Electrospinning of nylon-6,6 solutions into nanofibers: Rheology and morphology relationships

The relationship between the rheological properties of nylon-6,6 solutions and the morphology of their electrospun nanofibers was established. The viscosity of nylon-6,6 in formic acid(90%) was measured in the concentration range of 5 wt%-25 wt% using a programmable viscometer. Electrospinning of nylon-6,6 solutions was carried out under controlled parameters. The chemical structure, morphology and thermal properties of the obtained nanofibers were investigated using Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC), respectively. Entanglement concentration(ce) was found to be 15 wt% and a power law relationship between specific viscosity and solution concentration was observed with exponents of 2.0 and 3.3 for semi-dilute unentangled(c ce) and semi-dilute entangled(c ce) regimes, respectively. The diameter and uniformity of the nanofibers were found to be dependent on the viscosity. Moreover, the average diameter of electrospun nanofibers was found to be dependent on zero shear rate viscosity and normalized concentration(c/ce) in a power law relationship with exponents of 0.298 and 0.816, respectively. For nylon-6,6 solutions, the entanglement concentration(ce = 15 wt%) provides the threshold viscosity required for the formation of a stable polymeric jet during electrospinning and producing uniform beadless fibers. For concentrations less than ce, beaded fibers with some irregularities are formed. DSC analysis showed an increase in crystallinity of all electrospun samples compared to original polymer. Furthermore, Based on FTIR spectroscopy, α phase is dominant in electrospun nanofibers and minor amount of β and γ phases is also available.     

Synthesis of Some Novel Imidazopyrazole and Pyrazolopyrimidine Derivatives

5‐Amino‐3‐anilino‐1H‐pyrazole‐4‐carbonitrile 1 was alkylated with various halo reagents under phase transfer conditions to give the corresponding imidazopyrazole derivatives 2a , 2b , 2c , 3 , 4 , 5 , 6 . Pyrazolo[1,5‐a] pyrimidine derivatives 11 , 12 , 13 , 14 were prepared by treating compound 1 with different dicarbonyl reagents, namely, diethymalonate, ethyl 3‐oxo‐3‐phenylpropanoate, pentane‐2,4‐dione or ethyl 3‐oxobutanoate.     

Synthesis of Novel Modified Guanidines: Reaction of Dicyandiamide with Amino Acids,Amides, and Amines in Aqueous Medium

Reaction of dicyandiamide with series of amino acids afforded guanidinyl pyrazolones 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , respectively. Although reaction of dicyandiamide with urea, acetamide, bezamide, allantion, p‐aminobenzoic acid, sulphanilic acid, and adenine gave biguanides 20 , 21 , 22 , 23 , 24 , 25 , 26 , respectively. All compounds have been characterized on the basis of IR and ¹H‐NMR.     

Prednisone/Cyclodextrin Inclusion Complexation: Phase Solubility,Thermodynamic, Physicochemical and Computational Analysis

Guest–host interaction of prednisone (PN) with cyclodextrins (CDs) have been investigated using phase solubility diagrams (PSD), differential scanning calorimetry (DSC), X-ray powder diffractometry (XRPD), scanning electron microscopy (SEM) and molecular mechanical modeling (MM). Estimates of the complex formation constant (K ₁₁) show that the tendency of PN to complex with CDs follows the order: β-CD>γ-CD>HP-β-CD>α-CD. At the same pH of 7.0, β-CD forms soluble 1:1 and insoluble 1:2 PN/CD complexes (B_S-type PSDs). The thermodynamic functions for 1:1 PN/β-CD estimated at pH = 7.0 (ΔG ₁₁^o=−20.8 kJ⋅mol⁻¹) show that complexation is driven by enthalpy (−30.7 kJ⋅mol⁻¹) but retarded by entropy (ΔS ₁₁^o=−33.1 J⋅mol⁻¹⋅K⁻¹) changes. The MM modeling study indicates the formation of different isomeric 1:1 complexes with CDs. PSD, DSC, XRPD, SEM and MM studies established the formation of inclusion complexes in solution and the solid state.     

A heterogeneous and reusable nanopolymer-supported palladium catalyst for the copper- and phosphine-free Sonogashira coupling reaction under aerobic conditions in water

We report here the synthesis of a nanopolymer-supported palladium(II) complex catalyst, [PS-tet-Pd(II)] using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR, and energy dispersive X-ray spectroscopy (EDS). PS-tet-Pd(II) proves to be a useful heterogeneous catalyst in the copper- and phosphine-free Sonogashira coupling reaction in water. The catalyst can be recovered from the reaction mixture by simple filtration and reused several times without any significant loss of catalytic activity.     

PHOTOCHEMISTRY OF PESTICIDES, 71. REGIOSELECTIVE PHOTODIMERIZATION OF o,o-DIETHYL-o-(3-CHLORO-4-METHYLCOUMARIN-7-YL)-THIOPHOSPHATE (COUMAPHOS)

Abstract

UV-irradiation (λ > 313 nm) of o,o-diethyl-o-(3-chloro-4-methyl-coumarin-7-yl)-thiophosphate (Coumaphos; 1) in chloroform results in an regioselective dimerization reaction to afford the head-to-tail anti-dimer 2. The structure of 2 is established by single crystal x-ray diffraction. Singlet oxygen does not affect the formation of 2.     

A Simple Synthesis of Stable Phosphoranes Derived from Imidazole Derivatives

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, in the presence of strong NH-acids, such as imidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, benzimidazole, and 5,6-dimethylbezimidazole. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group.