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.

Rigid Rod-like Viscoelastic Behaviors of Methyl Cellulose Samples with a Wide Range of Molar Masses Dissolved in Aqueous Solutions.

The viscoelastic behaviors of aqueous solutions of commercially available methyl cellulose (MC) samples with a degree of substitution of 1.8 and a wide range of weight average molar masses (Mw) were investigated over a wide concentration (c) range at some temperatures from -10 to 25 °C. The viscoelastic parameters useful to discuss the structure and dynamics of MC-forming particles in aqueous solutions were precisely determined, such as the zero-shear viscosity (η0), the steady-state compliance (Je), the average relaxation time (τw), and the activation energy (E*) of τw. Because previously obtained scattering and intrinsic viscosity ([η]) data revealed that the MC samples possess a rigid rod-like structure in dilute aqueous solutions over the entire Mw range examined, the viscoelastic data obtained in this study were discussed in detail based on the concept of rigid rod particle suspension rheology. The obtained Je-1 was proportional to the number density of sample molecules (ν = cNAMw-1, where NA means the Avogadro's constant) over the ν range examined irrespective of Mw. The reduced relaxation time (4NAτw(3νJe [η]ηmMw)-1), where ηm means the medium viscosity, was proportional to (νL3)2, L; the average particle length depending on Mw for each sample was determined in a previous study; and the reduced specific viscosity (ηspNAL3(Mw [η])-1), where ηsp means the specific viscosity, was proportional to (νL3)3 in a range of νL3 < 3 × 102. These findings were typical characteristics of the rigid rod suspension rheology. Therefore, the MC samples behave as entangling rigid rod particles in the νL3 range from rheological points of view. A stepwise increase in E* was clearly observed in a c range higher than the [η]-1 value irrespective of Mw. This observation proposes that contact or entanglement formation between particles formed by MC molecules results in an increase in E*.

Structure and Conformation of Hydroxypropylmethyl Cellulose with a Wide Range of Molar Masses in Aqueous Solution─Effects of Hydroxypropyl Group Addition.

The structure of hydroxypropylmethyl cellulose (HpMC) samples with a wide range of weight average molar masses (Mw) from 23 to 5000 kg mol-1, a controlled degree of substitution (DS) of 1.9 by methyl groups, and a molar substitution number (MS) of 0.25 by hydroxypropyl groups dissolved in aqueous solution was examined using static light scattering (SLS), dynamic light scattering (DLS), small-to-wide angle neutron scattering (S-WANS) techniques, and intrinsic viscosity ([η]) measurements. The determined Mw and the radius of gyration (Rg) showed the relationships Rg ∝ Mw1.0 and [η] ∝ Mw1.7 in a range of Mw < 100 kg mol-1, similar to rigid rod molecules in solution. However, exponents in the relationships decreased gradually with increasing Mw and reached ∼0.5 in a high Mw region, which is a typical value of flexible chain molecules for both Rg and [η]. These observations suggest that the HpMC samples behave as semiflexible rods with a certain persistence length (lp). The ratios of the hydrodynamic radius via DLS measurements to Rg also supported semiflexible rod behavior. Particle form factors and the average lengths (L) resulting from SLS and S-WANS experiments are well described with rigid rod particles in the range of Mw < 100 kg mol-1 and semiflexible rods with lp ∼ 100 nm in Mw > 100 kg mol-1. Because the average contour length (lc) calculated from Mw is approximately twice as long as L in the Mw range < 100 kg mol-1, the formed HpMC particles possess a folded hairpin-like elongated rigid rod structure. However, the lc/L value increases gradually in the range Mw > 200 kg mol-1, where the formed HpMC particles behave as semiflexible rods. The formed particle structure was substantially different from that found in methyl cellulose samples with a similar DS value, which showed rod-like behavior over a wide Mw range. The addition of hydroxypropyl groups only at MS = 0.25 effectively changed the formed particle structure.

Hydrogen-Bond Configurations of Hydration Water around Glycerol Investigated by HOH Bending and OH Stretching Analysis.

Toward a comprehensive understanding of the mechanism of glycerol as a moisturizer, studies on the hydrogen-bond (HB) structure of hydration water, which is known to be disordered by glycerol, are insufficient. To this aim, we evaluated the HB configurations based on the HOH bending and OH stretching spectra of the hydration water from those of glycerol/water mixtures by subtracting the contributions of bulk water and glycerol using dielectric relaxation spectroscopy. Analysis of the HOH bending band showed that hydration water-donating HBs lose the intermolecular bending coupling with increasing glycerol by replacing the water-water HBs with water-glycerol HBs. The OH stretching band provided more detailed insight into the HB configuration, indicating that the double-donor double-acceptor and double-donor single-acceptor configurations in bulk water change to a predominantly double-donor single-acceptor configuration in hydration water around glycerol. The formation of more donor HBs than acceptor HBs may be due to the steric constrains by glycerol and/or differences in the partial charge on the oxygen atom between water and glycerol.

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.

Evidence of Long Two-Dimensional Folding Chain Structure Formation of Poly(vinylidene fluoride) in N-Methylpyrrolidone Solution: Total Form Factor Determination by Combining Multiscattering Data.

Very recently, we proposed that poly(vinylidene fluoride) (PVDF) dissolves in a long rectangular column conformation induced by the formation of a two-dimensional folding chain structure in an N-methylpyrrolidone (NMP) solution based on the results obtained from static light scattering (SLS), small- to wide-angle X-ray scattering (S-WAXS), and viscometric experiments. Small- to wide-angle neutron scattering (S-WANS) experiments were able to provide clear decisive evidence for the presence of such a two-dimensional folding chain structure in a deuterated (d)NMP solution of PVDF samples with two different weight average molar masses (M w) of 100 and 1200 kg mol-1, even under dilute conditions at concentrations less than the overlapping concentrations due to the quite high neutron scattering contrast obtained by using (d)NMP as a solvent. An increase in M w from 100 to 1200 kg mol-1 substantially increases the particle length and width from L = 80 to 350 nm and w 2 = 5.0 to 15 nm, respectively, while the thickness, w 1, is maintained at 0.3 nm. Since L is much longer than w 2 irrespective of M w, the particles formed by PVDF molecules in NMP simply behave as long rigid rods in a scattering vector (q) range covered by SLS measurements. A combination study of S-WANS and S-WAXS experiments covering a higher q range with the SLS techniques could clearly reveal increases in both the L and w 2 values with increasing M w.

First Observation of the Hydration Layer around Polymer Chain by Scattering and Its Relationship to Thromboresistance: Dilute Solution Properties of PMEA in THF/Water.

Poly(2-methoxyethyl acrylate) (PMEA) is known to exhibit excellent thromboresistance, i.e., hardly causing blood-clot formation on its surface. Hence, PMEA and its analogues have been commercially used for blood-contacting materials in medical devices. In this study, we investigated the conformation and solvation state of PMEA in mixtures of tetrahydrofuran (THF) and water with various water volume fractions (ϕwater) by viscosity, sedimentation equilibrium, small-angle X-ray scattering (SAXS), and dielectric relaxation measurements. We also comparatively investigated those of poly[2-(2-methoxyethoxy)ethyl methacrylate] (PMe2MA) and polystyrene (PS). For all of these, THF is a good solvent and water is a nonsolvent or poor solvent. PMe2MA and PMEA show equally good thromboresistance, while PS does not at all. The solution properties of PMe2MA and PMEA were found to be quite different from PS. There are clear attractive interactions (or correlation) between the PMEA chain (or PMe2MA) and the waters in the vicinity of the chain despite their water insolubility. These correlated waters give additional scattering and the angular dependence of SAXS was analyzed in terms of the hydration layer model that has been used in protein solution scattering. The hydration is related to increasing both the chain stiffness and excluded volume. These distinctive properties are likely related to the origin of its good thromboresistance.

Low Quality of Warfarin Therapy is Associated With Female Gender but Not With Polypharmacy in Patients With Atrial Fibrillation.

Background: We examined the impact of polypharmacy on the quality of the anticoagulation therapy in patients with atrial fibrillation. We also examined the factors that affect the stability of warfarin therapy. Methods and Results: This retrospective study was conducted using data from 157 consecutive outpatients with atrial fibrillation in a single tertiary referral hospital. Patients who were prescribed warfarin continuously and for whom PT-INR was examined at least three times in a year were included in this study. We examined the quality of warfarin therapy using time in the therapeutic INR range (TTR), percentage of PT-INR determinations in range (PINRR), and the coefficient variation (CV) of PT-INR. We found that the number of prescribed medicines was significantly associated with high BMI and low eGFR, but not with TTR, PINRR, and the coefficient variation of PT-INR in patients with atrial fibrillation. We also found that female gender was independently associated with low PINRR in this study population. Conclusion: Polypharmacy did not deteriorate the quality of warfarin therapy in patients with atrial fibrillation treated in the tertiary referral hospital. Female gender was an independent predictor of the low quality of warfarin therapy.

Hydration/Dehydration Behavior of Hydroxyethyl Cellulose Ether in Aqueous Solution.

Hydroxyethyl cellulose (HeC) maintains high water solubility over a wide temperature range even in a high temperature region where other nonionic chemically modified cellulose ethers, such as methyl cellulose (MC) and hydroxypropylmethyl cellulose (HpMC), demonstrate cloud points. In order to clarify the reason for the high solubility of HeC, the temperature dependence of the hydration number per glucopyranose unit, nH, for the HeC samples was examined by using extremely high frequency dielectric spectrum measuring techniques up to 50 GHz over a temperature range from 10 to 70 °C. HeC samples with a molar substitution number (MS) per glucopyranose unit by hydroxyethyl groups ranging from 1.3 to 3.6 were examined in this study. All HeC samples dissolve into water over the examined temperature range and did not show their cloud points. The value of nH for the HeC sample possessing the MS of 1.3 was 14 at 20 °C and decreased gently with increasing temperature and declined to 10 at 70 °C. The nH values of the HeC samples are substantially larger than the minimum critical nH value of ca. 5 necessary to be dissolved into water for cellulose ethers such as MC and HpMC, even in a high temperature range. Then, the HeC molecules possess water solubility over the wide temperature range. The temperature dependence of nH for the HeC samples and triethyleneglycol, which is a model compound for substitution groups of HeC, is gentle and they are similar to each other. This observation strongly suggests that the hydration/dehydration behavior of the HeC samples was essentially controlled by that of their substitution groups.

Polypharmacy Is Associated With Accelerated Deterioration of Renal Function in Cardiovascular Outpatients.

BACKGROUND: Polypharmacy is associated with poor prognosis of patients with various diseases. However, it has not been precisely addressed how polypharmacy affects the clinical characteristics of the cardiovascular outpatients. The aim of this study is to search for the clinical characteristics related to the number of prescribed drugs in the cardiovascular outpatients. Also, we examine whether the number of the prescribed drugs affects the worsening of renal function. METHODS: This retrospective study was conducted using the data of 259 continuous cardiovascular outpatients who were examined complete blood count (CBC) and serum creatinine. RESULTS: In the univariate analysis, the number of prescribed drugs were associated with the number of cardiovascular diseases or their risk factors, age, white blood cells, platelet, body mass index, anemia, and chronic kidney disease stage 3b or higher. In the multivariable analysis, independent variables that significantly correlated with the number of prescribed drugs were the number of cardiovascular diseases or their risk factors, anemia, and chronic kidney disease stage 3b or higher. Among 259 patients, 208 patients received follow-up examination of serum creatinine. The number of prescribed drugs was the only factor that was associated with accelerated deterioration of renal function. CONCLUSIONS: Polypharmacy is associated not only with poor renal function but with accelerated deterioration of renal function. Polypharmacy may be causally related with renal dysfunction.

Reconsideration of the conformation of methyl cellulose and hydroxypropyl methyl cellulose ethers in aqueous solution.

The structure and conformation of methyl cellulose (MC) and hydroxypropyl methyl cellulose (HpMC) ether samples dissolved in dilute aqueous (D2O) solutions at a temperature of 25 °C were reconsidered in detail based on the experimental results obtained using small- and wide-angle neutron scattering (S-WANS) techniques in a range of scattering vectors (q) from 0.05 to 100 nm-1. MC samples exhibited an average degree of substitution (DS) by methyl groups per glucose unit of DS = 1.8 and the weight average molar mass of M w = 37 × 103 and 79 × 103 g mol-1. On the other hand, HpMC samples possessed the average molar substitution number (MS) by hydroxypropyl groups per glucose unit of MS = 0.25, DS = 1.9, and M w = 50 × 103 and 71 × 103 g mol-1. The concentration-reduced scattering intensity data gathered into a curve for the solutions of identical sample species clearly demonstrated the relationship I(q)c -1 ∝ q -1 in a q range from 0.05 to 2.0 nm-1, and small interference peaks were found at q ∼ 7 and 17 nm-1 for all examined sample solutions. These observations strongly revealed that form factors for both the MC and HpMC samples were perfectly described with that for long, rigid rod particles with average diameters of 0.8 and 0.9 nm, respectively, and with an inner structure with characteristic mean spacing distances of ca. 0.9 and 0.37 nm, respectively, regardless of the chemically modified conditions and molar masses. A rationally speculated structure model for the MC and HpMC samples dissolved in aqueous solution was proposed.

Molecular motions, structure and hydration behaviour of glucose oligomers in aqueous solution.

The degree of polymerization and temperature dependencies of the molecular motions, configuration and hydration behaviour of glucose oligomers (Gn, n = 2 to 7, degree of polymerization) in aqueous solutions were investigated using extremely high-frequency dielectric spectrum measuring techniques up to 50 GHz. The obtained dielectric spectra for the aqueous Gn solutions were well decomposed into four Debye-type relaxation modes. The fastest relaxation mode j = 1 was assigned to the rotational process of free water molecules in the sample solution. The second fastest mode j = 2 was attributed to the exchange process of hydrated water molecules with free water molecules, and the third mode j = 3 was recognized as the rotational process of hydroxy groups attached to each repeating glucopyranoside (Glu) unit after their lifetimes of intramolecular hydrogen bonding. The slowest mode j = 4 at a relaxation time depending on n was assigned to the overall rotation of the Gn molecules possessing configurations similar to that of small fragments of single helical V-type crystalline structures at low temperatures. The presence of the dielectric mode j = 4 revealed that the Glu units possessed electric dipole moments carrying a component parallel to the Gn backbone aligned with the C1 → C4 direction. The number of hydrated water molecules per Glu unit (hydration number, nH) was determined for Gns in aqueous solutions in the temperature range from 10 °C to 70 °C via the relaxation strength of mode j = 1. The Gn oligomers were highly soluble in water within the temperature range examined, possessing nH values slightly dependent on n and demonstrated clear dehydration behaviour at approximately 30 °C with increasing temperature. These temperature dependencies of nH were substantially weaker than those of a model Glu unit compound, methyl α-d-glucopyranoside (G1). Then, the polymerization of glucose oligomers effectively depresses the dehydration behaviour of G1.

Anti-parallel dimer and tetramer formation of cyclic and open structure tertiary amides, N-methyl-2-pyrrolidone and N,N-dimethylacetamide, in solution of a non-polar solvent, benzene.

We examined the dielectric (DE) and nuclear magnetic resonance (NMR) spectroscopic behaviour of N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc), which are tertiary amide compounds that bear five-membered cyclic and open structures, respectively. They were examined to investigate the formation of anti-parallel dimers and tetramers in a dipole configuration in the pure liquid state and in benzene solution over a wide concentration range at 25 °C. Because the Kirkwood correlation factors of electric dipoles considerably decreased with increasing concentrations in both the NMP and DMAc systems and because the second DE relaxation modes were clearly observed to exhibit relaxation times that are longer than those of the first modes assigned to the rotational relaxation of monomeric molecules, anti-parallel dimers are formed due to dipole-dipole interactions with increasing concentrations. Assuming a chemical process between the monomers (MONs) and the anti-parallel dimer (DIM), 2MON ⇄ DIM, the equilibrium constants for the anti-parallel dimer formation were determined to be KDEd ∼ 1.2 M-1 for NMP and 0.35 M-1 for DMAc, based on the first DE relaxation strength. The fact that the evaluated KDEd values substantially increased with increasing concentrations in the range above ca. 1.0 M strongly suggested the formation of higher order intermolecular associations instead of dimers. Chemical shifts in the 1H-NMR spectra assigned to (N)CH3 and (5)CH2 protons of NMP and the two (Nα)CH3 and (Nß)CH3 protons of DMAc dissolved in (d)Bz substantially changed with increasing concentrations due to the formation of intermolecular associations. The states occupied by MONs, DIMs and tetramers (TETs) were evaluated from chemical shift data as a function of the concentrations in the NMP and DMAc systems. Then, the equilibrium constants for the dimer and tetramer formation (2DIM ⇄ TET) were determined to be KNMRd ∼ 1.2 M-1 and KNMRt ∼ 0.2 M-1 for NMP and KNMRd ∼ 0.35 M-1 and KNMRt ∼ 0.25 M-1 for DMAc. The reason for the differences in the equilibrium constants between NMP and DMAc may be related to the difference in motional freedom between the cyclic and open structures. The formation of anti-parallel DIMs and TETs was also confirmed by semi-empirical quantum chemical calculations for both NMP and DMAc molecules.

Transport Properties of Commercial Cellulose Nanocrystals in Aqueous Suspension Prepared from Chemical Pulp via Sulfuric Acid Hydrolysis.

A cellulose nanocrystal (CNC) sample prepared from chemical pulp via sulfuric acid hydrolysis procedures has been supplied by InnoTech Alberta Inc. in the shape of white dry powder as a prototype product. Some transport coefficients were precisely investigated for the CNC sample in aqueous suspensions at the room temperature of 25 °C such as the average rotational and translational diffusion coefficients (D r and D t) and viscoelastic relaxation times (τv) at dilute conditions. The determined values, D r ≈ 2.3 × 103 s-1 and D t ≈ 1.0 × 10-11 m2 s-1, using depolarized and usual dynamic light scattering (DLS) techniques, respectively, proposed the consistent length and width of L ≈ 170 nm and W ≈ 7.6 nm via a theoretical model for monodisperse rigid rods dispersed in pure water. The viscoelastic behavior for aqueous CNC suspensions containing spherical probe particles was examined using DLS rheological techniques. The obtained value of τv = 1.0 × 10-4 s fairly agrees with that of (6D r)-1 ≈ 7.4 × 10-5 s. Because the theoretical model for monodisperse rods denotes the relationship τv = (6D r)-1, this observation strongly confirms that the CNC sample behaves as approximately monodisperse rigid rodlike particles. Transmission electron microscopy (TEM) images clearly demonstrated a bimodal distribution in rod length with major and small minor peaks at ca. 150 and 240 nm, respectively. Then, the reason for the observed disagreement between the L values resulted from the transport coefficients and the major peak in TEM images is the presence of the small minor component with L ≈ 240 nm. Consequently, individual nanosize rodlike crystalline particles in the CNC sample well disperse without forming large aggregations because of strong interactions and behave as isolated individual rods in dilute aqueous suspensions.

Relationship between global and segmental dynamics of poly(butylene oxide) studied by broadband dielectric spectroscopy.

Relationship between segmental relaxation and normal-mode relaxation has been studied for molten poly(butylene oxide)s having various molecular weights by broadband dielectric spectroscopy over a wide temperature (T) range. We found that T dependence of the segmental relaxation time, τs, was weaker than the normal mode time, τn, at high T(>250 K ∼ Tg + 50 K), and the τn/τs ratio systematically decreased with increasing temperature. This high temperature complexity, whose mechanism has not been discussed in detail so far, was quantitatively explained by assuming the two step processes: local conformation change of polymers (elementary process) occurs first, and then the motion of a segment unit (second process) occurs. It was also found that the elementary process was strongly correlated with the experimentally observed ß-relaxation.

Pravastatin reduces radiation-induced damage in normal tissues.

Pravastatin is an inhibitor of 3-hydroxy-3-methyl- glutaryl-coenzyme A reductase that has been reported to have therapeutic applications in a range of inflammatory conditions. The aim of the present study was to assess the radioprotective effects of pravastatin in an experimental animal model. Mice were divided into two groups: The control group received ionizing radiation with no prior medication, while the pravastatin group received pravastatin prior to ionizing radiation. Pravastatin was administered orally at 30 mg/kg body weight in drinking water at 24 and 4 h before irradiation. Intestinal crypt epithelial cell survival and the incidence of apoptosis in the intestine and lung were measured post-irradiation. The effect of pravastatin on intestinal DNA damage was determined by immunohistochemistry. Finally, the effect of pravastatin on tumor response to radiotherapy was examined in a mouse mesothelioma xenograft model. Pravastatin increased the number of viable intestinal crypts and this effect was statistically significant in the ileum (P<0.0001). The pravastatin group showed significantly lower apoptotic indices in all examined parts of the intestine (P<0.0001) and tended to show reduced apoptosis in the lung. Pravastatin reduced the intestinal expression of ataxia-telangiectasia mutated and gamma-H2AX after irradiation. No apparent pravastatin-related differences were observed in the response of xenograft tumors to irradiation. In conclusion, pravastatin had radioprotective effects on the intestine and lung and reduced radiation-induced DNA double-strand breaks. Pravastatin may increase the therapeutic index of radiotherapy.

Polaprezinc protects normal intestinal epithelium against exposure to ionizing radiation in mice.

Polaprezinc (PZ), an antiulcer drug, has been reported to have antioxidant effects. The purpose of the present study was to assess the radioprotective effects of PZ in the normal intestine of C57BL/6J mice. PZ was orally administered at 100 mg/kg body weight in the drinking water. Firstly, the present study compared the survival of normal intestinal crypt epithelial cells with mice that received PZ prior to or following irradiation. Next, the present study examined the sequential changes of the incidence of apoptosis in the normal intestine of mice that received irradiation. The mice that received PZ prior to irradiation demonstrated a stronger protective effect on the normal intestine compared with those that received PZ after irradiation. The present study therefore administrated PZ 2 h before irradiation in the subsequent experiments. The mice receiving PZ developed fewer apoptotic cells in the duodenum, jejunum and ileum. Radiation-induced cell death occurred with a peak at position 10 or lower from the base of the crypt axis, and was subsequently reduced by PZ treatment. Pretreatment with PZ protected the normal intestinal tissues from radiation-induced apoptosis.

Pronounced Dielectric and Hydration/Dehydration Behaviors of Monopolar Poly(N-alkylglycine)s in Aqueous Solution.

Poly(N-methylglycine) (NMGn) and poly(N-ethylglycine) (NEGn) obtained by polymerization reactions initiated by benzylamine have no carboxy termini, such as those in normal polyamides, but have only amino termini, which exist primarily as cations in aqueous media at a pH value of ca. 9.5, observed in aqueous solutions without any buffer reagents. Therefore, polypeptoids, such as NMGn and NEGn, possessing a degree of polymerization (DP) higher than a certain value behave as cationic monopolar polymeric chain molecules in aqueous solution. It has not been clarified so far whether such a monopolar chain molecule exhibits dielectric relaxation (DR) behavior resulting from its molecular motions in aqueous media as dipolar chain molecules. DR measurements revealed that NMG19 and NEG17, possessing DPs of 19 and 17, respectively, dissolved in pure water clearly demonstrated pronounced DR behavior caused by fluctuating molecular motions of cationic termini at relaxation times of ca. 4 and 9 ns at 10 °C (283 K). The hydration numbers of NMG19 and NEG17 per monomeric residue (nm) in aqueous solution were also evaluated via DR data as functions of temperature, and the nm value of ca. 4.5 at 10 °C showed a remarkable reduction to ca. 2.0 around 40 °C (313 K) and 30 °C (303 K), depending on differences in the substituted group: methyl and ethyl groups. This temperature-dependent hydration/dehydration behavior found in NMG19 and NEG17 slightly influenced the sizes and molecular dynamics of the monopolar chain molecules in aqueous solution.