A new insight into the understanding of the collapsed form of poly(N-isopropylacrylamide) molecules

Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior.     

A Symmetric-Impulse Approximation Applied to the Faddeev Theory on the Charge Transfer Amplitude

Off-the-shell anomalous factors of the two-body Coulomb transition matrices appear in the integral form of the Faddeev second-order nuclear-electronic amplitude, for proton-hydrogen charge transfer scattering in a typical nlm → n′l′m′ transition. A symmetric-impulse approximation (SIA) is applied to eliminate these factors and an induction method is proposed to analytically calculate the remaining integrals. The nuclear-electronic amplitude is derived for the general case, and for totally symmetric collisions, in terms of generalized hypergeometric functions of two variables, F ₄, and of one variable, ₃ F ₂, respectively. The angular distribution of the second-order nuclear-electronic charge transfer amplitude shows the Thomas mechanism as a peak or a hump for symmetric and asymmetric collisions. There also exists a peak in the forward angular distribution of the second-order nuclear-electronic amplitude, which partly cancels the kinematic peak in the angular distribution of the charge transfer differential cross sections.     

Determination of a control parameter in a one-dimensional parabolic equation using the method of radial basis functions

In this work, the method of radial basis functions is used for finding the solution of an inverse problem with source control parameter. Because a much wider range of physical phenomena are modelled by nonclassical parabolic initial-boundary value problems, theoretical behavior and numerical approximation of these problems have been active areas of research. The radial basis functions (RBF) method is an efficient mesh free technique for the numerical solution of partial differential equations. The main advantage of numerical methods which use radial basis functions over traditional techniques is the meshless property of these methods. In a meshless method, a set of scattered nodes are used instead of meshing the domain of the problem. The results of numerical experiments are presented and some comparisons are made with several well-known finite difference schemes.     

Aromatic poly(sulfone sulfide amide imide)s as new types of soluble thermally stable polymers

A new diamine monomer containing flexible sulfone, sulfide, and amide units was prepared via three steps. Nucleophilic chloro displacement reaction of 4‐aminothiophenol with 4‐nitrobenzoyl chloride in the presence of propylene oxide afforded N‐(4‐mercapto‐phenyl)‐4‐nitrobenzamide and subsequent reduction of the nitro intermediate led to 4‐amino‐N‐(4‐mercapto‐phenyl)benzamide. Two moles of this amino thiophenol compound was reacted with bis‐(4‐chloro phenyl)sulfone to provide a novel diamine monomer. The diamine was reacted with aromatic dianhydrides to form polyimides via a two‐step polycondensation method, formation of poly(amic acid)s, followed by chemical imidization. The resulting polymers were characterized and their physical properties including thermal behavior, thermal stability, solubility and inherent viscosity were studied. Copyright © 2007 John Wiley & Sons, Ltd.     

An injectable chitosan-based hydrogel reinforced by oxidized nanocrystalline cellulose and mineral trioxide aggregate designed for tooth engineering applications

The complex anatomy of teeth limits the accessibility and efficacy of regenerative treatments. Therefore, the application of well-known inducers as injectable hydrogels for the regeneration of the dentin-pulp complex is considered a promising approach. In this regard, this study aimed to develop an injectable hydrogel containing mineral trioxide aggregate (MTA). The injectable chitosan/oxidized-nanocrystalline cellulose/MTA (CS/OCNC/MTA) hydrogels were prepared, and the physicochemical properties of these hydrogels were evaluated by TGA, FTIR, Rheological analysis, and SEM. Moreover, the effect of MTA on the swelling and degradability of scaffolds was assessed. The proliferative effects of synthesized hydrogels were also determined on human dental pulp stem cells (hDPSCs) by MTT assay. For induction of differentiation and biomineralization in these cells, the alkaline phosphatase activity and Alizarin Red S staining tests were performed in the presence of fabricated scaffolds. The proliferation of hDPSCs was significantly increased in the presence of these hydrogels. Moreover, the addition of MTA to hydrogel structure dramatically improved the differentiation of hDPSCs. These results suggested that this novel injectable hydrogel provides appropriate physiochemical properties and can be considered a promising scaffold for regenerative endodontic procedures.

Graphical abstract

     

Synthesis and characterization of novel heat resistant poly(amide imide)s

A series of new poly(amide imide)s was prepared from new diacid containing sulfone, ether, amide and imide groups with various aromatic diamines. The diacid was synthesized via four steps, starting from reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide afforded N-(4-hydroxy phenyl)-4-nitrobenzamide. In the second step, reduction of nitro group resulted in preparation of 4-amino-N-(4-hydroxy phenyl) benzamide. In the next step for the preparation of diamine, the reaction of 4-amino-N-(4-hydroxy phenyl) benzamide with bis-(4-chlorophenyl) sulfone in the presence of K₂CO₃ was achieved. The prepared sulfone ether amide diamine was reacted with two moles of trimellitic anhydride to synthesize related sulfone ether amide imide diacid. The precursors and final monomer were characterized by FT-IR, H-NMR and elemental analysis. Direct polycondensation reaction of the sulfone ether amide imide diacid with different diamines in the presence of triphenyl phosphite afforded five different poly (sulfone ether amide imide amide)s. The obtained polymers were fully characterized and their physical properties including thermal behavior, thermal stability, solubility, and inherent viscosity were studied.     

Characterization and determination of fatty acids in fish oil using gas chromatography-mass spectrometry coupled with chemometric resolution techniques

Characterization and determination of a complex mixture of fatty acid methyl esters was performed for commercial fish oil using two-dimensional GC-MS data coupled with resolution techniques. Various principle component analysis methods such as significant factor analysis and fixed size moving window evolving factor analysis were used for the number of factors, zero concentration and selective regions. Then, the convoluted chromatograms were resolved into pure chromatograms and mass spectra using heuristic evolving latent projections (HELP) method. Fatty acids of C16:1omega7, C18:4omega3, C18:1omega11, C18:1omega9, C18:0, C20:2omega6, C20:1omega9, C22:1omega11, C22:1omega9 and C24:1omega9 were resolved an fied by using similarity searches between deconvoluted mass spectra and MS database, in different parts of total ion current chromatogram. Window target testing factor analysis is also applied for confirming the presence or absence of target analytes. The results of the present work show that combination of hyphenated chromatographic methods and resolution techniques provide a complementary method for accurate analysis of real multi-component systems such as fish oil.     

Bis(m-phenylene)-32-crown-10-based cryptands, powerful hosts for paraquat derivatives

Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats.     

Synthesis and characterization of [Cu(Phca2en)(PPh3)X] (X=Cl, Br, I, NCS, N3) complexes: crystal structures of [Cu(Phca2en)(PPh3)Br] and [Cu(Phca2en)(PPh3)I]

New mixed-ligand copper(I) complexes, [Cu(Phca₂en)(PPh₃)X], [Phca₂en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N₃ (5)] have been synthesized and characterized by various techniques. ¹H and ¹³C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca₂en)(PPh₃)Br] (2) and [Cu(Phca₂en)(PPh₃)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh₃ moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.