Two-dimensional hydrogen-bonded polymers in the crystal structures of the ammonium salts of phenoxyacetic acid, (4-fluorophenoxy)acetic acid and (4-chloro-2-methylphenoxy)acetic acid

The structures of the ammonium salts of phenoxyacetic acid, NH4+ C8H6O3- (I), (4-fluorophenoxy)acetic acid NH4+ C8H5FO3- (II) and the herbicidally active (4-chloro-2-methylphenoxy)acetic acid (MCPA), NH4+ C9H8ClO3-. 0.5(H2O) (III) have been determined. All have two-dimensional layered structures based on inter-species ammonium N-H...O hydrogen-bonding associations which give core substructures consisting primarily of conjoined cyclic motifs. Crystals of (I) and (II) are isomorphous with the core comprising R2/1(5), R2/1(4) and centrosymmetric R2/4(8) ring motifs, giving two-dimensional layers lying parallel to (100). In (III), the water molecule of solvation lies on a crystallographic twofold rotation axis and bridges two carboxyl O-atoms in an R4/4(12) hydrogen-bonded motif, creating two R3/4(10) rings which together with a conjoined centrosymmetric R2/4(8) ring incorporating both ammonium cations, generate two-dimensional layers lying parallel to (100). No pi-pi ring associations are present in any of the structures.

Response of segmented bored transit tunnels to surface blast

Increasing threat of terrorism highlights the importance of enhancing the resilience of underground tunnels to all hazards. This paper develops, applies and compares the Arbitrary Lagrangian Eulerian (ALE) and Smooth Particle Hydrodynamics (SPH) techniques to treat the response of buried tunnels to surface explosions. The results and outcomes of the two techniques were compared, along with results from existing test data. The comparison shows that the ALE technique is a better method for describing the tunnel response for above ground explosion with regards to modeling accuracy and computational efficiency. The ALE technique was then applied to treat the blast response of different types of segmented bored tunnels buried in dry sand. Results indicate that the most used modern ring type segmented tunnels were more flexible for in-plane response, however, they suffered permanent drifts between the rings. Hexagonal segmented tunnels responded with negligible drifts in the longitudinal direction, but the magnitudes of in-plane drifts were large and hence hazardous for the tunnel. Interlocking segmented tunnels suffered from permanent drifts in both the longitudinal and transverse directions. Multi-surface radial joints in both the hexagonal and interlocking segments affected the flexibility of the tunnel in the transverse direction. The findings offer significant new information in the behavior of segmented bored tunnels to guide their future implementation in civil engineering applications.

Blast response of segmented bored tunnel using coupled SPH–FE method

Underground transport tunnels are vulnerable to blast events. This paper develops and applies a fully coupled technique involving the Smooth Particle Hydrodynamics and Finite Element techniques to investigate the blast response of segmented bored tunnels. Findings indicate that several bolts failed in the longitudinal direction due to redistribution of blast loading to adjacent tunnel rings. The tunnel segments respond as arch mechanisms in the transverse direction and suffered damage mainly due to high bending stresses. The novel information from the present study will enable safer designs of buried tunnels and provide a benchmark reference for future developments in this area.

Field and Service Robotics: Results of the 9th International Conference

The Field and Service Robotics (FSR) conference is a single track conference with a specific focus on field and service applications of robotics technology. The goal of FSR is to report and encourage the development of field and service robotics. These are non-factory robots, typically mobile, that must operate in complex and dynamic environments. Typical field robotics applications include mining, agriculture, building and construction, forestry, cargo handling and so on. Field robots may operate on the ground (of Earth or planets), under the ground, underwater, in the air or in space. Service robots are those that work closely with humans, importantly the elderly and sick, to help them with their lives. The first FSR conference was held in Canberra, Australia, in 1997. Since then the meeting has been held every 2 years in Asia, America, Europe and Australia. It has been held in Canberra, Australia (1997), Pittsburgh, USA (1999), Helsinki, Finland (2001), Mount Fuji, Japan (2003), Port Douglas, Australia (2005), Chamonix, France (2007), Cambridge, USA (2009), Sendai, Japan (2012) and most recently in Brisbane, Australia (2013). This year we had 54 submissions of which 36 were selected for oral presentation. The organisers would like to thank the international committee for their invaluable contribution in the review process ensuring the overall quality of contributions. The organising committee would also like to thank Ben Upcroft, Felipe Gonzalez and Aaron McFadyen for helping with the organisation and proceedings. and proceedings. The conference was sponsored by the Australian Robotics and Automation Association (ARAA), CSIRO, Queensland University of Technology (QUT), Defence Science and Technology Organisation Australia (DSTO) and the Rio Tinto Centre for Mine Automation, University of Sydney.

Carbon nanotube-based super nanotubes: Tunable thermal conductivity in three dimensions

Advances in nanomaterials/nanostructures offer the possibility of fabricating multifunctional materials for use in engineering applications. Carbon nanotube (CNT)-based nanostructures are a representative building block for these multifunctional materials. Based on a series of in silico studies, we investigated the possibility of tuning the thermal conductivity of a three-dimensional CNT-based nanostructure: a single-walled CNT-based super-nanotube. The thermal conductivity of the super-nanotubes was shown to vary with different connecting carbon rings and super-nanotubes with longer constituent single-walled CNTs and larger diameters had a smaller thermal conductivity. The inverse of the thermal conductivity of the super-nanotubes showed a good linear relationship with the inverse of the length. The thermal conductivity was approximately proportional to the inverse of the temperature, but was insensitive to the axial strain as a result of the Poisson ratio. These results provide a fundamental understanding of the thermal conductivity of the super-nanotubes and will guide their future design/fabrication and engineering applications.

Tuning the resonance properties of 2D carbon nanotube networks towards a mechanical resonator

The capabilities of the mechanical resonator-based nanosensors in detecting ultra-small mass or force shifts have driven a continuing exploration of the palette of nanomaterials for such application purposes. Based on large-scale molecular dynamics simulations, we have assessed the applicability of a new class of carbon nanomaterials for nanoresonator usage, i.e. the single-wall carbon nanotube (SWNT) network. It is found that SWNT networks inherit excellent mechanical properties from the constituent SWNTs, possessing a high natural frequency. However, although a high quality factor is suggested from the simulation results, it is hard to obtain an unambiguous Q-factor due to the existence of vibration modes in addition to the dominant mode. The nonlinearities resulting from these extra vibration modes are found to exist uniformly under various testing conditions including different initial actuations and temperatures. Further testing shows that these modes can be effectively suppressed through the introduction of axial strain, leading to an extremely high quality factor in the order of 109 estimated from the SWNT network with 2% tensile strain. Additional studies indicate that the carbon rings connecting the SWNTs can also be used to alter the vibrational properties of the resulting network. This study suggests that the SWNT network can be a good candidate for applications as nanoresonators.

On the biomechanical significance of inter-lamellar interfaces in the intervertebral disc

The intervertebral disc (IVD) is a unique soft tissue structure which provides structural support and flexibility in the axial skeleton of vertebrates. From a structural perspective, the disc behaves somewhat like a thick walled pressure vessel, where the walls are comprised of a series of composite annular rings (lamellae). However, a prior study (Marchand and Ahmed, 1990) found a high proportion of circumferentially discontinuous lamellae in human lumbar IVDs. The presence of these discontinuities raises important structural questions, because discontinuous lamellae cannot withstand high nucleus pressures via the generation of circumferential (hoop) stress. A possible alternative mechanism may be that inter-lamellar cohesion allows shear stress transfer between adjacent annular layers. The aim of the present study was therefore to investigate the importance of inter-lamellar shear resistance in the intervertebral disc. This work found that inter-lamellar shear resistance has a strong influence on the compressive stiffness of the intervertebral disc, with a change in interface condition from tied (no slip) to frictionless (no shear resistance) reducing disc compressive stiffness by 40%. However, it appears that substantial inter-lamellar shear resistance is present in the bovine tail disc. Decreases in inter-lamellar shear resistance due to degradation of bridging collagenous or elastic fibre structures could therefore be an important part of the process of disc degeneration.

Multimodal imaging of the collagen and elastic fibre networks in the bovine intervertebral disc

INTRODUCTION. The intervertebral disc is the largest avascular structure in the human body, withstanding transient loads of up to nine times body weight during rigorous physical activity. The key structural elements of the disc are a gel-like nucleus pulposus surrounded by concentric lamellar rings containing criss-crossed collagen fibres. The disc also contains an elastic fiber network which has been suggested to play a structural role, but to date the relationship between the collagen and elastic fiber networks is unclear. CONCLUSION. The multimodal transmitted and reflected polarized light microscopy technique developed here allows clear differentiation between the collagen and elastic fiber networks of the intervertebral disc. The ability to image unstained specimens avoids concerns with uneven stain penetration or specificity of staining. In bovine tail discs, the elastic fiber network is intimately associated with the collagen network.

Inhibition of myeloperoxidase- and neutrophil-mediated oxidant production by tetraethyl and tetramethyl nitroxides

The powerful oxidant HOCl (hypochlorous acid and its corresponding anion, −OCl) generated by the myeloperoxidase (MPO)–H2O2–Cl− system of activated leukocytes is strongly associated with multiple human inflammatory diseases; consequently there is considerable interest in inhibition of this enzyme. Nitroxides are established antioxidants of low toxicity that can attenuate oxidation in animal models, with this ascribed to superoxide dismutase or radical-scavenging activities. We have shown (M.D. Rees et al., Biochem. J. 421, 79–86, 2009) that nitroxides, including 4-amino-TEMPO (4-amino-2,2,6,6-tetramethylpiperidin-1-yloxyl radical), are potent inhibitors of HOCl formation by isolated MPO and activated neutrophils, with IC50 values of ~1 and ~6 µM respectively. The utility of tetramethyl-substituted nitroxides is, however, limited by their rapid reduction by biological reductants. The corresponding tetraethyl-substituted nitroxides have, however, been reported to be less susceptible to reduction. In this study we show that the tetraethyl species were reduced less rapidly than the tetramethyl species by both human plasma (89–99% decreased rate of reduction) and activated human neutrophils (62–75% decreased rate). The tetraethyl-substituted nitroxides retained their ability to inhibit HOCl production by MPO and activated neutrophils with IC50 values in the low-micromolar range; in some cases inhibition was enhanced compared to tetramethyl substitution. Nitroxides with rigid structures (fused oxaspiro rings) were, however, inactive. Overall, these data indicate that tetraethyl-substituted nitroxides are potent inhibitors of oxidant formation by MPO, with longer plasma and cellular half-lives compared to the tetramethyl species, potentially allowing lower doses to be employed.

Multifocal electroretinogram responses in Nepalese diabetic patients without retinopathy

Purpose To determine neuroretinal function with multifocal electroretinogram (mfERG) in diabetic subjects without retinopathy. Methods Multifocal electroretinogram (mfERG) was performed in 18 eyes of 18 diabetic subjects without retinopathy and 17 eyes of 17 age and gender-matched healthy control participants. Among 18 diabetic subjects, two had type 1 and 16 had type 2 diabetes. MfERG responses were averaged by the retinal areas of six concentric rings and four quadrants, and 103 retinal locations; N1–P1 amplitude and P1-implicit time were analysed. Results Average mfERG N1–P1 amplitude (in nv/deg2) of 103 retinal locations was 56.3 ± 17.2 (mean ± SD) in type 1 diabetic subjects, 47.2 ± 9.3 in type 2 diabetic subjects and 71.5 ± 12.7 in controls. Average P1-implicit time (in ms) was 43.0 ± 1.3 in type 1 diabetic subjects, 43.9 ± 2.3 in type 2 diabetic subjects and 41.9 ± 2.1 in controls. There was significant reduction in average N1–P1 amplitude and delay in P1-implicit time in type 2 diabetic subjects in comparison to controls. mfERG amplitude did not show any significant correlation with diabetes duration and blood sugar level. However, implicit time showed a positive correlation with diabetes duration in type 2 diabetic subjects with diabetes duration ≥5 years. Conclusions This is the first study in a Nepalese population with diabetes using multifocal electroretinography. We present novel findings that mfERG N1–P1 amplitude is markedly reduced along with delay in P1-implicit time in type 2 diabetic subjects without retinopathy. These findings indicate that there might be significant dysfunction of inner retina before the development of diabetic retinopathy in the study population, which have higher prevalence of diabetes than the global estimate and uncontrolled blood sugar level.

X-Ray Studies On The Bilayer Structure Of Trypsin-Treated Rat-Brain Myelin

Trypsin-treated rat brain myelin was subjected to biochemical and X-ray studies. Untreated myelin gave rise to a pattern of three rings with a fundamental repeat period of 155 Angstrom consisting of two bilayers per repeat period, whereas myelin treated with trypsin showed a fundamental repeat period of 75 Angstrom with one bilayer per repeat period. The integrated raw intensity of the h=4 reflection with respect to the h=2 reflection is 0.38 for untreated myelin. The corresponding value reduced to 0.23, 0.18, 0.17 for myelin treated with 5, 10, 40 units of trypsin per mg of myelin, respectively, for 30 min at 30 degrees C. The decrease in relative raw intensity of the higher-order reflection relative to the lower-order reflection is suggestive of a disordering of the phosphate groups upon trypsin treatment or an increased mosaicity of the membrane or a combination of both these effects, However, trypsin treatment does not lead to a complete breakdown of the membrane, The integrated intensity of the h=1 reflection, though weak, is above the measurable threshold for untreated myelin, whereas the corresponding intensity is below the measurable threshold for trypsin-treated myelin, indicating a possible asymmetric to symmetric transition of the myelin bilayer structure about its centre after trypsin treatment.

2-[2-(Hydroxymethyl)phenyl]-1-phenylethanol

The title compound, C15H16O2, has a dihedral angle of 19.10 (5)degrees between the mean planes of the two benzene rings. There is an intramolecular O-H center dot center dot center dot O hydrogen bond and the C-C-C-C torsion angle across the bridge between the two rings is 173.13 (14)degrees. The molecules form intermolecular O-H center dot center dot center dot O hydrogen-bonded chains extending along the a axis. C-H center dot center dot center dot pi contacts are also observed between molecules within the chains.

1,3-Dimethyl-2,6-diphenylpiperidin-4-one

In the title moleclue, C19H21NO, the 4-piperidone ring adopts a chair conformation in which the two benzene rings and the methyl group attached to C atoms all have equatorial orientations. In the crystal structure, centrosymmetric dimers are formed through weak intermolecular C-H center dot center dot center dot O hydrogen bonds [the dihedral angle between the aromatic rings is 58.51 (5)degrees].

Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)(5)P-4(OPh)(2) 2 and its monoxide (EtN)(5)P-4(O)(OPh)(2) 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)(5)P-4(O)(OPh)(2) 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)(5)P-4(O)(OPh)(2)(O2C6Cl4) 5 in which the junction phosphorus atom becomes five-co-ordinated. Treatment of 2 or 3a with [Mo(CO)(4)(nbd)] (nbd = norbornadiene, bicyclo[2.2.1]hepta-2,5-diene), on the other hand, yielded the chelate complex [Mo(CO)(4){(EtN)(5)P-4(O)(n)(OPh)(2)}] (n = 0 or 1; 6 or 7) in which the peripheral phosphorus atoms are bonded to the metal. The structures of 3a and 5-7 have been confirmed by single-crystal X-ray diffraction studies. The two P3N3 rings in 3a and 5 adopt twist/twist and irregular/twist conformations respectively; the phenoxy substituents occupy the 'pseudo axial' positions. However, an ideal chair conformation is observed for the P3N3 rings in 6 and 7 with the phenoxy substituents taking up the 'pseudo equatorial' positions. The NMR spectroscopic data for the compounds are discussed.

Synthesis, structure and spectroscopic studies on hydroxo-bridged heterotrinuclear complexes of cobalt(m) with ethane-l,2-diamine and ammonia as terminal ligands

Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have envelope conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.