Emissions and Exposures Associated with the Use of an Inconel Powder during Directed Energy Deposition Additive Manufacturing.

Additive manufacturing (AM) has been linked to potential exposure-related health risks, however, there is a paucity of sufficient research. This study aimed to supply information regarding emissions and exposure during directed energy deposition (DED) AM using inconel 718, with the main constituents being nickel, chromium, and cobalt. By using standardized occupational hygiene methods, the measurement strategy consisted of a combined approach, including powder characterization, particle emission monitoring, and personal exposure monitoring of AM operators. Powder characterization of virgin and used powder indicated no significant difference in particle size, shape, or elemental composition. Particle number emissions ranged between 102 and 105 p/cm3 for submicron particles (<1 µm in size). There was no significant difference in the particle emission rate between the three phases of AM or the two types of DED machines (p > 0.05). The particle emission rate for submicron particles peaked at 2.8 × 109 p/min. Metals of concern to human health were detected during the AM process but were considerably lower than the relevant exposure limits. This study confirms particle emissions, predominantly in the submicron range, above the background concentration during DED AM and, although insignificant in terms of potential health effects, AM operators are exposed to detectable concentrations of the metal constituents of inconel.

Malignant extracranial germ cell tumours: A first national report by the South African Children's Cancer Study Group.

OBJECTIVE: To determine the overall survival (OS) and prognostic factors influencing outcomes in children and adolescents with malignant extracranial germ cell tumours (MEGCTs) in preparation for the development of a harmonised national treatment protocol. METHODS: A retrospective folder review was undertaken at nine South African paediatric oncology units to document patient profiles, tumour and treatment-related data and outcomes for all children with biopsy-proven MEGCTs from birth up to and including 16 years of age. RESULTS: Between 1 January 2000 and 31 December 2015, 218 patients were diagnosed with MEGCTs. Female sex (hazard ratio [HR] 0.284, p = .037) and higher socio-economic status (SES) (HR 0.071, p = .039) were associated with a significantly lower risk of death. Advanced clinical stage at diagnosis significantly affected 5-year OS: stage I: 96%; stage II: 94.3%; stage III: 75.5% (p = .017) and stage IV (60.1%; p < .001). There was a significant association between earlier stage at presentation and higher SES (p = .03). Patients with a serum alpha-fetoprotein (AFP) level of more than 33,000 ng/ml at diagnosis had significantly poorer outcomes (p = .002). The use of chemotherapy significantly improved survival, irrespective of the regimen used (p < .001). CONCLUSIONS: The cohort demonstrated a 5-year OS of 80.3% with an event-free survival (EFS) of 75.3%. Stage, the use of chemotherapy and an elevated serum AFP level of more than 33,000 ng/ml were independently predictive of outcome. The relationship between SES and outcome is important as the implementation of the new national protocol hopes to standardise care across the socio-economic divide.

Large-Format Additive Manufacturing and Machining Using High-Melt-Temperature Polymers. Part I: Real-Time Particulate and Gas-Phase Emissions.

The literature on emissions during material extrusion additive manufacturing with 3-D printers is expanding; however, there is a paucity of data for large-format additive manufacturing (LFAM) machines that can extrude high-melt-temperature polymers. Emissions from two LFAM machines were monitored during extrusion of six polymers: acrylonitrile butadiene styrene (ABS), polycarbonate (PC), high-melt-temperature polysulfone (PSU), poly(ether sulfone) (PESU), polyphenylene sulfide (PPS), and Ultem (poly(ether imide)). Particle number, total volatile organic compound (TVOC), carbon monoxide (CO), and carbon dioxide (CO2) concentrations were monitored in real-time. Particle emission rate values (no./min) were as follows: ABS (1.7 × 1011 to 7.7 × 1013), PC (5.2 × 1011 to 3.6 × 1013), Ultem (5.7 × 1012 to 3.1 × 1013), PPS (4.6 × 1011 to 6.2 × 1012), PSU (1.5 × 1012 to 3.4 × 1013), and PESU (2.0 to 5.0 × 1013). For print jobs where the mass of extruded polymer was known, particle yield values (g-1 extruded) were as follows: ABS (4.5 × 108 to 2.9 × 1011), PC (1.0 × 109 to 1.7 × 1011), PSU (5.1 × 109 to 1.2 × 1011), and PESU (0.8 × 1011 to 1.7 × 1011). TVOC emission yields ranged from 0.005 mg/g extruded (PESU) to 0.7 mg/g extruded (ABS). The use of wall-mounted exhaust ventilation fans was insufficient to completely remove airborne particulate and TVOC from the print room. Real-time CO monitoring was not a useful marker of particulate and TVOC emission profiles for Ultem, PPS, or PSU. Average CO2 and particle concentrations were moderately correlated (r s = 0.76) for PC polymer. Extrusion of ABS, PC, and four high-melt-temperature polymers by LFAM machines released particulate and TVOC at levels that could warrant consideration of engineering controls. LFAM particle emission yields for some polymers were similar to those of common desktop-scale 3-D printers.

Large-Format Additive Manufacturing and Machining Using High-Melt-Temperature Polymers. Part II: Characterization of Particles and Gases.

Extrusion of high-melt-temperature polymers on large-format additive manufacturing (LFAM) machines releases particles and gases, though there is no data describing their physical and chemical characteristics. Emissions from two LFAM machines were monitored during extrusion of acrylonitrile butadiene styrene (ABS) and polycarbonate (PC) polymers as well as high-melt-temperature Ultem (poly(ether imide)), polysulfone (PSU), poly(ether sulfone) (PESU), and polyphenylene sulfide (PPS) polymers. Filter samples of particles were collected for quantification of elements and bisphenol A and S (BPA, BPS) and visualization of morphology. Individual gases were quantified on substance-specific media. Aerosol sampling demonstrated that concentrations of elements were generally low for all polymers, with a maximum of 1.6 mg/m3 for iron during extrusion of Ultem. BPA, an endocrine disruptor, was released into air during extrusion of PC (range: 0.4 ± 0.1 to 21.3 ± 5.3 µg/m3). BPA and BPS (also an endocrine disruptor) were released into air during extrusion of PESU (BPA, 2.0-8.7 µg/m3; BPS, 0.03-0.07 µg/m3). Work surfaces and printed parts were contaminated with BPA (<8-587 ng/100 cm2) and BPS (<0.22-2.5 ng/100 cm2). Gas-phase sampling quantified low levels of respiratory irritants (phenol, SO2, toluene, xylenes), possible or known asthmagens (caprolactam, methyl methacrylate, 4-oxopentanal, styrene), and possible occupational carcinogens (benzene, formaldehyde, acetaldehyde) in air. Characteristics of particles and gases released by high-melt-temperature polymers during LFAM varied, which indicated the need for polymer-specific exposure and risk assessments. The presence of BPA and BPS on surfaces revealed a previously unrecognized source of dermal exposure for additive manufacturing workers using PC and PESU polymers.

Associations of outdoor fine particulate air pollution and cardiovascular disease in 157 436 individuals from 21 high-income, middle-income, and low-income countries (PURE): a prospective cohort study.

BACKGROUND: Most studies of long-term exposure to outdoor fine particulate matter (PM2·5) and cardiovascular disease are from high-income countries with relatively low PM2·5 concentrations. It is unclear whether risks are similar in low-income and middle-income countries (LMICs) and how outdoor PM2·5 contributes to the global burden of cardiovascular disease. In our analysis of the Prospective Urban and Rural Epidemiology (PURE) study, we aimed to investigate the association between long-term exposure to PM2·5 concentrations and cardiovascular disease in a large cohort of adults from 21 high-income, middle-income, and low-income countries. METHODS: In this multinational, prospective cohort study, we studied 157 436 adults aged 35-70 years who were enrolled in the PURE study in countries with ambient PM2·5 estimates, for whom follow-up data were available. Cox proportional hazard frailty models were used to estimate the associations between long-term mean community outdoor PM2·5 concentrations and cardiovascular disease events (fatal and non-fatal), cardiovascular disease mortality, and other non-accidental mortality. FINDINGS: Between Jan 1, 2003, and July 14, 2018, 157 436 adults from 747 communities in 21 high-income, middle-income, and low-income countries were enrolled and followed up, of whom 140 020 participants resided in LMICs. During a median follow-up period of 9·3 years (IQR 7·8-10·8; corresponding to 1·4 million person-years), we documented 9996 non-accidental deaths, of which 3219 were attributed to cardiovascular disease. 9152 (5·8%) of 157 436 participants had cardiovascular disease events (fatal and non-fatal incident cardiovascular disease), including 4083 myocardial infarctions and 4139 strokes. Mean 3-year PM2·5 at cohort baseline was 47·5 µg/m3 (range 6-140). In models adjusted for individual, household, and geographical factors, a 10 µg/m3 increase in PM2·5 was associated with increased risk for cardiovascular disease events (hazard ratio 1·05 [95% CI 1·03-1·07]), myocardial infarction (1·03 [1·00-1·05]), stroke (1·07 [1·04-1·10]), and cardiovascular disease mortality (1·03 [1·00-1·05]). Results were similar for LMICs and communities with high PM2·5 concentrations (>35 µg/m3). The population attributable fraction for PM2·5 in the PURE cohort was 13·9% (95% CI 8·8-18·6) for cardiovascular disease events, 8·4% (0·0-15·4) for myocardial infarction, 19·6% (13·0-25·8) for stroke, and 8·3% (0·0-15·2) for cardiovascular disease mortality. We identified no consistent associations between PM2·5 and risk for non-cardiovascular disease deaths. INTERPRETATION: Long-term outdoor PM2·5 concentrations were associated with increased risks of cardiovascular disease in adults aged 35-70 years. Air pollution is an important global risk factor for cardiovascular disease and a need exists to reduce air pollution concentrations, especially in LMICs, where air pollution levels are highest. FUNDING: Full funding sources are listed at the end of the paper (see Acknowledgments).

Health Effects of Household Solid Fuel Use: Findings from 11 Countries within the Prospective Urban and Rural Epidemiology Study.

BACKGROUND: Household air pollution (HAP) from solid fuel use for cooking affects 2.5 billion individuals globally and may contribute substantially to disease burden. However, few prospective studies have assessed the impact of HAP on mortality and cardiorespiratory disease. OBJECTIVES: Our goal was to evaluate associations between HAP and mortality, cardiovascular disease (CVD), and respiratory disease in the prospective urban and rural epidemiology (PURE) study. METHODS: We studied 91,350 adults 35­70 y of age from 467 urban and rural communities in 11 countries (Bangladesh, Brazil, Chile, China, Colombia, India, Pakistan, Philippines, South Africa, Tanzania, and Zimbabwe). After a median follow-up period of 9.1 y, we recorded 6,595 deaths, 5,472 incident cases of CVD (CVD death or nonfatal myocardial infarction, stroke, or heart failure), and 2,436 incident cases of respiratory disease (respiratory death or nonfatal chronic obstructive pulmonary disease, pulmonary tuberculosis, pneumonia, or lung cancer). We used Cox proportional hazards models adjusted for individual, household, and community-level characteristics to compare events for individuals living in households that used solid fuels for cooking to those using electricity or gas. RESULTS: We found that 41.8% of participants lived in households using solid fuels as their primary cooking fuel. Compared with electricity or gas, solid fuel use was associated with fully adjusted hazard ratios of 1.12 (95% CI: 1.04, 1.21) for all-cause mortality, 1.08 (95% CI: 0.99, 1.17) for fatal or nonfatal CVD, 1.14 (95% CI: 1.00, 1.30) for fatal or nonfatal respiratory disease, and 1.12 (95% CI: 1.06, 1.19) for mortality from any cause or the first incidence of a nonfatal cardiorespiratory outcome. Associations persisted in extensive sensitivity analyses, but small differences were observed across study regions and across individual and household characteristics. DISCUSSION: Use of solid fuels for cooking is a risk factor for mortality and cardiorespiratory disease. Continued efforts to replace solid fuels with cleaner alternatives are needed to reduce premature mortality and morbidity in developing countries. https://doi.org/10.1289/EHP3915.

Transepidermal water loss, stratum corneum hydration, and skin surface pH of female African and Caucasian nursing students.

BACKGROUND: Conflicting evidence exists on how skin barrier function compares between Africans and Caucasians. This study measured skin barrier function of South African first year nursing students before their practical training started to compare skin barrier function between the racial groups. METHODS: Transepidermal water loss (TEWL), stratum corneum (SC) hydration, and skin surface (SS) pH was measured on female first year nursing students (19 African and 31 Caucasian; age range 18-40 years). Geometric means and ranges were calculated and the influence of anatomical areas and racial differences were evaluated respectively. RESULTS: No significant difference in TEWL was established between the racial groups. SC hydration was significantly lower (P ≤ 0.05) and SS-pH was significantly higher (P ≤ 0.0001) in African nursing students when compared to Caucasians. African nursing students had significantly lower (P ≤ 0.05) SC hydration on their palms when compared to the other anatomical areas. CONCLUSION: Stratum corneum hydration and SS-pH differed significantly between African and Caucasian skin, while no difference was found for TEWL, the primary parameter used to evaluate skin barrier function. Low SC hydration and high SS-pH of African nursing students prior to their practical training, may suggest a higher risk for developing occupational skin diseases.

Measurement of Skin Surface pH.

The acidic nature of the skin surface was recognised more than a century ago and has been measured since 1928. Several non-invasive methods for measuring skin surface pH have been developed ever since and have contributed to our understanding of healthy and diseased skin. This chapter summarises the endogenous physiological, exogenous and environmental factors that influence skin surface pH and its measurement as well as the different measurement methods for skin surface pH, with specific emphasis on the classic planar glass electrode method. Also, practical guidance for measurement of skin surface pH using the planar glass electrode method is provided. Adherence to practical skin surface pH measurement (method) guidelines with due consideration and practicable control of all factors that may affect skin surface pH will ensure credible pH measurement results in our continuous pursuit of understanding especially diseased skin.

Combining radar and direct observation to estimate pelican collision risk at a proposed wind farm on the Cape west coast, South Africa.

Pre-construction assessments of bird collision risk at proposed wind farms are often confounded by insufficient or poor quality data describing avian flight paths through the development area. These limitations can compromise the practical value of wind farm impact studies. We used radar- and observer-based methods to quantify great white pelican flights in the vicinity of a planned wind farm on the Cape west coast, South Africa, and modelled turbine collision risk under various scenarios. Model outputs were combined with pre-existing demographic data to evaluate the possible influence of the wind farm on the pelican population, and to examine impact mitigation options. We recorded high volumes of great white pelican movement through the wind farm area, coincident with the breeding cycle of the nearby colony and associated with flights to feeding areas located about 50 km away. Pelicans were exposed to collision risk at a mean rate of 2.02 High Risk flights.h-1. Risk was confined to daylight hours, highest during the middle of the day and in conditions of strong north-westerly winds, and 82% of High Risk flights were focused on only five of the proposed 35 turbine placements. Predicted mean mortality rates (22 fatalities.yr-1, 95% Cl, 16-29, with average bird and blade speeds and 95% avoidance rates) were not sustainable, resulting in a negative population growth rate (λ = 0.991). Models suggested that removal of the five highest risk turbines from the project, or institution of a curtailment regimen that shuts down at least these turbines at peak traffic times, could theoretically reduce impacts to manageable levels. However, in spite of the large quantities of high quality data used in our analyses, our collision risk model remains compromised by untested assumptions about pelican avoidance rates and uncertainties about the existing dynamics of the pelican population, and our findings are probably not reliable enough to ensure sustainable development.

A retrospective analysis of nickel exposure data at a South African base metal refinery.

This study aimed to analyze historical soluble nickel exposure data from a South African base metal refinery and to identify trends in the soluble nickel exposure from 1981 until 2014 in the electrowinning department. Exposure data were presented in an exposure matrix, which described exposure profiles for both area and personal exposures inside two tankhouses. Exposure data were standardized by converting total nickel aerosol concentrations to inhalable nickel concentrations (correction factor 3.0). One-way analyses of variances (ANOVA) were conducted to identify significant differences in log-transformed area and personal exposures from 1982 until 2014, and the trends were assessed with linear regression. Differences were evaluated in area exposure between sections inside the tankhouses, i.e., East, West, and Center bays and in personal exposure between occupations, i.e., cell workers, crane drivers, and supervisors. Area exposure in Tankhouse 1 declined significantly (p ≤ 0.0001) between 1982 and 1986 with a factor of 29. However, after 1986 no significant downward trend in area exposure was evident in Tankhouse 1. Personal exposures in Tankhouse 1 significantly (p ≤ 0.0001) decreased with a factor of three between 1991 and 2014. No significant trends were evident in area and personal exposure in Tankhouse 2. Downward exposure trends were evident in Tankhouse 1 and may be ascribed to the implementation of various control measures and process changes, e.g., increasing polypropylene bead load. Limited data were available for Tankhouse 2, therefore, no trend in exposure could be established. Retrospective analyses may be used to identify trends and anomalies in exposure which might not have been identified during daily exposure monitoring.

Lung function, inflammation and cardiovascular mortality in Africans.

BACKGROUND: The link between impaired lung function and cardiovascular outcome is well established in European and American populations. It is possible that this association may be driven by a systemic spillover of inflammation occurring within the lungs. As several studies have found an increased level of inflammatory markers in African populations, we aimed to establish the contribution of lung function in predicting all-cause and cardiovascular mortality in Africans, whilst taking inflammatory markers into account. DESIGN: We followed 1442 black South Africans from the North West Province participating in the South African leg of the Prospective Urban and Rural Epidemiology (PURE) study, over a five-year period. Spirometry, cardiovascular and metabolic measures were performed, and cardiovascular mortality as well as all-cause mortality used as endpoints. RESULTS: In univariate Cox regression models, both forced expiratory volume in 1-s (FEV1 ) and forced vital capacity (FVC) predicted all-cause (P = 0·022; P < 0·001) and cardiovascular mortality (P = 0·004; P < 0·001). In multivariate adjusted standardized Cox regression analyses, only FVC predicted cardiovascular mortality independent of several covariates (hazard ratio, 0·57 [0·35-0·94]), including C-reactive protein (CRP). When CRP was replaced by interleukin-6 in the model, the significance of FVC was lost (hazard ratio, 0·85 [0·55-1·30]). CONCLUSION: FVC, but not FEV1 , is a strong predictor of both all-cause and CV mortality in black South Africans, which may be mediated by inflammation.

Diffuse Reflectance Spectroscopy Versus Mexameter(®) MX18 Measurements of Melanin and Erythema in an African Population.

Melanin provides protection against excess exposure to solar ultraviolet radiation (UVR) and related adverse health effects. Diffuse reflectance spectroscopy (DRS) can be used to calculate cutaneous melanin and erythema, but this is complex and has been mostly used for light-to-medium pigmented skin. Handheld reflectance spectrophotometers, such as the Mexameter(®) MX18, can also be used. We compared DRS-calculated melanin and erythema values with Mexameter melanin and erythema index values to understand how these techniques/measurements correlate in an African population of predominantly deeply pigmented skin. Five hundred and three participants comprised 68.5% self-identified Black African, 9.9% Indian/Asian, 18.4% White and 2.9% Colored. The majority of Black African (45%), Indian/Asian (34%) and Colored (53%) participants self-identified their skin as being "brown." Measured melanin levels increased with darker self-reported skin color. DRS-calculated and Mexameter melanin values demonstrated a positive correlation (Spearman rho = 0.87, P < 0.001). The results from both instruments showed erythema values were strongly correlated with their own melanin values. This finding is considered spurious and may result from the complexity of separating brown and red pigment when using narrowband reflectance techniques. Further work is needed to understand melanin, erythema and color in Black skin given sun-related health risks in vulnerable groups in Africa.

Inflammation as Possible Mediator for the Relationship Between Lung and Arterial Function.

INTRODUCTION: Reduced lung function is associated with a risk for the development of cardiovascular disease. This association may be due to chronic inflammation which is often present in those with reduced lung function. PURPOSE: We investigated the possible role of systemic inflammation as the mediator between lung function and arterial stiffness in 1534 black South Africans. METHODS: Spirometric data including forced expiratory volume in 1 s (FEV1) and forced vital capacity (FVC) were obtained. C-reactive protein (CRP), interleukin-6 (IL-6), blood pressure (BP) and carotid-radial pulse wave velocity (PWV) were determined. RESULTS: In multivariable-adjusted models, an independent inverse association was found between IL-6 and FEV1 (ß = -0.20, p < 0.001) and FVC (ß = -0.18, p < 0.001). Similar results were found for CRP. PWV was inversely associated with FEV1 (ß = -0.06, p = 0.037). No association was found between inflammatory markers, BP or PWV. CONCLUSION: Reduced lung function was associated with increased inflammation and arterial stiffness. The lack of association between arterial stiffness and inflammatory markers suggests that inflammation may not be the mediating link between lung and vascular function in this population.

Towards task shifting? A comparison of the accuracy of acute trauma-radiograph reporting by medical officers and senior radiographers in an African hospital.

INTRODUCTION: Due to the universal shortage of radiologists, medical officers are largely responsible for acute trauma radiograph reporting in public sector healthcare facilities in well-resourced countries. In poorly-resourced countries, a shortage of medical officers results in most acute trauma radiographs being unreported. In the European Union (EU), experienced radiographers with no specific training have been shown to be more accurate than medical officers in trauma radiograph reporting, while EU radiographers who receive additional training can reach accuracies comparable to radiologists. In some EU countries, the role of the radiographer has been extended to include trauma reporting. However, there has been no study of the accuracy of trauma radiograph reporting by radiographers in Africa, where task-shifting could yield potentially greater benefits, due to shortages of both radiologists and medical officers. The aim of this study was therefore to compare the accuracy of acute trauma-radiograph reporting by medical officers and senior radiographers in an African setting. METHODS: A prospective study was conducted at a South African hospital from November 2013-April 2014. Medical officers and senior radiographers reported the same set of appendicular skeleton trauma radiographs. Reporting accuracy, sensitivity and specificity were calculated using a consultant radiologist's report as the reference standard. Differences were evaluated using the Mann-Whitney U test, with p < 0.05 significant. RESULTS: Senior radiographers achieved significantly higher reporting accuracy and sensitivity than medical officers (81.5% vs 67.8%, p = 0.002). CONCLUSION: Senior radiographers represent a potentially important resource for acute trauma-radiograph reporting in the public healthcare sector in Africa.

Self-reported skin colour and erythemal sensitivity vs. objectively measured constitutive skin colour in an African population with predominantly dark skin.

BACKGROUND: Skin colour is an important factor in skin-related diseases. Accurate determination of skin colour is important for disease prevention and supporting healthy sun behaviour, yet such data are lacking for dark skin types. METHODS: Self-perceived, natural skin colour and sun-skin reaction were compared with objectively measured skin colour among an African population with predominantly dark skin. Unexposed skin of 556 adults (70.1% Black) was measured with a reflectance spectrophotometer to calculate an individual typology angle (°ITA). Participants reported self-perceived skin colour and erythemal sensitivity. RESULTS: There was a strong, positive monotonic correlation between self-reported and measured skin colour (Spearman ρ = 0.6438, P < 0.001), but only a weak correlation between self-reported erythemal sensitivity and measured skin colour (Spearman ρ = 0.2713, P < 0.001). Self-report biases in underestimation and overestimation of skin colour were evident. Many participants with 'dark brown' and 'black' skin had difficulty in classifying erythemal sensitivity. CONCLUSIONS: In Africa, self-reported skin colour could potentially be used in lieu of spectrophotometer measurements, but options for questions on sunburn and tanning require suitable adjustment. Our study provides evidence of range in °ITA values among residents in Africa and reinforces previous results that self-report may be reliable for determining skin colour, but not erythemal sensitivity, for dark skin individuals.

South African and international reference values for lung function and its relationship with blood pressure in Africans.

BACKGROUND: In South Africa respiratory diseases are highly prevalent, with cardiovascular disease being a manifestation. However, international reference values for lung function are commonly used, which may not be appropriate to correctly identify reduced lung function. An inverse relationship exists between lung function and blood pressure (BP) but is not investigated extensively in black South Africans. METHODS: We included 2010 Africans from the PURE (Prospective Urban Rural Epidemiology) study (aged > 35 years) in the North West Province. Spirometry was performed and predicted values for forced expiratory volume in one second (FEV1) and forced vital capacity (FVC) were calculated from South African, European and United States prediction equations. RESULTS: With the exception of the European predicted values, all other predicted mean FEV1 and FVC were above 80%. South African reference values displayed the highest percentages of the predicted values for FEV1 and FVC (87.9 and 99.7%, respectively.) BP increased from quintiles five to one for both FEV1 and FVC, (p for trend <0.001). After adjustment the differences remained (p<0.05). CONCLUSIONS: South African reference values yielded higher percentages of predicted FEV1 and FVC values than European and US equations suggesting that South African prediction equations may be more useful when investigating lung function in black South Africans. Elevated BP is related to reduced lung function, highlighting the importance in managing both respiratory- and cardiovascular disease.

Toward complete miniaturisation of flow injection analysis systems: microfluidic enhancement of chemiluminescent detection.

Conventional flow injection systems for aquatic environmental analysis typically comprise large laboratory benchscale equipment, which place considerable constraints for portable field use. Here, we demonstrate the use of an integrated acoustically driven microfluidic mixing scheme to enhance detection of a chemiluminescent species tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate-a common chemiluminescent reagent widely used for the analysis of a wide range of compounds such as illicit drugs, pharmaceuticals, and pesticides-such that rapid in-line quantification can be carried out with sufficient on-chip sensitivity. Specifically, we employ surface acoustic waves (SAWs) to drive intense chaotic streaming within a 100 µL chamber cast in polydimethoxylsiloxane (PDMS) atop a microfluidic chip consisting of a single crystal piezoelectric material. By optimizing the power, duration, and orientation of the SAW input, we show that the mixing intensity of the sample and reagent fed into the chamber can be increased by one to two orders of magnitude, leading to a similar enhancement in the detection sensitivity of the chemiluminescent species and thus achieving a theoretical limit of detection of 0.02 ppb (0.2 nM) of l-proline-a decade improvement over the industry gold-standard and two orders of magnitude more sensitive than that achievable with conventional systems-simply using a portable photodetector and without requiring sample preconcentration. This on-chip microfluidic mixing strategy, together with the integrated miniature photodetector and the possibility for chip-scale microfluidic actuation, then alludes to the attractive possibility of a completely miniaturized platform for portable field-use microanalytical systems.

Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids.

The first members of a promising new family of hybrid amino acid-polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium-tungstoarsenate structural backbone, followed by crystallization with p-methylbenzylammonium (p-MeBzNH3(+)) cations, affords (p-MeBzNH3)6K2(GlyH)[As(III)4(Y(III)W(VI)3)W(VI)44Y(III)4O159(Gly)8(H2O)14]⋅47 H2O (1) and enantiomorphs (p-MeBzNH3)15(NleH)3[As(III)4(Mo(V)2Mo(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11][As(III)4(Mo(VI)2W(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11] (generically designated 2: L-Nle, 2 a; D-Nle, 2 b). An intensive structural, spectroscopic, electrochemical, magnetochemical and theoretical investigation has allowed the elucidation of site-selective metal substitution and photoreduction of the tetranuclear core of the hybrid polyanions. In the solid state, markedly different crystal packing is evident for the compounds, which indicates the role of noncovalent interactions involving the amino acid ligands. In solution, mass spectrometric and small-angle X-ray scattering studies confirm maintenance of the structure of the polyanions of 2, while circular dichroism demonstrates that the chirality is also maintained. The combination of all of these features in a single modular family emphasizes the potential of such hybrid polyoxometalates to provide nanoscale molecular materials with tunable properties.

Fabrication of boron nitride nanotube-gold nanoparticle hybrids using pulsed plasma in liquid.

Plasma, generated in liquid at atmospheric pressure by a nanosecond pulsed voltage, was used to fabricate hybrid structures from boron nitride nanotubes and gold nanoparticles in deionized water. The pH was greatly reduced, conductivity was significantly increased, and concentrations of reactive oxygen and nitrogen species in the water were increased by the plasma treatment. The treatment reduced the length of the nanotubes, giving more individual cuplike structures, and introduced functional groups onto the surface. Gold nanoparticles were successively assembled onto the functionalized surfaces. The reactive species from the liquid plasma along with the nanosecond pulsed electric field seem to play a role in the shortening and functionalization of the nanotubes and the assembly of gold nanoparticles. The potential for targeted drug delivery was tested in a preliminary investigation using doxorubicin-loaded plasma-treated nanotubes which were effective at killing ∼99% of prostate cancer cells.