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Vascular oligonucleotide transfer facilitated by a polymer-coated stent
Radke, P. W., U. Griesenbach, et al. (2005), Hum Gene Ther 16(6): 734-40.
Abstract: To evaluate the potential of clinically used phosphorylcholine (PC)-coated stents for their ability to load and release small decoy oligonucleotides (ODNs). Stents were loaded with 41 +/- 6 microg ODNs. Ex vivo deployment of ODN-loaded stents in explanted rabbit aortas showed significant vascular ODN transfer, with 18 +/- 12% of intimal or medial cell nuclei containing ODNs. In proof-of-principle in vivo experiments (using the double-injury rabbit model) there was no difference in fluorescent signal intensity between animals receiving ODNloaded stents or controls. However, a significant increase in signal intensity was detected in the kidneys of animals receiving ODN-loaded stents. PC-coated stents can be loaded with ODNs. Despite successful ex vivo ODN deposition and nuclear uptake in the vessel wall, in vivo vascular ODN transfer was not achieved. Rapid intravascular release of ODN before implantation and potential vascular barriers for gene transfer are most likely responsible for the currently unsatisfactory in vivo release kinetics.

Vascular PET prostheses surface modification with cyclodextrin coating: development of a new drug delivery system
Blanchemain, N., S. Haulon, et al. (2005), Eur J Vasc Endovasc Surg 29(6): 628-32.
Abstract: PURPOSE: Cyclodextrins (CDs) are torus shaped cyclic oligosaccharides with a hydrophobic internal cavity and a hydrophilic external surface. We performed and analysed an antibiotic binding on Dacron (polyethyleneterephtalate, PET) vascular grafts, previously coated with CDs based polymers. METHODS: The CDs coating process was based on the pad-dry-cure method patented in our laboratory. The Dacron prostheses were immersed into a solution containing a polycarboxylic acid, a cyclodextrin and a catalyst, and placed into a thermofixation oven before impregnation with an antibiotic solution (Vancomycin). Biocompatibility tests were performed with L132 human epithelial cells. The antibiotic release in an aqueous medium was assessed by batch type experiments using UV spectroscopy. RESULTS: Viability tests confirmed that the CDs polymers coating the Dacron fibers were not toxic towards L132 cell. Cell proliferation was similar on coated and uncoated grafts. A linear release of Vancomycin was observed over 50 days. CONCLUSION: Our results demonstrate the feasibility of coating CDs onto vascular Dacron grafts. Biological tests show no toxicity of the different cyclodextrins coated. A linear release of antibiotics was depicted over 50 days, demonstrating that cyclodextrin grafting was an efficient drug delivery system.

Versatility of transmucosal implants with zirconium ring. Case report
Masini, V. (2005), Minerva Stomatol 54(1-2): 69-77.
Abstract: Utiling zirconium characteristics, a biomaterial with high affinity with bone and gum, we have positioned in the same patient 2 transmucosal implants in titanium with a coronal ring in zirconium in 2 different manners. The first fixture was positioned with the ring in zirconium at the same level of the gum in order to obtain a good periodontal healing and esthetic without metallic transparencies. The second postestractive implant was positioned with the zirconium ring at the level of the crestal bone in order to reduce the gap between the fixture and the alveolar bone and to avoid the use of a resorbable barrier relying on the osteointegrative properties of zirconium.

Vertebral body reconstruction with injectable hydroxyapatite cement for the management of unstable thoracolumbar burst fractures: a preliminary report
Christodoulou, A., A. Ploumis, et al. (2005), Acta Orthop Belg 71(5): 597-603.
Abstract: The aim of this prospective study was to evaluate the efficacy of an injectable hydroxyapatite cement in combination with long posterior transpedicular instrumentation, without fusion, for the treatment of unstable thoracolumbar burst fractures. Ten patients with this type of fracture were treated in the period 1999-2000 with bisegmental posterior transpedicular stabilisation above and below the fracture site, indirect reduction of the fracture, and transpedicular injection of hydroxyapatite cement into the fractured vertebral body. Postoperatively the mean Cobb kyphotic deformity angle (CKDA) and vertebral compression index (VCI) were statistically improved (p < 0.001). Both variables deteriorated slightly between surgery and follow-up after +/- 39 months; this was statistically not significant for the CKDA (p > 0.05), but significant for the VCI (p < 0.001). These data suggest that hydroxyapatite cement can be a reliable way to reinforce the fractured vertebral body in the thoracolumbar region.

Vibrational circular dichroism in general anisotropic thin solid films: measurement and theoretical approach
Buffeteau, T., F. Lagugne-Labarthet, et al. (2005), Appl Spectrosc 59(6): 732-45.
Abstract: In this study, the measurement of the true vibrational circular dichroism (VCD) spectrum is considered from an experimental and theoretical approach for any general anisotropic thin solid sample exhibiting linear as well as circular birefringence (LB, CB) and dichroism (LD, CD) properties. For this purpose, we have made use of a simple model alpha-helix polypeptide, namely, the poly(gamma-benzyl-L-glutamate) or PBLG, reference sample possessing a well-known VCD spectrum and giving rise to slightly oriented films by deposition onto a solid substrate. Also, we have used a different Fourier transform infrared modulation of polarization (PM-FTIR) optical setup with two-channel electronic processing in order to record the PM-VLD and PM-VCD spectra for various sample orientations in its film plane. All the corresponding general relations of the expected intensities in these experiments and the related properly designed calibration measurements were established using the Stokes-Mueller formalism; in addition, the residual birefringence of the optical setup and the transmittance anisotropy of the detector were estimated. From a comparative study of the results obtained in solution and in the solid state, we then propose a simple new experimental procedure to extract the true VCD spectrum of an oriented PBLG thin film: its consists of calculating the half-sum of two spectra recorded at theta and at theta +/- 90 degrees sample orientations. Moreover, the complete linear and circular birefringence and dichroism properties of the ordered PBLG thin film are estimated in the amide I and amide II vibrational regions. This allows us to establish for any sample orientation various theoretical simulations of the VCD spectra that agree nicely with the observed experimental results; this confirms that the measurement of LD and LB is in this case a prerequisite in simulating the true VCD spectrum of a partly oriented anisotropic sample. This validates our combined experimental and theoretical approach and opens the route to promising future vibrational CD studies on other macroscopic anisotropic thin film samples.

Viscoelastic and mechanical behavior of recombinant protein elastomers
Nagapudi, K., W. T. Brinkman, et al. (2005), Biomaterials 26(23): 4695-706.
Abstract: Recombinant DNA synthesis was employed to produce elastin-mimetic protein triblock copolymers containing chemically distinct midblocks. These materials displayed a broad range of mechanical and viscoelastic responses ranging from plastic to elastic when examined as hydrated gels and films. These properties could be related in a predictable fashion to polymer block size and structure. While these materials could be easily processed into films and gels, electrospinning proved a feasible strategy for creating protein fibers. All told, the range of properties exhibited by this new class of protein triblock copolymer in combination with their easy processability suggests potential utility in a variety of soft prosthetic and tissue engineering applications.

Viscoelastic behavior of organic materials: consequences of a logarithmic dependence of force on strain rate
Jager, I. L. (2005), J Biomech 38(7): 1451-8.
Abstract: The viscoelastic and -plastic behavior of organic materials like bone, tendon or wood, as well as technical polymers, is amply documented. It is usually modeled using linear "Newtonian" friction, i.e., a viscous force proportional to the deformation rate. If the experimental results cannot be fitted with the resulting exponential "Debye" curves, a multitude of relaxation mechanisms or a spectrum of relaxation times is invoked. In this contribution experimental evidence is compiled which indicates that for polymers and organic materials a logarithmic dependence of the deformation force on the deformation rate is more appropriate. The corresponding equation of motion is solved in the quasi-static approximation and the solutions display just the typical deviations from the Debye behavior found experimentally, without any complications from multi-mechanism relaxation.

Viscoelastic properties of three vocal-fold injectable biomaterials at low audio frequencies
Klemuk, S. A. and I. R. Titze (2004), Laryngoscope 114(9): 1597-603.
Abstract: OBJECTIVES: Previous measurements of viscoelastic properties of Zyderm were to be extended to low audio frequencies, and properties of two other biomaterials not previously measured, thiolated hyaluronic acid (HA-DTPH) and Cymetra, were obtained. STUDY DESIGN: Rheologic investigation. METHODS: Oscillatory shear stress was applied to each sample using a controlled stress rheometer at frequencies between 0.01 and 100 Hz with a parallel plate apparatus. Versuscoelastic moduli were recorded at each frequency. The calculated resonance frequency of the machine and sample were then used to determine the maximum frequency at which reliable data existed. Extrapolation functions were fit to viscoelastic parameters, which predicted the properties up to 1,000 Hz. RESULTS: Frequency trends of Zyderm were similar to those previously reported, whereas magnitudes were different. The elastic moduli logarithmically increased with frequency, whereas dynamic viscosity demonstrated shear thinning, a condition of primary importance for humans to vocalize over a broad frequency range. Previous measurements were extended from 15 Hz up to 74 Hz. Differences in magnitude between a previous study and the present study were attributed to particulate orientation during testing. Cymetra was found to have nearly identical viscoelastic properties to those of bovine collagen, both in magnitude and frequency trend, with reliable measures extending up to 81 Hz. Rheologic properties of the hyaluronic acid gel were the closest match to cadaveric vocal fold mucosa in magnitude and frequency trend. CONCLUSIONS: Viscoelastic properties of Cymetra and Zyderm are nearly the same and are significantly greater than those of vocal fold mucosa. HA-DTPH possesses a good viscoelastic match to vocal fold mucosa and may be useful in future lamina propria repair.

Viscoelasticity of dental tissue conditioners during the sol-gel transition
Murata, H., H. Chimori, et al. (2005), J Dent Res 84(4): 376-81.
Abstract: Formation of tissue conditioners is a process of polymer chain entanglements. This study evaluated the influence of composition and structure on dynamic viscoelasticity of concentrated polymer solutions based on poly(ethyl methacrylate) (PEMA) used as tissue conditioners through the sol-gel transition. The hypothesis was that the ethanol content is the most influential factor in determining gelation speed. Rheological parameters were determined with the use of a controlled-stress rheometer. Analysis of variance by orthogonal array L(16)(4(5)) indicated that the strong polar bonding of ethanol (contribution ratio rho = 53.8%; confirming the hypothesis) and molecular weight of polymer powders (rho = 26.7%) had a greater influence on the gelation times of PEMA-based systems than did the molar volume of plasticizers (rho = 9.0%) and concentration of polymers (i.e., powder/liquid ratio) (rho = 4.5%). The results suggest that the gelation of tissue conditioners based on PEMA can be controlled over a wide range by varying the polymer molecular weight, and especially ethanol content.

Viscosities of implantable biomaterials in vocal fold augmentation surgery
Chan, R. W. and I. R. Titze (1998), Laryngoscope 108(5): 725-31.
Abstract: Vocal fold vibration depends critically on the viscoelasticity of vocal fold tissues. For instance, phonation threshold pressure, a measure of the "ease" of phonation, has been shown to be directly related to the viscosity of the vibrating mucosa. Various implantable biomaterials have been used in vocal fold augmentation surgery, with implantation sites sometimes close to or inside the mucosa. Yet their viscosities or other mechanical properties are seldom known. This study attempts to provide data on viscosities of commonly used phonosurgical biomaterials. Using a parallel-plate rotational rheometer, oscillatory shear experiments were performed on implantable polytetrafluoroethylene (Teflon or Polytef; Mentor Inc., Hingham, MA), collagen (Zyderm; Collagen Corp., Palo Alto, CA), glutaraldehyde crosslinked (GAX) collagen (Phonagel or Zyplast; Collagen Corp.), absorbable gelatin (Gelfoam; Upjohn Co., Kalamazoo, MI), and human abdominal subcutaneous fat. Samples of human vocal fold mucosal tissues were also tested. Under sinusoidal oscillatory shear at 10 Hz and at 37 degrees C, the dynamic viscosity was 116 Pascal-seconds (Pa-s) for polytetrafluoroethylene, 21 Pa-s for gelatin, 8-13 Pa-s for the two types of collagen, 3 Pa-s for fat, and 1 to 3 Pa-s for vocal fold mucosa. Results extrapolated to 100 Hz also show similar differences among the biomaterials, but all values are an order of magnitude lower because of the typical inverse frequency relation (shear thinning effect) for polymeric and biologic materials. The data suggest that the use of fat for vocal fold augmentation may be more conducive to the "ease" of phonation because of its relatively low viscosity, which is closest to physiologic levels. This implication is probably the most relevant in predicting initial outcome of the postoperative voice before there is any significant assimilation (e.g., resorption and fibrosis) of the implanted biomaterial.

Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis
Sun, B., E. P. Reddy, et al. (2005), Environ Sci Technol 39(16): 6251-9.
Abstract: Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.

Visible light induced photodegradation of organic pollutants on nitrogen and fluorine co-doped TiO2 photocatalyst
Wang, Z. P., J. Xu, et al. (2005), J Environ Sci (China) 17(1): 76-80.
Abstract: The nitrogen and fluorine co-doped TiO2 polycrystalline powder was synthesized by calcinations of the hydrolysis product of tetrabutyl titanate with ammonium fluoride. Nitrogen and fluorine co-doping causes the absorption edge of TiO2 to shift to a lower energy region. The photocatalytic activity of co-doped TiO2 with anatase phases was found to be 2.4 times higher than that of the commercial TiO2 photocatalyst Degussa P25 for phenol decomposition under visible light irradiation. The co-doped TiO2 powders only contain anatase phases even at 1000 degrees C. Apparently, ammonium fluoride added retarded phase transformation of the TiO2 powders from anatase to rutile. The substitutional fluorine and interstitial nitrogen atoms in co-doped TiO2 polycrystalline powder were responsible for the vis light response and caused the absorption edge of TiO2 to shift to a lower energy region.

Vitamin E as an antioxidant for poly(etherurethane urea): in vivo studies. Student Research Award in the Doctoral Degree Candidate Category, Fifth World Biomaterials Congress (22nd Annual Meeting of the Society for Biomaterials), Toronto, Canada, May 29-June 2, 1996
Schubert, M. A., M. J. Wiggins, et al. (1996), J Biomed Mater Res 32(4): 493-504.
Abstract: Poly(etherurethane) elastomers are useful materials in medical devices because of their mechanical properties and biocompatibility. However, it is necessary to stabilize these elastomers against the oxidation of their ether soft segments. Synthetic antioxidants such as Santowhite and Irganox are often satisfactory; however, particularly for biomedical applications, it was of interest to test the natural antioxidant vitamin E in poly(etherurethane urea) (PEUU) elastomers in vivo. The alpha-tocopherol form of vitamin E was added to PEUU at 5% by weight. Biaxially strained PEUU specimens with and without vitamin E were tested in vivo in the cage implant system. The influence of vitamin E on PEUU biostability was analyzed by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and scanning electron microscopic (SEM) characterization of the PEUU surface. ATR-FTIR results showed that vitamin E prevented chemical degradation of the PEUU surface up to 5 weeks implantation, and at 10 weeks 82% of the ether remained. In contrast, without an antioxidant, only 18% of the ether remained after 10 weeks. No surface pitting or cracking was observed by SEM on PEUU with vitamin E; PEUU without antioxidant ruptured owing to extensive pitting and cracking. It was concluded that the antioxidant properties of vitamin E prevented oxidation of strained PEUU elastomers in vivo. The influence of vitamin E on PEUU biocompatibility was characterized by exudate leukocyte counts, density of leukocytes adherent to the PEUU, and morphology of adherent leukocytes. These results indicated decreased leukocyte counts in the exudate and less active adherent cells on the PEUU with vitamin E compared to PEUU without antioxidant. A proposed cell-polymer feedback system demonstrates how vitamin E improves both biostability and biocompatibility of PEUU elastomers in vivo.

Voltammetric study of interaction between polymers (PEI and TMO) and pDNA on a hanging mercury drop electrode
Gherghi, I., S. T. Girousi, et al. (2005), J Pharm Biomed Anal 39(1-2): 177-80.
Abstract: Electrochemical DNA biosensors can become a powerful tool for the investigation of potent changes on the plasmid DNA structure caused by polymers used as non-viral vectors in gene delivery. Trimethylated chitosan oligomer (TMO) and polyethylenimine (PEI), offering biocompatibility, low immunogenicity and minimal cytotoxicity, are being studied as model non-viral carriers. The information obtained is intended to serve as a basis for developing a new analytical system for the study of the effect of any physically or chemically synthesized polymer on DNA structure.

Water as a biomaterial
Andrade, J. D., H. B. Lee, et al. (1973), Trans Am Soc Artif Intern Organs 19: 1-7.

Water purification through bioconversion of phenol compounds by tyrosinase and chemical adsorption by chitosan beads
Yamada, K., Y. Akiba, et al. (2005), Biotechnol Prog 21(3): 823-9.
Abstract: Enzymatic removal of various phenol compounds from artificial wastewater was undertaken by the combined use of mushroom tyrosinase (EC and chitosan beads as function of pH value, temperature, tyrosinase dose, and hydrogen peroxide-to-substrate ratio. Chitosan film incubated in a p-crersol+tyrosinase mixture had the main peaks at 400-470 nm assigned to chemically adsorbed quinone derivatives, which increased over the immersion time. These results indicate that removal of phenol compounds is caused by their tyrosinase-catalyzed oxidation to the corresponding quinone derivatives and the subsequent chemical adsorption on the chitosan film. The optimum conditions for quinone adsorption were determined to be pH 7 and 45 degrees C for p-cresol. Some alkyl-substituted phenol compounds were removed by adsorption of quinone derivatives enzymatically generated on the chitosan beads, and the % removal for p-cresol, 4-ethylphenol, 4-n-propylphenol, 4-n-butylphenol, and p-chlorophenol went up to 93%. In addition, 4-tert-butylphenol underwent tyrosinase-catalyzed oxidation in the presence of hydrogen peroxide. This procedure was applicable to removal of chlorophenols and alkyl-substituted phenols.

Water sorption, solubility, and tensile bond strength of resilient denture lining materials polymerized by different methods after thermal cycling
Leon, B. L., A. A. Del Bel Cury, et al. (2005), J Prosthet Dent 93(3): 282-7.
Abstract: STATEMENT OF PROBLEM: The clinical properties of resilient denture lining materials may be influenced by the methods used to polymerize them. PURPOSE: This study evaluated and compared water sorption, solubility, and tensile bond strength of 2 resilient liner materials polymerized by different methods after being thermal cycled. MATERIAL AND METHODS: Two acrylic resin-based resilient liner materials were evaluated: 1 (Light Liner) polymerized by visible light, and 1 (Ever-Soft) processed by 2 different methods: hot water bath and microwave energy. To evaluate water sorption and solubility, 10 disc-shaped specimens (50 x 0.5 mm) were fabricated for each polymerization method, using acetate matrices. The specimens were dried and thermal cycled (2000 cycles) between baths of 5 degrees C and 55 degrees C. After thermal cycling, the specimens were weighed, dried, and weighed again to calculate the water sorption values and solubility. For tensile bond strength assessment, 12 rectangular specimens measuring 83 mm in total length and with a cross-sectional area of 10 x 10 mm were fabricated using each polymerization method. The specimens were also thermal cycled (2000 cycles) and, afterwards, tested in a universal testing machine at a crosshead speed of 6 mm/min with 100 Kg load cell. The type of failure was determined by use of stereoscopic microscopy. The data (for water sorption and solubility, n = 30, and for tensile bond strength, n = 36) were submitted to 1-way analysis of variance. The means were compared using the Bonferroni test (alpha=.05). RESULTS: For water sorption the results showed no significant differences among the polymerization methods. Light Liner showed the lowest solubility values (5.3% +/- 0.3%) when compared to Ever-Soft (hot water bath: 7.3% +/- 1.1% and microwave energy: 7.8 +/- 0.9%). For tensile bond strength, Ever-Soft polymerized by microwave energy (0.7 +/- 0.0 MPa) showed the greatest and most significant (P <.05) value when compared to Ever-Soft polymerized by hot water bath (0.5 +/- 0.1 MPa) and Light Liner polymerized by visible light (0.5 +/- 0.0 MPa). Most Ever-Soft specimens polymerized by microwave energy and Light Liner specimens showed adhesive/cohesive failures. However, Ever-Soft polymerized by hot water bath showed 50% adhesive/cohesive and 50% adhesive failures. The results at the reline material-resin bond interface showed the absence of cohesive failures. CONCLUSION: Within the limitations of this study, Light Liner showed the lowest solubility values. Ever-Soft should be polymerized by microwave energy to obtain the greatest tensile bond strength values. Materials polymerized by microwave energy and visible light showed predominantly adhesive/cohesive failures.

Water-borne, in situ crosslinked biomaterials from phase-segregated precursors
Vernon, B., N. Tirelli, et al. (2003), J Biomed Mater Res A 64(3): 447-56.
Abstract: A novel process for the preparation of water-borne biomaterials for hard tissue repair from injectable precursors is described, where the precursors form crosslinked materials in situ under physiological conditions. The precursors react by means of a Michael-type addition reaction that makes use of addition donors such as pentaerythritol tetrakis 3'-mercaptopropionate (QT) and addition acceptors such as poly(ethylene glycol) diacrylate 570 MW (PEGDA), pentaerythritol triacrylate (TA), and poly(propylene glycol) diacrylate 900 MW (PPODA). These crosslinked materials (at 75 wt% solid), prepared from water dispersions or reverse emulsions, showed ultimate strengths in compression of 1.8 +/- 0.2 and 6.7 +/- 0.5 MPa and ultimate deformations of 35 +/- 2+/- and 37 +/- 2%, respectively. Scanning electron microscopy (SEM) shows that the morphology of the precursors templated the morphology of the final materials. The current study indicates that it is possible to obtain injectable high-modulus materials that have appropriate mechanical properties and gelation kinetics for tissue augmentation and stabilization applications such as mechanical stabilization of the intervertebral disc annulus.

Water-photolysis properties of micron-length highly-ordered titania nanotube-arrays
Varghese, O. K., M. Paulose, et al. (2005), J Nanosci Nanotechnol 5(7): 1158-65.
Abstract: We report the water photoelectrolysis and photoelectrochemical properties of the titania nanotube arrays as a function of nanotube crystallinity, length (up to 6.4 microm), and pore size. Most noteworthy of our results, under 320-400 nm illumination (98 mW/cm2) the titania nanotube-array photoanodes (area 1 cm2), pore size 110 nm, wall thickness 20 nm, and 6 microm length, generate hydrogen by water photoelectrolysis at a rate of 7.6 mL/hr, with a photoconversion efficiency of 12.25%. The energy-time normalized hydrogen evolution rate is 80 mL/hrW, the largest reported hydrogen photoelectrolysis generation rate for any material system by a factor of four. The highly-ordered nanotubular architecture appears to allow for superior charge separation and charge transport, with a calculated quantum efficiency of over 80% for incident photons with energies larger than the titania bandgap.

We thank Drs Sluzewski and van Rooij for their critcisms of the ACTIVE Study
Moret, J. and F. Vinuela (2005), AJNR Am J Neuroradiol 26(8): 2163.

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Last Modified: 8 February 2006