Colloidal synthesis of pt nanoparticles: on the formation and stability of nanowires

Catalytic properties of Pt nanoparticles can significantly depend on the crystallite shape, which renders shape control an important aim in the chemical synthesis. Starting from a colloidal synthesis of quasispherical Pt nanocrystals capped with dodecylamine ligands, systematic variations of different synthesis parameters were performed in the present work in order to obtain Pt nanowires. Mechanistic investigations revealed that nanowires can form by aggregation of quasispherical particles. The process of wire formation was found to be influenced by parameters such as the concentration of the stabilizing ligands on the particle surface. Furthermore, the thermal stability of the obtained nanoparticles was examined. The nanowires were found to be stable up to approximately 140-160 degrees C. In this temperature range a structural transition to a more spherical crystallite shape occurred, which can be understood by thermodynamic considerations.     

Analysis and classification of bacteria by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and a chemometric approach

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a useful technique for the identification of bacteria on the basis of their characteristic protein mass spectrum fingerprint. Highly standardized instrumental analytical performance and bacterial culture conditions are required to achieve useful information. A chemometric approach based on multivariate analysis techniques was developed for the analysis of MALDI data of different bacteria to allow their identification from their fingerprint. Principal component analysis, linear discriminant analysis (LDA) and soft independent modelling of class analogy (SIMCA) were applied to the analysis of the MALDI MS mass spectra of two pathogenic bacteria, Escherichia coli O157:H7 and Yersinia enterocolitica, and the non-pathogenic E. coli MC1061. Spectra variability was assessed by growing bacteria in different media and analysing them at different culture growth times. After selection of the relevant variables, which allows the evaluation of an m/z value pattern with high discriminant power, the identification of bacteria by LDA and SIMCA was performed independently of the experimental conditions used. In order to better evaluate the analytical performance of the approach used, the ability to correctly classify different bacteria, six wild-type strains of E. coli O157:H7, was also studied and a combination of different chemometric techniques with a severe validation was developed. The analysis of spiked bovine meat samples and the agreement with an independent chemiluminescent enzyme immunoassay demonstrated the applicability of the method developed for the detection of bacteria in real samples. The easy automation of the MALDI method and the ability of multivariate techniques to reduce interlaboratory variability associated with bacterial growth time and conditions suggest the usefulness of the proposed MALDI MS approach for rapid routine food safety checks. Figure Workflow of the developed MALDI-TOF MS and chemometric approach for the analysis and classification of bacteria Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Influence of summer daylight saving time on scattered erythemal solar ultraviolet exposures

The research question of whether there are any influences in the scattered or diffuse erythemal UV exposures to a horizontal plane over a five month period due to the change from standard time to daylight saving time, has been investigated by using physical measurements and applying them to both standard time and daylight saving time. The diffuse erythemal UV was considered for fixed lunch break times and fixed morning and afternoon break times. The cases considered were for groups of the population who are predominantly indoors and who spend their break times outdoors in shade. The biggest influence on the diffuse UV exposures of changing to daylight saving time is the timing of the outdoor meal and break times. The change causes a reduction in diffuse erythemal exposure for early or morning breaks and an increase in the diffuse erythemal exposure for late or afternoon breaks. Similarly, for the lunch break times, the changes in exposure are influenced by the timing of the break with respect to solar noon. Indoor workers who take their breaks outside in a shaded area may have a change in their exposure to diffuse UV due to a shift to daylight saving time, however the magnitude of this change and whether it is a positive or negative change in exposure will depend on the timing of the break. The increase in diffuse UV exposure due to the afternoon break may be negated by the decrease in exposure due to the morning break. In this case, the effect on diffuse UV exposures due to changing to daylight saving time will be minimal.     

A cyclodextrin-based nanoassembly with bimodal photodynamic action

We have developed a supramolecular nanoassembly capable of inducing remarkable levels of cancer cell mortality through a bimodal action based on the simultaneous photogeneration of nitric oxide (NO) and singlet oxygen ((1)O(2)). This was achieved through the appropriate incorporation of an anionic porphyrin (as (1)O(2) photosensitizer) and of a tailored NO photodonor in different compartments of biocompatible nanoparticles based on cationic amphiphilic cyclodextrins. The combination of steady-state and time-resolved spectroscopic techniques showed the absence of significant intra- and interchromophoric interaction between the two photoactive centers embedded in the nanoparticles, with consequent preservation of their photodynamic properties. Photodelivery of NO and (1)O(2) from the nanoassembly on visible light excitation was unambiguously demonstrated by direct and real-time monitoring of these transient species through amperometric and time-resolved infrared luminescence measurements, respectively. The typical red fluorescence of the porphyrin units was essentially unaffected in the bichromophoric nanoassembly, allowing its localization in living cells. The convergence of the dual therapeutic action and the imaging capacities in one single structure makes this supramolecular architecture an appealing, multifunctional candidate for applications in biomedical research.     

A Host–Guest Supramolecular Complex with Photoregulated Delivery of Nitric Oxide and Fluorescence Imaging Capacity in Cancer Cells

Herein we report the design, preparation, and properties of a supramolecular system based on a tailored nitric oxide (NO) photodonor and a rhodamine‐labeled β‐cyclodextrin conjugate. The combination of spectroscopic and photochemical experiments shows the absence of significant interchromophoric interactions between the host and the guest in the excited states. As a result, the complex is able to release NO under the exclusive control of visible light, as unambiguously demonstrated by direct detection of this transient species through an amperometric technique, and exhibits the typical red fluorescence of the rhodamine appendage. The supramolecular complex effectively internalizes in HeLa cancer cells as proven by fluorescence microscopy, shows a satisfactory biocompatibility in the dark, and induces about 50 % of cell mortality upon irradiation with visible light. The convergence of all these properties in one single complex makes the present host–guest ensemble an appealing candidate for further delevopment of photoactivatable nanoscaled systems addressed to photostimulated NO‐based therapy.     

Critical slowing down exponents of mode coupling theory

A method is provided to compute the exponent parameter λ yielding the dynamic exponents of critical slowing down in mode coupling theory. It is independent from the dynamic approach and based on the formulation of an effective static field theory. Expressions of λ in terms of third order coefficients of the action expansion or, equivalently, in terms of six point cumulants are provided. Applications are reported to a number of mean-field models: with hard and soft variables and both fully connected and dilute interactions. Comparisons with existing results for the Potts glass model, the random orthogonal model, hard and soft-spin Sherrington-Kirkpatrick, and p-spin models are presented.     

High-efficiency 1.9 µm Tm3+:LiLuF4 thin-disk laser

We present the first demonstration of a 792 nm diode-pumped Tm3+:LiLuF4 thin-disk laser operation around 1.9 μm. In multimode configuration, up to 21 W of output power and a maximal slope efficiency of 49% with an optical-to-optical efficiency of 40% was demonstrated. A tuning range from 1899 nm to 1927 nm could be achieved by inserting an etalon into the cavity.     

Serial Cross-Sectional Observations of Sun-Protective Behaviors at an Annual Outdoor Motorsport Event in Tropical Queensland,Australia

Skin cancer, the most prevalent cancer in Caucasians residing at low latitudes, can primarily be prevented by avoiding overexposure to sunlight. Serial cross-sectional observations were conducted at an outdoor motorsport event held in Townsville, Queensland each July (Southern winter) to determine whether sun-protection habits changed over time. Most (71.1%) of the 1337 attendees observed (97.6% lightly pigmented skin, 64.0% male) wore a hat (any style shading the face), while few (18.5%) wore three-quarter or full-length sleeves. While hat-wearing rates (any style) were similar in 2009 (326, 72.6%) and 2013 (625, 70.4%), the use of sun-protective styles (wide-brimmed/bucket/legionnaires) decreased from 29.2% to 18.6% over the same period, primarily because the use of sun-protective hats halved (from 28.7% to 14.0%) among females, while decreasing from 29.4% to 21.1% in males. Although relatively few individuals wore sun-protective (three-quarter-length or full-length) sleeves regardless of year (OR = 0.117, P < 0.0001), encouragingly, the use of sun-protective sleeves more than doubled between 2009 (10.5%) and 2013 (22.5%). Interestingly females, albeit the minority, at this sporting event were less likely to wear a hat (OR = 0.473, P < 0.0001) than males. These findings highlight the need for continued momentum toward skin cancer primary prevention through sun protection with a dedicated focus on outdoor sporting settings.     

The Playground Shade Index: A New Design Metric for Measuring Shade and Seasonal Ultraviolet Protection Characteristics of Parks and Playgrounds

Current shading strategies used to protect outdoor playgrounds from harmful solar radiation include the placement of artificial cloth weaves or permanent roofing over a playground site, planting trees in proximity to playground equipment, and using vegetation or surface texture variations to cool playground surfaces. How and where an artificial shade structure is placed or a tree is planted to maximize the shade protection over specific playground areas, requires careful assessment of local seasonal sun exposure patterns. The Playground Shade Index (PSI) is introduced here as a design metric to enable shade and solar ultraviolet exposure patterns to be derived in an outdoor space using conventional aerial views of suburban park maps. The implementation of the PSI is demonstrated by incorporating a machine learning design tool to classify the position of trees from an aerial image, thus enabling the mapping of seasonal shade and ultraviolet exposure patterns within an existing 7180 m² parkland. This is achieved by modeling the relative position of the sun with respect to nearby buildings, shade structures, and the identified evergreen and deciduous tree species surrounding an outdoor playground.