The role of defects, or active states, in surface electrochemistry with particular reference to gold in neutral solution

Metastable, active, or nonequilibrium states due to the presence of abnormal structures and various types of defects are well known in metallurgy. The role of such states at gold surfaces in neutral aqueous media (an important electrode system in the microsensor area) was explored using cyclic voltammetry. It was demonstrated that, as postulated in earlier work from this laboratory, there is a close relationship between premonolayer oxidation, multilayer hydrous oxide reduction and electrocatalytic behaviour in the case of this and other metal electrode systems. Some of the most active, and therefore most important, entities at surfaces (e.g., metal adatoms) are not readily imageable or detectable by high resolution surface microscopy techniques. Cyclic voltammetry, however, provides significant, though not highly specific, information about such species. The main conclusion is that further practical and theoretical work on active states of metal surfaces is highly desirable as their behaviour is not simple and is of major importance in many electrocatalytic processes.

Observation of ions and particles near busy roads using a Neutral Cluster and Air Ion Spectrometer (NAIS)

Motor vehicles emit large quantities of ions in the form of both charged particles and molecular cluster ions. While, the health effects of inhalation of charged particles is largely unexplored, the concentrations near busy roads and the distance to which these particles and ions are carried have important implications for the exposure of the large percentage of the population that lives close to such roadways. We measured ion concentrations using a neutral cluster and air ion spectrometer (NAIS) near seven busy roads carrying on the average approximately 7000 vehicles hr-1 including about 15% heavy duty diesel vehicles. In this study, charged particle concentrations were measured as a function of downwind distance from the road for the first time. We show that, at a moderate wind speed of 2.0 m s-1, mean charged particle concentrations at the kerb were of the order of 2x104 cm-3 and, more importantly, decreased as d 0.6 where d is the distance from the road. While cluster ions were rapidly depleted by attachment to particles and were not carried to more than about 20 m from the road, elevated concentrations of charged particle were detected up to at least 400 m from the road. Most of the charge on the downwind side was carried on the larger particles, with no excess charge on particles smaller than about 10 nm. At 30 nm, particles carried more than double the charge they would normally carry in equilibrium. There are very few measurements of ions near road traffic and this is the first study of the spatial dispersion of charged particles from a road.

Experimental verification of the modified spring-mass theory of fiber Bragg grating accelerometers using transverse forces

A fiber Bragg grating (FBG) accelerometer using transverse forces is more sensitive than one using axial forces with the same mass of the inertial object, because a barely stretched FBG fixed at its two ends is much more sensitive to transverse forces than axial ones. The spring-mass theory, with the assumption that the axial force changes little during the vibration, cannot accurately predict its sensitivity and resonant frequency in the gravitational direction because the assumption does not hold due to the fact that the FBG is barely prestretched. It was modified but still required experimental verification due to the limitations in the original experiments, such as the (1) friction between the inertial object and shell; (2) errors involved in estimating the time-domain records; (3) limited data; and (4) large interval ∼5 Hz between the tested frequencies in the frequency-response experiments. The experiments presented here have verified the modified theory by overcoming those limitations. On the frequency responses, it is observed that the optimal condition for simultaneously achieving high sensitivity and resonant frequency is at the infinitesimal prestretch. On the sensitivity at the same frequency, the experimental sensitivities of the FBG accelerometer with a 5.71 gram inertial object at 6 Hz (1.29, 1.19, 0.88, 0.64, and 0.31 nm/g at the 0.03, 0.69, 1.41, 1.93, and 3.16 nm prestretches, respectively) agree with the static sensitivities predicted (1.25, 1.14, 0.83, 0.61, and 0.29 nm/g, correspondingly). On the resonant frequency, (1) its assumption that the resonant frequencies in the forced and free vibrations are similar is experimentally verified; (2) its dependence on the distance between the FBG’s fixed ends is examined, showing it to be independent; (3) the predictions of the spring-mass theory and modified theory are compared with the experimental results, showing that the modified theory predicts more accurately. The modified theory can be used more confidently in guiding its design by predicting its static sensitivity and resonant frequency, and may have applications in other fields for the scenario where the spring-mass theory fails.

An Artificial Neutral Network (ANN) model for predicting biodiesel kinetic viscosity as a function of temperature and chemical compositions

An Artificial Neural Network (ANN) is a computational modeling tool which has found extensive acceptance in many disciplines for modeling complex real world problems. An ANN can model problems through learning by example, rather than by fully understanding the detailed characteristics and physics of the system. In the present study, the accuracy and predictive power of an ANN was evaluated in predicting kinetic viscosity of biodiesels over a wide range of temperatures typically encountered in diesel engine operation. In this model, temperature and chemical composition of biodiesel were used as input variables. In order to obtain the necessary data for model development, the chemical composition and temperature dependent fuel properties of ten different types of biodiesels were measured experimentally using laboratory standard testing equipments following internationally recognized testing procedures. The Neural Networks Toolbox of MatLab R2012a software was used to train, validate and simulate the ANN model on a personal computer. The network architecture was optimised following a trial and error method to obtain the best prediction of the kinematic viscosity. The predictive performance of the model was determined by calculating the absolute fraction of variance (R2), root mean squared (RMS) and maximum average error percentage (MAEP) between predicted and experimental results. This study found that ANN is highly accurate in predicting the viscosity of biodiesel and demonstrates the ability of the ANN model to find a meaningful relationship between biodiesel chemical composition and fuel properties at different temperature levels. Therefore the model developed in this study can be a useful tool in accurately predict biodiesel fuel properties instead of undertaking costly and time consuming experimental tests.

Comparing skin biopsy with confocal microscopy : diagnostic yield of nerve fiber density

Background and aims: The assessment of intra-epidermal nerve fiber density (IENFD) in skin biopsies and corneal nerve fiber density (CNFD) using corneal confocal microscopy (CCM) provides promising techniques to detect small nerve fiber damage in patients with peripheral neuropathy. To help define the clinical utility of each of these techniques in patients with diabetic neuropathy we have assessed sensitivity and specificity of IENFD and CNFD in predicting the following: 1) diabetic polyneuropathy (DPN); 2) risk of foot ulceration (RFU); 3) initial small fiber neuropathy (iSFN); 4) severe small fiber neuropathy (sSFN)...

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Conversion of neutral C2COC2 to C4CO. potential interstellar molecules

Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.

Neutral and charged boron-doped fullerenes for CO2 adsorption

Recently, the capture and storage of CO2 have attracted research interest as a strategy to reduce the global emissions of greenhouse gases. It is crucial to find suitable materials to achieve an efficient CO2 capture. Here we report our study of CO2 adsorption on boron-doped C60 fullerene in the neutral state and in the 1e−-charged state. We use first principle density functional calculations to simulate the CO2 adsorption. The results show that CO2 can form weak interactions with the BC59 cage in its neutral state and the interactions can be enhanced significantly by introducing an extra electron to the system.

Syntheses of NCN and NC3N from ionic precursors in the gas phase and an unusual rearrangement of neutral NC3N : A joint experimental and theoretical study

Neutral NCN is made in a mass spectrometer by charge stripping of NCN-., while neutral dicyanocarbene NCCCN can be formed by neutralization of either the corresponding anionic and cationic species, NCCCN-. and NCCCN+.. Theoretical calculations at the RCCSD(T)/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory indicate that the (3)Sigma (-)(g) State of NCCCN is 18 kcal mol(-1) more stable than the (1)A(1) state. While the majority of neutrals formed from either NCCCN-. or NCCCN+. correspond to NCCCN, a proportion of the neutral NCCCN molecules have sufficient excess energy to effect rearrangement, as evidenced by a loss of atomic carbon in the neutralization reionization (NR) spectra of either NCCCN+. and NCCCN-.. C-13 labeling studies indicate that loss of carbon occurs statistically following or accompanied by scrambling of all three carbon atoms. A theoretical study at the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) level of theory indicates that C loss is a consequence of the rearrangement sequence NCCCN --> CNCCN --> CNCNC and that C scrambling occurs within singlet CNCCN via the intermediacy of a four-membered C-2v-symmetrical transition structure.

Formation of neutral C7H2 isomers from pour isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations \[E3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)\] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) \[(HC equivalent to C)(2)C=C=C\](-.) \[from the reaction between (HC equivalent to C)(3)COCH3 and HO- \], (ii) \[HC=C=C=C=C=C=CH\](-.) \[from the reaction between HC equivalent to C-C equivalent to C-CD(OH)-C equivalent to CH and HO-\], (iii) \[C=C=C=C=C=C=CH2\](-.) \[from the reaction between DC equivalent to C-C equivalent to C-C equivalent to C-CH2OCH2CH3 and HO-\], and (iv) \[C equivalent to C-CH2-C equivalent to C-C equivalent to C\](-.) \[from the bis desilylation reaction of (CH3)(3)Si-C equivalent to C-CH2-C equivalent to C-C equivalent to C-Si (CH3)(3)With SF6-.\]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10(-6) s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

Formation of neutral C7H2 isomers from four isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations [B3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) [(HC≡C)2C=C=C]-̇ [from the reaction between (HC≡C)3COCH3 and HO- ], (ii) [HC=C=C=C=C=C=CH]-̇ [from the reaction between HC≡C-C≡C- CD(OH)-C≡CH and HO-], (iii) [C=C=C=C=C=C=CH2]-̇ [from the reaction between DC≡C-C≡C- C≡C-CH2OCH2CH3 and HO-], and (iv) [C≡C-CH2-C≡C-C≡C]-̇ [from the bis desilylation reaction of (CH3)3Si-C≡C-CH2-C≡C-C≡C-Si (CH3)3 with SF6 -̇]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10-6 s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

Formation of neutral molecules of potential stellar interest by neutralisation of negative ions in a mass spectrometer - The application of experiment and molecular modelling in concert

This paper is a modified version of a lecture which describes the synthesis, structure and reactivity of some neutral molecules of stellar significance. The neutrals are formed in the collision cell of a mass spectrometer following vertical Franck-Condon one electron oxidation of anions of known bond connectivity. Neutrals are characterised by conversion to positive ions and by extensive theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Four systems are considered in detail, viz (i) the formation of linear C-4 and its conversion to the rhombus C-4, (ii) linear C-5 and the atom scrambling of this system when energised, (iii) the stable cumulene oxide CCCCCO, and (iv) the elusive species O2C-CO. This paper is not intended to be a review of interstellar chemistry: examples are selected from our own work in this area. (C) 2002 Elsevier Science Inc. All rights reserved.

Dense plasmas in magnetic traps : generation of focused ion beams with controlled ion-to-neutral flux ratios

Customized magnetic traps were developed to produce a domain of dense plasmas with a narrow ion beam directed to a particular area of the processed substrate. A planar magnetron coupled with an arc discharge source created the magnetic traps to confine the plasma electrons and generate the ion beam with the controlled ratio of ion-to-neutral fluxes. Images of the plasma jet patterns and numerical vizualizations help explaining the observed phenomena.

Deterministic nanoassembly : Neutral or plasma route?

It is shown that, owing to selective delivery of ionic and neutral building blocks directly from the ionized gas phase and via surface migration, plasma environments offer a better deal of deterministic synthesis of ordered nanoassemblies compared to thermal chemical vapor deposition. The results of hybrid Monte Carlo (gas phase) and adatom self-organization (surface) simulation suggest that higher aspect ratios and better size and pattern uniformity of carbon nanotip microemitters can be achieved via the plasma route. © 2006 American Institute of Physics.