Stueckelberg Oscillations in a Two‐State Two‐Path Model of a Conical Intersection

The two‐state two‐path model is introduced as a minimized model to describe the quantum dynamics of an electronic wave packet in the vicinity of a conical intersection. It involves two electronic potential energy surfaces each of which hosts a pair of quasi‐classical trajectories over which the wave packet is assumed to be delocalized. When both trajectories evolve dynamically either diabatically or adiabatically, the full wave packet dynamics shows only features of the dynamics around avoided level crossings in the vicinity of the conical intersection. When one trajectory evolves adiabatically whereas the other trajectory follows a diabatic evolution, quantum mechanical interference of the wave packet components on each path generates Stueckelberg oscillations in the transition probability. These are surprisingly robust against a dissipative environment and, thus, should be a marker for conical intersections.     

Finite Order Batalin-Fradkin-Tyutin Method for Chiral Bosons in Non- Commutative Space

The recently improved finite order BFT Hamiltonian embedding method is applied to the two dimensional chiral bosons in non-commutative space. It is then systematically converted to a first class constraint model. Performing the momentum integrations, the corresponding fully gauge symmetry Lagrangian as well as its partition function in phase space are obtained.     

Computational prediction and experimental selectivity coefficients for hydroxyzine and cetirizine molecularly imprinted polymer based potentiometric sensors

In spite of the increasing usages number of molecularly imprinted polymers (MIPs) in many scientific applications, the theoretical aspects of participating intra molecular forces are not fully understood. This work investigates effects of the electrostatic force, the Mulliken charge and the role of cavity's backbone atoms on the selectivity of MIPs. Moreover, charge distribution, which is a computational parameter, was proposed for the prediction of the selectivity coefficients of MIP-based sensors. In the computational approaches and experimental study, methacrylic acid (MAA) was chosen as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the cross linker for hydroxyzine and cetirizine imprinted polymers. Ab initio, DFT B3LYP method was carried out on molecular optimization. With regard to results obtained from molecules optimization and hydrogen bonding properties, possible configurations of 1:n (n ≤ 5) template/monomer complexes were designed and optimized. The binding energy for each complex in gas phase was calculated. Depending on the most stable configuration, hydroxyzine and cetirizine imprinted polymer models were designed. The calculations including the porogen were also investigated. The theoretical charge distributions for the template and some potential interfering molecules were calculated. The results showed a correlation between the selectivity coefficients and the theoretical charge distributions. The results surprisingly show that charge distribution based model was able to predict the selectivity coefficients of MIP based potentiometric sensors.     

Regiochemistry of reactions of α-alkoxyallylphosphine oxide ylides with electrophiles.

Anions $\text{4}$, derived from α-methoxyallylphosphine oxides $\text{3}$, react with electrophiles in a highly regioselective fashion to give products of α-attack or γ-attack depending upon the substitution pattern of the ylid $\text{4}$ and the nature of the electrophile.     

Large diameter open tubular columns in gas chromatographic analysis

Large diameter open tubular columns provide the packed column chromatographer with a simple route to higher resolution gas chromatography. They can be operated in a high-flow (lower resolution) mode that permits their direct substitution for a packed column, or they can be operated in a low-flow (higher resolution) mode that maximizes separation at the cost of longer analysis times. Inlet design and column installation can influence both the chromatographic results and quantiative reliability. Make-up gas is not required in the high-flow mode, and its benefits in the low-flow mode are restricted to enhanced detector sensitivity, provided the outlet end of the column resides in the detector jet (FID). The columns seem fully compatible with all common modes of detection.     

Carbon Paste Electrode Modified with Functionalized Nanoporous Silica Gel as a New Sensor for Determination of Silver Ion

A new dipyridyl‐functionalized silica gel (DPSG) was synthesized. The potentiometric response of silver ion was investigated at a carbon paste electrode chemically modified with functionalized nanoporous silica gel. The electrodes with a DPSG proportions of 10.1% (w/w), showed very stable potential. Calibration plots with Nernstian slopes for Ag⁺ were observed, 58.7 (±0.9) mV decade^?1, over a wide linear range of concentration (5.0×10^?7 to 1.0×10^?1 M). The electrode has a detection limit of 1.0×10^?7 M. The selectivity coefficients measured by the match potential method in acetate buffer, pH 5.5, were investigated. The electrode has fast response time, high performance, high sensitivity in wide cation activity ranges, and good long term stability (more than 6 months). The method was satisfactory and used to determine the concentration of silver ion in waste waters contaminated by this metal.     

Accelerator mass spectrometry of small biological samples

Accelerator mass spectrometry (AMS) is an ultra-sensitive technique for isotopic ratio measurements. In the biomedical field, AMS can be used to measure femtomolar concentrations of labeled drugs in body fluids, with direct applications in early drug development such as Microdosing. Likewise, the regenerative properties of cells which are of fundamental significance in stem-cell research can be determined with an accuracy of a few years by AMS analysis of human DNA. However, AMS nominally requires about 1 mg of carbon per sample which is not always available when dealing with specific body substances such as localized, organ-specific DNA samples. Consequently, it is of analytical interest to develop methods for the routine analysis of small samples in the range of a few tens of microg. We have used a 5 MV Pelletron tandem accelerator to study small biological samples using AMS. Different methods are presented and compared. A (12)C-carrier sample preparation method is described which is potentially more sensitive and less susceptible to contamination than the standard procedures.     

Stripping Voltammetry of Cerium(IIl) with a Chemically Modified Carbon Paste Electrode Containing Functionalized Nanoporous Silica Gel

This research introduces the design of an adsorptive stripping voltammetric method for the cerium(III) determination at a carbon paste electrode, chemically modified with dipyridyl‐functionalized nanoporous silica gel (DPNSG‐CPE). The electroanalytical procedure comprised two steps: the Ce(III) chemical accumulation at ?200 mV followed by the electrochemical detection of the Ce(III)/dipyridyl complex, using anodic stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting electrode demonstrated a linear response over a wide range of Ce(III) concentration (1.0–28 ng mL^?1). The precision for seven determinations of 4 and 10 ng mL^?1 Ce(III) was 3.2% and 2.5% (relative standard deviation), respectively. The prepared electrode was used for the cerium determination in real samples and very good recovery results were obtained.