Strengthening of the halogen-bonding by an aerogen bond interaction: substitution and cooperative effects in O3Z···NCX···NCY (Z = Ar,Kr, Xe; X = Cl,Br, I; Y = H,F, OH) complexes

The geometry, interaction energy and bonding properties of ternary complexes O₃Z···NCX···NCY (Z= Ar, Kr, Xe; X = Cl, Br, I and Y = H, F, OH) are investigated with ab initio calculations at the MP2/aug-cc-pVTZ level. Two different types of intermolecular interactions are present in these complexes, namely, aerogen bond (Z···N) and halogen bond (X···N). The formation mechanism and bonding properties of these complexes are analysed with molecular electrostatic potentials, quantum theory of atoms in molecules and non-covalent interaction index. It is found that the cooperativity energies in the ternary complexes are all negative; that is, the interaction energy of the ternary complex is greater (more negative) than the sum of the interaction energies of the corresponding binary systems. Also, the cooperativity energies increase with the increase of the interaction energies. The cooperative effects in the ternary complexes make a decrease in the total spin–spin coupling constants across the aerogen bonding, J(Z–N), which can be regarded as a proof for the reinforce of Z···N interactions in the ternary complexes with respect to the binary systems.     

Synthesis of pyrido[3′,2′:4,5]thieno[2,3-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-one derivatives

Some new pyrido[3′,2′:4,5]thieno[2,3-e]-[1,2,4]triazolo[4,3-a] pyrimidin-5(4H)-ones were prepared through heterocyclization of ethyl 3-aminothieno[2,3-b]pyridine-2-carboxylate with phenyl or ethyl isothiocyanate followed by nucleophilic displacement with hydrazine, and finally cyclocondensation with orthoesters. Correspondence: Abolghasem Davoodnia, Department of Chemistry, School of Sciences, Islamic Azad University, Mashhad Branch, Mashhad 91735-413, Iran.     

Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials

A new class of energetic biopolymers, which contain nitrate ester (O-NO₂) and nitramine (N-NO₂) as explosophoric groups, was successfully synthesized by surface modification of renewable pristine cellulose (PC) and microcrystalline cellulose (MCC) via epichlorohydrin-mediated amination followed by nitration process to produce new promising energetic aminated and nitrated cellulose and microcrystalline cellulose (APCN and AMCCN). Their structural, thermal, crystallinity and morphological features were examined and compared to those of the common cellulose nitrate. Furthermore, their energetic performances were evaluated by EXPLO5 V6.04 software. Experimental results confirm the successful chemical functionalization process to develop insensitive APCN and AMCCN with outstanding features such as nitrogen content of 15.01% and 15.39%, density of 1.692 g/cm³ and 1.708 g/cm³, and detonation velocity of 7526 m/s and 7752 m/s, respectively, which are significantly higher than those of the nitrated unmodified cellulosic biopolymers. The present investigation provides a suitable pathway to design new insensitive and energy-rich dense cellulosic biopolymers for potential application in high-performance solid propellants and composite explosives.

     

CuBr/Et3N‐Promoted Reactions of 2‐Aminobenzamides and Isothiocyanates: Efficient Synthesis of Novel Quinazolin‐4(3H)‐ones

A series of novel quinazolin‐4(3H)‐one derivatives were efficiently synthesized starting from isatoic anhydride. First, reaction of isatoic anhydride and amines in H₂O at room temperature afforded 2‐aminobenzamides. Then, CuBr/Et₃N promoted reaction of 2‐aminobenzamides and different aryl isothiocyanates in DMF at 80° afforded the title compounds in good yield.     

The dual role of halogen,chalcogen, and pnictogen atoms as Lewis acid and base: Triangular XBr:SHX:PH2X complexes (X = F,Cl, Br,CN, NC,OH, NH2, and OCH3)

Using ab initio calculations, we have investigated the possibility of formation of triangular XBr:SHX:PH₂X complexes, where X = F, Cl, Br, CN, NC, OH, NH₂, and OCH₃. These complexes are formed through the interaction of a positive electrostatic potential region (σ‐hole) on a molecule with the negative region in another one. The results show that the combined halogen, chalcogen, and pnictogen interactions can give rise to stable cyclic structures. The interaction energies of these complexes span over a wide range, from ?3.55 to ?24.93 kcal/mol. Nice quadratic correlations are found between the interaction energies and binding distances in the trimers. To understand the nature of the interactions in these complexes, molecular electrostatic potential and quantum theory of atoms in molecule analyses are performed. © 2015 Wiley Periodicals, Inc.     

Synthesis of a new class of azathia crown macrocycles containing two 1,2,4-triazole or two 1,3,4-thiadiazole rings as subunits

A series of new 1,2/1,3-bis[o-(N-methylidenamino-5-aryl-3-thiol-4H-1,2,4-triazole-4-yl)phenoxy]alkane derivatives 3a-d and bis[o-(N-methylidenamino-2-thiol-1,3,4-thiadiazole-5-yl)phenoxy]alkanes 6a-c were prepared by condensation of 4-amino-5-(aroyl)-4H-1,2,4-triazole-3-thiols 2a-b or 2-amino-5-mercapto-1,3,4-thiadiazole with bis-aldehydes 1a-c. Further reaction of compounds 3a-d and 6a-c with dibromoalkanes afforded the new macrocycles 5a-f and 8a-d. The cyclization does not require high dilution techniques and provides the expected azathia macrocycles in good yields, ranging from 55% to 68%.     

Local similarity solution for the flow of a “second-grade” viscoelastic fluid above a moving plate

The boundary layer flow of a viscoelastic fluid of the second-grade type over a rigid continuous plate moving through an otherwise quiescent fluid with constant velocity U is studied. Assuming the flow to be laminar and two-dimensional, local similarity solution is found with fluid's elasticity and plate's withdrawal speed as the main variables. Results are presented for velocity profiles, boundary layer thickness, wall skin friction coefficient and fluid entrainment in terms of the local Deborah number. A marked formation of boundary layer is predicted, even at low Reynolds numbers, provided the Deborah number is sufficiently large. The boundary layer thickness and the wall skin friction coefficient are found to scale with fluid's elasticity—both decreasing the higher the fluid's elasticity. The amount of fluid entrained is also predicted to decrease whenever a fluid exhibits elastic behavior.     

Triple-Diffusive Mixed Convection in a Porous Open Cavity

The triple-diffusive mixed convection heat and mass transfer of a mixture is analyzed in an enclosure filled with a Darcy porous medium. The mass transfer buoyancy effects due to concentration gradients of the dispersed components (pollutant components) are taken into account using the Boussinesq approximation model. The governing equations are transformed into a non-dimensional form, and six groups of non-dimensional parameters, including Darcy–Rayleigh number, Peclet number, two Lewis numbers for pollutant components 1 and 2 and two buoyancy ratio parameters for pollutant components 1 and 2, are introduced. The governing equations are numerically solved for various combinations of non-dimensional parameters using the finite element method. The effect of each group of non-dimensional parameters on the pollutant distribution and the heat transfer in the cavity is discussed. The results indicate that the presence of one pollutant component can significantly affect the pollutant distribution of the other component. When the Lewis number of a pollutant component is small, the increase in the bouncy ratio parameter of the proposed component always increases the Nusselt and Sherwood numbers in the cavity.     

On-Line coupling of supercritical fluid extraction with high performance liquid chromatography

Supercritical fluid extraction was coupled directly with high performance liquid chromatograph. The system was evaluated for direct injection of supercritical CO₂ and modified supercritical CO₂ at high pressure and temperature onto a HPLC system with varying mobile phase compositions and flow rates. Injection of 9 μL supercritical CO₂ onto the HPLC using methanol/water mobile phases from 100% methanol to 80% with a flow of 1.0 mL/min did not adversely affect the baseline of UV detector. However at higher percentages of water, CO₂ solubility in the mobile phase decreased and caused baseline interferences on the UV detector. At higher HPLC mobile phase flow rates, supercritical CO₂ was injected to higher percentages of water without any effect on the UV baseline. Also, increasing the extraction pressure or modifier concentration did not change the results. Separations of polynuclear aromatic hydrocarbons and linear alkenebenzene sulfonate test mixtures were obtained using on-line SFE/HPLC interfaced system.     

Synthesis of the novel pyrimido[1,6-a]pyrimidine and imidazo[1,2-c]pyrimidine derivatives based on heterocyclic ketene aminals

A concise and efficient route for the synthesis of pyrimido[1,6-a]pyrimidines and imidazo[1,2-c]pyrimidines by simply refluxing a reaction mixture of different heterocyclic ketene aminals and N,N′-bis(arylmethylidene)arylmethane was developed. This protocol provides an alternative method for application in combinatorial and parallel synthesis in drug discovery.