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S J Marshall

Publications and source records attributed to S J Marshall.

At least 19 recordsLinked to original sources

Aquatic risk assessment of alcohol ethoxylates in North America and Europe.

An environmental risk assessment for alcohol ethoxylates (AE) is presented that integrates wastewater treatment plant monitoring, fate, and ecotoxicity research with a new application of mixture toxicity theory based on simple similar concentration addition of AE homologs in a species-sensitivity distribution (SSD) context. AEs are nonionic surfactants composed of a homologous series of molecules that range in alkyl chain length from 12 to 18 carbons and ethoxylates from 0 to 18 units. Chronic ecotoxicity of AE is summarized for 17 species in 60 tests and then normalized to monitoring data for AE mixtures. To do so, chronic aquatic toxicity was first expressed as EC10 per species (the concentration predicted to cause a 10% reduction in an important ecological endpoint). Normalization integrated several new quantitative structure-activity relationships for algae, daphnids, fish, and mesocosms and provided an interpretation of toxicity test data as a function of individual homologs in an AE mixture. SSDs were constructed for each homolog and the HC5 (hazardous concentration protective of 95% of species based on a small biological effect [the chronic EC10]) was predicted. Total mass of AE in monitored effluents from 29 sites in Europe, Canada, and the United States averaged 6.8, 2.8, and 3.55 microg/L, respectively. For risk assessment purposes, correction of exposure to account for fatty alcohol derived from sources other than AE and for sorbed components based on experimental evidence was used to determine AE concentrations in undiluted (100%) effluents from North America and Europe. Exposure and effect findings were integrated in a toxic unit (TU)-based model that considers the measured distribution of individual AE homologs in effluent with their corresponding SSDs. Use of environmentally relevant exposure corrections (bioavailability and accounting for AE-derived alcohol) resulted in TUs ranging from 0.015 to 0.212. Low levels of risk are concluded for AE in the aquatic environments of Europe and North America.

Adsorption↗

Ecotoxicity quantitative structure-activity relationships for alcohol ethoxylate mixtures based on substance-specific toxicity predictions.

Traditionally, ecotoxicity quantitative structure-activity relationships (QSARs) for alcohol ethoxylate (AE) surfactants have been developed by assigning the measured ecotoxicity for commercial products to the average structures (alkyl chain length and ethoxylate chain length) of these materials. Acute Daphnia magna toxicity tests for binary mixtures indicate that mixtures are more toxic than the individual AE substances corresponding with their average structures (due to the nonlinear relation of toxicity with structure). Consequently, the ecotoxicity value (expressed as effects concentration) attributed to the average structures that are used to develop the existing QSARs is expected to be too low. A new QSAR technique for complex substances, which interprets the mixture toxicity with regard to the "ethoxymers" distribution (i.e., the individual AE components) rather than the average structure, was developed. This new technique was then applied to develop new AE ecotoxicity QSARs for invertebrates, fish, and mesocosms. Despite the higher complexity, the fit and accuracy of the new QSARs are at least as good as those for the existing QSARs based on the same data set. As expected from typical ethoxymer distributions of commercial AEs, the new QSAR generally predicts less toxicity than the QSARs based on average structure.

Alcohols↗

The dentin-enamel junction and the fracture of human teeth.

The dentin-enamel junction (DEJ), which is the interfacial region between the dentin and outer enamel coating in teeth, is known for its unique biomechanical properties that provide a crack-arrest barrier for flaws formed in the brittle enamel1. In this work, we re-examine how cracks propagate in the proximity of the DEJ, and specifically quantify, using interfacial fracture mechanics, the fracture toughness of the DEJ region. Careful observation of crack penetration through the interface and the new estimate of the DEJ toughness ( approximately 5 to 10 times higher than enamel but approximately 75% lower than dentin) shed new light on the mechanism of crack arrest. We conclude that the critical role of this region, in preventing cracks formed in enamel from traversing the interface and causing catastrophic tooth fractures, is not associated with the crack-arrest capabilities of the interface itself; rather, cracks tend to penetrate the (optical) DEJ and arrest when they enter the tougher mantle dentin adjacent to the interface due to the development of crack-tip shielding from uncracked-ligament bridging.

Dental Enamel↗

Amelogenin control over apatite crystal growth is affected by the pH and degree of ionic saturation.

OBJECTIVE: To study the mechanisms which promote the interactions of amelogenin proteins with the forming mineral to establish suitable conditions for the biomimetic synthesis of enamel in vitro. DESIGN: Saturated calcium phosphate solutions were used in conjunction with recombinant amelogenin proteins to induce mineral formation on glass-ceramics substrates containing oriented fluoroapatite crystals (FAP). The height of mineral layers formed on these substrates within 24 h was measured by atomic force microscopy (AFM). EXPERIMENTAL VARIABLES: The effect of protein concentration, pH and degree of saturation (DS) on the growth of apatite mineral was evaluated. Mineralization experiments were performed at 0, 0.4 and 1.6 mg/ml amelogenin concentrations. Mineralization solutions were used at pH values of 6.5, 7.4, 8.0 and 8.8 and DS of calcium and phosphate between 9 and 13. OUTCOME MEASURE: Height and morphology of mineralized layer formed on glass-ceramic substrates as determined from AFM measurements. RESULTS: Homogeneous nucleation and crystal growth of thin layers on the FAP were observed, when calcium and phosphate ions were added. The height of these layers grown on (001) planes of FAP was strongly dependent on the protein concentration and pH. At concentrations of 0 and 0.4 mg/ml crystal grew 5-15 nm on the FAP, while they grew approximately to 200 nm at 1.6 mg/ml. The enhanced crystal growth was observed only at pH 6.5, 7.4 and 8.0, while layers only 20 nm thick were obtained at pH 8.8. An increase in DS resulted in uncontrolled growth of calcium phosphate mineral covering large areas of the substrate. CONCLUSIONS: Protein concentration, pH and the saturation of the mineralizing solution need to be considered carefully to provide suitable conditions for amelogenin-guided growth of apatite crystals.

Amelogenesis↗

Dentin erosion simulation by cantilever beam fatigue and pH change.

Exposed root surfaces frequently exhibit non-carious notches representing material loss by abrasion, erosion, and/or abfraction. Although a contribution from mechanical stress is often mentioned, no definitive proof exists of a cause-effect relationship. To address this, we examined dimensional changes in dentin subjected to cyclic fatigue in two different pH environments. Human dentin cantilever-beams were fatigued under load control in pH = 6 (n = 13) or pH = 7 (n = 13) buffer, with a load ratio (R = minimum load/maximum load) of 0.1 and frequency of 2 Hz, and stresses between 5.5 and 55 MPa. Material loss was measured at high- and low-stress locations before and after cycling. Of the 23 beams, 7 withstood 1,000,000 cycles; others cracked earlier. Mean material loss in high-stress areas was greater than in low-stress areas, and losses were greater at pH = 6 than at pH = 7, suggesting that mechanical stress and lower pH both accelerate erosion of dentin surfaces.

Dental Stress Analysis↗

Micro-Raman spectroscopic investigation of dental calcified tissues.

The purpose of this study was to determine if dental calcified junctions (DEJs/CDJs) in human teeth contain different compositional phases compared to the adjacent dental calcified tissues. Peak positions and intensities were determined from micro-Raman spectra for PO(3-) (4) and the C--H modes and compared among the mineralized tissues and their junctions. Values of width were determined from the intersections of intensity regression lines through the junctions and in the adjacent tissues. The peaks were measured in 1-microm steps along a l00-microm line across the junction. High-resolution analysis revealed that PO(3-) (4) band peaks for dentin, the DEJ, enamel, the CDJ, and cementum were at the same position (959 cm(-1)), while for the C--H stretching mode a significant shift of 4.6 cm(-1) was found between enamel, the DEJ, and dentin. The mean width of the DEJ was 7.6 (+/- 2.8) microm using the PO(3-) (4) band and 8.6 (+/- 3.6) microm using the C--H stretching mode. Across the DEJ, the mineral content monotonically decreased from enamel to dentin while the organic component monotonically increased. The DEJ width was in agreement with prior nanoindentation studies. No width estimate was possible for the CDJ because the compositional differences between cementum and dentin were small.

Apatites↗

Ultrastructure and nanomechanical properties of cementum dentin junction.

The attachment between cementum and dentin has been given several definitions and nomenclature, including: interzonal layer, intermediate cementum, collagen hiatus, Hopewell-Smith's hyaline layer, and more commonly, cementum-dentin junction (CDJ). Understanding the attachment of two structurally dissimilar hard tissues such as cementum and dentin defined by a junction may provide information necessary to engineer functionally graded materials that can be used for efficient tooth restorations in clinical dentistry and other bioengineering applications. Hence, in this study, as a first step toward understanding the CDJ using a biomechanical approach, it was hypothesized that the CDJ between cementum and dentin is a wide zone with mechanical properties significantly lower than the neighboring tissues. The structure of the CDJ was studied using an atomic force microscope (AFM), and site-specific mechanical response of the three regions; cementum, CDJ, and dentin were determined using an AFM-nanoindenter under dry and wet conditions. The AFM results of the CDJ demonstrated a valley under dry conditions and a peak under wet conditions. The magnitude of the depth of the valley was approximately the same as the height of the peak of the CDJ, ranging from 10 to 40 microm. The nanomechanical properties under dry conditions indicated no significant difference (p > 0.05) in elastic modulus and hardness of the CDJ (Er = 17.5 +/- 2.7 GPa, H = 0.6 +/- 0.1 GPa) and cementum (Er = 18.7 +/- 2.5 GPa, H = 0.6 +/- 0.1 GPa). The mechanical properties of the CDJ were significantly lower (p << 0.05) than dentin (Er = 19.9 +/- 2.9 GPa, H = 0.6 +/- 0.1 GPa) under dry conditions. However, under more relevant hydrated conditions, the mechanical properties of CDJ (Er 3.0 +/- 0.7 GPa, H = 0.1 +/- 0.0 GPa) were significantly lower (p << 0.05) than those of cementum (Er 6.8 +/- 1.9 GPa, H = 0.2 +/- 0.1 GPa) and dentin (Er 9.4 +/- 2.3 GPa, H = 0.3 +/- 0.1 GPa). Based on the results from this study, it can be concluded that the CDJ can be regarded as a wide zone containing large quantities of proteins including collagen that contribute to hydration and significantly reduce mechanical properties, compared with the adjacent hard tissues, cementum, and dentin. The lower mechanical properties of the CDJ may make it possible for it to redistribute occlusal loads to the alveolar bone.

Aged↗

Resonant ultrasound spectroscopy measurements of the elastic constants of human dentin.

The technique of resonant ultrasound spectroscopy (RUS) was used to measure the second-order elastic constants of hydrated human dentin. Specimens were placed between two transducers, and the resonant frequencies of vibration were measured between 0.5 and 1.4 MHz. The elastic constants determined from the measured resonant frequencies in hydrated dentin exhibited slight hexagonal anisotropy, with the stiffest direction being perpendicular to the axis of the tubules (E11 = 25.1GPA) This hexagonal anisotropy was small (E33/E11 = 0.92), and almost disappeared when the specimens were dried. In addition, there was a pronounced anisotropy in the Poisson's ratio of wet dentin: v21 = 0.45; v31 = 0.29. With drying in air, this anisotropy vanished: v21 = v31 = 0.29. The isotropic Young's modulus of dried dentin was 28.1 GPa. RUS shows promise for determining the elastic constants in mineralized tissues.

Anisotropy↗

Evaluation of a new modulus mapping technique to investigate microstructural features of human teeth.

Teeth contain several calcified tissues with junctions that provide interfaces between dissimilar tissues. These junctions have been difficult to characterize because of their small size. In this work a new technique using a combination of atomic force microscopy (AFM) and a force-displacement transducer was used to simultaneously study the surface topography and map mechanical properties of the junctions and adjacent hard tissues. Prepared specimens from human third molars were scanned by an AFM piezo-tube in contact mode. To measure the dynamic viscoelastic properties of the material a small sinusoidal force was superimposed on the contact force and the resulting displacement amplitude and the phase shift between the force and amplitude were measured. This force modulation technique was used to map the local variation of nanomechanical properties of intertubular dentin, peritubular dentin, enamel, dentin-enamel junction (DEJ) and peritubular-intertubular dentin junction (PIJ). This new technique allowed us to measure the widths of these junctions in addition to local variation in dentin and enamel without causing plastic deformation to the material and with 2 orders of magnitude increase in spatial resolution compared with previous studies that used discrete nanoindentation techniques. Due to the ability to analyze the sample line-by-line, the distribution functions associated with the width of the DEJ and PIJ were conveniently obtained for specific intratooth locations. The data suggested, for three third molar specimens, a DEJ width of 2-3 microm with full-width half-maximum (FWHM) of 0.7 microm and PIJ width of 0.5-1.0 microm with 0.3 microm FWHM. The intertubular dentin storage modulus variation was between 17 and 23 GPa with a mean value of 21 GPa. The range of storage modulus for enamel near the DEJ was between 51 and 74 GPa with a mean value of 63 GPa.

Dental Enamel↗

Relationships between media use, body fatness and physical activity in children and youth: a meta-analysis.

OBJECTIVE: To review the empirical evidence of associations between television (TV) viewing, video/computer game use and (a) body fatness, and (b) physical activity. DESIGN: Meta-analysis. METHOD: Published English-language studies were located from computerized literature searches, bibliographies of primary studies and narrative reviews, and manual searches of personal archives. Included studies presented at least one empirical association between TV viewing, video/computer game use and body fatness or physical activity among samples of children and youth aged 3-18 y. MAIN OUTCOME MEASURE: The mean sample-weighted corrected effect size (Pearson r). RESULTS: Based on data from 52 independent samples, the mean sample-weighted effect size between TV viewing and body fatness was 0.066 (95% CI=0.056-0.078; total N=44,707). The sample-weighted fully corrected effect size was 0.084. Based on data from six independent samples, the mean sample-weighted effect size between video/computer game use and body fatness was 0.070 (95% CI=-0.048 to 0.188; total N=1,722). The sample-weighted fully corrected effect size was 0.128. Based on data from 39 independent samples, the mean sample-weighted effect size between TV viewing and physical activity was -0.096 (95% CI=-0.080 to -0.112; total N=141,505). The sample-weighted fully corrected effect size was -0.129. Based on data from 10 independent samples, the mean sample-weighted effect size between video/computer game use and physical activity was -0.104 (95% CI=-0.080 to -0.128; total N=119,942). The sample-weighted fully corrected effect size was -0.141. CONCLUSION: A statistically significant relationship exists between TV viewing and body fatness among children and youth although it is likely to be too small to be of substantial clinical relevance. The relationship between TV viewing and physical activity is small but negative. The strength of these relationships remains virtually unchanged even after correcting for common sources of bias known to impact study outcomes. While the total amount of time per day engaged in sedentary behavior is inevitably prohibitive of physical activity, media-based inactivity may be unfairly implicated in recent epidemiologic trends of overweight and obesity among children and youth. Relationships between sedentary behavior and health are unlikely to be explained using single markers of inactivity, such as TV viewing or video/computer game use.

Adolescent↗

On the in vitro fatigue behavior of human dentin: effect of mean stress.

Human dentin is susceptible to failure under repetitive cyclic-fatigue loading. This investigation seeks to address the paucity of data that reliably quantify this phenomenon. Specifically, the effect of alternating vs. mean stresses, characterized by the stress- or load-ratio R (ratio of minimum-to-maximum stress), was investigated for three R values (-1, 0.1, and 0.5). Dentin was observed to be prone to fatigue failure under cyclic stresses, with susceptibility varying, depending upon the stress level. The "stress-life" (S/N) data obtained are discussed in the context of constant-life diagrams for fatigue failure. The results provide the first fatigue data for human dentin under tension-compression loading and serve to map out safe and unsafe regimes for failure over a wide range of in vitro fatigue lives (< 10(3) to > 10(6) cycles).

Algorithms↗

Amelogenin-guided crystal growth on fluoroapatite glass-ceramics.

The formation of aligned fibrous apatite crystals in enamel is predominantly attributed to the involvement of amelogenin proteins. We developed a model to study interactions of matrix proteins with apatite mineral in vitro and tested the hypothesis that amelogenin solubility affects the ability to induce protein-guided mineralization. Crystal growth experiments were performed on fluoroapatite (FAP) glass-ceramics in mineralizing solutions containing recombinant full-length amelogenin (rH174) at different concentrations. Using atomic force microscopy, we observed that mineral precipitated randomly on the substrate, but also formed thin layers (height, 10 nm) on FAP within 24 hrs. This growth pattern was unaffected when 0.4 mg/mL of rH174 was added. In contrast, crystals grew on FAP at a rate up to 20 times higher, at 1.6 mg/mL protein. Furthermore, nanospheres and mineral bound specifically to FAP and aligned in strings approximately parallel to the c-axis of FAP, leading us to the conclusion that amelogenin proteins indeed control direction and rate of growth of apatite in enamel.

Amelogenin↗

In vitro fatigue behavior of human dentin with implications for life prediction.

Although human dentin is known to be susceptible to failure under repetitive cyclic fatigue loading, there are few reports in the literature that reliably quantify this phenomenon. This study seeks to address the paucity of fatigue data through a systematic investigation of the effects of prolonged cyclical loading on human dentin in an environment of ambient temperature Hank's balanced salt solution (HBSS) at cyclic frequencies of 2 and 20 Hz. The "stress-life" (S/N) data thus obtained are discussed in the context of possible mechanisms of fatigue damage and failure in this material. In addition, stiffness loss data collected in situ during the S/N tests are used to deduce crack velocities and the thresholds for such cracking. These results are presented in a fracture mechanics context as plots of fatigue-crack propagation rates (da/dN) as a function of the stress-intensity range (Delta K). Such S/N and da/dN-Delta K data are discussed in light of the development of a framework for a fracture-mechanics-based methodology for the prediction of the fatigue life of teeth. It is concluded that the presence of small (on the order of 250 microm) incipient flaws in human teeth will not radically affect their useful life.

Apatites↗

Optical spectroscopy and imaging of the dentin-enamel junction in human third molars.

A 351-nm laser excitation source was used to perform autofluorescence microscopy of dentin, enamel, and the dentin-enamel junction (DEJ) to obtain information regarding their morphology and spectral characteristics. The emission spectra of these calcified dental tissues were different from one another, and this enabled the DEJ to be imaged and dimensionalized. The DEJ displayed sharp and clearly delineated borders at both its enamel and dentin margins. The dentinal tubules and the enamel prisms appeared to terminate abruptly at the DEJ. The median DEJ width was 10 microm, ranging from 7 to 15 microm, and it did not appear to depend on intratooth position.

Dental Enamel↗

Screening of plant extracts for antiprotozoal and cytotoxic activities.

Methanolic and aqueous extracts derived from 43 plant species, selected either from ethnobotanical or chemotaxonomical data, were screened for their antiprotozoal activity against Leishmania donovani and Trypanosoma brucei brucei. The cytotoxic activity against KB cells was also determined. Eight extracts had IC50 values of less than 10 microg/ml against Leishmania donovani. The most active was Triclisia patens with an IC50 value of 1.5 microg/ml against Leishmania donovani. Annona purpurea and Alstonia macrophylla had IC50 values below 10 microg/ml against Trypanosoma brucei brucei. Annona purpurea was the most cytotoxic against KB cells.

Animals↗

The importance of intrafibrillar mineralization of collagen on the mechanical properties of dentin.

It is widely held that the hardness and modulus of dentin increase in proportion to the mineral concentration. To test this belief, we measured hardness and modulus of normal dentin and an altered form of dentin without gap-zone mineralization in wet and dry conditions by AFM nanoindentation to determine if the modulus and hardness scale linearly with mineral concentration. Mineral concentrations in the mid-coronal location of the normal and altered dentins were 44.4 vol% and 30.9 vol%, respectively. Surrounding the pulp of the altered dentin was a region of higher mineralization, 40.5 vol%. The indentation modulus of normal dentin was 23.9 (SD = 1.1) GPa dry and 20.0 (SD = 1.0) GPa wet. In mid-coronal regions of the altered dentin, the indentation modulus was 13.8 (SD = 2.0) GPa dry and 5.7 (SD = 1.4) GPa wet. In the more mineralized regions of the altered dentin, the modulus was 20.4 (SD = 1.8) GPa dry and 5.3 (SD = 0.8) GPa wet; the properties of the altered wet dentin did not correlate with mineral concentration. The results of this study raise doubt as to whether mineral concentration alone is a sufficient endpoint for assessing the success or failure of remineralization approaches in restorative dentistry.

Adolescent↗

The mechanical properties of human dentin: a critical review and re-evaluation of the dental literature.

The past 50 years of research on the mechanical properties of human dentin are reviewed. Since the body of work in this field is highly inconsistent, it was often necessary to re-analyze prior studies, when possible, and to re-assess them within the framework of composite mechanics and dentin structure. A critical re-evaluation of the literature indicates that the magnitudes of the elastic constants of dentin must be revised considerably upward. The Young's and shear moduli lie between 20-25 GPa and 7-10 GPa, respectively. Viscoelastic behavior (time-dependent stress relaxation) measurably reduces these values at strain rates of physiological relevance; the reduced modulus (infinite relaxation time) is about 12 GPa. Furthermore, it appears as if the elastic properties are anisotropic (not the same in all directions); sonic methods detect hexagonal anisotropy, although its magnitude appears to be small. Strength data are re-interpreted within the framework of the Weibull distribution function. The large coefficients of variation cited in all strength studies can then be understood in terms of a distribution of flaws within the dentin specimens. The apparent size-effect in the tensile and shear strength data has its origins in this flaw distribution, and can be quantified by the Weibull analysis. Finally, the relatively few fracture mechanics and fatigue studies are discussed. Dentin has a fatigue limit. For stresses smaller than the normal stresses of mastication, approximately 30 MPa, a flaw-free dentin specimen apparently will not fail. However, a more conservative approach based on fatigue crack growth rates indicates that if there is a pre-existing flaw of sufficient size (approximately 0.3-1.0 mm), it can grow to catastrophic proportion with cyclic loading at stresses below 30 MPa.

Biomechanical Phenomena↗

Dentin shear strength: effect of distance from the pulp.

OBJECTIVE: Dentin structure varies with orientation and location. Ultimate shear strength (USS) has also been found in previous studies to vary with location. The present study further explores this relationship between USS and various locations in coronal dentin as well as distance from the pulp. METHODS: Stick specimens were prepared from coronal dentin located in the center or under cusps of human molar teeth. These were tested in the shear mode at various distances from the pulp. RESULTS: Median values ranged from 52.7 (range 29.0-73.1) MPa near the pulp to 76.7 (range 53.9-104.0) MPa near the dentino-enamel junction. No differences were found among the buccal, central or lingual locations, however, the USS near the pulp was found to be significantly lower. SIGNIFICANCE: The properties of coronal dentin vary with distance from the pulp, which may affect adhesion and other aspects of restorative dentistry.

Anisotropy↗