Polyurea-functionalized multiwalled carbon nanotubes: synthesis, morphology, and Raman spectroscopy

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloride-functionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl2). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH2). In the presence of MWNT-NH2, the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4'-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flat- or flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of the carbon nanotubes were strongly attenuated after polyurea was chemically tethered to the MWNT surfaces. Comparative experiments showed that the grafted polymer species and structures have a strong effect on the Raman signals of polymer-functionalized MWNTs.     

An exploratory study of ring closures of aryl radicals onto cyclopropyl- and oxiranyl-isocyanate acceptors

The idea that ring closures of C-centred radicals onto isocyanates could be made permanent by designing the cyclised radical to undergo a rapid onward beta-scission, was investigated for the 2-(2-isocyanato)cyclopropylphenyl and 2-(2-isocyanato)oxiranylphenyl radicals. The radical precursors, trans- and cis-1-bromo-(2-isocyanatocyclopropyl)benzene and (2-bromophenyl)-3-isocyanatooxirane, were prepared from the corresponding bromophenylcyclopropane and bromophenyloxirane carboxylic acids via Curtius rearrangements of the derived azides. The structure of the trans-2-(2-isocyanato)cyclopropylphenyl radical prevents cyclization, however, it was shown that isomerisation to the analogous cis-radical occurred, probably by scission of the disubstituted cyclopropane bond followed by internal rotation of the resulting resonance stabilised diradical. It was found, however, that the main product from homolytic reactions of both trans- and cis-isocyanatocyclopropyl compounds, with tributyltin hydride and tris(trimethylsilyl)silane, was the direct reduction product, trans-(2-isocyanatocyclopropyl)benzene. Only traces of cyclised products, that were probably 4,5-dihydrobenzo[c]azepin-1-one from the cyclopropane precursor and 5H-6-oxa-8-azabenzocyclohepten-9-one from the oxirane precursor, were detected. We conclude, therefore, that the rate of cyclization onto isocyanate acceptor groups must be slower in these systems than hex-5-enyl cyclization or that the reverse ring-opening process must be faster than for analogous radicals.     

An electron spin resonance study of azaallyl radicals

The ESR spectrum of the 2-aza-allyl radical, Me2CNCMe₂, has been recorded. A series of 1-aza-allyl radicals have been generated by reaction of 2-alkyl-4,4-dimethyloxazolines with t-butoxyl radicals and their ESR spectra studied. In this reaction 2-alkyl-4,4-dimethyloxazolin-5-yl radicals are also formed.     

Alkenylthioimidoyl radicals: competition between beta-scission and cyclization to dihydrothiophen-2-ylidene-amines

[reaction: see text] But-3-enylthioimidoyl radicals were shown by EPR spectroscopy and end product analysis to ring-close predominantly in the 5-exo mode with a rate constant of 2.4 x 10(4) s(-)(1) at 300 K to afford substituted dihydrothiophenylmethyl radicals. This ring closure was in competition with dissociation to but-3-enyl radicals and an isothiocyanate. The dissociation predominated at temperatures above ca. 300 K.     

Investigation of hydrothermal routes to mixed-metal cerium titanium oxides and metal oxidation state assignment using XANES

The reaction between TiF(3) or TiO(2) and Ce(3+) in sodium hydroxide solutions yields highly crystalline NaCeTi(2)O(6) at room temperature and under mild hydrothermal conditions (T < or = 240 degrees C). There is no evidence for the formation of ternary Ce-Ti-O materials by this method, and the use of bases other than NaOH always produces poorly crystalline materials. The material NaCeTi(2)O(6) has a distorted perovskite structure with sodium and cerium ions randomly occupying the A sites: Pnma, a = 5.4517(8) A, b = 7.7292(6) A, c =5.4573(3) A. XANES spectroscopy at the Ti K edge and Ce L(III) edge, with reference to crystalline model compounds, reveals that cerium is found solely as Ce(III) and titanium as Ti(IV) in NaCeTi(2)O(6). Isomorphous substitution of Ce(3+) by Nd(3+) or Ti(4+) by V(4+) is found to be very facile under hydrothermal conditions (at a temperature of 240 degrees C), by addition of appropriate amounts of metal salts to the hydrothermal reaction mixtures. The series NaCe(1-x)Nd(x)Ti2O6 (0 < or = x < or = 1) and NaCeTi(2-x)V(x)O6 (0 相似文献   

Improved morphed potentials for Ar-HBr including scaling to the experimentally determined dissociation energy

A lead salt diode infrared laser spectrometer has been employed to investigate the rotational predissociation in Ar-HBr for transitions up to J' = 79 in the v(1) HBr stretching vibration of the complex using a slit jet and static gas phase. Line-shape analysis and modeling of the predissociation lifetimes have been used to determine a ground-state dissociation energy D(0) of 130(1) cm(-1). In addition, potential energy surfaces based on ab initio calculations are scaled, shifted, and dilated to generate three-dimensional morphed potentials for Ar-HBr that reproduce the measured value of D(0) and that have predictive capabilities for spectroscopic data with nearly experimental uncertainty. Such calculations also provide a basis for making a comprehensive comparison of the different morphed potentials generated using the methodologies applied.     

Synthesis and lyotropic phase behavior of novel nonionic surfactants for the crystallization of integral membrane proteins

A series of new sugar-based nonionic surfactants have been synthesized and their lyotropic liquid crystalline properties characterized. When in contact with water, these surfactants formed a range of lyotropic liquid crystalline phases, including cubic, hexagonal, and lamellar, as well as a separate micellar phase. These are features that have promise for the crystallization of integral membrane proteins.