An in situ temperature‐programmed XPS study of the surface chemical reactions of thiophene with Ag/titania

The Ag/titania sorbent for the ultradeep desulfurization of liquid fuels was characterized by electron spin resonance and was found to contain nearly the stoichiometric titania, without significant concentration of Ti³⁺ or the reactive oxygen species. The surface chemical reactions of thiophene adsorbed on the Ag/titania were studied by temperature‐programmed XPS from 25 to 525 °C upon in situ thermal annealing in high vacuum and in situ oxidation by oxygen gas. The titania support is not chemically reactive under those conditions. Silver oxide in the Ag/titania sorbent is converted to Ag₂ S without formation of the transient surface sulfates or sulfites and is further oxidized by molecular oxygen. Copyright © 2010 John Wiley & Sons, Ltd.     

Single step modification of copper electrode for the highly sensitive and selective non-enzymatic determination of glucose

A non-enzymatic sensor was developed for the determination of glucose in alkaline medium by anodisation of copper in sodium potassium tartrate solution. The morphology of the modified copper electrode was studied by scanning electron microscopy, and its electrochemical behavior by cyclic voltammetry and electrochemical impedance spectroscopy. The electrode enables direct electrocatalytic oxidation of glucose on a CuO/Cu electrode at 0.7 V in 0.1 M sodium hydroxide. At this potential, the sensor is highly selective to glucose even in the presence of ascorbic acid, uric acid, or dopamine which are common interfering species. The sensor displays a sensitivity of 761.9 μA mM^?1 cm^?2, a linear detection range from 2 μM to 20 mM, a response time of <1 s, and a detection limit of 1 μM (S/N = 3). It was tested for determination of glucose level in blood serum.     

Studies on Cu(II) ternary complexes involving an aminopenicillin drug and imidazole containing ligands

Equilibrium studies on the ternary complex systems involving ampicillin (amp) as ligand (A) and imidazole containing ligands viz., imidazole (Him), benzimidazole (Hbim), histamine (Hist) and histidine (His) as ligands (B) at 37 °C and I = 0.15 mol dm^?3 (NaClO₄) show the presence of CuABH, CuAB and CuAB₂. The proton in the CuABH species is attached to ligand A. In the ternary complexes the ligand, amp(A) binds the metal ion via amino nitrogen and carbonyl oxygen atom. The CuAB (B = Hist/His)/CuAB₂ (B = Him/Hbim) species have also been isolated and the analytical data confirmed its formation. Non-electrolytic behavior and monomeric type of chelates have been assessed from their low conductance and magnetic susceptibility values. The electronic and vibrational spectral results were interpreted to find the mode of binding of ligands to metal and geometry of the complexes. This is also supported by the g tensor values calculated from ESR spectra. The thermal behaviour of complexes were studied by TGA/DTA. The redox behavior of the complexes has been studied by cyclic voltammetry. The antimicrobial activity and CT DNA cleavage study of the complexes show higher activity for ternary complexes.     

Characterization, sintering and dielectric properties of nanocrystalline zinc oxide prepared by a citric acid-based combustion route

Nanosized zinc oxide has been synthesized through a novel single step solution combustion route using citric acid as fuel. The X-ray diffraction (XRD) analysis revealed that the synthesized ZnO nanopowder has the pure wurtzite structure. The phase purity of the nanopowder has been confirmed using differential thermal analysis (DTA), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The morphology and crystalline size of the as-prepared nanopowder characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the powder consisted of a mixture of nanoparticles and nanorods. The nanocrystalline ZnO could be sintered to ∼97% of the theoretical density at 1200 °C in 4 h. The dielectric constant (ε_r) and dielectric loss (ε_i) of sintered ZnO pellets at 5 MHz were 1.38 and 9×10⁻², respectively, at room temperature.     

Facile synthesis of thiol-stabilized CdSexTe1−x nanocrystals

CdSe_xTe_1−x nanocrystals (x=0.25, 0.40, 0.50, 0.60 and 0.75) were synthesized using thioglycerol as a stabilizing agent. The composition of the CdSe_xTe_1−x nanocrystals was precisely controlled by tuning the precursor (Se/Te) ratio. The structural, morphological and optical properties of the nanocrystals were analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), diffused reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. It is found that the Se/Te ratio significantly affects the properties of the resultant CdSe_xTe_1−x nanocrystals. XRD pattern of the CdSe_xTe_1−x nanocrystals revealed cubic, hexagonal and mixed phases depending on the ratio of Se:Te. Surface morphology of the CdSe_xTe_1−x nanocrystals showed nanoclusters of sizes ∼50 nm, with the adjacent cluster interlinking each other. DRS revealed the size dependence band gap energy prevailing in the CdSe_xTe_1−x nanocrystals from 1.52 to 2.66 eV due to the optical bowing effect. PL measurements exhibited band edge emission in the visible spectral region, and are red shifted with increase in Se concentration. The facile route employed in the present work to synthesis the CdSe_xTe_1−x nanocrystals in an aqueous medium is simple and controllable, and the strategy presented will be handy in preparing diverse semiconducting nanocrystals.     

Voice Analysis of Postlingually Deaf Adults Pre- and Postcochlear Implantation

Objectives

To ascertain whether cochlear implantation (CI), without specific vocal rehabilitation, is associated with changes in perceptual and acoustic vocal parameters in adults with severe to profound postlingual deafness.

Hypothesis

Merely restoring auditory feedback could allow the individual to make necessary adjustments in vocal pattern.

Study Design

Prospective and longitudinal.

Methods

The experimental group composed of 40 postlingually deaf adults (20 males and 20 females) with no previous laryngeal or voice disorders. Participants’ voices were recorded before CI and 6–9 months after CI. To check for chance modifications between two evaluations, a control group of 12 postlingually deaf adults, six male and six female, without CI was also evaluated. All sessions composed of the recording of read sentences from Consensus Auditory-Perceptual Evaluation of Voice and sustained vowel /a/. Auditory and acoustic analyses were then conducted.

Results

We found a statistically significant reduction in overall severity, strain, loudness, and instability in auditory analysis. In vocal acoustic analysis, we found statistically significant reduction fundamental frequency (F0) values (in male participants) and F0 variability (in both genders). The control group showed no statistically significant changes in most vocal parameters assessed, apart from pitch and F0 (in female participants only). On comparing the interval of variation of results between the experimental and control groups, we found no statistically significant difference in vocal parameters between CI recipients and nonrecipients, with the exception of F0 variability in male participants.

Conclusions

The patients in our sample showed changes in overall severity, strain, loudness, and instability values, and reductions in F0 and its variability. On comparing the variation of results between the groups, we were able to prove in our study that implant recipients postlingually deaf adults (experimental group), without specific vocal rehabilitation, differed from nonrecipients (control group) in loudness and F0 variability sustained vowel /a/ in male participants.     

Single-layer behavior and its breakdown in twisted graphene layers

We report high magnetic field scanning tunneling microscopy and Landau level spectroscopy of twisted graphene layers grown by chemical vapor deposition. For twist angles exceeding ~3° the low energy carriers exhibit Landau level spectra characteristic of massless Dirac fermions. Above 20° the layers effectively decouple and the electronic properties are indistinguishable from those in single-layer graphene, while for smaller angles we observe a slowdown of the carrier velocity which is strongly angle dependent. At the smallest angles the spectra are dominated by twist-induced van Hove singularities and the Dirac fermions eventually become localized. An unexpected electron-hole asymmetry is observed which is substantially larger than the asymmetry in either single or untwisted bilayer graphene.     

Regularized collocation method for Fredholm integral equations of the first kind

In this paper we consider a collocation method for solving Fredholm integral equations of the first kind, which is known to be an ill-posed problem. An “unregularized” use of this method can give reliable results in the case when the rate at which smallest singular values of the collocation matrices decrease is known a priori. In this case the number of collocation points plays the role of a regularization parameter. If the a priori information mentioned above is not available, then a combination of collocation with Tikhonov regularization can be the method of choice. We analyze such regularized collocation in a rather general setting, when a solution smoothness is given as a source condition with an operator monotone index function. This setting covers all types of smoothness studied so far in the theory of Tikhonov regularization. One more issue discussed in this paper is an a posteriori choice of the regularization parameter, which allows us to reach an optimal order of accuracy for deterministic noise model without any knowledge of solution smoothness.     

A traffic shaping model for optimizing network operations

The management of technology in multi-service computer networks, such as university networks, has become a challenge with the explosive growth of entertainment oriented peer-to-peer (P2P) traffic. Traffic shaping is one of the tools used to manage bandwidth to improve system performance by allocating bandwidth between P2P and non-peer-to-peer (NP2P) traffic. We present a model for traffic shaping and bandwidth management that considers the trade-offs from allocating different amounts of bandwidths for different application categories and use data from a university network. The current policy allocates varying bandwidths over the day to P2P and NP2P traffic to reflect the importance of not letting entertainment based traffic choke the network during the day time at the expense of the more important traffic, such as Web traffic. We highlight the difficulties in obtaining data in the form required for analysis, and the need to estimate demand for allocations not covered by current policy. We present a goal programming model for this estimation task. We also model the traffic shaping problem as a Markov decision process and develop an algorithm for determining the optimal bandwidth allocation to maximize the utility of all users. Finally we use a numerical example to illustrate our approach.