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Shiv Nadar University

(SoNS) School of Natural Sciences

The sum of independent Wishart matrices, taken from distributions with unequal covariance matrices, plays a crucial role in multivariate statistics, and has applications in the fields of quantitative finance and telecommunication. However, analytical results concerning the corresponding eigenvalue statistics have remained unavailable, even for the sum of two Wishart matrices. This can be attributed to the complicated and rotationally noninvariant nature of the matrix distribution that makes extracting the information about eigenvalues a nontrivial task. Using a generalization of the Harish-Chandra-Itzykson-Zuber integral, we find exact solution to this problem for the complex Wishart case when one of the covariance matrices is proportional to the identity matrix, while the other is arbitrary. We derive exact and compact expressions for the joint probability density and marginal density of eigenvalues. The analytical results are compared with numerical simulations and we find perfect agreement. © EPLA, 2014.

Physics

Fulltext

Eigenvalue statistics for the sum of two complex Wishart matrices

Scattering is a ubiquitous phenomenon which is observed in a variety of physical systems which span a wide range of length scales. The scattering matrix is the key quantity which provides a complete description of the scattering process. The universal features of scattering in chaotic systems is most generally modeled by the Heidelberg approach which introduces stochasticity to the scattering matrix at the level of the Hamiltonian describing the scattering center. The statistics of the scattering matrix is obtained by averaging over the ensemble of random Hamiltonians of appropriate symmetry. We derive exact results for the distributions of the real and imaginary parts of the off-diagonal scattering matrix elements applicable to orthogonally-invariant and unitarily-invariant Hamiltonians, thereby solving a long standing problem. © 2013 Elsevier Inc.

World University root node

Annals of Physics

Distributions of off-diagonal scattering matrix elements: Exact results

Peroxidase, such as horseradish peroxidase (HRP), conjugated to antibodies are routinely used for the detection of proteins via an ELISA type assay in which a critical step is the catalytic signal amplification by the enzyme to generate a detectable signal. Synthesis of functional mimics of peroxidase enzyme that display catalytic activity which far exceeds the native enzyme is extremely important for the precise and accurate determination of very low quantities of proteins (fM and lower) that is necessary for early clinical diagnosis. Despite great advancements, analyzing proteins of very low abundance colorimetrically, a method that is most sought after since it requires no equipment for the analysis, still faces great challenges. Most reported HRP mimics that show catalytic activity greater than native enzyme (∼10-fold) are based on metal/metal-oxide nanoparticles such as Fe3O 4. In this paper, we describe a second generation hybrid material developed by us in which approximately 25 000 alkyne tagged biuret modified Fe-tetraamido macrocyclic ligand (Fe-TAML), a very powerful small molecule synthetic HRP mimic, was covalently attached inside a 40 nm mesoporous silica nanoparticle (MSN). Biuret-modified Fe-TAMLs represent one of the best small molecule functional mimics of the enzyme HRP with reaction rates in water close to the native enzyme and operational stability (pH, ionic strength) far exceeding the natural enzyme. The catalytic activity of this hybrid material is around 1000-fold higher than that of natural HRP and 100-fold higher than that of most metal/metal oxide nanoparticle based HRP mimics reported to date. We also show that using antibody conjugates of this hybrid material it is possible to detect and, most importantly, quantify femtomolar quantities of proteins colorimetrically in an ELISA type assay. This represents at least 10-fold higher sensitivity than other colorimetric protein assays that have been reported using metal/metal oxide nanoparticles as HRP mimic. Using a human IgG expressing cell line, we were able to demonstrate that the protein of interest human IgG could be detected from a mixture of interfering proteins in our assay. © 2014 American Chemical Society.

Chemistry

ACS Applied Materials and Interfaces

Fe-TAML encapsulated inside mesoporous silica nanoparticles as peroxidase mimic: Femtomolar protein detection

Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising a sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts that mimic the oxygen-evolving complex of photosystem II, which is involved in oxidation of water to O2 during natural photosynthesis, represents a major challenge. Further, understanding the exact mechanism, including elucidation of the role of active metal-oxo intermediates during water oxidation (WO), is critical to the development of more efficient catalysts. Herein, we report FeIII complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML; 1a and 1b) that catalyze fast, homogeneous, photochemical WO to give O2, with moderate efficiency (maximum TON = 220, TOF = 0.76 s-1). Previous studies on photochemical WO using iron complexes resulted in demetalation of the iron complexes with concomitant formation of iron oxide nanoparticles (NPs) that were responsible for WO. Herein, we show for the first time that a high valent FeV(O) intermediate species is photochemically generated as the active intermediate for the oxidation of water to O2. To the best of our knowledge, this represents the first example of a molecular iron complex catalyzing photochemical WO through a FeV(O) intermediate. © 2014 American Chemical Society.

Journal of the American Chemical Society

Homogeneous photochemical water oxidation by biuret-modified Fe-TAML: Evidence of FeV(O) intermediate

An FeV(O) complex has been synthesized from equimolar solutions of (Et4N)2[FeIII(Cl)(biuret-amide)] and mCPBA in CH3CN at room temperature. The FeV(O) complex has been characterized by UV-vis, EPR, Mössbauer, and HRMS and shown to be capable of oxidizing a series of alkanes having C-H bond dissociation energies ranging from 99.3 kcal mol-1 (cyclohexane) to 84.5 kcal mol-1 (cumene). Linearity in the Bell-Evans-Polayni graph and the finding of a large kinetic isotope effect suggest that hydrogen abstraction is engaged the rate-determining step. © 2014 American Chemical Society.

Formation of a room temperature stable Fev(o) complex: Reactivity toward unactivated c-h bonds

Lack of control on the chirality or diameter of single-wall carbon nanotubes (SWCNTs) during synthesis is a major impediment in the path of their widespread commercialization. We demonstrate that the humble technique of catalytic chemical vapor deposition of methane, without any sophisticated catalyst preparation, can provide significant control on the diameter of the synthesized SWCNTs. The catalyst used is a solid solution of the bimetals Fe-Mo or Co-Mo in MgO. The radial breathing modes (RBMs) in the Raman spectra of SWCNTs were used to find out the diameters. Kataura plot along with RBMs was used to study the chirality of the tubes. High concentration of the catalysts (Co:Mo:MgO = 1:0.5:15 and Fe:Mo:MgO = 1:0.5:30) resulted in high yields. However, most of these carbonaceous materials were impurities. Reducing the concentration not only improved the purity and crystallinity (I D /I G ratio ∼0.1), but most importantly reduced the diameter spread of the SWCNTs. Majority of the SWCNTs grown using the low concentration catalysts (Co:Mo:MgO = 1:0.5:300 and Fe:Mo:MgO = 1:0.5:200) were estimated to have diameters lying between 1.13 and 1.65 nm. This narrowing of diameter spread happened for both Fe and Co catalyst systems and depended only on the concentration of the catalyst. © 2014 Elsevier B.V. All rights reserved.

Applied Surface Science

Diameter control of single wall carbon nanotubes synthesized using chemical vapor deposition

The accumulation of water and hydrocarbons molecules on pure Au smooth surfaces were monitored during 100 eV electron bombardment at various beam current levels. Our studies showed that these low energy electrons could accelerate the physical adsorption processes of the gaseous contaminant molecules on the mirror surface. The 100 eV electron beam was used to provide a rough simulation of the secondary electrons generated during the interaction between the EUV beam at 13.5 nm wavelength and the mirror surface in an EUVL device. The adsorption enhancement phenomenon was explained in accordance with Langmuir's Adsorption model by the increase of the sticking coefficient of adsorbed molecules onto the mirror surface. We have also shown that a positive biasing of the top of mirror surface can be used for preventing the secondary electron emission from the mirror surface. © 2013 Elsevier B.V.

Electron irradiation-enhanced water and hydrocarbon adsorption in EUV lithography devices

Development of phosphate (P)-deficiency tolerant rice cultivars is constrained by lack of suitable, reproducible, and consistent seedling stage screening methods in breeding programs. This study reports the screening and characterization of M5 mutants derived from an ethyl methane sulfonate treated population of rice cv. Nagina 22 (N22) in low-P field (soil Olsen P 1.94-2.01 mg kg-1; alkaline Vertisol; pH 7.94) for high yield. The present study showed that seedling growth responses such as increase in root weight, root length, root/shoot weight, and dry weight in P-deficient medium can be taken as indices of low-P tolerance in mature plants in field. Total phosphorus content in seedlings showed an inverse relationship with total phosphorus content and low-P tolerance in mature plants in the field. But, phosphorus content in seeds and acid phosphatase activity in the seedling stage were positively correlated with survival and seed set in low-P field. In low-P field, plant height correlated most with yield per plant, and the number of productive tillers in mature plants was highly correlated with tiller number at vegetative stage. These mutants (NH776, NH710, and NH719) have agronomic importance because of their ability to grow and give higher yield than N22 in P-deficient field. © 2013 Taylor &amp; Francis.

Life Sciences

Archives of Agronomy and Soil Science

Hydroponic experiment for identification of tolerance traits developed by rice Nagina 22 mutants to low-phosphorus in field condition

K-antigen capsule, a key virulence determinant of the oral pathogen Porphyromonas gingivalis, is synthesized by proteins encoded in a series of genes transcribed as a large polycistronic message. Previously, we identified a 77-base pair inverted repeat region with the potential to form a large stem-loop structure at the 59 end of this locus. PG0121, one of two genes flanking the capsule operon, was found to be co-transcribed with the operon and to share high similarity to the DNA binding protein HU from Escherichia coli. A null mutation in PG0121 results in down-regulation of transcription of the capsule synthesis genes and production of capsule. Furthermore, we have also shown that PG0121 gene can complement multiple deficiencies in a strain of E. coli that is deficient for both the alpha and beta subunits of HU. Here, we examined the biochemical properties of the interaction of PG0121 to DNA with the emphasis on the kinds of nucleic acid architectures that may be encountered at the 77-bp inverted repeat. We have concluded that although some DNA binding characteristics are shared with E. coli HU, HU PG0121 also shows some distinct characteristics that set it apart from other HU-like proteins tested to date. We discuss our results in the context of how PG0121 may affect the regulation of the K-antigen capsule expression. © 2014 Tjokro et al.

PLoS ONE

A biochemical analysis of the interaction of Porphyromonas gingivalis HU PG0121 protein with DNA

Background: There has been increasing interest recently in the plasticity of mesenchymal stem cells (MSCs) and their potential to differentiate into neural lineages. To unravel the roles and effects of different growth factors in the differentiation of MSCs into neural lineages, we have differentiated MSCs into neural lineages using different combinations of growth factors. Based on previous studies of the roles of insulin-like growth factor 1 (IGF-1) in neural stem cell isolation in the laboratory, we hypothesized that IGF-1 can enhance proliferation and reduce apoptosis in neural progenitor-like cells (NPCs) during differentiation of MSCs into NCPs.We induced MSCs differentiation under four different combinations of growth factors: (A) EGF + bFGF, (B) EGF + bFGF + IGF-1, (C) EGF + bFGF + LIF, (D) EGF + bFGF + BDNF, and (E) without growth factors, as a negative control. The neurospheres formed were characterized by immunofluorescence staining against nestin, and the expression was measured by flow cytometry. Cell proliferation and apoptosis were also studied by MTS and Annexin V assay, respectively, at three different time intervals (24 hr, 3 days, and 5 days). The neurospheres formed in the four groups were then terminally differentiated into neuron and glial cells.Results: The four derived NPCs showed a significantly higher expression of nestin than was shown by the negative control. Among the groups treated with growth factors, NPCs treated with IGF-1 showed the highest expression of nestin. Furthermore, NPCs derived using IGF-1 exhibited the highest cell proliferation and cell survival among the treated groups. The NPCs derived from IGF-1 treatment also resulted in a better yield after the terminal differentiation into neurons and glial cells than that of the other treated groups.Conclusions: Our results suggested that IGF-1 has a crucial role in the differentiation of MSCs into neuronal lineage by enhancing the proliferation and reducing the apoptosis in the NPCs. This information will be beneficial in the long run for improving both cell-based and cell-free therapy for neurodegenerative diseases. © 2014 Huat et al.; licensee BioMed Central Ltd.