Comparison of the Chemical and Oxidative Characteristics of Particulate Matter (PM) Collected by Different Methods: Filters,Impactors, and BioSamplers

In this study, we compare the chemical and oxidative characteristics of concentration-enriched PM_2.5 samples simultaneously collected by a filter, a Nano-Micro-Orifice Uniform Deposition Impactor, and a BioSampler. Gravimetric measurements showed considerable agreement in particulate matter (PM) collection efficiency for all three samplers. Accordingly, samples from the three collectors exhibited similar chemical compositions. The mass fractions of their inorganic ions, labile and nonlabile, were comparable. Moreover, the organic carbon (OC) content of the BioSampler slurry was similar to that of the filter, while water-soluble OC levels of the filter and impactor samples were close to a 100% agreement. Lastly, linear regression analyses demonstrated that the water-soluble elements existed in similar proportions for the filter and impactor samples. Their respective total components were also in very good agreement. By contrast, the recoverable elements from the BioSampler slurry, determined by high-resolution magnetic sector inductively coupled plasma mass spectrometry, were in good agreement with the water-soluble elements of the filter and impactor samples but not their corresponding total components. In spite of the overall agreement among the samples on their chemical composition, findings from a macrophage reactive oxygen species (ROS), a dithiothreitol (DTT), and a dihydroxybenzoate (DHBA) assay revealed that the oxidative potential of aqueous extracts of the filter and impactor substrates was similar yet substantially lower than that of the BioSampler slurry. However, filtering of the BioSampler slurry, i.e., removal of insoluble PM components, attenuated its ROS activity to about the same level as that of the water extracts of the filter and impactor samples. These findings first indicate that insoluble PM species are potentially redox active, and second that particle collection by the BioSampler, which circumvents the need for PM extraction, constitutes a viable alternative for collecting concentrated particles for characterization of the oxidative properties of PM.     

The thought translation device: a neurophysiological approach to communication in total motor paralysis

A thought translation device (TTD) for brain-computer communication is described. Three patients diagnosed with amyotrophic lateral sclerosis (ALS), with total motor paralysis, were trained for several months. In order to enable such patients to communicate without any motor activity, a technique was developed where subjects learn to control their slow cortical potentials (SCP) in a 2-s rhythm, producing either cortical negativity or positivity according to the task requirement. SCP differences between a baseline interval and an active control interval are transformed into vertical or horizontal cursor movements on a computer screen. Learning SCP self regulation followed an operant-conditioning paradigm with individualized shaping procedures. After prolonged training over more than 100 sessions, all patients achieved self-control, leading to a 70-80% accuracy for two patients. The learned cortical skill enabled the patients to select letters or words in a language-supporting program (LSP) developed for inter-personal communication. The results demonstrate that the fast and stable SCP self-control can be achieved with operant training and without mediation of any muscle activity. The acquired skill allows communication even in total locked-in states.     

Influence of Si:Al ratio on the microstructural and mechanical properties of a fine-limestone aggregate alkali-activated slag concrete

Three series of fine limestone aggregate, alkali-activated blast furnace slag (AAS) concretes were fabricated and tested; two through activation with waterglass/NaOH solution, of which one included NaCl as a retarding agent, and one activated by Na₂CO₃. Each of these series was made up of three formulae containing different amounts of Al₂O₃. The compressive strengths of the series activated by waterglass/NaOH after 28 days were ≈65 ± 5.3 MPa, a 22% increase compared to previously reported formulae containing no additional Al₂O₃. Increasing the amount of Al₂O₃ did not further increase strength, however. The Na₂CO₃-activated formulae had strengths of ≈35 ± 3 MPa after 28 days, representing no increase in strength over formulae not containing Al₂O₃ previously reported. X-ray diffraction showed the main binding phase to be calcium silicate hydrate (C–S–H) gel, as is commonly found in ordinary Portland cement (OPC). Fourier transform infrared spectroscopy showed little difference from the previously reported results for formulae not containing Al₂O₃ and strongly resemble the spectra reported elsewhere for C–S–H. Electron microscopy, coupled with energy dispersive spectroscopy, showed the cementing phase to be a single homogenous phase—not a mixed system of geopolymer and C–S–H gel—with a lower volume fraction of unreacted slag than formulae without Al₂O₃. The reason for the increase in strength of Al₂O₃-containing formulae is unclear, but is unlikely to be ascribed to the formation of large amounts of ‘geopolymers’ and may be related to a possible increase in reaction temperature of between 2 and 5°C, depending on amount of additive.     

Carbon Nanotube–CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability

Transition metal fluorides (MF_x) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion‐type cathode materials for lithium ion batteries. Here, a scalable and low‐cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near‐theoretical, ) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MF_x‐based materials in batteries with load‐bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g⁻¹ and over 50% after 10 000 cycles at the current density of 1000 mA g⁻¹.     

Patterns and predictors of personal exposure to indoor air pollution from biomass combustion among women and children in rural China

Indoor air pollution (IAP) from domestic biomass combustion is an important health risk factor, yet direct measurements of personal IAP exposure are scarce. We measured 24-h integrated gravimetric exposure to particles < 2.5 μm in aerodynamic diameter (particulate matter, PM?.?) in 280 adult women and 240 children in rural Yunnan, China. We also measured indoor PM?.? concentrations in a random sample of 44 kitchens. The geometric mean winter PM?.? exposure among adult women was twice that of summer exposure [117 μg/m3 (95% CI: 107, 128) vs. 55 μg/m3 (95% CI: 49, 62)]. Children's geometric mean exposure in summer was 53 μg/m3 (95% CI: 46, 61). Indoor PM?.? concentrations were moderately correlated with women's personal exposure (r=0.58), but not for children. Ventilation during cooking, cookstove maintenance, and kitchen structure were significant predictors of personal PM?.? exposure among women primarily cooking with biomass. These findings can be used to develop exposure assessment models for future epidemiologic research and inform interventions and policies aimed at reducing IAP exposure. PRACTICAL IMPLICATIONS: Our results suggest that reducing overall PM pollution exposure in this population may be best achieved by reducing winter exposure. Behavioral interventions such as increasing ventilation during cooking or encouraging stove cleaning and maintenance may help achieve these reductions.     

Structure, function and metabolism of sialic acids

Sialic acids represent a family of sugar molecules with an unusual and highly variable chemical structure that are found mostly in the terminal position of oligosaccharide chains on the surface of cells and molecules. These special features enable them to fulfil several important and even diametrical biological functions. Because of the great importance of sialic acids, it is also worth having a look at their metabolism in order to get an idea of the intimate connection between structure and function of these fascinating molecules and the often serious consequences that results from disturbances in the balance of metabolic reactions. The latter can be due to genetic disorders that result in the absence of certain enzyme activity, leading to severe illness or even to death.     

Effect of cysteine modifications on the activity of the 'small' Clostridium perfringens sialidase

The 'small' (43 kDa) sialidase of Clostridium perfringens is inhibited by low concentrations of mercury ions. For the investigation of possible functional roles of the enzyme's four cysteine residues at the amino acid positions 2, 282, 333 and 349, they were separately altered to serine by site-directed mutagenesis. The four mutant sialidases expressed in E. coli and purified by metal chelate chromatography were markedly reduced in specific activity when compared to the wild-type enzyme but with the exception of C282S exhibited similar K(M)-values indicating an unchanged mode of substrate binding. The substrate specificity was also conserved for C2S, C282S, and C333S. Only the C349S sialidase exhibited a higher relative activity with colominic acid and the alpha2,6-linked sialic acid of sialyllactose compared to the alpha2,3-linked isomer than the other mutants. Chemical modifications with the thiol-blocking reagents N-ethylmaleimide (NEM), p-chloromercuribenzoate (pCMB) and HgCl2 had little effect on the C282S sialidase, e.g., 6% inhibition by 5 mM NEM compared to reductions in activity between 65 and 90% for the wild-type and other mutant enzymes, supporting the idea that among the enzyme's cysteines, Cys-282 has the highest structural or functional significance. The results also explain the higher mercury tolerance of Salmonella typhimurium and Clostridium tertium sialidases, which have the positions equivalent to Cys-282 altered to Val and Thr, respectively, indicating that the thiol group of Cys-282, despite being situated near the active site, is not involved in catalysis.     

Characterization of the enzymatic 7-O-acetylation of sialic acids and evidence for enzymatic O-acetyl migration from C-7 to C-9 in bovine submandibular gland

BACKGROUND: Although the anticancer effects of progesterone therapy for patients with endometrial carcinoma are widely acknowledged, a detailed assessment of the resultant morphologic alterations in tumor tissue kinetics has hitherto been lacking. METHODS: Biopsy and hysterectomy specimens of 14 endometrial carcinomas (endometrioid-type) before and during progesterone therapy were studied to clarify changes in apoptosis and cell proliferation and their relation to morphologic alterations. The extent of squamous differentiation within tumor lesions was also examined. RESULTS: In the good-response group, tumor cells took on characteristics of normal endometrial gland cells in the secretory phase. A positive correlation between reduction in the mitotic index and the degree of morphologic alterations during hormone therapy was observed, but the frequency of apoptotic cells did not vary. In both the good-response and poor-response groups, development or enlargement of squamous areas was observed, in comparison with the initial biopsy specimens. CONCLUSIONS: These results suggest that prolonged progesterone administration can suppress cell proliferation in endometrial carcinomas through tumor cell differentiation without altering apoptosis, resulting in a shift in tissue kinetics toward a relative predominance of cell deletion. In addition, increases in the occurrence of squamous areas within tumors do not always appear to be related to treatment efficacy.