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.

Two-mode quantum systems: Invariant classification of squeezing transformations and squeezed states

A general analysis of squeezing transformations for two-mode systems is given based on the four-dimensional real symplectic group Sp(4, R). Within the framework of the unitary (metaplectic) representation of this group, a distinction between compact photon-number-conserving and noncompact photon-number-nonconserving squeezing transformations is made. We exploit the U(2) invariant squeezing criterion to divide the set of all squeezing transformations into a two-parameter family of distinct equivalence classes with representative elements chosen for each class. Familiar two-mode squeezing transformations in the literature are recognized in our framework and seen to form a set of measure zero. Examples of squeezed coherent and thermal states are worked out. The need to extend the heterodyne detection scheme to encompass all of U(2) is emphasized, and known experimental situations where all U(2) elements can be reproduced are briefly described.

Bile acids in asymmetric synthesis and molecular recognition

This account summarizes the progress made in our laboratory towards the development of new uses of naturally occurring bile acids. Applications in Asymmetric Synthesis (intramolecular coupling, and intermolecular reactions) and Molecular Recognition are described with suitable examples.

Fusion of Complementary Online and Offline Strategies for Recognition of Handwritten Kannada Characters

This work describes an online handwritten character recognition system working in combination with an offline recognition system. The online input data is also converted into an offline image, and parallely recognized by both online and offline strategies. Features are proposed for offline recognition and a disambiguation step is employed in the offline system for the samples for which the confidence level of the classifier is low. The outputs are then combined probabilistically resulting in a classifier out-performing both individual systems. Experiments are performed for Kannada, a South Indian Language, over a database of 295 classes. The accuracy of the online recognizer improves by 11% when the combination with offline system is used.

Choice of Classifiers in Hierarchical Recognition of Online Handwritten Kannada and Tamil Aksharas

In this paper, we propose a novel dexterous technique for fast and accurate recognition of online handwritten Kannada and Tamil characters. Based on the primary classifier output and prior knowledge, the best classifier is chosen from set of three classifiers for second stage classification. Prior knowledge is obtained through analysis of the confusion matrix of primary classifier which helped in identifying the multiple sets of confused characters. Further, studies were carried out to check the performance of secondary classifiers in disambiguating among the confusion sets. Using this technique we have achieved an average accuracy of 92.6% for Kannada characters on the MILE lab dataset and 90.2% for Tamil characters on the HP Labs dataset.

DNA recognition by the EcoP15I and EcoPI modification methyltransferases

The DNA-binding properties of the EcoP15I DNA methyltransferase (M . EcoP15I; MTase) were studied using electrophoretic mobility shift assays. We show by molecular size-exclusion chromatography and dimethyl suberimidate crosslinking that M . EcoP15I is a dimer in solution. While M . EcoP15I binds approx. threefold more tightly to its recognition sequence, 5'-CAGCAG-3', than to non-specific sequences in the presence of AdoMet or its analogs, the discrimination between specific and non-specific sequences significantly increases in presence of ATP. These results suggest for the first time a role for ATP in DNA recognition by type-III restriction-modification enzymes. Furthermore, we show that although c2 EcoPI mutant MTases are defective in AdoMet binding, they are still able to bind DNA in a sequence-specific manner.

Machine recognition of printed Kannada text

This paper presents the design of a full fledged OCR system for printed Kannada text. The machine recognition of Kannada characters is difficult due to similarity in the shapes of different characters, script complexity and non-uniqueness in the representation of diacritics. The document image is subject to line segmentation, word segmentation and zone detection. From the zonal information, base characters, vowel modifiers and consonant conjucts are separated. Knowledge based approach is employed for recognizing the base characters. Various features are employed for recognising the characters. These include the coefficients of the Discrete Cosine Transform, Discrete Wavelet Transform and Karhunen-Louve Transform. These features are fed to different classifiers. Structural features are used in the subsequent levels to discriminate confused characters. Use of structural features, increases recognition rate from 93% to 98%. Apart from the classical pattern classification technique of nearest neighbour, Artificial Neural Network (ANN) based classifiers like Back Propogation and Radial Basis Function (RBF) Networks have also been studied. The ANN classifiers are trained in supervised mode using the transform features. Highest recognition rate of 99% is obtained with RBF using second level approximation coefficients of Haar wavelets as the features on presegmented base characters.

DNA recognition by the first tail-to-tail linked distamycin-like oligopeptide dimers

Sequence-specific bidentate binding to double-stranded (ds)-DNA by 'tail-to-tail' linked dimeric, distamycin analogues is described; compared to their monomeric analogues, these dimers exhibit greater affinity and longer binding site size and open up a novel avenue in the design of minor groove binders that overcome the phasing problem.

Investigation on the Sources of Reflection at the Junction of Tall Grounded Object and Lightning Channel

During lightning strike to a tall grounded object (TGO), reflections of current waves are known to occur at either ends of the TGO. These reflection modify the channel current and hence, the lightning electromagnetic fields. This study aims to identify the possible contributing factors to reflection at a TGO-channel junction for the current waves ascending on the TGO. Possible sources of reflection identified are corona sheath and discontinuity of resistance and radius. For analyzing the contribution of corona sheath and discontinuity of resistance at the junction, a macroscopic physical model for the return stroke developed in our earlier work is employed. NEC-2D is used for assessing the contribution of abrupt change in radii at a TGO-channel junction. The wire-cage model adopted for the same is validated using laboratory experiments. Detailed investigation revealed the following. The main contributor for reflection at a TGO-channel junction is the difference between TGO and channel core radii. Also, the discontinuity of resistance at a TGO-channel junction can be of some relevance only for the first microsecond regime. Further, corona sheath does not play any significant role in the reflection.

Conformational basis for substrate recognition and regulation of catalytic activity in Staphylococcus aureus nucleoside di-phosphate kinase

Nucleoside diphosphate kinases (NDK) are characterized by high catalytic turnover rates and diverse substrate specificity. These features make this enzyme an effective activator of a pro-drug an application that has been actively pursued for a variety of therapeutic strategies. The catalytic mechanism of this enzyme is governed by a conserved histidine that coordinates a magnesium ion at the active site. Despite substantial structural and biochemical information on NDK, the mechanistic feature of the phospho-transfer that leads to auto-phosphorylation remains unclear. While the role of the histidine residue is well documented, the other active site residues, in particular the conserved serine remains poorly characterized. Studies on some homologues suggest no role for the serine residue at the active site, while others suggest a crucial role for this serine in the regulation and quaternary association of this enzyme in some species. Here we report the biochemical features of the Staphylococcus aureus NDK and the mutant enzymes. We also describe the crystal structures of the apo-NDK, as a transition state mimic with vanadate and in complex with different nucleotide substrates. These structures formed the basis for molecular dynamics simulations to understand the broad substrate specificity of this enzyme and the role of active site residues in the phospho-transfer mechanism and oligomerization. Put together, these data suggest that concerted changes in the conformation of specific residues facilitate the stabilization of nucleotide complexes thereby enabling the steps involved in the ping-pong reaction mechanism without large changes to the overall structure of this enzyme. (C) 2011 Elsevier B.V. All rights reserved.