Cellulose Crystals Research Articles

Molecular-Level Insight into the Interaction of Phospholipid Bilayers with Cellulose.

Molecular-level insight into the interactions of phospholipid molecules with cellulose is crucial for the development of novel cellulose-based materials for wound dressing. Here we employ the state-of-the-art computer simulations to unlock for the first time the molecular mechanisms behind such interactions. To this end, we performed a series of atomic-scale molecular dynamics simulations of phospholipid bilayers on a crystalline cellulose support at various hydration levels of the bilayer leaflets next to the cellulose surface. Our findings clearly demonstrate the existence of strong interactions between polar lipid head groups and the hydrophilic surface of a cellulose crystal. We identified two major types of interactions between phospholipid molecules and cellulose chains: (i) direct attractive interactions between lipid choline groups and oxygens of hydroxyl (hydroxymethyl) groups of cellulose and (ii) hydrogen bonding between phosphate groups of lipids and cellulose's hydroxymethyl/hydroxyl groups. When the hydration level of the interfacial bilayer/support region is low, these interactions lead to a pronounced asymmetry in the properties of the opposite bilayer leaflets. In particular, the mass density profiles of the proximal leaflets are split into two peaks and lipid head groups become more horizontally oriented with respect to the bilayer surface. Furthermore, the lateral mobility of lipids in the leaflets next to the cellulose surface is found to slow down considerably. Most of these cellulose-induced effects are likely due to hydrogen bonding between lipid phosphate groups and hydroxymethyl/hydroxyl groups of cellulose: the lipid phosphate groups are pulled toward the water/lipid interface due to the formation of hydrogen bonds. Overall, our findings shed light on the molecular details of the interactions between phospholipid bilayers and cellulose nanocrystals and can be used for identifying possible strategies for improving the properties of cellulose-based dressing materials via, e.g., chemical modification of their surface.

The action of cellulose-based and conventional flotation reagents under dry and wet conditions correlating inverse gas chromatography to microflotation studies

The fundamental formation of the three phase contact in flotation is an intensively and controversially discussed phenomenon and the contact angle method is usually employed to characterise the wettability of solid surfaces. A more recent technique to explore the hydrophobicity of solid particulate phases is inverse gas chromatography (iGC) which is used to quantify the wettability of solid surfaces through thermodynamic parameters. In this article, the recently introduced net free energy of interaction between particles and bubbles immersed in water ΔGpwb is derived from the surface free energy analysis and its correlation to the flotability of solid phases is evaluated. At the same time, a more detailed analysis on the action of flotation reagents is presented performing iGC measurements under dry and flotation experiments under aqueous conditions. In general, flotation reagents have to satisfy required features to adsorb selectively, render the solid surface wetting property sufficiently, and comply current regulations concerning the preservation of the environment. Consequently, many conventional reagents are increasingly subjected to restrictions. One potential alternative candidate is nanocellulose due to the versatile chemical composition and functionality. The synthesis of cellulose nanocrystals (CNCs) includes different mechanical and chemical modification routes to lower the crystal sizes and integrate specific functional groups and organic components into the cellulose structure. This study is concentrated on the investigation of aminated CNCs for the flotation of quartz in comparison to conventional reagents. The employment of CNCs asa renewable and sustainable alternative to conventional chemicals is challenging due to the more complex structure of cellulose crystals and leads to new perspectives regarding the action of flotation reagents at the interface of a mineral under dry and wet environments.

Preparation and characterization of starch-based composite films reinfoced by polysaccharide-based crystals

Starch based films, reinforced by two types of polysaccharide-based crystals, were prepared and compared. The films were transparent and their surface was smooth in appearance. Addition of crystals increased the Young's modulus and tensile strength of starch-based materials and decreased elongation at break. Scanning electron microscopic observation indicated good compatibility between starch matrix and the reinforcing fillers due to same chemical unit (glucose). Cellulose crystals have higher thermal stability than that of starch crystals; this provides better processibility and superior mechanical properties to starch films filled with cellulose crystals. On the other hand, starch films filled with starch crystals demonstrated higher protection againstUV radiation. Since all the components used in this work belong to food sources, the prepared films are biodegradable, safe for food packaging and can also be used to developed ible films (such as wrappers for candies) and medicinal capsules (both soft and hard capsules).

TEMPO-Oxidized Cellulose with High Degree of Oxidation.

In this paper, water-soluble 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose with a high degree of oxidation was prepared by a two-step process using bamboo dissolving pulp. The first step was to destroy the cellulose crystal I by NaOH/urea solution to obtain cellulose powder with decreased crystallinity. The second step was to oxidize the cellulose powder by TEMPO oxidation. The TEMPO-oxidized cellulose was analyzed by Fourier transform infrared spectroscopy (FTIR), conductimetry, X-ray diffraction (XRD), fiber analyzer, and transmission electron microscopy (TEM). FTIR showed that the hydroxymethyl groups in cellulose chains were converted into carboxyl groups. The degree of oxidation measured by conductimetry titration was as high as 91.0%. The TEMPO-oxidized cellulose was soluble in water for valuable polyelectrolytes and intermediates.

Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals

Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, χijk(2), of the SFG-active phase as a function of its spatial arrangement in the bulk as well as the polarizations of the probe lights. This study reports the full analysis of the azimuth angle and polarization dependence of SFG signals from a control sample consisting of uniaxially aligned cellulose Iβ crystals. The χijk(2) terms of cellulose were estimated from quantum mechanics calculations using time-dependent density functional theory (TD-DFT), and a simple structural model was built with truncated glucose dimers. The theoretical azimuth angle and polarization dependences of characteristic CH/CH2 and OH stretch modes of cellulose were compared with the experimentally observed trends. These comparisons revealed that the relative polarity of crystallites within the SFG coherence length, the random q...

Glucose, not cellobiose, is the repeating unit of cellulose and why that is important

Despite nomenclature conventions of the International Union of Pure and Applied Chemistry and the International Union of Biochemistry and Molecular Biology, the repeating unit of cellulose is often said to be cellobiose instead of glucose. This review covers arguments regarding the repeating unit in cellulose molecules and crystals based on biosynthesis, shape, crystallographic symmetry, and linkage position. It is concluded that there is no good reason to disagree with the official nomenclature. Statements that cellobiose is the repeating unit add confusion and limit thinking on the range of possible shapes of cellulose. Other frequent flaws in drawings with cellobiose as the repeating unit include incorporation of O-1 as the linkage oxygen atom instead of O-4 (the O-1 hydroxyl is the leaving group in glycoside synthesis). Also, n often erroneously represents the number of cellobiose units when n should denote the degree of polymerization i.e., the number of glucose residues in the polysaccharide.

XRD and FTIR Studies of Nanocrystalline Cellulose from Water Hyacinth (<i>Eichornia crassipes</i>) Fiber

The isolation and characterization of nanocrystalline cellulose (NCC) from water hyacinth (WH) fibers were carried out. There are two treatments to obtain NCC from WH fibers by chemical and mechanical treatments. The chemical treatment involved alkalization with NaOH 25% in a highly-pressured tube, acid hydrolysis with 5M HCl, and bleaching with (NaClO2:CH3COOH) in ratio 5:2. The mechanical treatment was performed by using ultrasonic homogenizing at 12000 Rpm for 2 h. The morphological surface was observed by Transmission Electron Microscopy (TEM). TEM reported that the size of NCC was 10–40 nm. Crystallinity index and functional group analysis of the NCC WH fibers were also examined using X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) techniques. XRD reported that the crystallinity index increased significantly after chemical and mechanical treatment due to the presents of crystalline area in the WH fibers. The crystallinity index of raw fiber, digester, bleaching, and ultrasonic homogenizing were 7%, 68%, 69%, and 73% respectively. The content cellulose of final product was 68% as measured by the chemical composition test. Meanwhile, FTIR reported that WH fibers after being given chemical treatment lead the functional group change due to removal hemicellulose and lignin. The result of XRD and FTIR were indicated that the sample of NCC WH fibers presents the structure of cellulose crystal type I.

Physicochemical, microstructural and functional characterization of dietary fibers extracted from lemon, orange and grapefruit seeds press meals

The aim of this study was to characterize dietary fibers extracted from defatted press meals of lemon, orange and grapefruit seeds. After an ultrasound-assisted aqueous extraction, the fibers were investigated for proximate composition, soluble/insoluble fiber contents, color, viscosity, degradation temperature and enthalpy, near infrared (NIR) spectra, X-ray diffraction patterns, scanning electron microscopy (SEM) images, and functional (water and oil holding capacity, swelling capacity) properties. The fibers contain 2.0–3.45mg/g phytate, 1.36–2.26% ash, 4.95–7.95% soluble fiber, 75.95–82.24% insoluble fiber. NIR spectra showed the presence of cellulose and lignin as main components with corresponding bands. Major peak at 22–23Å X-ray diffraction also indicated presence of cellulose crystals. Crystallinity values of 33–80% were measured. SEM images showed the microfibrillar structures present in the samples. Water and oil holding capacities (4.79–7.76g/g and 3.44–4.19g/g), and swelling capacities (22.44–24.55mL/g) proved that the fibers are functional, and especially good for oil containing foods. The utilization of these new fiber sources would be important in terms of by-product valorisation. The data presented in this study may provoke further studies and/or applications of these new dietary fibers.

Nanocellulose as a green and sustainable emerging material in energy applications: a review

In this review, a recent prospect on application of nanocellulose in energy application has been highlighted. To achieve high capacities that are essential for effective extraction of interesting ions and for faster charging and discharging in the energy storage devices, nanocellulose in the conducting matrix must obviously assist the dual purpose of mechanically improving and reinforcing the specific charge capacity. The abundant number of nanocellulose hydroxyl groups on the surface favors the formation of hydrogen bonding in an ordered structure and lead to it having high strength and stiffness properties at low density. This brought up the idea of utilizing nanocellulose as a reinforcement and energy adsorption agent originating from the possibility of exploiting the high strength and stiffness of cellulose crystals in composite applications. Copyright © 2017 John Wiley & Sons, Ltd.

Surface-Induced Frustration in Solid State Polymorphic Transition of Native Cellulose Nanocrystals.

The presence of an interface generally influences crystallization of polymers from melt or from solution. Here, by contrast, we explore the effect of surface immobilization in a direct solid state polymorphic transition on individual cellulose nanocrystals (CNCs), extracted from a plant-based origin. The conversion from native cellulose I to cellulose III crystal occurred via a host-guest inclusion of ethylene diamine inside the crystal. A 60% reduction in CNC width (height) in atomic force microscopy images suggested that when immobilized on a flat modified silica surface, the stresses caused by the inclusion or the subsequent regeneration resulted in exfoliation, hypothetically, between the van der Waals bonded sheets within the crystal. Virtually no changes in dimensions were visible when the polymorphic transition was performed to nonimmobilized CNCs in bulk dispersion. With reservations and by acknowledging the obvious dissimilarities, the exfoliation of cellulose crystal sheets can be viewed as analogous to exfoliation of 2D structures like graphene from a van der Waals stacked solid. Here, the detachment is triggered by an inclusion of a guest molecule inside a host cellulose crystal and the stresses caused by the firm attachment of the CNC on a solid substrate, leading to detachment of molecular sheets or stacks of sheets.

Dependence of Sum Frequency Generation (SFG) Spectral Features on the Mesoscale Arrangement of SFG-Active Crystalline Domains Interspersed in SFG-Inactive Matrix: A Case Study with Cellulose in Uniaxially Aligned Control Samples and Alkali-Treated Secondary Cell Walls of Plants

Vibrational sum frequency generation (SFG) spectroscopy can selectively detect not only molecules at two-dimensional (2D) interfaces but also noncentrosymmetric domains interspersed in amorphous three-dimensional (3D) matrixes. However, the SFG analysis of 3D systems is more complicated than 2D systems because more variables are involved. One such variable is the distance between SFG-active domains in SFG-inactive matrixes. In this study, we fabricated control samples in which SFG-active cellulose crystals were uniaxially aligned in an amorphous matrix. Assuming uniform separation distances between cellulose crystals, the relative intensities of alkyl (CH) and hydroxyl (OH) SFG peaks of cellulose could be related to the intercrystallite distance. The experimentally measured CH/OH intensity ratio as a function of the intercrystallite distance could be explained reasonably well with a model constructed using the theoretically calculated hyperpolarizabilities of cellulose and the symmetry cancellation princi...

Pharmacognostic evaluation of the leaves and stem-bark of <i>Commiphora africana</i> (A. Rich) Engl. (Burseraceae)

The study establishes some important pharmacognostic profile of Commiphora africana leaf and stem-bark with the hope of assisting in its proper identification as well as standardization for quality and sample purity. Evaluation of the fresh, powdered and anatomical sections of the leaves and stem bark were carried out to determine the macromorphological, micromorphological, chemomicroscopic and some physicochemical parameters. Macroscopical studies indicated presence of leaf with trifoliate arrangement, crenate margin with ovate shape, acute apex, cuneate base, petiolate with pinnate venation. The microscopy revealed the dorsiventral nature of the leaf and was observed to be hypostomatic with anomocytic type of stomata, with numerous unicellular covering and glandular trichomes on the abaxial surface. Chemomicroscopic characters present include; lignin, starch, cellulose, tannin, suberin and calcium oxalate crystals. The physicochemical parameters evaluated include moisture contents (8.1%), total ash value (9.3%), water soluble ash (5.5%), acid insoluble ash (3.2%), ethanol extractive values (22.3%) and water extractive values (19.0%). For quantitative leaf microscopy, on the average, stomatal number (38.0) and index (25.0), palisade ratio (11.7), vein termination numbers (5.7) and vein islets (1.3). The microscopy of stem bark revealed some prominent features like the cork, prism types and microcrystal of calcium oxalate crystals, fibres, phloem parenchyma cells, secretion canal and medullary ray. The physicochemical parameters evaluated include moisture contents (8.6%), total ash value (11.3%), water soluble ash (7.0%), acid insoluble ash (2.7%), ethanol extractive values (12.3%) and water extractive values (9.3%). Keywords: Commiphora africana, Macroscopic, Microscopic, Physicochemical parameters

Remote sensing of microfluidic tracers by light scattering from microcrystals under magnetic fields

This paper presents a new magnetic method for microfluidic visualization using low-density, highly buoyant, strongly reflective and magnetically responsive microcrystals. Microcrystal suspensions were passed through a channel with or without exposure to a magnetic field using a permanent magnet. This approach enhanced the contrast of the flow patterns. We also observed the movements of microcrystals in a paramagnetic aqueous solution containing MnCl2. In the paramagnetic solution, guanine crystals showed migration both to and from the higher magnetic fields in the microfluidic path. In contrast, microcrystals with diamagnetic susceptibility caused a stream only towards lower magnetic fields. Flow pattern measurements were also carried out using microcrystalline cellulose and boron nitride crystals. The methods developed here are expected to be useful for advancing microfluidic mechanics through the use of magnetic field effects on microcrystals in liquids.

Sticking to cellulose: exploiting Arabidopsis seed coat mucilage to understand cellulose biosynthesis and cell wall polysaccharide interactions.

The cell wall defines the shape of cells and ultimately plant architecture. It provides mechanical resistance to osmotic pressure while still being malleable and allowing cells to grow and divide. These properties are determined by the different components of the wall and the interactions between them. The major components of the cell wall are the polysaccharides cellulose, hemicellulose and pectin. Cellulose biosynthesis has been extensively studied in Arabidopsis hypocotyls, and more recently in the mucilage-producing epidermal cells of the seed coat. The latter has emerged as an excellent system to study cellulose biosynthesis and the interactions between cellulose and other cell wall polymers. Here we review some of the major advances in our understanding of cellulose biosynthesis in the seed coat, and how mucilage has aided our understanding of the interactions between cellulose and other cell wall components required for wall cohesion. Recently, 10 genes involved in cellulose or hemicellulose biosynthesis in mucilage have been identified. These discoveries have helped to demonstrate that xylan side-chains on rhamnogalacturonan I act to link this pectin directly to cellulose. We also examine other factors that, either directly or indirectly, influence cellulose organization or crystallization in mucilage.

Preparation and characterization of a novel bacterial cellulose/chitosan bio-hydrogel

Composites of chitosan chloride and bacterial cellulose were successfully prepared by in situ method. Composites of bacterial cellulose/chitosan and pristine bacterial cellulose were investigated by means of scanning electron microscope, atomic force microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, and bacteriostatic test. The crystallization of bacterial cellulose was interfered and weakened by the chitosan chloride included in the growth media, resulting in lower crystallinity index and thermal stability. And interaction between two polymers is verified by the thermal gravimetric analysis. The ultrafine nanofibril network structure of bacterial cellulose was retained by the composites, while the diameters were larger and the aperture inside were smaller than those of pristine bacterial cellulose, as shown through scanning electron microscope and atomic force microscope figures. The antimicrobial effects were enhanced by the increasing concentration of chitosan in composites. All the characteristics of the composites provide evidence for the miscibility of chitosan and cellulose. Their biocompatibility is proved through our published data. It is strongly indicated that bacterial cellulose–chitosan nanocomposites have great potential in tissue engineering or pharmaceutical applications in the near future.

From cellulose to kerogen: molecular simulation of a geological process.

The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man's land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

Cellulose dissolution: insights on the contributions of solvent-induced decrystallization and chain disentanglement

The dissolution of cellulose is a critical step for the efficient utilization of this renewable resource as a starting material for the synthesis of high value-added functional polymers and chemicals and also for biofuel production. The recalcitrance of semicrystalline cellulose microfibrils presents a major barrier to cellulose dissolution. Despite research efforts, important aspects of cellulose dissolution such as solvent-induced decrystallization and chain disentanglement are not well-understood. Here we address these fundamental issues with the practical goal of gaining insights into the swelling and dissolution of cellulose that cannot be obtained from macroscopic experimental data. To this end, we have used a newly-developed phenomenological model that captures the phenomena governing the dissolution of semicrystalline polymers as well as the thermodynamics and kinetics of dissolution. This model fits well experimental data for swelling and dissolution of cotton fibers in the ionic liquid [bmim]Cl, and allows the quantification of two important aspects, i.e., solvent effectiveness in cellulose (1) decrystallization and (2) chain disentanglement, the balance of which controls the mechanism and kinetics of cellulose dissolution. The activation parameters of cellulose decrystallization, estimated using the obtained decrystallization constant values, reveal that the decrystallization of cellulose in [bmim]Cl is associated with positive enthalpy and entropy and it is also very sensitive to temperature. When the solvent effectiveness in the disruption of cellulose crystals is relatively lower than its ability to disentangle the chains, the kinetics of dissolution are controlled by decrystallization. Furthermore, conditions that facilitate cellulose chain disentanglement, in addition to increasing the rate of dissolution, can result in faster decrystallization. The solvent effectiveness in chain disentanglement is the only factor that determines the decrease of the cellulose fiber radius. In cases where the fiber dissolution rate is lower than the decrystallization rate, the dissolution of cellulose is mostly controlled by the solvent ability to disentangle the chains. The insights obtained from this study improve the understanding of cellulose–solvent interactions underlying decrystallization and disentanglement and their contributions in controlling the kinetics of cellulose swelling and dissolution.

Room temperature dissolution of cellulose in tetra-butylammonium hydroxide aqueous solvent through adjustment of solvent amphiphilicity

The amphiphilicity of solvent systems is realized for adjusting the dissolution of natural cellulose by making use of tetra-butylammonium hydroxide (TBAH) as an example. TBAH aqueous solution is found to have an obvious effect on adjusting its amphiphilicity, along with a flexible concentration ranging from 40 to 60 wt% for dissolving cellulose. With a suitable amphiphilic property, cellulose can be dissolved by a TBAH aqueous system . The experimental results demonstrate that with the introduction of urea (more than 0.2:1, w:v) into a TBAH aqueous system, the dissolution process of cellulose can be dramatically promoted, leading to a transparent solution of cellulose. Herein, a complex solvent of TBAH/urea has been proposed for mild and effective dissolution of cellulose under ambient conditions. In the TBAH/urea complex solvent, the structure of the hybrid hydrate of TBAH and urea formed. Urea served as a hydrophobic contributor adjusting the amphiphilicity of the solvent system, allowing interfacial resistance between the amphiphilic crystal surfaces of the natural cellulose and solvent to be reduced. After that, the crystal of natural cellulose could be fully infiltrated and subsequently dissolved by the TBAH/urea aqueous solvent. The performances of the aqueous solvent and ambient temperature dissolution make aqueous TBAH/urea a potential and green solvent of cellulose for broad applications, such as composites, films or wet spinning of cellulose, in laboratories or industries.

Exploring crystalline-structural variations of cellulose during alkaline pretreatment for enhanced enzymatic hydrolysis

The study aimed to explore the crystallinity and crystalline structure of alkaline pretreated cellulose. The enzymatic hydrolysis followed by pretreatment was conducted for measuring the efficiency of sugar conversion. For cellulose Iβ dominated samples, alkaline pretreatment (<8wt%) caused increased cellulose crystallinity and depolymerized hemicelluloses, that were superimposed to affect the enzymatic conversion to glucose. Varying crystallite sizes and lattice spacings indicated the separation of cellulose crystals during mercerization (8–12wt% NaOH). Completion of mercerization was proved under higher alkaline concentration (14–18wt% NaOH), leading to distortion of crystalline cellulose to some extent. Cellulose II crystallinity showed a stimulative impact on enzymatic hydrolysis due to the weakened hydrophobic interactions within cellulose chains. The current study may provide innovative explanations for enhanced enzymatic digestibility of alkaline pretreated lignocellulosic materials.

Degradation and Crystallization of Cellulose in Hydrogen Chloride Vapor for High-Yield Isolation of Cellulose Nanocrystals.

Despite the structural, load-bearing role of cellulose in the plant kingdom, countless efforts have been devoted to degrading this recalcitrant polysaccharide, particularly in the context of biofuels and renewable nanomaterials. Herein, we show how the exposure of plant-based fibers to HCl vapor results in rapid degradation with simultaneous crystallization. Because of the unchanged sample texture and the lack of mass transfer out of the substrate in the gas/solid system, the changes in the crystallinity could be reliably monitored. Furthermore, we describe the preparation of cellulose nanocrystals in high yields and with minimal water consumption. The study serves as a starting point for the solid-state tuning of the supramolecular properties of morphologically heterogeneous biological materials.