Anisotropic rotations in 1-naphthylamine. Existence of a red-edge transition moment normal to the ring plane

The rotational motions of 1-naphthylamine in propylene glycol are investigated by means of steady-state flourescence polarization measurements and differential polarized phase flourometry, on excitation at various wavelengths. For excitation at 370 nm the average rotational rate is faster than for excitation at shorter wavelength and the rotations are clearly anisotropic. On excitation from 370nm to the red edge of the spectrum (390 nm) the average rotational rate slows down by a factor of two and the rotations become nearly isotropic. The results reveal the possible existence of an excited state generated preferentially by excitation at the edge of the absorption, in which the transition moments in both absorption and emission are prependicular to the plane of the aromatic rings.     

Local quantum chemistry: The local space approximation for Møller–Plesset perturbation theory

The local space approximation is an accurate technique for describing a relatively small cluster embedded within an extended system. It has previously been developed for the Hartree-Fock, local density functional, configuration interaction, and coupled cluster electronic structure methods. Here it is extended to Møller-Plesset perturbation theory. © 1995 John Wiley & Sons, Inc.     

Transition metalcarbon bonds XXXVII. platinum acetylide complexes formed from ethynyl alcohols or ethers

Several new platinum(II) acetylide complexes, trans-{Pt[CCCR₁R₂(OR₃)]₂-L₂} (R₁, R₂  H, Me, Et; CR₁R₂  cyclohexylidene; R₃  H, Me or Ph), trans-[Pt(CCCH₂CH₂OH)₂L₂], trans-[Pt(p-tolylacetylide)₂L₂] and trans-[PtX(p-tolylacetylide)L₂] (L  PMe₂Ph or in one case, AsMe₂Ph) have been prepared. Platinum(II) acetylide complexes with tertiary hydroxyl groups are easily dehydrated by acetic anhydride/pyridine to give platinum-enyne complexes. Analogous compounds with primary hydroxyl groups do not dehydrate but give acetates. ¹H and ¹³C NMR data are given and the shift reagent Eu(fod)₃ was used to analyse the ¹H NMR spectrum of trans-[Pt(CCCH₂CH₂OH)₂(PMe₂Ph)₂].     

New polyphenylquinoxalines linked by m-terphenyl flexibilizing groups

Three new monomers with phenylglyoxyloyl groups fixed on the 4,4′-, 4,6′-, and 4,4″-positions of m-terphenyl were synthesized by different pathways. They were used to prepare a series of polyphenylquinoxalines by solution polycondensation with 3,3′-diaminobenzidine and 3,3′,4,4′-tetraaminodiphenyl ether. These polymers exhibited excellent oxidative and thermal stability as shown by thermogravimetric analysis and isothermal aging in circulating air between 300 and 450°C. Clear yellow films, cast from m-cresol solution, were used to measure their softening temperature by thermomechanical analysis (TMA). Numerical data thus obtained, indicated a thermoplastic behavior in the temperature range 300 ± 15°C. Crosslinking of the linear polymers by isothermal heat exposure under argon between 300 and 500°C was investigated by means of TMA. Molded materials were fabricated under constant pressure (996 psi) at 500–525°C with an Instron testing machine. These polymers were also used for preliminary evaluation as matrices for 181-E glass reinforced composites. Flexural values obtained after isothermal aging in air up to 400°C indicated a potential use varying from 150 hr at 350°C to 24 hr at 400°C.     

FLUORESCENCE PROPERTIES OF PORPHYRIN-GLOBIN FROM HUMAN HEMOGLOBIN

Fluorescence excitation and emission spectra, decays, and quantum yields are reported for the porphyrin-globin of hemoglobin (Hb^desFe) in aqueous solution of pH 8, at 4°C. A very weak fluorescence was observed in the UV (maximum at 334 nm), due to tryptophan and tyrosine residues, in addition to the strong porphyrin emission in the visible (maxima at 624 and 692 nm) reported previously. The absorption and fluorescence properties of the porphyrins of Hb^desFe were compared to those for free porphyrin in organic solvents and in aqueous solution. The close similarity of the fluorescence decays and quantum yields in Hb^desFe and in solution indicate the absence of stronger, specific porphyrin-protein interactions; however, slight spectral shifts point to the existence of water molecules in the Hb^desFe porphyrin environment. The fluorescence study also demonstrates the existence of efficient Trp-porphyrin energy transfer of Förster type. The extent of transfer is in satisfactory agreement with the value expected from crystallographic data for hemoglobin. The results are discussed and compared to previous fluorescence studies of hemoglobin and apohemoglobin. An improved method for the preparation of Hb^desFe is reported.     

Conditional solubility versus pO2− of cerium(III) oxide in molten equimolar NaCl+KCl at 727°C

Reactions between cerium trichloride and oxide ions were studied in NaCl+KCl (1/1) at 1000°K, by potentiometry with a calcia-stabilized zirconia membrane electrode. Titration curves clearly demonstrated the existence of soluble cerium oxychloride (CeO⁺) and precipitated cerium oxide (Ce₂O₃), with respective dissociation constants 10^?11 and 10^?30 (molality scale). The corresponding conditional solubility diagram {log S (Ce^III)=f(pO^2?)} is presented and discussed.     

Nucleophilic Substitution in Dipolar Aprotic Solvents: Hexamethylphosphoric triamide

The rate of the reaction between ethyl tosylate and chloride as well as bromide ion has been measured in hexamethylphosphoric triamide in the presence of several counterions. Rate constants for the free ions at 25.0° are 14.4 mole^?1 for chloride and 2.0 mole^?1min^?1 for bromide, both independent of the cation used. The equilibrium constants for ion pair dissociation of lithium-, ammonium- and tetra-n-butylammonium chloride are 3.97 × 10^?2, 1.52 × 10^?3 and 6.36 × 10^?3 mole, and for the corresponding bromides 3.30 × 10^?2, 9.65 × 10^?3, and 9.62 × 10^?3 mole.     

Effect of Ion and Binding Site on the Conformation of Chosen Glycosaminoglycans at the Albumin Surface

Albumin is one of the major components of synovial fluid. Due to its negative surface charge, it plays an essential role in many physiological processes, including the ability to form molecular complexes. In addition, glycosaminoglycans such as hyaluronic acid and chondroitin sulfate are crucial components of synovial fluid involved in the boundary lubrication regime. This study presents the influence of Na+, Mg2+ and Ca2+ ions on human serum albumin–hyaluronan/chondroitin-6-sulfate interactions examined using molecular docking followed by molecular dynamics simulations. We analyze chosen glycosaminoglycans binding by employing a conformational entropy approach. In addition, several protein–polymer complexes have been studied to check how the binding site and presence of ions influence affinity. The presence of divalent cations contributes to the decrease of conformational entropy near carboxyl and sulfate groups. This observation can indicate the higher affinity between glycosaminoglycans and albumin. Moreover, domains IIIA and IIIB of albumin have the highest affinity as those are two domains that show a positive net charge that allows for binding with negatively charged glycosaminoglycans. Finally, in discussion, we suggest some research path to find particular features that would carry information about the dynamics of the particular type of polymers or ions.     

Access to nonisocyanate poly(thio)urethanes: A comparative study

This article describes the synthesis of new cyclic compounds able to react with amines to get nonisocyanate polyurethanes (NIPUs). The contribution of the most studied five‐membered cyclic carbonate was compared to five‐membered cyclic dithiocarbonate analogous and to a six‐membered cyclic carbonate. Difunctional reactive species were obtained by a simple substitution reaction or an efficient thiol–ene coupling reaction. The products, obtained with high yields, were characterized by 1H NMR, 13C NMR, and Fourier tansform infrared spectroscopy analysis. The dicyclocarbonates were then used to synthesize NIPUs by step growth polymerization with several diamines. These materials exhibited glass transition temperatures from 19 to ?29 °C, molar mass from 1800 to 20,400 g mol^?1, and a 20% mass loss temperature (T_d = 20%) between 249 and 296 °C. Such materials are interesting candidates for coating applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3284–3296