Can the regenerative potential of an alkali-free bioactive glass composition be enhanced when mixed with resorbable β-TCP?

The addition of resorbable β-tricalcium phosphate (β-TCP) to other bone substitute materials such as hydroxyapatite (HA) has been pointed out as a suitable strategy to enhance the regenerative potential of bone grafts made thereof. To check the generalization of this hypothesis, a new synthetic composite bone graft material consisting of a mixture of 30 vol% of pure β-TCP and 70 vol% of FastOs^®BG (an alkali-free bioactive glass - BG) was prepared and tested in vivo. The in vivo performance of the new synthetic bone graft (30β-TCP-70FastOs^®BG) was compared with those of FastOs^®BG alone and of adbone^®BCP, a biphasic calcium phosphate, consisting of 75% of HA and 25% of β-TCP. Two defects with 4 mm diameter were performed in Wistar rats calvaria and filled with the bone graft materials. The animals were sacrificed after 9 weeks of implantation and the calvaria was excised. Empty bone defects were used as negative control. The percentages of new bone formed (von Kossa staining) were always higher in the treated groups (FastOs^®BG, 30β-TCP-70FastOs^®BG and adbone^®BCP) than in empty group. There were differences with statistical significance between empty and FastOs^®BG groups and between empty and adbone^®BCP groups. But the differences observed between empty and 30β-TCP-70FastOs^®BG groups were less remarkable. The results demonstrated the superior bone regeneration ability of FastOs^®BG alone, which was not further enhanced by adding β-TCP in the composition, confirming its already proven regenerative potential.     

The effect of cupric ion on the radiation grafting of N-vinyl-2-pyrrolidone and other hydrophilic monomers onto silicone rubber

Radiation grafting systems containing cupric ion, N-vinyl-2-pyrrolidone (N-VP) and other hydrophilic monomers were studied. Such systems, in certain Cu⁺⁺ion concentration ranges were found capable of producing extremely high levels of graft on silicone rubber and other polymers. Gellation of the homopolymer surrounding the grafted film was inhibited by the presence of cupric salts. An increase in the graft water content and decrease in the wettability of the grafted film surface was noted as the Cu⁺⁺ ion concentration in the grafting solution was increased. Based upon attenuated total reflectance infrared spectroscopic examination of the grafted materials, these effects could be explained by variations in the copolymer composition of the graft and increased penetration of the graft into the silicone rubber with increasing cupric ion concentration. The Cu⁺⁺/N-VP system allows many monomers which would ordinarily graft only with great difficulty to be readily grafted to polymeric surfaces. It also allows control over a number of graft parameters such as graft water content composition and penetration. Therefore, this system should be ideal for preparing a series of radiation grafted hydrogels to be used to evaluate important variables in the interactions of hydrophilic biomaterials and biological systems.     

Grafting vinyl monomers onto silk fibers. VIII. Graft copolymerization of methyl methacrylate onto silk using tetravalent manganese–oxalic acid redox system

The graft copolymerization of methyl methacrylate onto silk fibers was investigated in aqueous solution using the Mn(IV)–oxalic acid redox system. The copolymerization reaction was carried out under a variety of conditions such as different monomer, initiator, oxalic acid, acid concentrations, and temperatures. The graft yield increases with increasing initiator concentration up to 5 × 10^?2M, and with further increase of the initiator concentration it decreases. The graft yield also increases with increasing sulfuric acid concentration up to 15 × 10^?2M, and decreases thereafter. The rate of grafting also increases with increase in oxalic acid concentration up to 1.5 × 10^?2M and 84.592 × 10^?2M, respectively, and thereafter the rate of grafting shows down. The effect of temperature, solvents, and salts on graft yield has also been investigated and a plausible rate expression has been derived.     

Preliminary studies on the aromaticity of Australian coals: Solid state n.m.r. techniques

The aromaticities of samples from nine Australian coal seams, including pairs of hand-picked vitrains and durains, have been determined by ¹³C cross-polarization n.m.r. spectroscopy with magic angle sample spinning. The results clearly show that the aromaticity (f_a) of the coals increases with increase in vitrinite reflectance and carbon content and decrease in atomic H/C ratio. For a given coal seam, durain (inertinite-rich coal) has a higher f_a value than vitrain (vitrinite-tich coal). The trends for carbon content and atomic H/C are in good agreement with results from North American coals, although the aromaticities of Australian coals obtained in this study appear to be slightly lower than some of those reported for North American coals of similar carbon content.     

Characterization of vitrinite concentrates. 2. Magic-angle 13C nuclear magnetic resonance studies

The fraction aromaticity determined by ¹³C n.m.r. with cross-polarization and magic-angle spinning of 19 vitrinite concentrates obtained from the Lower Kittaning seam shows a range of values from ≈ 0.65 for the samples of lowest rank (83 wt% C (dmmf) to about 0.83 for those of highest rank (91 wt%C (dmmf)). It was determined that the wt% aromatic carbon correlates to the wt% fixed carbon and is in good agreement with the results reported by other authors. The combination of the ¹³C n.m.r. results with FTIR measurements allows a number of coal parameters to be estimated. The atomic ratios of aliphatic hydrogen to carbon were demonstrated to vary from 1.8–2.0 to between 2.4–2.6 and previous assumptions that a single value can be used in calculating structural parameters for coal of any rank are not strictly valid. The calculation of the aromatic $\text{H}\text{C}$ ratio indicates that in mean structural units there is approximately one aromatic hydrogen atom for every six carbons in vitrinites of carbon content 83 wt%C (dmmf) and that this ratio changes progressively with rank to a value of about one aromatic hydrogen for every four carbons for vitrinites of carbon content 91 wt%C (dmmf).     

Modified chitosan. I. Optimized cerium ammonium nitrate‐induced synthesis of chitosan‐graft‐polyacrylonitrile

Chitin was extracted from shrimp shells and then deacetylated to obtain chitosan. The degree of deacetylation of the chitosan was determined to be 0.76 using pH‐metric titration. A large number of cyanide functional groups were introduced onto chitosan by grafting with polyacrylonitrile as an efficient way of modification. The graft copolymerization reactions were carried out under argon atmosphere in a homogeneous aqueous phase (containing a small portion of acetic acid) by using ceric ammonium nitrate as an initiator. Evidence of grafting was obtained by comparing FTIR spectra of chitosan and the graft copolymer as well as solubility characteristics of the products. The synthetic conditions were systematically optimized through studying the influential factors, including temperature and concentrations of the initiator, acrylonitrile monomer (AN), acetic acid, and chitosan. The effect of individual factors was investigated by calculating and monitoring the variations of the grafting parameters [i.e., grafting ratio (Gr), grafting efficiency (Ge), add‐on value (Ad), homopolymer content (Hp), and total conversion (Ct)]. Under optimum conditions, the grafting parameters were achieved as 535, 98, 81, 2, and 102%, respectively. A mechanism for the free‐radical grafting was proposed. As empirical rates of polymerization and graft copolymerization were plotted against [AN] and [Ce⁴⁺]^1/2, the experimental kinetic data displayed a good match to a reported rate statement. The overall activation energy for the graft copolymerization was determined to be 44.9 kJ/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2048–2054, 2003     

Influence of magnesium and aluminium ions on the copper a.c. deposition into aluminium anodic oxide film nanotubes

The influence of Mg²⁺ and Al³⁺ ions on a.c. deposition of copper nanowires into aluminium anodic oxide film (AOF) nanotubes has been studied using cyclic voltammetry and d.c. plasma emission spectrometry. From the analysis of copper quantities deposited into the Al AOF nanotubes (m _Cu), 0.02 M MgSO₄ concentration was found to be optimal for Cu(II) solutions. Moreover, it was shown that Mg²⁺ and Al³⁺ ions not only prevent the breakdown of the barrier layer of AOF, but change the rate of copper deposition and modify the shape of the m _Cu against pH plots depending on the a.c. voltage applied. From the analysis of the quantities of magnesium (m _Mg) incorporated into the Al AOF nanotubes, presumably in the form of Mg(OH)₂, the m _Mg against pH dependences were determined in MgSO₄ and MgSO₄ + CuSO₄ solutions. An increase in m _Mg from 30 g dm^–2 to 1 mg dm^–2 at pH 1.5 and from 6 g dm^–2 to 16 g dm^–2 at pH 7.0 was found under the same a.c. treatment conditions from MgSO₄ solutions without and with Cu²⁺ ions, respectively, indicating the incorporation of Mg(OH)₂ into the Al AOF nanotubes to be lower up to about one hundred times in the case of Cu deposition. Based on the experimental results, it was suggested that incorporation of the Mg(OH)₂ particles into the Al AOF nanotubes occurred simultaneously with growing copper nanowires under a.c. bias is insignificant, if the pH of the CuSO₄ + MgSO₄ solution is 2.5.     

Analysis of epoxidized natural rubber. A comparative study of d.s.c., n.m.r., elemental analysis and direct titration methods

A comparative analysis of epoxidized natural rubber samples by ¹H and ¹³C n.m.r., titrimetric, elemental and d.s.c. techniques has been made. Whereas the titrimetric method is only applicable at low epoxy contents (< 15 mol%) both n.m.r. methods give reasonable precision over the compositional range of 20–75 mol%. Elemental analysis appears less reliable. D.s.c. analysis through measurement of T_g provides the highest precision of measurement but requires independent calibration by one or more of the primary methods. The epoxy content may also be related to the polymer density.     

Studies on graft copolymerization of methyl methacrylate onto chemically modified tussa silk fibers. Peroxydisulfate-thiourea redox system

The graft copolymerization of methyl methacrylate (MMA) onto chemically modified tussa silk fibers in aqueous media using potassium peroxodisulfate-thiourea redox initiator system was studied at 60°C. The effects of time of reaction, concentrations of oxidant, thiourea (TU), monomer (M), amount of silk fibers on graft yield have been studied. The effects of reaction medium, acid concentration, and some inorganic salts and organic solvents on grafting have also been investigated. A significant increase in percent of grafting was observed with increasing monomer concentration to 65.86 · 10^?2 mol · 1^?1; a further increase of monomer concentration is associated with the decrease of graft yield. The graft yield increases with an increase of thiourea concentration up to 10 · 10^?1 mol · 1^?1, beyond which it decreases very significantly. A measurable increase of the graft yield was also observed with an increase of the oxidant concentration up to 0.08 mol · 1^?1 beyond which the graft yield decreased. The graft yield was medium dependent. The reaction mechanism of the grafting process has been proposed and a rate expression has been derived on the basis of experimental findings. IR spectra of the grafted fiber and original fiber have been taken and their characteristic bands have been identified. The thermal behaviour of the original and grafted silk fibers has been studied by TGA and DTG analysis. Grafting has improved thermal stability as well as the light fastness of silk dyed with Rhodamine B.     

Synthesis of graft copolymers of polycaprolactam fibre by preliminary introduction of hydroperoxide groups

Conclusions 1. We have obtained graft copolymers of polycaprolactam fibre with various vinyl monomers by introducing peroxide and hydroperoxide groups into the fibre by oxidation with an Fe³⁺-H₂O₂ system.2. We have studied the effect of the oxidation and graft copolymerisation conditions on the yield of graft copolymer. The feasbility of obtaining modified polycaprolactam fibre with practically any content of graft polymer has been demonstrated.All-Union Correspondence Institute for the Textile and Light Industry (VZITLP); Moscow Textile Institute. Translated from Khimicheskie Volokna, No. 6, pp. 15–17, November–December, 1969.     

Synthesis of amphiphilic poly(phthalazinone ether sulfone ketone)‐graft‐poly(ethylene glycol) graft copolymers via Williamson etherification

Amphiphilic graft copolymers consisting of poly(phthalazinone ether sulfone ketone) (PPESK) backbones and poly(ethylene glycol) (PEG) side chains were synthesized via reaction of chloromethylated PPESK (CMPPESK) with a sodium alkoxide of methoxyl PEG (PEG‐ ONa). The reactive precursor, CMPPESK, was prepared by the chloromethylation of PPESK with chloromethylether (CME) using concentrated H₂SO₄ as reaction medium. FTIR spectroscopy, ¹H‐NMR and Solid‐state ¹³C CP‐MAS NMR analysis confirmed the covalent linking of PEG with PPESK backbones. The PEG content in the graft copolymers from ¹H‐NMR analysis varied from 21.0 to 37.2 wt %, which was approximately in agreement with that calculated from TGA tests. The graft products have good solubility in many aprotic polar solvents and can be slightly swelled by water and ethanol, but water insoluble. Contact angle measurements revealed that the hydrophilicity of PPESK was significantly improved by the introduction of PEG graft chains, indicating the graft copolymer is a potential hydrophilic additive for PPESK membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Quantitative solid-state C n.m.r. measurements on cokes, chars and coal tar pitch fractions

Bloch decay or single pulse excitation (SPE) ¹³C n.m.r., generally recognized as the best approach to obtain quantitatively reliable aromaticity values and other skeletal parameters for coals, was applied to partly carbonized coal samples, a biomass char and the toluene-insolubles from a coal tar and a corresponding pitch. As found previously for coals, the aromaticities and non-protonated carbon concentrations were generally higher than those estimated by cross-polarization (CP). Furthermore, in terms of accumulation times, the shorter ¹³C T₁'s of low-temperature chars makes SPE a more efficient technique than for coals. The higher concentrations of paramagnetic centres responsible for the shorter ¹³C T₁'s still result in observability of 75% of the carbon in the chars by the SPE technique. The ratios derived from the SPE measurements agree well with those obtained from elemental analysis.     

Grafting vinyl monomers onto wool fibers. VIII. Graft copolymerization of methyl methacrylate onto wool using peroxydiphosphate–fructose redox system

The graft copolymerization of methyl methacrylate onto wool fibers was investigated in aqueous solution using the peroxydiphosphate–fructose redox system. The rate of grafting was determined by varying monomer, acidity of the medium, temperature, nature of wool, and reaction medium. The graft yield increases with increase in peroxydiphosphate concentration. With increase in concentration of fructose up to 7.5 × 10^?4 mole/l., there is a significant increase in graft yield; and with further increase in concentration of fructose the graft yield decreases. The graft yield increases with increase in monomer concentration up to 65.72 × 10^?2 mole/l. and decreases thereafter. The grafting is considerably influenced by chemical modification prior to grafting. The effect of acid, temperature, and solvent on the rate of grafting has been investigated and a suitable rate expression has been derived.     

Glycidyl methacrylate grafted natural rubber: Synthesis,characterization, and mechanical property

Glycidyl methacrylate (GMA) was grafted onto natural rubber (NR) using emulsion polymerization method. The structures of copolymers were characterized by ¹H nuclear magnetic resonance (¹H‐NMR), solid state ¹³C‐NMR spectroscopy, and Fourier transform infrared spectrometer (FTIR). The %grafting obtained from the gravimetric method and the absorbance ratio were compared. Effects of reaction temperature, GMA content, and reaction time on %grafting, grafting efficiency, and %conversion of GMA monomer were determined. Effect of %grafting on mechanical properties of the graft copolymer was studied. Experimental result showed that the appropriate reaction time was 8 h at a reaction temperature of 30°C. Moreover, tensile strength and modulus of the graft copolymer increased with increasing %grafting. However, elongation at break of the graft copolymer decreased with increasing %grafting. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 3152–3159, 2011     

Grafting vinyl monomers onto polyester fibers. VI. Graft copolymerization of methyl methacrylate onto PET fibers using tetravalent cerium as initiator

The graft copolymerization of methyl methacrylate onto polyester fibers (PET) was investigated using tetravalent cerium as the initiator. The rate of grafting was found to increase progressively with the initiator and monomer concentrations up to 2.5 × 10^?2M and 70.41 × 10^?2M, respectively. The reaction was found to be catalysed by acid up to 15.0 × 10^?2M. The graft yield increased by increasing temperature. The effect of addition of some solvents and thiourea on the rate of grafting was also investigated. A suitable kinetic scheme has been pictured, and rate equations have been derived.     

Structural characterization of Saudi Arabian heavy crude oil by n.m.r. spectroscopy

Saudi Arabian heavy crude oil was separated into six fractions, including five distillate fractions (<93, 93–204, 204–260, 260–343 and 343–454 °C) and a >454 °C distillation residue. Each fraction was analysed by ¹H and ¹³C n.m.r. spectroscopy, and combined gained information from these analyses provided reliable average structural parameters. These included estimation of aliphatic and aromatic content, average paraffinic chain length, and estimation of hydrogen, methyl and alkyl bearing aromatic carbons for each of the six fractions. The extent of branching in paraffinic chains and amount of aromatic bridgehead carbons were also calculated.     

PAN-Grafted guaran. II. Short-chain grafting

The room-temperature grafting of polyacrylonitrile (PAN) onto guaran (guar gum) in 2.5 × 10^?3 M aqueous sols or aqueous-methanolic suspensions, initiated by (NH₄)₄ Ce(NO₃)₆ in 1M HNO₃, leads to PAN-branched polysaccharides with graft contents of 11 – 53%. Main chain degradation by treatment with boiling aqueous HCl results in detachment of the PAN side chains, for which number-average molecular masses of ca. 15000 – 48000 are determined viscometrically with the aid of the known Mark-Houwink relationship (K = 3.92 × 10^?4, a = 0.75). Grafting frequencies are in the range of 0.004 – 0.012, equivalent to an average of 80 – 250 non-grafted repeat units for every singly grafted unit in the guaran main chain. The graft copolymers are of interest as precursors of carboxyl-functionalized, water-soluble polysaccharides to serve as polymeric micronutrient and drug carriers of future studies.     

Preparation and Characterization of Graft Copolymer EVA-g-PU

Via melting graft reaction, a new type of graft copolymer EVA-g-PU was synthesized. The characterization of Fourier transform infrared and ¹³C -nuclear magnetic resonance indicated that the polyether-polyurethane prepolymer was grafted on the EVA main chain successfully. Differential scanning calorimetry testing showed that the melting temperature increased with the increase of PU prepolymer content. The enhanced storage modulus of EVA-g-PU was characterized by dynamic mechanical thermal analysis. The enhanced degree in the storage modulus of EVA-g-PU increased with the increase of PU prepolymer content. Thermal gravimetric analysis testing showed that thermal stabilities of EVA-g-PU increased with the increase of PU prepolymer content.     

Starch‐graft copolymers of N‐vinylformamide and acrylamide modified with montmorillonite manufactured by reactive extrusion

Graft copolymers of potato starch with acrylamide, acrylamide, and acrylic acid or N‐vinylformamide in the presence of 1–16 wt % montmorillonite were manufactured via reactive extrusion. XRD and TEM measurements exhibited intercalated structure of clay dispersion (d001 distance up to 2.3 nm). The influence of graft polymer(s) system and montmorillonite content on thermal properties, water sorption as well as polyvalent metal cation (Cd²⁺ and Fe³⁺) sorption of obtained starch graft copolymers has been determined. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of 4-vinyl pyridine-grafted SBS triblock copolymer

Study on the graft of 4-vinyl pyridine to styrene-butadiene-styrene triblock copolymer by solution polymerization shows that the catalyst concentration, temperature, and reaction time are the major influencing factors. Graft efficiency increases with temperature and time but levels off when temperature is higher than 65°C. Increasing concentration of catalyst also promotes graft, but when it is higher than 1.0 × 10^?2 M, the reaction system begins to gel. A cast film of the graft copolymer was dried, cross-linked with S₂Cl₂ in nitromethane solution, sulfonated, and chloromethylated. The water content of the membrane is 13.5%. Its anionic and cationic exchange capacities are 0.066 mEq per dry gram and 0.273 mEq per dry gram, respectively. The anionic-cationic capacity ratio is thus 0.26. The nitrogen content of the graft copolymers was determined with a CHN elemental analyzer, and qualitative analysis was carried out with infrared spectroscopy. Transmitting electronic microscopy was used to study the morphology and feasibility of preparing a charged mosaic membrane for piezodialysis.