Deuterium and Cellulose: A Comprehensive Review

Reishofer, David; Spirk, Stefan

doi:10.1007/12_2015_321

Cited by 11 publications

(4 citation statements)

References 67 publications

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“…201 A common method by which to quantify the availability of hydroxy groups in cellulosic materials is to substitute the hydrogen in available hydroxy groups for deuterium through a water/deuterium oxide (H−D) solvent exchange. 202 The availability of hydroxy groups for solvent exchange is dependent on a number of factors: (i) their position in the cellulose chain (i.e., 2-, 3-, or 6-position), (ii) whether they are within the ordered or disordered region of the cellulose microfibril, and (iii) whether they are located on the surface or embedded within the crystallite (microfibril). The hydrogen atoms in the HO(2) and HO (6) hydroxy groups can act as hydrogen-bond donors to water, but the HO(3) behaves as a hydrogen-bond acceptor from water and donor to their intrachain neighbors O(5) (see, Figure 1).…”

Section: Water and Nanocellulosementioning

confidence: 99%

“…While cellulose–cellulose hydrogen bonds often take precedence over cellulose–water hydrogen bonds (hence the insolubility of cellulose in water), there is also an abundance of hydroxy groups on the crystallite surface that have the propensity to hydrogen bond with water . A common method by which to quantify the availability of hydroxy groups in cellulosic materials is to substitute the hydrogen in available hydroxy groups for deuterium through a water/deuterium oxide (H–D) solvent exchange . The availability of hydroxy groups for solvent exchange is dependent on a number of factors: (i) their position in the cellulose chain (i.e., 2-, 3-, or 6-position), (ii) whether they are within the ordered or disordered region of the cellulose microfibril, and (iii) whether they are located on the surface or embedded within the crystallite (microfibril).…”

Section: Fundamentals Of Cellulose– and Nanocellulose–water Interactionsmentioning

confidence: 99%

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Understanding Nanocellulose–Water Interactions: Turning a Detriment into an Asset

et al. 2023

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Modern technology has enabled the isolation of nanocellulose from plant-based fibers, and the current trend focuses on utilizing nanocellulose in a broad range of sustainable materials applications. Water is generally seen as a detrimental component when in contact with nanocellulose-based materials, just like it is harmful for traditional cellulosic materials such as paper or cardboard. However, water is an integral component in plants, and many applications of nanocellulose already accept the presence of water or make use of it. This review gives a comprehensive account of nanocellulose–water interactions and their repercussions in all key areas of contemporary research: fundamental physical chemistry, chemical modification of nanocellulose, materials applications, and analytical methods to map the water interactions and the effect of water on a nanocellulose matrix.

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Section: Water and Nanocellulosementioning

confidence: 99%

Section: Fundamentals Of Cellulose– and Nanocellulose–water Interactionsmentioning

confidence: 99%

Understanding Nanocellulose–Water Interactions: Turning a Detriment into an Asset

et al. 2023

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“…In terms of cellulosic materials, one of the main interaction parameters in solution, and in the solid state, is hydrogen bonding. , The O–H vibrations are typically very prominent in IR spectra and can be used to track changes in the supramolecular structure of cellulose, as well as to indicate interactions with alien substances. − In combination with rheometry, IR spectroscopy is capable of highlighting the failures of hydrogen-bonded networks upon shear. In the case of CNCs, this can be exploited to detect the failure of hydrogen bonds in a gel or in dispersions as a function of shear.…”

Section: Analysis Of Cncsmentioning

confidence: 99%

Cellulose Nanocrystal Liquid Crystal Phases: Progress and Challenges in Characterization Using Rheology Coupled to Optics, Scattering, and Spectroscopy

2021

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Cellulose nanocrystals (CNCs) self-assemble and can be flow-assembled to liquid crystalline orders in a water suspension. The orders range from nano- to macroscale with the contributions of individual crystals, their micron clusters, and macroscopic assemblies. The resulting hierarchies are optically active materials that exhibit iridescence, reflectance, and light transmission. Although these assemblies have the potential for future renewable materials, details about structures on different hierarchical levels that span from the nano- to the macroscale are still not unraveled. Rheological characterization is essential for investigating flow properties; however, bulk material properties make it difficult to capture the various length-scales during assembly of the suspensions, for example, in simple shear flow. Rheometry is combined with other characterization methods to allow direct analysis of the structure development in the individual hierarchical levels. While optical techniques, scattering, and spectroscopy are often used to complement rheological observations, coupling them in situ to allow simultaneous observation is paramount to fully understand the details of CNC assembly from liquid to solid. This Review provides an overview of achievements in the coupled analytics, as well as our current opinion about opportunities to unravel the structural distinctiveness of cellulose nanomaterials.

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“…Deuterium ( 2 H or D) and deuterated water (D 2 O) have been widely utilized to study the accessibility of wood polymers to water (Altgen and Rautkari 2020;Reishofer and Spirk 2015;Thybring et al 2017). This approach is based on the H-to-D exchange (deuteration) of OH groups in direct contact with water, which can be observed as changes in mass or infrared spectrum.…”

Section: Introductionmentioning

confidence: 99%

Water-accessibility of interfibrillar spaces in spruce wood cell walls

et al. 2021

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Water interactions and accessibility of the nanoscale components of plant cell walls influence their properties and processability in relation to many applications. We investigated the water-accessibility of nanoscale pores within the fibrillar structures of unmodified Norway spruce cell walls by small-angle neutron scattering (SANS) and Fourier-transform infra-red (FTIR) spectroscopy. The different sensitivity of SANS to hydrogenated ($$\hbox {H}_2\hbox {O}$$ H 2 O ) and deuterated water ($$\hbox {D}_2\hbox {O}$$ D 2 O ) was utilized to follow the exchange kinetics of water among cellulose microfibrils. FTIR spectroscopy was used to study the time-dependent re-exchange of OD groups to OH in wood samples transferred from liquid $$\hbox {D}_2\hbox {O}$$ D 2 O to $$\hbox {H}_2\hbox {O}$$ H 2 O . In addition, the effects of drying on the nanoscale structure and its water-accessibility were addressed by comparing SANS results and the kinetics of water exchange between never-dried and dried/rewetted wood samples. The results of the kinetic analyses allowed to identify two processes with different timescales. The diffusion-driven exchange of water in the spaces between microfibrils, which was observed with both SANS and FTIR, takes place within minutes and rather homogeneously. The second, slower process appeared only in the OD/OH re-exchange followed by FTIR, and it still continued after several weeks of immersion in $$\hbox {H}_2\hbox {O}$$ H 2 O . SANS could not detect any significant difference between the never-dried and dried/rewetted samples, whereas FTIR revealed a small portion of OD groups that resisted the re-exchange and this portion became larger with drying. Graphic abstract

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Deuterium and Cellulose: A Comprehensive Review

Cited by 11 publications

References 67 publications

Understanding Nanocellulose–Water Interactions: Turning a Detriment into an Asset

Understanding Nanocellulose–Water Interactions: Turning a Detriment into an Asset

Cellulose Nanocrystal Liquid Crystal Phases: Progress and Challenges in Characterization Using Rheology Coupled to Optics, Scattering, and Spectroscopy

Water-accessibility of interfibrillar spaces in spruce wood cell walls

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