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At least 991 records · Page 55Linked to original sources
PubMed2003

A conceptual model integrating spatial information to assess target volume coverage for IMRT treatment planning.

PURPOSE: We propose a model that integrates the spatial location of each voxel within a clinical target volume (CTV) to differentiate the merit of intensity-modulated radiation therapy (IMRT) plans with similar dose-volume histogram (DVH). This conceptual model is based on the hypothesis that various subregions within a given CTV that may carry different degree of risk in containing microscopic disease. METHODS AND MATERIALS: We hypothesize that a correlation between the probability of microscopic tumor extension and the risk of lymph node metastasis of a particular voxel point within CTV can be inferred based on its distance from the surface of radiographically evident gross disease. A preliminary observation was gathered from existing clinicopathologic data, and, based on these observations, a conceptual model for exponential-decay microscopic-extension probability function around primary tumor and linear function parameters relating the likelihood of lymph node metastasis to the distance from primary tumor was proposed. This model was generated to provide scoring functions to examine the merit of IMRT plans. To test the feasibility of this model, we generated two IMRT plans with similar and clinically acceptable DVH-based CTV coverage. Planning data were transferred to a data analysis software package (Matlab, The Mathworks Inc.). A 3D scoring function was calculated for each voxel inside the CTV. The adequacy of target coverage was evaluated by several novel approaches: 2D dose-volume scoring-function histograms (DVSH), the integral probability of relative residual tumor burden (RRTB), and tumor control probabilities (TCP) employing the scoring function as a pseudo-clonogen density distribution. RESULTS: Incorporating parameters for the risk of containing microscopic disease in each voxel into the scoring function algorithm, 2D DVSHs, RRTBs, integral RRTBs, and TCPs were computed. On each axial image, an RRTB map could locate the regions at greatest risk. These scoring functions were able to differentiate the merit of CTV coverage of clinically different IMRT plans but having very similar DVHs; one with cold spots centrally located over the gross tumor, and the other with more acceptable cold spots on the periphery of the CTV further away from the gross tumor volume. CONCLUSIONS: We demonstrated the feasibility and potential utility of an IMRT scoring method derived from this conceptual modeling approach. These methods are capable of ranking treatment plans with similar DVH profiles but different underdosed regions within the target. We will examine the accuracy of model parameters by performing tumor-specific image-pathologic correlation studies. Upon validation of these parameters, incorporating this scoring function model into plan optimization may have the potential to avoid underdosing subvolumes within CTV that harbor a higher likelihood of microscopic disease.

Humans↗
PubMed1996

Maximum volume coverage in spiral computed tomography scanning.

RATIONALE AND OBJECTIVES: Given a slice thickness and an image noise level, volume coverage in spiral computed tomography (CT) scanning was maximized with respect to detector collimation and table increment. METHODS: The maximization was analytically performed on the basis of the following relationships: (1) With the half-scan interpolation method, the slice sensitivity profile (SSP) in spiral CT scanning is the convolution of a rectangular detector response function (the width is equal to the detector collimation) and a triangular table motion function (the base is equal to the table increment); (2) the SSP variance is equal to the sum of squared detector collimation divided by 12 and squared table increment divided by 24; (3) the image noise variance is inversely proportional to tube current and detector collimation; and (4) the maximum continuous scanning time is inversely proportional to tube current. RESULTS: Given a limited tube heat capability, a slice thickness, and an image noise level, we proved that the maximum volume coverage is reached with a pitch of square root of 2. CONCLUSION: With a heat-limited tube and for a specified image quality in terms of slice thickness and image noise, a pitch of 1.4 should be used for maximum volume coverage in spiral CT scanning.

Humans↗
PubMed1996

Impact of incomplete coverage of neonatal dried blood spot screening on estimating HIV-1 seroprevalence.

The aim of this study was to determine the extent to which selective under-coverage of births to mothers more likely to be at risk of HIV-1 infection will result in a significant under-estimation of the true neonatal seroprevalence. Census data, local birth statistics, maternity data and data from the prevalence monitoring programme were used to produce a model to predict the effects of under-coverage in the uptake of neonatal metabolic screening which has been observed in babies with a mother of ethnic group black African. The adjustment factor which allows for under-coverage is the relative inclusion ratio (RIR); the probability that samples from a group at different risk of HIV infection were included in the survey divided by the probability of inclusion for samples from all other babies. The RIR was found to be close to unity (0.97), indicating a minimal bias. Under usual conditions only if the relative inclusion ratio (RIR) declined to values of 0.87 or below would there be a substantial bias. Despite some selective under representation, the results obtained from the Unlinked Anonymous HIV Monitoring Programme Dried Blood Spot Survey would seem to identify levels of prevalence in the population of child-bearing women with a good degree of accuracy and remains a useful tool for resource allocation, planning of services, provision of care and counselling.

Adolescent↗
PubMed2000

A fluorescence-based method for determining the surface coverage and hybridization efficiency of thiol-capped oligonucleotides bound to gold thin films and nanoparticles.

Using a fluorescence-based method, we have determined the number of thiol-derivatized single-stranded oligonucleotides bound to gold nanoparticles and their extent of hybridization with complementary oligonucleotides in solution. Oligonucleotide surface coverages of hexanethiol 12-mer oligonucleotides on gold nanoparticles (34 +/- 1 pmol/cm2) were significantly higher than on planar gold thin films (18 +/- 3 pmol/cm2), while the percentage of hybridizable strands on the gold nanoparticles (1.3 +/- 0.3 pmol/cm2, 4%) was lower than for gold thin films (6 +/- 2 pmol/cm2, 33%). A gradual increase in electrolyte concentration over the course of oligonucleotide deposition significantly increases surface coverage and consequently particle stability. In addition, oligonucleotide spacer sequences improve the hybridization efficiency of oligonucleotide-modified nanoparticles from approximately 4 to 44%. The surface coverage of recognition strands can be tailored using coadsorbed diluent oligonucleotides. This provides a means of indirectly controlling the average number of hybridized strands per nanoparticle. The work presented here has important implications with regard to understanding interactions between modified oligonucleotides and metal nanoparticles, as well as optimizing the sensitivity of gold nanoparticle-based oligonucleotide detection methods.

Gold↗
PubMed2001

Surface coverages of bonded-phase ligands on silica: a computational study.

A computational study of the packing of various bonded-phase ligands bound to chromatographic silica is presented. This is done with the intention of examing the type of surface structures that are typically found in real chromatographic systems. Utilizing the surface structure of the (111) face of the beta-cristobalite crystal, it is shown that the maximum surface coverages of dimethyloctylsilane, dimethyloctadecylsilane, triisopropylsilane, diisopropyloctylsilane, and diisopropyloctadecylsilane can be calculated that are in good agreement with experiment. The maximum surface coverages are also calculated for the (100) face of the beta-cristobalite crystal and for a set of random silica surfaces. The coverages for the latter two surfaces types are found to be significantly lower than the experimental values for chromatographic silica surfaces. These results further suggest that chromatographic silica surfaces may resemble crystalline surface sites similar to the (111) face of beta-cristobalite, as has been previously suggested in the literature. Hence, these structures can be reliably utilized in molecular simulations of bonded-phase chromatography where the atomic-level detail of the silica surface has been previously lacking.

Journal Article↗
PubMed2005

Molecular dynamics simulations of alkylsilane stationary-phase order and disorder. 1. Effects of surface coverage and bonding chemistry.

"Shape-selective" polymeric alkylsilane stationary phases are routinely employed over the more common monomeric phases in reversed-phase liquid chromatography (RPLC) to improve the separation of geometric isomers of shape-constrained solutes. We have investigated the molecular dynamics of chromatographic models that represent both monomeric and polymeric stationary phases with alkylsilane surface coverages and bonding chemistries typical of actual materials in an effort to elucidate the molecular-level structural features that control shape-selective separations. The structural characterization of these models is consistent with previous experimental observations of alkyl chain order and disorder: (1) alkyl chain order increases with increased surface coverage; and (2) monomeric and polymeric phases with similar surface coverages yield similar alkyl chain order (although subtle differences exist). In addition, a significant portion of the alkyl chain proximal to the silica surface is disordered (primarily gauche conformations) and the distal end is most ordered. Models that represent shape-selective RPLC phases possess a significant region of distal end chain order with primarily trans dihedral angle conformations. This is consistent with the view that the alkyl chains comprising polymeric stationary phases contain a series of well-defined and rigid voids in which shape-constrained solutes can penetrate and hence be selectively retained.

Journal Article↗
PubMed1982

Chemical Abstracts coverage of the preclinical sciences journal literature.

This study examines Chemical Abstracts (CA) coverage of the journal literature cited by researchers from preclinical science departments affiliated with medical schools. Using references from 70 dissertations written between 1973 and 1977 in the fields of anatomy, biochemistry, immunology, microbiology, pathology, pharmacology, and physiology, coverage of journal articles was studied. Approximately 57% of the cited literature was covered. Biochemistry (83.5%), pharmacology (80.4%), and microbiology (76.2%) were covered the best while pathology (27.8%) was covered the worst. Coverage of anatomy (55.4%), immunology (40.1%), and physiology (42.4%) was dependent upon the research being conducted. With the advent of multidata base searching, Chemical Abstracts should be considered as a source of references for preclinical science researchers.

Abstracting and Indexing↗
PubMed2006

Influence of copper loading and surface coverage on the reactivity of granular iron toward 1,1,1-trichloroethane.

Although iron-based bimetallic reductants offer promise in treating organohalides, the influence of additive mass loading and two-dimensional surface coverage on reductant reactivity has not been fully elucidated. In this study we examine 1,1,1-trichloroethane reduction by Cu/Fe bimetals as a function of Cu loading and surface coverage. Information from a suite of complementary techniques (X-ray photoelectron spectroscopy, Auger electron spectroscopy, and cross-sectional energy-dispersive X-ray spectroscopy) indicates that displacement plating produces a heterogeneous metallic copper overlayer on iron. The dependence of pseudo-first-order rate constants (k(obs) values) for 1,1,1-trichloroethane reduction on Cu loading exhibits two distinct regimes. At Cu loadings less than 1 monolayer equivalent (approximately 10 micromol Cu/g Fe), a pronounced increase in k(obs) is associated with a corresponding increase in the two-dimensional surface coverage of Cu. A weaker dependence of k(obs) on Cu mass is exhibited at loadings in excess of 1 monolayer equivalent, which we ascribe to an increase in the volume of the metallic overlayer. The observed relationship between k(oba) and loading suggests that 1,1,1-trichloroethane reduction occurs on the Cu surface rather than at the interface between the Cu overlayer and the iron substrate.

Copper↗
PubMed2005

Determination of O[H] and CO coverage and adsorption sites on PtRu electrodes in an operating PEM fuel cell.

A special in situ PEM fuel cell has been developed to allow X-ray absorption measurements during real fuel cell operation. Variations in both the coverage of O[H] (O[H] indicates O and/or OH) and CO (applying a novel Deltamu(L3) = mu(L3)(V) - mu(L3)(ref) difference technique), as well as in the geometric (EXAFS) and electronic (atomic XAFS) structure of the anode catalyst, are monitored as a function of the current. In hydrogen, the N(Pt)(-)(Ru) coordination number increases much slower than the N(Pt)(-)(Pt) with increasing current, indicating a more reluctant reduction of the surface Pt atoms near the hydrous Ru oxide islands. In methanol, both O[H] and CO adsorption are separately visible with the Deltamu technique and reveal a drop in CO and an increase in OH coverage in the range of 65-90 mA/cm(2). With increasing OH coverage, the Pt-O coordination number and the AXAFS intensity increase. The data allow the direct observation of the preignition and ignition regions for OH formation and CO oxidation, during the methanol fuel cell operation. It can be concluded that both a bifunctional mechanism and an electronic ligand effect are active in CO oxidation from a PtRu surface in a PEM fuel cell.

Alloys↗
PubMed2005

A compact all-carbon tripodal tether affords high coverage of porphyrins on silicon surfaces.

[Structure: See text] Redox-active molecules designed to give high charge density on electroactive surfaces are essential for applications in molecular information storage. To achieve a small molecular footprint and thereby high surface charge density, a compound consisting of a triallyl tripod attached via a p-phenylene unit to a porphyrin (1) has been synthesized. The zinc chelate of 1 (Zn-1) was attached to Si(100). Electrochemical measurements indicate that the molecular footprint (75 A) in the monolayer is only approximately 50% larger than the minimum achievable, indicating high surface coverage. IR spectroscopy indicates that the bands due to the nu(C=C) (1638 cm(-1)) and gamma(CH) (915 cm(-1)) vibrations present in the solid sample (KBr pellet) are absent from the spectra of the monolayers of Zn-1, consistent with saturation of the double bond in each of the three legs of the tripod upon the hydrosilylation process accompanying attachment. Comparison of the relative intensities of the in-plane (998 cm(-1)) versus out-of-plane (797 cm(-1)) porphyrin modes indicates the average tilt angle (alpha) of the porphyrin ring with respect to the surface normal is approximately 46 degrees , a value also observed for analogous porphyrins tethered to Si(100) via monopodal carbon linkers. Accordingly, the higher packing densities afforded by the compact tripodal linker are not due to a more upright orientation on the surface. The charge-retention half-lives (t1/2) for the first oxidation state of the Zn-1 monolayers increase from 10 to 50 s at low surface coverage (1-5 x 10(-11) mol.cm(-2)) to near 200 s at saturation coverage (approximately 2 x 10(-10) mol.cm(-2)). Taken together, the high surface charge density (despite the lack of upright orientation) of the triallyl-tripodal porphyrin makes this construct a viable candidate for molecular information storage applications.

Journal Article↗
PubMed2005

Effect of sulfur coverage on Fe(110) adhesion: a DFT study.

The effect of adsorbed S at different coverages on the adhesion of Fe(110) surfaces in match and mismatch is examined using density functional theory (DFT). S is adsorbed in atop, bridge, and 4-fold hollow sites on one side of the interface in c(2 x 2) and p(1 x 1) arrangements, corresponding to coverages of 1/2 and 1 monolayer, respectively. The calculated adhesion energy values at different interfacial separations are fitted to the universal binding energy relation, and the effect of the S coverages on the adhesive strength is analyzed. The effect of relaxation of the interfaces at equilibrium is also investigated, and the resulting interfacial structures and related magnetic and charge density properties are compared.

Journal Article↗
PubMed2005

Surface products and coverage dependence of dissociative ethane adsorption on Pt{110}-(1 x 2).

The dissociation of ethane on Pt{110}-(1 x 2) has been studied using supersonic molecular beam and temperature-programmed reaction techniques. The study unequivocally shows that the stable dissociation product of ethane on Pt{110}-(1 x 2) at all coverages is CCH2 at 350-400 K and CCH at 440 K. Temperature-programmed-reaction (TPR) experiments indicate that the CCH2 species decomposes to CCH with a reaction-limited peak temperature of 430 K. Above 450 K, the CCH species becomes unstable and decomposes with a peak temperature of 540 K. By 600 K, ethane dehydrogenates completely to form a surface carbon layer. The sticking probability is initially 0.02 at 370 K and 0.03 at 600 K and follows a linear (1-2theta) dependence for coverages of up to theta = 0.4 ML, where theta is defined as the number of C2Hx units per (1 x 2) unit cell. However, a much weaker coverage dependence at 800 K suggests that the carbon agglomerates into high-density islands.

Journal Article↗
PubMed2005

Determination of anisotropic optical constants and surface coverage of molecular films using polarized visible ATR spectroscopy. Application to adsorbed cytochrome c films.

This article describes a method to determine the anisotropic optical constants and surface coverage of molecular films using polarized attenuated total reflectance (ATR) absorbance measurements. We have extended the transfer-matrix formalism to describe birefringent and dichroic films in ATR geometries and have combined it with an iterative numerical procedure to determine the anisotropic values of both the real (n) and imaginary (k) parts of the complex refractive index of the film under investigation. Anisotropic values of the imaginary part of the refractive index (k) allow for the determination of the surface coverage and one order parameter of the film. To illustrate this approach, we have used cytochrome c (cyt c) protein films adsorbed to glass and indium tin oxide (ITO) surfaces. Experimental results show that cyt c films on these surfaces, which were formed under identical conditions, have significant differences in their surface coverages (11.2 +/- 0.4 pmol/cm(2) on glass and 21.7 +/- 0.9 pmol/cm(2) on ITO); however, their order parameters are similar (0.30 +/- 0.02 on glass and 0.36 +/- 0.04 on ITO).

Adsorption↗
PubMed2005

Determination of O and OH adsorption sites and coverage in situ on Pt electrodes from Pt L(2,3) X-ray absorption spectroscopy.

The adsorption of atomic oxygen and hydroxide on a platinum electrode in 0.1 M HClO4 or H2SO4 electrolytes was studied in situ with Pt L(2,3) X-ray absorption spectroscopy (EXAFS and XANES). The Pt L3 edge absorption data, mu, were collected at room temperature in transmission mode on beamline X-11A at the National Synchrotron Light Source using a custom built cell. The Pt electrode was formed of highly dispersed 1.5-3 nm particles supported on carbon. A novel difference procedure (delta mu = mu(O[H]/Pt) - mu(Pt)) utilizing the L3 XANES spectra at different applied voltages was used to isolate the effects of O[H] (O or OH) adsorption in the XANES spectra. The Deltamu results are compared with results obtained from real-space full-multiple scattering calculations utilizing the FEFF8 code on model clusters. The experimental results, when compared with theoretical calculations, allow the adsorption site to be identified. At low coverages OH adsorbs primarily in 1-fold coordinated atop sites. As the coverage increases, O binds in the bridge/fcc sites, and at still higher coverages above 1.05 V RHE, O adsorbs into a higher coordinated n-fold or subsurface site, which is thought to be the result of Pt-O site exchange and oxide formation. These results are similar to those found in the gas phase. Direct specific adsorption of bisulfate anions in H2SO4 is spectroscopically seen in both the EXAFS and XANES data and is seen to impede oxygen adsorption consistent with previous reports.

Journal Article↗
PubMed2005

A coverage-dependent study of pt spontaneously deposited onto Au and Ru surfaces: direct experimental evidence of the ensemble effect for methanol electro-oxidation on Pt.

Direct experimental evidence that can be unambiguously attributed to the need of an ensemble of a minimum number of neighboring Pt atoms for methanol electro-oxidation has been observed for the first time. This was realized by a Pt coverage-dependent investigation of methanol and CO electro-oxidation on Pt sites generated via spontaneous deposition onto both Au and Ru surfaces. CO stripping voltammograms also show clear evidence of a substantially strengthened CO-Pt bonding for submonolayer Pt deposited on the Au substrate over a range of ca. 0.22 to 0.77, which is in qualitative agreement with the theoretical prediction based on the Hammer-Nørskov d-band center model. However, the degree of the bond strengthening depends on the Pt coverage, being stronger for lower coverage. Additionally, evidence of an Ostwald ripening process for Pt islands formation has also been observed.

Journal Article↗
PubMed2006

Photochronocoulometric measurement of the coverage of surface-bound dyes on titanium dioxide crystal surfaces.

Atomically flat terraced single-crystal anatase and rutile surfaces can be prepared allowing for the reproducible adsorption of covalently attached sensitizing dyes. Once reproducible surfaces and dye coverages are achieved, a photochronocoulometric technique is developed to measure the surface coverage of the dyes, an important parameter in determining the efficiency of sensitization. The surface-bound dyes are irreversibly oxidized by exposure to a light pulse with the n-type oxide semiconductor electrode held in depletion. A double-exponential decay of the subsequent photocurrent is then measured, where the integration of the faster decay is associated with the adsorbed dye coverage and the second much slower decay is attributed to trace regenerators, including water, in the nonaqueous electrolyte. The ruthenium-based N3 dye shows the expected linear dependence of the rate constant on light intensity whereas a dicarboxylated thiacyanine dye shows a square root dependence of its photooxidation rate on light intensity. The sublinear response of the thiacyanine dye is discussed in terms of the more complex surface chemistry that is known for this family of sensitizing dyes.

Adsorption↗
PubMed2004

Electrochemical methods for the preparation of gold-coated TiO2 nanoparticles with variable coverages.

We report here the first electrochemical methods to prepare elemental Au0-coated TiO2 nanoparticles with controllable coverages. First, Au substrates were cycled in a deoxygenated aqueous solution containing 0.1 N HCl and 1 mM TiO2 nanoparticles from -0.28 to +1.22 V versus Ag/AgCl at 500 mV/s with different numbers of scans. The durations at the cathodic and anodic vertexes were 10 and 5 s, respectively. After this process, positively charged Au-coated TiO2 nanoparticles were formed in the solutions. Then a cathodic overpotential of 0.6 V from the open circuit potential of ca. 0.82 V versus Ag/AgCl was applied under sonication to synthesize elemental Au0-coated TiO2 nanoparticles. The coverage of Au shells in the elemental Au-coated TiO2 nanoparticles is varied from 10% to 95% by increasing the number of scans from 10 to 50 in preparing the positively charged Au-coated TiO2 nanoparticles. The extremely high coverage of 95% in this study is notable, as compared with other methods to prepare Au-coated TiO2 nanoparticles.

Journal Article↗
PubMed2006

Quantifying surface coverage of colloidal silica by a cationic peptide using a combined centrifugation/time-resolved fluorescence anisotropy approach.

Recent experimental studies have shown that time-resolved fluorescence anisotropy (TRFA) is a promising methodology for in situ characterization of the surface modification of aqueous silica nanocolloids. Here we provide a more fundamental insight into the principle of this approach and discuss how the adsorption parameters for a cationic peptide, Lys-Trp-Lys (denoted using the standard shortform KWK), onto Ludox nanoparticles (NPs) are linked to the rotational dynamics of rhodamine 6G (R6G) dispersed in the KWK/Ludox mixture. First, the adsorption isotherm of KWK on hydrophilic controlled pore glass (CPG-3000) was obtained using the traditional centrifugation method, which provides the total molar amount of KWK per unit surface area of the silica. Assuming that both CPG and Ludox particles possess identical surface properties when suspended in the same aqueous buffer, both materials should also have identical adsorption properties. Thus, the adsorbed amount of KWK per unit area at a given total KWK concentration, as determined by the centrifugation method, can be plotted against the fractions of R6G anisotropy decay components at the same KWK concentration to relate the anisotropy components to the absolute surface coverage. Using this approach, it was determined that the concentration of KWK at which the CPG surface was saturated corresponded to the condition g = 0 in the R6G decay, where g is the fraction of the nondecaying anisotropy component. This condition means that there is no R6G bound to the fraction of Ludox NPs with a radius R > 2.5 nm at maximum KWK coverage, consistent with the adsorbed peptide forming a continuous layer on the Ludox surface. Hence, the g value obtained from TRFA analysis can be used to assess the absolute surface coverage of monolayer coatings on colloidal nanoparticles.

Centrifugation↗