Conductivity and characterization of polyurea electrolytes with carboxylic acid

Polyurea, which was synthesized from 4,4′‐diphenylmethane diisocyanate, Jeffamine‐ED2001 (weight‐average molecular weight: 2000), and 3,5‐diaminobanzoic acid (DABA) were doped with lithium perchlorate (LiClO₄) as the polyelectrolyte. Differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and ⁷Li magic‐angle spinning (MAS) solid‐state NMR were used to monitor changes in the morphology of polyurea electrolytes corresponding to the concentration of LiClO₄ dopants. DSC showed the glass‐transition temperature of the hard and soft segments increases with salt concentration. FTIR indicated the carboxylic group of DABA coordinates with the Li⁺ ion, and the ordered hydrogen‐bonded urea carbonyl groups are destroyed when the salt concentration exceeds 0.5 mmole of LiClO₄ (gPUrea)^?1. The ⁷Li MAS solid‐state NMR investigation of the polyurea electrolytes revealed the presence of two Li⁺ environments at lower temperature. Impedance spectroscopy measurements showed that the conductivity behavior followed the Arrhenius equation, and the maximum conductivity occurred when the crystalline structure of polyurea was disrupted. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 4007–4016, 2003     

Some heterocyclic sulfonyl chlorides and derivatives

The syntheses of 4- and 5-chlorosulfonylfuran-2-carboxylic acid (Ia,IIa), 4-chlorosulfonylfuran-2-carboxamide (Ib), 3,5-dimethylpyrazole and isoxazole-4-sulfonyl chlorides (IIIa,IVa) and 2,4-dimethylthiazole-5-sulfonyl chloride (Va) are described. The sulfonyl chlorides were converted into a range of amides, hydrazides and azides. Condensation of the sulfonohydrazides with β-dicarbonyl compounds, gave the corresponding β-ketohydrazones (VII), which, with the exception of the derivatives (VIIe,f,g,i), were converted to the sulfonylpyrazoles (VIII). The structures and spectral data of these compounds are briefly discussed. The reaction of the sodio derivative of acetylacetone with thiophene-2-sulfonyl chloride (VIc) gave 3-(thiophene-2-sulfonyl)pentane-2,4-dione (XII), which with hydrazine gave 4-(thiophene-2-sulfonyl)-3,5-dimethylpyrazole (XIII). However, the analogous reaction with thiophene-2-sulfonohydrazide (VIa) failed to give the expected 1,4-bisthiophenesulfonylpyrazole.     

Fluoro-organofunctional silicon compounds. Synthesis of acetoxy,carbethoxy and hydroxy derivatives

The synthesis of fluoro-organosilicon compounds containing acetoxy, carbethoxy, or hydroxy groups in the organic portion of the molecule is described.     

A numerical method for calculating the mean intensity in an inhomogeneous rayleigh scattering atmosphere

We describe a method for calculating directly the mean integrated intensity in an inhomogeneous Rayleigh scattering atmosphere using a combined variational and iterative technique. This method is particularly useful for computing dissociation rates in aeronomical problems. Simple semi-analytic expressions are derived.     

The Syntheses and Reactions of 3‐Arylsydnone‐4‐carboxamide Phenylhydrazones

Reactions of aniline with 3‐arylsydnone‐4‐carbohydroximic acid chlorides ( 1 ) gave the de sired substitution products 5 . 3‐Arylsydnone‐4‐carboxamide phenylhydrazones ( 7 ) were obtained unexpectedly by the reaction of carbohydroximic acid chlorides 1 with phenylhydrazine in suitable conditions. Compounds 7 could react with both aromatic and aliphatic aldehydes in the presence of acid catalyst to give 3‐aryl‐4‐(1′‐phenyl‐5′‐substituted‐1′,2′,4′‐triazol‐3′‐yl)sydnones ( 11 ).     

The Syntheses of 4‐Arylamino‐1,2,3‐Triazoles and Stable 6‐Sydnonyl Verdazyls from Sydnone Derivatives and Their Fragments

α‐Chloroformylarylhydrazones 1 and α‐chloroformylarylhydrazones of sydnonecarbaldehydes 3 have been prepared by a new synthetic route: α‐chloroformylarylhydrazines hydrochlorides 2 reacted with corresponding carbonyl compounds. Reactions of compounds 3 with various hydrazines to give 6‐sydnonyl‐1,2,4,5‐tetrazinan‐3‐ones 7 and/or carbazones 8 were also investigated. By oxidization with lead dioxide, compounds 7 were trans formed to stable 6‐sydnonyl‐3,4‐dihydro‐3‐oxo‐1,2,4,5‐tetrazin‐1(2H)‐yl radical derivatives 9 (sydnonyl verdazyls). Furthermore, sydnonecarbaldehydes arylhydrazones 5 through acidic conditions could be transferred to 4‐arylamino‐1,2,3‐triazoles 6 which were also obtained by means of acidic decompositions of 4‐formylsydnones 10 .     

Distance distribution functions of replication origins in HeLa and glioma human cells according to the data of confocal microscopy

The distribution of replication origins in the nuclei of different cells is studied by confocal microscopy. Based on the obtained images, three-dimensional maps of the positions of the origin centers is constructed and the distribution functions of the pair distances between them are calculated. It is established that the distance distribution function for HeLa and glioma human cells is linear at sizes up to 2 μm, which indicates that the size of the origin system is close to 2. The amplitude of the distance distribution function at small sizes has a power dependence on the nucleus size and is inversely proportional to the nucleus volume to the power of 0.9. Thus, the replication-origin distribution in a nucleus cannot be described by a model with a single Hausdorff dimension in the whole range of sizes.     

Polypeptide/Multiwalled carbon nanotube hybrid complexes stabilized through noncovalent bonding interactions

In this study, we used click chemistry to synthesize new linear polypeptide‐g‐pyrene polymers from a mono‐azido‐functionalized pyrene derivative (N₃‐Py) and several poly(γ‐propargyl‐l ‐glutamate) (PPLG) oligomers. Incorporating the pyrene units as side chains enhanced the α‐helical conformations of these PPLG oligomers in the solid state, as determined using Fourier transform infrared (FTIR) spectroscopy; it also increased the temperature stability of the α‐helical secondary structures of the grafted PPLG oligomers, relative to those of the pure PPLG species, as revealed through temperature‐dependent FTIR spectroscopic analyses. In addition, the thermal properties of the PPLG‐g‐Py polypeptides (e.g., glass transition temperatures increased by ca. 100 °C) were superior to those of pure PPLG oligomers. Mixing the PPLG‐g‐Py oligomers with multiwalled carbon nanotubes (MWCNTs) in dimethylformamide led to the formation of highly dispersible PPLG‐g‐Py/MWCNT organic/inorganic hybrid complex materials. Fluorescence emission spectra revealed significant π–π stacking between the PPLG‐g‐Py oligomers and the MWCNTs in these complexes. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 321–329