Translocation of compact polymer chains through a nanopore

We perform dynamical Monte Carlo simulation to study the forced translocation of compact polymer chains in three-dimensional lattices. The chains are driven through a nanopore connecting two infinite channels by an external field. The scaling properties of average translocation time τ and translocation time distribution (TTD) are studied. The effects of contact energy (?_C), electric field strength (E), and nanopore width (L) on the scaling exponent (α) of average translocation time τ ∼ N^α and the TTD are investigated. For the scaling behavior of τ ∼ N^α, we have found that there is no crossover behavior with weak field strength when the nanopore width is one lattice spacing, which is less than average bond length, while crossover behaviors are observed for larger nanopore widths. The scaling exponent α also depends on contact energy ?_C and electric field strength E. For the TTD, it shifts from the Gaussian to a right-skew distribution with the electric field E increasing for short chains; while for long chains, multi-peak distributions are observed. As a primary and simple model, compact polymer chains are extensively used to capture the structure and thermodynamic properties of proteins, therefore we can investigate the protein translocation by simulating compact chain translocation, and this study will be useful for exploring the complex translocation behaviors of proteins.     

Revisiting of dimensional scaling of linear chains in dilute solutions

The dimensions of linear polymer chains are scaled to their molar mass (M) as R = kM^α with α = 1/2 and 3/5 in a theta and an athermal solvent, respectively. In a good solvent, both k and α are a function of the solvent quality and chain length range. A high-temperature laser light-scattering spectrometer was used to measure the average radius of gyration (〈R_g〉) and hydrodynamic radius (〈R_h〉) of a set of narrowly distributed linear polystyrene chains in decalin over a wide temperature range. k and α in the scaling experimentally varying with T over a chain length range was analyzed. The results reveal that for 〈R_g〉, α = 0.59 − 0.09exp(−τ/0.066) and k = 0.60τ^2α−1, reasonably agreeing with the thermal blob theory. For 〈R_h〉, α = 0.59 − 0.09exp(−τ/0.106), but k deviates from the relationship of k ∝ τ^2α−1, reflecting that the hydrodynamic interaction and chain draining are not considered in the thermal blob theory.     

Polymer translocation through a nanopore in mesoscopic simulations

Dissipative particle dynamics (DPD) simulations are carried out to study the translocation of a single polymer chain through a pore under fluid field. The influences of the field strength E, the chain length N, the solvent quality α_sp, and the pore size h on the translocation time are evaluated. The translocation time τ, which is defined as the time that the chain moves through the pore completely in the direction of the driving force, scales with the field strength E as τ ∼ E^{−0.48±0.01}. We find that the translocation time is proportional to the chain length, which is in agreement with the experimental results and theoretical predictions. Tracing the variation of the square radius of gyration, , and the polymer configuration during translocation, we observe that the chain is elongated when it is passing through the pore, which manifests that the chain is not in equilibrium during the translocation process. We also find that the worse the solvent quality is, the less time it will take to translocate, no matter what the size of the pore is. If the size of the pore is enlarged, the translocation time will be shorter. The information we gain from this study may benefit to the DNA sequencing.     

Novel conjugated alternating copolymer based on 2,7-carbazole and 2,1,3-benzoselenadiazole

A novel conjugated alternating copolymer (PCzDBSe) based on N-9′-heptadecanyl-2,7-carbazole and 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) was synthesized by Suzuki polycondensation. The polymer reveals excellent thermal stabilities with the decomposition temperature (5% weight loss) of 390 °C and the glass-transition temperature of 140 °C. The absorption peaks of the polymer are located at 412 and 626 nm, respectively, while the absorption onset is extended to 716 nm, which is 56 nm red-shifted as compared with its analogue, poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT). The HOMO and LUMO levels of the polymer were estimated to be −5.28 and −3.55 eV, respectively, with an optical bandgap of 1.73 eV. The hole mobility of PCzDBSe as deduced from a solution-processed organic field effect transistor (OFET) was found to be 3.9 × 10⁻⁴ cm² V⁻¹ s⁻¹. Polymer solar cells (PSCs) based on the blends of PCzDBSe and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) with a weight ratio of 1:4 were fabricated. Under AM 1.5 (AM, air mass), 100 mW cm⁻² illumination, the devices were found to have an open-circuit (V_oc) of 0.75 V, a short-circuit current density (J_sc) of 7.23 mA cm⁻², a fill factor (FF) of 45% and a power conversion efficiency (PCE) of 2.58%. The primary results indicate that 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) is a promising unit for low bandgap polymer for polymer solar cells.     

Adsorption dynamics and interfacial properties of thiol-based cobalt terpyridine monolayers

Spontaneously adsorbed monolayers of [Co(ttp-CH₂-SH)₂](PF₆)₂ have been formed on platinum microelectrodes by exposure to micromolar solutions of the complex in 0.1 M TBABF₄ in acetonitrile, ttp-CH₂-SH is 4′-(p-(thiolmethyl)-phenyl)-2,2′:6′,2″-terpyridine. Resonance Raman spectroscopy on roughened polycrystalline platinum macro electrodes show that the molecule undergoes adsorption through the sulphur atom onto the platinum surface. The monolayers show reversible and well defined cyclic voltammetry when switched between Co²⁺ and Co³⁺ forms, with a peak to peak splitting of 0.040 ± 0.005 V up to 200 V s⁻¹ and an FWHM of 0.138 ± 0.010 V. Adsorption is irreversible leading to the maximum surface coverage, 6.3 ± 0.3 × 10⁻¹¹ mol cm⁻² for 2.5 ≤ [Co(ttp-CH₂-SH)₂] ≤ 10 μM. The rate of monolayer formation appears to be controlled not by mass transport or interfacial binding but by surface diffusion of the complex. The surface diffusion coefficient is 5.5 ± 1.1 × 10⁻⁷ cm² s⁻¹ indicating that prior to formation of an equilibrated monolayer, the adsorbates have significant mobility on the surface. The electron transfer process across the monolayer-electrode interface has been probed by high speed chronoamperometry and the standard heterogeneous electron transfer rate constant, k°, is approximately 3.06 ± 0.03 × 10⁴ s⁻¹. The reorganization energy is at least 18.5 kJ mol⁻¹.     

Microstructure of free volume in SMA copolymers II. Local free volume from PALS

The structure of the free volume and its temperature dependence between, at maximum 133 and 503 K of copolymers of styrene with maleic-anhydride, SMA (0-35 mol% MA), is studied by pressure-volume-temperature (PVT) experiments and positron annihilation lifetime spectroscopy (PALS). In this second part of the work, PALS data are reported from which the temperature dependence of the mean size and size distribution of local free volumes (subnanometer size holes) is analysed. The mean hole volume, ν_h, varies in PS between 80 Å³ (133 K) and 212 Å³ (503 K) and shows a systematic decrease with increasing MA content for a given temperature above T_g. The specific number of holes, N_h′, estimated from a comparison of PVT and PALS results, increases slightly with MA content from N_h′=(0.60±0.02)×10²¹ g⁻¹ to N_h′=(0.70±0.02)×10²¹ g⁻¹ which corresponds to N_h(T_g)=N_h′/V_g=0.62-0.82 nm⁻³ (V_g is the material's specific volume at T_g) and 1/N_h(T_g)=1.6-1.2 nm³ for the volume which contains one hole. The analysed size distributions of the holes above T_g follow the compressibility of the free volume as it is predicted by the theory of thermal volume fluctuation. We also comment on the connection between the hole size as measured by PALS and the size of a cluster of randomly distributed unoccupied cells as defined by the Simha-Somcynsky theory.     

Effect of fluorine in the preparation of Li(Ni1/3Co1/3Mn1/3)O2 via hydroxide co-precipitation

Uniform and spherical Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ powders were synthesized via NH₃ and F⁻ coordination hydroxide co-precipitation. The effect of F⁻ coordination agent on the morphology, structure and electrochemical properties of the Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ were studied. The morphology, size, and distribution of (Ni_1/3Co_1/3Mn_1/3)(OH)_(2−δ)F_δ particle diameter were improved in a shorter reaction time through the addition of F⁻. The study suggested that the added F improves the layered characteristics of the lattice and the cyclic performance of Li(Ni_1/3Co_1/3Mn_1/3)O₂ in the voltage range of 2.8-4.6 V. The initial capacity of the Li(Ni_1/3Co_1/3Mn_1/3)O_1.96F_0.04 was 178 mAh g⁻¹, the maximum capacity was 186 mAh g⁻¹ and the capacity after 50 cycles was 179 mAh g⁻¹ in the voltage range of 2.8-4.6 V.     

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods: Part 1. ATR-FTIRAS spectra of CO adsorbed on highly dispersed Pt catalyst on carbon black and carbon un-supported Pt black

Elecrochemical ATR-FTIRAS measurements were conducted for the first time to investigate nature of CO adsorbed under potential control on a highly dispersed Pt catalyst with average particle size of 2.6 nm supported on carbon black (Pt/C) and carbon un-supported Pt black catalyst (Pt-B). Each catalyst was uniformly dispersed by 10 μg Pt/cm² and fixed by Nafion^® film of 0.05 μm thick on a gold film chemically deposited on a Si ATR prism window. Adsorption of CO was conducted at 0.05 V on the catalysts in 1 and 100% CO atmospheres, for which CO coverage, θ_CO, was 0.69 and 1, respectively. Two well-defined ν(CO) bands free from band anomalies assigned to atop CO (CO(L)) and symmetrically bridge bonded CO (CO(B)_sym.) were observed. It was newly found that the CO(L) band was spitted into two well-defined peaks, particularly in 1% CO, from very early stage of adsorption, which was interpreted in terms of simultaneous occupation of terrace and step-edge sites, denoted as CO(L)_terrace and CO(L)_edge, respectively. This simultaneous occupation was commonly observed in our work both on Pt/C and Pt-B. A new band was also observed around 1950 cm⁻¹ in addition to the bands of CO(L) and CO(B)_sym., which was assigned to asymmetric bridge CO, CO(B)_asym., adsorbed on (1 0 0) terraces, based on our previous ECSTM observation of CO adsorption structures on (1 0 0) facet. The CO(B)_asym. on the Pt/C, particularly in 100% CO atmosphere, results in growth of a sharp band at 3650 cm⁻¹ accompanied by a concomitant development of a band around 3500 cm⁻¹. The former and the latter are assigned to ν(OH) vibrations of non-hydrogen bonded and hydrogen bonded water molecules adsorbed on Pt, respectively, interpreted in term of results from a bond scission of the existing hydrogen bonded networks by CO(L)s and from a promotion of new hydrogen bonding among water molecules presumably by CO(B)_asym..It was found that the frequency ν(CO) of CO(L) both on Pt/C and Pt-B is lower than that on bulky polycrystalline electrode Pt(poly) or different crystal planes of Pt single-crystal electrodes by 30-40 cm⁻¹ at corresponding potentials, which implies a stronger electronic interaction between CO and Pt nano-particles and/or an increased contribution of step-edge sites on the particles. Determination of the band intensities of CO(L), CO(B)_asym. and CO(B)_sym. has led us to conclude a much higher bridged occupation of sites at Pt nano-particles than Pt(poly) electrodes.     

Yellowish green-emitting KSrPO4:Tb phosphors with various doping concentrations prepared by using microwave assisted sintering

KSr_1−xPO₄:xTb³⁺ phosphors with various concentrations (x = 0.05, 0.06, 0.07, 0.08) of Tb³⁺ ions were synthesized in succession by using microwave assisted sintering. The sintering condition was set at 1200 °C for 1 h in air. The microstructural and luminescent characteristics of KSrPO₄:Tb³⁺ phosphors were investigated and are discussed here. The XRD result shows that the prepared KSr_1−xPO₄:xTb³⁺ phosphors would have an impure phase as the Tb³⁺ ion increases to more than x = 0.06. The photoluminescence measurement shows that the series of the emission-state ⁵D₄ → ⁷F₆, ⁵D₄ → ⁷F₄, and ⁵D₄ → ⁷F₃, corresponding to the typical 4f → 4f intra-configuration forbidden transitions of Tb³⁺, are appeared and the major emission peak is around at 542 nm. Moreover, the maximum photoluminescence intensity is appeared when the molar concentration of Tb³⁺ is 0.06. The decay time value of the KSr_1−xPO₄:xTb³⁺ phosphors with x = 0.06 is about 0.27 ms.     

Electrochemical and density functional theory study of bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) cationic complexes

The electrochemical behaviour of fluorinated bis(cyclopentadienyl) mono(β-diketonato) titanium(IV) complexes, of general formula [Cp₂Ti(R′COCHCOR)]⁺ClO₄⁻ with Cp = cyclopentadienyl and R′, R = CF₃, C₄H₃S; CF₃, C₄H₃O; CF₃, Ph (C₆H₅); CF₃, CH₃; CH₃, CH₃; Ph, Ph and Ph, CH₃ is described. Both metal and ligand based redox processes are observed. The chemically and electrochemically reversible Ti^IV/Ti^III couple is followed by an irreversible ligand reduction at a considerably more negative (cathodic) potential. A comparison of the ligand reduction in its free and chelated state indicates that the β-diketonato ligand (R′COCHCOR)⁻ in [Cp₂Ti(R′COCHCOR)]⁺ClO₄⁻ is electroactive at more negative potentials. A theoretical density functional theory (DFT) study shows that a highly localized metal centred frontier orbital dominates the Ti^IV/Ti^III redox chemistry resulting in a non-linear relationship between the formal redox potential (E°′) and the sum of the group electronegativities of the R and R′ groups, χ_R + χ_R′, of the ligand. Linear relationships, however, are obtained between the DFT calculated electron affinity (EA) of the complexes and χ_R + χ_R′, the pK_a of the free β-diketones R′COCH₂COR and the carbonyl stretching frequency, v_CO, of the complexes. The DFT calculated electronic structure of the second reduced species [Cp₂Ti(β-diketonato)]⁻ shows that it is best described as Ti(III) coupled to a β-diketonato radical.     

Dielectric relaxation and molecular dynamics in poly(vinyl pyrrolidone)-ethyl alcohol mixtures in pure liquid state and in non-polar solvent

Dielectric relaxation and molecular dynamics in poly(vinyl pyrrolidone)-ethyl alcohol (PVP-E) mixtures with varying concentration in pure state and also in very dilute solutions of benzene were studied for their molecular conformation at 35 °C. Dielectric permittivity ε′ and dielectric loss ε″ of PVP-E mixtures were measured by a time domain reflectometry technique in the frequency range 10 MHz to 10 GHz. The value of static dielectric constant ε₀, dielectric relaxation time τ, and dielectric free energy of activation ΔF_τ has been evaluated by fitting the complex dielectric data into Debye equation. The variation in ε₀ was discussed by considering the volume effect and the structuring effects of the PVP on ethyl alcohol molecules. The formation of cooperative domains between PVP and ethyl alcohol molecules, CD_PVP-E and between the ethyl alcohol-ethyl alcohol molecules CD_E and their dynamics in the PVP-E mixtures were explored by using the evaluated values of τ and ΔF_τ.The PVP-E mixtures of low PVP concentration were also studied in very dilute solutions of benzene at 10.1 GHz. The value of average relaxation time τ₀, distribution parameter α, and relaxation time corresponding to the motion of small multimer species of alcohol molecules τ₁ and group rotation τ₂ has been determined. It has been observed that in dilute solution of benzene the value of τ₀ and τ₁ increases with the increase in concentration of PVP in PVP-E mixture but the τ₂ value is found independent of the mixture constituent concentration. The entanglement of the CD_PVP-E and the increase in the length of CD_E in dilute solution of benzene due to dissociation of the complexes between carbonyl and hydroxyl groups has been explored. The value of τ₂ is assigned to the rotation of -OH group about C-O bond in the ethyl alcohol species in dynamic equilibrium with larger steric hindrance due to hydrogen bonding.     

IBLC effect leading to colossal dielectric constant in layered structured Eu2CuO4 ceramic

Dielectric (ε_r′) studies of phase pure T′-type Eu₂CuO₄ ceramics of two markedly different grain sizes (D), prepared by (i) conventional powder mixing and (ii) citrate complexation-Pechini process, have been carried out in the frequency range 0.1 Hz to 1 MHz, and at temperatures −100 °C to 150 °C. ε_r′ is found to be highly grain size dependent. For the sample with coarse bar-like grains (D²~17×6 μm²) ε_r′ is >10³, and for the finer grain size sample with bimodal distribution (D₁~1 μm, D₂~3 μm) ε_r′ is ~10⁵; for both the samples, high ε_r′ value is nearly frequency independent over 500 Hz≤f<100 kHz and T≥30 °C. The impedance spectroscopy (IS) study has clearly shown that both, the coarse- and the fine-grained samples consist of semiconducting grains and insulating grain boundaries that primarily lead to an internal barrier layer capacitance (IBLC) effect. And thus, manifest colossal dielectric constant (ε_r′>10³) in Eu₂CuO₄ ceramics. The smaller grain size (Pechini) sample, with over an order higher number of grains and grain boundary network, showing over an order higher ε_r′ (~10⁵) compared to the coarse grained one, further endorses the IBLC effect.     

Kinetics of dissociative adsorption of ethylene glycol on Pt(1 0 0) electrode surface in sulfuric acid solutions

The dissociative adsorption of ethylene glycol (EG) on Pt(1 0 0) electrode surface cooled in air after flame annealing was investigated by using programmed potential step technique and in situ FTIR spectroscopy. The stable adsorbates derived from EG dissociative adsorption on Pt(1 0 0) were determined by in situ FTIR spectroscopy as linear- and bridge-bonded CO. The quantitative results demonstrated that the average rate of dissociative adsorption of EG on Pt(1 0 0) surface varies with electrode potential, yielding a volcano-type distribution with a maximum value located near 0.10 V versus SCE. From the variation of the quantity of CO adsorbates generated in EG dissociative adsorption with the adsorption time t_ad, the initial rate (ν_i) of this surface reaction was evaluated quantitatively. The maximum value of ν_i has been determined to be 2.64 × 10⁻¹¹ mol cm⁻² s⁻¹ in a solution containing 2 × 10⁻³ mol L⁻¹ EG. The influence of the surface structure of Pt(1 0 0) electrode obtained by different pretreatment as well as of the specific adsorption of (bi)sulfate anions on the kinetics of EG dissociative adsorption has been also investigated and discussed. In comparison with a Pt(1 0 0) surface cooled in air atmosphere after flame treatment, the Pt(1 0 0) surface cooled in an Ar-H₂ stream or subjected to a treatment of fast potential cycling decreased significantly the initial rate ν_i of EG dissociative adsorption. Similar effect was also observed for the specific adsorption of (bi)sulfate anions. However, the maximum attainable coverage () of adsorbates derived from EG dissociative adsorption is not affected either by the surface structure of Pt(1 0 0) or by (bi)sulfate anions adsorption.     

Dynamic aspects of cerium dioxide sintering: HT-ESEM study of grain growth and pore elimination

Sintering of CeO₂ is studied in situ by high temperature scanning environmental microscopy (HT-ESEM) at T = 1400 °C. The morphological modifications of a single grains population are recorded for 6 h. Kinetic parameters are extracted from image series. The local grain growth determined from the single population studied in situ is compared to the general grain growth obtained by classical ex situ technique. Using HT-ESEM for sintering study is validated. The grain boundary velocities range between 0 and 5 μm h⁻¹, with a mean value of about 1 μm h⁻¹. The migration of the intragranular surface pores is described. Their velocities range between 0.4 and 1.2 μm h⁻¹ and depend on pore diameters: the smaller the pore, the faster the pore velocity. The time required to fill a pore that arises at the sample surface is determined as a function of pore diameter. The time for pore elimination dependence with the pore diameters is also established.     

Modification of glassy carbon electrode with multi-walled carbon nanotubes and iron(III)-porphyrin film: Application to chlorate, bromate and iodate detection

In this study, multi-wall carbon nanotubes (MWCTs) is evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on iron-porphyrin. 5,10,15,20-Tetraphenyl-21H,23H-porphine iron(III) chloride (Fe(III)P) adsorbed on MWCNTs immobilized on the surface of glassy carbon electrode. Cyclic voltammograms of the Fe(III)P-incorporated-MWCNTs indicate a pair of well-defined and nearly reversible redox couple with surface confined characteristics at wide pH range (2-12). The surface coverage (Γ) and charge transfer rate constant (k_s) of Fe(III)P immobilized on MWCNTs were 7.68 × 10⁻⁹ mol cm⁻² and 1.8 s⁻¹, respectively, indicating high loading ability of MWCNTs for Fe(III)P and great facilitation of the electron transfer between Fe(III)P and carbon nanotubes immobilized on the electrode surface. Modified electrodes exhibit excellent electrocatalytic activity toward reduction of ClO₃⁻, IO₃⁻ and BrO₃⁻ in acidic solutions. The catalytic rate constants for catalytic reduction of bromate, chlorate and iodate were 6.8 × 10³, 7.4 × 10³ and 4.8 × 10² M⁻¹ s⁻¹, respectively. The hydrodynamic amperometry of rotating-modified electrode at constant potential versus reference electrode was used for detection of bromate, chlorate and iodate. The detection limit, linear calibration range and sensitivity for chlorate, bromate and iodate detections were 0.5 μM, 2 μM to 1 mM, 8.4 nA/μM, 0.6 μM, 2 μM to 0.15 mM, 11 nA/μM, and 2.5 μM, 10 μM to 4 mM and 1.5 nA/μM, respectively. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantages of this sensor. The obtained results show promising practical application of the Fe(III)P-MWCNTs-modified electrode as an amperometric sensor for chlorate, iodate and bromate detections.     

Microstructure and electromagnetic properties of flake-like Nd-Fe-B nanocomposite powders with different milling times

The microstructure and electromagnetic properties of melt-spun Nd-Fe-B nanocomposites, which have been dealt with by the ball milling process with different milling times, are studied specifically in this paper. The powder size ranges from 20 μm to 5 μm after different milling times. Moreover the powder particles even remain flake-like shape after 11 h milling time. X-ray diffraction spectra strongly suggest that all samples only have the single α-Fe phase. By using the complex permeability (μ = μ′ − μ″) and permittivity (ε = ε′ − ε″) within 2 to 18 GHz frequency range, determined by vector network analysis, the experiment shows that the permeability of flake-like Nd₃Fe₆₈Co₁₈B₁₁ can be increased while its permittivity is decreased by increasing the milling time. For the sample with 11 h milling time, its imaginary permeability μ″ can be increased to an abnormal state below the frequency of 6 GHz. Based on transmission line theory, it is calculated that the Nd₃Fe₆₈Co₁₈B₁₁ composites can achieve their optimal reflection loss (RL = − 8 dB) at 3.7 GHz with a matching thickness of 1.5 mm. This paper shows the possibility to obtain good microwave absorbing properties at a proper milling time for melt spun Nd-Fe-B nanocomposites.     

Structure and dynamics of a vinylidene fluoride oligomer and its cyclodextrin inclusion compounds as studied by solid-state F MAS and H → F CP/MAS NMR spectroscopy

The molecular structure and dynamics of a vinylidene fluoride oligomer telomerized by carbon tetrachloride (Cl-OVDF) and its inclusion compound (IC) with β-cyclodextrin (β-CD) have been investigated using solid-state ¹⁹F magic angle spinning (MAS) and ¹H → ¹⁹F cross-polarization (CP)/MAS NMR spectroscopy. The preferential IC formation of the lower-molecular-weight components with β-CD was used to refine as-received Cl-OVDF. The refined Cl-OVDF with larger molecular weight readily takes γ-form (tttg⁺tttg⁻) conformation, and it also forms ICs with β-CD (Cl-OVDF/β-CD IC) under a certain condition. ¹⁹F MAS NMR indicates that Cl-OVDF chains virtually isolated in the β-CD cavities take no specific conformations even at −40 °C. The temperature dependence of the magnetic relaxation times (T₁^F, T_1ρ^F) indicates that the Cl-OVDF chains in ICs undergo molecular motions similar to the amorphous phase in the bulk, although the intramolecular spin diffusion among ¹⁹F nuclei is more significant in the former because of the one-dimensional confinement.     

Micromolar determination of sulfur oxoanions and sulfide at a renewable sol-gel carbon ceramic electrode modified with nickel powder

The sol-gel technique was used to fabricate nickel powder carbon composite electrode (CCE). The nickel powder successfully used to deposit NiO_x thin film on conductive carbon ceramic electrode for large surface area catalytic application. Repetitive cycling in potential range −0.2 to 1.0 V was used to form of a thin nickel oxide film on the surface carbon composite electrode. The thin film exhibits an excellent electro-catalytic activity for oxidation of SO₃²⁻, S₂O₄²⁻, S₂O₃²⁻, S₄O₆²⁻ and S²⁻ in alkaline pH range 10-14. Optimum pH values for detection of all sulfur derivatives is 13 and catalytic rate constants are in range 2.4 × 10³-8.9 × 10³ M⁻¹ s⁻¹. The hydrodynamic amperometry at rotating modified CCE at constant potential versus reference electrode was used for detection of sulfur derivatives. Under optimized conditions the calibration plots are linear in the concentration range 10 μM-15 mM and detection limit 1.2-34 μM and 0.53-7.58 nA/μM (sensitivity) for electrode surface area 0.0314 cm². The nickel powder doped modified carbon ceramic electrode shows good reproducibility, a short response time (2.0 s), remarkable long term stability, less expense, simplicity of preparation, good chemical and mechanical stability, and especially good surface renewability by simple mechanical polishing and repetitive potential cycling. This sensor can be used into the design of a simple and cheap chromatographic amperometry detector for analysis of sulfur derivatives.     

Mass transfer limitations on fixed-bed reactor for Fischer-Tropsch synthesis

Mass transfer limitations on fixed-bed for Fischer-Tropsch synthesis were investigated by changing synthesis gas superficial velocity, catalyst pellet size, and catalyst amount. To study external mass transfer limitation, synthesis gas superficial velocity was changed from 8.47 × 10^− 4 m s^− 1 to 3.39 × 10^− 3 m s^− 1. As a result, the synthesis gas superficial velocity of 3.39 × 10^− 3 m s^− 1 was most suitable for hydrocarbon chain growth resulting to liquid hydrocarbon formation. In case of internal mass transfer limitations, the effects of catalyst pellet size and catalyst amount (W_cat/F) were discussed. The large catalyst pellet showed higher C₅₊ selectivity and a lower α value compared to the small pellet because of more severe internal mass transfer limitations of α-olefin and long-chained hydrocarbons in the large pellet, respectively. Catalyst amount (W_cat/F) was inversely proportional to the internal mass transfer limitation because increased catalyst amount gave more time for liquid hydrocarbon products to diffuse from the catalyst pellet and, therefore, the catalyst amount of 4.5 g (W_cat/F = 45 g_cat min L^− 1) was most appropriate for liquid hydrocarbon formation.     

TiO2 films prepared by micro-plasma oxidation method for dye-sensitized solar cell

Nanocrystalline TiO₂ films are widely investigated as the electrodes of dye-sensitized solar cell(s) with different preparation methods. In this paper, thin titanium dioxide films have been prepared on titanium plates by the micro-plasma oxidation method in the sulfuric acid solution. The thin TiO₂ films were sensitized with a cis-RuL₂(SCN)₂·2H₂O (L = cis-2,2′-bipyridine-4,4′-dicarboxylic acid) ruthenium complex and implemented into a dye-sensitized solar cell configuration. The influence of reaction current density (10, 15, 20, 25 and 30 A dm⁻²) on the structural and the surface morphology of the films was investigated by X-ray diffraction, scanning electron microscopy, atom force microscopy and X-ray photoelectricity spectroscopy. Impedance analysis for dye-sensitized solar cells was carried out by electrochemical impedance spectroscopy. The results show that the rise of current density leads to the increase in the amount of rutile and the thickness of the TiO₂ film, which makes the TiO₂ films have different photovoltages and photocurrents. The relatively higher photoelectricity properties were obtained in the TiO₂ films prepared at a current density of 20 A dm⁻². The open-circuit voltage and the short-circuit current are 605 mV and 165 μA cm⁻², respectively.