Polyvinyl Formal Research Articles

ポリビニルホルマールの摩耗特性(第2報)(S04-4 医療とバイオエンジニアリング,工学技術の医療応用(4),S04 医療とバイオエンジニアリング,工学技術の医療応用)

Wear characteristics have been investigated in polyvinyl formal (PVF) as an artificial articular cartilage for joint prostheses. This bearing of the joint has been designed and constructed to produce larger initial contact areas and thicker theoretical film thickness than the conventional UHMWPE bearing. The main advantage of using the bearing may be associated with micro-elastohydrodynamic lubrication, and the low elastic modulus layer may also produce local deformations, which enhance squeeze film action. Wear tests were performed with a knee joint simulator. The PVF was adopted as the articular cartilage for the flat tibial component. The compliant bearing had a spherical surface that was made of stainless steel. The results showed that no detectable wear debris was generated in the simulation tests conducted over 1.0 million cycles. Although there still remain some problems to solve, the PVF seems to be a very interesting and promising material, which meets the requirements of artificial articular cartilage.

Polyvinyl formal resin plates impregnated with lipase-entrapped sol–gel polymer for flavor ester synthesis

Polyvinyl formal (PVF) resin plate was used as a support for forming organic–inorganic hybrid sol–gel polymer within its pores. Candida cylindracea lipase immobilized by entrapment in such hybrid sol–gel polymers made from tetramethoxysilane (TMOS) and propyltrimethoxysilane (PTMS) could efficiently catalyze direct esterification reaction between geraniol and acetic acid in anhydrous hexane for synthesis of the flavor ester geranyl acetate. The optimum formulation of the sol–gel solution for enzyme activity should be made with PVF plate with 250 μm mean pore diameter, PTMS molar percentage=80%, enzyme loading at 60 mg lipase/g gel, water to silane molar ratio=25, and 4 ml PVA solution (4% w/w). The specific activity of the immobilized enzyme is 7.4 times that of the free enzyme with a protein immobilizing efficiency of 93%. The substrate inhibition by acetic acid was alleviated with the optimum acetic acid concentration, which gives the highest enzyme activity, increasing from 15 to 35 mM after enzyme immobilization. Excellent thermal stability was found for the immobilized enzyme, where full retention of enzyme activity was found after incubated at 90 °C for 2 h. When stored at room temperature, the immobilized enzyme did not show any activity loss for up to 1 month. The operational stability also increased 51-fold after entrapment in sol–gel polymer.

632 ポリビニルホルマールの摩耗特性

632 ポリビニルホルマールの摩耗特性

Charging transient in polyvinyl formal

In the present paper charging and discharging transient currents in polyvinyl formal (PVF) were measured as a function of temperatures (40–80°C), poling fields (90 ×103−9.0 × 104 V/cm) and electrode combinations (Al-Al, Au-Al, Zn-Al, Bi-Al, Cu-Al and Ag-Al). The current-time characteristics have different values of slope lying between 0.42–0.56 and 1.42–1.63. The polarization is considered to be due to dipolar reorientation associated with structural motions and space charge relaxations due to trapping of injected charge carriers in energetically distributed traps.

Electric current arising from unpolarized polyvinyl formal

An appreciable electric current is observed in a system consisting of a polyvinyl formal (PVF) film in a sandwich configuration, in the temperature range 30–110°C. The maximum value of the current during first heating is found to be of the order of 10−10 A and its thermograms exhibit one transition (i.e. current peak) at around 60°C. The position of the current peak in thermal spectrum shifts with the heating rate. A temperature dependence of the open circuit voltage is also observed. The activation energy of the process responsible for the current is determined. The magnitude of the current is more in the case of dissimilar electrode systems. It is proposed that the electric current arising from unpolarized metal-polymer-metal system is a water activated phenomenon, which is influenced by the transitional changes of the polymer.

Production of recombinant protein by baculovirus-infected insect cells in immobilized culture using porous biomass support particles

Immobilization of insect cells using porous biomass support particles (BSPs) and production of a recombinant protein by the immobilized cells after infection with a baculovirus were investigated in a shake-flask culture. Sf9 cells were passively immobilized in reticulated polyvinyl formal (PVF) resin BSPs (2 × 2 × 2 mm cubes) with matrices of 60 μm mean pore diameter in situ in shake-flasks. The cell density in the BSPs was over 5 × 10 7 cells/cm 3-BSP in cultures with regular replacement of the culture medium, as estimated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. After infection with a recombinant baculovirus carrying the β-galactosidase gene, immobilized cells within the BSPs showed a high specific productivity, comparable to the maximum productivity in shake-flask cultures of non-immobilized cells, as long as nutrients in the medium were not depleted. Even when immobilized cells at a high density of 5 × 10 7 cells/cm 3-BSP were infected with the baculovirus, efficient β-galactosidase production with a high specific productivity was possible by replacing the medium at appropriate intervals to avoid nutrient depletion.

A high-density culture of hepatocytes using porous substrate for use as a bioartificial liver

High-density, large-scale culture of hepatocytes is a key requirement in the development of a bioartificial liver that can replace liver functions in patients with severe liver insufficiency. We have applied a porous polymer, polyvinyl formal (PVF) resin, as a cell-supporting material for hepatocyte culture. We evaluated the performance of the culture system using PVF resin under three different culture conditions: a shake culture on conventional dishes, perfusion culture with sheet-shaped PVF, and a packed-bed-type module. Among them, the packed-bed reactor using PVF resin enabled high-density culture of hepatocytes (2×107 cells/cm3-PVF). The hepatocytes immobilized in the PVF resin maintained satisfactory metabolic functions (ammonium metabolism and albumin secretion) comparable to those of the monolayer dish cultures. Furthermore, by maintaining dissolved oxygen concentration at a relatively high level (260–460μM), the metabolic functions of the hepatocytes were improved. It was concluded that the packed-bed reactor using PVF resin is a promising system for developing a bioartificial liver using hepatocytes.

Solute–solvent interaction dynamics studied by photon echo spectroscopies in polymer glasses

The influence of coupling strength and temperature on the solute–solvent interaction of two chromophores in polymer glass is reported. The three-pulse photon echo peak shift method was used to study the dye IR144 in polyvinylformal (PVF) and the dye DTTCI (3,3′-diethylthiatricarbocyanine iodide) in polymethylmethacrylate (PMMA). IR144 is more strongly coupled (larger reorganization energy) to both its intramolecular modes and to the solvent than is DTTCI. Our results can be well described by the linearly coupled harmonic bath model over the range 300 to 30 K. In particular, the strikingly different temperature sensitivities of the long-time (asymptotic) peak shift are well described by the theory. Temperature-independent spectral densities and inhomogeneous widths suffice to quantitatively describe the peak shift data over this temperature range and a number of numerical predictions based on the theoretical model are experimentally confirmed. An ultrafast component corresponding to a decay of ∼100 fs time scale in the transition frequency correlation function is found in all cases, though the amplitude is small for the DTTCI solutions. This ultrafast response is assigned to the inertial response of the solvent. The inertial response measured for DTTCI in PMMA is very similar to our previous measurements of the inertial response for IR144 in PMMA, suggesting that a general characteristic of the solvent is being probed. The weaker coupling of DTTCI produces a drastic increase in the width of the photon echo signal as predicted by theory and strong vibrational quantum beats at 30 K. By contrast, such beats are not observed in the echo signal for IR144.

Improvement of metabolic performance of hepatocytes cultured in vitro in a packed-bed reactor for use as a bioartificial liver.

A packed-bed reactor using reticulated polyvinyl formal (PVF) resin as a support material is a useful configuration to achieve high density culture of hepatocytes for use as a bioartificial liver. The authors investigated the effects of oxygen concentrations of the culture medium on the metabolic performance of hepatocytes cultured in the reactor. A packed-bed reactor loaded with 250 PVF resin cubes (2 x 2 x 2 mm) was used. Hepatocytes obtained from male Wistar rats were inoculated into the reactor. Culture medium was perfused from the reservoir into the reactor through an oxygenator using a roller pump. Concentration of the dissolved oxygen in the medium was controlled by changing the gas mixture ratio supplied to the oxygenator. Hepatocytes cultured in the packed-bed reactor (cell density: 8.6 x 10(6) cells/cm3 PVF) under conditions of high dissolved oxygen concentrations ranging from 260 to 460 micromol/L showed 30% higher ammonium metabolic activity and 85% higher albumin secretion activity compared with those from the monolayer culture in the earlier culture stage (up to 2 days). However, low oxygen concentrations in the medium (<100 micromol/L) impaired activities of cultured hepatocytes.

Hepatocyte culture utilizing porous polyvinyl formal resin maintains long-term stable albumin secretion activity

To investigate the effects of culture conditions on the maintenance of metabolic functions of cultured hepatocytes, long-term hepatocyte culture lasting 20 days was performed under two different culture conditions, i.e. stationary cultures utilizing porous polymer (polyvinyl formal (PVF) resin) as a substratum and conventional monolayer dish cultures without PVF. Metabolic activities specific to hepatocytes were evaluated in terms of ammonia metabolism, urea synthesis, and albumin secretion. Concerning ammonia metabolic and urea synthetic activities, no significant differences in maintenance of these activities were found between the two culture conditions, and these activities rapidly decreased with the elapse of the culture period, especially during the early stage of the experiments. However, after day 10, these activities in the stationary cultures were maintained at a slightly more favorable level than in the monolayer cultures. On the other hand, compared with ammonia metabolism and urea synthesis, stable and well-maintained albumin secretion of hepatocytes (60% of the activity in day 1) was exhibited in the stationary culture experiments, despite that this particular activity under the monolayer culture condition gradually reduced to a very low level (5.7% of that on day 1) at the end of the culture. From the morphological observations, hepatocytes immobilized in the PVF resin revealed individual spherical shapes without forming multicellular aggregation, and it was suggested that this characteristic structure contributed to good albumin secretion of hepatocytes. In conclusion, the advantages of the hepatocyte culture technique utilizing PVF resin over the conventional dish culture in maintaining some representative metabolic function specific to hepatocytes were clarified.

Packed-bed type reactor to attain high density culture of hepatocytes for use as a bioartificial liver.

In an attempt to develop a bioartificial liver using cultured hepatocytes, we investigated the short-term and long-term viability and metabolic functions of hepatocytes cultured in a new type of packed-bed type reactor using reticulated polyvinyl formal (PVF) resin as a supporting material. Perfusion culture experiments using this reactor, as well as monolayer cultures using conventional collagen-coated Petri dishes as control experiments, were performed. It was found that the highest density of immobilized hepatocytes attained with PVF resin was on the order of 10(7) cells/cm3 PVF and that hepatocytes cultured in this type of module for up to a week showed a sufficient level of liver-specific metabolic functions, such as ammonium metabolism, urea-N synthesis, and albumin secretion, to be comparable to those in the monolayer culture. It is concluded that the packed-bed reactor system utilizing PVF resin is a promising means to develop a bioartificial organ using hepatocytes.

Long-term performance of albumin secretion of hepatocytes cultured in a packed-bed reactor utilizing porous resin.

A packed-bed reactor utilizing the porous polymer, polyvinyl formal (PVF) resin, as a supporting material was applied for the long-term culture of rat hepatocytes. Perfusion cultures using this reactor, as well as monolayer cultures, were performed for up to 1 week under 3 different media conditions. When serum-free or epidermal growth factor-containing medium was used, albumin secretion rates showed constant decreases in both the perfusion and the monolayer cultures, and approximately 10% of the activity exhibited on Day 1 was preserved at the end of the cultures. In contrast, the hepatocytes supplemented with serum-containing medium exhibited stable ability of albumin secretion throughout the culture period under the perfusion culture condition using PVF resin. From the microscopic observation, the immobilized hepatocytes in this medium revealed round shapes, and a cluster of cell aggregates was scarcely seen.

Transient and thermally stimulated depolarization currents in pure and iodine doped polyvinyl formal (PVF) films

Transient currents, measured with pure and iodine doped polyvinyl formal (PVF) films as a function of poling field (15–100 kV/cm) and temperature (30–95°C), have been found to follow Curie-von Schweidler law characterized with two slopes in short and long time regions. The isochronals (i.e. current/temperature plots at constant times) have been found to give rise to a peak located at 75°C. The order of current has been found to increase with increase in poling field, temperature and iodine mixing. The comparative studies of the isochronals with the thermally stimulated discharge current (TSDC) indicated the strong resemblance between the two studies. It is suggested that both the dipolar orientation due to molecular mechanism of motions with the side chains and space charge due to trapping of injected charge carriers in energetically distributed traps may be responsible for the observed currents. The dependence of current and activation energy on iodine mixing is explained on the basis of a charge transfer type of interaction.

Incorporation of 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1, 2-tricyanoethanide in crosslinked polyvinylformal: Formation and properties of the Copper(II) complex in the matrix

The metal(II) coordinating anion 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (C11N7H 2 − , L′, λmax = 570 nm) has been incorporated by impregnation as the sodium salt in a membrane (0.1 mm thick) of crosslinked polyvinylformal (PVF) at a concentration 1.5 × 10−3 M. The L′-doped PVF membrane, soaked in a concentrated aqueous solution of Cu2+ (0.1 M), changes colour from violet to blue on formation of the corresponding pure bis-pyrrolizinato complex CuL2 (λmax = 660 nm). The CuL2-doped PVF membrane reacts in the gas phase on exposure to species (X) that are copper-coordinating ligands stronger than L, generating the reverse colour change to violet. The remarkable stability towards water of CuL2/PVF is a promising indication for prospective use of ML2 complexes, incorporated in polymeric membranes, for the detection of (X) species in the atmosphere even in the presence of moisture, or directly in aqueous solutions.

Transient and thermally stimulated depolarization currents in polyvinyl formal films

AbstractTransient currents in double‐sided vacuum aluminized polyvinyl formal (PVF) film samples of thickness 40 μm were investigated in the charge and discharge modes at different temperatures and fileds. The results observed suggest that the transient currents are governed by charge injection processes leading to space charge effects. Comparative studies of the isochronal characteristics (i.e. current–temperature plots at fixed times) with the thermally stimulated discharge current (TSDC) indicated a strong resemblance between the two techniques. These studies suggest that the simultaneous mechanism of movement of charges through microscopic distances coupled with dipolar orientation may be responsible for the TSDC peak observed at 100°C.

Long‐Term continuous culture of hepatocytes in a packed‐bed reactor utilizing porous resin

As part of our attempt to develop a hybrid artificial liver support system using cultured hepatocytes, we investigated the long-term metabolic function of hepatocytes incubated in a packed-bed type reactor using reticulated polyvinyl formal (PVF) resin as a supporting material. Long-term (up to 1 week) perfusion culture experiments using the packed-bed reactor (20 mm i.d.) loaded with 500 PVF resin cubes (mean pore size 250 mum, 2 x 2 x 2 mm), together with conventional monolayer culture experiments as controls, were performed in serum-free or serum-containing medium. Ammonium metabolism and urea synthesis activities were evaluated quantitatively based on reaction kinetic analyses. Initial rates of ammonium metabolism and urea-N synthesis, as well as GPT enzyme activities, were adopted as indexes of the metabolic performance of the reactor and activities of the cultured hepatocytes.When serum-free medium was used in the perfusion cultures, ammonium metabolic and urea-N synthetic rates showed significant decay with elapse of the culture period, being less than 10% of those measured on day 1. This loss of activity was more prominent in the perfusion culture than in the monolayer cultures using this medium. In contrast, when serum-containing medium was used, approximately 50% of these activities obtained on day 1 were maintained even at the end of the cultures both in the perfusion and monolayer culture experiments.We concluded that the packed-bed reactor using PVF resin enabled high-density culture of hepatocytes, and showed a satisfactory ability to maintain the metabolic function of immobilized hepatocytes for relatively long periods of up to 1 week. This type of reactor is thus considered to represent a breakthrough in overcoming the difficulties involved in the development of a hybridtype artificial liver support system. (c) 1994 John Wiley & Sons, Inc.

Protein-free culture of VERO cells: a substrate for replication of human pathogenic viruses

A protein-free chemically defined medium designated PFEK-1 was developed for culture of VERO cells on polyvinyl formal (PVF) culture surface without serum or other macromolecular supplements. VERO cells proliferated in PFEK-1 medium on PVF surface to a similar extent as cells in serum-supplemented medium without previous adaptation from serum-containing conditions. The protein-free culture infected with coxsackievirus B4, herpes simplex virus types 1 and 2, measles virus and poliovirus types 1, 2 and 3 developed viral titers comparable to those found in conventionally grown cells. The results demonstrated that VERO cells in protein-free culture provide a sensitive substrate for the production of human pathogenic viruses which are not contaminated by serum or other protein factors usually added to a culture medium.

A study of the surface anchoring at a polymer/liquid crystal interface in the neighbourhood of the glass transition

Abstract Recently, we have observed dramatic changes in the electro-optic properties of PDLC films composed of droplets of the liquid crystal E7 in a matrix of polyvinylformal (PVFM) in the vicinity of the glass transition temperature of the matrix. One plausible explanation for these changes is a decrease in the surface anchoring strength on passing through the glass transition. For this reason, we undertook a study of the surface anchoring strength between E7 and a thin film of PVFM using the technique of Yokoyama and van Sprang. To mimic the properties of the matrix more closely, we dissolved 20 per cent E7 liquid crystal into the PVFM film. The surface anchoring for this film was compared with that of a pure PVFM film. From these data, we observed no obvious changes in the surface anchoring on passing through the glass transition of the matrix. However, the incorporation of liquid crystal into the matrix did cause a decrease in the surface anchoring strength. We discuss the impact of these results on ...

Effect of polymer matrix glass transition temperature on polymer dispersed liquid crystal electro-optics

We have studied the electro-optic properties as a function of temperature of a polymer dispersed liquid crystal film composed of E7 dispersed as droplets in a polyvinylformal (PVFM) matrix. The drive voltage and turn-off time change abruptly as the temperature is raised above the glass transition temperature (Tg) of the PVFM matrix. There is essentially no hysteresis below, but significant hysteresis above Tg. These temperature effects are completely reversible. The rapid change in electro-optic properties cannot be entirely explained by changes in the polymer dielectric properties or droplet shape. Freedericksz measurements show no abrupt change in the surface anchoring energy at Tg, which may be responsible for the changes observed in the electro-optic response.

A packed-bed reactor utilizing porous resin enables high density culture of hepatocytes.

To enable high density culture of hepatocytes for use as a hybrid artificial liver support system or a bioreactor system, a packed-bed reactor using collagen-coated reticulated polyvinyl formal (PVF) resin was applied to a primary culture of hepatocytes. Cubic PVF resins (2 x 2 x 2 mm, mean pore size: 100, 250 or 500 microns) were used as supporting substrates to immobilize hepatocytes. Two hundred and fifty cubes were packed in a cylindrical column, and 2.6-11.3 x 10(7) hepatocytes were seeded in the column by irrigating with 3 ml of the medium containing hepatocytes. Perfusion culture experiments using this packed-bed reactor, as well as monolayer cultures using conventional collagen-coated petri dishes as control experiments, were performed. Sufficient amounts of hepatocytes were found to be immobilized in the reticulated structure of the PVF resins. The highest density of immobilized hepatocytes attained with PVF resin was 1.2 x 10(7) cells/cm3 PVF, which showed levels of ammonium removal and urea-N secretion comparable to those in the monolayer culture. It is concluded that the packed-bed reactor system utilizing PVF resin is a promising process for developing a bioreactor or a bioartificial organ using hepatocytes.