Dioxygen activation at non-heme diiron centers: characterization of intermediates in a mutant form of toluene/o-xylene monooxygenase hydroxylase

We report the generation and characterization of an intermediate in a mutant form of the toluene/o-xylene monooxygenase hydroxylase component from Pseudomonas stutzeri OX1. The reaction of chemically reduced I100W variant in the presence of the coupling protein, ToMOD, with dioxygen was monitored by stopped-flow UV/visible spectroscopy. Rapid-freeze quench (RFQ) samples were also generated for EPR and M?ssbauer spectroscopy. A transient species is observed in the UV/visible spectrum with an absorption maximum at 500 nm. EPR and M?ssbauer spectra of RFQ samples identified this species as a diiron(III,IV) cluster spin-coupled to a neutral W radical. A diamagnetic precursor to the mixed-valent diiron(III,IV) was also observed at an earlier time point, with M?ssbauer parameters typical of high-spin FeIII. We have tentatively assigned this antiferromagnetically coupled diiron(III) intermediate as a peroxo-bridged cluster, and this complex has also been observed in preliminary studies of the wild-type hydroxylase.     

Spectral investigations of Sm3+ doped lead bismuth magnesium borophosphate glasses

The multicomponent lead bismuth magnesium borophosphate glass systems (LBMBPS) doped with Samarium ions with the molar compositions of (50?x)PbOxBi₂O₃25MgHPO₄24B₂O₃1Sm₂O₃ (where x=10, 20, 30, and 40) were fabricated using conventional melt quenching technique. The amorphous nature of these glass samples was confirmed with XRD studies. The spectral data from the optical absorption studies were employed to compute various spectroscopic parameters such as Judd–Ofelt intensity parameters. The Judd–Ofelt parameterization employed reflects the covalency and vibration frequencies of the ligands with Samarium ions. The radiative parameters such as radiative transition probabilities (A), the total radiative transitional probabilities (A_T), radiative life times (τ_R), branching ratios (β) and absorption cross sections (Σ) were computed for certain lasing levels. The glass systems thus developed indicate their potential lasing candidature. The emission cross sections (σ_E) for the significant lasing transitions ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, and ⁴G_5/2→⁶H_9/2 evaluated from the photoluminescence spectra were reported. The radiative properties obtained in our investigations suggest their lasing candidature.     

A study on wavelength dependence and dynamic range of the quadratic response of commercial grade light emitting diodes

Experimental results of a study on the wavelength dependence and the dynamic range of the quadratic response of commercial grade light emitting diodes (LEDs) are reported over a broad spectral range of 680 nm to 1080 nm using ~ 100 fs duration laser pulses from cw mode locked laser oscillator. A large dynamic range of the quadratic response has been demonstrated in a reverse biased LED. The observed dynamic range compares well with that obtained using a biased photomultiplier tube with large internal gain.     

Single-shot full-field interferometric polarimeter with an integrated calibration scheme

A simple interferometric polarimeter with an integrated calibration scheme is proposed for accurate and fast mapping of the state of polarization (SOP). Conventional single-shot polarimeters that detect the amplitude and phase of orthogonally polarized field components by interferometry using Fourier fringe analysis suffers from errors caused by the imperfect reference beam and ambiguity in the spatial carrier frequency in the fringe pattern. In the proposed system, the integrated calibration scheme eliminates those error sources and enables accurate measurement of SOP without prior knowledge of the reference beam and the spatial carrier frequency.     

Raman spectroscopic investigation of frozen and deparaffinized tissue sections of pediatric tumors: neuroblastoma and ganglioneuroma

Raman spectroscopy is a nondestructive technique that can provide information at the molecular level about the biochemicals in tissues. We have investigated the cellular regions in neuroblastoma and ganglioneuroma using Raman spectroscopy and compared their spectral characteristics with those of the corresponding normal adrenal gland. Thin sections from both the frozen and the corresponding formalin‐fixed paraffin‐processed (FFPP) tissues were studied in conjunction with the pathological examination of the tissues. Investigation of the spectral data shows that the normal adrenal gland tissues have higher levels of carotenoids, lipids, and cholesterol compared with the neuroblastoma and ganglioneuroma frozen tissues. However, in comparison with the frozen tissues, the FFPP tissues show a significant alteration of several biochemicals, including the complete removal of carotenoids, lipids, and cholesterol in the adrenal tissues. A quantitative analysis using chemometric methods of principal component analysis and discriminant function analysis of the Raman spectral data obtained from the frozen tissues show a clear‐cut classification among pathological groups with high sensitivity and specificity. We have validated the classification results of the FFPP tissues against a training set data obtained from the archived FFPP tissues of nine other patients. The validation process correctly identified and grouped the data with the training set of normal adrenal gland (>97% of the time) and neuroblastoma (100% of the time) tissues, whereas the validation was not so strong for ganglioneuroma. This study shows that Raman spectroscopy combined with chemometric methods can be successfully used to distinguish neuroblastoma and ganglioneuroma at cellular level in frozen tissue sections. This study also shows that formalin fixation and paraffinization/deparaffinization of tissues can alter their biochemical composition. Copyright © 2012 John Wiley & Sons, Ltd.