Intermolecular Interactions and Thermodynamic Properties of 3,6-Diamino-1,2,4,5-tetrazine-1,4-dioxide Dimers: A Density Functional Theoretical Study

Three fully optimized structures of 3,6-diamino-1,2,4,5-tetrazine-1,4-dioxide (LAX-112) dimers have been obtained with the density functional theory (DFT) method at the B3LYP/6-311++G level. Vibrational frequency calculations were carried out to ascertain that each structure is a minimum (no imaginary frequencies). The intermolecular interaction energy is calculated with the basis set superposition error (BSSE) correction and zero point energy (ZPE) correction. The greatest corrected binding energy among the three dimers is –42.38 kJ mol–1. The charge redistribution mainly occurs on the adjacent O(N)……H atoms between submolecules and the charge transfer between two subsystems is very small. Natural bond orbital (NBO) analysis was performed to reveal the origin of the interaction. Based on the vibrational analysis, the standard thermodynamic functions (heat capacities (cop), entropies (Som ) and enthalpies (Hom)) and the changes of thermodynamic properties from the monomer to dimer with the temperature ranging from 200.00 K to 800.00 K have been obtained using statistical thermodynamics. The results show that the strong hydrogen bonds dominantly contribute to the dimers, while the bonding energies are not only determined by the hydrogen bonding. The dimerization process of dimer II can occur spontaneously at room temperature.KEYWORDS 3,6-Diamino-1,2,4,5-tetrazine-1,4-dioxide (LAX-112), intermolecular interaction, density functional theory (DFT), natural bond orbital (NBO) analysis, thermodynamic properties

Insecticidal activity of essential oil of Cinnamomum cassia and its main constituent, trans-Cinnamaldehyde, against the booklice, Liposcelis bostrychophila

Purpose: To investigate the insecticidal activity of the essential oil of Cinnamomum cassis and its main constituent compound, trans-cinnamaldehyde, against the booklice, Liposcelis bostrychophila．Methods: Steam distillation of C. cassis twigs was carried out using a Clavenger apparatus in order to obtain the volatile oils. Gas chromatography/mass spectrometric (GC/MS) analyses (HP-5MS column) of the essential oil were performed and its contact (using impregnated filter paper method) and fumigant toxicity (sealed space) determined. The bioactive constituent compound, trans-cinnamaldehyde was isolated and identified from the oil based on bioactivity-directed fractionation.Results: A total of 35 components, accounting for 97.44 % of the essential oil of C. cassis, were identified. The principal compounds in the essential oil were trans-cinnamaldehyde (49.33 %), acetophenone (6.94 %), trans-cinnamic acid (5.45 %) and cis-cinnamaldehyde (4.44 %) followed by omethoxycinnamaldehyde (3.48 %), coumarin (3.42 %) and (E)-cinnamyl alcohol (3.21 %). The essential oil displayed contact toxicity against adult L. bostrychophila with a median lethal concentration (LC50) of 55.68 μg/cm2 as well as fumigant toxicity (LC50, 1.33 mg/l air). Trans-cinnamaldehyde exhibited strong contact and fumigant toxicity with LC50 and 1.29 mg/l air, respectively.Conclusion: The findings suggest that the essential oil of C. cassis and its constituent compound, trans-cinnamaldehyde, possess potentials for development into natural fumigants/insecticides for the control of booklice.Keywords: Liposcelis bostrychophila, Cinnamomum cassis, Contact toxicity, Fumigant, trans- Cinnamaldehyde, Essential oi

Thermal Behaviour and Detonation Characterization of N-Benzoyl-3,3-dinitroazetidine

N-benzoyl-3,3-dinitroazetidine(BDNAZ) is a derivative of 3,3-dinitroazetidine (DNAZ). Its thermal behaviour was studied by DSC methods. The results show that there are one melting process and two exothermic decomposition processes. The kinetic parameters of the intense exothermic decomposition process were obtained from the analysis of the DSC curves. The apparent activation energy, pre-exponential factor and the mechanism function are 170.77 kJ mol–1, 1014.12 s–1 and f(α) = (1–a)–1/2, respectively. The specific heat capacity of BDNAZ was determined with a continuous Cp mode of a micro-calorimeter. The standard mole specific heat capacity ofBDNAZwas 286.31 J mol1 K–1 at 298.15 K. Using the relationship between Cp and T with the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion, tTIAD), the self-accelerating decomposition temperature (TSADT), thermal ignition temperature (TTIT), critical temperatures of thermal explosion (Tb) and period of validity (t0.9) were obtained to evaluate its thermal safety. The detonation velocity (D) and pressure (P) of BDNAZ were estimated by using the nitrogen equivalent equation according to the experimental density.KEYWORDS N-benzoyl-3,3-dinitroazetidine(BDNAZ), thermalbehaviour, non-isothermalkinetics, thermalsafety, detonation characterization

Ranks of ideals in inverse semigroups of difunctional binary relations

The set Dn of all difunctional relations on an n element set is an inverse semigroup under a variation of the usual composition operation. We solve an open problem of Kudryavtseva and Maltcev (Publ Math Debrecen 78(2):253–282, 2011), which asks: What is the rank (smallest size of a generating set) of Dn? Specifically, we show that the rank of Dn is B(n)+n, where B(n) is the nth Bell number. We also give the rank of an arbitrary ideal of Dn. Although Dn bears many similarities with families such as the full transformation semigroups and symmetric inverse semigroups (all contain the symmetric group and have a chain of J-classes), we note that the fast growth of rank(Dn) as a function of n is a property not shared with these other families

Microbial ligand costimulation drives neutrophilic steroid-refractory asthma

Funding: The authors thank the Wellcome Trust (102705) and the Universities of Aberdeen and Cape Town for funding. This research was also supported, in part, by National Institutes of Health GM53522 and GM083016 to DLW. KF and BNL are funded by the Fonds Wetenschappelijk Onderzoek, BNL is the recipient of an European Research Commission consolidator grant and participates in the European Union FP7 programs EUBIOPRED and MedALL. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.Peer reviewedPublisher PD

Polarisation dynamics of vector soliton molecules in mode locked fibre laser

Two fundamental laser physics phenomena - dissipative soliton and polarisation of light are recently merged to the concept of vector dissipative soliton (VDS), viz. train of short pulses with specific state of polarisation (SOP) and shape defined by an interplay between anisotropy, gain/loss, dispersion, and nonlinearity. Emergence of VDSs is both of the fundamental scientific interest and is also a promising technique for control of dynamic SOPs important for numerous applications from nano-optics to high capacity fibre optic communications. Using specially designed and developed fast polarimeter, we present here the first experimental results on SOP evolution of vector soliton molecules with periodic polarisation switching between two and three SOPs and superposition of polarisation switching with SOP precessing. The underlying physics presents an interplay between linear and circular birefringence of a laser cavity along with light induced anisotropy caused by polarisation hole burning

Seeking legitimacy through CSR: Institutional Pressures and Corporate Responses of Multinationals in Sri Lanka

Arguably, the corporate social responsibility (CSR) practices of multinational enterprises (MNEs) are influenced by a wide range of both internal and external factors. Perhaps most critical among the exogenous forces operating on MNEs are those exerted by state and other key institutional actors in host countries. Crucially, academic research conducted to date offers little data about how MNEs use their CSR activities to strategically manage their relationship with those actors in order to gain legitimisation advantages in host countries. This paper addresses that gap by exploring interactions between external institutional pressures and firm-level CSR activities, which take the form of community initiatives, to examine how MNEs develop their legitimacy-seeking policies and practices. In focusing on a developing country, Sri Lanka, this paper provides valuable insights into how MNEs instrumentally utilise community initiatives in a country where relationship-building with governmental and other powerful non-governmental actors can be vitally important for the long-term viability of the business. Drawing on neo-institutional theory and CSR literature, this paper examines and contributes to the embryonic but emerging debate about the instrumental and political implications of CSR. The evidence presented and discussed here reveals the extent to which, and the reasons why, MNEs engage in complex legitimacy-seeking relationships with Sri Lankan institutions