Structure Of Cellulose Nanocrystals Research Articles

Broadband Circularly Polarized Luminescent Films Based on the Heterogeneous Assembly of Cellulose Nanocrystals.

Broadband circularly polarized films display promising applications for multiwavelength lasers and "smart" windows in buildings. Herein, broadband films are fabricated through the heterogeneous assembly of cellulose nanocrystals (CNCs) and thermoplastic polyurethane (TPU) particles in mixed solvents of water and DMF. During the heterogeneous assembly process, a portion of the small TPU particles coassembled with CNCs to form chiral nematic structures and another portion of the TPU particles fused together to form large aggregates. These large aggregates are located around the helical structures of CNCs and induce a twisting effect on the helical axis of the chiral nematic phase. Helical axis twisting continuously occurs in various directions, leading to broad-band reflections of the films. Additionally, multicolor and white right-handed circularly polarized luminescent (CPL) films have been attained by integrating three organic dyes into the chiral structures of CNCs. A high dissymmetry factor value of -0.47 was achieved for the white CPL film.

Polysaccharide Nanocrystals-Based Chiral Nematic Structures: From Self-Assembly Mechanisms, Regulation, to Applications.

Chiral architectures, one of the key structural features of natural systems ranging from the nanoscale to macroscale, are an infinite source of inspiration for functional materials. Researchers have been, and still are, strongly pursuing the goal of constructing such structures with renewable and sustainable building blocks via simple and efficient strategies. With the merits of high sustainability, renewability, and the ability to self-assemble into chiral nematic structures in aqueous suspensions that can be preserved in the solid state, polysaccharide nanocrystals (PNs) including cellulose nanocrystals (CNCs) and chitin nanocrystals (ChNCs) offer opportunities to reach the target. We herein provide a comprehensive review that focuses on the development of CNCs and ChNCs for the use in advanced functional materials. First, the introduction of CNCs and ChNCs, and cellulose- and chitin-formed chiral nematic organizations in the natural world, are given. Then, the self-assembly process of such PNs and the factors influencing this process are comprehensively discussed. After that, we showcased the emerging applications of the self-assembled chiral nematic structures of CNCs and ChNCs. Finally, this review concludes with perspectives on the challenges and opportunities in this field.

Cellulose nanocrystals isolated from sugarcane bagasse using the formic/peroxyformic acid process: Structural, chemical, and thermal properties

Sugarcane bagasse (SCB) is a renewable biomass source for cellulose extraction. In the pretreatment, SCB is processed to break down the cellulose-lignin-hemicellulose matrix and isolate components. This work proposes a formic/peroxyformic acid process for extracting cellulose nanocrystals (CNCs) from SCB. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and solid-state 13C nuclear magnetic resonance (ss- 13C NMR) were employed to evidence the removal of wax, hemicellulose, and lignin from the raw SCB. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) were used for analyzing crystallinity, morphology, and thermal properties. SEM results showed that after lignin removal, the size of purified cellulose fibrils decreased significantly, and the structure of cellulose microfibers became smoother and more apparent. After acid hydrolysis of bleached cellulose microfibers, XRD analysis showed CNCs had the highest crystallinity (70.8 %). In TEM images, rod-like structures of CNCs were measured to be 23 ± 2.7 nm wide and 610 ± 18 nm long. The eco-friendly formic/peroxyformic acid procedure with a chlorine-free bleaching stage produced a white, cellulose-rich solid powder of CNCs.

Cellulose nanocrystals from marine algae Cladophora glomerata by using microwave-assisted extraction

Algae of the order Cladophorales are the source of a unique nanocellulose with high crystallinity and a large aspect ratio, enabling broad surface modification. Cellulose nanocrystals (CNCs) are obtained via acid hydrolysis of nanocellulose, which is highly crystalline. However, the production of CNCs from Cladophorales algae is limited and still uses a conventional heating method. Thus, this study aimed to develop a microwave-assisted extraction (MAE) method for fast and efficient extraction of CNCs from Cladophora glomerata algae. Additionally, we replaced the use of hypochlorite with H2O2, which is more environmentally friendly, and compared the CNCs obtained from the conventional methods with our new method. The functional structure of CNCs was confirmed by Fourier-transform infrared spectroscopy. Single-step H2O2 bleaching with MAE yielded the smallest-sized CNCs. Our developed method resulted in the production of CNCs with a high crystallinity index, high thermal stability, and high purity of native cellulose. Additionally, none of the CNCs were toxic to primary normal human dermal fibroblasts. The properties of the isolated CNCs may make them useful materials in pharmaceutical and cosmetic formulations.

Preparation and characterization of cellulose nanocrystals with high stability from okara by green solvent pretreatment assisted TEMPO oxidation

Because the traditional preparation methods of cellulose nanocrystals (CNCs) involve chemical pollution issues, in this study, two typical green solvents, alkali/urea solvent (AUS) and deep-eutectic solvent (DES), were used to dissolve insoluble soybean fibers (ISF) extracted from okara and prepare regenerated CNCs (AUS/CNC and DES/CNC), which were further modified by TEMPO oxidation (AUS/T-CNC and DES/T-CNC). The recoveries of AUS and DES were 82.58 % and 84.00 %, respectively. Chemical composition analysis showed high cellulose purity (>95 %) of the regenerated CNCs. FTIR, XRD and 13C NMR analysis indicated the cellulose structure and polymorph of CNCs. Thermal analysis revealed that the maximum degradation peak of regenerated CNC shifted to a lower temperature. AFM revealed that CNCs exhibited rod-like fiber structures, while AUS-pretreated CNCs exhibited some special spherical fibers. TEMPO oxidation showed an enhancement effect on the characteristics of AUS/T-CNC and DES/T-CNC; DES/T-CNC exhibited higher stability and apparent viscosity than AUS/T-CNC. The DES/T-CNC-based cryogel displayed a higher adsorption capacity for anthocyanin (0.40 g/g) and curcumin (1.09 g/g) with good controlled release capacity. These results indicated that green solvent pretreatment-assisted TEMPO oxidation is a new environmentally friendly and low-cost method for the preparation of CNCs and shows excellent potential in the field of drug loading and controlled release.

Reinforcement of Acrylamide Hydrogels with Cellulose Nanocrystals Using Gamma Radiation for Antibiotic Drug Delivery.

In this paper, we report the synthesis of acrylamide hydrogels (net-AAm) reinforced with cellulose nanocrystals (CNCs) using gamma radiation, a powerful tool to obtain crosslinked polymers without the use of chemical initiators and crosslinking agents. Some slight changes in the chemical structure and crystallinity of CNCs took place during gamma irradiation without affecting the nanofiller function. In fact, cellulose nanocrystals had a notable influence over the swelling and mechanical properties on the reinforced hydrogels (net-AAm/CNC), obtaining more rigid material since the Young compression modulus increased from 11 kPa for unreinforced net-AAm to 30 kPa for net-AAm/CNC (4% w/w). Moreover, the studies of retention and release of ciprofloxacin (Cx), a quinolone antibiotic drug, showed that reinforced hydrogels were able to load large amounts of ciprofloxacin (1.2-2.8 mg g-1) but they distributed 100% of the drug very quickly (<100 min). Despite this, they exhibited better mechanical properties than the control sample, allowing their handling, and could be used as wound dressings of first response because they can absorb the exudate and at the same time deliver an antibiotic drug directly over the injury.

Synthesis and properties of thiol-modified CNC via surface tosylation

SH-containing polymers and nanoparticles are a significant direction in the creation of novel materials. The aim of this work is the synthesis of cellulose nanocrystals (CNC) with a surface modified by tosyl functions (CNC-Ts) and their further modification into SH-containing nanocrystals (CNC-SH). CNC-Ts were synthesized in an aqueous-organic emulsion from never-dried particles, while maintaining the size and supramolecular structure of CNC; the content of Ts-functions is up to 2.5 mmol·g−1. Structure of the derivatives was analyzed by TEM, XRD, CP/MAS 13C NMR and FTIR spectroscopies. Nucleophilic substitution and hydrolysis of the obtained thioisouronium salts leads to the production of CNC-SH. To quantify SH-groups we used elemental analysis, potentiometric titration and Folin-Ciocalteu and Ellman's reagents. It is shown that SH-groups on the surface are partially oxidized and are involved in a dense network of hydrogen bonds. Rheological properties of CNC-SH hydrosols are close to those of CNC, addition of H2O2 at acidic pH leads to an increase in viscosity of the system; H2O2 added at neutral pH causes opposite effect – viscosity decreases. CNC-SH have a high capacity for sorption of Cr(VI) in acidic environments and exhibit photoreductive properties under UV irradiation.

Spray-Drying Hydrophobic Cellulose Nanocrystal Coatings with Degradable Biocide Release for Marine Antifouling.

With increasing awareness about the ecological environment, increased attention has been paid to the application of eco-friendly materials in the field of marine antifouling. In this work, a novel coating having good mechanical strength and static marine antifouling characteristics was fabricated using cellulose nanocrystals (CNCs) as the skeleton material, with in situ growth of SiO2 as the basic superhydrophobic material and introducing hexadecyl trimethyl ammonium bromide (CTAB) and 4-bromo2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (Econea) into the coating. Due to the high strength and rod structure of CNCs, the coating maintained super-hydrophobicity after 50 cycles of abrasion tests. Moreover, the addition of CTAB during the synthesis of SiO2 led to the hydrolysis and polycondensation of tetraethyl orthosilicate at the micellar interface. Econea was fully mixed with SiO2 nanoparticles, thus slowing down the rate of release of Econea. Meanwhile, the adhesion between the coating and the substrate reached 1.9 MPa, which can meet the application requirements for marine environments. The bioassay using bacteria (Escherichia coli) and diatoms (Nitzschia closterium) showed that the rate of inhibition of the coating on bacteria and diatoms could reach 99 and 90%, respectively, after immersion in artificial seawater for 28 days. This research provides a facile and promising fabricating solution of an eco-friendly CNC-based coating having strong antifouling characteristics suitable for marine environments.

The effects of aspect ratio of cellulose nanocrystals on the properties of all CNC films: Tunicate and wood CNCs

In this study, the physicochemical, mechanical, and thermal properties of films made from cellulose nanocrystals (CNCs) obtained from two sources – wood and tunicate - and their hybrids were investigated. It was found that different morphologies affect the properties of CNC films. Specifically, the surface morphology of tunicate CNC (TCNC) films differed significantly from wood CNC (WCNC) films, and the structure of hybrid CNC (HCNC) films was also different. Compared to wood CNC-containing films, tunicate CNC films exhibited significantly higher BET surface areas, superior thermal properties, greater surface roughness, and very low (≈1 wt.%) dispersibility in water due to their ability to form long-range connectivity. The average BET surface area of TCNC films was measured at 91.9 ± 2.1 m2/g, and this value decreased with the addition of WCNCs to the film structure. The pore diameter also decreased from 11.362 nm for TCNC films to 0.437 nm for WCNC films, indicating the filler effect of WCNCs on the TCNC films. The chiral nematic phase exhibited by WCNC films was confirmed by their iridescent appearance, as observed through cross-sectional SEM images. The TS for TCNC and HCNC3 was measured at 185.2 ± 10.5 MPa and 182.9 ± 13.7 MPa, respectively, which were the highest values among the samples. The lowest TS value of 113.1 ± 9.5 MPa was observed in the WCNC films. A similar decline was observed in the EB values, from 1.76 ± 0.37% for TCNC to 0.9 ± 0.22% for WCNC. This study provides information and knowledge useful for understanding the impact of biomass source on the properties of CNC films for a variety of purposes, including packaging materials, biodegradable coatings, flexible electronics, and membrane applications.

Morphological, Spectroscopic and Thermal Analysis of Cellulose Nanocrystals Extracted from Waste Jute Fiber by Acid Hydrolysis

Natural cellulose, a sustainable bioresource, is highly abundant in nature. Cellulosic materials, particularly those that explore and employ such materials for industrial use, have recently attracted significant global attention in the field of material science because of the unique properties of cellulose. The hydroxyl groups enable the formation of intra- and inter-molecular hydrogen bonding and the arrangement of cellulose chains in a highly ordered crystalline zone, with the remaining disordered structure referred to as an amorphous region. The crystalline areas of cellulose are well-known as cellulose nanocrystals (CNCs). In the present study, we extracted CNCs from pure cellulose isolated from waste jute fibers by sulfuric acid hydrolysis, followed by characterization. Pure cellulose was isolated from jute fibers by treating with sodium hydroxide (20% w/w) and anthraquinone (0.5%) solution at 170 °C for 2 h, followed by bleaching with chlorine dioxide and hydrogen peroxide solution. CNCs were isolated from pure cellulose by treating with different concentrations (58% to 62%) of sulfuric acid at different time intervals (20 min to 45 min). The FTIR study of the CNCs reveals no peak at 1738 cm-1, which confirms the absence of hemicellulose in the samples. The CNCs obtained after 45 min of acid hydrolysis are rod-shaped, having an average length of 800 ± 100 nm and width of 55 ± 10 nm, with a high crystallinity index (90%). Zeta potential significantly increased due to the attachment of SO42- ions on the surface of CNC from -1.0 mV to about -30 mV, with the increment of the reaction time from 20 min to 45 min, which proved the higher stability of CNC suspension. Crystallinity increased from 80% to 90% when the reaction time was increased from 20 to 45 min, respectively, while a crystallite size from 2.705 to 4.56 nm was obtained with an increment of the acid concentration. Acid hydrolysis enhanced crystallinity but attenuated the temperature corresponding to major decomposition (Tmax) at 260 °C and the beginning of degradation (Ti) at 200 °C due to the attachment of SO42- ions on the surface, which decreased the thermal stability of CNC. The second degradation at 360 °C indicated the stable crystal structure of CNC. The endothermic peak at 255 °C in the DTA study provided evidence of sulfated nanocrystal decomposition and the recrystallization of cellulose I to cellulose II, the most stable structure among the other four celluloses. The proposed easy-to-reproduce method can successfully and efficiently produce CNCs from waste jute fibers in a straightforward way.

Physico-chemical and structural characterization of cellulose nanocrystals obtained by two drying methods: Freeze-drying and spray-drying

This study evaluated the physical-chemical properties and structure of cellulose nanocrystals (CNC) produced from pine cellulose pulp, and dried by two different methods: Spray-Drying (SD) or Freeze-Drying (FD). After drying, CNC were characterized in terms of size, z-potential, elemental analysis, conductometric titration, crystallinity and thermogravimetry. Complementary, analysis by force microscopy, dynamic sorption and infrared spectroscopy were carried out.Results showed that different drying methods did not produce significant differences in zeta potential, crystallinity and degradation temperature. However, CNC dried by FD showed smaller size but higher aspect ratio, and higher sulfur content, which would explain the significant higher sorption observed in CNC-FD at relative humidity higher than 80%. Drying method does not influence the formation or modification of cellulose bonds as FTIR suggested.Our study suggests that how CNC is dried will influence the CNC's structure and will modify some of their physico-chemical properties. This information is relevant since it can be used as an input for the scale-up processing of CNC and would define the performance in some of their technological applications.

Preparation of cellulose nanocrystals from purple sweet potato peels by ultrasound-assisted maleic acid hydrolysis

This study aimed at realizing high value utilization of purple sweet potato (PSP) peels. Firstly, ultrasonic assisted ethanol method was used to extract anthocyanins from PSP peels, and the individual anthocyanin composition and antioxidant activity were analyzed. Then the technological parameters of preparing cellulose nanocrystals (CNCs) by ultrasonic-assisted maleic acid hydrolysis were optimized, and Zeta-potential, chemical structure, thermal stability and crystallinity of CNCs were analyzed. Results showed the optimal technological parameters were as follows: the ratio between PSP peel residues and 75 wt% maleic acid was 1:10 (g/mL, W/W), and ultrasonic-assisted hydrolysis was carried out at 60℃ for 1 h, followed by 120℃ for 2.5 h. The yield and Zeta-potential of CNCs were 8.17 % and −57.7 mV, respectively. The chemical structure and physical properties of CNCs were similar to those of commercial CNCs. In conclusion, ultrasound-assisted maleic acid hydrolysis has great potential to realize the industrialization of CNCs.

Non-iridescent and Wide-Color-Range Structural Coloration Enabled by Cellulose Nanocrystals with a Controlled Long-Range Photonic Structure and Helical Pitch

Bioinspired coloration of cellulose nanocrystals (CNCs) has advanced a new era of wide applications for decoration, sensing, and anti-counterfeiting. However, the solid structural color films suffer from strong angle-dependent iridescence and a limited color range due to the spatial arrangement caused by kinetic arrest during evaporation-induced self-assembly of CNCs. Here, a ternary co-assembly approach is demonstrated to prepare CNC films with weak/non-angular optical response and wide-range colors. Structural coloration is enabled by the long-range and short-range ordered photonic structure of CNCs. A cationic polymer, poly(dimethyl diallyl ammonium chloride), is introduced to influence the CNC self-assembly through electrostatic attraction, inducing the structural transition to the long-range disordered/short-range ordered structure as well as presenting the gradual change from iridescent structural colors to non-iridescent colors. Additionally, a hydrophilic small compound, glycerol, is used to adjust the helical pitch of nanostructured CNC arrays, offering the broad-range coloration. The CNC-based composite material is further used as an optical coating for anti-counterfeiting and realizing color patterning and angle-dependent selective color changes.

Thermal degradation and hemocompatibility of polyurethane cellulose nanocomposites

Bio based polymers are reinforced with natural fibers as a good candidate to the replacement of synthetic materials. In this work biobased polyurethane cellulose nanocomposites (PUCNs) prepared from hydroxylated olive oil and diphenyl methane - 4, 4 - diisocyanate,in the presence of dibutyl tin dilaurate as catalyst and incorporated with varying concentration of cellulose nanocrystals. The polyurethane cellulose nanocomposites films have been characterized by FTIR, XRD, SEM and TGA/DTA studies. The compatibility of the nanocomposites is evaluated by invitro hemolytic assay method. The FTIR analysis indicates the presence of the cellulose nanocrystals in the polyurethane matrix. The formation of urethane linkage is confirmed by the stretching vibrations of the peak around 3330 cm-1. XRD diffraction pattern of the samples shows a increase of 2% crystallinity by the addition of cellulose nanoparticles. The average size of cellulose nanocrystals is calculated as 16nm. SEM images shows a rod like structure of cellulose nanocrystals and the fine dispersion of cellulose nanocrystals in the polymer matrix. The degradation of PUCNs is more pronounced in different chemical environments than polyurethane. Thermogravimetric analysis observed that the addition of cellulose nanocrystals increases the thermal stability of PUCNs upto 300oC.

Highly Tough, Stretchable, and Solvent-Resistant Cellulose Nanocrystal Photonic Films for Mechanochromism and Actuator Properties.

Cellulose nanocrystals (CNCs)-derived photonic materials have confirmed great potential in producing renewable optical and engineering areas. However, it remains challenging to simultaneously possess toughness, strength, and multiple responses for developing high-performance sensors, intelligent coatings, flexible textiles, and multifunctional devices. Herein, the authors report a facile and robust strategy that poly(ethylene glycol) dimethacrylate (PEGDMA) can be converged into the chiral nematic structure of CNCs by ultraviolet-triggered free radical polymerization in an N,N-dimethylformamide solvent system. The resulting CNC-poly(PEGDMA) composite exhibits impressive strength (42MPa), stretchability (104%), toughness (31MJm-3 ), and solvent resistance. Notably, it preserves vivid optical iridescence, displaying stretchable variation from red, yellow, to green responding to the applied mechanical stimuli. More interestingly, upon exposure to spraying moisture, it executes sensitive actuation (4.6°s-1 ) and multiple complex 3D deformation behaviors, accompanied by synergistic iridescent appearances. Due to its structural anisotropy of CNC with typical left-handedness, the actuation shows the capability to generate a high probability (63%) of right-handed helical shapes, mimicking a coiled tendril. The authors envision that this versatile system with sustainability, robustness, mechanochromism, and specific actuating ability will open a sustainable avenue in mechanical sensors, stretchable optics, intelligent actuators, and soft robots.

Acid Hydrolysis Process of Mengkuang Cellulose

Cellulose nanocrystals (CNC) are involved in many applications due to their unique properties. Thus, the understanding hydrolysis process help to control the preparation conditions and the chemical reactions during the different uses. Cellulose from mengkuang leaves (Pandanus tectorius) was used in this research to prepare CNC. Sulfuric acid (H2SO4 60 wt.%) hydrolysis was carried out over different times to produce the nanocrystals. The effects of hydrolysis time on the morphology, chemical structure, and crystallinity index of CNC were examined using transmission electron microscopy (TEM), Fourier transforms infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The degradation process is dependent on the time of hydrolysis and the crystalline domains of cellulose fibers. The process starts by expanding the cellulose chains. FTIR results showed that no change in the chemical structure of the nanocrystals during the hydrolysis reaction. The results demonstrated that the optimum hydrolysis time to produce cellulose nanocrystals from mengkuang cellulose, with a crystallinity index of about 74% and aspect ratio of 15, was 45 min at 45 °C using 60 wt% H2SO4.

Artemisia annua Stems a New Sustainable Source for Cellulosic Materials: Production and Characterization of Cellulose Microfibers and Nanocrystals.

In this study, Artemisia annua stem waste was identified, for the first time, as a potential natural source to produce cellulose microfibers (CMF), as well as cellulose nanocrystals (CNC) with unique functionalities by using various organic acids. The CMF extraction was carried out using alkali and bleaching treatments, while the CNC were isolated under acid hydrolysis by using sulfuric acid (S-CNC), phosphoric acid (P-CNC), and hydrochloric acid / citric acid mixture (C-CNC). The CMF and CNC physicochemical, structural, morphological, dimensional, and thermal properties were characterized. CMF with a yield of 53%, diameter of 5 to 30 µm and crystallinity of 57% were successfully obtained. In contrast, CNC showed a rod-like shape with an aspect ratio of 53, 95, and 64 and a crystallinity index of 84, 79, and 72% for S-CNC, P-CNC, and C-CNC, respectively. Results suggested that the type of acid significantly influenced the structure, morphology, and thermal stability of CNCs. Based on these results, Artemisia annua stem waste is a great candidate source for cellulose derivatives with excellent characteristics.Graphical

Co‐Assembled Cellulose Nanocrystal‐Based Materials with Enhanced Long‐Term Stabilization in the Air of Black Phosphorus Nanosheets via Integrating Physical Coverage with Chemical Interactions

AbstractBlack phosphorus nanosheets (BPNS) cannot be directly applied in moist air due to their chemical instability from their thin layer structures adsorbed and transferred oxygen atoms easily. Here, a universal strategy for stabilizing BPNS is proposed by exfoliating black phosphorus with one‐dimensional nanoparticles based on cellulose nanocrystals (CNCs). Thin layers of BPNS are obtained in water and then co‐assembled with CNCs to construct composite membranes. Meanwhile, the co‐assembling technology and the chemical structure of CNCs are adjusted to obtain flexible membranes and high photothermal energy‐conversion efficiency (19.6%). The infrared illumination test proves that BPNS can exist stably in the black phosphorus (BP)/CNC‐based membranes and the photothermal conversion efficiency is kept at 19.6% after 30 days in ambient air. The mechanism study based on atomic force microscopy (AFM) and XPS show that the stability comes from the effects of physical covering and chemical covalent‐bond stabilization of CNC‐based materials. These BP/CNC‐based co‐assembled membranes can be practically applied in the military field for infrared ignition, night vision, and photothermal sensing.

Major Factors Influencing the Size Distribution Analysis of Cellulose Nanocrystals Imaged in Transmission Electron Microscopy.

Size distributions of cellulose nanocrystals (CNCs), extracted from softwood pulp via strong sulfuric acid hydrolysis, exhibit large variability when analyzed from transmission electron microscopy (TEM) images. In this article, the causes of this variability are studied and discussed. In order to obtain results comparable with those reported, a reference material of CNCs (CNCD-1) was used to evaluate size distribution. CNC TEM specimens were prepared as-stained and dried with a rapid-flushing staining method or hydrated and embedded in vitreous ice with the plunge-freezing method. Several sets of bright-field TEM (BF-TEM), annular dark-field scanning TEM (ADF-STEM) and cryogenic-TEM (cryo-TEM) images were acquired for size distribution analysis to study the contributing factors. The rapid-flushing staining method was found to be the most effective for contrast enhancement of CNCs, not only revealing the helical structure of single CNCs but also resolving the laterally jointed CNCs. During TEM specimen preparation, CNCs were fractionated on TEM grids driven by the coffee-ring effect, as observed from contrast variation of CNCs with a stain-depth gradient. From the edge to the center of the TEM grids, the width of CNCs increases, while the aspect ratio (length to width) decreases. This fractionated dispersion of CNCs suggests that images taken near the center of a droplet would give a larger mean width. In addition to particle fractionation driven by the coffee-ring effect, the arrangement and orientation of CNC particles on the substrate significantly affect the size measurement when CNC aggregation cannot be resolved in images. The coexistence of asymmetric cross-section CNC particles introduces a large variation in size measurement, as TEM images of CNCs are mixed projections of the width and height of particles. As a demonstration of how this contributes to inflated size measurement, twisted CNC particles, rectangular cross-section particles and end-to-end jointed CNCs were revealed in reconstructed three-dimensional (3D) micrographs by electron tomography (ET).

Stimuli-responsive flexible membrane via co-assembling sodium alginate into assembly membranes of rod-like cellulose nanocrystals with an achiral array

Uniaxially assembling cellulose nanocrystals (CNCs) can induce strong solid-state emission based on optical inelastic scattering, whereas the CNC assembly membranes are not flexible enough for further applications. Thus, we introduced CNC into flexible sodium alginate (SA) and further controlled the assembly structure of CNC to increase the membrane toughness and maintain the emission properties. The results indicated that the stretchability increased from 0.027 % to 37 % when 33–37% when 33 % SA was introduced. The assembly achirality was controlled by tuning CNC concentration in suspension, and the co-assembly could further control the wavelength of the assembly-induced emission from 420 nm to 440 nm. Furthermore, the improved stretchability made assembly membrane an optical sensor, whose excitation wavelength blue-shifted about 30 nm under a 30 % strain. The emission of the co-assembly membrane could also respond to humidity, and this cellulose-based material should have great potential in biosensor and wearable devices.