Preparation, Physical-Chemical Characterization, and Cytocompatibility of Polymeric Calcium Phosphate Cements

Aim. Physicochemical mechanical and in vitro biological properties of novel formulations of polymeric calcium phosphate cements (CPCs) were investigated. Methods. Monocalcium phosphate, calcium oxide, and synthetic hydroxyapatite were combined with either modified polyacrylic acid, light activated polyalkenoic acid, or polymethyl vinyl ether maleic acid to obtain Types I, II, and III CPCs. Setting time, compressive and diametral strength of CPCs was compared with zinc polycarboxylate cement (control). Specimens were characterized using X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. In vitro cytotoxicity of CPCs and control was assessed. Results. X-ray diffraction analysis showed hydroxyapatite, monetite, and brushite. Acid-base reaction was confirmed by the appearance of stretching peaks in IR spectra of set cements. SEM revealed rod-like crystals and platy crystals. Setting time of cements was 5–12 min. Type III showed significantly higher strength values compared to control. Type III yielded high biocompatibility. Conclusions. Type III CPCs show promise for dental applications

Structure and Thermochemistry of Perrhenate Sodalite and Mixed Guest Perrhenate/Pertechnetate Sodalite.

Treatment and immobilization of technetium-99 (99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P4̅3n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4- anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4- anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4- anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments

Radioactive Demonstration Of Mineralized Waste Forms Made From Hanford Low Activity Waste (Tank SX-105 And AN-103) By Fluidized Bed Steam Reformation

One of the immobilization technologies under consideration as a Supplemental Treatment for Hanford’s Low Activity Waste (LAW) is Fluidized Bed Steam Reforming (FBSR). The FBSR technology forms a mineral waste form at moderate processing temperatures thus retaining and atomically bonding the halides, sulfates, and technetium in the mineral phases (nepheline, sodalite, nosean, carnegieite). Additions of kaolin clay are used instead of glass formers and the minerals formed by the FBSR technology offers (1) atomic bonding of the radionuclides and constituents of concern (COC) comparable to glass, (2) short and long term durability comparable to glass, (3) disposal volumes comparable to glass, and (4) higher Na2O and SO{sub 4} waste loadings than glass. The higher FBSR Na{sub 2}O and SO{sub 4} waste loadings contribute to the low disposal volumes but also provide for more rapid processing of the LAW. Recent FBSR processing and testing of Hanford radioactive LAW (Tank SX-105 and AN-103) waste is reported and compared to previous radioactive and non-radioactive LAW processing and testing

Insights Into the Dolomitization Process and Porosity Modification in Sucrosic Dolostones, Avon Park Formation (Middle Eocene), East-Central Florida, U.S.A.

The Avon Park Formation (middle Eocene) in central Florida, U.S.A., contains shallow-water carbonates that have been replaced by dolomite to varying degrees, ranging from partially replaced limestones, to highly porous sucrosic dolostones, to, less commonly, low-porosity dense dolostones. The relationships between dolomitization and porosity and permeability were studied focusing on three 305-m-long cores taken in the City of Daytona Beach. Stable-isotope data from pure dolostones (mean {delta}18O = +3.91{per thousand} V-PDB) indicate dolomite precipitation in Eocene penesaline pore waters, which would be expected to have been at or above saturation with respect to calcite. Nuclear magnetic log-derived porosity and permeability data indicate that dolomitization did not materially change total porosity values at the bed and formation scale, but did result in a general increase in pore size and an associated substantial increase in permeability compared to limestone precursors. Dolomitization differentially affects the porosity and permeability of carbonate strata on the scale of individual crystals, beds, and formations. At the crystal scale, dolomitization occurs in a volume-for-volume manner in which the space occupied by the former porous calcium carbonate is replaced by a solid dolomite crystal with an associated reduction in porosity. Dolomite crystal precipitation was principally responsible for calcite dissolution both at the actual site of dolomite crystal growth and in the adjoining rock mass. Carbonate is passively scavenged from the formation, which results in no significant porosity change at the formation scale. Moldic pores after allochems formed mainly in beds that experienced high degrees of dolomitization, which demonstrates the intimate association of the dolomitization process with carbonate dissolution. The model of force of crystallization-controlled replacement provides a plausible explanation for key observations concerning the dolomitization process in the Avon Park Formation and elsewhere: (1) volume-for-volume replacement at a crystal scale, (2) coupled growth of dolomite crystals and dissolution of host calcium carbonate matrix, and (3) automorphic replacement by euhedral dolomite crystals. The force-of-crystallization model also does not require an influx of externally derived water that is undersaturated with respect to calcite to dissolve calcite, a fact that could simplify diagenetic models of porosity generation in dolostones. The later addition of external carbonate can result in a substantial reduction in porosity by the precipitation of dolomite cement, which could convert a high porosity sucrosic dolostone into a dense "Paleozoic type" dolostone

Metaphors and Models: The ASR Bubble in the Floridan Aquifer

Studies at the intersection of cognitive science and linguistics have revealed the crucial role that metaphors play in shaping our thoughts about phenomena we cannot see. According to the domains interaction theory of cognition, a metaphoric expression sets up mappings between a target domain that we wish to understand and a familiar source domain. The source domain contains elements (“commonplaces”) that we manipulate mentally, like parts of an analogue model, to illuminate the target domain. This paper applies the structure of domains interaction theory to analyze the dynamics of a metaphor in hydrogeology: the so-called bubble formed by water injected into an aquifer during aquifer storage and recovery (ASR). Of the four commonplaces of bubbles—(1) they are discrete; (2) they are geometrically simple; (3) they rise; and (4) they burst—we focus on the first two using both displacement and dispersion (tracer) models for both homogeneous and heterogeneous storage zones patterned from geological studies of the Suwannee Limestone of Sarasota County, Florida. The displacement model easily shows that “bottle brush” better represents the geometric complexity predicted from the known and inferred heterogeneity. There is virtually no difference, however, in the prediction of recovery efficiency using the dispersion model for a bubble (homogeneous flow zone) vs. bottle brush (heterogeneous flow zone). On the other hand, only the bottle brush reveals that unrecovered tracer is located preferentially in the low-permeability layers that lie adjacent to high-permeability channels in the flow zones

The α-defensin salt-bridge induces backbone stability to facilitate folding and confer proteolytic resistance

Salt-bridge interactions between acidic and basic amino acids contribute to the structural stability of proteins and to protein-protein interactions. A conserved salt-bridge is a canonical feature of the alpha-defensin antimicrobial peptide family, but the role of this common structural element has not been fully elucidated. We have investigated mouse Paneth cell alpha-defensin cryptdin-4 (Crp4) and peptide variants with mutations at Arg(7) or Glu(15) residue positions to disrupt the salt-bridge and assess the consequences on Crp4 structure, function, and stability. NMR analyses showed that both (R7G)-Crp4 and (E15G)-Crp4 adopt native-like structures, evidence of fold plasticity that allows peptides to reshuffle side chains and stabilize the structure in the absence of the salt-bridge. In contrast, introduction of a large hydrophobic side chain at position 15, as in (E15L)-Crp4 cannot be accommodated in the context of the Crp4 primary structure. Regardless of which side of the salt-bridge was mutated, salt-bridge variants retained bactericidal peptide activity with differential microbicidal effects against certain bacterial cell targets, confirming that the salt-bridge does not determine bactericidal activity per se. The increased structural flexibility induced by salt-bridge disruption enhanced peptide sensitivity to proteolysis. Although sensitivity to proteolysis by MMP7 was unaffected by most Arg(7) and Glu(15) substitutions, every salt-bridge variant was degraded extensively by trypsin. Moreover, the salt-bridge facilitates adoption of the characteristic alpha-defensin fold as shown by the impaired in vitro refolding of (E15D)-proCrp4, the most conservative salt-bridge disrupting replacement. In Crp4, therefore, the canonical alpha-defensin salt-bridge facilitates adoption of the characteristic alpha-defensin fold, which decreases structural flexibility and confers resistance to degradation by proteinases