Multitechnique surface spectroscopic studies of plasma modified polymers III. H2O and O2/H2O plasma modified poly(methyl methacrylate)s

The surfaces of poly(methyl methacrylate) (PMMA) films modified by O₂H₂O and H₂O radio-frequency glow discharge plasmas were studied using electron spectroscopy for chemical analysis (ESCA or XPS), low energy ion scattering (LEISS or ISS), Fourier transform IR spectroscopy (FTIR) with attenuated total reflectance (ATR) sampling, and critical surface energy from contact angle measurements. The extent and nature of modification with respect to promotion of a hydrophilic surface compared to the hydrophobic surface of the unmodified PMMA has been probed. Results show drastic decreases in C/O ratio at the near surface, which increases to that of the unmodified PMMA as deeper cross sections are analyzed. In addition peak fitting of ESCA data correlated with FTIR functional group information allows for the qualitative and quantitative analysis of the resulting bonding and structure of the modified layer. From these results combined with the polarity and surface energy differences obtained from contact angle measurements, the structural changes are discussed with respect to plasma reaction mechanisms and differences in the structure of the modified polymer films.     

A density functional study on a biomimetic non-heme iron catalyst: insights into alkane hydroxylation by a formally HO-FeV=O oxidant

The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane.     

Anodic stripping voltammetry of sulphide at a nickel film: towards the development of a reagentless sensor

The determination of sulphide at an electrochemically generated nickel oxide layer at glassy carbon and screen-printed electrodes in acidic media has been examined and appraised. The NiO layer was found to produce a stripping-like signal to sulphide and gave a linear peak current response from 20 to 90 μM. The response was further enhanced by repetitive cycling allowing accumulation of nickel sulphide at the electrode surface such that lower micromolar levels of sulphide (i.e. 5 μM) can be determined. The response at the NiO layer to sulphide is shown to be reproducible over a period of 24 h, thereby offering the development of a disposable amperometric sensor for sulphide.     

Voltammetric Detection of Free Sulfhydryl Compounds in Food Flours

Cyclic voltammetry has been applied to the rapid measurement of free SH‐compounds in food flours samples. The protocol is based on the electrochemical adaptation of the Ellman's test, where the DTNB reacts with SH‐compounds present in food flour extracts, resulting in the equimolar production of the electroactive compound TNBA which, in turns, reacts with phenylendiamine. The reaction is found to provide an analytical signal from which to quantify indirectly free sulfhydryl compounds in flours extracts.     

An insight into the aromaticity of fullerene anions: experimental evidence for diamagnetic ring currents in the five-membered rings of C(60)(6-) and C(70)(6-)

Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles.     

Synthesis and characterization of Di-π-cyclopentadienyl- metal pentasulfides of titanium(IV) and vanadium (IV):an operational test of the influence of an unpaired electron on the molecular geometry

Our preparation of Ti(h⁵?C₅H₅)₂ S₅ by the reaction of elemental sulfur with Ti(h⁵?C₅H₅)₂(CO)₂ in hexane and of V(h⁵?C₅H₅)₂S₅?$\text{1}\text{2}$ H₂O by the reacti of V(h⁵?C₅H₅)₂ Cl₂ with Na₂S₅ in THF and structural analyses by single crystal X-ray diffraction (together with infrared, solution EPR, and temperaturedependent magnetic susceptibility measurements) represent an extension of our previous work on M(h⁵?C₅H₅)₂ (SC₆H₅)₂ (M = Ti, V). The crystallographic results provide further support of our previous conclusions that the Ballhausen—Dahl model is not valid for M(h⁵?C₅H₅)₂L₂ systems. The structuralfeatures of the chair-like titanium and vanadium pentasulfide molecules are compared to the corresponding phenylmercapto analogs and to the chair-like cyclohexasulfur molecule in rhombohedral sulfur. Ti(h⁵?C₅H₅)₂S₅ was isolated as a mixture of monoclinic and orthorhombic Crystalline phases-which were both characterized by preliminary X-ray data. A complete Structural determination and refinement of the monoclinic phase, which contains two independent molecules in a cell of dimensions a 22.843(2), b 7.958(1), c 14.465(1) Å, β 90.074(4)° and symmetry P2₁/c, yielded R₁ 5.3 % and R₂ 5.9 % for 2168 independent diffractometry-collected data with I≥ 2.5o(I). V(h⁵?C₅H₅)₂S₅-$\text{1}\text{2}$ H₂O contains four V(h⁵?C₅H₅)₂S₅ molecules and two water molecules of hydration (of crystallographic site symmetry C₂-2) in onorthorhombic unit cell of symmetry P2₁2₁2 and of dimensions a 13.491(1), b 12.748(1), c 7.715(1) Å. Least-squares refinement of 750 diffractometry data with I≥2.0σ(I) gave R₁ 2.4% and R₂ 3.0% Both of these compounds were independently synthesized and Spectroscopically characterized by Köpf and co-workers, and-a Complete X-ray diffraction study was performed by Epstein and Bernal on a different monoclinic phase of Ti(h⁵?C₅H₅)₂S₅ (isolated by-Köpf). An extraction of V(h⁵?C₅H₅)₂S₅ with re fluxing benzene under nitrogen atmosphere in a Soxhlet apparatus led to the formation of the previously reported [V₂ (h⁵?C₅H₅)₂S₅]_n compound which was characterized by physical measurements including a preliminary X-ray diffraction study.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2: An organometallic complex containing a chelating acetate ligand

The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH₃CO₂)Mn(CO)₂[P(C₆H₅)₃]₂, has been accomplished by the reaction of NaMn(CO)₅ with (CH₃)₃SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry $\text{P}\text{2}{}_1\text{c}$ and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C₆H₅)₃ bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C₆H₅)₃ bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.     

High-resolution electron microscopy of montmorillonite and montmorillonite/epoxy nanocomposites

With the use of high-resolution transmission electron microscopy the structure and morphology of montmorillonite (MMT), a material of current interest for use in polymer nanocomposites, was characterized. Using both imaging theory and experiment, the procedures needed to generate lattice images from MMT were established. These procedures involve careful control of the microscope's objective lens defocus to maximize contrast from features of a certain size, as well as limiting the total dose of electrons received by the sample. Direct images of the MMT lattice were obtained from neat Na+ MMT, organically modified MMT, and organically modified MMT/epoxy nanocomposites. The degree of crystallinity and turbostratic disorder were characterized using electron diffraction and high-resolution electron microscopy (HREM). Also, the extent of the MMT sheets to bend when processed into an epoxy matrix was directly visualized. A minimum radius of curvature tolerable for a single MMT sheet during bending deformation was estimated to be 15 nm, and from this value a critical failure strain of 0.033 was calculated. HREM can be used to improve the understanding of the structure of polymer nanocomposites at the nanometer-length scale.     

MO Study of flavin–protein interactions in flavodoxin catalysis

MINDO /3 calculations have been performed on the Clostridium MP flavodoxin active site (a complex of the redox active coenzyme flavin mononucleotide sandwiched between the side chains of methionine and tryptophan) at various redox levels using coordinates derived from x-ray diffraction studies of the holoenzyme. Frontier orbital indices were calculated and indicate that reduction of the flavin is accompanied by induced polar states in the amino acid side chains. This stabilization of charge by the amino acid side chains could account for the reaction rate enhancement of flavin reduction catalyzed by flavodoxin. Frontier orbitals for free flavin, for the flavodoxin bound flavin without the amino acid side chains, and for the oxidized Desulfovibrio vulgaris flavodoxin active site were computed for comparison.     

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)₂]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)₂] as solvent.