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Biomedical subjects

J M White

Publications and source records attributed to J M White.

At least 19 recordsLinked to original sources
PubMed2006

Imaging water dissociation on TiO2(110): Evidence for inequivalent geminate OH groups.

Identical regions of partially reduced TiO2(110) surfaces with bridge-bonded oxygen vacancy (BBO(V)) concentrations of approximately 10% ML (1 ML = 5.2 x 10(14) cm(-2)) were imaged using scanning tunneling microscopy (STM) before and after dosing H2O at ambient temperature (approximately 300 K). Atomically resolved images confirm that H2O adsorbs dissociatively on the BBO(V) sites, producing two hydroxyl species, one positioned at BBO(V) and denoted OH(V) and the other, denoted OH(B), formed by protonation at either of the two nearest-neighbor bridge-bonded oxygen atoms. Hydrogen hopping along the [001] direction is observed at ambient temperature, with a strong preference for OH(B) (approximately 10x) hydrogen motion. This powerful imbalance demonstrates the inequality of OH(V) and OH(B) and suggests differences in their charge and/or binding configuration.

Journal Article↗
PubMed2006

Growth and analysis of octadecylsiloxane monolayers on Al2O3 (0001).

On solvent-cleaned and piranha-etched single-crystal Al2O3(0001) surfaces, uniform, robust, self-assembled monolayers of octadecylsiloxane (ODS) are formed by 48 h exposure to a solution containing octadecyltrichlorosilane (OTS) in an anhydrous atmosphere. X-ray photoelectron spectroscopy, atomic force microscopy, ellipsometry, and water contact angle measurements confirm the presence of a uniform, complete monolayer. Reducing the exposure time or omitting the piranha-etch leads to much less uniform coverage. The ODS monolayers are stable when stored in ambient atmospheres for month-long periods. Thermal desorption in a vacuum environment (10(-9) Torr) shows the ODS monolayer is thermally stable up to at least 420 K. When heated in 200 mTorr of flowing forming gas (N2-10% H2) for 1 h at 520 K, slow loss of ODS was indicated. A schematic model is proposed which involves island nucleation by covalent bonding of OTS to surface hydroxyl groups followed by growth through the addition of mobile ODS species.

Aluminum Oxide↗
PubMed2006

Low-temperature preparation of anatase thin films on tantalum.

Titanium dioxide thin films were grown on oxidized Ta surfaces using a cyclic layer-by-layer wet chemistry method: successive-ionic-layer-adsorption-and-reaction (SILAR). Film thicknesses varied monotonically and approximately linearly with the number of cycles. As-grown (AG) films were amorphous and rougher (16.2 nm root-mean-square (rms)) than the Ta substrate (10.2 nm rms). After hydrothermal annealing (AN) at a remarkably low temperature of 393 K, the films exhibited anatase crystallites (10 nm dimensions) and reduced roughness (11.8 nm rms). The atomic composition of both AG and AN films was consistent with that of TiO2 containing no more than 4 atom % carbon. A small Si impurity (<1 atom %) was eliminated by using polypropylene beakers and sample holders in the SILAR steps.

Membranes, Artificial↗
PubMed2006

Water activated by atomic oxygen on Au(111) to oxidize CO at low temperatures.

The Au(111) surface was populated with atomic oxygen [16O] followed by oxygen-labeled water [H218O] at surface temperatures as low as 77 K. When a CO beam was impinged on this surface, both [C16O16O] and [C16O18O] were produced. The results strongly suggest the direct involvement and promoting role of water in CO oxidation on oxygen covered Au(111) at low temperatures.

Journal Article↗
PubMed2006

Imaging adsorbate O-H bond cleavage: methanol on TiO2(110).

We investigated methanol adsorption and dissociation on bridge-bonded oxygen vacancies of the TiO2(110)-(1x1) surface using in situ scanning tunneling microscopy. We provide the first direct evidence that methanol dissociates on oxygen vacancies via O-H bond scission rather than C-O scission. For CH3OH coverages lower than the oxygen vacancy concentration, stationary methoxy-hydroxyl pairs form. At CH3OH coverages close to the oxygen vacancy concentration undissociated mobile CH3OH interacts with methoxy-hydroxyl pairs and facilitates the movement of hydroxyl away from the methoxy group.

Journal Article↗
PubMed2006

Two-photon photoemission spectroscopy study of 1,3-butadiene on Cu(111): electronic structures and excitation mechanism.

The characteristics of 1,3-butadiene (C(4)H(6)) adsorbed on Cu(111) were investigated with temperature-programmed desorption (TPD) and two-photon photoemission spectroscopy (2PPE). Dosed at 90 K, the work function drops by 0.4 eV and TPD provides no evidence for dissociation, but there are four coverage-dependent local maxima located at 195, 135, 121, and 115 K. From the 2PPE spectra, three unoccupied electronic states of the C(4)H(6)-Cu(111) system were identified: the LUMO (pi(1)*, 2a(u)), LUMO + 1 (pi(2)*, 2b(g)), and LUMO + 2 (sigma*, 7b(u)), lying 1.3, 3.4, and 4.8 eV above the Fermi level, respectively. Although the excitation mechanisms for the LUMO and LUMO + 1 are substrate mediated, the excitation of the LUMO + 2 is attributed to intramolecular excitation.

Journal Article↗
PubMed2006

Vaccine coverage in England: the impact of health service reorganisation.

AIM: To evaluate the impact of reorganisation of the health service and a change in the definition used to collect immunisation coverage statistics on vaccine coverage data in England. METHODS: Denominator data from the Cover Of Vaccination Evaluated Rapidly (COVER) programme, the national programme for the collection of immunisation coverage statistics, were compared to the Office for National Statistics (ONS) population data; the impact of any discrepancies between the two data sources on vaccine coverage was assessed. RESULTS: ONS populations were generally larger than COVER populations. This was particularly true for 2002, the year Primary Care Trusts (PCTs) came into existence, suggesting that some children are being missed by the COVER programme. On average, in 1998-2001 around 10,000 children per year (approximately 2%) were lost to the COVER population estimates compared to data from ONS. This increased to around 20,000-40,000 (approximately 3-8%) children in 2002, but decreased again in 2003 to 2000-8000 (approximately 1%) children. Assuming all the "lost" COVER children were vaccinated, vaccine coverage appeared very similar to that seen in the COVER programme for all antigens. However, assuming all the "lost" children were unvaccinated, coverage would be substantially lower for all antigens (range 2.7-3.5%). DISCUSSION: This analysis provides a quantitative example of how changes such as restructuring of the health service directly impact on public health surveillance. Such changes have potential risks for information and may affect important data used to inform public health policy.

Child Health Services↗
PubMed2006

The addition of oral idarubicin to a chlorambucil/dexamethasone combination has a significant impact on time to treatment failure but none on overall survival in patients with low grade non-Hodgkin's lymphoma: Results of the Scotland and Newcastle Lymphoma Group randomized NHL VIII trial.

Two hundred untreated patients with low grade NHL (KIEL), including 155 follicular NHL, were randomized to six courses of treatment with chlorambucil 20 mg m-2 for 3 days and dexamethasone 4 mg bd for 5 days (CD) vs the same regimen plus oral idarubicin 10 mg m-2 for 3 days (CID). Responding patients could be randomized to no further treatment or maintenance treatment for up to 36 months with alpha interferon. Complete remissions/CRu were more frequent in the CID arm (35% vs 24%) but the overall response rate was similar; 87/91 (96%) vs 86/92 (93%). Overall survival (OS) did not differ between the two arms. Time to treatment failure (TTTF) was prolonged in the CID arm, p = 0.03; median time 28 vs 19 months. TTTF for the B-cell follicular group alone was for CID (77 patients) 33 months vs 18 months for CD (78 patients). Interferon conferred no apparent benefit. The Follicular Lymphoma International Prognostic Index (FLIPI) is confirmed as a good predictor of risk groups including a group of 23% with shorter survival. The addition of the oral anthracycline, idarubicin, led to a significant improvement in TTTF with low toxicity. The use of radiotherapy in this sub-group may have contributed to this result. CID is a potential for combination with antibody therapy particularly in older patient groups.

Administration, Oral↗
PubMed2006

BCL2 gene abnormalities define distinct clinical subsets of follicular lymphoma.

AIMS: Follicular lymphoma (FL) arising primarily in the skin has recently been proposed as a distinct entity on the basis of a low incidence of t(14;18)(q32;q21) and bcl-2 expression, with a very high percentage of patients surviving more than 5 years. However, cases of t(14;18)(q32;q21)-positive primary cutaneous FL (PCFL) and examples of t(14;18)(q32;q21)-negative FL at nodal and other extranodal sites, are well documented. The aim of this study was to test the hypothesis that there is a subtype of FL lacking t(14;18)(q32;q21), which preferentially involves certain sites but is not restricted by anatomical location. METHODS AND RESULTS: A cohort of 47 stage 1 FL was stratified according to the presence or absence of t(14;18)(q32;q21) using conventional cytogenetics, polymerase chain reaction and interphase fluorescence in situ hybridization. Compared with t(14;18)(q32;q21)-positive cases, FL lacking the translocation were less likely to express CD10 or bcl-2 (P<0.01), made up a significantly greater proportion of cases arising at extranodal sites (P<0.001) and had a significantly better overall and disease-specific 5-year survival (P<0.01). CONCLUSIONS: These results support the concept of a subtype of FL lacking t(14;18)(q32;q21), characterized by low-intensity bcl-2 expression, a predilection for extranodal sites, particularly the skin, and a more favourable outcome than t(14;18)(q32;q21)-positive FL.

Adult↗
PubMed2005

Thermal and photochemistry of tert-butyl iodide on rutile TiO2(110).

The thermal and photochemistry of tert-butyl iodide (t-buI) dosed at 100 K on rutile TiO2(110) has been studied using isothermal and temperature programmed desorption mass spectrometry. Nondissociative adsorption and desorption dominate the thermal behavior with dose-dependent t-buI desorption peaks at nominally 220 and 150 K. Ultraviolet photochemistry occurs readily, but the behavior of submonolayers and multilayers differ qualitatively. Ejection of t-buI and i-C4H8 dominate during submonolayer photolysis at 100 K. Multilayer photolysis results are also dominated by ejection during irradiation, but the t-buI component is strongly suppressed, and the maximum rates of i-C4H8 and HI ejection did not occur at the outset. A mechanistic model capturing the observations involves both direct and substrate-mediated electronic excitation of t-buI. According to this model, ejection of t-buI occurs only from transient substrate-mediated formation of anionic t-buI. For either excitation path, the C-I dissociation probability is significant, and the excited tert-butyl product rearranges readily to form i-C4H8 that is ejected. For any local region where there is multilayer coverage, products formed at the adsorbate-vacuum interface are ejected promptly, but products formed within the multilayer are trapped. Thus, ejection of t-buI is suppressed, and trapped primary photodissociation products, tert-butyl and I, react to either reform t-buI or rearrange to i-C4H8 and HI. The latter two products remain trapped and are subsequently induced to desorb by acquisition of momentum from collisions with subsequently formed translationally excited photodissociation products.

Journal Article↗
PubMed2005

Trimethyl acetate on TiO2(110): preparation and anaerobic photolysis.

The preparation and anaerobic ultraviolet photolysis of trimethyl acetate (TMA) on rutile TiO(2)(110) have been examined with an emphasis on reaction paths. Substrates for photolysis were prepared by dosing trimethyl acetic acid at 100, 300, and 550 K. The chemistry was characterized by mass spectrometry during dosing and by H(2)O adsorption and temperature programmed desorption (TPD) after dosing. Using TPD after photolysis and mass spectrometry during photolysis, the products ejected and retained during photolysis were sought. The photolysis results are interpreted using the following mechanistic model. Photons with energies exceeding 3 eV create electron-hole pairs in the substrate. With probabilities of 10(-5) or lower, the holes initiate TMA chemistry by extracting an electron from the pi orbital of the carboxylate moiety. The accompanying electrons are trapped at the surface and inhibit subsequent events of this chemistry. The electron-deficient intermediate, TMA, decarboxylates to form CO(2) and either chemisorbed tert-butyl (-C(CH(3))(3)) or physisorbed i-butene. For photolysis at 100 or 200 K, the -C(CH(3))(3) accumulates and there is a slow photon-driven secondary reaction that, with a source of H, hydrogenates adsorbed tert-butyl to physisorbed i-butane. For photolysis at 300 K, -C(CH(3))(3) thermally reacts to form and desorb i-butene and i-butane during photolysis.

Journal Article↗
PubMed2005

Self-assembled silane monolayers: fabrication with nanoscale uniformity.

Illustrating direct connections between surface chemical events and mechanical and topological characteristics of self-assembled monolayers derived from octadecyltrichlorosilane (OTS) adsorption on Si(100), layers prepared in the presence and absence of moisture have been characterized. Uniform and robust self-assembled monolayers are demonstrated provided the Si(100) surface is fully hydroxylated by treatment in piranha solution and the dried surface is exposed to OTS under strict anhydrous conditions. With nanoscale resolution, the uniform mechanical properties are confirmed by interfacial force microscopy while the uniform topological properties are evident in atomic force microscopy images. The monolayer character of the OTS coverage is confirmed by X-ray photoelectron spectroscopy, ellipsometry, and patterning experiments. Analogous surfaces, prepared in the presence of moisture, exhibit nonuniform topological and mechanical properties.

Journal Article↗
PubMed2005

The many mechanisms of viral membrane fusion proteins.

Every enveloped virus fuses its membrane with a host cell membrane, thereby releasing its genome into the cytoplasm and initiating the viral replication cycle. In each case, one or a small set of viral surface transmembrane glycoproteins mediates fusion. Viral fusion proteins vary in their mode of activation and in structural class. These features combine to yield many different fusion mechanisms. Despite their differences, common principles for how fusion proteins function are emerging: In response to an activating trigger, the metastable fusion protein converts to an extended, in some cases rodlike structure, which inserts into the target membrane via its fusion peptide. A subsequent conformational change causes the fusion protein to fold back upon itself, thereby bringing its fusion peptide and its transmembrane domain-and their attached target and viral membranes-into intimate contact. Fusion ensues as the initial lipid stalk progresses through local hemifusion, and then opening and enlargement of a fusion pore. Here we review recent advances in our understanding of how fusion proteins are activated, how fusion proteins change conformation during fusion, and what is happening to the lipids during fusion. We also briefly discuss the therapeutic potential of fusion inhibitors in treating viral infections.

Animals↗
PubMed2005

Temperature rise of the post and on the root surface during ultrasonic post removal.

AIM: To determine the temperature rise on the root surface caused by ultrasonic post removal using different devices and techniques in a laboratory setting. METHODOLOGY: Two ultrasonic devices, one piezoelectrical (Pi) and one magnetostrictive (Ma), were investigated. A serrated titanium post was placed into the distal root canal of a human mandibular first molar. Four coolant parameters were utilized: no air, no water, no evacuation (NN), air only with high-speed evacuation (A), 15 mL min(-1) water coolant with high-speed evacuation (W15) and 30 mL min(-1) water coolant with high-speed evacuation (W30). Five simulated post removals were measured at two locations, the post (P) and the root (R), for each coolant parameter. Temperature rise was measured at 30, 60, 90 and 120 s intervals using calibrated infrared thermography (n = 80). Temperatures were recorded at 45 ms intervals. Data were analysed using repeated measures anova with the Scheffe post hoc test (P < or = 0.05). RESULTS: The overall mean pooled effect showed that temperature rise for P = 20.1 +/- 27.9 degrees C and R = 10.9 +/- 7.9 degrees C were significantly different. Significant differences in temperature rise were: Pi > Ma, P > R, NN > A = W15 = W30 however, A > W30. CONCLUSIONS: There were significant differences in temperature rise as a function of ultrasonic device, location on the tooth and cooling method utilized for post removal.

Air↗
PubMed2004

Directly probing the hybrid bonding of styrene on Cu111.

The interfacial electronic structure of chemisorbed styrene on Cu(111) was successfully investigated with two-photon photoemission spectroscopy. We observed unoccupied states 3.5 eV above the Fermi level and occupied states 2.0 eV below the Fermi level. Polarization results reveal that the occupied and unoccupied states arise from bonding and antibonding orbitals formed by hybridization of copper (surface state and d-band orbitals) and styrene (pi1* and pi2* orbitals).

Journal Article↗
PubMed2004

Clusters of meningococcal disease in school and preschool settings in England and Wales: what is the risk?

AIMS: To assess the risk of further cases in educational settings in order to inform policy on managing cases and clusters of meningococcal disease. METHODS: Between 1 April 1995 and 31 March 2001, surveillance in preschool and school settings in England and Wales identified 114 clusters of meningococcal disease. Twenty clusters were reported in preschool settings, 43 in primary, 46 in secondary, and five in independent schools. Seventy three clusters (64%) consisted of two or more confirmed cases, of which 30 had two or more serogroup C cases. Following the introduction of the national meningococcal serogroup C vaccination programme in 1999, no serogroup C clusters were observed between April 2000 and March 2001. RESULTS: The relative risk of further cases in the four weeks after a single case compared with the background rate was raised in all settings, ranging from RR 27.6 (95% CI 15.2 to 39.9) in preschool settings to RR 3.6 (95% CI 2.5 to 4.6) in secondary schools. Absolute risk estimates ranged from 70/100 000 in preschool settings to 3.0/100 000 in secondary schools. The relative risk of clustering was similar for serogroup B and C strains. Most (68%) second cases occurred within seven days of the first case. CONCLUSIONS: Although there was a higher risk of further cases of meningococcal disease in schools and especially in preschool settings, it is not known whether widespread antibiotic use after single cases reduces risk of further cases and if there is a real risk of harm. Evidence of risk reduction is needed to inform public health policy.

Child↗