Sulfur-containing amide-based [2]rotaxanes and molecular shuttles

We report the synthesis, structure and properties of [2]rotaxanes prepared by the assembly of benzylic amide macrocycles around a series of amide and sulfide-/sulfoxide-/sulfone-containing threads. The efficacy of rotaxane formation is related to the hydrogen bond accepting properties of the various sulfur-containing functional groups in the thread, with the highest yields (up to 63% with a rigid vinyl spacer in the template site) obtained for sulfoxide rotaxanes. X-Ray crystallography of a sulfoxide rotaxane, 5, shows that the macrocycle adopts a highly symmetrical chair-like conformation in the solid state, with short hydrogen bonds between the macrocycle isophthalamide NH-protons and the amide carbonyl and sulfoxide S-O of the thread. In contrast, in the X-ray crystal structures of the analogous sulfide (4) and sulfone (6) rotaxanes the macrocycle adopts boat-like conformations with long intercomponent NH…O=SO and NH…S hydrogen bonds (in addition to several intercomponent amide-amide hydrogen bonds). Taking advantage of the different hydrogen bonding modes of the sulfur-based functional groups, a switchable molecular shuttle was prepared in which the oxidation level of sulfur determines the position of the macrocycle on the thread.

Determination of dimethyl sulfide in gas samples by single photon ionization time of flight mass spectrometry

It is difficult to determine sulfur-containing volatile organic compounds in the atmosphere because of their reactivity. Primary off-line techniques may suffer losses of analytes during the transportation from field to laboratory and sample preparation. In this study, a novel method was developed to directly measure dimethyl sulfide at parts-per-billion concentration levels in the atmosphere using vacuum ultraviolet single photon ionization time-of-flight mass spectrometry. This technique offers continuous sampling at a response rate of one measurement per second, or cumulative measurements over longer time periods. Laboratory prepared samples of different concentrations of dimethyl sulfide in pure nitrogen gas were analyzed at several sampling frequencies. Good precision was achieved using sampling periods of at least 60 seconds with a relative standard deviation of less than 25%. The detection limit for dimethyl sulfide was below the 3 ppb olfactory threshold. These results demonstrate that single photon ionization time-of-flight mass spectrometry is a valuable tool for rapid, real-time measurements of sulfur-containing organic compounds in the air.

Preparation and characterization of poly(lactic-co-glycolic acid) microparticles containing DNA molecules encoding a malaria vaccine candidate

Background A novel ultrasonic atomization approach for the formulation of biodegradable poly(lactic-co-glycolic acid) (PLGA) microparticles of a malaria DNA vaccine is presented. A 40 kHz ultrasonic atomization device was used to create the microparticles from a feedstock containing 5 volumes of 0.5% w/v PLGA in acetone and 1 volume of condensed DNA which was fed at a flow rate of 18ml h-1. The plasmid DNA vectors encoding a malaria protein were condensed with a cationic polymer before atomization. Results High levels of gene expression in vitro were observed in COS-7 cells transfected with condensed DNA at a nitrogen to phosphate (N/P) ratio of 10. At this N/P ratio, the condensed DNA exhibited a monodispersed nanoparticle size (Z-average diameter of 60.8 nm) and a highly positive zeta potential of 38.8mV. The microparticle formulations of malaria DNA vaccine were quality assessed and it was shown that themicroparticles displayed high encapsulation efficiencies between 82-96% and a narrow size distribution in the range of 0.8-1.9 μm. In vitro release profile revealed that approximately 82% of the DNA was released within 30 days via a predominantly diffusion controlledmass transfer system. Conclusions This ultrasonic atomization technique showed excellent particle size reproducibility and displayed potential as an industrially viable approach for the formulation of controlled release particles.

Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well-defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. Observed Raman bands were attributed to the (AsO3OH)2- stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Non-interpreted Raman spectra of koritnigite from the RRUFF database, and published infrared spectra of cobaltkoritnigite were used for comparison. The O-H...O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2- units in the crystal structure of koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Electrospraying of polymers with therapeutic molecules : state of the art

The encapsulation and release of bioactive molecules from polymeric vehicles represents the holy grail of drug and growth factor delivery therapies, whereby sustained and controlled release is crucial in eliciting a positive therapeutic effect. To this end, electrospraying is rapidly emerging as a popular technology for the production of polymeric particles containing bioactive molecules. Compared with traditional emulsion fabrication techniques, electrospraying has the potential to reduce denaturation of protein drugs and affords tighter regulation over particle size distribution and morphology. In this article, we review the importance of the electrospraying parameters that enable reproducible tailoring of the particles' physical and in vitro drug release characteristics, along with discussion of existing in vivo data. Controlled morphology and monodispersity of particles can be achieved with electrospraying, with high encapsulation efficiencies and without unfavorable denaturation of bioactive molecules throughout the process. Finally, the combination of electrospraying with electrospun scaffolds, with an emphasis on tissue regeneration is reviewed, depicting a technique in its relative infancy but holding great promise for the future of regenerative medicine.

Anionic migration reactions in aromatic systems effected by collisional activation : Deprotonated anilides containing methoxycarbonyl substituents

Long-range cross-ring reactions are of minor importance in the collision-induced mass spectra (MS/MS) of [M - H]- ions of CH2OCO-C6H4-NHCOR systems: e.g. the loss of 'CD3CO2CH3' from CH3OCO-C6H4-(N) over bar COCD3. Major processes involve (i) losses of radicals to form stable radical anions, e.g. loss of a ring hydrogen atom and losses from the ester (CH3 ., CH3O . and . CO2CH3), (ii) losses of neutral molecules from the amide moiety [e.g. CO (R = H) and CH2CO (R = CH3), and proximity effects when the two substituents are ortho [e.g. loss of (CH3OD+CO2) from o-CH3OCO-C6H4 (N) over bar COCD3].

Diffusion-driven formation of MoS2 nanotube bundles containing MoS2 nanopods

MoS2 nanotube bundles along with embedded nested fullerenes were formed in a gas phase reaction of molybdenum carbonyl and H2S gas with the assistance of I2. The amorphous Mo-S-I intermediates obtained through quenching a modified MOCVD reaction in a large temperature gradient were annealed at elevated temperature in an inert atmosphere. Under the influence of the iodine the amorphous precursor formed a surface film with an enhanced mobility of the molybdenum and sulfur components. Point defects within the MoS2 layers combined with the enhanced surface diffusion lead to a scrolling of the inherently instable MoS2 lamellae.

Isostructural co-crystals derived from molecules with different supramolecular topologies

In this article, we report the crystal structures of five halogen bonded co-crystals comprising quaternary ammonium cations, halide anions (Cl– and Br–), and one of either 1,2-, 1,3-, or 1,4-diiodotetrafluorobenzene (DITFB). Three of the co-crystals are chemical isomers: 1,4-DITFB[TEA-CH2Cl]Cl, 1,2-DITFB[TEA-CH2Cl]Cl, and 1,3-DITFB[TEA-CH2Cl]Cl (where TEA-CH2Cl is chloromethyltriethylammonium ion). In each structure, the chloride anions link DITFB molecules through halogen bonds to produce 1D chains propagating with (a) linear topology in the structure containing 1,4-DITFB, (b) zigzag topology with 60° angle of propagation in that containing 1,2-DITFB, and (c) 120° angle of propagation with 1,3-DITFB. While the individual chains have highly distinctive and different topologies, they combine through π-stacking of the DITFB molecules to produce remarkably similar overall arrangements of molecules. Structures of 1,4-DITFB[TEA-CH2Br]Br and 1,3-DITFB[TEA-CH2Br]Br are also reported and are isomorphous with their chloro/chloride analogues, further illustrating the robustness of the overall supramolecular architecture. The usual approach to crystal engineering is to make structural changes to molecular components to effect specific changes to the resulting crystal structure. The results reported herein encourage pursuit of a somewhat different approach to crystal engineering. That is, to investigate the possibilities for engineering the same overall arrangement of molecules in crystals while employing molecular components that aggregate with entirely different supramolecular connectivity.

Sustainable Australia : containing travel in master planned estates

Low density suburban development and excessive use of automobiles are associated with serious urban and environmental problems. These problems include traffic congestion, longer commuting times, high automobile dependency, air and water pollution, and increased depletion of natural resources. Master planned development suggests itself as a possible palliative for the ills of low density and high travel. The following study examines the patterns and dynamics of movement in a selection of master planned estates in Australia. The study develops new approaches for assessing the containment of travel within planned development. Its key aim is to clarify and map the relationships between trip generation and urban form and structure. The initial conceptual framework of the paper is developed in a review of literature related to urban form and travel behaviour. These concepts are tested empirically in a pilot study of suburban travel activity in master planned estates. A geographical information systems methodology is used to determine regional journey-to-work patterns and travel containment rates. Factors that influence selfcontainment patterns are estimated with a regression model. This research is a useful preliminary examination of travel self-containment in Australian master planned estates.

Research Monograph : Sustainable Australia : Containing travel in master planned estates

Low density suburban development and excessive use of automobiles are associated with serious urban and environmental problems. These problems include traffic congestion, longer commuting times, high automobile dependency, air and water pollution, and increased depletion of natural resources. Master planned development suggests itself as a possible palliative for the ills of low density and high travel. The following study examines the patterns and dynamics of movement in a selection of master planned estates in Australia. The study develops new approaches for assessing the containment of travel within planned development. Its key aim is to clarify and map the relationships between trip generation and urban form and structure. The initial conceptual framework of the report is developed in a review of literature related to urban form and travel behaviour. These concepts are tested empirically in a pilot study of suburban travel activity in master planned estates. A geographical information systems (GIS) methodology is used to determine regional journey-to-work patterns and travel containment rates. Factors that influence self-containment patterns are estimated with a regression model. The key research findings of the pilot study are: - There is a strong relation between urban structural form and patterns of trip generation; - The travel self-containment of Australian master planned estates is lower than the scholarly literature implies would occur if appropriate planning principles to achieve sustainable urban travel were followed; - Proximity to the central business district, income level and education status are positively correlated with travel containment; - Master planned estates depend more on local and regional centres for employment than on the central business district; - The service sector is the major employer in and around master planned estates. It tends to provide part-time and casual employment rather than full-time employment; - Travel self-containment is negative correlated with car dependency. Master planned estates with less car dependent residents, and with good access to public transport, appear to be more self-contained and, consequently, more sustainable than the norm. This research is a useful preliminary examination of travel self-containment in Australian master planned estates. It by no means exhausts the subject. In future research we hope to further assess sustainable travel patterns with more detailed spatial analysis.

Operation and control of a microgrid containing inertial and non-inertial micro sources

In this paper, a new power sharing control method for a microgrid with several distributed generation units is proposed. The presence of both inertial and noninertial sources with different power ratings, maximum power point tracking, and various types of loads pose a great challenge for the power sharing and system stability. The conventional droop control method is modified to achieve the desired power sharing ensuring system stability in a highly resistive network. A transformation matrix is formed to derive equivalent real and reactive power output of the converter and equivalent feedback gain matrix for the modified droop equation. The proposed control strategy, aimed for the prototype microgrid planned at Queensland University of Technology, is validated through extensive simulation results using PSCAD/EMTDC software.

An inverse time admittance relay for fault detection in distribution networks containing DGs

Isolation of a faulted segment, from either side of a fault, in a radial feeder that has several converter interfaced DGs is a challenging task when current sensing protective devices are employed. The protective device, even if it senses a downstream fault, may not operate if fault current level is low due to the current limiting operation of converters. In this paper, a new inverse type relay is introduced based on line admittance measurement to protect a distribution network, which has several converter interfaced DGs. The basic operation of this relay, its grading and reach settings are explained. Moreover a method is proposed to compensate the fault resistance such that the relay operation under this condition is reliable. Then designed relay performances are evaluated in a radial distribution network. The results are validated through PSCAD/EMTDC simulation and MATLAB calculations.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.