A novel solvent system, lithium chloride/dimethyl sulfoxide (LiCl/DMSO), was developed for dissolving milled wood. This system completely dissolved beech and spruce milled woods prepared from the Wiley woods (coarse wood meals prepared by a Wiley mill) by 2 h planetary ball-milling under the milling conditions employed. The dependence of the structural change of lignin on the degree of milling was examined to evaluate the correlation between the dissolution and lignin structure. The nitrobenzene oxidation analyses showed that the 2 h milling caused almost no structural change in the aromatic part of lignin in the milled woods. The ozonation analyses suggested that the decrease of the erythro ratio [erythro/(erythro + threo)] obtained from beta-O-4 structure in lignin is only 0.35% after the 2 h milling. Although the yield decrease of the ozonation products was 9.8% after the 2 h milling, this value was fairly smaller than that after a longer time milling. When it is taken into consideration that the other solvent systems for dissolution of wood meal, which are proposed by Lu and Ralph, require 5 h of milling under the same milling conditions to dissolve the milled woods, it is safely stated that the LiCl/DMSO solvent system completely dissolves milled wood, the lignin of which is structurally less altered and, thus, is expected to provide an improved method for structural analysis of the entire lignin fraction in wood cell wall.
High
yield (>85%) and low-energy deconstruction of never-dried
residual marine biomass is proposed following partial deacetylation
and microfluidization. This process results in chitin nanofibrils
(nanochitin, NCh) of ultrahigh axial size (aspect ratios of up to
500), one of the largest for bioderived nanomaterials. The nanochitins
are colloidally stable in water (ζ-potential = +95 mV) and produce
highly entangled networks upon pH shift. Viscoelastic and strong hydrogels
are formed by ice templating upon freezing and thawing with simultaneous
cross-linking. Slow supercooling and ice nucleation at −20
°C make ice crystals grow slowly and exclude nanochitin and cross-linkers,
becoming spatially confined at the interface. At a nanochitin concentration
as low as 0.4 wt %, highly viscoelastic hydrogels are formed, with
a storage modulus of ∼16 kPa, at least an order of magnitude
larger compared to those measured for the strongest chitin-derived
hydrogels reported so far. Moreover, the water absorption capacity
of the hydrogels reaches a value of 466 g g
–1
. Lyophilization
is effective in producing cryogels with a density that can be tailored
in a wide range of values, from 0.89 to 10.83 mg·cm
–3
, and corresponding porosity, between 99.24 and 99.94%. Nitrogen
adsorption results indicate reversible adsorption and desorption cycles
of macroporous structures. A fast shape recovery is registered from
compressive stress–strain hysteresis loops. After 80% compressive
strain, the cryogels recovered fast and completely upon load release.
The extreme values in these and other physical properties have not
been achieved before for neither chitin nor nanocellulosic cryogels.
They are explained to be the result of (a) the ultrahigh axial ratio
of the fibrils and strong covalent interactions; (b) the avoidance
of drying before and during processing, a subtle but critical aspect
in nanomanufacturing with biobased materials; and (c) ice templating,
which makes the hydrogels and cryogels suitable for advanced biobased
materials.
Recently-discovered lignocellulosic solvent, 8%(w/w) lithium chloride/dimethyl sulfoxide (LiCl/DMSO), was found to dissolve cellulose of varied crystal forms and degree of polymerization. Cellulose samples could be activated for dissolution by complexation with ethylenediamine (EDA), giving EDA contents of 20-23% (w/w) in the complex irrespective of the cellulose type. The cellulose solution gave well-resolved 13 C NMR spectrum, confirming molecular dispersion. Cellulose could be coagulated by ethanol to give translucent cellulose gels, which could be converted to highly porous aerogels via solvent exchange drying. Nitrogen adsorption analysis gave their specific surface areas of 190-213 m 2 /g, with typical mesopore sizes of 10-60 nm. Scanning electron microscopy revealed the network structure of aerogel composed of relatively straight fibril segments, approx. 20 nm wide and 100-1,000 nm long. X-ray diffraction showed that the material is poorly crystalline cellulose II.
Inspired
by its unique porous structure, high value-added functional
hydrogels combined with metal nanoparticles can lead to applications
in different areas, including environmental catalysis. For this purpose,
controlling the metal nanoparticle size is paramount. Herein, the
porous lignocellulose hydrogel (LCG) with different lignin contents
served as the matrix for in situ-synthesizing silver–lignin
nanoparticles (Ag-L NPs), with lignin in the LCG as the reducing and
capping agent of Ag-L NPs and the lignin content to control the size
of Ag-L NPs. The well-dispersed lignin in the LCG network ensures
immobilization and dispersion of Ag-L NPs. The particle size of Ag-L
NPs is tailored by adjusting the lignin content (0.5, 6.5, 11.6, and
18.4%) of the LCG: the higher the lignin content, the smaller the
Ag-L NPs. The smallest Ag-L NPs obtained were of 9.5 nm. The as-prepared
Ag-L NPs/LCG composite samples showed outstanding catalytic reduction
capability, with superior stability/reusability when applied for the
catalytic reduction of 4-nitrophenol. Moreover, the Ag-L NPs/LCG composites
exhibited high antibacterial activity, thus contributing to long-term
storage stability.
Deep eutectic solvents (DESs) have potential applications in biomass conversion and green chemicals due to their cost-effectiveness and environmentally friendly properties. This study reports on a feasible method of using DESs for lignin selective extraction from poplar wood meal. DESs obtained from various hydrogen-bond donors and acceptors were used to evaluate the dissolving capacity of lignin from poplar wood meal. Among the various DESs, lactic acid: choline chloride (9 : 1) exhibits the optimal extraction capacity, which is capable of selectively dissolving 95% of lignin from poplar wood meal at 120°C for 6 h. The purity of isolated lignin reaches 98% after regeneration in water. From Fourier Transform-IR, nitrobenzene oxidation and nuclear magnetic resonance analysis, the results demonstrate that the DESs can selectively cleave ether linkages and damage the non-condensation section of lignin, thereby facilitating lignin dissolution from wood meal. Thus, this study provides a promising route for the extraction of high-purity lignin from biomass materials.
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