Crystal structures and hydrogen bonding in the proton transfer salts of nicotine with 3,5-dinitrosalicylic acid and 5-sulfosalicylic acid

The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-dinitrosalicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 2-carboxy-4,6-dinitrophenolate, C10H15N2+ C7H3N2O7-, (I) and (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 3-carboxy-4-hydroxybenzenesulfonate, C10H15N2+ C7H5O6S-, (II) are reported. The asymmetric units of both (I) and (II) comprise two independent nicotinium cations (C and D) and either two DNSA or two 5-SSA anions (A and B), respectively. One of the DNSA anions shows a 25% rotational disorder in the benzene ring system. In the crystal of (I), inter-unit pyrrolidinium N-H...N(pyridine) hydrogen bonds generate zigzag NIC cation chains which extend along a while the DNSA anions are not involved in any formal inter-species hydrogen bonding but instead form pi--pi associated stacks which parallel the NIC chains along a [ring centroid separation, 3.857(2)A]. Weak C-H...O interactions between chain substructures give an overall three-dimensional structure. With (II), A and B anions form independent zigzag chains with C and D cations, respectively, through carboxylic acid O-H...N(pyridine) hydrogen bonds. These chains, which extend along b are pseudo-centrosymmetrically related and give pi--pi interactions between the benzene rings of anions A and B and the pyridine rings of the NIC cations C and D, respectively [ring centroid separations, 3.6422(19) and 3.7117(19)A]. Present also are weak intermolecular C-H...O hydrogen-bonding interactions between the chains, giving an overall three-dimensional structure.

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.

Analytical study of implementation issues of NTRU

Nth-Dimensional Truncated Polynomial Ring (NTRU) is a lattice-based public-key cryptosystem that offers encryption and digital signature solutions. It was designed by Silverman, Hoffstein and Pipher. The NTRU cryptosystem was patented by NTRU Cryptosystems Inc. (which was later acquired by Security Innovations) and available as IEEE 1363.1 and X9.98 standards. NTRU is resistant to attacks based on Quantum computing, to which the standard RSA and ECC public-key cryptosystems are vulnerable to. In addition, NTRU has higher performance advantages over these cryptosystems. Considering this importance of NTRU, it is highly recommended to adopt NTRU as part of a cipher suite along with widely used cryptosystems for internet security protocols and applications. In this paper, we present our analytical study on the implementation of NTRU encryption scheme which serves as a guideline for security practitioners who are novice to lattice-based cryptography or even cryptography. In particular, we show some non-trivial issues that should be considered towards a secure and efficient NTRU implementation.

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.

Customer agility, smart shopping apps and their implications: Customer relationship management systems in the digital age

This thesis examines the complementarities and vulnerabilities of customer connectivity that contemporary firms achieved through ubiquitous digital technologies. Taking the example of deployment of smart shopping apps to connect with consumers in the context of Australian retail, the study examines how such customer connectivity positively influences firm performances through firm's customer agility whilst creating implications for firms' digital business strategy through altered customer cognitions. Employing Oliver's (1977) Expectation Confirmation Theory, this study empirically tests a conceptual model involving digital connectivity, digital expectations, experiences and satisfaction of the customers who uses smart shopping apps in Australian consumer retail.

Spine curvature analysis between participants with obesity and normal weight participants: A biplanar electromagnetic device measurement

To analyse and compare standing thoracolumbar curves in normal weight participants and participants with obesity, using an electromagnetic device, and to analyse the measurement reliability. Material and Methods. Cross-sectional study was carried out. 36 individuals were divided into two groups (normal-weight and participants with obesity) according to their waist circumference. The reference points (T1–T8–L1–L5 and both posterior superior iliac spines) were used to perform a description of thoracolumbar curvature in the sagittal and coronal planes. A transformation from the global coordinate system was performed and thoracolumbar curves were adjusted by fifth-order polynomial equations. The tangents of the first and fifth lumbar vertebrae and the first thoracic vertebra were determined from their derivatives. The reliability of the measurement was assessed according to the internal consistency of the measure and the thoracolumbar curvature angles were compared between groups. Results. Cronbach’s alpha values ranged between 0.824 (95% CI: 0.776–0.847) and 0.918 (95% CI: 0.903–0.949). In the coronal plane, no significant differences were found between groups; however, in sagittal plane, significant differences were observed for thoracic kyphosis. Conclusion. There were significant differences in thoracic kyphosis in the sagittal plane between two groups of young adults grouped according to their waist circumference.

Stochastic analysis of a radial-inflow turbine in the presence of parametric uncertainties

This paper presents an uncertainty quantification study of the performance analysis of the high pressure ratio single stage radial-inflow turbine used in the Sundstrand Power Systems T-100 Multi-purpose Small Power Unit. A deterministic 3D volume-averaged Computational Fluid Dynamics (CFD) solver is coupled with a non-statistical generalized Polynomial Chaos (gPC) representation based on a pseudo-spectral projection method. One of the advantages of this approach is that it does not require any modification of the CFD code for the propagation of random disturbances in the aerodynamic and geometric fields. The stochastic results highlight the importance of the blade thickness and trailing edge tip radius on the total-to-static efficiency of the turbine compared to the angular velocity and trailing edge tip length. From a theoretical point of view, the use of the gPC representation on an arbitrary grid also allows the investigation of the sensitivity of the blade thickness profiles on the turbine efficiency. The gPC approach is also applied to coupled random parameters. The results show that the most influential coupled random variables are trailing edge tip radius coupled with the angular velocity.

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.

Value congruence and job-related attitudes in a nonprofit organization: A competing values approach

Researchers have highlighted the importance of the nonprofit sector, its continued growth, and a relative lack of literature particularly related to nonprofit organizational values. Therefore, this study investigates organizational culture in a human services nonprofit organization. The relationship between person-organization value congruence and employee and volunteer job-related attitudes is examined (N = 227). Following initial qualitative enquiry, confirmatory factor analyses of the Competing Values Framework and additional values revealed five dimensions of organizational values. The relationship between value congruence, and employee and volunteers' job-related attitudes was examined using polynomial regression techniques. Analyses revealed that for employees, job-related attitudes were influenced strongly by organization values ratings, particularly when exceeding person ratings of the same values. For volunteers, person value ratings exceeding organization value ratings were especially detrimental to their job-related attitudes. Findings are discussed in terms of their theoretical and practical implications.

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.

Reproducibility of fatmax and fat oxidation rates during exercise in recreationally trained males

Aerobic exercise training performed at the intensity eliciting maximal fat oxidation (Fatmax) has been shown to improve the metabolic profile of obese patients. However, limited information is available on the reproducibility of Fatmax and related physiological measures. The aim of this study was to assess the intra-individual variability of: a) Fatmax measurements determined using three different data analysis approaches and b) fat and carbohydrate oxidation rates at rest and at each stage of an individualized graded test. Fifteen healthy males [body mass index 23.1±0.6 kg/m2, maximal oxygen consumption () 52.0±2.0 ml/kg/min] completed a maximal test and two identical submaximal incremental tests on ergocycle (30-min rest followed by 5-min stages with increments of 7.5% of the maximal power output). Fat and carbohydrate oxidation rates were determined using indirect calorimetry. Fatmax was determined with three approaches: the sine model (SIN), measured values (MV) and 3rd polynomial curve (P3). Intra-individual coefficients of variation (CVs) and limits of agreement were calculated. CV for Fatmax determined with SIN was 16.4% and tended to be lower than with P3 and MV (18.6% and 20.8%, respectively). Limits of agreement for Fatmax were −2±27% of with SIN, −4±32 with P3 and −4±28 with MV. CVs of oxygen uptake, carbon dioxide production and respiratory exchange rate were <10% at rest and <5% during exercise. Conversely, CVs of fat oxidation rates (20% at rest and 24–49% during exercise) and carbohydrate oxidation rates (33.5% at rest, 8.5–12.9% during exercise) were higher. The intra-individual variability of Fatmax and fat oxidation rates was high (CV>15%), regardless of the data analysis approach employed. Further research on the determinants of the variability of Fatmax and fat oxidation rates is required.

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.