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There is a growing interest in photonic integrated circuits for biophotonic applications. Here, we present such a circuit operating in the ultraviolet that allows us to implement super-resolved label-free structured illumination on yeast cells.

There is an increasing interest in atomic layer deposition (ALD) on polymers for the development of membranes, electronics, (3D) nanostructures and specially for the development of hermetic packaging of the new generation of flexible implantable micro-devices. This evolution demands a better understanding of the ALD nucleation process on polymers, which has not been reported in a visual way. Herein, a visual study of ALD nucleation on polymers is presented, based on the different dry etching speeds between polymers (fast) and metal oxides (slow). An etching process removes the polyimide with the nucleating ALD acting as a mask, making the nucleation features visible through secondary electron microscopy analyses. The nucleation of both Al2O3 and HfO2 on polyimide was investigated. Both materials followed an island-coalescence nucleation. First, local islands formed, progressively coalescing into filaments, which connected and formed meshes. These meshes evolved into porous layers that eventually grew to a full layer, marking the end of the nucleation. Cross-sections were analyzed, observing no sub-surface growth. This approach was used to evaluate the influence of plasma-activating polyimide on the nucleation. Plasma-induced oxygen functionalities provided additional surface reactive sites for the ALD precursors to adsorb and start the nucleation. The presented nucleation study proved to be a straightforward and simple way to evaluate ALD nucleation on polymers.

We demonstrate far-field UV structured illumination implemented with in-tegrated aluminum oxide (AlOx) waveguide gratings. Based on simulation and experi-mental results, we discuss the performances of two AlO x waveguide gratings operating at λ = 360nm.

A novel 3D elemental and morphological analysis approach is presented combining X-ray computed tomography (μCT), X-ray fluorescence (XRF) tomography, and confocal XRF analysis in a single laboratory instrument (Herakles). Each end station of Herakles (μCT, XRF-CT, and confocal XRF) represents the state-of-the-art of currently available laboratory techniques. The integration of these techniques enables linking the (quantitative) spatial distribution of chemical elements within the investigated materials to their three-dimensional (3D) internal morphology/structure down to 1-10 μm resolution level, which has not been achieved so-far using laboratory X-ray techniques. The concept of Herakles relies strongly on its high precision (around 100 nm) air-bearing motor system that connects the different end-stations, allowing combined measurements based on the above X-ray techniques while retaining the coordinate system. In-house developed control and analysis software further ensures a smooth integration of the techniques. Case studies on a Cu test pattern, a Daphnia magna model organism and a perlite biocatalyst support material demonstrate the attainable resolution, elemental sensitivity of the instrument, and the strength of combining these three complementary methodologies.

Barrier layers for the long-term encapsulation of implantable medical devices play a crucial role in the devices&rsquo, performance and reliability. Typically, to understand the stability and predict the lifetime of barriers (therefore, the implantable devices), the device is subjected to accelerated testing at higher temperatures compared to its service parameters. Nevertheless, at high temperatures, reaction and degradation mechanisms might be different, resulting in false accelerated test results. In this study, the maximum valid temperatures for the accelerated testing of two barrier layers were investigated: atomic layer deposited (ALD) Al2O3 and stacked ALD HfO2/Al2O3/HfO2, hereinafter referred to as ALD-3. The in-house developed standard barrier performance test is based on continuous electrical resistance monitoring and microscopic inspection of Cu patterns covered with the barrier and immersed in phosphate buffered saline (PBS) at temperatures up to 95 &deg, C. The results demonstrate the valid temperature window to perform temperature acceleration tests. In addition, the optimized ALD layer in combination with polyimide (polyimide/ALD-3/polyimide) works as effective barrier at 60 &deg, C for 1215 days, suggesting the potential applicability to the encapsulation of long-term implants.

Long-term packaging of miniaturized, flexible implantable medical devices is essential for the next generation of medical devices. Polymer materials that are biocompatible and flexible have attracted extensive interest for the packaging of implantable medical devices, however realizing these devices with long-term hermeticity up to several years remains a great challenge. Here, polyimide (PI) based hermetic encapsulation was greatly improved by atomic layer deposition (ALD) of a nanoscale-thin, biocompatible sandwich stack of HfO2/Al2O3/HfO2 (ALD-3) between two polyimide layers. A thin copper film covered with a PI/ALD-3/PI barrier maintained excellent electrochemical performance over 1028 days (2.8 years) during acceleration tests at 60 &deg, C in phosphate buffered saline solution (PBS). This stability is equivalent to approximately 14 years at 37 &deg, C. The coatings were monitored in situ through electrochemical impedance spectroscopy (EIS), were inspected by microscope, and were further analyzed using equivalent circuit modeling. The failure mode of ALD Al2O3, ALD-3, and PI soaking in PBS is discussed. Encapsulation using ultrathin ALD-3 combined with PI for the packaging of implantable medical devices is robust at the acceleration temperature condition for more than 2.8 years, showing that it has great potential as reliable packaging for long-term implantable devices.

Varying physico-chemical properties of synthetic hydrogels and introducing additives can induce a cell interactive response of hydrogels. Hydrogels were developed based on acrylate-endcapped urethane-based poly(ethylene glycol) precursors with varying backbone molecular weight (2000–8000 g/mol), in combination with the nanoclay Laponite to explore effects on swelling, mechanical and in vitro biological properties. The combined effect of molecular weight and Laponite concentration enables the development of hybrid materials useful for different biomedical applications. Gel fractions approximating 100% along with tunable swelling (4–11 g/g polymer) and mechanical properties (Young's Modulus 0.1–0.6 MPa) are obtained. All materials are non-cytotoxic and AUPs without Laponite are non cell-interative rendering them suitable for non-adherent biomedical applications. Hydrogels composed of Laponite (0.5 or 1 wt%) and PEG backbone molecular weight of 2000 g/mol promote cell proliferation useful to function as synthetic dermal matrices or scaffolds for tissue engineering applications.

Objective Bioactive glasses (BAG) form, in contrast to formerly used implant materials, a stable bond with tissues, especially bone, when implanted. Nowadays BAGs are often mixed with a cement/composite that hardens in situ to broaden its applications in dentistry or orthopedics. The bioactivity and biocompatibility of possible BAG candidates for BAG-cement/composite development were evaluated. Methods Two fluoride containing BAGs were tested: a Na + -containing (45S5F), based on the first commercial BAG, and a Na + -free BAG (CF9), with a higher Ca 2+ and PO 4 3− content. BAGs were tested on their bioactivity upon immersion in SBF for 7 days by evaluating the surface changes by FT-IR, SEM, EDS and PO 4 3− and Ca 2+ uptake and/or release from SBF. Moreover, the biocompatibility of the BAGs was investigated with a direct contact cell viability study with HFF cells and a cell adhesion study with MG-63 cells. Results The Na + -free BAG, CF9, showed the highest potential to bioactivate cements because of its high Ca 2+ -release and apatite (Ap) formation, as evidenced by SEM pictures and corresponding EDX patterns. FT-IR confirmed the formation of an Ap layer. Moreover CF9 had a higher biocompatibility than 45S5F. Significance For the bioactivation of GICs/composites in order to enhance bonding and remineralization of surrounding tissues, fluoride containing BAG may have advantages over other BAGs as a more stable fluorapatite can be formed. CF9 may be an excellent candidate therefore.

Biocompatible BPA-PPD polyimide is widely used in the packaging of implantable devices. Plasma activation can improve its interaction with the surrounding tissue upon implantation. The influence of He, air, N2 and Ar plasma activation on polyimide's surface hydrophilicity, roughness, topography, composition and cell-surface interaction was evaluated, along with the influence of hydrophobic recovery on such properties. All plasma activations increased the surface hydrophilicity but neither the roughness nor topography changed. The increase was attributed to the incorporated O- and N-functionalities. 24 h after the activations the surface hydrophilicity decreased while maintaining the functionalities, due to the functionalities’ reorientation/migration towards the bulk of polyimide. Air and N2 activations improved the cell-surface interactions with fibroblasts. These were equally influenced by the surface hydrophilicity and the surface functionalities availability. The hydrophobic recovery lowered the initial cell adhesion but not the cell proliferation, as the hydrophobic recovery was progressively reversed in the culture media.

In vascular tissue engineering, great attention is paid to the immobilization of biomolecules onto synthetic grafts to increase bio- and hemocompatibility-two critical milestones in the field. The surface modification field of poly(ethylene terephthalate) (PET), a well-known vascular-graft material, is matured and oversaturated. Nevertheless, most developed methods are laborious multistep procedures generally accompanied by coating instability or toxicity issues. Herein, a straightforward surface modification procedure is presented engineered to simultaneously promote surface endothelialization and anticoagulation properties via the covalent immobilization of gelatin through a photoactivated azide derivative. A complete physicochemical characterization and biological study including cytotoxicity and endotoxin testing are performed. In addition, biocompatibility toward small (diameter ≤ 6 mm) and/or large caliber (diameter ≥ 6 mm) vessels is assessed by micro- and macrovascular endothelial cell assays. Superior bio- and hemocompatibility properties are seen for the gelatin-covalently modified PET surfaces compared to the conventional surface-modification procedures based on physisorption.

In this paper the influence of the epoxy roughness, surface modifications and ELD (electroless copper deposition) temperatures on the adhesive strength of the copper is studied. Good adhesion at low roughness values is targeted due to their applicability in high density electronic circuits. Roughened epoxy surfaces are modified with adsorbed polyamines, polydopamine and polyamines grafted to polydopamine. Next the, adhesive strength of ELD copper is determined with peel strength measurements and the interphases are examined with SEM (scanning electron microscopy). Polydopamine and polyamines grafted to polydopamine can lead to increased adhesive strength at lower roughness values compared to the non-modified samples at specific plating temperatures.

Gellan gum hydrogels functionalized with alkaline phosphatase were enzymatically mineralized with phosphates in mineralization medium containing calcium (Ca) and zinc (Zn) to improve their suitability as biomaterials for bone regeneration. The aims of the study were to endow mineralized hydrogels with antibacterial activity by incorporation of Zn in the inorganic phase, and to investigate the effect of Zn incorporation on the amount and type of mineral formed, the compressive modulus of the mineralized hydrogels and on their ability to support adhesion and growth of MC3T3-E1 osteoblast-like cells. Mineralization medium contained glycerophosphate (0.05 m) and three different molar Ca:Zn ratios, 0.05:0, 0.04:0.01 and 0.025:0.025 (all mol/dm3 ), hereafter referred to as A, B and C, respectively. FTIR, SAED and TEM analysis revealed that incubation for 14 days caused the formation of predominantly amorphous mineral phases in sample groups A, B and C. The presence of Zn in sample groups B and C was associated with a drop in the amount of mineral formed and a smaller mineral deposit morphology, as observed by SEM. ICP-OES revealed that Zn was preferentially incorporated into mineral compared to Ca. Mechanical testing revealed a decrease in compressive modulus in sample group C. Sample groups B and C, but not A, showed antibacterial activity against biofilm-forming, methicillin-resistant Staphylococcus aureus. All sample groups supported cell growth. Zn incorporation increased the viable cell number. The highest values were seen on sample group C. In conclusion, the sample group containing the most Zn, i.e. group C, appears to be the most promising. Copyright © 2015 John Wiley & Sons, Ltd.

Polycaprolactone (PCL) is a biodegradable and biocompatible polyester whose low melting point facilitates production of 3D porous scaffolds with precisely defined dimensions and internal architecture by rapid prototyping techniques. To improve the suitability of such PCL scaffolds for bone regeneration applications, they were coated with inorganic layers of calcium phosphate (CaP) and CaP doped with 0.6% w/v magnesium (CaP+Mg) using pulsed laser deposition (PLD) and characterized in vitro using osteoblast-like Saos-2 cells. Saos-2 cells were able to adhere to all scaffolds. CaP+Mg coatings significantly increased activity of alkaline phosphatase (ALP), an early differentiation marker, after 7 days. However, gene expression of ALP after 7 days was markedly lower on the same scaffolds. These data show the feasibility of coating PCL with CaP layers by PLD and the possibility of influencing osteoblastic differentiation by magnesium doping of the CaP coating.

This paper presents an alcohol vapor sensor realized using stretchable optical waveguides doped with commercially available fluorescent dyes. The fabrication technology is based on a cost-efficient replication method, employing polydimethylsiloxane materials mixed with the dye Nile red. Upon introduction of ethanol vapors, the fluorescent emission was found to have a wavelength shift of ~20 nm with a response time of ~10 s. Observing the fluorescence intensity of the shifted emission spectrum in a periodically varying environment inside a gas-sensing setup showed a respective variation with introduction of ethanol vapor. The intensity variation also showed the reversibility of the sensor. The sensing platform is found to hold much promise for further integration and multiplexing.

To realize optimal recording and stimulation of peripheral nerve cells, a CMOS chip is made with a multitude of electrodes which can be individually addressed in order to select after implantation the 16 best positioned electrodes. Since the Foreign Body Reaction should be minimal for optimum electrode-nerve contact, the CMOS chip is thinned down to 35um and fully packaged resulting in a 75um thin encapsulated chip. The chip is embedded in a biocompatible stack consisting of polymers and inorganic diffusion barriers deposited using atomic layer deposition (ALD). A biocompatible metallization is realized using gold and platinum sandwiched between polymers and ALD layers for flexible interconnects, and iridium oxide (IrOx) is selected as electrode material for optimal charge injection during stimulation. After this dedicated packaging based on the FITEP technology platform (Flexible Implantable Thin Electronic Package), the CMOS chip is still fully functional, which was tested dry (in air) as well as during submersion in saline. The form factor of the packaged chip is optimized for intra-fascicular implantation with minimum tissue damage. First acute in vivo stimulation tests proved that the stimulation capabilities of the IrOx electrodes are very good.

Advanced bionic prosthetics that can restore both the motor functionality and sensory perception of an amputee, require high-resolution recording and stimulation interfaces targeting the peripheral nervous system (PNS). To provide high nerve fiber selectivity, we propose a low-noise (3.67μVrms) low-power (2.24mW) and high-density CMOS microelectrode probe for intra-neural implantation. The probe is composed of two ICs, encapsulated in a biocompatible and hermetic package, each featuring 64 recording and 16 stimulation electrodes. A backend IC digitizes the recorded signals at 31.25kS/s and provides spike detection.

Hydrogel biomaterials can be easily enriched with bioactive substances such as the mineralization-promoting enzyme alkaline phosphatase (ALP). In this study, poly(vinyl alcohol) (PVA) hydrogels designed for osteochondral regeneration containing incorporated ALP were mineralized with calcium phosphate (CaP) and magnesium phosphate (MgP) by incubation in solutions of 0.1 M calcium or magnesium glycerophosphate (CaGP, MgGP). Hydrogels incubated in water served as controls. More mineral was formed in hydrogels incubated in CaGP than in MgGP. Rheometry revealed that mechanical strength (storage modulus) decreased in the order: CaGP>MgGP>water. Physicochemical charaterization showed that hydrogels incubated in CaGP appeared to be mineralized with apatite and amorphous CaP, while hydrogels incubated in MgGP appeared to be mineralized with plate-like MgP crystals and amorphous MgP. Hydrogels incubated in water were devoid of mineralization. Cell viability testing showed that proliferation on hydrogels incubated in MgGP was comparable to that on non-mineralized samples and superior to that on hydrogels incubated in CaGP. The results prove the principle of enzymatic mineralization of PVA hydrogels with CaP and MgP. Further work may concentrate on in vivo evaluation of the suitability of these mineralized hydrogels for bone or osteochondral regeneration applications.

Objective. In this work, the development of an active high-density transverse intrafascicular micro-electrode (hd-TIME) probe to interface with the peripheral nervous system is presented. Approach. The TIME approach is combined with an active probe chip, resulting in improved selectivity and excellent signal-to-noise ratio. The integrated multiplexing capabilities reduce the number of external electrical connections and facilitate the positioning of the probe during implantation, as the most interesting electrodes of the electrode array can be selected after implantation. The probe chip is packaged using thin-film manufacturing techniques to allow for a minimally invasive electronic package. Special attention is paid to the miniaturization, the mechanical flexibility and the hermetic encapsulation of the device. Main results. A customized probe chip was designed and packaged using a flexible, implantable thin electronic package (FITEP) process platform. The platform is specifically developed for making slim, ultra-compliant, implantable complementary metal-oxide-semiconductor based electronic devices. Multilayer stacks of polyimide films and HfO2/Al2O3/HfO2 layers deposited via atomic layer deposition act as bidirectional diffusion barriers and are key to the hermetic encapsulation. Their efficacy was demonstrated both by water vapor transmission rate tests and accelerated immersion tests in phosphate buffered saline at 60 °C. Using the hd-TIME probe, an innovative implantation method is developed to prevent the fascicles from moving away when the epineurium is pierced. In addition, by transversally implanting the hd-TIME probe in the proximal sciatic nerve of a rat, selective activation within the nerve was demonstrated. Significance. The FITEP process platform can be applied to a broader range of integrated circuits and can be considered as an enabler for other biomedical applications.

Mineralization of hydrogels, desirable for bone regeneration applications, may be achieved enzymatically by incorporation of alkaline phosphatase (ALP). ALP-loaded gellan gum (GG) hydrogels were mineralized by incubation in mineralization media containing calcium and/or magnesium glycerophosphate (CaGP, MgGP). Mineralization media with CaGP:MgGP concentrations 0.1:0, 0.075:0.025, 0.05:0.05, 0.025:0.075 and 0:0.1 (all values mol/dm3, denoted A, B, C, D and E, respectively) were compared. Mineral formation was confirmed by IR and Raman, SEM, ICP-OES, XRD, TEM, SAED, TGA and increases in the the mass fraction of the hydrogel not consisting of water. Ca was incorporated into mineral to a greater extent than Mg in samples mineralized in media A–D. Mg content and amorphicity of mineral formed increased in the order A B > C > D, but were significantly higher for samples mineralized in medium E. The attachment and vitality of osteoblastic MC3T3-E1 cells were higher on samples mineralized in media B–E (containing Mg) than in those mineralized in medium A (not containing Mg). All samples underwent degradation and supported the adhesion of RAW 264.7 monocytic cells, and samples mineralized in media A and B supported osteoclast-like cell formation. Copyright © 2014 John Wiley & Sons, Ltd.

Various types of nanofibers are increasingly used in tissue engineering, mainly for their ability to mimic the archi- tecture of tissue at the nanoscale. We evaluated the adhesion, growth, viability, and differentiation of human osteoblast-like MG 63 cells on polylactide (PLA) nanofibers prepared by needle-less electrospinning and loaded with 5 or 15 wt % of hydroxyapatite (HA) nanoparticles. On day 7 after seeding, the cell number was the highest on samples with 15 wt % of HA. This result was confirmed by the XTT test, especially after dynamic cultivation, when the number of metabolically active cells on these samples was even higher than on control poly- styrene. Staining with a live/dead kit showed that the viability of cells on all nanofibrous scaffolds was very high and compa- rable to that on control polystyrene dishes. An enzyme-linked immunosorbent assay revealed that the concentration of osteocalcin was also higher in cells on samples with 15 wt % of HA. There was no immune activation of cells (measured by production of TNF-alpha), associated with the incorporation of HA. Moreover, the addition of HA suppressed the creep behav- ior of the scaffolds in their dry state. Thus, nanofibrous PLA scaffolds have potential for bone tissue engineering, particu- larly those with 15 wt % of HA. V

Selective laser patterning of thin organic films is an important aspect in the roll-to-roll production of organic electronic devices such as organic light emitting diodes (OLEDs). An excimer laser is well suited for the patterning and structuring of polymer thin films as their UV absorption is significant. Selective removal of a transparent conducting polymer PEDOT:PSS (poly(3,4-ethylene dioxythiophene): polystyrene sulfonate) on a multilayered (inorganic-organic-inorganic) barrier and a flexible PEN (polyethylene napthalate) substrate has been studied using a KrF excimer laser. The ablation craters were characterized with electron microscopy and profilometry. For the first time, chemical surface analysis of the patterned area was performed with Time-Of-Flight Static Secondary Ion Mass Spectrometry (TOF-S-SIMS), providing a detailed insight of the surface composition after laser ablation and plasma post-treatments. (C) 2013 Elsevier B.V. All rights reserved.

A contact lens embeddable display using electro-optic modulation was designed and fabricated. Using a guest–host liquid crystal configuration, a spherically deformed liquid crystal cell was fabricated comprising poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT : PSS) as a conductive layer and obliquely evaporated SiO2 as an alignment layer. An additional SiO2 buffer layer was evaporated on top of the PEDOT : PSS to overcome compatibility problems with the patterning of the photolithographically defined spacers. Although the contrast is modest, a patterned modulation could clearly be observed, indicating that our approach and fabrication process could eventually lead to a fully pixelated contact lens display.

Injectable composites for tissue regeneration can be developed by dispersion of inorganic microparticles and cells in a hydrogel phase. In this study, multifunctional carbonate microparticles containing different amounts of calcium, magnesium and zinc were mixed with solutions of gellan gum (GG), an anionic polysaccharide, to form injectable hydrogel-microparticle composites, containing Zn, Ca and Mg. Zn and Ca were incorporated into microparticle preparations to a greater extent than Mg. Microparticle groups were heterogeneous and contained microparticles of differing shape and elemental composition. Zn-rich microparticles were 'star shaped' and appeared to consist of small crystallites, while Zn-poor, Ca- and Mg-rich microparticles were irregular in shape and appeared to contain lager crystallites. Zn-free microparticle groups exhibited the best cytocompatibility and, unexpectedly, Zn-free composites showed the highest antibacterial activity towards methicilin-resistant Staphylococcus aureus. Composites containing Zn-free microparticles were cytocompatible and therefore appear most suitable for applications as an injectable biomaterial. This study proves the principle of creating bi- and tri-elemental microparticles to induce the gelation of GG to create injectable hydrogel-microparticle composites.

Mineralization of hydrogels is desirable prior to applications in bone regeneration. CaCO3 is a widely used bone regeneration material, and Mg, when used as a component of calcium phosphate biomaterials, has promoted bone-forming cell adhesion and proliferation and bone regeneration. In this study, gellan gum hydrogels were mineralized with carbonates containing different amounts of calcium (Ca) and magnesium (Mg) by alternate soaking in, firstly, a calcium and/or magnesium ion solution and, secondly, a carbonate ion solution. This alternate soaking cycle was repeated five times. Five different calcium and/or magnesium ion solutions, containing different molar ratios of Ca to Mg ranging from Mg free to Ca free were compared. Carbonate mineral formed in all sample groups subjected to the alternate soaking cycle. Ca : Mg elemental ratio in the mineral formed was higher than in the respective mineralizing solution. Mineral formed in the absence of Mg was predominantly CaCO3 in the form of a mixture of calcite and vaterite. Increasing the Mg content in the mineral formed led to the formation of magnesian calcite and decreased the total amount of the mineral formed and its crystallinity. Hydrogel mineralization and increasing Mg content in mineral formed did not obviously improve proliferation of MC3T3-E1 osteoblast-like cells or differentiation after 7 days.

Biocompatible polymeric coatings for metallic stents are desired, as currently used materials present limitations such as deformation during degradation and exponential loss of mechanical properties after implantation. These concerns, together with the present risks of the drug-eluting stents, namely, thrombosis and restenosis, require new materials to be studied. For this purpose, novel poly(polyol sebacate)-derived polymers are investigated as coatings for metallic stents. All pre-polymers reveal a low molecular weight between 3000 and 18 000 g mol−1. The cured polymers range from flexible to more rigid, with E-modulus between 0.6 and 3.8 MPa. Their advantages include straightforward synthesis, biodegradability, easy processing through different scaffolding techniques, and easy transfer to industrial production. Furthermore, electrospraying and dip-coating procedures are used as proof-of-concept to create coatings on metallic stents. Biocompatibility tests using adipose stem cells lead to promising results for the use of these materials as coatings for metallic coronary stents. Fil: Navarro, Lucila. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico Para la Industria Química; Argentina Fil: Mogosanu, Diana. Ghent University; Bélgica Fil: de Jong, Thijs. Academic Centre for Dentistry Amsterdam; Países Bajos Fil: Bakker, Astrid. Academic Centre for Dentistry Amsterdam; Países Bajos Fil: Schaubroeck, David. Ghent University; Bélgica Fil: Luna, Julio Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico Para la Industria Química; Argentina Fil: Rintoul, Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico Para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico Para la Industria Química; Argentina Fil: Vanfleteren, Jan. Ghent University; Bélgica Fil: Dubruel, Peter. Ghent University; Bélgica

In the last decade, substantial research in the field of post-plasma grafting surface modification has focussed on the introduction of carboxylic acids on surfaces by grafting acrylic acid (AAc). In the present work, we report on an alternative approach for biomaterial surface functionalisation. Thin poly-ε-caprolactone (PCL) films were subjected to a dielectric barrier discharge Ar-plasma followed by the grafting of 2-aminoethyl methacrylate (AEMA) under UV-irradiation. X-ray photoelectron spectroscopy (XPS) confirmed the presence of nitrogen. The ninhydrin assay demonstrated, both quantitatively and qualitatively, the presence of free amines on the surface. Confocal fluorescence microscopy (CFM), atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to visualise the grafted surfaces, indicating the presence of pAEMA. Static contact angle (SCA) measurements indicated a permanent increase in hydrophilicity. Furthermore, the AEMA grafted surfaces were applied for comparing the physisorption and covalent immobilisation of gelatin. CFM demonstrated that only the covalent immobilisation lead to a complete coverage of the surface. Those gelatin-coated surfaces obtained were further coated using fibronectin. Osteosarcoma cells demonstrated better cell-adhesion and cell-viability on the modified surfaces, compared to the pure PCL films.

The introduction of amine groups on the surface of dielectric resins improves the adhesion with electrochemically deposited metals. In this work, etched epoxy resin surfaces are modified with aliphatic amines via a two step wet chemical reaction approach. First, cyanuric chloride is introduced on the surface. Next, the remaining reactive sites of cyanuric chloride are used to couple an aliphatic polyamine. Both reaction steps are optimized by variation of reaction parameters such as concentration, chemicals, temperature and time. A detailed surface characterization after each reaction step is provided using following techniques: ATR-IR, SEM–EDS, XPS and AFM.

Despite its widespread application in the fields of ophthalmology, orthopedics and dentistry and the stringent need for polymer packagings that induce in vivo tissue integration, the full potential of poly(methyl methacrylate) (PMMA) and its derivatives as medical device packaging material has not been explored yet. We therefore elaborated on the development of a universal coating for methacrylate-based materials which ideally should reveal cell-interactivity irrespective of the polymer substrate bulk properties. Within this perspective, the present work reports on the UV-induced synthesis of PMMA and its more flexible poly(ethyleneglycol) (PEG)-based derivative (PMMAPEG) and its subsequent surface decoration using polydopamine (PDA) as well as PDA combined with gelatin B (Gel B). Successful application of both layers was confirmed by multiple surface characterization techniques. The cell interactivity of the materials was studied by performing live-dead assays and immunostainings of the cytoskeletal components of fibroblasts. It can be concluded that only the combination of PDA and Gel B yields materials posessing similar cell interactivities, irrespective of the physicochemical properties of the underlying substrate. The proposed coating outperforms both the PDA functionalized and the pristine polymer surfaces. A universal cell-interactive coating for methacrylate-based medical device packaging materials has thus been realized.

© 2015 Elsevier B.V. All rights reserved. Cracks are concrete's worst problem. External, passive treatments are expensive and time consuming. pH-responsive superabsorbent polymers (SAPs) offer an internal active solution. When cracks occur, the SAPs can swell, fill the crack (self-sealing) and assist in the formation of healing products (self-healing). In previous work, a range of (superabsorbent) polymers have been synthesized and characterized. Based on these results, the two best performing SAPs were chosen for further characterization. The results indicate that the SAPs developed do not show degradation in cement filtrate solutions. Upon addition of SAPs, a decrease in mortar strength occurred, yet a positive effect on self-sealing was observed since the water permeability decreased. Furthermore, the formation of products became apparent at the sealed cracks of the mortar samples containing 1 m% SAPs. Identification using scanning electron microscopy, infrared spectroscopy and thermogravimetric analysis indicated that the products mainly consisted of healing products (more specifically CaCO3) which is illustrative for self-healing. ispartof: REACTIVE & FUNCTIONAL POLYMERS vol:93 pages:68-76 status: published

Introduction: Mineralization of hydrogel biomaterials is considered desirable to improve their suitability as materials for bone regeneration[1],[2]. Hydrogels have been most commonly mineralized with calcium phosphate (CaP), but hydrogel-CaCO3 composites have received less attention. Magnesium (Mg) has been added to CaP to stimulate cell adhesion and proliferation and bone regeneration in vivo, but its effect as a component of carbonate-based biomaterials remains uninvestigated. In this study, gellan gum (GG) hydrogels were mineralized enzymatically with (CaCO3), Mg-enriched CaCO3 and magnesium carbonate to generate composite biomaterials for bone regeneration. GG is an inexpensive, biotechnologically produced anionic polysaccharide, from which hydrogels for cartilage regeneration have been formed by crosslinking with divalent ions[3].Methods: GG hydrogels were loaded with the enzyme urease by incubation in 5% (w/v) urease solution and mineralized for 5 days in five different media denoted as UA, UB, UC, UD and UE, which contained urea (0.17 M) and different concentrations of CaCl2 and MgCl2 (270:0, 202.5:67.5, 135:135, 67.5:202.5 and 0:250, respectively (mmol dm-3)). Discs were autoclaved and subjected to physiochemical, mechanical and cell biological characterization.Results: FTIR, SEM, TGA and XRD analysis revealed that increasing magnesium concentration decreased mineral crystallinity. At low magnesium concentrations calcite was formed, while at higher concentrations magnesian calcite was formed. Hydromagnesite formed at high magnesium concentration in the absence of calcium. Amount of mineral formed and compressive strength decreased with increasing magnesium concentration in the mineralization medium. ICP analysis revealed that Ca:Mg elemental ratio in the mineral formed was higher than in the respective mineralization media. Mineralization of hydrogels promoted adhesion and growth of osteoblast-like cells, which were supported best on mineralized hydrogels containing no or little magnesium. Hydrogels mineralized with hydromagnesite displayed higher cytotoxicity.Discussion: Enzymatic mineralization of GG hydrogels with CaCO3 in the form of calcite successfully reinforced hydrogels and promoted osteoblast-like cell adhesion and growth, but Mg enrichment had no positive effect. This is in contrast with other studies reporting that incorporation of Mg into GG mineralized with CaP promotes cell adhesion and proliferation[4]. Conclusion: Sample groups UA and UB seem to be the most promising due to the superior amount of mineral formed and cell adhesion and proliferation.

A ruthenium based benzylidene complex bearing an O,N-bidentate Schiff base ligand exhibits poor olefin metathesis activity but generates a highly active catalyst system when treated with acidic cocatalysts. Various Lewis acids were able to boost the ring opening metathesis polymerization (ROMP) of cycloocta-1,5-diene (COD). The best results were obtained with trichlorosilane (HSiCl3), which was also found to improve metathesis activity of the Grubbs second generation catalyst [RuCl2( CHPh)(H2IMes)(PCy3)] in the ROMP of COD and the ring closing metathesis (RCM) of diethyl diallylmalonate.

This study describes the qualitative analysis of the polymerization reaction of DCPD (DiCycloPentaDiene) and its reaction products. The polymerization was carried out using WCl6/Si(allyl)4 (1), first generation Grubbs’ (2) and second generation Grubbs’ (3) catalysts. When system 1 was used as a catalyst, solution concentration determined whether soluble or insoluble polymer was obtained. When Grubbs’ catalysts were employed, insoluble polymer was formed in all cases. The ring opening metathesis polymerization (ROMP)-reaction and the resulting polymers were monitored in situ via FT-Raman-spectroscopy. Using FT-Raman-spectroscopy, the stereospecific nature of the forming polymer can be determined during the polymerization reaction. The obtained spectra illustrate that the linear polymer has a prevailing cis double bond configuration, while the polymer formed using the 1e generation Grubbs catalyst has a predominant trans double bond configuration. The second generation Grubbs catalyst exhibits a poor stereoselectivity. These results are in accordance to literature data where the stereospecific nature of these polymers where determined using NMR-spectroscopy.

Gellan gum hydrogels functionalized with alkaline phosphatase were enzymatically mineralized with phosphates in mineralization medium containing calcium (Ca) and zinc (Zn) to improve their suitability as biomaterials for bone regeneration. The aims of the study were to endow mineralized hydrogels with antibacterial activity by incorporation of Zn in the inorganic phase, and to investigate the effect of Zn incorporation on the amount and type of mineral formed, the compressive modulus of the mineralized hydrogels and on their ability to support adhesion and growth of MC3T3-E1 osteoblast-like cells. Mineralization medium contained glycerophosphate (0.05 m) and three different molar Ca:Zn ratios, 0.05:0, 0.04:0.01 and 0.025:0.025 (all mol/dm

Injectable composites for tissue regeneration can be developed by dispersion of inorganic microparticles and cells in a hydrogel phase. In this study, multifunctional carbonate microparticles containing different amounts of calcium, magnesium and zinc were mixed with solutions of gellan gum (GG), an anionic polysaccharide, to form injectable hydrogel-microparticle composites, containing Zn, Ca and Mg. Zn and Ca were incorporated into microparticle preparations to a greater extent than Mg. Microparticle groups were heterogeneous and contained microparticles of differing shape and elemental composition. Zn-rich microparticles were 'star shaped' and appeared to consist of small crystallites, while Zn-poor, Ca- and Mg-rich microparticles were irregular in shape and appeared to contain lager crystallites. Zn-free microparticle groups exhibited the best cytocompatibility and, unexpectedly, Zn-free composites showed the highest antibacterial activity towards methicilin-resistant Staphylococcus aureus. Composites containing Zn-free microparticles were cytocompatible and therefore appear most suitable for applications as an injectable biomaterial. This study proves the principle of creating bi- and tri-elemental microparticles to induce the gelation of GG to create injectable hydrogel-microparticle composites.

Porous biodegradable scaffolds represent promising candidates for tissue-engineering applications because of their capability to be preseeded with cells. We report an uncrosslinked chitosan scaffold designed with the aim of inducing and supporting enzyme-mediated formation of apatite minerals in the absence of osteogenic growth factors. To realize this, natural enzyme alkaline phosphatase (ALP) was incorporated into uncrosslinked chitosan scaffolds. The uncrosslinked chitosan makes available amine and alcohol functionalities to enhance the biomineralization process. The physicochemical findings revealed homogeneous mineralization, with the phase structure of the formed minerals resembling that of apatite at low mineral concentrations, and similar to dicalcium phosphate dihydrate (DCPD) with increasing ALP content. The MC3T3 cell activity clearly showed that the mineralization of the chitosan scaffolds was effective in improving cellular adhesion, proliferation and colonization. Copyright © 2015 John WileySons, Ltd.

Item does not contain fulltext Hydrogels of biocompatible calcium-crosslinkable polysaccharide gellan gum (GG) were enriched with bioglass particles to enhance (i) mineralization with calcium phosphate (CaP); (ii) antibacterial properties and (iii) growth of bone-forming cells for future bone regeneration applications. Three bioglasses were compared, namely one calcium-rich and one calcium-poor preparation both produced by a sol-gel technique (hereafter referred to as A2 and S2, respectively) and one preparation of composition close to that of the commonly used 45S5 type (hereafter referred to as NBG). Incubation in SBF for 7 d, 14 d and 21 d caused apatite formation in bioglass-containing but not in bioglass-free samples, as confirmed by FTIR, XRD, SEM, ICP-OES, and measurements of dry mass, i.e. mass attributable to polymer and mineral and not water. Mechanical testing revealed an increase in compressive modulus in samples containing S2 and NBG but not A2. Antibacterial testing using biofilm-forming meticillin-resistant staphylococcus aureus (MRSA) showed markedly higher antibacterial activity of samples containing A2 and S2 than samples containing NBG and bioglass-free samples. Cell biological characterization using rat mesenchymal stem cells (rMSCs) revealed a stimulatory effect of NBG on rMSC differentiation. The addition of bioglass thus promotes GG mineralizability and, depending on bioglass type, antibacterial properties and rMSC differentiation.

This paper describes the influence of polydopamine and polyamine surface modifications of an etched epoxy cresol novolak (ECN) resin on the initial electroless copper deposition. Three different strategies to introduce polyamines on a surface in aqueous environment are applied: via polyethyleneimine adsorption (PEI), via polydopamine and via polyamines grafted to polydopamine. Next, the influence of these surface modifications on the catalytic palladium activation is investigated through X-ray photoelectron spectroscopy (XPS) analysis. Finally, the initial electroless copper deposition on modified epoxy surfaces is evaluated using SEM and Energy Dispersive Spectroscopy (EDS). Grafted polyamines on polydopamine surface modifications result in a large increase of the initial deposited copper.

The fast growing market of organic electronics, including organic photovoltaics (OPV), stimulates the development of versatile technologies for structuring thin-film materials. Ultraviolet lasers have proven their full potential for patterning single organic layers, but in a multilayer organic device the obtained layer selectivity is limited as all organic layers show high UV absorption. In this paper, we introduce mid-infrared (IR) resonant ablation as an alternative approach, in which a short pulse mid-infrared laser can be wavelength tuned to one of the molecular vibrational transitions of the organic material to be ablated. As a result, the technique is selective in respect of processing a diversity of organics, which usually have different infrared absorption bands. Mid-IR resonant ablation is demonstrated for a variety of organic thin films, employing both nanosecond (15 ns) and picosecond (250 ps) laser pulses tunable between 3 and 4 microns. The nanosecond experimental set-up is based on a commercial laser at 1064 nm pumping a singly resonant Optical Parametric Oscillator (OPO) built around a Periodically-Poled Lithium Niobate (PPLN) crystal with several Quasi-Phase Matching (QPM) periods, delivering more than 0.3 W of mid-IR power, corresponding to 15 μJ pulses. The picosecond laser set-up is based on Optical Parametric Amplification (OPA) in a similar crystal, allowing for a comparison between both pulse length regimes. The wavelength of the mid-infrared laser can be tuned to one of the molecular vibrational transitions of the organic material to be ablated. For that reason, the IR absorption spectra of the organic materials used in a typical OPV device were characterized in the wavelength region that can be reached by the laser setups. Focus was on OPV substrate materials, transparent conductive materials, hole transport materials, and absorber materials. The process has been successfully demonstrated for selective thin film patterning, and the influence of the various laser parameters is discussed.

Superabsorbent polymers (SAPs) are particles which can take up a significant amount of fluid. In this paper workability, microstructure and strength properties were compared for mixtures with(out) SAPs and with(out) additional water. SAP particles reduce the flow, cause a densification of the matrix due to internal curing and also reduce the strength due to macro-pore formation. These characteristics need to be taken into account when using high amounts of SAPs in a mixture. The microstructure of mixtures with SAPs and additional water tends towards the one of the reference mixture without SAPs. The strength upon water addition, however, decreases slightly.

Various types of nanofibers are increasingly used in tissue engineering, mainly for their ability to mimic the architecture of tissue at the nanoscale. We evaluated the adhesion, growth, viability, and differentiation of human osteoblast-like MG 63 cells on polylactide (PLA) nanofibers prepared by needle-less electrospinning and loaded with 5 or 15 wt % of hydroxyapatite (HA) nanoparticles. On day 7 after seeding, the cell number was the highest on samples with 15 wt % of HA. This result was confirmed by the XTT test, especially after dynamic cultivation, when the number of metabolically active cells on these samples was even higher than on control polystyrene. Staining with a live/dead kit showed that the viability of cells on all nanofibrous scaffolds was very high and comparable to that on control polystyrene dishes. An enzyme-linked immunosorbent assay revealed that the concentration of osteocalcin was also higher in cells on samples with 15 wt % of HA. There was no immune activation of cells (measured by production of TNF-alpha), associated with the incorporation of HA. Moreover, the addition of HA suppressed the creep behavior of the scaffolds in their dry state. Thus, nanofibrous PLA scaffolds have potential for bone tissue engineering, particularly those with 15 wt % of HA.

Mineralization of hydrogels, desirable for bone regeneration applications, may be achieved enzymatically by incorporation of alkaline phosphatase (ALP). ALP-loaded gellan gum (GG) hydrogels were mineralized by incubation in mineralization media containing calcium and/or magnesium glycerophosphate (CaGP, MgGP). Mineralization media with CaGP:MgGP concentrations 0.1:0, 0.075:0.025, 0.05:0.05, 0.025:0.075 and 0:0.1 (all values mol/dm