Surface fluorination of PEEK film by selective wet-chemistry

The PEEK-OH film, obtained by surface reduction of the native PEEK him, was designed as a versatile key-intermediate for the development of mild and selective fluorination processes. Reaction with diethylaminosulfur trifluoride in CFCl3, and 4-trifluoromethylbenzamide in HOAc (H2SO4 catalysis) gave the PEEK-F and PEEK-PhCF(3) films, in 92% and 36% yields, respectively. Reaction of PEEK-ONa with heptadecafluoro-10-iododecane in DMF produced the PEEK-C8F17 film in 6% yield. The modified PEEK surfaces were analysed by X-ray photoelectron spectroscopy (X.p.s.). (C) 1997 Elsevier Science Ltd. All rights reserved

Fibronectin adsorption or/and covalent grafting on chemically modified PEEK film surfaces.

Poly(ether ether ketone) (PEEK) films were chemically modified, by surface wet chemistry, into PEEK-OH, PEEK-NH2, and PEEK-NCO. Fibronectin (FN) adsorption, in the presence or absence of two non-ionic surfactants, was compared onto PEEK, PEEK-OH, and PEEK-NH2 on which the protein can only be adsorbed, and onto PEEK-NCO on which FN could be covalently grafted. The amounts of FN present on the various supports were assayed by ELISA and LSC (with 125I-labeled FN). The remarkable effect of Pluronic F68 in preventing non-specific protein adhesion on the less hydrophilic surfaces was pointed out. Accordingly, a procedure could be proposed that allows minimal FN adhesion vs FN fixation on PEEK-NCO. The resulting PEEK-FN film, which immobilized 120-150 ng FN cm(-2), constitutes a new substratum for cell cultivation

Adhesion and growth of CaCo2 cells on surface-modified PEEK substrata.

A series of surface-functionalized poly(ether ether ketone) (PEEK) films has been prepared by selective wet-chemistry; they are hydroxylated polymer (PEEK-OH) obtained by reduction, aminated polymer (PEEK-[]-NH2) prepared by coupling a diisocyanate reagent to PEEK-OH (PEEK-[]-NCO) followed by hydrolysis, and carboxylated and aminocarboxylated polymers (PEEK-[]-GABA and PEEK-Lysine) resulting from the coupling of aminoacids to PEEK-[]-NCO. The aminated and carboxylated substrata promoted the adhesion and growth of CaCo2 cells in the presence of serum. Fibronectin (FN), an extra-cellular matrix protein, has been covalently fixed and/or adsorbed on various PEEK substrata, in the presence or not of a polymeric surfactant (Pluronic F68). The performances of the FN-grafted substrata (PEEK-[]-FN(1) and PEEK-[]-FN(2)) were significantly higher than those of reference substrata simply coated with FN (PEEK-OH(+FN)(1) and (2), PEEK-[]-NH2(+FN)(1) and (2)), considering the adhesion and spreading of CaCo2 cells in the absence of serum. Moreover, the stability of the adherent cells on the FN-adsorbed substrata dramatically depended on the experimental conditions applied during the PEEK coating with FN

Surface reduction of poly(aryl ether ether ketone) film: UV spectrophotometric, H-3 radiochemical, and X-ray photoelectron spectroscopic assays of the hydroxyl functions

The surface reduction of amorphous poly(aryl ether ether ketone) (PEEK) film was successfully achieved by wet chemistry using a solution of NaBH4 in DMSO at 120 degrees C for 3 h. The resulting PEEK-OH film was fully characterized by MIR, W-visible, and H-1 NMR spectroscopies; all the data were consistent with those of the references, 4-(4-methoxyphenoxy)benzhydrol and bulk-reduced PEEK (''PEEK-OH''). The surface of PEEK-OH film was analyzed by X-ray photoelectron spectroscopy (XPS). From the fine structures of the Cls and Ols peaks, we could determine a ratio of reduction reaching 75-85% of the monomer units contained in the 10 outermost atomic layers. The surface reactivity of the hydroxyl groups was assayed by derivatization with [H-3]acetic anhydride followed by liquid scintillation counting (LSC) of the sample-associated radioactivity. The PEEK-OH film was reacted with p-nitrophenyl chloroformate to furnish an activated surface (PEEK-OCO2PNP), the basic hydrolysis of which allowed the indirect spectrophotometric assay of the reactive OH groups. The PEEK-OCO2PNP film was further used to covalently fix amine derivatives via a carbamate Linkage. Using [H-3]lysine and trifluoroethylamine, we were able to assay the surface reactivity by LSC and XPS respectively. The ratios of surface derivatization were within 5-30%. The PEEK-OH film was used as substrate for the cultivation of CaCo2 epithelial cells; the presence of surface hydroxyl functions moderately improves the polymer biocompatibility

Di[bis(4-methoxyphenyl)methyl]ether As Dehydration Product of 4,4'-dimethoxybenzhydrol Under Unusually Mild Conditions

4,4'-Dimethoxybenzhydrol 1b was readily dehydrated by the isocyanate reagent 5 to furnish di[bis(4-methoxyphenyl)methyl] ether 4b. This symmetrical ether was similarly obtained upon treatment of 1b with diethylaminosulfur trifluoride (DAST)

Biological evaluation of RGD peptidomimetics, designed for the covalent derivatization of cell culture substrata, as potential promotors of cellular adhesion.

Our aim was to replace the proteins and peptides, generally used for the biocompatibilization of polymer substrata, with synthetic molecules mimicking the RGD (Arg-Gly-Asp) active sequence. Based on the (L)-tyrosine template, RGD peptidomimetics were constructed; one molecule 3 was equipped with an anchorage arm that allowed its covalent grafting on a culture substratum made from poly(ethylene terephthalate) (PET) microporous membrane. The amount of fixed molecules was readily determined by XPS, using a fluorine tag incorporated in the peptidomimetic structure. The binding of peptidomimetics 1-3 to the vitronectin (VN) and fibronectin (FN) receptors could not be revealed in a test of inhibition of MSC 80 cells adhesion, by the synthetic compounds in solution placed in competition with the adhesive proteins (VN and FN) coating polystyrene plates. However, the cell-attachment activity of peptidomimetic 3 was shown by culturing CaCo2 cells, in the absence of serum, on the PET substratum grafted with 3. The performance of this support was similar to that of PET grafted with the reference peptide RGDS (Arg-Gly-Asp-Ser), and only reduced by half comparatively to the PET grafted with FN

The origins of marine bioluminescence: turning oxygen defence mechanisms into deep-sea communication tools.

Bioluminescence, the emission of ecologically functional light by living organisms, emerged independently on several occasions, yet the evolutionary origins of most bioluminescent systems remain obscure. We propose that the luminescent substrates of the luminous reactions (luciferins) are the evolutionary core of most systems, while luciferases, the enzymes catalysing the photogenic oxidation of the luciferin, serve to optimise the expression of the endogenous chemiluminescent properties of the luciferin. Coelenterazine, a luciferin occurring in many marine bioluminescent groups, has strong antioxidative properties as it is highly reactive with reactive oxygen species such as the superoxide anion or peroxides. We suggest that the primary function of coelenterazine was originally the detoxification of the deleterious oxygen derivatives. The functional shift from its antioxidative to its light-emitting function might have occurred when the strength of selection for antioxidative defence mechanisms decreased. This might have been made possible when marine organisms began colonising deeper layers of the oceans, where exposure to oxidative stress is considerably reduced because of reduced light irradiance and lower oxygen levels. A reduction in metabolic activity with increasing depth would also have decreased the endogenous production of reactive oxygen species. Therefore, in these organisms, mechanisms for harnessing the chemiluminescence of coelenterazine in specialised organs could have developed, while the beneficial antioxidative properties were maintained in other tissues. The full range of graded irradiance in the mesopelagic zone, where the majority of organisms are bioluminescent, would have provided a continuum for the selection and improvement of proto-bioluminescence. Although the requirement for oxygen or reactive oxygen species observed in bioluminescent systems reflects the high energy required to produce visible light, it may suggest that oxygen-detoxifying mechanisms provided excellent foundations for the emergence of many bioluminescent systems

Influence of plasma pretreatment on shear bond strength of self-adhesive resin cements to polyetheretherketone

OBJECTIVES: The aim of this study is to evaluate the adhesion between PEEK and two self-adhesive resin cements after plasma treatment. METHODS: Eight hundred sixty-four polyetheretherketone (PEEK) disks were cut and polished to silicon carbide (SIC) P4000. One half of the specimens were randomly selected and pretreated with plasma, whereas the remaining 432 specimens remained untreated. Subsequently, specimens were randomly allocated to four groups (n = 108/group): Visio.link (Bredent), Signum PEEK Bond (Heraeus Kulzer), Ambarino P60 (Creamed), and a control group without additional treatment. Half of the specimens of each group (n = 54) were then cemented with either RelyX Unicem Automix 2 (3 M ESPE) or with Clearfil SA (Kuraray). All specimens were stored in water for 24 h (37 °C). Afterwards, specimens were divided into three groups (n = 18) for different aging levels: (1) no aging (baseline measurement), (2) thermal aging for 5,000 cycles (5/55 °C), and (3) thermal aging for 10,000 cycles (5/55 °C). Thereafter, shear bond strengths (SBS) were measured, and failure types (adhesive, mixed, and cohesive) were assessed. Data were analyzed using descriptive statistics, four- and one-way ANOVA followed by a post hoc Scheffé test (p < 0.05). RESULTS: No adhesion could be established without adhesive pretreatment, irrespectively, whether plasma was applied or not. Also, no bond strength was measured when Ambarino P60 was applied. In contrast, adhesive pretreatment resulted in SBS ranging between 8 and 15 MPa. No significant differences were found between the resin cements used. In general, no cohesive failures were observed. Groups without plasma treatment combined with Visio.link or Signum PEEK Bond showed predominantly mixed failure types. Control groups, plasma treated, or treated using Ambarino P60 groups fractured predominantly adhesively. CONCLUSION: The use of methyl methacrylate (MMA)-based adhesives allows bonding between PEEK and self-adhesive resin cements. Plasma treatment has no impact on bond to resin cements. CLINICAL SIGNIFICANCE: PEEK reconstructions can be cemented using self-adhesive resin cements combined with pretreatment with MMA-based adhesives