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D Scott Smith

Publications and source records attributed to D Scott Smith.

10 recordsLinked to original sources
PubMed2004

Determination of strong ligand sites in sewage effluent-impacted waters by competitive ligand titration with silver.

A competitive ligand titration, employing Ag+, is used to determine the binding capacity of the small amounts of strong ligands (SL) in natural water samples. Strong ligands are defined here as high-affinity binding sites for group 11 and 12 metals such as Cu(I), Hg(II), and Ag(I). In addition, the conditional binding strength (log K') is determined for Ag- and SL. Diethyldithiocarbamate (DEDC) is the competitive ligand employed. The system is set at constant pH (8.1), ionic strength (0.1 M), and excess-fixed DEDC (10 microM) to determine SLs with log K' for Ag+ of >10. Silver was chosen as the titrant metal because it binds predominantly with S(-II) versus other ligands and reduced sulfur is thought to comprise the majority of SLs in natural waters. A two-phase system, water and 1,2-dichloroethane (DCE), is required due to the insolubility of Ag-DEDC in water. Added silver partitions into Ag+ and Ag-SL in the aqueous phase and into Ag-DEDC in the DCE phase. An automated system is used to add aliquots of silver and measure Ag-DEDC by UV absorbance in the DCE phase and [Ag+] by specific ion electrode in the aqueous phase. Excess addition of silver and a "Gran's" analysis gives the binding capacity of SL. The stability constant can also be determined for each addition of silver for an overall one-site SL assumption. Cysteine was used to test the method, and urban waters revealed SL capacities from about 50 to 150 nM and log K'(Ag) of 11-12. An independent analysis of chromium-reducible sulfide correlates well with the SL capacity.

Binding Sites↗
PubMed2004

Reemerging leptospirosis, California.

Leptospirosis is a reemerging infectious disease in California. Leptospirosis is the most widespread zoonosis throughout the world, though it is infrequently diagnosed in the continental United States. From 1982 to 2001, most reported California cases occurred in previously healthy young adult white men after recreational exposures to contaminated freshwater. We report five recent cases of human leptospirosis acquired in California, including the first documented common-source outbreak of human leptospirosis acquired in this state, and describe the subsequent environmental investigation. Salient features in the California cases include high fever with uniform renal impairment and mild hepatitis. Because leptospirosis can progress rapidly if untreated, this reemerging infection deserves consideration in febrile patients with a history of recreational freshwater exposure, even in states with a low reported incidence of infection.

Adolescent↗
PubMed2003

Surface chemical heterogeneity of bacteriogenic iron oxides from a subterranean environment.

This study quantifies the surface chemical heterogeneity of bacteriogenic iron oxides (BIOS) and its end-members (2-line ferrihydrite and intermixed intact and fragmented bacteria). On a dry weight basis, BIOS consisted of 64.5 +/- 1.8% ferrihydrite and 34.5 +/- 1.8% organic matter. Enrichment of Al, Cu, Cr, Mn, Sr, and Zn was shown in the solid versus the aqueous phase (1.9 < log Kd < 4.2). Within the solid-phase Al (69.5%), Cu (78.7%), and Zn (77.9%) were associated with the bacteria, whereas Cr (59.8%), Mn (99.8%), and Sr (79.4%) preferred ferrihydrite. Acid-base titration data from the BIOS and bacteria were fitted using FOCUS pKa spectroscopy. The bacteria spectrum with pKa's of 4.18 +/- 0.37, 4.80 +/- 0.54, 6.98 +/- 0.45, and 9.75 +/- 0.68 was similar to discrete and continuous spectra for intact and fragmented bacteria. The BIOS spectrum recorded pKa's of 4.27 +/- 0.51, 6.61 +/- 0.51, 7.89 +/- 1.10, and 9.65 +/- 0.66 and was deconvoluted to remove overlapping binding site contributions from the bacteria. The resulting residual iron oxide spectrum coincided with discrete MUSIC spectra for goethite and lepidocrocite with pKa values of 4.10 +/- 0.43, 6.53 +/- 0.45, 7.81 +/- 0.76, and 9.51 +/- 0.68. Surface site density analysis showed that acidic sites (pKa < 6) were contributed by the bacteria (37%), whereas neutral sites (6 < pKa < 8) were characteristic of the iron oxide fraction (35%). Basic sites (8 < pKa) were higher in the bacteria (57%), than in the BIOS (44%) or iron oxide fractions (47%). This analysis suggested a high degree of bacterial group masking and a similarity between the BIOS and goethite surface reactivity. An understanding of the BIOS surface chemical heterogeneity and inherent proton and metal binding capacity was obtained through the use of FOCUS apparent pKa spectroscopy.

Bacteria↗
PubMed2003

Specific surface chemical interactions between hydrous ferric oxide and iron-reducing bacteria determined using pK(a) spectra.

A modified regularized least squares pK(a) spectrum approach is applied to determine disassociation constants and proton binding site concentrations on bacteria, hydrous ferric oxide (HFO), and bacteria/HFO composite surfaces. This involves fitting experimental acid-base titration data to a continuous binding site model for a chemically heterogeneous surface with a variety of reactive groups yielding a pK(a) spectrum. The modified parameter fitting method optimizes simultaneously for both smoothness of the pK(a) spectrum and goodness of fit, whereas other methods optimize for goodness of fit given a fixed smoothness factor. Uncertainty estimates in pK(a) spectra were made by taking the mean and standard deviation of the spectra from replicate titration data. Titration of Shewanella putrefaciens strain CN32, a facultative iron-reducing bacterial species, demonstrate five types of binding sites consistent with known cell surface groups on bacteria, with mean pK(a) values of 3.62, 4.97, 6.92, 8.22, and 9.97. Composite surfaces formed by precipitation of HFO onto bacteria surfaces were also titrated. These surfaces no longer yielded low pK(a) sites in pK(a) spectra, indicating that ferric iron interacts with the bacteria via carboxylic (low pK(a)) sites during precipitation. In addition, mechanically mixed HFO bacterial samples also showed removal of carboxylic binding sites, suggesting that solid phase HFO interacts directly with carboxylic sites on bacterial cells. Moreover, the pK(a) spectra for HFO bacterial composites were not dependent on how the composite was formed; the mechanically mixed or surface-precipitated samples exhibited very similar binding site distributions. The determined pK(a) spectra imply that the overall binding mechanism for bacteria interactions with HFO involve carboxylic groups on the bacteria binding to the most basic sites on the HFO surface in approximately 1:1 stoichiometry.

Ferric Compounds↗
PubMed2003

Diagnosis and treatment of chronic gastroparesis and chronic intestinal pseudo-obstruction.

Chronic gastroparesis and CIP are debilitating disorders that are difficult to treat with currently available therapies. Failure of proper migration and differentiation of enteric neurons or ICC can result from specific genetic mutations and lead to phenotypes of CIP with or without concomitant gastroparesis. Intestinal dysfunction in diabetes may reflect a depletion of NO production (and perhaps other neurotransmitters or modulators), which is manifest as a syndrome of gastroparesis, diarrhea, or constipation in individual patients. As the key molecular changes underlying these disorders are defined, clinicians will begin to understand their precise etiology and rational medical therapy may become possible. In the future, testable hypotheses regarding the etiology of other functional bowel disorders (e.g., functional dyspepsia, irritable bowel syndrome, and so forth) may be developed.

Adult↗
PubMed2003

Current concepts in diabetic gastroparesis.

Diabetic gastroparesis is a common and debilitating condition affecting millions of patients with diabetes mellitus worldwide. Although gastroparesis in diabetes has been known clinically for more than 50 years, treatment options remain very limited. Until recently, the scientific literature has offered few clues regarding the precise aetiology of gastric dysfunction in diabetes.Up to 50% of patients with diabetes may experience postprandial abdominal pain, nausea, vomiting and bloating secondary to gastric dysfunction. There is no clear association between length of disease and the onset of delayed gastric emptying. Gastroparesis affects both type 1 (insulin dependent) and type 2 (non- insulin dependent) forms of diabetes. Diagnosis requires identifying the proper symptom complex, while excluding other entities (peptic ulcer disease, rheumatological diseases, medication effects). The diagnosis of gastroparesis may be confirmed by demonstrating gastric emptying delay during a 4-hour scintigraphic study. Treatment options are limited and rely on dietary modifications, judicious use of available pharmacological agents, and occasionally surgical or endoscopic placement of gastrostomies or jejunostomies. Gastric pacing offers promise for patients with medically refractory gastroparesis but awaits further investigation. Current pharmacological agents for treating gastroparesis include metoclopramide, erythromycin, cisapride (only available via a company-sponsored programme) and domperidone (not US FDA approved). All of these drugs act as promotility agents that increase the number or the intensity of gastric contractions. These medications are not uniformly effective and all have adverse effects that limit their use. Cisapride has been removed from the open market as a result of over 200 reported cases of cardiac toxicity attributed to its use. Unfortunately, there is a paucity of clinical studies that clearly define the efficacy of these agents in diabetic gastroparesis and there are no studies that compare these drugs to each other. The molecular pathophysiology of diabetic gastroparesis is unknown, limiting the development of rational therapies. New studies, primarily in animals, point to a defect in the enteric nervous system as a major molecular cause of abnormal gastric motility in diabetes. This defect is characterised by a loss of nitric oxide signals from nerves to muscles in the gut resulting in delayed gastric emptying. Novel therapies designed to augment nitric oxide signalling are being studied.

Diabetes Complications↗
PubMed2002

Determination of intrinsic bacterial surface acidity constants using a donnan shell model and a continuous pK(a) distribution method.

Intrinsic acidity constants (pK(a)(int)) for Bacillus subtilis (Gram+) and Escherichia coli (Gram-) cells were calculated from potentiometric titration data at different salt concentrations. Master curves were generated by replotting charge excess data as a function of pH(S) (pH at the location of surface reactive sites) where pH(S) was determined as a function of Donnan potential, Psi(DON). This potential decreased in magnitude with increasing ionic strength, from -48.5+/-0.2 to -3.5+/-0.0 mV for B. subtilis and -47.9+/-0.3 to -3.5+/-0.0 mV for E. coli at 0.01 and 0.5 M K(+), respectively, indicating an efficient surface charge neutralization by counterions. A fully optimized continuous (FOCUS) pK(a) distribution method revealed four binding sites on B. subtilis and E. coli surfaces from the master curves with pK(a)(int) values of 3.59+/-0.38, 4.33+/-0.57, 5.94+/-0.66, and 8.64+/-0.57 for B. subtilis and 3.73+/-0.44, 4.85+/-0.71, 6.56+/-0.64, and 8.79+/-0.62 for E. coli. These were assigned to functional groups according to reported pK(a) ranges of 2.0-6.0 (carboxylic acid), 3.2-3.5 (phosphodiesters), 5.6-7.2 (phosphoric acid), and 9.0-11.0 (amine groups). Average points of zero salt effect (pH(pzse)) for B. subtilis experiments were 6.63+/-0.21 and 6.42+/-0.08 as a function of pH(bulk) and pH(S), respectively. Under the same criteria, E. coli calculations yielded 5.73+/-0.23 and 5.45+/-0.05. An understanding of metal and proton reactivity on bacterial cell surfaces can be addressed quantitatively through the use of electrostatic and chemical equilibrium modeling techniques proposed in this study. The results are consistent with those of electrical force microscopy studies used to document the intrinsic electrochemical heterogeneity of bacterial cell surfaces.

Bacillus subtilis↗
PubMed2002

Metal speciation in natural waters with emphasis on reduced sulfur groups as strong metal binding sites.

The proper application of biotic ligand models to predict metal toxicity depends on accurate prediction of metal binding to sites on natural organic matter (NOM) which compete with the 'biotic' ligand for available metal. A hard and soft metal classification along with associated ligand groups (carboxyl, phenolic, amino, sulfidic) are used as a basis to predict metal speciation in the presence of aqueous organic matter. Compilation of conditional metal formation constants (log K') are made for each ligand type using model ligands. Model ligands were chosen to reflect those found in NOM and bio-organic media. Total ligand concentration (L(T)) estimates for different natural settings and log K' values are then used to generate a L(T)-log K' distributions for a specific metal. A plot for Cu(II) gives a similar trend as a compilation of measured data for natural environments. A log K'-L(T) plot for Ag(I) shows a much more discrete binding pattern than for Cu(II). Estimation of speciation of a specific metal in a specific environmental setting and to design speciation and toxicological experiments requires accurate knowledge of the functional groups in NOM.

Animals↗