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The crystalline structure of the starch of six cultivars of rice for sake brewing were studied by small-/wide-angle X-ray scattering and X-ray diffraction by synchrotron radiation. The starch structures all provide a lamella structure of a crystal phase and an amorphous phase. The crystal phases of the starches show A-type starch and some B-type starch. The B-type starch content varied slightly between the different rice cultivars, with Yamadanishiki-type containing the most. The change in starch structure upon the early stage of sake brewing was also investigated. The crystal structure and lamella structure were maintained after soaking in water. However, the structure of starch changed to an amorphous phase upon steaming and gelatinization. While the steamed rice was cooled at 15 °C, the starch crystal structure, but not lamella structure, was recovered. Furthermore, the dependence of B-type starch content on the cultivars was also recovered. This result indicated that the crystals of starch destroyed imperfectly, but also crystalline nuclei remained after steaming.

A cellulose triacetate (CTA) dialysis membrane is generally regarded as a homogeneous membrane. The objective of the present study was to characterize the internal structure of CTA dialysis membranes. We used FB-150E, FB-150F, and FB-150UH CTA hollow-fiber membrane dialyzers. The pore-size distribution and porosity of the CTA membrane surfaces were calculated from surface image data obtained by using atomic force microscopy (AFM). The internal porosity of the CTA membranes was measured by weight analysis. Further, the pore diameter of the CTA membranes was calculated from data on pure-water permeability and diffusive permeability using a pore diffusion model. The pore diameters on the inner surface of the CTA membranes were much greater than those on the outer surface. The surface porosity determined using AFM was much lesser than the internal porosity determined using weight analysis. The pore diameters on the inner and outer surfaces of the CTA membranes determined using AFM were much lesser than pore diameter calculated on the basis of the permeability data. We conclude that the CTA dialysis membrane, which is generally regarded as a homogeneous membrane, is actually a multilayer membrane. The CTA dialysis membrane has tight layers at the inner and outer surfaces, and has a loose layer inside the membrane.

Near-field infrared microspectroscopy (NFIR) is a newly developed surface analysis method that is based on functional-group analysis and has a high spatial resolution. The objective of the present study is to perform nanoscale functional-group analysis of dialysis membrane surfaces by using NFIR. We focused on polyvinylpyrrolidone (PVP), which is employed as an additive to hydrophilize and create pores in synthetic polymer dialysis membranes, and evaluated the PVP distribution on the inner surface of the dialysis membranes. Dialysis membranes made from polysulfone (PSf) and polyester–polymer alloy (PEPA) were first assessed by NFIR and then by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). The nanoscale NFIR analysis showed heterogeneous distribution of PVP on the PSf membrane even though the amount of PVP on the membrane surface was high. PVP was homogeneously distributed on the PEPA membrane even though the amount of PVP on the membrane surface was low. In contrast, the microscale ATR-FTIR results showed that PVP was homogeneously distributed on both PSf and PEPA membranes. PVP-rich and PVP-poor regions were distinguishable by NFIR and not by ATR-FTIR, because the spatial resolution of NFIR is higher than that of ATR-FTIR. This study demonstrates for the first time that NFIR can provide nanoscale chemical information on the structures of porous membranes.

Membrane charge affects diffusive permeability for ions. Hence, evaluation of membrane charge density is necessary to clarify diffusive permeability for ions. The objective of the present study is to measure stable and reproducible membrane potentials with hollow-fiber membranes and to evaluate the electrostatic characteristics of dialysis membrane by applying membrane potential measurement method for flat membrane to hollow-fiber membranes. Membrane charge density was calculated from data on the membrane potential. Values for membrane charge density obtained as electrostatic characteristics of AM-UP150 (regenerated cellulose), KF-15C (ethylenevinylalcohol copolymer), PAN-150SF (polyacrylonitrile), AM-BC150X (polyethylene glycol-modified regenerated cellulose), FB-150U (cellulose triacetate), APS-150E (polysulfone), FLX-15GW (polyester–polymer alloy) and BLF-10GW (diethylaminoethyl-modified regenerated cellulose) were −0.9, −0.9, −0.7, −0.5, −0.1, +0.1, +0.35 and +3.1 mol/m 3 , respectively. This method allows determination of the membrane charge density of hollow-fiber dialysis membrane.

Hydrophilizing synthetic polymer dialysis membranes with polyvinylpyrrolidone (PVP) play an important role for inhibition of protein adsorption on membrane surface. In the present study, the effect of PVP on protein adsorption was evaluated from a nano-scale perspective. Swelling behavior of PVP present on wet polysulfone (PS)/PVP film surfaces was observed by atomic force microscopy (AFM). Fibrinogen and human serum albumin (HSA) were immobilized on the tip of AFM probes, with which a force-curve between protein and wet PS/PVP film surface was measured by AFM while scanning in order to visualize two-dimensional protein adsorbability on film surfaces. Furthermore, HSA adsorbability on non-PVP containing PEPA dialysis membrane (FLX-15GW) and PVP containing PEPA dialysis membrane (FDX-150GW) was evaluated by the AFM force-curve method. As a result, PS/PVP film surface was completely covered with hydrated and swollen PVP at 5 wt% or more PVP content. Protein adsorbability on PS/PVP film surfaces decreased greatly with increasing content of PVP. The adsorption of HSA was inhibited by the presence of PVP on film surfaces more significantly than that of more hydrophobic fibrinogen. HSA adsorbability on wet FLX-15GW dialysis membrane surface was 428 ± 174 pN whereas that on wet FDX-150GW dialysis membrane surface was 42 ± 29 pN.

The antioxidation property of vitamin E-coated dialysis membrane is effective for reduction of oxidative stress. Effect of amount of vitamin E coating on antioxidation property has been poorly understood yet. In the present study, we evaluated a relationship between amount of vitamin E coating and antioxidation property using a superoxide probe of 2-methyl-6-p-methoxyphenylethynylimidazopyrazinone (MPEC) by the optical fiber method to determine optimum amount of vitamin E coating and to improve antioxidation property of the vitamin E-coated dialysis membrane. Furthermore, from the viewpoint of reuse, we examined recovery of oxidized vitamin E by vitamin C treatment. In conclusion, it is necessary to coat polysulfone dialysis membranes with vitamin E at over 74 mg/m2. The antioxidation property is recoverable by treating dialysis membrane containing oxidized vitamin E with vitamin C. By administrating vitamin C, higher antioxidation property may be realized with a small amount of vitamin E coating.

The tortuous capillary pore diffusion model (TCPDM) has been used for estimating diffusive and pure water permeability from simple structure parameters such as pore diameter, surface porosity, wall thickness and tortuosity. The validity of this model for evaluation of homogeneous membrane has been already confirmed. Recently, there is a trend toward the use of asymmetrical dialysis membranes made of synthetic polymer such as poly(acrylonitrile) (PAN), polysulfone (PS) and a polyethersulfone polyarylate (PEPA) blend polymer. The purpose of the present study is to apply the TCPDM to evaluation of commercially available hollow-fiber dialysis membranes with asymmetrical structures by simplifying them to a double-layer membrane. The TCPDM is capable of estimating pore tortuosity of asymmetrical dialysis membranes having skin and supporting layers from data on membrane thickness, pore diameter, pure water permeability and water content. Values for diffusive permeability obtained by the TCPDM are in a good agreement with experimental data. This TCPDM model is useful for evaluation of not only homogeneous membrane but also asymmetrical membrane.

All available dialysis membranes prevent endotoxin (Et) from mixing with the blood under clinical conditions. However, maintenance dialysis patients are at risk of amyloidosis attributed to Et. This suggests that Et may affect the blood even if it does not mix with the blood. The objective of the present study is to evaluate the activity of Et trapped by membranes. We made mini modules out of hollow fibers using three different types of membranes and filtered Et solution. The lumen of the hollow fibers was then filled with limulus amebocyte lysate (LAL) for 15 min at 310 K. Et activity was then determined by measuring absorbance of the LAL reagent. The surfaces of test membranes were studied using an atomic force microscope. With polyester polymer alloy (PEPA), no Et leakage or Et activity was detected in the hollow fibers under any conditions. With polysulfone (PS) and polyether sulfone (PES), no Et leakage was detected under clinical conditions, but Et activity was detected in the hollow fibers. These results show that Et trapped by the inner skin may affect the blood, even if Et does not mix with the blood. Therefore, Et should be trapped by an outer skin or the part somewhat far from the blood which does not contact with the blood directly.

Polysulfone (PS) dialysis membranes hydrophilized by blending polyvinylpyrrolidone (PVP) are well known to have excellent biocompatibility in clinical use. The objective of the present study is thus to clarify how PVP improves biocompatibility of PS membranes and furthermore to develop a patient-friendly PS dialysis membrane with higher biocompatibility. Biocompatibility based on both lactate dehydrogenase (LDH) activity and amount of protein adsorption was greatly different among four commercially available PS hollow-fiber dialysis membranes. PVP present on the inner surface of the hollow fiber was quantitatively determined by X-ray photoelectron spectroscopy (XPS), demonstrating the amount of PVP to be varying for each membrane. Structure parameters such as surface roughness, three-dimensional surface area and polymer particle diameter, indications of the physicochemical properties of the membranes, were measured on the observed inner surface images in both wet and dry conditions by atomic force microscopy (AFM) to account for dependence of biocompatibility on these structure parameters. The higher regularity polymer particle structure has in the wet condition, the lower wet/dry ratio surface roughness has and the larger wet/dry ratio polymer particle diameter has, that is, the more greatly the polymer particles swell by wetting, the higher biocompatibility is achieved by “cushion effect”.

We revealed morphology and physicochemical behavior of a widely used powerful hydrophilizing agent, polyvinylpyrrolidone (PVP), present on polysulfone (PS)/PVP films by atomic force microscopy (AFM). This is the first time such clear PS/PVP phase-separated morphology was observed by nanoscopic technique. The film surfaces were observed by the identical observation mode, probe and scanning conditions to reveal the change of PVP morphology and behavior between dry and wet conditions. Morphology was related to biocompatibility by combining AFM data with results of surface element composition, contact angle, adhesion amount of rabbit platelet and relative amount of adsorbed fibrinogen. PVP nano-particles of one or several molecules were formed on the dry PS/PVP film surfaces. Amount of PVP present on the surfaces increased with the molecular weight of PVP. At a mixed amount of 1–5 wt%, PVP K90 formed crowded particles on the dry surface. When wet, they swelled, followed by their union to produce a smooth surface leading to improved biocompatibility. The highest biocompatibility with excellent mechanical strength is achieved by blending the highest molecular weight PVP K90 at 1–5 wt%.

We have reported a novel method of visualizing endotoxin (Et) distribution inside an Et-blocking filtration membrane using both fluorescence-labeled Et and a confocal laser scanning fluorescence microscope (CLSFM) in our previous paper [J. Membr. Sci. 210 (2002) 45]. The objective of the present study is to clarify Et-blocking mechanism of dialysis membranes. Six kinds of dialysis membranes with varying materials (hydrophilic and hydrophobic) and varying structures (pore diameter, skin layer location and thickness, and water content) were evaluated by CLSFM together with other techniques such as atomic force microscopy (AFM). Physicochemical property of a membrane material affects Et-adsorbing efficiency, and further membrane structure affects Et-plugging efficiency. Rejected Et distribution in the membranes with varying materials and structures is successfully visualized using fluorescence-labeled Et by CLSFM. Et adsorption on the membranes occurs first, followed by the narrowing of their pores, and afterward pore plugging is continued. Adsorption plays a vital role in Et-blocking. Double skin layer structure is valid for preventing of Et contamination than only inner skin layer structure because the double skin layer structure blocks Et more farther from blood-side surfaces than the only inner skin layer structure.

Effects of hollow fiber packing fraction on gas transfer rate, blood pressure drop and blood flow characteristics of an intravascular oxygenator (IVOX) were evaluated by in vitro experiments. An IVOX module was prepared by packing hollow fiber membranes, of which packing fraction ranged from 0.056 to 0.338, in a pipe corresponding to vena cava. Overall mass transfer coefficients for oxygen and carbon dioxide were evaluated using water, and gas transfer rates through blood were estimated. Blood flow in the IVOX was evaluated by both pulse response method and electrode method. Blood flow was not uniform and depended on the hollow fiber packing fraction. Easy-flow channels between vascular wall and bundle of the hollow fibers were produced and stagnation of blood flow occurred in the bundle of the hollow fibers at the blood inlet. More uniform blood flow was obtained by optimizing the hollow fiber packing fraction. With respect to gas transfer rate, blood pressure drop and uniformity of the blood flow, the optimum hollow fiber packing fraction was approximately 0.28 when the outside diameter of the hollow fiber was 300 μm. Effect of inner diameter of the hollow fibers was also evaluated, demonstrating that reduction in the inner diameter was an effective way to increase oxygen transfer rate.