Unique gelation behavior of cellulose in NaOH/urea aqueous solution

A transparent cellulose solution was prepared by mixing 7 wt % NaOH with 12 wt % urea aqueous solution which was precooled to below -10 degrees C and which was able to rapidly dissolve cellulose at ambient temperature. The rheological properties and behavior of the gel-formed cellulose solution were investigated by using dynamic viscoelastic measurement. The effects of temperature, time, cellulose molecular weight, and concentrations on both the shear storage modulus (G') and the loss modulus (G") were analyzed. The cellulose solution having a viscosity-average molecular weight (M(eta)) of 11.4 x 10(4) had its sol-gel transition temperature decreased from 60.3 to 30.5 degrees C with an increase of its concentration from 3 to 5 wt %. The gelation temperature of a 4 wt % cellulose solution dropped from 59.4 to 30.5 degrees C as the M(eta) value was increased from 4.5 x 10(4) to 11.4 x 10(4). Interestingly, at either higher temperature (above 30 degrees C), or lower temperature (below -3 degrees C), or for longer gelation time, gels could form in the cellulose solutions. However, the cellulose solution remains a liquid state for a long time at the temperature range from 0 to 5 degrees C. For the first time, we revealed an irreversible gelation in the cellulose solution system. The gel having been formed did not dissolve even when cooled to the temperature of -10 degrees C, at which it was dissolved previously. Therefore, this indicates that either heating or cooling treatment could not break such stable gels. A high apparent activation energy (E(a)) of the cellulose solution below 0 degrees C was obtained and was used to explain the gel formation under the cooling process.     

Direct dissolution of cellulose in NaOH/thiourea/urea aqueous solution

Untreated cellulose was directly and quickly dissolved in NaOH/thiourea/urea aqueous solution. The mechanism of dissolution was investigated by SEM, WXRD and (13)C NMR. The components of this solvent cannot dissolve cellulose on their own, and the interactions between NaOH and urea, as well as between NaOH and thiourea, play an important role in improving the dissolution of cellulose. Moreover, (13)C NMR spectra proved that NaOH, thiourea, and urea were bound to cellulose molecules, which brings cellulose molecules into aqueous solution to a certain extent and prevents cellulose macromolecules from associating. (13)C NMR spectra of the cellulose solution show that this novel mixture is a direct solvent. Optical microscopy and CP MAS (13)C NMR were used to study the process of dissolution. The results reveal that cellulose is dissolved completely and that cellulose I (cotton linter) first changes to amorphous cellulose chains in solution, and then to cellulose II during regeneration. Moreover, a new, more effective dissolution method is proposed, as confirmed by dynamic rheology measurements.     

Rheological behaviors and miscibility of mixture solution of polyaniline and cellulose dissolved in an aqueous system

In our previous work, supramolecular films composed of hydrophilic cellulose and hydrophobic polyaniline (PANI) dissolved in NaOH/urea aqueous solution at low temperature through rearrangement of hydrogen bonds have been constructed. To further understand the miscibility and processability of the complex solution, the dynamic rheological behaviors of the PANI/cellulose complex solution were investigated, for the first time, in the present work. Transmission electron microscope (TEM) results demonstrated that the inclusion complexes consisted of PANI and cellulose, existed in the aqueous solution, showing a good miscibility. Time-temperatures superposition (tTs) results indicated that the PANI/cellulose solution exhibited a homogeneous system, and the complex solution was more stable than the cellulose solution in the temperature range from 5 to 25 °C. Winter-Chambon theory was proved to be capable of describing the gelation behavior of the PANI/cellulose complex solution. The relaxation exponent at the gel point was calculated to be 0.74, lower than the cellulose solution, indicating strong interactions between PANI and cellulose chains. Relatively larger flow activation energy of the PANI/cellulose solution suggested the formation and rupture of linkages in "junction zones" during the gelation processes. Furthermore, PANI/cellulose gels could form at elevated temperature as a result of the physical cross-linking and chain entanglement, and it was a thermoirreversible process. Moreover, the PANI/cellulose solution remained a liquid state for a long time at the temperature range from 0 to 8 °C, which is important for the industry process.     

Morphologies and conformation transition of lentinan in aqueous NaOH solution

Molecular morphologies and conformation transition of lentinan, a beta-(1-->3)-D-glucan from Lentinus edodes, were studied in aqueous NaOH solution by atomic force microscopy (AFM), viscometry, multiangle laser light scattering, and optical rotation measurements. The results revealed that lentinan exists as triple-helical chains and as single random-coil chains at NaOH concentration lower than 0.05M and higher than 0.08M, respectively. Moreover, the dramatic changes in weight-average molecular weight Mw, radius of gyration [s2](1/2), intrinsic viscosity [eta], as well as specific optical rotation at 589 nm [alpha]589 occurred in a narrow range of NaOH concentration between 0.05 and 0.08M NaOH, indicating that the helix-coil conformation transition of lentinan was carried out more easily than that of native schizophyllan and scleroglucan, and was irreversible. For the first time, we confirmed that the denatured lentinan molecule, which was dissolved in 0.15M NaOH to be disrupted into single coil chains, could be renatured as triple helical chain by dialyzing against abundant water in the regenerated cellulose tube at ambient temperature (15 degrees C). In view of the AFM image, lentinan in aqueous solution exhibited the linear, circular, and branched species of triple helix compared with native linear schizophyllan or scleroglucan.     

Supermolecular structure of cellulose/amylose blends prepared from aqueous NaOH solutions and effects of amylose on structural formation of cellulose from its solution

We previously proposed a mechanism for the structural formation of cellulose from its solution using a molecular dynamics (MD) simulation and suggested that the initial structure from its solution plays a critical role in determining its final structure. Structural changes in the van der Waals-associated cellulose molecular sheet as the initial structure were examined by MD simulation; the molecular sheet was found to be disordered due to maltohexaoses as an amylose model in terms of the hydrogen bonding system of cellulose. The structure and properties of cellulose/amylose blends prepared from an aqueous NaOH solution were examined experimentally by wide-angle X-ray diffraction and dynamic viscoelasticity measurements. The crystallinity of cellulose in the cellulose/amylose blend films was lower than that of cellulose film. The diffraction peaks of the cellulose/amylose blends were slightly shifted; specifically, () was shifted to a higher angle, and (1 1 0) and (0 2 0) were shifted to lower angles. These experimental results probably resulted from the disordered molecular sheet, as revealed by MD simulations.     

Solubility and property of chitin in NaOH/urea aqueous solution

NaOH/urea aqueous solution has been used as a solvent for chitin for the first time. Effects of this solvent composition and temperature on the solubility and stability of chitin solution were studied with an optical microscope, from which 8 wt% NaOH/4 wt% urea concentrations were deduced as suitable and −20 °C as the appropriate temperature. The original and regenerated chitin were characterized by viscosity, elemental analysis, FI-IR and X-RD analysis, and the effect of solvent composition and temperature on chitin structure was investigated. It was inferred that 8 wt% NaOH/4 wt% urea solvent under low temperature adventitiously has little effect on chitin structure and the urea is of benefit to the stability of chitin solution. In addition, the rheological properties suggested that chitin aqueous solution in high concentration is a pseudoplastic fluid and that chitin aqueous solution in low concentrations is a Newtonian fluid. This chitin aqueous solution is sensitive to temperature and will transform it to a gel when temperature increases.     

Homogeneous quaternization of cellulose in NaOH/urea aqueous solutions as gene carriers

Quaternized celluloses (QCs) were homogeneously synthesized by reacting cellulose with 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC) in NaOH/urea aqueous solutions. The structure and solution properties of the QCs were characterized by using elemental analysis, FTIR, (13)C NMR, SEC-LLS, viscometer, and zeta-potential measurement. The results revealed that water-soluble QCs, with a degree of substitution (DS) value of 0.20-0.63, could be obtained by adjusting the molar ratio of CHPTAC to anhydroglucose unit (AGU) of cellulose and the reaction time. The QC solutions in water displayed a typical polyelectrolyte behavior, and the intrinsic viscosity ([eta]) value determined from the Fuoss-Strauss method increased with increasing DS value. Moreover, two QC samples (DS = 0.46 and 0.63) were selected and studied as gene carriers. The results of gel retardation assay suggested that QCs could condense DNA efficiently. QCs displayed relatively lower cytotoxicity as compared with PEI, and QC/DNA complexes exhibited effective transfection compared to the naked DNA in 293T cells. The quaternized cellulose derivatives prepared in NaOH/urea aqueous solutions could be considered as promising nonviral gene carriers.     

Rheological properties of aqueous solution containing xanthan gum and cationic cellulose JR400

Rheological properties of aqueous solution containing xanthan gum (XG) and cationic cellulose JR400 were investigated at different composition ratio, shear rate, pH and electrolyte concentrations. It was found that the mixing of XG and JR400 can induce a viscosity-increasing effect for the mixed solution. As the concentration fraction (f(JR)) of JR400 in the mixed solution increases from 0 to 0.40 with the total polymer concentration (c(t)) of 1%, the solution transforms from an elastic fluid into a viscoelastic one, while as f(JR) decreases from 1 to 0.78, the solution transforms from a viscous fluid into a viscoelastic one. At pH 5-10, both the viscosity and elasticity of XG/JR400 mixture (f(JR)=0.15) are independent of pH and the viscosity-increasing effect is obvious. Outside this pH range, the viscosity, elasticity and viscosity-increasing effect of the mixture decrease. The increase of added NaCl concentration and shear rate can induce the decrease of viscosity, elasticity and viscosity-increasing effect of the XG/JR400 mixture.     

Homogeneous synthesis and characterization of quaternized chitin in NaOH/urea aqueous solution

Water-soluble and white quaternized chitin (QC) was homogeneously synthesized by stirring transparent chitin solution (2%) in 8 wt%NaOH/4 wt% urea aqueous solution containing 2,3-Epoxypropyltrimethylammonium Chloride (EPTMAC) at 10 °C for 24 h. The structure and properties of quaternized chitin were characterized by FT-IR, XRD, ¹H NMR, GPC, element analysis and ζ-potential. The results indicate that quaternary groups were successfully incorporated onto chitin backbones and the degree of substitution (DS) of quaternary groups can be easily adjusted by changing the molar ratio of chitin unit to EPTMAC. Additionally, quaternized chitin shows better antibacterial activity against Escherichia coli and Staphylococcus aureus as compared with chitosan. Thus, this work provides a simply and “green” method to functionalize chitin and the resulting quaternized chitin may have potential applications in environmental, food and biomedical fields.     

Structure study of cellulose fibers wet-spun from environmentally friendly NaOH/urea aqueous solutions

In this study, structure changes of regenerated cellulose fibers wet-spun from a cotton linter pulp (degree of polymerization approximately 620) solution in an NaOH/urea solvent under different conditions were investigated by simultaneous synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). WAXD results indicated that the increase in flow rate during spinning produced a better crystal orientation and a higher degree of crystallinity, whereas a 2-fold increase in draw ratio only affected the crystal orientation. When coagulated in a H2SO4/Na2SO4 aqueous solution at 15 degrees C, the regenerated fibers exhibited the highest crystallinity and a crystal orientation comparable to that of commercial rayon fibers by the viscose method. SAXS patterns exhibited a pair of meridional maxima in all regenerated cellulose fibers, indicating the existence of a lamellar structure. A fibrillar superstructure was observed only at higher flow rates (>20 m/min). The conformation of cellulose molecules in NaOH/urea aqueous solution was also investigated by static and dynamic light scattering. It was found that cellulose chains formed aggregates with a radius of gyration, Rg, of about 232 nm and an apparent hydrodynamic radius, Rh, of about 172 nm. The NaOH/urea solvent system is low-cost and environmentally friendly, which may offer an alternative route to replace more hazardous existing methods for the production of regenerated cellulose fibers.     

The properties of enzyme-hydrolyzed cellulose in aqueous sodium hydroxide

Pure natural cellulose (softwood pulp) modified with cellulase is allowed to react with sodium hydroxide in a muller, and changes in structure and properties are investigated by FTIR and DSC. The reactivity of cellulose for some dissolving and derivatization processes is shown to be improved by an enzymatic hydrolysis and admixture with sodium hydroxide. The modified cellulose dissolved at 9% (wt) sodium hydroxide at -10 degrees C at 6% pulp consistency, while the DP of cellulose is >350.     

Dynamic measurement of the viscoelastic properties of skin

A wave propagation technique was used to measure the dynamic viscoelastic properties of excised skin when subjected to a low incremental strain. The propagation velocity, attenuation, and storage and loss moduli were determined from measured characteristics of a pulse propagating along a strip of skin. Experiments were conducted with the skin subjected to static stresses of 1500 Pa and 20,000 Pa. At low static stresses the skin response was viscoelastic with a loss tangent of approximately 0.6. In the frequency range of 0-1000 Hz, the wave velocity was relatively constant while the attenuation increased roughly linearly with frequency. However, results depended on the static stress. At the higher stress level the velocity was greater and the attenuation less than at the lower stress. At low stresses both the storage and loss moduli were relatively constant over the frequency range tested. The strong viscoelastic behavior of the tissue at higher frequencies is not predicted from models of the tissue determined from quasi-static test methods. In selecting a model to describe the behavior of skin, the test methods used for establishing the model must be consistent with its intended application.     

Effects of excluded volume and polydispersity on solution properties of lentinan in 0.1 M NaOH solution

Seven lentinan fractions of various weight-average molecular weights (M(w)), ranging from 1.45 x 10(5) to 1.13 x 10(6) g mol(-1) were investigated by static light scattering and viscometry in 0.1M NaOH solution at 25 degrees C. The intrinsic viscosity [eta] - M(w) and radius of gyration s(2)(z) (1/2) - M(w) relationships for lentinan in 0.1M NaOH solution were found to be represented by [eta] = 5.1 x 10(-3)M(w) (0.81) cm(3) g(-1) and s(2)(z) (1/2) = 2.3 x 10(-1)M(w) (0.58) nm, respectively. Focusing on the effects of the M(w) polydispersity with the Schulz-Zimm distribution function, the data of M(w), s(2)(z) (1/2), and [eta] was analyzed on the basis of the Yoshizaki-Nitta-Yamakawa theory for the unperturbed helical wormlike chain combined with the quasi-two-parameter (QTP) theory for excluded-volume effects. The persistence length, molecular weight per unit contour length, and the excluded-volume strength were determined roughly to be 6.2 nm, 980 nm(-1), and 0.1, respectively. Compared with the theoretical value calculated by the Monte Carlo model, the persistence length is longer than that of the single (1 --> 3)-beta-(D)-glucan chain. The results revealed that lentinan exists as single-stranded flexible chains in 0.1M NaOH solution with a certain degree of expansion due to the electrostatic repulsion from the interaction between the OH(-) anions and lentinan molecules.     

Solution properties of the acrylamide-modified cellulose polyelectrolytes in aqueous solutions

A novel cellulose-based polyelectrolyte (AM-C) containing acylamino (DS = 0.625) and carboxyl (DS = 0.148) groups was homogeneously synthesized from cellulose with acrylamide in NaOH/urea aqueous solutions. Solution properties of AM-C in aqueous solutions were investigated by laser light scattering, rheometry, and viscometry. The results indicated that AM-C could form large aggregates spontaneously in water with or without the addition of salts by the strong hydrogen bonds and electrostatic interaction between acylamino and carboxyl groups. Steady-shear flow study showed a Newtonian behavior of the solutions in the dilute regime while a shear-thinning behavior as the concentration increases. The critical concentration (c_e) for transition from dilute to concentrated solution was determined to be 0.7 wt %. Aqueous solutions of AM-C displayed good thermo-stability, reversible liquid-like characters attributing to the chemical modification. The derivation from Cox-Merz rule at relatively low concentration was related to the co-existence of single chain and large aggregates of AM-C in dilute regime. As the polymer concentration increased, the AM-C system was transformed into a homogeneous entanglement structure, resulting in the disappearance of deviations from the Cox-Merz rule.     

Preparation and properties of aqueous dispersions of cellulose nanospheres

A process for the formation of cellulose nanospheres appropriate as biodegraded bulking agent for composite materials has been considered. The properties of the starting material and resulting dispersions of cellulose nanospheres were studied. It was found that the characteristic structural modification of the cellulose nanospheres was cellulose II, and their size largely depended on the initial cellulose-containing precursor.     

Dynamic viscoelastic properties of solutions of shear-degraded deoxyribonucleic acid

Calf thymus and salmon sperm deoxyribouncleie acid were degraded by high-shear stirring to molecular weights M in the range of 1.3–3.2 × 10⁶ and purified by chromatography on methylated bovine serum albumin. Dynamic viscoelastic properties of the fragmented products, in aqueous glycerol solutions in the concentration range of c = 0.003–0.01 g./ml., were investigated with the apparatus of Birnboim and Ferry. At values of the product cM higher than 4 × 10³, the frequency dependence of the components of the complex shear modulus, G′ and G″, displayed a plateau region in which G′ > G″ – ων₁η_S, similar to that observed in concentrated solutions of coiling polymers where it is attributed to an entanglement network (ω is radian frequency, ν₁ volume fraction of solvent, and η₈, solvent viscosity). The width of this plateau region on the logarithmic frequency scale is given by Δ = 3.8 (log cM – 3.56). At lower values of cM, the frequency dependence is intermediate between those predicted by the theory of Zimm for flexible coiled macromolecules and by the theory of Kirkwood and Auer for rods. Fitting to the Zimm theory gives highly discrepant values for molecular weights, while fitting the low-frequency end of the dispersion to the Kirkwood-Auer theory gives reasonable agreement for both molecular weight and rotary diffusion coefficient. It is concluded that the helical fragments appear as nearly rigid rods in their behavior at very low frequencies, but at higher frequencies reveal substantial bending flexibility.     

Photochemical properties of Yt base in aqueous solution.

Photoreactivity of Yt base [I] has been studied in aqueous solution [pH approximately 6] saturated with oxygen. Two photoproducts (II,III], resulting from irradiation at lambda = 253.7 nm and lambda greater than or equal to 290 nm, were isolated and their structures determined. The quantum yield for Yt base disappearance [zeta dis] is 0.002 [lambda = 313 nm]. It was shown that dye-sensitized photooxidation of Yt base in aqueous solution occurs according to a Type I mechanism, as well as with participation of singlet state oxygen. Quantum yields, fluorescence decay times and phosphorescence of Yt base have been also determined.