Light-induced electron spin polarization in the ground state of water-soluble copper porphyrins

Light-induced spin-polarized transient EPR spectra are reported for several water-soluble copper porphyrins. The spectra are assigned to the doublet ground state, with emissive spin polarization resulting from photoexcitation and subsequent electronic relaxation. In contrast to other systems for which polarization of a doublet ground state has been observed, the exchange interactions in the copper porphyrins are strong and the geometry is fixed. It is proposed that intersystem crossing from the photoexcited trip-doublet to the trip-quartet state can lead to net polarization of the spin system and that this polarization is maintained during electronic decay, possibly via charge-transfer and exciplex states. The intensity of the observed spin polarization is essentially independent of the molecular orientation in the external field, but is strongly dependent on the nature of the charged peripheral groups. Possible reasons for this behavior are discussed.     

The band areas of proteins determined by fluorescent scanning in the commercial automated gel electrophoresis apparatus

An automated gel electrophoresis apparatus, recently available commercially, allows one to follow the band during electrophoresis in real time, and lends itself therefore to an evaluation of bandwidth as a function of migration time (the dispersion coefficient), resolution and band shape. These determinations assume the constancy of band area with migration time and at various gel concentrations. The purpose of the present study was to verify these assumptions. Representative proteins and sodium dodecyl sulfate (SDS)-proteins, either natively fluorescent or fluorescein carboxylate labeled, were found to exhibit band areas which approach constancy as a function of migration time in both agarose and polyacrylamide gel electrophoresis, provided that (i) the protein concentration under the band was low enough to obviate self-quenching of fluorescence; (ii) the separation of the protein of interest from contaminants had progressed sufficiently during the time at which band areas were measured; (iii) the baseline under the peak was sufficiently well defined. However, band areas decrease with increasing gel concentration. Protein peaks exhibited leading and trailing tails. The ratio of the combined tail area to total area appeared to be near-constant at varying migration times. However, that ratio increases with increasing gel concentration. The tail area does not appear to be an artifact of fluorometric detection since it is reproduced upon fluorimetric analysis of the protein eluted from gel slices after electrophoresis. However, it may be due to photochemical destruction under the conditions of repetitive fluorometric peak detection.     

Functional penetration of variability of motor neuron spike timing through a modulated neuromuscular system

Variability of the neuronal spike pattern is usually thought of in terms of the information that the different interspike intervals might be encoding. However, the very presence of the variability can have other kinds of functional significance. Here we consider the example of the B15/B16-ARC neuromuscular system of Aplysia, a model system for the study of neuromuscular modulation and control. We show that variability of motor neuron spike timing at the input to the system penetrates throughout the system, affecting all downstream variables including modulator release, modulator concentrations, modulatory actions, and the contraction of the muscle. Furthermore, not only does the variability penetrate through the system, but it is actually instrumental in maintaining its modulation and contractions at a robust, physiological level.     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Phase local approximation (PhaseLa) technique for phase unwrap from noisy data.

The local polynomial approximation (LPA) is a nonparametric regression technique with pointwise estimation in a sliding window. We apply the LPA of the argument of cos and sin in order to estimate the absolute phase from noisy wrapped phase data. Using the intersection of confidence interval (HCI) algorithm, the window size is selected as adaptive pointwise varying. This adaptation gives the phase estimate with the accuracy close to optimal in the mean squared sense. For calculations, we use a Gauss-Newton recursive procedure initiated by the phase estimates obtained for the neighboring points. It enables tracking properties of the algorithm and its ability to go beyond the principal interval [-pi, pi] and to reconstruct the absolute phase from wrapped phase observations even when the magnitude of the phase difference takes quite large values. The algorithm demonstrates a very good accuracy of the phase reconstruction which on many occasion overcomes the accuracy of the state-of-the-art algorithms developed for noisy phase unwrap. The theoretical analysis produced for the accuracy of the pointwise estimates is used for justification of the HCI adaptation algorithm.     

Recovery of SDS-protein and DNA using commercial automated gel electrophoresis apparatus

Forty-seven children afflicted with acute leukemia were studied at the Tata Memorial Hospital Bombay to record the occurrence of oral manifestations prior to and during chemotherapy. Lymphadenopathy was the most frequent single finding suggestive of leukemia during head and neck examination. Gingival abnormalities, bleeding gums and oral mucosal pallor were the other findings on initial oral examination. Due to immunosuppression caused by the chemotherapy drugs oral mucosal ulcerations, uncontrolled herpes, candidiasis and pseudomoniasis were observed.     

Quantum computing with spin qubits in semiconductor structures

We survey recent work on designing and evaluating quantum computing implementations based on nuclear or bound-electron spins in semiconductor heterostructures at low temperatures and in high magnetic fields. General overview is followed by a summary of results of our theoretical calculations of decoherence time scales and spin-spin interactions. The latter were carried out for systems for which the two-dimensional electron gas provides the dominant carrier for spin dynamics via exchange of spin-excitons in the integer quantum Hall regime.     

Compositions of Co – Cr – Mo Alloys Examined by Glow-Discharge Mass Spectrometry

A method has been developed for the quantitative elemental analysis of Co – Cr – Mo alloys which are used for making surgical implants, and which is done by glow-discharge mass spectrometry. There is a discussion of the effects of molecular ions and an estimate is made of the sensitivity limits in the detection of traces of toxic elements. A method has been devised for calculating the concentrations of molecular ions that increases the analysis reliability. It is shown that raising the argon pressure and discharge current substantially reduces the relative concentrations of molecular ions and allows one to raise the analysis sensitivity.