Development of Lignin-Based Mesoporous Carbons for the Adsorption of Humic Acid.

There is an increasing urge to make the transition toward biobased materials. Lignin, originating from lignocellulosic biomass, can be potentially valorized as humic acid (HA) adsorbents via lignin-based mesoporous carbon (MC). In this work, these materials were synthesized for the first time starting from modified lignin as the carbon precursor, using the soft-template methodology. The use of a novel synthetic approach, Claisen rearrangement of propargylated lignin, and a variety of surfactant templates (Pluronic, Kraton, and Solsperse) have been demonstrated to tune the properties of the resulting MCs. The obtained materials showed tunable properties (BET surface area: 95-367 m2/g, pore size: 3.3-36.6 nm, V BJH pore volume: 0.05-0.33 m3/g, and carbon and oxygen content: 55.5-91.1 and 3.0-12.2%, respectively) and good performance in terms of one of the highest HA adsorption capacities reported for carbon adsorbents (up to 175 mg/g).

Magnetic Properties of Silicon Steel after Plastic Deformation.

The energy efficiency of electric machines can be improved by optimizing their manufacturing process. During the manufacturing of ferromagnetic cores, silicon steel sheets are cut and stacked. This process introduces large stresses near cutting edges. The steel near cutting edges is in a plastically deformed stress state without external mechanical load. The magnetic properties of the steel in this stress state are investigated using a custom magnetomechanical measurement setup, stress strain measurements, electrical resistance measurements, and transmission electron microscopic (TEM) measurements. Analysis of the core energy losses is done by means of the loss separation technique. The silicon steel used in this paper is non-grain oriented (NGO) steel grade M270-35A. Three differently cut sets of M270-35A are investigated, which differ in the direction they are cut with respect to the rolling direction. The effect of sample deformation was measured-both before and after mechanical load release-on the magnetization curve and total core energy losses. It is known that the magnetic properties dramatically degrade with increasing sample deformation under mechanical load. In this paper, it was found that when the mechanical load is released, the magnetic properties degrade even further. Loss separation analysis has shown that the hysteresis loss is the main contributor to the additional core losses due to sample deformation. Releasing the mechanical load increased the hysteresis loss up to 270% at 10.4% pre-release strain. At this level of strain, the relative magnetic permeability decreased up to 45% after mechanical load release. Manufacturing processes that introduce plastic deformation are detrimental to the local magnetic material properties.

Ca:Mg:Zn:CO3 and Ca:Mg:CO3-tri- and bi-elemental carbonate microparticles for novel injectable self-gelling hydrogel-microparticle composites for tissue regeneration.

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.

Composites of gellan gum hydrogel enzymatically mineralized with calcium-zinc phosphate for bone regeneration with antibacterial activity.

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.

Novel injectable, self-gelling hydrogel-microparticle composites for bone regeneration consisting of gellan gum and calcium and magnesium carbonate microparticles.

The suitability of hydrogel biomaterials for bone regeneration can be improved by incorporation of an inorganic phase in particle form, thus maintaining hydrogel injectability. In this study, carbonate microparticles containing different amounts of calcium (Ca) and magnesium (Mg) were added to solutions of the anionic polysaccharide gellan gum (GG) to crosslink GG by release of Ca2+ and Mg2+ from microparticles and thereby induce formation of hydrogel-microparticle composites. It was hypothesized that increasing Mg content of microparticles would promote GG hydrogel formation. The effect of Mg incorporation on cytocompatibility and cell growth was also studied. Microparticles were formed by mixing Ca2+ and Mg2+ and [Formula: see text] ions in varying concentrations. Microparticles were characterized physiochemically and subsequently mixed with GG solution to form hydrogel-microparticle composites. The elemental Ca:Mg ratio in the mineral formed was similar to the Ca:Mg ratio of the ions added. In the absence of Mg, vaterite was formed. At low Mg content, magnesian calcite was formed. Increasing the Mg content further caused formation of amorphous mineral. Microparticles of vaterite and magnesium calcite did not induce GG hydrogel formation, but addition of Mg-richer amorphous microparticles induced gelation within 20 min. Microparticles were dispersed homogeneously in hydrogels. MG-63 osteoblast-like cells were cultured in eluate from hydrogel-microparticle composites and on the composites themselves. All composites were cytocompatible. Cell growth was highest on composites containing particles with an equimolar Ca:Mg ratio. In summary, carbonate microparticles containing a sufficient amount of Mg induced GG hydrogel formation, resulting in injectable, cytocompatible hydrogel-microparticle composites.

Correlative microscopy of a carbide-free bainitic steel.

In this work a carbide-free bainitic steel was examined by a novel correlative microscopy approach using transmission Kikuchi diffraction (TKD) and transmission electron microscopy (TEM). The individual microstructural constituents could be identified by TKD based on their different crystal structure for bainitic ferrite and retained austenite and by image quality for the martensite-austenite (M-A) constituent. Subsequently, the same area was investigated in the TEM and a good match of these two techniques regarding the identification of the area position and crystal orientation could be proven. Additionally, the M-A constituent was examined in the TEM for the first time after preceded unambiguous identification using a correlative microscopy approach. The selected area diffraction pattern showed satellites around the main reflexes which might indicate a structural modulation.

Generation of composites for bone tissue-engineering applications consisting of gellan gum hydrogels mineralized with calcium and magnesium phosphate phases by enzymatic means.

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. Mineral formed in media A and B was calcium-deficient hydroxyapatite (CDHA). Mineral formed in medium C was a combination of CDHA and an amorphous phase. Mineral formed in medium D was an amorphous phase. Mineral formed in medium E was a combination of crystalline and amorphous MgP. Young's moduli and storage moduli decreased in dependence of mineralization medium 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.

Development of thermosensitive hydrogels of chitosan, sodium and magnesium glycerophosphate for bone regeneration applications.

Thermosensitive injectable hydrogels based on chitosan neutralized with sodium beta-glycerophosphate (Na-ß-GP) have been studied as biomaterials for drug delivery and tissue regeneration. Magnesium (Mg) has been reported to stimulate adhesion and proliferation of bone forming cells. With the aim of improving the suitability of the aforementioned chitosan hydrogels as materials for bone regeneration, Mg was incorporated by partial substitution of Na-ß-GP with magnesium glycerophosphate (Mg-GP). Chitosan/Na-ß-GP and chitosan/Na-ß-GP/Mg-GP hydrogels were also loaded with the enzyme alkaline phosphatase (ALP) which induces hydrogel mineralization. Hydrogels were characterized physicochemically with respect to mineralizability and gelation kinetics, and biologically with respect to cytocompatibility and cell adhesion. Substitution of Na-ß-GP with Mg-GP did not negatively influence mineralizability. Cell biological testing showed that both chitosan/Na-ß-GP and chitosan/Na-ß-GP/Mg-GP hydrogels were cytocompatible towards MG63 osteoblast-like cells. Hence, chitosan/Na-ß-GP/Mg-GP hydrogels can be used as an alternative to chitosan/Na-ß-GP hydrogels for bone regeneration applications. However the incorporation of Mg in the hydrogels during hydrogel formation did not bring any appreciable physicochemical or biological benefit.

Magnesium-enhanced enzymatically mineralized platelet-rich fibrin for bone regeneration applications.

Membranes of the autologous blood-derived biomaterial platelet-rich fibrin (PRF) were mineralized enzymatically with calcium phosphate (CaP) by the incorporation of alkaline phosphatase (ALP) followed by incubation for 3 days in solutions of either 0.1 M calcium glycerophosphate (CaGP) or a combination of CaGP and magnesium glycerophosphate (CaGP:MgGP; both 0.05 M), resulting in the formation of two different PRF-mineral composites. Fourier transform infrared spectroscopy, transmission electron microscopy and selected area electron diffraction examinations showed that the CaP formed was amorphous. Inductively coupled plasma optical emission spectroscopy analysis revealed similar amounts of Ca and P in both composite types, while a smaller amount of Mg (Ca:Mg molar ratio = 10) was detected in the composites formed in the CaGP:MgGP solution, which was supported by the results of energy-dispersive x-ray spectroscopy-based elemental mapping. Scanning electron microscopy (SEM) imaging showed that the mineral deposits in PRF incubated in the CaGP:MgGP solution were markedly smaller. The mass percentage attributable to the mineral phase was similar in both composite types. MTT and WST tests with SAOS-2 cells revealed that incubation in the CaGP:MgGP solution had no negative effect on cytocompatibility and cell proliferation compared to the CaGP solution. Cells on all samples displayed a well-spread morphology as revealed by SEM imaging. In conclusion, the incorporation of Mg reduces mineral deposit dimensions and promotes cell proliferation.

Biosupported bimetallic Pd-Au nanocatalysts for dechlorination of environmental contaminants.

Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichlorethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L(-1) and reduced simultaneously by Shewanella oneidensis in the presence of H(2), the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.