Influence of tilt and surface roughness on the outflow wind field of an impinging jet

A physical and numerical steady flow impinging jet has been used to simulate the bulk characteristics of a downburst-like wind field. The influence of downdraft tilt and surface roughness on the ensuing wall jet flow has been investigated. It was found that a simulated downdraft impinging the surface at a non-normal angle has the potential for causing larger structural loads than the normal impingement case. It was also found that for the current impinging jet simulations, surface roughness played a minor role in determining the storm maximum wind structure, but this influence increased as the wall jet diverged. However, through comparison with previous research it was found that the influence of surface roughness is Reynolds number dependent and therefore may differ from that reported herein for full-scale downburst cases. Using the current experimental results an empirical model has been developed for laboratory-scale impinging jet velocity structure that includes the influence of both jet tilt and surface roughness.

Unusual cross-ring SN2 reactions of [MH]− ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

4-Methoxyanilinium 2-carboxy-4,5-dichlorobenzoate

In the structure of the title salt C7H10NO+ C8H3Cl2O4- the benzene planes of the cation and anion are essentially parallel [inter-ring dihedral angle 4.8(2)deg]. In the anion the carboxylic acid and carboxylate groups make dihedral angles of 19.0(2) and 79.5(2)\%, respectively, with the benzene ring. Aminium N-H...O, carboxylic acid O-H...O and weak aromatic C-H...O hydrogen-bonding associations with carboxyl O-atom acceptors together with cation-anion pi-pi ring interactions [minimum ring centroid separation = 3.734(3)Ang] give a two-dimensional sheet structure which lies parallel to (001).

Poly-[μ-aqua-μ5-[(2,3,6-trichlorophenyl)acetato)-caesium]

In the structure of the title complex [Cs(C8H4Cl3O2)(H2O)]n, the Cs salt of the commercial herbicide fenac [(2,3,6-trichlorophenyl)acetic acid], the irregular eight-coordination about Cs+ comprises a bidentate chelate (O:Cl) interaction involving a carboxyl O-atom and an ortho-related ring substituted Cl atom which is also bridging, a triple-bridging carboxyl O-atom and a bridging water molecule. A two-dimensional sheet polymer is generated, lying parallel to (100), within which there are water O---H...O(carboxyl) hydrogen-bonding interactions.

Poly[μ-aqua-aqua-μ5-(4-nitrobenzoato)-caesium]

In the structure of the title complex [Cs(C7H4N2O2)(H2O)2]n, the Cs salt of 4-nitrobenzoic acid, the irregular CsO9 coordination sphere comprises three bridging nitro O-donors, a bidentate carboxyl (O,O')-chelate interaction, a triple-bridging water molecule and a monodentate water molecule. A three-dimensional framework polymer is generated, within which there are water O-H...Ocarboxyl and water O-H...O(water) hydrogen-bonding interactions.

Poly[μ-aqua-bis(μ5-2,4-dichlorobenzoato)dipotassium

In the title compound, [K2(C7H3Cl2O2)2(H2O)]n, the potassium salt of 2,4-dichlorobenzoic acid, the repeating unit in the polymeric structure consists of two identical irregular KO6Cl complex units related by twofold rotational symmetry, linked by a bridging water molecule lying on the twofold axis. The coordination polyhedron about each K+ comprises a carboxyl O-atom and a Cl-atom donor from a bidentate chelate ligand interaction, four O-atom donors from a doubly bridging bidentate carboxyl (O,O')-chelate interaction and the water molecule. A two-dimensional layered coordination polymer structure lying parallel to (100) is generated through a series of conjoined cyclic bridges between K centres and is stabilized by water O-H...O(carboxyl) hydrogen-bonding interactions.

4-(4-Aminophenylsulfonyl)anilinium toluene-4-sulfonate

In the title p-toluenesulfonate salt of the drug dapsone, C12H13N2O2S+ C7H7O3S-, the dihedral angle between the two aromatic rings of the dapsone monocation is 70.19(17)deg. and those between these rings and that of the p-toluenesulfonate anion are 72.34(17) and 46.43(17)deg. All amine and aminium H-atoms are involved in intermolecular N-H...O hydrogen-bonding associations with sulfonyl O-atom acceptors as well as one of the sulfone O-atoms, giving a three-dimensional structure.

Poly[mu5-{hydrogen bis[(E)-cinnamato]}-caesium

In the structure of the title polymeric complex [Cs2(C9H7O2)(C9H8O2)]n, the Cs salt-adduct of trans-cinnamic acid, the Cs+ ions of the two individual irregular CsO8 coordination polyhedra lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two cinnamate ligand species. These two ligand components are inter-linked through a delocalized H atom within a short O...H...O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The crystal was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.

Poly[di-mu-aqua-bis{2-amino-4-nitrobenzoato)]-dirubidium

In the structure of title compound [Rb2(C7H5N2O4)2(H2O)2]n the asymmetric unit comprises two independent and different seven-coordinate Rb centres, one RbO7, the other RbO6N, with both having irregular stereochemistry. The RbO7 coordination comprises bridging oxygen donors from two water molecules, three carboxylate groups, and a nitro group, with one doubly bridging. The RbO6N coordination comprises the two bridging water molecules, one monodentate amine N donor, one carboxyl O donor and three O donors from nitro groups (one from the chelate bridge). The extension of the dinuclear unit gives a three-dimensional polymeric structure which is stabilized by both intra- and intermolecular amine N-H...O and water O-H...O hydrogen bonds to carboxyl and water O-atom acceptors, as well as a number of inter-ring \p--\p interactions [minimum ring centroid separation, 3.364(2) \%A]. This complex is both isostructural with the analogous Cs -nitroanthranilate monohydrate complex.

Three-dimensional hydrogen-bonded structures in the hydrated proton-transfer salts of isonipecotamide with the dicarboxylic oxalic and adipic acid analogues

The structures of the 1:1 hydrated proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with oxalic acid, 4-carbamoylpiperidinium hydrogen oxalate dihydrate, C6H13N2O+·C2HO4-·2H2O, (I), and with adipic acid, bis­(4-car­bam­oylpiperidinium) adipate dihydrate, 2C6H13N2O+·C6H8O42-·2H2O, (II), are three-dimensional hydrogen-bonded constructs involving several different types of enlarged water-bridged cyclic associations. In the structure of (I), the oxalate monoanions give head-to-tail carb­oxy­lic acid O-HOcarboxyl hydrogen-bonding inter­actions, forming C(5) chain substructures which extend along a. The isonipecotamide cations also give parallel chain substructures through amide N-HO hydrogen bonds, the chains being linked across b and down c by alternating water bridges involving both carboxyl and amide O-atom acceptors and amide and piperidinium N-HOcarboxyl hydrogen bonds, generating cyclic R43(10) and R32(11) motifs. In the structure of (II), the asymmetric unit comprises a piperidinium cation, half an adipate dianion, which lies across a crystallographic inversion centre, and a solvent water mol­ecule. In the crystal structure, the two inversion-related cations are inter­linked through the two water mol­ecules, which act as acceptors in dual amide N-HOwater hydrogen bonds, to give a cyclic R42(8) association which is conjoined with an R44(12) motif. Further N-HOwater, water O-HOamide and piperidinium N-HOcarbox­yl hydrogen bonds give the overall three-dimensional structure. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. The presence of solvent water mol­ecules in these structures is largely responsible for the non-occurrence of the common hydrogen-bonded amide-amide dimer, promoting instead various expanded cyclic hydrogen-bonding motifs.

Surface dosimetry for very small X-ray beams

Introduction The dose to skin surface is an important factor for many radiotherapy treatment techniques. It is known that TPS predicted surface doses can be significantly different from actual ICRP skin doses as defined at 70 lm. A number of methods have been implemented for the accurate determination of surface dose including use of specific dosimeters such as TLDs and radiochromic film as well as Monte Carlo calculations. Stereotactic radiosurgery involves delivering very high doses per treatment fraction using small X-ray fields. To date, there has been limited data on surface doses for these very small field sizes. The purpose of this work is to evaluate surface doses by both measurements and Monte Carlo calculations for very small field sizes. Methods All measurements were performed on a Novalis Tx linear accelerator which has a 6 MV SRS X-ray beam mode which uses a specially thin flattening filter. Beam collimation was achieved by circular cones with apertures that gave field sizes ranging from 4 to 30 mm at the isocentre. The relative surface doses were measured using Gafchromic EBT3 film which has the active layer at a depth similar to the ICRP skin dose depth. Monte Carlo calculations were performed using the BEAMnrc/EGSnrc Monte Carlo codes (V4 r225). The specifications of the linear accelerator, including the collimator, were provided by the manufacturer. Optimisation of the incident X-ray beam was achieved by an iterative adjustment of the energy, spatial distribution and radial spread of the incident electron beam striking the target. The energy cutoff parameters were PCUT = 0.01 MeV and ECUT = 0.700 - MeV. Directional bremsstrahlung splitting was switched on for all BEAMnrc calculations. Relative surface doses were determined in a layer defined in a water phantom of the same thickness and depth as compared to the active later in the film. Results Measured surface doses using the EBT3 film varied between 13 and 16 % for the different cones with an uncertainty of 3 %. Monte Carlo calculated surface doses were in agreement to better than 2 % to the measured doses for all the treatment cones. Discussion and conclusions This work has shown the consistency of surface dose measurements using EBT3 film with Monte Carlo predicted values within the uncertainty of the measurements. As such, EBT3 film is recommended for in vivo surface dose measurements.

Coordination polymeric structures in the sodium salt of 4-chloro-3-nitrobenzoic acid and the sodium and potassium salts of 4-nitroanthranilic acid

The structures of the hydrated sodium salts of 4-chloro-3-nitrobenzoic acid {poly[aqua(μ4-4-chloro-3-nitrobenzoato)sodium(I)], [Na(C7H3ClNO4)(H2O)]n, (I)} and 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ3-2-amino-4-nitrobenzoato)sodium(I)], [Na(C7H5N2O4)(H2O)2]n, (II)}, and the hydrated potassium salt of 2-amino-4-nitrobenzoic acid {poly[μ-aqua-aqua(μ5-2-amino-4-nitrobenzoato)potassium(I)], [K(C7H5N2O4)(H2O)]n, (III)} have been determined and their complex polymeric structures described. All three structures are stabilized by intra- and intermolecular hydrogen bonding and strong π–π ring interactions. In the structure of (I), the distorted trigonal bipyrimidal NaO5 coordination polyhedron comprises a monodentate water molecule and four bridging carboxylate O-atom donors, generating a two-dimensional polymeric structure lying parallel to (001). Intra-layer hydrogen-bonding associations and strong inter-ring π–π interactions are present. Structure (II) has a distorted octahedral NaO6 stereochemistry, with four bridging O-atom donors, two from a single carboxylate group and two from a single nitro group and three from the two water molecules, one of which is bridging. Na centres are linked through centrosymmetric four-membered duplex water bridges and through 18-membered duplex head-to-tail ligand bridges. Similar centrosymmetric bridges are found in the structure of (III), and in both (II) and (III) strong inter-ring π–π interactions are found. A two-dimensional layered structure lying parallel to (010) is generated in (II), whereas in (III) the structure is three-dimensional. With (III), the irregular KO7 coordination polyhedron comprises a doubly bridging water molecule, a single bidentate bridging carboxylate O-atom donor and three bridging O-atom donors from the two nitro groups. A three-dimensional structure is generated. These coordination polymer structures are among the few examples of metal complexes of any type with either 4-chloro-3-nitrobenzoic acid or 4-nitroanthranilic acid.

Hydrogen-bonded two- and three-dimensional polymeric structures in the ammonium salts of 3,5-dinitrobenzoic acid, 4-nitrobenzoic acid and 2,4-dichlorobenzoic acid

The structures of the ammonium salts of 3,5-dinitrobenzoic acid, NH4+ C7H3N2O6- (I), 4-nitrobenzoic acid, NH4+ C7H4N2O4- . 2H2O (II) and 2,4-dichlorobenzoic acid, NH4+ C7H3Cl2O2- . 0.5H2O (III), have been determined and their hydrogen-bonded structures are described. All salts form hydrogen-bonded polymeric structures, three-dimensional in (I) and two-dimensional in (II) and (III). With (I), a primary cation-anion cyclic association is formed [graph set R3/4(10)] through N-H...O hydrogen bonds, involving a carboxyl O,O' group on one side and a single carboxyl O-atom on the other. Structure extension involves both N-H...O hydrogen bonds to both carboxyl and nitro O-atom acceptors. With structure (II), the primary inter-species interactions and structure extension into layers lying parallel to (0 0 1) are through conjoined cyclic hydrogen-bonding motifs: R3/4(10) [one cation, a carboxyl (O,O') group and two water molecules] and centrosymmetric R2/4(8) [two cations and two water molecules]. The structure of (III) also has conjoined R3/4(10) and centrosymmetric R2/4(8) motifs in the layered structure but these differ in that he first involves one cation, a carboxyl (O,O') as well as a carboxyl (O) group and one water molecule, the second, two cations and two carboxyl O-groups. The layers lie parallel to (1 0 0). The structures of the salt hydrates (II) and (III) reported in this work, giving two-dimensional layered arrays through conjoined hydrogen-bonded nets provide further illustrations of a previously indicated trend among ammonium salts of carboxylic acids, but the anhydrous three-dimensional structure of (I) is inconsistent.

Effect of vertical misalignment of adjacent sleepers on the increase in dynamic loads around rail joints

In spite of the extensive usage of continuous welded rails, a number of rail joints still exist in the track. Although a number of them exist as part of turnouts in the yards where the speed is not of concern, the Insultated Rail Joints (IRJs) that exist in ballasted tracks remain a source of significant impact loading. A portion of the dynamic load generated at the rail joints due to wheel passage is transmitted to the support system which leads to permanent settlements of the ballast layer with subsequent vertical misalignment of the sleepers around the rail joints. The vertical misalignment of the adjacent sleepers forms a source of high frequency dynamic load raisers causing significant maintenance work including localised grinding of railhead around the joint, re-alignment of the sleepers and/or ballast tamping or track component renewals/repairs. These localised maintenance activities often require manual inspections and disruptions to the train traffic loading to significant costs to the rail industry. Whilst a number of studies have modelled the effect of joints as dips, none have specifically attended to the effect of vertical misalignment of the sleepers on the dynamic response of rail joints. This paper presents a coupled finite element track model and rigid body track-vehicle interaction model through which the effects of vertical of sleepers on the increase in dynamic loads around the IRJ are studied. The finite element track model is employed to determine the generated dip from elastic deformations as well as the vertical displacement of sleepers around the joint. These data (dip and vertical misalignments) are then imported into the rigid body vehicle-track interaction model to calculate the dynamic loads.

The project approach in early childhood education for sustainability : examplars from Korea and Australia

Sustainability is a global issue that urgently needs addressing, and for which the most serious consequences are for children and future generations. This insightful research text tackles one of the most significant contemporary issues of our times – the nexus between society and environment – and how early childhood education can contribute to sustainable living. By offering international and multidisciplinary research perspectives on Early Childhood Education for Sustainability, each chapter explores and investigates the complex topic of sustainability and its relationship to early childhood education. A particular emphasis that runs through this text is young children as empowered citizens, capable of both contributing to and creating change for sustainability. The chapter authors work from, or are aligned with, a transformative education paradigm that suggests the socio-constructivist frameworks currently underpinning Early Childhood Education require reframing in light of the social transformations necessary to address humanity’s unsustainable, unjust and unhealthy living patterns. This research text is designed to be provocative and challenging; in so doing it seeks to encourage exploration of current understandings about Early Childhood Education for Sustainability, offers new dimensions for more deeply informed practice, and proposes avenues for further research in this field.