Purification of 3,5-Dichlorocatechol 1,2-Dioxygenase, a Nonheme Iron Dioxygenase and a Key Enzyme in the Biodegradation of a Herbicide, 2,4-Dichlorophenoxyacetic acid (2,4-D), from Pseudomonas cepacia CSV90

An enzyme which cleaves the benzene ring of 3,5-dichiorocatechol has been purified to homogeneity from Pseudomonas cepacia CSV90, grown with 2,4-dichlorophenoxyacetic acid (2,4-D) as the sole carbon source. The enzyme was a nonheme ferric dioxygenase and catalyzed the intradiol cleavage of all the examined catechol derivatives, 3,5-dichlorocatechol having the highest specificity constant of 7.3 μM−1 s−1 in an air-saturated buffer. No extradiol-cleaving activity was observed. Thus, the enzyme was designated as 3,5-dichlorocatechol 1,2-dioxygenase. The molecular weight of the native enzyme was ascertained to be 56,000 by light scattering method, while the Mr value of the enzyme denatured with 6 M guanidine-HCl or sodium dodecyl sulfate was 29,000 or 31,600, respectively, suggesting that the enzyme was a homodimer. The iron content was estimated to be 0.89 mol per mole of enzyme. The enzyme was deep red and exhibited a broad absorption spectrum with a maximum at around 425 nm, which was bleached by sodium dithionite, and shifted to 515 nm upon anaerobic 3,5-dichlorocatechol binding. The catalytic constant and the Km values for 3,5-dichlorocatechol and oxygen were 34.7 s−1 and 4.4 and 652 μM, respectively, at pH 8 and 25°C. Some heavy metal ions, chelating agents and sulfhydryl reagents inhibited the activity. The NH2-terminal sequence was determined up to 44 amino acid residues and compared with those of the other catechol dioxygenases previously reported.

Interior Photon Absorption Based Adaptive Regularization Improves Diffuse Optical Tomography

An adaptive regularization algorithm that combines elementwise photon absorption and data misfit is proposed to stabilize the non-linear ill-posed inverse problem. The diffuse photon distribution is low near the target compared to the normal region. A Hessian is proposed based on light and tissue interaction, and is estimated using adjoint method by distributing the sources inside the discretized domain. As iteration progresses, the photon absorption near the inhomogeneity becomes high and carries more weightage to the regularization matrix. The domain's interior photon absorption and misfit based adaptive regularization method improves quality of the reconstructed Diffuse Optical Tomographic images.

Synthesis and photocatalytic properties of AgLi1/3Ru2/3]O-2: A new delafossite oxide

A new delafossite oxide, AgLi1/3Ru2/3]O-2, synthesized by ion-exchanging interlayer-Li+ with Ag+ in layered Li2RuO3, is reported. The transformation of layered Li2RuO3 (monoclinic, space group C2/c) to AgLi1/3Ru2/3]O-2 possessing a delafossite structure (space group R (3) over barm) has been established with powder X-ray diffraction. The successful conversion of LiLi1/3Ru2/3]O-2 to AgLi1/3Ru2/3]O-2 is further confirmed by EDAX analysis. The diffuse reflectance spectrum of AgLi1/3Ru2/3]O-2 shows broad absorption in the UV-visible region suggesting its use as a photocatalyst. The photocatalytic activity of AgLi1/3Ru2/3]O-2 has been investigated by degrading various dyes. It showed significant photocatalytic activity for dye degradation both under UV and solar radiation. (C) 2010 Elsevier B.V. All rights reserved.

Geometry and quadratic nonlinearity of charge transfer complexes in solution: A theoretical study

In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO/S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, beta(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases. (C) 2011 American Institute of Physics. doi:10.1063/1.3526748]

Absorption-resorption heating cycles with the new working pairs R21-NMP and R21-DMA

The new working pairs, R21-NMP and R21-DMA, find potential application as working pairs for the single stage Resorption Heat Pump (RHP) and the Resorption Heat Transformer (RHT) cycles. A thermodynamic cycle analysis with these pairs shows that single stage RHPs have high COPs in their entire range of operation. RHTs show higher temperature boosts (up to 47 K) than the simple absorption heat transformers. Absorber temperatures of up to 400 K can be achieved in a single stage RHT system using R21 as the refrigerant. However, absorption-resorption systems have inherent limitations on the range of operating temperatures. Besides, they necessitate a higher pump work as compared to simple single stage absorption heating systems.

Absorption, translocation and metabolism of fluchloralin in groundnut (Arachis hypogaea) and pigweed (Amaranthus viridis)

Root absorption and translocation of [C-14]fluchloralin were determined in groundnut (Arachis hypogaea L.) cv. TMV-2 and pigweed (Amaranthus viridis L.) grown in nutrient solution culture under greenhouse conditions. Root-applied fluchloralin toxicity to groundnut and pigweed was also examined. A growth reduction of 50% occurred in groundnut that received fluchloralin at a concentration of 9.0 mum. Root absorption was similar for both groundnut and pigweed at one day after application (DAA), but groundnut absorbed about twice the amount of fluchloralin during 4 and 8 days of continuous application, compared with pigweed. Groundnut absorbed 25% of the total applied fluchloralin after 8 days. Translocation to leaves from treated roots was low and roots of groundnut contained 80% of the total absorbed C-14, 8 DAA. Contrary to the observations in groundnut, transport from the roots and leaves following root application in pigweed was rapid: 1 and 8 DAA, leaves of pigweed contained 45 and 70% of the total absorbed C-14, respectively. Different patterns of fluchloralin metabolism were observed in pigweed and groundnut. Pigweed metabolized most of the fluchloralin absorbed by roots. The fluchloralin tolerance of pigweed could partially be accounted for by absorption, translocation and metabolism.

Recognition of Polycyclic Aromatic Hydrocarbons and Their Derivatives by the 1,3-Dinaphthalimide Conjugate of Calix4]arene: Emission, Absorption, Crystal Structures, and Computational Studies

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants as well as well-known carcinogens. Therefore, it is important to develop an effective receptor for the detection and quantification of such molecules in solution. In view of this, a 1,3-dinaphthalimide derivative of calix4]arene (L) has been synthesized and characterized, and the structure has been established by single crystal XRD. In the crystal lattice, intermolecular arm-to-arm pi center dot center dot center dot pi overlap dominates and thus L becomes a promising receptor for providing interactions with the aromatic species in solution, which can be monitored by following the changes that occur in its fluorescence and absorption spectra. On the basis of the solution studies carried out with about 17 derivatives of the aromatic guest molecular systems, it may be concluded that the changes that occur in the fluorescence intensity seem to be proportional to the number of aromatic rings present and thus proportional to the extent of pi center dot center dot center dot pi interaction present between the naphthalimide moieties and the aromatic portion of the guest molecule. Though the nonaromatic portion of the guest species affects the fluorescence quenching, the trend is still based on the number of rings present in these. Four guest aldehydes are bound to L with K-ass of 2000-6000 M-1 and their minimum detection limit is in the range of 8-35 mu M. The crystal structure of a naphthaldehyde complex, L.2b, exhibits intermolecular arm-to-arm as well as arm-to-naphthaldehyde pi center dot center dot center dot pi interactions. Molecular dynamics studies of L carried out in the presence of aromatic aldehydes under vacuum as well as in acetonitrile resulted in exhibiting interactions observed in the solid state and hence the changes observed in the fluorescence and absorption spectra are attributable for such interactions. Complex formation has also been delineated through ESI MS studies. Thus L is a promising receptor that can recognize PAHs by providing spectral changes proportional to the aromatic conjugation of the guest and the extent of aromatic pi center dot center dot center dot pi interactions present between L and the guest.

Application of a modified z-cosy experiment for the analysis of spectra of oriented molecules - the spectrum of cis,cis-mucanonitrile

NMR spectra of cis,cis-mucanonitrile oriented in a liquid crystal have been analysed using the connectivity information obtained from a modified Z-COSY experiment which provided crucial clues for the starting parameters for the iterative analysis. The proton spectra with and without C-13 satellites and the C-13 spectra have thus been interpreted. The indirect spin-spin couplings required for the analyses have been obtained from the corresponding isotropic spectra. The H-1-H-1 and C-13-H-1 dipolar couplings so obtained have been utilized to determine the relative internuclear distances. The results indicate that the molecule is planar. (C) 1994 Academic Press, Inc.

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10(3) cm(-1)) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Omega cm and carrier concentration 1.52 x 10(15) cm(-3). Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices. (C) 2011 Elsevier B.V. All rights reserved.

Nanoscale ZnO/CdS heterostructures with engineered interfaces for high photocatalytic activity under solar radiation

Semiconductor based nanoscale heterostructures are promising candidates for photocatalytic and photovoltaic applications with the sensitization of a wide bandgap semiconductor with a narrow bandgap material being the most viable strategy to maximize the utilization of the solar spectrum. Here, we present a simple wet chemical route to obtain nanoscale heterostructures of ZnO/CdS without using any molecular linker. Our method involves the nucleation of a Cd-precursor on ZnO nanorods with a subsequent sulfidation step leading to the formation of the ZnO/CdS nanoscale heterostructures. Excellent control over the loading of CdS and the microstructure is realized by merely changing the initial concentration of the sulfiding agent. We show that the heterostructures with the lowest CdS loading exhibit an exceptionally high activity for the degradation of methylene blue (MB) under solar irradiation conditions; microstructural and surface analysis reveals that the higher activity in this case is related to the dispersion of the CdS nanoparticles on the ZnO nanorod surface and to the higher concentration of surface hydroxyl species. Detailed analysis of the mechanism of formation of the nanoscale heterostructures reveals that it is possible to obtain deterministic control over the nature of the interfaces. Our synthesis method is general and applicable for other heterostructures where the interfaces need to be engineered for optimal properties. In particular, the absence of any molecular linker at the interface makes our method appealing for photovoltaic applications where faster rates of electron transfer at the heterojunctions are highly desirable.

Cooperative Spectrum Sensing Algorithms For OFDM Systems with Frequency Selective Channels

This paper considers the problem of spectrum sensing in cognitive radio networks when the primary user employs Orthogonal Frequency Division Multiplexing (OFDM). We specifically consider the scenario when the channel between the primary and a secondary user is frequency selective. We develop cooperative sequential detection algorithms based on energy detectors. We modify the detectors to mitigate the effects of some common model uncertainties such as timing and frequency offset, IQ-imbalance and uncertainty in noise and transmit power. The performance of the proposed algorithms are studied via simulations. We show that the performance of the energy detector is not affected by the frequency selective channel. We also provide a theoretical analysis for some of our algorithms.

Bayesian Decentralized Spectrum Sensing in Cognitive Radio Networks

This paper considers the problem of spectrum sensing, i.e., the detection of whether or not a primary user is transmitting data by a cognitive radio. The Bayesian framework is adopted, with the performance measure being the probability of detection error. A decentralized setup, where N sensors use M observations each to arrive at individual decisions that are combined at a fusion center to form the overall decision is considered. The unknown fading channel between the primary sensor and the cognitive radios makes the individual decision rule computationally complex, hence, a generalized likelihood ratio test (GLRT)-based approach is adopted. Analysis of the probabilities of false alarm and miss detection of the proposed method reveals that the error exponent with respect to M is zero. Also, the fusion of N individual decisions offers a diversity advantage, similar to diversity reception in communication systems, and a tight bound on the error exponent is presented. Through an analysis in the low power regime, the number of observations needed as a function of received power, to achieve a given probability of error is determined. Monte-Carlo simulations confirm the accuracy of the analysis.

Use of running fractal dimension for the analysis of changing patterns in electroencephalograms

Running fractal dimensions were measured on four channels of an electroencephalogram (EEG) recorded from a normal volunteer. The changes in the background activity due to eye closure were clearly differentiated by the fractal method. The compressed spectral array (CSA) and the running fractal dimensions of the EEG showed corresponding changes with respect to change in the background activity. The fractal method was also successful in detecting low amplitude spikes and the changes in the patterns in the EEG. The effects of different window lengths and shifts on the running fractal dimension have also been studied. The utility of fractal method for EEG data compression is highlighted.

Optical absorption and photoluminescence studies of Nd3 doped alkali boro germanate glasses

Optical absorption and photoluminescence studies have been carried out at room temperature in 25 R2O-25 GeO2-49.5 B2O3-0.5 Nd2O3 glass systems, (Composition in mol%, R= Li, Na, K and Rb). Judd Ofelt Intensity parameters and other parameters like Racah (E-1, E-2 and E-3), Slater-Condon-Shortley (F-2, F-4 and F-6) Spin-Orbit Coupling (xi(4f)) and Configuration Interaction (alpha,beta and gamma) for Nd3+ ion in the glass system are calculated. The variation of the 02 parameters are interpreted in terms of the covalency of the RE ion in the glass matrix. Further the hypersensitive transition I-4(9/2) -> (4)G(5/2), (2)G(7/2) is analyzed with respect to the intensity ratio I-L/I-S and is found to be dependent on the type of alkali in the glass matrix. The Photoluminescence studies do not show any appreciable shift in the peak emission wavelength of the F-4(3/2) to I-4(11/2) transition with the change in alkali type. (C) 2010 Elsevier B.V. All rights reserved.