Synthesis of some triazole,tetrazole, and tetrazine derivatives from N-β-naphthalenesulfonylbenzohydrazidoyl chlorides

A series of N-β-naphthalenesulfonylbenzohydrazidoyl chlorides 8a-d has been prepared by the action of thionyl chloride on the corresponding hydrazides 7a-d . Treatment of 8 with triethylamine and morpholine afforded the tetrazines 10 and the amidrazones 11 respectively. Acid hydrolysis of 11 yielded the hydrazides 7 . Reaction of 8 with phenylhydrazine gave 3,5-diaryltetrazoles 14 . However, reaction of 8 with aroylhyrazines yielded 3,5-diaryl-4-β-naphthalenesulfonylamino-4H-1,2,4-triazoles 15 . The structures of the products were assigned upon the basis of their spectra, elemental analyses and alternate synthesis whereever possible.     

Laminar free convection heat transfer and separated flow structure in a vertical channel with isothermal walls and two adiabatic opposing fins

Results of numerical study of laminar free convection and heat transfer in a vertical plane-parallel channel with two thin adiabatic fins on its walls are presented. The channel has the open inlet and outlet, and its surfaces are maintained at the same temperature. The channel height is unchanged with elongation parameter A = L/w = 10, and the fins are located in the middle of the channel toward each other. Fin height l/w = 0 ÷ 0.4 and Rayleigh number Ra = 10² ÷ 10⁵ are varied in calculations. The effect of these parameters on the flow structure, temperature field, local and integral heat transfer, and gas flow caused by gravitational forces are analyzed in detail. Numerical analysis is based on solving the full Navier–Stokes and energy equations in twodimensional statement and Boussinesq approximation. To determine the dynamic and thermal parameters at the inlet and outlet, the calculation is carried out with two large volumes attached to the inlet and outlet. The features of the flow and heat transfer at separated flow around the channel fins are studied in detail in this work.     

3D and Porous RGDC‐Functionalized Polyester‐Based Scaffolds as a Niche to Induce Osteogenic Differentiation of Human Bone Marrow Stem Cells

Polyester‐based scaffolds covalently functionalized with arginine‐glycine‐aspartic acid‐cysteine (RGDC) peptide sequences support the proliferation and osteogenic differentiation of stem cells. The aim is to create an optimized 3D niche to sustain human bone marrow stem cell (hBMSC) viability and osteogenic commitment, without reliance on differentiation media. Scaffolds consisting of poly(lactide‐co‐trimethylene carbonate), poly(LA‐co‐TMC), and functionalized poly(lactide) copolymers with pendant thiol groups are prepared by salt‐leaching technique. The availability of functional groups on scaffold surfaces allows for an easy and straightforward method to covalently attach RGDC peptide motifs without affecting the polymerization degree. The strategy enables the chemical binding of bioactive motifs on the surfaces of 3D scaffolds and avoids conventional methods that require harsh conditions. Gene and protein levels and mineral deposition indicate the osteogenic commitment of hBMSC cultured on the RGDC functionalized surfaces. The osteogenic commitment of hBMSC is enhanced on functionalized surfaces compared with nonfunctionalized surfaces and without supplementing media with osteogenic factors. Poly(LA‐co‐TMC) scaffolds have potential as scaffolds for osteoblast culture and bone grafts. Furthermore, these results contribute to the development of biomimetic materials and allow a deeper comprehension of the importance of RGD peptides on stem cell transition toward osteoblastic lineage.     

Effect of reduced glutathione on the stability of pigments in paprika powders studied by multiwavelength spectrometry and high-performance liquid chromatography

Multiwavelength spectrometry and reversed-phase high-performance liquid chromatography have been employed for the study of the effect of reduced glutathione and storage time on the pigments of paprika powders. The evaluation of the data by principal component analysis and cluster analysis proved that the storage time exerts the highest effect of the decomposition rate of pigments. The stability of some pigment fractions was modified in the presence of reduced glutathione. However, the effect was of secondary importance. Multiwavelength spectrometry combined with HPLC can be successfully used for the study of the stability of pigments of paprika powder.     

A Full-Height Waveguide to Thin-Film Microstrip Transition with Exceptional RF Bandwidth and Coupling Efficiency

We describe a waveguide to thin-film microstrip transition for high-performance submillimetre wave and teraherz applications. The proposed constant-radius probe couples thin-film microstrip line, to full-height rectangular waveguide with better than 99% efficiency (VSWR 1.20) and 45% fractional bandwidth. Extensive HFSS simulations, backed by scale-model measurements, are presented in the paper. By selecting the substrate material and probe radius, any real impedance between 15-60 can be achieved. The radial probe gives significantly improved performance over other designs discussed in the literature. Although our primary application is submillimetre wave superconducting mixers, we show that membrane techniques should allow broad-band waveguide components to be constructed for the THz frequency range.     

The interaction between polymerization initiators and inhibitors in solution—IV: The reaction of benzoyl peroxide with hydroquinone in solution

The reaction between benzoyl peroxide and hydroquinone in a wide variety of solvents has been investigated by isolation and identification of the products. Benzoic acid, p-benzoquinone and benzoyloxy derivatives of p-benzoquinone are obtained under all conditions. Their relative amounts are largely determined by the molar ratios of the reactants and the nature of the solvent. In strongly polar solvents of high solvation power, p-benzoquinone is formed in preference to its derivatives. Nevertheless, the yield of 2,5-dibenzoyloxy p-benzoquinone reaches a maximum in acrylonitrile. Only in this solvent, at equal molar ratios of reactants, is full substitution in the hydroquinone nucleus achieved with the formation of tetrabenzoyloxy hydroquinone. These facts, together with the partial polymerization of acrylonitrile at room temperature at slightly higher peroxide/hydroquinone ratios and the complete suppression of the polymerization when perchloric acid is added, could be explained by a heterolytic mechanism involving the formation and controlled separation of ion pairs derived from the reactants.     

A horn-reflector antenna for high-performance submillimetre-wave imaging arrays

We have developed an antenna for high-performance submillimetrewave imaging arrays. The antenna comprises a corrugated horn with an off-axis paraboloidal reflector at its aperture. The corrugated horn is machined directly into two halves of a split aluminium block. This approach avoids electroforming and is compatible with E-plane circuit technology. The resulting antenna is light weight and is ideal for space applications. For compatibility with submillimetre-wave optics, the the behaviour has been calculated by using Gaussian-Hermite modes, and the integrity of the theory has been verified by modelling the behaviour of a 17GHz antenna. The manufacturing procedure has been investigated by machining and testing a horn-reflector antenna for 450–500GHz. Our next step is to extend the technique to 1THz.     

Excimer state of a conjugate polymer (MEH-PPV) in liquid solutions

The conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) is an important electrooptical material, which is useable as an excellent laser media. In this paper, we present the absorption and fluorescence spectral characteristics of MEH-PPV in a few organic solvents. The paper shows that MEH-PPV exists in an excimeric state in benzene, and that the laser action as shown here arises from a liquid excimeric state.     

On the Interchange Ability of the N‐donor Position in the Rare Earth Coordination Polymers $^{1}_{\infty}\rm [Ln(Btz)_{3}(L)]$, L = BtzH,Ph(NH2)2, NH3, and Pyridine

Benzotriazolates of the rare earth elements form chain like coordination polymers of the formula . An additional neutral ligand L saturates the coordination spheres of the trivalent lanthanide ions and, depending on the reaction conditions, can be a varying donor (L = BtzH, Ph(NH₂)₂, NH₃ and Py). Reactions in the BtzH (1H‐benzotriazole) melt result in coordination of benzotriazole and its thermal decomposition products as L. We have now investigated if the site occupied by L can be exchanged with other N donor ligands. Pyridine can substitute BtzH, Ph(NH₂)₂ and NH₃ under solvothermal conditions giving the coordination polymer even for the biggest Ln^III cation lanthanum without changing the overall strand structure. Chains proof to be the chemically favoured and stable structure fragment with the L position being the chemically variable site.     

Hydrogen rearrangement and ring cleavage reactions study of progesterone by triple quadrupole mass spectrometry and density functional theory

The fragmentation mechanisms of progesterone have been studied by triple quadrupole tandem mass spectrometry (MSMS) and density functional theory (DFT). Mechanisms leading to major product ions are proposed. The data suggest that progesterone fragments preferentially via hydrogen and other rearrangements lead to neutral losses. These fragmentations are quite complex and are preceded by σ-bond cleavages in most cases. Four major pathways for progesterone fragmentation are proposed involving: (1) cleavage of ring B at C9-C10, (2) cleavage of C6-C7 bond in ring B through m/z 191, (3) two types of cleavages of ring D, and (4) ketene elimination in ring A. Pathways (1)-(3) proceed via charge-remote fragmentations while pathway (4) proceeds via charge-site initiated mechanism. The geometry of product ions in these pathways were optimized using DFT at the B3LYP/6-311G(d,p) level of theory from which the free energies of the pathways were calculated. The effect that the choice of basis sets and density functionals has on the results was tested by performing additional calculations using B3LYP/6-31G(d) and B3PW91/6-311G(d,p).