Oxygen deficient α-Fe2O3 photoelectrodes: a balance between enhanced electrical properties and trap-mediated losses

Intrinsic doping of hematite through the inclusion of oxygen vacancies (V_O) is being increasingly explored as a simple, low temperature route to preparing active water splitting α-Fe₂O_3–x photoelectrodes. Whilst it is widely accepted that the introduction of V_O leads to improved conductivities, little else is verified regarding the actual mechanism of enhancement. Here we employ transient absorption (TA) spectroscopy to build a comprehensive kinetic model for water oxidation on α-Fe₂O_3–x. In contrast to previous suggestions, the primary effect of introducing V_O is to block very slow (ms) surface hole – bulk electron recombination pathways. In light of our mechanistic research we are also able to identify and address a cause of the high photocurrent onset potential, a common issue with this class of electrodes. Atomic layer deposition (ALD) of Al₂O₃ is found to be particularly effective with α-Fe₂O_3–x, leading to the photocurrent onset potential shifting by ca. 200 mV. Significantly TA measurements on these ALD passivated electrodes also provide important insights into the role of passivating layers, that are relevant to the wider development of α-Fe₂O₃ photoelectrodes.     

Twist-Bend Nematic Glasses: The Synthesis and Characterisation of Pyrene-based Nonsymmetric Dimers

A selection of pyrene-based liquid crystal dimers have been prepared, containing either methylene-ether or diether linked spacers of varying length and parity. All the diether linked materials, CBOnO.Py (n=5, 6, 11, 12), exhibit conventional nematic and smectic A phases, with the exception of CBO11O.Py which is exclusively nematic. The methylene-ether linked dimer, CBnO.Py, with an even-membered spacer (n=5) was solely nematogenic, but odd-members (n=6, 8, 10) exhibited both nematic and twist-bend nematic phases. Replacement of the cyanobiphenyl fragment by cyanoterphenyl giving CT6O.Py, gave elevated melting and nematic-isotropic transition temperatures, and SmA and SmC_A phases were observed on cooling the nematic phase. Intermolecular face-to-face associations of the pyrene moieties drive glass formation, and all these materials have a glass transition temperature at or above room temperature. The stability of the glassy twist-bend nematic phase allowed for its study using AFM, and the helical pitch length, P_TB, was measured as 6.3 and 6.7 nm for CB6O.Py and CB8O.Py, respectively. These values are comparable to the shortest pitch of a twist-bend nematic phase measured to date.     

Characterization of the Reaction of Chloroacetaldehyde with Single and Double Stranded DNA

Chloroacetaldehyde reacts with viral M13mp18 single and double stranded DNA to form the highly fluorescent adducts, etheno-AMP and etheno-CMP.

Absorbance and fluorescence spectroscopy can be used to monitor and characterize these reactions. Both single and double stranded DNA showed increases in the absorbance following reaction with the aldehyde. The fluorescence also increased in these two groups and continued to rise with increasing time of incubation until a point of saturation was reached. The fluorescence of the double stranded moiety was considerably enhanced following reaction with the aldehyde while that of the single stranded population was not, making this method appropriate for the separation of small quantities of the two populations of DNA.     

Pyrolysis GC/MS analysis of a bacterial population in a saline activated sludge system—Identification of the origin of the pyrolysis product 2-methylpyrimidine

During the investigation of problems with the physical handling of sludge from a saline activated sludge wastewater system, pyrolysis/GC/MS was used in an attempt to determine whether changes in the bacterial population in the sludge were occurring. The pyrolysis GC/MS analysis revealed an unknown peak among other typical bacterial pyrolysis products. This unknown was identified as 2-methylpyrimidine. This pyrolysis product was only found in appreciable amounts in samples from other saline systems but not in freshwater systems analyzed as points of comparison for the system of concern. Further investigation confirmed the source of 2-methylpyrimidine to be ectoine, a compound produced by halophilic bacteria as a compatible solute for osmoadaptation. Pyrolysis GC/MS was shown to be a useful tool to indicate the presence of ectoine in halophilic bacteria.     

Effect of artificial mucus properties on the characteristics of airborne bioaerosol droplets generated during simulated coughing

The effect of viscoelastic properties and surface tension of artificial mucus simulant samples on the size distribution and volume concentration of bioaerosol droplets generated during simulated coughing was investigated through in vitro experiments. The mucus simulant samples had viscoelastic properties in a similar range as those of real human airway mucus. The mucus simulant gels were prepared by mixing various proportions of 0.5–1.7% locust bean gum solution and 0.1 M sodium tetraborate (XLB) solution. Surface tension of one set of samples was varied by adding different amounts of SDS (sodium dodecyl sulfate) surfactant while the measurement of surface tension was performed using ADSA (axisymmetric drop shape analysis) method. The viscoelastic properties of the samples were measured using a Bohlin Gemini 200 HR (Malvern, UK) nano-rheometer with peltier plate assembly. An artificial cough machine was used to simulate human cough, generating aerosol droplets in a model trachea attached to the front of the cough machine. The size distribution and volume concentration of the droplets generated through simulated cough were measured using a laser diffraction particle sizer (SprayTec, Malvern, USA). The surface tension was found to have negligible effect on the characteristic of generated droplets within the range of this investigation. The experimental results showed a decrease in particle size as the samples changed from a viscous fluid type to a viscoelastic to an elastic solid type sample. The volume concentration also changed significantly as the viscoelasticity of the samples was varied.     

The Neutron Structure of the Formyl Peptide Receptor Antagonist Cyclosporin H (CsH) Unambiguously Determines the Solvent and Hydrogen-Bonding Structure for Crystal Form II

Abstract  

Single-crystal neutron diffraction data were collected at 20 K to a resolution of 1.05 ? on a crystal of the inverse formyl peptide receptor agonist cyclosporin H, CsH, (crystal form II, CsH-II) on the Laue diffractometer VIVALDI at the Institut Laue-Langevin (Grenoble). The solvent structure and hydrogen bonding network of CsH-II have been unambiguously determined by single-crystal neutron diffraction; the agreement factor R(F ²) is 13.5% for all 2726 reflections. All hydrogen atom positions, including methyl-group orientations, have been determined by crystallographic refinement. The neutron structure of cyclosporin provides unique and complementary insights into methyl orientation, hydrogen-bonding, and solvent interactions that are not available from X-ray analysis alone.     

A modeling concept of a mechanical system having a piecewise linear spring property for its diagnosis

Machine condition monitoring and fault diagnosis of rotating machinery are very important because of the wide use of rotating machinery in industry. Couplings and gears are used in many mechanical systems to connect elements and transmit power. The system is usually modeled as a single-degree-of-freedom system with a piecewise linear spring property, where the mass of main machine is only considered. In the present study, the dynamic behavior of a system with an unsymmetrical nonlinearity and a significant mass of the connecting part was investigated both experimentally and by numerical simulation. In the experiment, a 1/3 sub-harmonic oscillation was observed, but this oscillation was not found in the simulation using a single-degree-of-freedom system, in which the mass of the connecting part was ignored. However, when a two-degrees-of-freedom system was used that considered both the mass of the connecting part and the impact property, the 1/3 sub-harmonic oscillation was observed. Thus it is recognized that an adequate mathematical model for diagnosis in the early stage of abnormality must be selected on the basis of the mass ratio between the connecting part and the main body.     

Facile synthesis of core‐surface crosslinked nanoparticles by interblock RAFT polymerization

A new, efficient method for synthesizing stable nanoparticles with poly(ethylene oxide) (PEO) functionalities on the core surface, in which the micellization and crosslinking reactions occur in one pot, has been developed. First, amphiphilic PEO‐b‐PS copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization of styrene using (PEO)‐based trithiocarbonate as a macro‐RAFT agent. The low molecular weight PEO‐b‐PS copolymer was dissolved in isopropyl alcohol where the block copolymer self‐assembled as core‐shell micelles, and then the core‐shell interface crosslink was performed using divinylbenzene as a crosslinking agent and 2,2′‐azobisisobutyronitrile as an initiator. The design of the amphiphilic RAFT agent is critical for the successful preparation of core‐shell interface crosslinked micellar nanoparticles, because of RAFT functional groups interconnect PEO and polystyrene blocks. The PEO functionality of the nanoparticles surface was confirmed by ¹H NMR and FTIR. The size and morphology of the nanoparticles was confirmed by scanning electron microscopy, transmission electron microscopy, and dynamic laser light scattering analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Long-Range 31P-31P Spin Coupling Constants in the 31P NMR Spectra of Phosphite Triesters

Abstract

Data are presented on the magnitudes of ⁵ J _pp and ⁶ J _PP spin-spin coupling constants in the ³¹P NMR spectra of a variety of novel polyphosphite triesters.     

Application of the single comparator method to instrumental photon activation analysis

Journal of Radioanalytical and Nuclear Chemistry - Instrumental photon activation analysis (IPAA) is nondestructive and multi-elemental analysis method like instrumental neutron activation...