Investigation of coherence transfer between “CH3” and “CH2” groups in ethanol with time-resolved multiplex CARS technique

The coherence transfer between stretching vibration modes of C–H bonds in the ethanol is detected by time-resolved multiplex CARS technique and it occurs via “through-bond transfer” pathway. The time scale and velocity of coherence transfer are estimated at 90 fs and 1670 m/s. Moreover, coherence transfer process requires vibrational modes of acceptor and donor are different.     

Minor and trace element contents in pituitary gland of “normal” humans: an evaluation of analytical data

In the study of trace elements in the different human brain areas, a critical evaluation of the values available in the literature is of great importance in attempting to establish reliable baseline levels, i.e., Reference Values (RVs) for toxicological assessment studies.This paper reviews the published values of minor and trace elements in the pituitary gland (hypophysis) of “normal” humans.Eighteen published papers are taken into account, 15 of which refer to the entire gland, whereas in three of them, only the adenohypophysis is considered.It turns out that essential elements such as Cu, Fe, Se and Zn were more frequently determined, whereas As, Br, Ca, Co, Cr, Cs, K, Mg, Mn, Ni and Rb were seldom investigated.Mercury was determined by several authors because of the concern caused by Hg release from dental amalgam fillings.Most values were obtained by Neutron Activation Analysis (NAA), which appears to have played a pioneer role in this field.Literature data on trace element levels in pituitary gland are at present insufficient to establish RVs; rather, they can be considered only as indicative values.Future investigations based on large populations of control subjects, with standardization of the preanalytical factors and the use of fit-for-purpose Standard or Certified Reference Materials (SRMs, CRMs) should therefore be envisaged.     

An experimental study on the “sequential order” rules in generalized two-dimensional correlation spectroscopy

Following our theoretical analysis on the “sequential order” rules in generalized two-dimensional (2D) correlation spectroscopy (H. Huang, Anal. Chem. 79 (2007) 8281–8292), an experimental study was conducted to test the “sequential order” rules using the FT-NIR data of poly(3-hydroxybutyrate) (PHB)/poly(l-lactic acid) (PLA) blends under uniaxial elongation and parallel polarization. The local sequential order concept proposed for the generalized two-dimensional (2D) correlation spectroscopy is now more clearly stated; “the intensity change at ν1 occurs predominantly before ν2” means that the starting time of the intensity change at ν1 is prior to that at ν2. It is this local sequential order which reflects the real and intuitive sequential order between two events in generalized situations. It has been found that the integrated/overall sequential order results obtained from the 2D correlation analysis may be contradictory to the intuitive local sequential order. In addition, different integrated/overall sequential orders could be obtained by selection of different sampling intervals from a certain set of experimental data, or choosing different number of the contours for the same sampling interval. These new experimental findings are a perfect reinforcement to our previous theoretical study and have further demonstrated the uncertainty of applying the “sequential order” rules in generalized 2D correlation spectroscopy.     

Structural and magnetic properties of “one-dimensional” barium vanadium triselenide

BaVSe₃ has been synthesized and its crystal structure determined at 293(2)°K. The structure was solved in the hexagonal space group P6₃/mmc (D⁴_6h), with a = 6.9990(11) and c = 5.8621(13) Å. Scans (2 Θ) of a polycrystalline sample revealed that BaVSe₃ undergoes a transition to an orthorhombic unit cell (b′ 3^1/2 a, a′ a, c′ c) at 303(5)°K. Magnetic susceptibility measurements between 4 and 300°K indicate that BaVSe₃ is paramagnetic down to 41(1)°K, where magnetic ordering occurs, with a magnetic moment in the ordered phase of 0.2 μ_B per vanadium atom. The orthorhombic lattice distortion may be caused by the “freezing in” of “soft” vibrational modes.     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

Sequential speciation of selenium by flow injection cathodic stripping voltammetry

A semi-automatic continuous method for the determination of Se(IV) based on flow-injection cathodic stripping voltammetry (FICSV) is reported. The flow injection approach incorporates a thin mercury film on glassy carbon as the working electrode, on which Se(IV) is deposited at an applied potential of 0.0 V. A cathodic scan (from 0.0 to –0.9 V) is applied and the Se is stripped at –0.54 V, providing a current intensity proportional to the Se(IV) concentration in the sample. This method features a linear determination range between 0.5 and 30 ng/ml (r²=0.998, RSD=3.6%). The non-interference levels (foreign species to analyte ratio) are 2.5:1 for Cu(II), 7.5:1 for Pb(II), 35:1 for Cd(II), 250:1 for Zn(II) and 500:1 for Fe(III). After developing the method for Se(IV), the speciation of this element has been performed by sequential injection of the dissolved sample into a carrier which may or may not have been previously reduced off-line thus determining the sum (Se(IV)+Se(VI)) or only Se(IV), respectively. The method has been applied to selenium speciation in water samples.     

Synthesis and structural characterization of Se-modified carbon-supported Ru nanoparticles for the oxygen reduction reaction

This work is part of a continued research aimed at the understanding of the promoting role of Se in the enhancement of the electrocatalytic activity of Ru in the oxygen reduction reaction. The objective of this paper is to systematically investigate the transformation of Ru nanoparticles upon their modification with the increasing amounts of Se. The Se-modified Ru/C samples with Se:Ru ratio from 0 to 1 were prepared by reacting carbon-supported Ru nanoparticles with SeO2 followed by reductive annealing and characterized using high-resolution transmission electron microscopy, energy-dispersive X-ray, X-ray diffraction analysis, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure. The results suggest that Se strongly interacts with Ru, resulting in the chemical bond between Ru and Se and formation of Ru selenide clusters whose core at low Se content can be described as Ru2Se2O0.5. At Se:Ru = 1, high-resolution electron microscopy shows evidence of formation of core-shell particles, comprising a hexagonally packed Ru core and a Ru selenide shell with lamellar morphology. Modification of Ru nanoparticles with Se enhances their electrocatalytic activity in the oxygen reduction reaction, which is explained by the role of Se in inhibiting surface oxidation.     

Synthesis of highly luminescent Cd(Se,S) nanocrystals

Highly luminescent semiconductor nanocrystals with graded band gap were synthesized using a hot injection method. The band gap of nanocrystals were controlled by gradual incorporation of sulfur to CdSe nanocrystals by applying severely asymmetric composition of reactants [(Cd)/(Se,S) ? 1]. The maximum emission wavelength of the grown nanocrystals was varied by controlling the concentration ratio of VI group element, i.e. Se and S. A green light was emitted from Cd(Se,S) nanocrystals with [Se]:[S] = 1:3 in the reactant mixture and the maximum quantum yield measured by comparing with Rhodamine 6G was larger than 80%.

     

Surface Stoichiometry of CdSe Nanocrystals Determined by Rutherford Backscattering Spectroscopy

Rutherford backscattering spectroscopy has been applied to study the surface stoichiometry of CdSe nanocrystals prepared by the high temperature pyrolysis of organometallics in trioctylphosphine oxide (TOPO). The diameter of the nanocrystals was varied from 22 to 56 Å. For all nanocrystal sizes we find the nanocrystals are Cd rich with an average Cd:Se ratio of 1.2±0.1. The Cd:Se stoichiometry is independent of the Cd:Se starting ratio used for the nanocrystal synthesis, indicating the excess Cd is not associated with the initial abundance of Cd but is an intrinsic property of nanocrystals prepared by this method. The surface coverage of the passivating TOPO ligands has also been determined and is larger than reported in previous X-ray photoelectron spectroscopy (XPS) studies of Bowen Katari et al.[1] The origin and structural implications of nonstoichiometric nanocrystals are discussed.     

Determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal slurries by CVG-ETV-ICP-MS using external or isotopic dilution calibration

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes ²⁰¹Hg, ²⁰⁶Pb, ⁷⁷Se and ¹¹⁹Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g^− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g^− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.     

Elaboration by high-energy ball milling of copper/palladium composite materials – characterization and electrocatalytic activity for the reduction of nitrate in alkaline medium

In this study, an original approach was explored to decorate copper particles with palladium and well-defined bimetallic copper/palladium powders were elaborated through a two-step ball milling procedure. First, copper powder was milled with previously determined optimal conditions (ball-to-powder mass ratio of 2, milling duration of 6 h under argon) in order to obtain spherical nanocrystalline copper particles with an average diameter of 800 μm. Then, an additional milling in presence of 1 at.% of palladium powder was performed, leading to the formation of Cu–Pd composite materials. Palladium surface concentrations from 3 to 62 at.% were obtained by varying both the ball-to-powder mass ratio (2:1 or 10:1) and the milling duration (from 5 to 30 min). Scanning electron microscopy, optical microscopy, X-ray photoelectron spectroscopy and X-ray diffraction analyses confirmed that the more intense the milling is, the easier the palladium diffuses into the copper matrix and smaller the palladium concentration on copper particles is. Cyclic voltammetry and electrolysis experiments showed that palladium inclusions on copper improve greatly the electrocatalytic activity for nitrate reduction in alkaline media. The key role of Pd in the Pd–Cu composite electrodes is to accelerate the reduction of nitrite, formed by the electrochemical reduction of nitrate on Cu sites. Also different nitrate electroreduction behaviors were observed at copper and copper–palladium electrodes leading to the preferential formation of nitrite or ammonia depending on the applied potential and the Pd surface concentration.     

“Green” approach for self-assembly of platinum nanoparticles into nanowires in aqueous glucose solutions

A completely “green” synthetic approach has been developed for the reduction and stabilization of Pt nanoparticles followed by self-assembly into nanowires in an aqueous β-d-glucose solution. Hydrothermal treatment initiated the reduction of Pt(IV) ions dispersed in a pH 8.0 β-d-glucose solution. The Pt nanoparticles were stabilized with oxidized glucose molecules. The Pt nanoparticles continued growing into nanowires followed by transformation into cubic nanocrystals with a rough needle surface. Evidence from TEM and FT-IR spectra reveal that carboxylate groups, which are generated by the oxidation of β-d-glucose, strongly interact with and stabilize the surface of these Pt nanostructures.     

Band-gap engineering of semiconductor nanowires through composition modulation

Alloyed ternary CdS(1-x)Se(x) nanowires were synthesized by template-assisted electrodeposition, in which the ratio of S to Se in the nanowires was controlled by adjusting the relative amounts of the starting materials. Higher-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) showed that the alloyed ternary CdS(1-x)Se(x) nanowires are highly crystalline, and no phase-separated Cd was observed in these nanowires. Optical measurements indicated that the band-gap engineering can be realized in these CdS(1-x)Se(x) nanowires through modulating the composition of S and Se. With broadly tunable optical and electrical properties, these alloyed nanowires could be used in color-tuned nanolasers, biological labels, and nanoelectronics.     

Optimization of electrochemical aspects for epitaxial depositing nanoscale ZnSe thin films

Studies of the electrochemical optimization of ZnSe thin film deposition on polycrystalline Au substrates using electrochemical atomic layer epitaxy are reported. Electrochemical aspects were characterized by means of cyclic voltammetry, differential pulse voltammetry, and coulometry. To study the growth mechanism of the underpotential deposition in the formation of ZnSe, the effects of Zn and Se deposition potentials and a Se-stripping potential were adjusted to optimize the deposition program. The deposit, grown using the optimized program, was proved to be a single-phase ZnSe compound with a strong (220)-preferred orientation by X-ray diffraction analysis, and scanning electronic microscopy observation shows the deposit consisted of nanoscale particles with an average size about 100 nm. The right 1:1 stoichiometric ratio of Zn to Se according to the coulometry suggests that ZnSe is formed.     

Control of metal-ion composition in the synthesis of ternary II-II'-VI nanoparticles by using a mixed-metal cluster precursor approach

The ternary molecular nanoclusters [Zn(x)Cd(10-x)Se4(SePh)12(PnPr3)4] (x = 1.8, 1 a; x = 2.6, 1 b) were employed as single-source precursors for the synthesis of high-quality hexagonal Zn(x)Cd(1-x)Se nanocrystals. The tellurium clusters [Zn(x)Cd(10-x)Te4(TePh)12(PnPr3)4] (x = 1.8, 2 a; x = 2.6, 2 b) are equally convenient precursors for the synthesis cubic Zn(x)Cd(1-x)E nanoparticles. The thermolysis of the cluster molecules in hexadecylamine provides an efficient system in which the inherent metal-ion stoichiometry of the clusters is retained in the nanocrystalline products, whilst also affording control of particle size within the 2-5 nm range. In all cases, the nanoparticles are monodisperse, and luminescence spectra exhibit emission energies close to the absorption edge. Analysis of the optical spectra and X-ray diffraction patterns of these materials indicates a metal-ion concentration gradient within the structures of the nanocrystals, with Zn(II) ions predominantly located near the surface of the particles.     

Kinetics and mechanism of “reduced CO2” electrooxidation on electrodispersed platinum in different acid solutions

The electrooxidation of “reduced CO₂” electroadsorbates on electrodispersed platinum electrodes has been investigated in 0.05 M HClO₄, 1 M HClO₄, 0.5 M H₂SO₄ and 1 M H₃PO₄ at 25° C through voltammetry and potential step techniques. The overall reaction comprises three distinguishable processes, namely a first order triggering process, and two second order surface processes. The latter are influenced remarkably by the solution composition (anions). The second order reaction mechanism involves two distinguishable “ reduced CO₂” electroadsorbates which react independently with the OH species formed from H₂O electrooxidation on the bare platinum sites as the reaction proceeds. An interaction term has to be included in the rate equations to account for the experimental results. The mechanistic interpretation accounts for the values of the number of electrons per site ranging from 1 to 2.     

“Through-space” nuclear spin–spin couplings in ferrocenyl polyphosphanes and diphosphino cavitands: A new way of gathering structural information in constrained P(III) ligands by NMR

Nuclear magnetic resonance is an invaluable technique for investigating a variety of important issues ranging from the determination of molecular structure to therapeutic medical imaging. In this respect, the indirect nuclear spin–spin coupling involving common nuclei such as ¹H, ¹³C or ³¹P provides, via the J constant, conclusive data for compound characterization in solution. This electron-mediated nuclear spin coupling is usually regarded as being transmitted by covalently bonded magnetic atoms. However, several experimental and theoretical studies, first focused on constrained organofluorides, and more recently devoted to phosphane ligands highlighted the existence of very intense J-couplings operating “through-space”. Herein, the intramolecular “through-space” ³¹P³¹P and ³¹P¹³C couplings are discussed in the light of recent examples found in constrained phosphorus-containing ligands such as phosphinocalixarenes, phosphinocyclodextrins and ferrocenyl phosphanes. The emphasis is put on the origin and transmitting mode of these nonbonded spin–spin couplings as well as on the relevant structural information they provide in solution.     

“In situ” ESR and UV-visible spectroscopic studies of iron phthalocyanine films deposited on gold electrodes

The electrochemical behaviour of iron phthalocyanine (Fe^IIPc) films, supported on gold substrates, was studied in 3.5 M NaOH solution, using cyclic voltammetry and coupled “in situ” ESR and UV-visible spectroscopic techniques. Two types of electron transfer were observed in the potential range from −0.45 to −1.0 V vs. Hg/HgO. According to the “in situ” spectroscopy investigations, these two processes were assigned respectively to electron transfers involving first the ligand ring, and then the centre iron ion.     

Selenium speciation in foods: Preliminary results on potatoes

The present paper deals with the speciation of selenium in potatoes (enriched or not in selenium). The study was carried out by using differential pulse cathodic stripping voltammetry (DPCSV) for quantifying selenium. Results obtained provide evidence that the selenium content in the protein fraction is rather independent from the selenium added to the plants during their growth. On the contrary, the amount of Se in the non-protein fraction (water and starch) in Se-enriched sample is significantly higher than in non-enriched one, suggesting that it is the main selenium-storing site. In this fraction the Se(VI)/Se(IV) ratio seems independent from selenium application but it may be related to the redox conditions. The accumulation of selenium in the non-protein fraction is tentatively ascribed to the “Se–starch interaction” that should be able to modulate both the Se absorption into proteins and, possibly, its toxic effect for the plant itself.     

Iron-modified mesoporous SBA-15 silica: Preparation and characterization studies

Fe-SBA-15 materials with different Si/Fe ratios (Si/Fe = 100, 60, 15) have been synthesized by hydrothermal method and characterized by several spectroscopic techniques. Electron spin resonance and Mössbauer spectroscopy, along with electron microscopy and X-ray diffraction, allowed differentiation of several iron species. These species correspond to hematite particles, very small “isolated” or oligomeric Fe^III species possibly incorporated in the mesoporous silica wall, and Fe^III oxide clusters either isolated or agglomerated, forming “rafts” at the surface of the silica and exhibiting ferromagnetic ordering. Because of their agglomeration, these clusters appear with a two-peak size distribution, with one peak corresponding to the isolated clusters formed in the mesopores and still embedded in them and the other corresponding to the agglomerates spread on the surface of the mesoporous silica particles.