Sensitivity enhancement of CE and CE-MS for the analysis of peptides by a dynamic pH junction

An analytical method of CE-MS and CE with an online preconcentration technique induced by a dynamic pH junction, addition of organic solvent and large volume injection was developed for sensitive determination of peptides in biological samples. Leucine enkephalin, methionine enkephalin, dynorphin A, β-endorphin and angiotensin II were used as model peptides. The optimal online preconcentration conditions were obtained at a sample matrix consisting of 100?mM borate buffer (pH 10.0) with 50% v/v acetonitrile and a BGE containing 1?M formic acid at pH 2.0, along with a 25-cm injection length. Under the optimized conditions, a 4.0×10(3)-1.1×10(4)-fold increase in peak intensity was achieved without degrading the peak shape. This online preconcentration method was applied to analyze the intracellular angiotensin II within the peptides extracted from HL1 cells and approximately increase of 1×10(4)-fold sensitivity was achieved compared to normal condition. Thus, the developed method could be applied to the analysis of various peptides for peptidomics study in biological samples.     

Two-step on-particle ionization/enrichment via a washing- and separation-free approach: multifunctional TiO2 nanoparticles as desalting, accelerating, and affinity probes for microwave-assisted tryptic digestion of phosphoproteins in ESI-MS and MALDI-MS: comparison with microscale TiO2

We introduce a simplified sample preparation method using bare TiO₂ nanoparticles (NPs) to serve as multifunctional nanoprobes (desalting, accelerating, and affinity probes) for effective enrichment of phosphopeptides from microwave-assisted tryptic digestion of phosphoproteins (α-casein, β-casein and milk) in Electrospray Ionization Mass Spectrometry (ESI-MS) and Matrix Assisted Laser Desorption Ionization Mass Spectrometry (MALDI-MS). The results demonstrate that TiO₂ NPs can effectively enrich and accelerate the digestion reactions of phosphoproteins in aqueous solutions and also from complex real samples. After the microwave experiments, we directly injected the resulting solutions into the ESI-MS and MALDI-MS systems for analysis, and excellent sensitivity was achieved without the need for any washing procedure or separation process. The reasons are attributed to the high binding affinity and selectivity of TiO₂ NPs toward phosphopeptides. Thus, phosphopeptides can be adsorbed onto the TiO₂ NP surface. The digested or partially digested phosphoproteins can be concentrated onto the TiO₂ NP surface. This results in the effective or complete digestion of phosphoproteins in a short period of time (45 s). In addition, high sensitivity and sequence coverage of phosphopeptide can be obtained using TiO₂ NPs as microwave absorbers and affinity probes in MALDI-MS and ESI-MS. This is due to the photocatalytic nature of the TiO₂ NPs because the absorption of microwave radiation that can accelerate the activation of trypsin for efficient digestion of phosphoproteins and enhances the ionization of phosphopeptides. The lowest concentrations detected for ESI-MS and MALDI-MS were 0.1 μM and 10 fmol, respectively, for α-casein. Comparing the two-step approach of TiO₂ NPs with microscale TiO₂ particles, the microscale TiO₂ particles shows no effect on the microwave-assisted tryptic digestion of phosphoproteins. The current approach offers multiple advantages, such as great simplicity, high sensitivity and selectivity, straightforward and separation/washing-free technique for phosphorpeptide enrichment analysis.     

Structural properties of trans‐cyclohexane‐1,2‐diamine complexes of copper(II) and zinc(II) acesulfamates

The title compounds, trans‐bis(trans‐cyclohexane‐1,2‐diamine)bis(6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ido)copper(II), [Cu(C₄H₄NO₄S)₂(C₆H₁₄N₂)₂], (I), and trans‐diaquabis(cyclohexane‐1,2‐diamine)zinc(II) 6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ide dihydrate, [Zn(C₆H₁₄N₂)₂(H₂O)₂](C₄H₄NO₄S)₂·2H₂O, (II), are two‐dimensional hydrogen‐bonded supramolecular complexes. In (I), the Cu^II ion resides on a centre of symmetry in a neutral complex, in a tetragonally distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two N atoms of two acesulfamate ligands. Intermolecular N—H...O and C—H...O hydrogen bonds produce R₂²(12) motif rings which lead to two‐dimensional polymeric networks. In contrast, the Zn^II ion in (II) resides on a centre of symmetry in a complex dication with a less distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two O atoms from aqua ligands. In (II), an extensive two‐dimensional network of N—H...O, O—H...O and C—H...O hydrogen bonds includes R₂¹(6) and R₄⁴(16) motif rings.     

Manipulating atomic fragmentation processes by controlling the projectile coherence

We have measured the scattering angle dependence of cross sections for ionization in p+H2 collisions for a fixed projectile energy loss. Depending on the projectile coherence, interference due to indistinguishable diffraction of the projectile from the two atomic centers was either present or absent in the data. This shows that, due to the fundamentals of quantum mechanics, the preparation of the beam must be included in theoretical calculations. The results have far-reaching implications on formal atomic scattering theory because this critical aspect has been overlooked for several decades.     

Electrogravitational stability of oscillating streaming fluid cylinder

The electrogravitational instability of on oscillating streaming fluid cylinder under the action of the selfgravitating, capillary and electrodynamic forces has been discussed. The model is governed by the Mathieu second order integro-differential equation. Some limiting cases are recovering from the present general one. The capillary force is destabilizing in a small axisymmetric domain 0<x<1 and stabilizing otherwise. In the absence of electric fields, we found that the model is unstable in a small domain while it is selfgravitating stable in all other domains. The presence of the electric field led to the presence of a great number of stable waves. The electric field has a strong stabilizing influence on the selfgravitating instability of the model. The capillary force has a strong destabilizing influence on the selfgravitating instability of the model.Generally, the uniform stream supports the unstable waves, while the oscillating streaming has stability tendency.     

Impedance spectroscopy and investigation of conduction mechanism in BaMnO3 nanorods

BaMnO₃ nanorods were synthesized at 200 °C and atmospheric pressure using the composite-hydroxide mediated method. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were used to investigate the structure, size, morphology, phase purity and elemental composition of BaMnO₃ nanorods. Electrical characterization of BaMnO₃ pellet was performed at 300-400 K and in the frequency range 200 Hz-2 MHz. Temperature dependence of AC conductivity suggests that the BaMnO₃ pellet behaves as a semiconducting material and conduction across the pellet can be explained by the correlated barrier hopping model. Impedance analysis was performed using the equivalent circuit model (R₁Q₁C₁)(R₂C₂) and it suggests a single relaxation process in the BaMnO₃ pellet at a particular temperature. The analysis reveals that the BaMnO₃ pellet behaves like an n-type semiconductor material due to the presence of oxygen vacancies and some disorder. Modulus spectroscopy also supports the impedance results.     

A selective sensor for nanolevel detection of lead (II) in hazardous wastes using ionic-liquid/Schiff base/MWCNTs/nanosilica as a highly sensitive composite

An effective potentiometric sensor had been fabricated for the rapid determination of Pb²⁺ based on carbon paste electrode consisting of room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF₆), multiwalled carbon nanotubes (MWCNTs), nanosilica, synthesized Schiff base, as an ionophore, and graphite powder. The constructed nanocomposite electrode showed better sensitivity, selectivity, response time, response stability, and lifetime in comparison with typical Pb²⁺ carbon paste electrode for the successfully determination of Pb²⁺ ions in water and in waste water samples. The best response for nanocomposite electrode was obtained with electrode composition of 18% ionophore, 20% BMIM-PF₆, 49% graphite powder, 10% MWCNT, and 3% nanosilica. The new electrode exhibited a Nernstian response (29.76?±?0.10 mV decade^?1) toward Pb²⁺ ions in the range of 5?×?10^?9?C1.0?×?10^?1 mol L^?1 with a detection limit of 2.51?×?10^?9 mol L^?1. The potentiometric response of prepared sensor is independent of the pH of test solution in the pH range of 4.5?C8.0. It has quick response with response time of about 6 s. The proposed electrode show fairly good selectivity over some alkali, alkaline earth, transition, and heavy metal ions.     

A fuzzy stochastic model for telecommunications bandwidth brokers under probabilistic QoS measures

In this paper, we model and solve profit maximization problem of a telecommunications Bandwidth Broker (BB) under uncertain market and network infrastructure conditions. The BB may lease network capacity from a set of Backbone Providers (BPs) or from other BBs in order to gain profit by leasing already purchased capacity to end-users. BB’s problem becomes harder to deal with when bandwidth requests of end-users, profit and cost margins are not known in advance. The novelty of the proposed work is the development of a mechanism via combining fuzzy and stochastic programming methodologies for solving complex BP selection and bandwidth demand allocation problem in communication networks, based on the fact that information needed for making these decisions is not available prior to leasing capacity. In addition, suggested model aims to maximize BB’s decision maker’s satisfaction ratio rather than just profit. As a solution strategy, the resulting fuzzy stochastic programming model is transformed into deterministic crisp equivalent form and then solved to optimality. Finally, the numerical experiments show that on the average, proposed approach provides 14.30% more profit and 69.50% more satisfaction ratio compared to deterministic approaches in which randomness and vagueness in the market and infrastructure are ignored.     

Temperature independent length optimization of L-band EDFAs providing flat gain

In this study, single stage (SS), double-stage (DS), and gain flattened (GF) DS L-band erbium-doped fiber amplifier (EDFA) configurations are designed in order to obtain a flat gain amplifier. Temperature dependence of the mentioned configurations is also analyzed. Maximum spectral dependence of EDFA gain with respect to temperature is obtained for SS EDFA design while smaller spectral dependence of gains is obtained for both DS and GF DS L-EDFA configurations. It is observed that the maximum temperature dependence is in the range of 1570-1580 nm band for all configurations. It has also been found that for all configurations, reducing the temperature has greater effect than raising the temperature on EDFA gain. The overall results show that a temperature independent L-band configuration has not been possible. However, for some signal wavelengths, the erbium-doped fiber (EDF) lengths at which the gain is temperature independent are observed.