stretching, C-H stretching, C-O-C stretching, CH2 stretching, and C-O stretching, respectively (Poletto et al 2014;Aalbers et al 2019;Shojaeiarani et al 2019). The infrared spectra of cellulose and regenerated cellulose from the DMAc/LiCl solvent were essentially the same.…”

Section: Fourier Transfer Infrared Spectroscopy Analysis Of Betaine-modified Cellulosementioning

confidence: 82%

Esterification of cellulose with betaine using p-toluenesulfonyl chloride for the in-situ activation of betaine

Liu

Wang

Sun

2021

BioRes

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A novel synthesis method was developed for betaine-modified cellulose ester using a mixed N,N-dimethylacetamide/lithium chloride solvent system; p-toluenesulfonyl chloride was used for the in-situ activation of the betaine. The influence of the reaction temperature and time, as well as the anhydroglucose unit to p-toluenesulfonyl chloride to betaine mass ratio on the degree of substitution of the product was evaluated. Increasing the proportion of betaine and p-toluenesulfonyl chloride was beneficial to the esterification reaction. The degree of substitution was 1.68 at 90 °C for 32 h with an anhydroglucose unit to p-toluenesulfonyl chloride to betaine molar ratio of 1 to 2 to 3. The physicochemical properties of the betaine-modified cellulose were closely related to the degree of substitution. Major changes in the morphologies, crystallinity, thermal properties, porosity, and the average degree of polymerization resulted from the modification. The introduction of betaine made cellulose esters thermally less stable than neat cellulose but more difficult to completely degrade. The crystalline structure of the cellulose esters was destroyed, and the products exhibited a porous nature. Dye sorption studies demonstrated that the betaine-modified cellulose holds the potential of adsorbing anionic substances, which is the premise of its application.

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Section: Fourier Transfer Infrared Spectroscopy Analysis Of Betaine-modified Cellulosementioning

confidence: 82%

Esterification of cellulose with betaine using p-toluenesulfonyl chloride for the in-situ activation of betaine

Liu

Wang

Sun

2021

BioRes

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“…Steric hindrance of the thiol compound can be critical to reactivity; bulky thiols may shield some of the surface groups, preventing them from being functionalized 32 . According to previous reports on the surface functionalization of cellulose nanocrystals, 32 the bulkier thiols (i.e. NDM and PFD) yielded a lower proportion of functionalized glucose units, whereas the smaller thiols (i.e.…”

Section: Resultsmentioning

confidence: 99%

“…The values for the extent of conversion of α 13 GB with PFD, NDM and MPD were 48.3%, 27.8% and 81.5%, respectively. Steric hindrance of the thiol compound can be critical to reactivity; bulky thiols may shield some of the surface groups, preventing them from being functionalized 32 . According to previous reports on the surface functionalization of cellulose nanocrystals, 32 the bulkier thiols (i.e.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of α‐1,3‐ and β‐1,3‐glucan esters with carbon–carbon double bonds and their surface modification

Hori

Enomoto-Rogers

Kimura

et al. 2020

Polymer International

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⊍-1,3-glucan and ⊎-1,3-glucan esters with carbon-carbon double bonds (C=C), namely, ⊍-1,3-glucan butenoate (⊍ 13 GB) and ⊎-1,3-glucan butenoate (⊎ 13 GB), were synthesized from 3-butenoic acid and trifluoroacetic anhydride. NMR analysis of the two esters revealed that the 3-butenoyl groups were partially transformed to 2-butenoyl groups. The total degree of substitution (DS total ) of the esters was calculated to be 3.0. According to gel permeation chromatography analysis, ⊍ 13 GB had a molecular weight (M w ) of 2.2 × 10 5 and ⊎ 13 GB had an M w of 11.0 × 10 5 , which was unexpectedly higher than that of the original glucan. This suggests that the ⊎ 13 GB chains were partially and intramolecularly crosslinked via the C=C bond. The ⊍ 13 GB and ⊎ 13 GB obtained had thermal degradation temperatures of 398 and 375°C, respectively, and glass transition temperatures of 117 and 119°C, respectively, which were higher than those of the corresponding saturated glucan butyrates. The surfaces of cast films of the esters were modified with 1H,1H,2H,2H-perfluorodecanethiol, n-dodecyl mercaptan or 3-mercapto-1,-2-propanediol via thiol-ene reactions. Attenuated total reflection Fourier transform infrared spectroscopy and scanning electron microscopy energy-dispersive X-ray spectroscopy analyses revealed that the surface of ⊍ 13 GB was more successfully modified with these thiol compounds than that of ⊎ 13 GB. The water contact angle of the surface of each cast film was measured to evaluate its hydrophobicity and hydrophilicity, and indicated the successful surface modification of the film by the thiol compounds

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“…prepared porous cellulose grafted with epoxidized soybean oil (ESO) in mild conditions, but most notably reported crude oil initial absorption capacity of 37 g/g which after 30 adsorption cycles decreased to 33 g/g or above 90% of initial capacity [193]. Aalbers et al prepared CNC foams functionalized with a methacrylate and then further modified them using thiol-ene click chemistry to prepare five different types of surface modifications, but the authors noted that extensive modification and use of organic solvents lead to the collapse of porous structure and the best result yielded on average 2.90 mL/g per five repeated cycles of xylene absorption [194].…”

Section: Functionalization As a Tool To Enhance The Properties Of Ligmentioning

confidence: 99%

Biorefinery Approach for Aerogels

et al. 2020

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According to the International Energy Agency, biorefinery is “the sustainable processing of biomass into a spectrum of marketable bio-based products (chemicals, materials) and bioenergy (fuels, power, heat)”. In this review, we survey how the biorefinery approach can be applied to highly porous and nanostructured materials, namely aerogels. Historically, aerogels were first developed using inorganic matter. Subsequently, synthetic polymers were also employed. At the beginning of the 21st century, new aerogels were created based on biomass. Which sources of biomass can be used to make aerogels and how? This review answers these questions, paying special attention to bio-aerogels’ environmental and biomedical applications. The article is a result of fruitful exchanges in the frame of the European project COST Action “CA 18125 AERoGELS: Advanced Engineering and Research of aeroGels for Environment and Life Sciences”.

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Post-modification of Cellulose Nanocrystal Aerogels with Thiol–Ene Click Chemistry

Cited by 30 publications

References 47 publications

Esterification of cellulose with betaine using p-toluenesulfonyl chloride for the in-situ activation of betaine

Esterification of cellulose with betaine using p-toluenesulfonyl chloride for the in-situ activation of betaine

Synthesis of α‐1,3‐ and β‐1,3‐glucan esters with carbon–carbon double bonds and their surface modification

Biorefinery Approach for Aerogels

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