[en] Amelogenin is the predominant protein found during enamel development and has been shown to be essential to proper enamel formation. LRAP is a naturally occurring splice variant that preserves the charged N- and C-termini of full length amelogenin, regions thought to be crucial in interacting with hydroxyapatite. Particularly, the highly charged C-terminal hexapeptide (KREEVD) is thought to be the region most intimately interacting with HAP. We investigated the structure of this charged region, as well as the proximity to the surface and the mobility of two of the residues. We found the structure to be consistent with a random coil or more extended structure, as has been found for more internalized residues in the C-terminus. The backbone K₅₄(¹³C(prime)), V₅₈(¹³C(prime)) and V₅₈(¹⁵N) were all found to be very close to the surface of HAP, ∼ 6.0 (angstrom), suggesting a strong interaction and emphasizing the importance of these residues in interacting with HAP. However, both ends of the hexapeptide, at residues K₅₄ and V₅₈, experience significant mobility under hydrated conditions, implying that another portion of the protein helps to stabilize the strong LRAP-HAP interaction. Interestingly, the backbone of the C-terminal third of the protein is consistently 6.0 (angstrom) from the HAP surface, suggesting that this region of the protein is laying flat on the surface with no 3-dimensional folding. The combination of these features, i.e., a random coil structure, a significant mobility and a lack of three-dimensional folding in this region of the protein may be important in a functional role, allowing the C-terminus to effectively interact with HAP while at the same time allowing maximum crystal inhibition

[en] This report summarizes advances of the above-mentioned EMSP project during the period July 1, 2001-June 30, 2002. The project focuses on the effects of organic chemicals in stored nuclear waste and their impact on pretreatment and tank closure issues. Managing the tank wastes and site cleanup activities requires understanding of the chemistry of organics in aqueous basic solutions that contain high nitrate and nitrite concentrations under the field of g and b irradiation. The goal of this EMSP project is to quantitatively characterize the important chemical processes that are induced by radiolysis of the organic complexants, and their degradation products, during the storage in tanks. Furthermore, concerns that arise from pretreatment and tank closure issues, e.g., Tc speciation, can be rationalized with the mechanistic knowledge provided here. Recognizing that experiments cannot reproduce every conceivable realistic scenario, the project emphasizes computational methodologies . None of the Hanford tanks is currently on a watch list, partially due to the predictive understanding of the tanks' chemistry that was developed by these projects and their predecessor activities. The project is closely coupled to another EMSP project (81883) and exchange of information between the two related studies is frequent

[en] This article tells in images and chunky captions the story of a study into the durability of four component glass. The information from this study is of interest to vitrification experts and geochemists.

[en] Using solution-state NMR spectroscopy, new insights into the early intermolecular interactions stabilizing amelogenin supramolecular assembly and the potential role of calcium ions have been discovered. Two-dimensional 1H-15N spectra were recorded for 15N-labeled amelogenin as a function of increasing Ca2+ concentration starting from monomeric conditions. Evidence for protein-protein interactions were observed between residues E18 and E40 in the N-terminus. At higher Ca2+ concentrations there was concurrent involvement of residues in both the N- (Y12-Q56) and the C-terminus (Q144-T171). Neither specific residues nor their stepwise interaction have previously been identified in the initial stages of nanosphere assembly

[en] The mixed ligand complex (Ni(dppp)(PPh2NBz2))(BF4)2, 3, (where P₂^PhN₂^Bz is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane and dppp is 1,3-bis(diphenylphosphino)propane) has been synthesized. Treatment of this complex with H₂ and triethylamine results in the formation of the Ni⁰ complex, Ni(dppp)(P₂^PhN₂^Bz), 4, whose structure has been determined by a single crystal X-ray diffraction study. Heterolytic cleavage of H₂ by 3 at room temperature forms (HNi(dppp)(P₂^PhN^Bz(μ-H)N^Bz))(BF₄)₂, 5a, in which one proton interacts with two nitrogen atoms of the cyclic diphosphine ligand and a hydride ligand is bound to nickel. Two intermediates are observed for this reaction using low-temperature NMR spectroscopy. One species is a dihydride, ((H)₂Ni(dppp)(P₂^PhN₂^Bz))(BF₄)₂, 5b, and the other is (Ni(dppp)(P₂^PhN₂^BzH₂))(BF₄)₂, 5c, in which both protons are bound to the N atoms in an endo geometry with respect to nickel. These two species interconvert via a rapid and reversible intramolecular proton exchange between nickel and the nitrogen atoms of the diphosphine ligand. Complex 3 is a catalyst for the electrochemical oxidation of H₂ in the presence of base, and new insights into the mechanism derived from low temperature NMR and thermodynamic studies are presented. A comparison of the rate and thermodynamics of H₂ addition for this complex to related catalysts studied previously indicates that for NiII complexes containing two diphosphine ligands, the activation of H₂ is favored by the presence of two positioned pendant bases

[en] The dissolution kinetics of five chemically complex and two chemically simple borosilicate glass compositions (Na-B-Si ± Al) were determined over a range of solution saturation values by varying the flow-through rates (1 to 100 mL d-1) in a dynamic single-pass flow-through (SPFT) apparatus. The chemically complex borosilicate glasses are representative of prospective hosts for radioactive waste disposal and are characterized by relatively high molar Si/(Si+Al) and Na/(Al+B) ratios (>0.7 and >1.0, respectively). Analysis by x-ray absorption spectroscopy (XAS) indicates that the fraction of ^ivB to ⁱⁱⁱB (N₄) varies from 0.66 to 0.70. Despite large differences in bulk chemistry, values of (delta)²⁹Si peak shift determined by MAS-NMR varies only by about 7 ppm ((delta)²⁹Si = -94 to -87 ppm), indicating small differences in polymerization state for the glasses. Forward rates of reaction measured in dynamic experiments converge (average log₁₀ rate [40 C, pH 9] = -1.87 ± 0.79 [g/(m² d)]) at high values of flow-rate (q) to sample surface area (S). Dissolution rates are independent of total Free Energy of Hydration (FEH) and this model appears to overestimate the impact of excess Na on chemical durability. For borosilicate glass compositions in which molar Na > Al + B, further addition of Na appears to stabilize the glass structure with respect to hydrolysis and dissolution. Compared to other borosilicate and aluminosilicate glasses, the glass specimens from this study dissolve at nearly the same rate (0 to ∼55x) as the more polymerized glasses, such as vitreous reedmergnerite (NaBSi3O8), albite, and silica. Dissolution of glass follows the order: boroaluminosilicate glass > vitreous reedmergnerite > vitreous albite > silica glass, which is the same order of increasingly negative ²⁹Si chemical shifts. The chemical shift of ²⁹Si is a measure of the extent of bond overlap between Si and O and correlates with the forward rate of reaction. Thus, dissolution appears to be rate-limited by rupture of the Si-O bond, which is consistent with the tenants of Transition State Theory (TST). Therefore, dissolution at far from equilibrium conditions is dependent upon the speed of the rate-controlling elementary reaction and not on the sum of the free energies of hydration of the constituents of boroaluminosilicate glass

[en] This document presents the climatological data measured at the U. S. Department of Energy's Hanford Site for calendar year 2001. Pacific Northwest National Laboratory operates the Hanford Meteorology Station and the Hanford Meteorological Monitoring Network from which these data were collected. This report contains updated historical information for temperature, precipitation, normal and extreme values of temperature and precipitation, and other miscellaneous meteorological parameters. Further, the data are adjunct to and update Hoitink (and others) (1999, 2000, 2001) and Hoitink and Burk (1994, 1995, 1996, 1997, 1998); however, data from Appendix B--Wind Climatology (Hoitink (and others) 1994) are excluded. Calendar year 2001 was slightly warmer than normal at the Hanford Meteorology Station with an average temperature of 54.3 F, 0.7 F above normal (53.6 F). The hottest temperature was 106 F on July 4, while the coldest was 16 F on December 25. For the 12-month period, 8 months were warmer than normal, and 4 months were cooler than normal. Precipitation for 2001 totaled 6.66 inches, 95% of normal (6.98 inches); calendar year snowfall totaled 15.1 inches (compared to the normal of 15.4 inches). Calendar year 2001 had an average wind speed of 7.6 mph, which was normal (7.6 mph). There were 31 days with peak gusts (ge)40 mph, compared to a yearly average of 27 days. The peak gust during the year was 69 mph on December 16. November 2001 established new records for both days and hours with dense fog (visibility (le)1/4 mile). There were 14 days and 99.4 hours of dense fog reported, compared to an average of 5.5 days with 22.0 hours. The previous record was 13 days in 1965 and 71.4 hours in 1952. The heating-degree days for 2000-2001 were 5,516 (7% above the 5,160 normal). Cooling-degree days for 2001 were 1,092 (8% above the 1,014 normal)

[en] The synthesis of carbamoylphosphonate silanes (CMPO analogs) designed for sequestering actinide cations in self-assembled monolayers on mesoporous supports (SAMMS) is described

[en] This data package documents the experimentally derived input data on the representative waste glasses; LAWA44, LAWB45, and LAWC22. This data will be used for Subsurface Transport Over Reactive Multi-phases (STORM) simulations of the Integrated Disposal Facility (IDF) for immobilized low-activity waste (ILAW). The STORM code will be used to provide the near-field radionuclide release source term for a performance assessment to be issued in July 2005. Documented in this data package are data related to (1) kinetic rate law parameters for glass dissolution, (2) alkali (Na+)-hydrogen (H+) ion exchange rate, (3) chemical reaction network of secondary phases that form in accelerated weathering tests, and (4) thermodynamic equilibrium constants assigned to these secondary phases. The kinetic rate law and Na+-H+ ion exchange rate were determined from single-pass flow-through experiments. Pressurized unsaturated flow (PUF) and product consistency (PCT) tests where used for accelerated weathering or aging of the glasses in order to determine a chemical reaction network of secondary phases that form. The majority of the thermodynamic data used in this data package were extracted from the thermodynamic database package shipped with the geochemical code EQ3/6, version 8.0. Because of the expected importance of 129I release from secondary waste streams being sent to IDF from various thermal treatment processes, parameter estimates for diffusional release and solubility-controlled release from cementitious waste forms were estimated from the available literature

[en] Single-pass flow-through tests were conducted to determine the pH (7-12) and temperature (23-90 deg. C) dependence of kinetic rate law parameters; k_o, η, and E_a, for the dissolution of glass in aqueous solution. Experiments were performed with three prototypic nuclear waste glasses that span a wide compositional range, which covers, with high probability, the expected processing composition range for candidate immobilized low-activity waste (ILAW) glasses. Comparison of the B to Na release rates for one glass was incongruent at 23 and 40 deg. C, and pH (23 deg. C) = 7.0 and 8.0, suggesting two distinct mechanisms are responsible for the Na⁺ release, namely Na⁺-H⁺ ion-exchange and matrix dissolution. Matrix dissolution became the dominant dissolution mechanism for all glasses at the forward rate and pH values greater than 9.0 as evident by the congruent release of Al, B, Na and Si to solution. By combining the results collected for each ILAW glass at pH values greater than 9.0, pH and temperature-dependent rate law parameters were determined for Al, B, Na and Si release. A comparison of the pH power-law coefficient for Al, B, Na and Si at each temperature suggest that η does not depend on temperature within experimental error and suggests the release of these elements into solution is controlled by the same dissolution mechanism at the forward rate of reaction. The activation energies (E_a), based on B release, range from 52 ± 4 to 56 ± 6 kJ/mol which suggest that dissolution is a surface-controlled reaction mechanism. The data presented in this manuscript suggest that for these three ILAW glasses the chemical durability for each glass is similar under these test conditions. A lack of compositional dependence on the forward dissolution rate is observed even though there is as much as a 39 kJ/mol difference in the free energy of hydration (ΔG_hyd) among the borosilicate waste glasses tested. This similarity in the forward dissolution rate despite the large ΔG_hyd difference is almost certainly because these glasses have similar, if not identical, polymerization states. This is evident from the almost identical ²⁹Si chemical shifts for each of these glasses. The polymerization state is an indication of the number of framework SiO₄ linkages contained in the glass network. In general, the greater the number of framework SiO₄ linkages the more durable the glass. Finally, in agreement with previous work, these results suggest breakage of the Si-O bond is the rate-determining dissolution mechanism under alkaline conditions [pH (23 deg. C) > 9.0] far from saturation with respect to an alteration phase or phases