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At least 631 records · Page 35Linked to original sources

Porous graphitic carbon as stationary phase for LC-ICPMS separation of arsenic compounds in water.

A new liquid chromatographic separation method was developed for the speciation of the four main arsenic compounds present in water. Arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate (As(V)) were separated on a recently introduced stationary phase: porous graphitic carbon (PGC). The separation was first obtained under formic acid gradient conditions, but an adsorption phenomenon of As(V) on PGC was observed. To overcome this problem, As(V) was backflushed, and an efficient separation of the four solutes was achieved within 10 min. Extremely low detection limits (ranging from 10 to 70 ng x L(-1)) were obtained by coupling LC with an ICPMS. The method was successfully applied to different spiked mineral waters and a naturally arsenic-containing freshwater.

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PVC membrane and coated graphite potentiometric sensors based on Et4todit for selective determination of samarium(III).

Solution studies on the binding properties of 4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione (Et(4)todit) toward a number of cationic species including some lanthanide ions revealed the occurrence of a selective 1:1 complexation of the ligand with Sm(3+) ion. Consequently, Et(4)todit was used as a suitable neutral ionophore for the preparation of novel polymeric membrane (PME) and coated graphite (CGE) Sm(3+)-selective electrodes. The electrodes exhibit a Nernstian behavior for Sm(3+) ions over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M for PME and 1.0 x 10(-7)-1.0 x 10(-1) M for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 1.6 x 10(-8) M for CGE). The proposed potentiometric sensors manifest advantages of relatively fast response, and, most importantly, good selectivities relative to wide variety of other cations, including other lanthanide ions. The selectivity behavior of the proposed Sm(3+)-selective electrodes revealed a great improvement compared to the best previously reported electrode for samarium(III) ion. The potentiometric responses of the electrodes are independent of the pH of the test solution in the pH range 4.0-6.5. The electrodes were successfully applied to the recovery of Sm(3+) ion from tap water samples and also, as an indicator electrode, in potentiometric titration of samarium(III) ions.

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On-column derivatization using redox activity of porous graphitic carbon stationary phase: an approach to enhancement of separation selectivity of liquid chromatography.

A new on-column derivatization method based on the redox activity of porous graphitic carbon (PGC) packing materials was presented for enhancement of separation selectivity of HPLC. Two PGC packing materials were used as the solid redox agents as well as the stationary phase, and their redox activities were investigated using trans-1,2-diaminocyclohexanetetraacetate (DCTA) complexes of some metal ions as probe compounds. It was found that the redox property of PGC was modified by treating them with a solution containing a reducing agent, sodium sulfite or hydroxylammonium chloride. The original PGC packings oxidized Co(II)-DCTA to Co(III)-DCTA during elution, while the PGC treated with a reducing agent showed reduction activity converting Co(III)-DCTA to Co(II)-DCTA. These two cobalt complexes do not form their individual chromatographic zones but migrate as a single zone of their mixture on the PGC column contrary to the chromatographic behavior on a C18 bonded silica, on which Co(II)-DCTA and Co(III)-DCTA can be separated. Treatment of the PGC column with a reducing agent solution transforms the oxidative activity of the original PGC packing to a reductive one from the upper part of the column, so that the retention time of the cobalt complex can be controlled by changing the volume of the reducing agent solution to be used for treatment of the PGC column. The selective separation and determination of cobalt in a reference manganese nodule sample by the developed method was demonstrated.

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Direct DNA hybridization at disposable graphite electrodes modified with carbon nanotubes.

The performance of glassy carbon (GCE) and graphite pencil electrodes (PGE) modified with multiwalled carbon nanotubes (CNTs) are compared, based on the direct electrochemical detection of nucleic acids. This is accomplished by monitoring the differential pulse voltammetry changes of the guanine signal. CNT-modified PGE compares favorably to that of the commonly used CNT-modified GCE owing to the intrinsic improved performance of the supporting PGE. The better intrinsic characteristics of the PGE are related to its composite structure and higher level of porosity compared to GCE. The performance characteristics of the direct DNA hybridization on the disposable CNT-modified PGE are studied in terms of optimum analytical conditions such as probe concentration, target concentration, hybridization time, and selectivity. The new DNA biosensor described here has shown some important advantages such being inexpensive, sensitive, selective, and able to generate reproducible results using a simple and direct electrochemical protocol.

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Pentaheptite modifications of the graphite sheet.

Pentaheptites (three-coordinate tilings of the plane by pentagons and heptagons only) are classified under the chemically motivated restriction that all pentagons occur in isolated pairs and all heptagons have three heptagonal neighbors. They span a continuum between the two lattices exemplified by the boron nets in ThMoB4 (cmm) and YCrB4 (pgg), in analogy with the crossover from cubic-close-packed to hexagonal-close-packed packings in 3D. Symmetries realizable for these pentaheptite layers are three strip groups (periodic in one dimension), p1a1, p112, and p111, and five Fedorov groups (periodic in two dimensions), cmm, pgg, pg, p2, and p1. All can be constructed by simultaneous rotation of the central bonds of pyrene tilings of the graphite sheet. The unique lattice of cmm symmetry corresponds to the previously proposed pentaheptite carbon metal. Analogous pentagon-heptagon tilings on other surfaces including the torus, Klein bottle, and cylinder, face-regular tilings of pentagons and b-gons, and a full characterization of tilings involving isolated pairs and/or triples of pentagons are presented. The Kelvin paradigm of a continuum of structures arising from propagation of two original motifs has many potential applications in 2D and 3D.

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The eight classes of positive-curvature graphitic nanocones.

The eight different classes of single-wall positive-curvature graphitic nanocones are emphasized, characterized, and illustrated. Local transformations among different possible apex-region structures within a common class are investigated, it being noted that there is no short sequence of such transformations which convert from any one of these eight classes to another. Attention is directed to class identification and to nanocone codes, especially for "buckycones" comprised solely from pentagonal and hexagonal rings.

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Voltammetry of Plastocyanin at a Graphite Electrode: Effects of Structure, Charge, and Electrolyte.

Comparative voltammetric studies on Anabaena variabilis plastocyanin (positively charged at neutral pH) and spinach and poplar plastocyanins (negatively charged at neutral pH) have been undertaken at an edge-plane graphite electrode as a function of ionic strength, pH, and Mg(2+) concentration at 3 degrees C. The aim was to provide a more detailed understanding of the influence of the electrode-protein (solution) interfacial characteristics, as well as the variation of the formal potential with both the nature of the plastocyanin species and the pH. As might be expected, some of the interfacial properties associated with the positive charge on A. variabilis plastocyanin are the opposite of those observed with the negatively charged plastocyanins. For example, the linear diffusion component of the mass transport process for A. variabilis plastocyanin under the conditions of cyclic voltammetry is decreased and the radial diffusion component is increased by the addition of Mg(2+), whereas the reverse occurs with poplar and spinach plastocyanins. The voltammetrically determined reversible potentials for A. variabilis plastocyanin are considerably less positive than those for spinach and poplar plastocyanins, in agreement with values calculated from chemically based redox studies. Ionic strength effects, as determined by addition of NaClO(4) over the concentration range 0.005-0.20 M, are negligible for all three proteins. The addition of Mg(2+) causes a significant shift in the reversible potential toward more positive values for spinach and poplar plastocyanin but only a small positive shift for A. variabilis plastocyanin. The difference is attributed to a specific binding effect. The addition of Mg(2+) also dramatically alters the pH dependence of the reversible potential, indicating that the equilibrium between the protonated and unprotonated forms of reduced plastocyanin is modified by binding of Mg(2+) to the protein. It is concluded that the effects of biologically relevant redox-inactive cations such as Mg(2+) or Ca(2+) have to be considered carefully in studies of the redox chemistry of metalloproteins.

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Bonding of atomic phosphorus to polycyclic hydrocarbons and curved graphitic surfaces.

We present a theoretical study of the bonding of atomic phosphorus to planar hydrocarbons and to curved graphite-like surfaces. We find that bonding of phosphorus to planar polycyclic hydrocarbons induces curvature away from the phosphorus atom, as defined by the pyramidalization angle. Similarly, bonding of atomic phosphorus to the [5,5] fulvalene-circulene semifullerene and buckminsterfullerene is only possible on the convex side of the carbon surface. On the other hand, we find the interaction of atomic phosphorus with the concave side of fullerene-like surfaces to be nonbonding for both quartet and doublet spin states. We find the prerequisite for stable epoxy-type bonds within these systems is the ability of the carbon atoms to maintain or induce curvature away from the P.C=C bond.

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Formation, structure, and structural properties of a new filamentary tubular form: hollow conical-helix of graphitic boron nitride.

A novel tubular form of graphitic boron nitride (BN) displaying a hollow conical-helix was discovered. It was generated via wrapping a single beltlike filament according to the geometry of an Archimedes spiral. Cone apex angles of helical-conical nanotubes (HCNTs) were found to exhibit specific values, each of which refers to a certain coincidence site lattice. A unique structural property of HCNTs was observed, displaying the transformation of apex angles during the annealing process. The observed apex angles were reduced with decreasing annealing temperature, which is in accordance with an estimated HCNT strain energy decrease for a given tubular radius. It is suggested that the curvature and apex angle of a HCNT are determined by a sole dynamic element, that is, enthalpy (DeltaH), whereas the HCNT disclination configuration changes through helical sliding of the filament.

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Synthesis of polyphenylene dendrimers related to "cubic graphite".

Four large, 6-fold symmetric, polyphenylene hydrocarbons have been prepared by short syntheses that chiefly employed alkyne trimerization, palladium-catalyzed coupling, and Diels-Alder reactions. The two largest of these molecules, hexakis[4'-(pentaphenylphenyl)biphenyl-4-yl]benzene (4, C(294)H(198)) and hexakis[4'-(2,3,4,5-tetraphenylphenyl)biphenyl-4-yl]benzene (5, C(258)H(174)) are substructures of "phenylogous cubic graphite", and the other two, hexakis(2',3',4',5',6'-pentaphenylbiphenyl-4-yl)benzene (26, C(258)H(174)) and hexakis(2',3',4',5'-tetraphenylbiphenyl-4-yl)benzene (25, C(222)H(150)) are strongly pitched, six-bladed molecular propellers. The X-ray crystal structure of compound 26 has also been determined; dendrimer 26 is at present the largest crystallographically characterized hydrocarbon.

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Structure and reactivity of Ru nanoparticles supported on modified graphite surfaces: a study of the model catalysts for ammonia synthesis.

Supported ruthenium metal catalysts have higher activity than traditional iron-based catalysts used industrially for ammonia synthesis. A study of a model Ru/C catalyst was carried out to advance the understanding of structure and reactivity correlations in this structure-sensitive reaction where dinitrogen dissociation is the rate-limiting step. Ru particles were grown by chemical vapor deposition (CVD) via a Ru(3)(CO)(12) precursor on a highly oriented pyrolytic graphite (HOPG) surface modified with one-atomic-layer-deep holes mimicking activated carbon support. Scanning tunneling microscopy (STM) has been used to investigate the growth, structure, and morphology of the Ru particles. Thermal desorption of dissociatively adsorbed nitrogen has been used to evaluate the reactivity of the Ru/HOPG model catalysts. Two different Ru particle structures with different reactivities to N(2) dissociation have been identified. The initial sticking coefficient for N(2) dissociative adsorption on the Ru/HOPG model catalysts is approximately 10(-6), 4 orders larger compared to that of Ru single-crystal surfaces.

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Melem (2,5,8-triamino-tri-s-triazine), an important intermediate during condensation of melamine rings to graphitic carbon nitride: synthesis, structure determination by X-ray powder diffractometry, solid-state NMR, and theoretical studies.

Single-phase melem (2,5,8-triamino-tri-s-triazine) C(6)N(7)(NH(2))(3) was obtained as a crystalline powder by thermal treatment of different less condensed C-N-H compounds (e.g., melamine C(3)N(3)(NH(2))(3), dicyandiamide H(4)C(2)N(4), ammonium dicyanamide NH(4)[N(CN)(2)], or cyanamide H(2)CN(2), respectively) at temperatures up to 450 degrees C in sealed glass ampules. The crystal structure was determined ab initio by X-ray powder diffractometry (Cu K alpha(1): P2(1)/c (No. 14), a = 739.92(1) pm, b = 865.28(3) pm, c = 1338.16(4) pm, beta = 99.912(2) degrees, and Z = 4). In the solid, melem consists of nearly planar C(6)N(7)(NH(2))(3) molecules which are arranged into parallel layers with an interplanar distance of 327 pm. Detailed (13)C and (15)N MAS NMR investigations were performed. The presence of the triamino form instead of other possible tautomers was confirmed by a CPPI (cross-polarization combined with polarization inversion) experiment. Furthermore, the compound was characterized using mass spectrometry, vibrational (IR, Raman), and photoluminescence spectroscopy. The structural and vibrational properties of molecular melem were theoretically studied on both the B3LYP and the MP2 level. A structural optimization in the extended state was performed employing density functional methods utilizing LDA and GGA. A good agreement was found between the observed and calculated structural parameters and also for the vibrational frequencies of melem. According to temperature-dependent X-ray powder diffractometry investigations above 560 degrees C, melem transforms into a graphite-like C-N material.

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Graphitic molecules with partial "zig/zag" periphery.

A new synthetic protocol that affords novel hexa-peri-hexabenzocoronene (HBC) derivatives with partial "zig/zag" periphery and dramatically different electronic properties has been developed, which represents an important step toward understanding structure-property relationships of graphitic materials. The scope of this methodology was broadened by application to a much larger polycyclic aromatic hydrocarbon (PAH) with a more extended "zig/zag" character.

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Controlled self-assembly triggered by olefin metathesis: cross-linked graphitic nanotubes from an amphiphilic hexa-peri-hexabenzocoronene.

Acyclic diene metathesis (ADMET) in CH2Cl2 of a Gemini-shaped nonionic hexabenzocoronene amphiphile (2), bearing triethylene glycol chains with terminal allylic functionalities, resulted in spontaneous formation of graphitic nanotubes with a cross-linked surface. Without ADMET, 2 did not self-assemble to form a tubular structure due to a high solubility in CH2Cl2. Although 2 formed nanotubes in THF, ADMET on the surface of the preformed nanotubes in THF proceeded only sluggishly and resulted in partial disruption of the tubular structure. The cross-linked nanotubes showed a softening temperature (244 degrees C) higher than that of the uncross-linked version (195 degrees C) and preserved their hollow structure much longer upon heating.

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Perfectly straight nanowires of fullerenes bearing long alkyl chains on graphite.

Fullerene derivatives bearing long alkyl chains epitaxially adsorb on the basal plane of graphite forming well-ordered one-dimensional lamellae. Within the lamellae, the C60 moieties are organized in a zigzag-type fashion. The ordering is mainly governed by the substitution pattern and chain length of the alkyl chains. The electrochemical activity of the C60 groups is fully maintained in the surface-confined assemblies.

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