All-Aqueous Bicontinuous Structured Liquid Crystal Emulsion through Intraphase Trapping of Cellulose Nanoparticles.

Here, we describe the all-aqueous bicontinuous emulsions with cholesteric liquid crystal domains through hierarchical colloidal self-assembly of nanoparticles. This is achieved by homogenization of a rod-like cellulose nanocrystal (CNC) with two immiscible, phase separating polyethylene glycol (PEG) and dextran polymer solutions. The dispersed CNCs exhibit unequal affinity for the binary polymer mixtures that depends on the balance of osmotic and chemical potential between the two phases. Once at the critical concentration, CNC particles are constrained within one component of the polymer phases and self-assemble into a cholesteric organization. The obtained liquid crystal emulsion demonstrates a confined three-dimensional percolating bicontinuous network with cholesteric self-assembly of CNC within the PEG phase; meanwhile, the nanoparticles in the dextran phase remain isotropic instead. Our results provide an alternative way to arrest bicontinuous structures through intraphase trapping and assembling of nanoparticles, which is a viable and flexible route to extend for a wide range of colloidal systems.

Synthesis of a robust, water-stable, and biodegradable pulp foam by poly-lactic acid coating towards a zero-plastic earth.

Biodegradable cellulosic pulp foams with robustness and water resistance are urgently needed in nowadays to replace petroleum-based plastic foams for environmental sustainability. In this work, a facile protocol to fabricate robust poly-lactic acid (PLA) coated cellulose foams (PCCF) was developed through a combined water-based foaming and PLA melt-coating process using pulp as the raw material. In the synthesis, the so-called PLA coating was realized through melting PLA powders dispersed between fibers by an in-situ heating and post cooling process. Performance tests revealed that the incorporation of PLA coating significantly enhances mechanical strength, water stability, and biodegradability of the synthesized PCCF samples compared with conventional cellulosic foams. Specifically, the low-density PCCF were observed with mechanical strength up to 81.24 kPa, high water stability, and more than 95% degradation in 56 days. As the fabrication process is simple and pulp is highly cost competitive, our proposed synthesis strategy makes the PCCF a promising substitute for petroleum-based plastic foams at large-scale production.

Efficient Shaping of Cellulose Nanocrystals Based on Allomorphic Modification: Understanding the Correlation between Morphology and Allomorphs.

Cellulose nanocrystals (CNC) are green, safe, and renewable nanomaterials with a variety of excellent performances but their morphologies are notoriously difficult to control as this is unfavorable to the diversification of the end products. Allomorphic conversion plays an important role in diversifying the morphology of CNC. However, this further complicates the prediction, design, and control of the geometric dimensions of CNC. Herein, allomorphically modified cellulose (mercerized cellulose, ethylenediamine (EDA)-treated cellulose, and ball-milled cellulose) is designed and used as the starting material for CNC isolation. Subsequently, the morphological evolution of cellulose particles during acid hydrolysis is traced by scanning electron microscopy observations. A mechanism that facilitates further understanding of CNC shaping during sulfuric acid hydrolysis is proposed. According to the CNC shaping mechanism, precise prediction, design, and efficient control of the morphology of CNC (needle-like, ribbon-like, ellipsoid, and spherical) can be realized. CNC with various morphologies are favorable for their applications, such as templating synthesis of porous materials and Pickering emulsion dispersion.

Residual lignin in cellulose nanofibrils enhances the interfacial stabilization of Pickering emulsions.

Lignocellulose nanofibrils (LCNF) were used to prepare oil-in-water Pickering emulsions and to assess the role residual lignin in interfacial stabilization. Two LCNF fractions of similar morphology (length ∼700 nm and width ∼8 nm) and structure (polymorphism and crystallinity) were obtained by microfluidization of fibers obtained by hydrothermal treatment of wood with a recyclable organic acid. The LCNF with higher residual lignin was less hydrophilic and, correspondingly, performed better as Pickering stabilizer, producing emulsions of smaller droplet size and higher resistance to creaming. Long-term emulsion stabilization (over 40 days) was achieved with LCNF at concentrations as low as 0.24 (w/v)% based on emulsion volume. We conclude that LCNF-stabilized Pickering emulsions can be finely tuned by varying the residual lignin content, providing a rationale for LCNF selection according to lignin type and concentration as variables affecting stabilization. Complementary considerations include the possible benefits of the residual lignin in LCNF, including antioxidant and UV absorption properties.

Antibacterial Performance of a Mussel-Inspired Polydopamine-Treated Ag/Graphene Nanocomposite Material.

Graphene-based nanocomposites have attracted tremendous attention in recent years. In this study, a facile yet effective approach was developed to synthesize reduced graphene oxide and an Ag-graphene nanocomposite. The basic strategy involved in the preparation of reduced graphene oxide includes reducing graphene oxide with dopamine, followed by in situ syntheses of the Ag-PDA-reducing graphene oxide (RGO) nanocomposite through adding AgNO3 solution and a small amount of dopamine. The nanocomposite was characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), FTIR spectra, Raman spectra, ultraviolet-visible (UV-vis), and X-ray photoelectron spectroscopy (XPS), results indicated that a uniform PDA film is formed on the surface of the GO and GO is successfully reduced. Besides, the in situ synthesized Ag nanoparticles (AgNPs) were evenly distributed on the RGO surface. To investigate antibacterial properties Ag-PDA-RGO, different dosages were selected for evaluating the antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli. The Ag-PDA-RGO nanocomposites displayed excellent antibacterial property. The antibacterial ratio reached 99.9% against S. aureus and 90.9% against E. coli when the dosage of 100 mg/L Ag-PDA-RGO nanocomposites was 100 µL. The novel Ag-PDA-RGO nanocomposite prepared by a facile yet effective, environmentally friendly, and low-cost method holds great promise in a wide range of modern biomedical applications.

A comparative study on the preparation and characterization of cellulose nanocrystals with various polymorphs.

Polymorphic changes of cellulose nanocrystals (CNCs) are strongly associated with its properties and applications. In this study, CNCs with different polymorphs were produced by a simple polymorphic transformation treatment. Cellulose I nanocrystals were produced by typical sulfuric acid hydrolysis (CNC-I). Cellulose II nanocrystals were prepared by two different methods: (1) sulfuric acid hydrolysis of cellulose previously mercerized with 18.5 wt% NaOH (CNC-II), (2) mercerization of CNC-I with 18.5 wt% NaOH (MCNC-II). Cellulose III nanocrystals were prepared by ethylenediamine treatment of CNC-I (ECNC-III). The polymorphic changes of CNCs, and their properties including morphology, crystallinity, thermal stability, and re-dispersion ability were systematically investigated. The results showed that the other properties of CNC-II and MCNC-II were quite different from each other except for the morphology. The morphology of polymorphic transformed CNCs were strongly relate to the fashion of cellulose chains arrangement. Both CNC-II and MCNC-II exhibited a rod-like shape with short lengths, whereas the ECNC-III showed relatively long length, like CNC-I.

Cellulose nanocrystals (CNCs) with different crystalline allomorph for oil in water Pickering emulsions.

In recent years, nanocelluloses have attracted a lot of interests as promising stabilizers for Pickering emulsion particularly in food, cosmetics and pharmaceutics industries. In this work, two cellulose nanocrystals (named CNCs-I and CNCs-II) with different crystalline allomorph were investigated as stabilizers for oil-water Pickering emulsion. CNCs were prepared by sulfuric acid hydrolysis of unmodified and mercerized microcrystalline cellulose (MCC), respectively. CNCs-I was needle-like particles (length - 200 nm, width - 16.4 nm), while CNCs-II was individual granules (length - 18.8 nm, width - 10.9 nm) with ellipsoid shapes. Both CNCs had surface charge density higher than 0.1 e/nm2. Pickering emulsions stabilized by CNCs-I had larger emulsion ratio, two times smaller droplet size and superior performance of stability than CNCs-II. It is concluded that crystalline allomorph of CNCs played more dominating roles to the stabilization of Pickering emulsion than morphologies of CNCs themselves in this work, and CNCs-II is not the good candidates as stabilizer for Pickering emulsion compared to CNCs-I.

Bio-based polyurethane foam preparation employing lignin from corn stalk enzymatic hydrolysis residues.

Enzymatic hydrolysis residues (EHR) from corn stalk are industrial waste from the cellulosic ethanol industry. Lignin was separated as a bio-based polyol from EHR replacing partial petroleum-based polyether polyol to prepare bio-based polyurethane (BPU) foams without any other biomass pretreatment. Single factor experiment and response surface methodology (RSM) were employed to optimize separation conditions and reveal the significant influence of the interaction of conditions on the yield of separated lignin (SL). The effect of SL content (2.5, 5.0, 7.5, 10 and 15%) on the foams morphology and mechanical properties was assessed. Scanning electron microscopy (SEM) results implied that the cell shape was considerably affected by the large SL content, which contributed to an irregular, inhomogeneous, and thick cell wall. An astonishing 9.56 times increase in the compressive modulus and exponential 97.93 times boost in the compressive strength of BPU foams were attributed to the content of 15% SL without any further surface chemical modification. This present paper reports a green, potential and promising method for complete utilization of lignin from EHR in consideration of their abundant supply to greatly enhance the mechanical properties of BPU foams.

The decontamination of bleaching effluent by pilot-scale solar Fenton process.

A solar Fenton process was applied as post-treatment to selectively eliminate organic pollutants and toxicants in bleaching effluents of kraft pulp mills. Experiments were conducted to study the effect of system parameters (pH, initial concentration of H2O2, molar ratio of Fe2+/H2O2 and solar-UV irradiance) on the removals of chemical oxygen demand and colour. The results showed 92.8% of COD and 99.6% of colour were removed at pH 3.5, H2O2 30 mM/ L, Fe2+/H2O2 1:100, solar-UV irradiance 11070 mW/m2, reaction time 120 min. The first-order kinetic model was used to study the dependence of the reaction rate on solar-UV irradiance: a linear relationship was shown to exist between reaction rate constants and solar-UV irradiance. The results of gas chromatography mass spectrometry analysis showed that the toxicity of the bleaching effluents was mainly derived from the presence of mononuclear aromatics, polycyclic aromatic hydrocarbons and organochlorides, which were all degraded into harmless organic acids under the attack of hydroxyl radicals generated from the solar Fenton reaction.