Isoprene epoxydiols as precursors to secondary organic aerosol formation: acid-catalyzed reactive uptake studies with authentic compounds

Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NO(x) conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7-6.4% for β-IEPOX and 3.4-5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C(5)-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NO(x), isoprene-dominated regions influenced by the presence of acidic aerosols.     

Photoactivation and Detection of Photoexcited Molecules and Photochemical Products

Aerobic photoactivation of photosensitizing dye molecules can lead to the formation of oxygen radicals, singlet oxygen and other partially reduced oxygen species, collectively called reactive oxygen species (ROS), which are responsible for photodynamic damage and the accompanying cytotoxicity. This review briefly describes basic photophysical phenomena involved in the formation of electronically excited states and photochemical processes that play a key role in the generation of ROS. Physicochemical properties of the excited states of the photosensitizing dye molecules and of ROS, particularly their chemical reactivity with selected substrate molecules, as well as major spectroscopic and analytical methods used for the detection and characterization of reactive intermediates involved in photodynamic phenomena, are critically discussed in this paper.     

Theory and data for simulating fine-scale human movement in an urban environment

Individual-based models of infectious disease transmission depend on accurate quantification of fine-scale patterns of human movement. Existing models of movement either pertain to overly coarse scales, simulate some aspects of movement but not others, or were designed specifically for populations in developed countries. Here, we propose a generalizable framework for simulating the locations that an individual visits, time allocation across those locations, and population-level variation therein. As a case study, we fit alternative models for each of five aspects of movement (number, distance from home and types of locations visited; frequency and duration of visits) to interview data from 157 residents of the city of Iquitos, Peru. Comparison of alternative models showed that location type and distance from home were significant determinants of the locations that individuals visited and how much time they spent there. We also found that for most locations, residents of two neighbourhoods displayed indistinguishable preferences for visiting locations at various distances, despite differing distributions of locations around those neighbourhoods. Finally, simulated patterns of time allocation matched the interview data in a number of ways, suggesting that our framework constitutes a sound basis for simulating fine-scale movement and for investigating factors that influence it.     

Improvement of dynamic response in an impact absorber by frictional elements

A novel device that uses friction between one or more pairs of elastic conical rings to dissipate the energy from an impacting body is presented. The device consists of one moving and one stationary cylinders coupled to each other using two pairs of conical rings and a spring. The spring is used to restore the system to its original configuration after the impact. The dynamic response of the system to the impact forces during impact events is analysed numerically and experimentally. The effects of several governing parameters, such as the mass ratio between the cylinders, the duration of the transient response of the device, the magnitude of the rest zone of the moving element and the peak impact force are investigated. The proposed system is applicable in sequential impact scenarios, in which remarkable improvements were observed over traditional solid-rod impact absorbers. The present study may serve as a guide for the design of improved damping devices for impact applications.     

Viscosity changes of aqueous carboxymethyl starch by partial crosslinking and montmorillonite addition

Slightly crosslinked carboxymethyl starch (cCMS) with degree of substitution (DS) 0.8–0.9 was prepared using mono‐ and di‐chloroacetic acids (MCA and DCA, respectively). Constant molar ratio of halogenated acetic acid derivatives to anhydroglucosidic unit (AGU) was adjusted (MCA+DCA):AGU=1.75:1; whereas, DCA:AGU ratio was changed in a range 0–0.10:1. The viscosity of 2 wt % cCMS aqueous solutions increased substantially for very slightly crosslinked product (DCA:AGU molar ratio 0.0075), in comparison to unmodified CMS, up to 170,000 mPa·s at 1 rpm, and 16,000 mPa·s, respectively. Some viscosity decrease of cCMS solutions during storing was observed. The explanation of this phenomenon was discussed and supported by ¹H NMR results. The rheological properties of cCMS solutions as well as aqueous cCMS/clay dispersions with various type of montmorillonite (MMT): sodium, calcium and organophilized as shear‐thinning systems were evaluated on a basis of power law model. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40793.     

Parallel‐connected monolithic dye‐sensitised solar modules

Light‐soaking and high‐temperature storage testing of monolithic dye‐sensitised solar modules with total area module efficiencies above 5% have been performed. Our experiences from the development of a four‐layer monolithic dye‐sensitised solar test cell for comparative testing of material components for dye‐sensitised solar cells have directed our module development to a novel device design consisting of parallel‐connection of individual monolithic cells. The results from the accelerated testing of the modules (total area of 17.0 cm²) with four parallel‐connected cells (active area of 3.38 cm²/cell) are equivalent to those obtained for the monolithic single test cells when using identical device components. The successful transfer from cell to module stability is an important milestone in our ambition to develop a low‐cost Photovoltaic (PV) technology. Moreover, our results indicate that intensified research and development to define the procedures for relevant accelerated testing of dye‐sensitised solar modules is urgently required. Copyright © 2010 John Wiley & Sons, Ltd.     

Side diffusion modeling by the explicit consideration of a space-charge buildup under the mask during strip waveguide formation in the Ag+ -Na+ field-assisted ion-exchange process

A space-charge buildup under the blocking mask in a field-assisted Ag+ -Na+ ion-exchange modeling is assumed. It results in the distortion of electric field lines in the direction under the mask edges. As a result, side diffusion occurs and the numerical model shows the same range of side diffusion as the experimental data. Explicit consideration of the space-charge buildup under the mask and solving the Poisson equation for the electric field determination make it possible to use more realistic boundary conditions in the numerical model, compared to the boundary conditions generally used.