A New Concept for Interpretation of the Viscoelastic Behavior of Aqueous Sodium Carboxymethyl Cellulose Systems.

Viscoelastic behaviors of aqueous systems of commercially available sodium carboxymethyl cellulose (NaCMC) samples with the degrees of substitution (DS) of approximately 0.68 and 1.3, and the weight-average molar masses (Mw) higher than 200 kg mol-1 dissolved in pure water and aqueous sodium chloride solutions were investigated over a wide concentration (c) range of NaCMC samples. The dependencies of the specific viscosity (ηsp), the average relaxation time (τw), and the reciprocal of the steady-state compliance (Je-1) on c were discussed. The relationships ηsp ∝ c3, τw ∝ c2, and Je-1 ∝ c, characteristic of the rod particle suspensions, were clearly observed in a range lower than the c where the critical gel behavior was observed. Thus, a new concept based on the rheology of rod particle suspensions was employed to interpret the viscoelastic behaviors obtained in the c range. In this context, NaCMC polymer molecules are assumed to behave as extended rod particles with length (L) and diameter (d), including effective electrostatic repulsive distances, due to the dissociation of Na+ in aqueous systems. Thus, the number density of polymer molecules is given to be ν = c/Mw, and viscoelastic parameters such as ηsp, τw, and Je-1 are calculated using the theoretical model for rod particle suspensions proposed by Doi and Edwards. This concept reasonably described not only the viscoelastic data obtained in this study but also those from other groups using NaCMC samples with different DS and Mw values.

Evidence of a Rod-like Structure for Hydroxypropyl Cellulose Samples in Aqueous Solution.

Because hydroxypropyl cellulose (HpC) is a popular polymeric material that forms a liquid crystalline phase in solutions with various kinds of solvents, including water, it is commonly thought that HpC has a typical rod-like structure in solution. In this study, the structures of commercial HpC samples in aqueous solution with average molar substitution numbers (MS) ranging from 3.6 to 3.9 and weight-average molar masses (Mw) ranging from 36 to 740 kg mol-1 were investigated in detail. We first used multiple techniques, including standard static and dynamic light scattering (SLS and DLS), neutron and X-ray scattering experiments, and viscometric measurements, to obtain clear evidence of rod-like structures quantitatively. The dependence of excess scattering intensities for HpC samples under dilute conditions on the magnitude of the scattering vector over a wide range from 8.9 × 10-3 to 3.0 × 10 nm-1 was reasonably described by the form factor of rod particles with length (L) and diameter (d). Although the determined L value was close to the contour length (lc) calculated from the Mw values in the lower Mw range, L became obviously less than lc with increasing Mw. The radius of gyration (Rg) determined via SLS measurements was proportional to L by a factor of approximately 3.5 ∼ √12 over the Mw range examined. These observations revealed that the conformation of HpC molecules changes from an elongated single chain to a certain folded structure, maintaining the shape of the rod-shaped particles. Moreover, the Mw dependencies of the intrinsic viscosities and translational diffusion coefficients of the HpC samples resulting from DLS measurements were reasonably described with a theoretical rod-like particle model, assuming that L and d are identical to those resulting from the scattering behaviors.

Conformation and Structure of Hydroxyethyl Cellulose Ether with a Wide Range of Average Molar Masses in Aqueous Solutions.

The solution properties of a water-soluble chemically modified cellulose ether, hydroxyethyl cellulose (HeC), were examined using static light scattering (SLS), dynamic light scattering (DLS), small-to-wide-angle neutron scattering (S-WANS), small-to-wide-angle X-ray scattering (S-WAXS) and viscometric techniques at 25 °C. The examined HeC samples had average molar substitution numbers ranging from 2.36 to 2.41 and weight average molar masses (Mw) that fell within a wide range from 87 to 1500 kg mol-1. Although the relationship between the determined radius of gyration (Rg) and Mw was described as Rg ∝ Mw~0.6, as is observed usually in flexible polymer solutions in good solvents, the observed scattering vector (q) dependencies of excess Rayleigh ratios were well interpreted using a rigid rod particle model, even in high-Mw samples. Moreover, the ratios of the formed particle length (L) evaluated assuming the model for rigid rods to the determined Rg showed the relationship LRg-1 ~ 3.5 irrespective of Mw and were close to those theoretically predicted for rigid rod particle systems, i.e., LRg-1 = 12. The observed SLS behavior suggested that HeC molecules behave just like rigid rods in aqueous solution. As the L values were not simply proportional to the average molecular contour length calculated from the Mw, the chain conformation or structure of the formed particles by HeC molecules in aqueous solution changed with increasing Mw. The q dependencies of excess scattering intensities observed using the S-WANS and S-WAXS experiments demonstrated that HeC molecules with Mw less than 200 kg mol-1 have a diameter of ~1.4 nm and possess an extended rigid rod-like local structure, the size of which increases gradually with increasing Mw. The observed Mw dependencies of the translational and rotational diffusion coefficients and the intrinsic viscosity of the particle suspensions strongly support the idea that the HeC molecules behave as rigid rod particles irrespective of their Mw.

Elongated Rodlike Particle Formation of Methyl Cellulose in Aqueous Solution.

The conformation and structure of methyl cellulose (MC) ether samples dissolved in pure water under dilute conditions were carefully reconsidered based on the results obtained using small-to-wide-angle neutron scattering (S-WANS), static light scattering (SLS), dynamic light scattering (DLS), and viscometric techniques. The examined MC samples possessed an average degree of substitution by methyl groups per glucose unit of ca 1.8 and weight average molar masses (M w), ranging from 23 to 790 kg mol-1. S-WANS experiments clearly demonstrated that the samples possess highly elongated rigid rodlike local structures in deuterium oxide solutions with weak periodicities of ca 0.4 and 1.0 nm on a length scale, which correspond to the average intermolecular distance between molecular chain portions facing each other in the formed rodlike structure and the repeating length of the monomeric cellobiose unit of molecular chains, respectively. Ratios of the particle length (L) to the radius of gyration (R g) determined by SLS techniques approximately showed the relationship LR g -1 = holding in rigid rods over the entire M w range examined in this study. However, the folding number, defined as the ratio of the average molecular contour length (l) to L, remained at the value of lL -1 ∼ 2, representing an elongated one-folded hairpin structure, until M w ∼ 300 kg mol-1 and increased substantially up to ca 4.9 at the highest M w of 790 kg mol-1. The observed increase in the lL -1 value corresponded well with an increase in the diameter of the formed rod with increasing M w observed in the S-WANS data. The M w dependencies of the translational diffusion coefficient determined via DLS measurements and that of the intrinsic viscosity detected via viscometric techniques also distinctly demonstrated that particles formed by the MC samples dissolved in aqueous solution behave as elongated rigid rods irrespective of M w.

Clinical analysis of the pediatric inpatients with lower respiratory tract infection due to human metapneumovirus.

Human metapneumovirus (hMPV) is known as one of popular agents of acute respiratory infection in children. We reviewed the patients' background, result of initial blood test, bacterial culture, chest X-ray and clinical features of hospitalized children with lower respiratory tract infections caused by hMPV from March 2014 to February 2015 and compared them with the infections due to respiratory syncytial virus (RSV) and other causative agents. Of 419 patients tested by rapid virus antigen tests, 35 were positive for hMPV, 145 were positive for RSV, and 239 were negative for both viruses. Most of hMPV infections occurred between March and June, and 72% of households of hMPV-positive children got sick. hMPV-positive children did not have any specific symptoms such as wheezing in RSV- positive children. However, many of them were admitted due to prolonged high fever and/or ill appearance despite of no respiratory distress. Although it is said that hMPV-positive children admitted to hospitals tend to have pneumonia, the ratio of children'with pneumonia in this study was less than 60%.

Antioxidant and osteogenic properties of anodically oxidized titanium.

Cells adhering onto implant surfaces are subjected to oxidative stress during wound healing processes. Although titanium and its alloys are among the most frequently used biomaterials in orthopedic and dental implants, titanium surfaces do not have antioxidant properties, and cells grown on these surfaces can show permanent oxidative stress. The present study assessed the antioxidant property and osteogenic properties of titanium samples with or without oxidation treatments. A thick rutile TiO2 film was observed on thermally oxidized titanium surfaces, while amorphous anatase TiO2 formed on anodically oxidized titanium surfaces prepared by discharging in 1 M Na2HPO4. A resistance to the depletion of reduced glutathione in adherent osteoblasts, which correlates with antioxidant behavior, occurred on anodically oxidized titanium. Enhanced osteogenic gene expressions and nano-biomechanical properties of mineralized tissue were achieved on anodically oxidized titanium, in comparison with thermally oxidized or untreated titanium. Thus, anodic oxidation by discharging in electrolyte is expected to be a useful surface modification for titanium implants.

Antimicrobial and osteogenic properties of a hydrophilic-modified nanoscale hydroxyapatite coating on titanium.

Hydroxyapatite (HA)-coated titanium (Ti) is commonly used for implantable medical devices. This study examined in vitro osteoblast gene expression and antimicrobial activity against early and late colonizers of supra-gingival plaque on nanoscale HA-coated Ti prepared by discharge in a physiological buffered solution. The HA-coated Ti surface showed super-hydrophilicity, whereas the densely sintered HA and Ti surfaces alone showed lower hydrophilicity. The sintered HA and HA-coated Ti surfaces enhanced osteoblast phenotypes in comparison with the bare Ti surface. The HA-coated Ti enabled antimicrobial activity against early colonizers of supra-gingival plaques, namely Streptococcus mitis and Streptococcus gordonii. Such antimicrobial activity may be caused by the surface hydrophilicity, thereby leading to a repulsion force between the HA-coated Ti surface and the bacterial cell membranes. On the contrary, the sintered HA sample was susceptible to infection of microorganisms. Thus, hydrophilic-modified HA-coated Ti may have potential for use in implantable medical devices. From the Clinical Editor: This study establishes that Hydroxyapatite (HA)-coated titanium (Ti) surface of implanted devices may result in an optimal microenvironment to control and prevent infections and may have potential future clinical applications.