Cd, Hg, and Pb Compounds of Benzene-1,3-diamidoethanethiol (BDETH(2)).

Benzene-1,3-diamidoethanethiol (BDETH2) is an exceptional precipitant for removing soft heavy metals from water. The present work will detail the bonding arrangement of BDETH2 to the metals Cd, Hg, and Pb, along with the full characterization data of the BDET-M compounds. It was found that the Hg compound has a linear S-M-S geometry. The characterization data consisted of Mp, EA, IR, Raman, MS, XANES, EXAFS, and solid-state multinuclear NMR.

Reactivity and derivatization of five-coordinate, chelated aluminum.

The convenient five-coordinate starting materials, Salen((t)Bu)AlCl (Salen((t)Bu) = N,N'-alkylene (or arylene) bis (3,5-di-tert-butyl-2-hydroxybenzylideneamine) (1-4) can be used in a wide range of reactions to form five-coordinate aluminum compounds. Herein, these reagents were used to produce new five-coordinate azides, LAlN(3) (L = Salen((t)Bu) (5), Salpen((t)Bu) (6), and Salomphen((t)Bu) (7)) through trimethylsilylhalide elimination. The decomposition of the azides produce first hydroxide (LAlOH (L = Salen((t)Bu) (8)) and, subsequently in the presence of chlorotrimethylsilane, the siloxide compounds, LAlOSiMe(3) (L = Salen((t)Bu) (9), Salpen((t)Bu) (10), and Salomphen((t)Bu) (11)). Alkane elimination reactions may also be used to access this type of compound as evidenced by the formation of Salomphen((t)Bu)AlOSiPh(3) (12). Additionally, the first structurally characterized five-coordinate monomeric amide, Salcen((t)Bu)AlN(SiMe(3))(2) (13), can prepared by a salt elimination utilizing Salcen((t)Bu)AlCl (4). The compounds were characterized by spectroscopic methods ((1)H and (27)Al NMR, MS, and IR) and, in the case of 2 (Salpen((t)Bu)AlCl), 3 (Salomphen((t)Bu)AlCl) 9, 11, 12, and 13, by X-ray analysis. Several of the compounds were explored as potential catalysts for the living polymerization of propylene oxide.

Group 13 compounds incorporating Salen ligands.

In a previous review it was predicted that "the reactivity of five-coordinate complexes would certainly be different than that of the four-coordinate derivatives". Structurally and spectroscopically, there is very little difference in the higher-coordinate compounds when compared to the four-coordinate derivatives. However, the prediction was remarkably accurate, if not a bit understated, for the reactivity of these compounds. There appears to be a tremendous potential in catalysis and synthesis for the five-coordinate derivatives, far more possibilities than exist for the lower-coordinate derivatives. Furthermore, the higher-coordinate derivatives are rarely air or moisture sensitive and, thus, may be handled under a wider range of conditions. Although reactions such as oxirane and lactide polymerizations are fairly well-known now with five- and six-coordinate aluminum compounds, the potential of these compounds has only begun to be developed. It is easy to imagine that these types of compounds will see wider use than the related transition-metal compounds.

Aqueous leaching properties and environmental implications of cadmium, lead and zinc trimercaptotriazine (TMT) compounds.

2,4,6-Trimercaptotriazine, trisodium salt nonahydrate (TMT-55) is a commercial product that is widely used to chemically precipitate cadmium, lead, zinc and other heavy metals from wastewaters and contaminated natural waters. When mixed with aqueous solutions of TMT-55, aqueous solutions of either reagent-grade zinc, cadmium, or lead salts precipitate crystalline "Zn-TMT", amorphous or crystalline "Cd-TMT" or amorphous "Pb-TMT" (M3[S3C3N3]2.nH2O, where M=Cd2+, Pb2+, and Zn2+ and n> or = 0) that may eventually crystallize if stored in air. Laboratory aqueous leaching studies over 78-106 days using pH 3 HCl, distilled water (pH 6) and pH 9-10 NaOH evaluated the stability of the Cd-, Pb-, and Zn-TMT precipitates. Under pH 3 conditions, the amorphous Cd- and Pb-TMT compounds converted to their crystalline forms and amorphous Cd-TMT also crystallized in distilled water. Otherwise, no decomposition products were detected in the leached solid residues. When compared with the aqueous solubilities of corresponding sulfides and most hydroxides, the TMT compounds were significantly more soluble in distilled water and pH 3 HCl.

Chemistry of 2,4,6-trimercapto-1,3,5-triazine (TMT): acid dissociation constants and group 2 complexes.

The acid dissociation constants of 2,4,6-trimercaptotriazine (H(3)TMT, 1) were determined and now can be employed in the preparation of complexes having specific M-TMT (M = divalent metal; TMT = 2,4,6-trimercapto-1,3,5-triazinide, C(3)N(3)S(3)(3-)) ratios. For example, the combination of H(3)TMT (1) with Mg(OH)(2) at pH 7.1 leads to the crystallization of Mg(H(2)TMT)(2).6H(2)O (4). With the appropriate pH adjustment, the contiguous series of compounds Ba(3)(TMT)(2).8H(2)O (3), Ba(H(2)TMT)(2).7H(2)O (5), and BaHTMT.3H(2)O (6) can be isolated. The compounds were characterized by mp, IR, TGA, elemental analysis, and, in the cases of 4, 5, and 6, crystallography. The comparison of 4 with 5 and 6 offers an interesting view of the difference in hard and soft bonding with TMT. In the saltlike Mg structure of 4, there is extensive hydrogen bonding, but in the Ba structures, 5 and 6, covalent Ba-S bonding dominates.

Irreversible precipitation of mercury and lead.

There are immediate concerns with current commercial reagents that are used for heavy metal precipitation; in particular the fact that the reagents are not specifically designed to bind the targeted metals. The current literature reveals that not only do commercial reagents lack sufficient ability to strongly bind the metals, but they also fail to provide long-term stability as ligand-metal complexes under a variety of moderate conditions. For this reason a new ligand was designed and synthesized: 1,3-benzenediamidoethanethiol (BDETH2). It offers multiple, concerted, bonding sites for heavy metals and forms a stable metal-ligand precipitate. In this study, the formation of compounds comprised of this ligand with the divalent metals, lead and mercury, was explored and the pH stability of the water insoluble precipitates was determined. The leaching properties of the metal-ligand precipitates were determined using inductively coupled plasma (ICP) spectroscopy and cold vapor atomic fluorescence spectroscopy (CVAF). The results indicate that a 50.00 ppm lead solution at a pH of 4.0 may be reduced to a concentration of 0.05 ppm (99.9% lead removal) and to 0.13 ppm (99.7% lead removal) at a pH 6.0. A 50.00 ppm mercury solution at pH 4.0 may be reduced to a concentration of 0.02 ppm (99.97% mercury removal) and to 0.02 ppm (99.97% mercury removal) at a pH of 6.0.

A pyridine-thiol ligand with multiple bonding sites for heavy metal precipitation.

There are immediate concerns with current commercial ligands that are used for heavy metal precipitation, especially the limited arrays of bonding sites. Previous research has indicated that not only do commercial reagents lack sufficient bonding criteria, but they also fail to provide long-term stability as ligand-metal complexes. For this reason, we have developed a pyridine-based thiol ligand (DTPY) which not only offers multiple bonding sites for heavy metals but also should form stable metal-ligand precipitates. In this study, we used the divalent metals cadmium and copper to model the reactivity and pH stability of divalent metal complexes with the DTPY ligand. Using inductively-coupled plasma spectrometry (ICP), results indicate that a 50.00ppm (parts per million) copper solution, pH of 4.5, can be reduced to below the ICP detection limits of 0.00093ppm (>99.99% removal), and a 50.00ppm cadmium solution, pH of 6.0, can be reduced to 0.06ppm (99.88%).

Monomeric uni-ligated aluminates.

The tetradentate ligand, common name Salban(But)H4 (N,N'-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1,4-diaminobutane) combines with appropriate amounts of LiAlH4 to produce the unique monomeric, uni-ligated aluminate [Salban(But)Al]Li(thf)2 (1) and the bimetallic derivative Salban(But)(AlH2Li(thf)2)2 (2).

Animal model for evaluating the effect of systemic estrogen deficiency on residual ridge resorption.

The rate of resorption of residual ridges after tooth extraction varies among subjects. Despite many human studies, the etiologic factors of severe forms of resorption of residual ridges are unknown and probably multifactorial. To facilitate investigations of resorption of residual ridges, it is preferable to use an animal model with a dentoalveolar component similar to that of human beings. This study developed a rapid, nonhuman primate model in which one could measure resorption of residual ridges at the most critical period, with the least amount of time, minimal operation, and the least interference with normal nutrition. Three female Macaca fascicularis monkeys, 7 to 9 years old, were selected for simple extraction of four maxillary incisors, four mandibular incisors, and two mandibular canines. Lateral cephalographs were taken at weeks 0, 1, 2 to 3, 5 to 6, 8 to 9, 11 to 12, and 26 to 28 after extraction with a newly constructed cephalostat that allowed easy reproducibility of animal placement in the prone position. Height and area measurements were made of maxillary and mandibular anterior residual ridges in the superimposed cephalographs. Sequential mean bone loss data produced bone loss curves similar to those observed in humans. One animal underwent ovariectomy. The plasma levels of both estrogen and progesterone decreased over 25 days and stayed below the detection limits thereafter. Tooth extraction was done 4 weeks after the ovariectomy and the bone resorption pattern was able to be observed longitudinally with the newly established monkey cephalostat. The results indicated that Macaca fascicularis need not be sacrificed when used in longitudinal studies of resorption of residual ridges in a relatively short period of experimental time. This model can provide an excellent opportunity to investigate a causal relationship between the rate of resorption of residual ridges and predisposing systemic factors such as estrogen deficiency.

The knife-edge tendency in mandibular residual ridges in women.

To investigate the bone resorption pattern of the residual alveolar bone, the morphologic change that occurred in mandibles was analyzed with standardized lateral cephalographs of 30 edentulous patients (15 women and 15 men). The longitudinal morphologic changes were measured at the sagittal sections of the mandibular bony contour at the symphysis area on superimposed cephalographic tracings. To quantify the morphologic change, a knife-edge index (KEI) was developed as the area change divided by the height change. Geometrically, the higher value of KEI represents the greater tendency to become a narrow residual ridge. The KEI values were statistically higher in the women than in the men (p less than 0.002). In addition, the value of KEI seems to correlate with osteopenic change at the center point of the body of the second vertebra (p less than 0.01). The continuous bone resorption activity in the edentulous mandible of women seems to be emphasized at the labial and lingual surfaces of the residual alveolar bone, resulting in a knife-edge type of residual ridge.

A local pathophysiologic mechanism of the resorption of residual ridges: prostaglandin as a mediator of bone resorption.

The role of PG as a bone resorption mediator in RRR was investigated in the rat model and the following may be concluded from the data. 1. PG is suggested to be a mediator of the RRR. 2. The continuous and localized bone resorption in RRR may be caused by continuous synthesis of local PG. 3. PG producing cells and specific stimuli responsible for RRR are still unknown.

Need and effective demand for prosthodontic treatment.

The unmet and met need for prosthodontic services in the United States have been estimated and projected to the year 2000. Based on need-for-treatment estimates within the U.S. population collected by oral examination in 1971 to 1974, some 214.7 million hours of unmet need were estimated. By the year 2000, the projected need is expected to increase to approximately 264.7 million hours (if edentulism is assumed to be zero) or to approximately 293.8 million hours (if prevalence of prosthodontic need is assumed to remain stable). A concomitant rise in effective demand is also expected from 44.7 million hours in 1976 to 1977 to approximately 62.2 million hours in the year 2000. Thus, despite an assumption of declining edentulism, the unmet need for prosthodontic services will remain high.

Resorption of residual ridges (RRR) in rats.

The post-extraction resorption of residual ridges (RRR) is a major and largely unsolved health problem, probably of multifactorial etiology. In order for one to study the role of specific factors in the pathophysiology of RRR, the use of animal models is desirable. The purpose of this study was to establish a reliable animal model and a standardized assay system to measure RRR for future experiments. A new oblique cephalometric device was designed to take pairs of xeroradiographs on the right and left sides of the rat skull and mandible at a 45-degree angle to the horizontal plane. Preliminary studies confirmed the reproducibility of the technique. All molars were extracted with minimal trauma from the right maxilla and mandible in five male Sprague-Dawley rats (40 days old). Longitudinal cephalographic examinations were performed before and immediately after extraction and at two, four, eight, and 12 weeks after extraction. Alveolar bone resorption was measured on enlarged cephalographs (5.7 X) at a point mesial to the mandibular first molar. Sequential mean bone resorption was 0.8 +/- 0.2 mm (S.D.), 1.0 +/- 0.3, 1.3 +/- 0.3, and 1.5 +/- 0.4, respectively. Graphically, these findings produced bone loss curves similar to those observed in man. These results indicate that the rat model may be utilized in longitudinal studies of the resorption of the residual ridge.