Ternary Iron(III) complex showing photocleavage of DNA in the photodynamic therapy window

A new ternary iron(III) complex [FeL(dpq)] containing dipyridoquinoxaline (dpq) and 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (H3L) is prepared and structurally characterized by X-ray crystallography. The high-spin complex with a FeN3O3 core shows a quasi-reversible iron(III)/iron(II) redox couple at -0.62 V (vs SCE) in DMF/0.1 M TBAP and a broad visible band at 470 nm in DMF/Tris buffer. Laser photoexcitation of this phenolate (L)-to-iron(III) charge-transfer band at visible wavelengths including red light of >= 630 nm leads to cleavage of supercoiled pUC19 DNA to its nicked circular form via a photoredox pathway forming hydroxyl radicals.

Rationalizing the effects of amino acid side chain, pyridine, and imidazole on the assembly and reversible disassembly of a octanuclear Cu(III) complex

This paper reports the observation of a reversible disassembly process for a previously reported octanuclear Cu(II) complex with imidazole. To identify the factors responsible for the process, five Cu(II) complexes of different nuclearity with different amino acid-derived tetradentate ligands were structurally characterized. The results show that the coordination geometry preference of Cu(II), the tendency of imidazole to act as in-plane ligand, and H-bonding played important role in the formation and disassembly of the octanuclear complex. A general scheme describing the effect of different amino acid side arms, solvents, and exogenous ligands on the nuclearity of the Cu(II) complexes has been presented. The crystals of the complexes also showed formation of multifaceted networks in the resulting complexes.

Context-dependency of a complex fruit-frugivore mutualism: temporal variation in crop size and neighborhood effects

The quantity of fruit consumed by dispersers is highly variable among individuals within plant populations. The outcome Of Such selection operated by firugivores has been examined mostly with respect to changing spatial contexts. The influence of varying temporal contexts on frugivore choice, and their possible demographic and evolutionary consequences is poorly understood. We examined if temporal variation in fruit availability across a hierarchy of nested temporal levels (interannual, intraseasonal, 120 h, 24 h) altered frugivore choice for a complex seed dispersal system in dry tropical forests of southern India. The interactions between Phyllanthus emblica and its primary disperser (ruminants) was mediated by another frugivore (a primate),which made large quantities of fruit available on the ground to ruminants. The direction and strength of crop size and neighborhood effects on this interaction varied with changing temporal contexts.Fruit availability was higher in the first of the two study years, and at the start of the season in both years. Fruit persistence on trees,determined by primate foraging, was influenced by crop size andconspecific neighborhood densities only in the high fruit availability year. Fruit removal by ruminants was influenced by crop size in both years and neighborhood densities only in the high availability year. In both years, these effects were stronger at the start of the season.Intraseasonal reduction in fruit availability diminished inequalities in fruit removal by ruminants and the influence of crop size and fruiting neighborhoods. All trees were not equally attractive to frugivores in a P. emblica population at all points of time. Temporal asymmetry in frugivore-mediated selection could reduce potential for co-evolution between firugivores and plants by diluting selective pressures. Inter-dependencies; formed between disparate animal consumers can add additional levels of complexity to plant-frugivore mutualistic networks and have potential reproductive consequences for specific individuals within populations.

Robust heuristics for scalable optimization of complex SQL queries

Modern database systems incorporate a query optimizer to identify the most efficient "query execution plan" for executing the declarative SQL queries submitted by users. A dynamic-programming-based approach is used to exhaustively enumerate the combinatorially large search space of plan alternatives and, using a cost model, to identify the optimal choice. While dynamic programming (DP) works very well for moderately complex queries with up to around a dozen base relations, it usually fails to scale beyond this stage due to its inherent exponential space and time complexity. Therefore, DP becomes practically infeasible for complex queries with a large number of base relations, such as those found in current decision-support and enterprise management applications. To address the above problem, a variety of approaches have been proposed in the literature. Some completely jettison the DP approach and resort to alternative techniques such as randomized algorithms, whereas others have retained DP by using heuristics to prune the search space to computationally manageable levels. In the latter class, a well-known strategy is "iterative dynamic programming" (IDP) wherein DP is employed bottom-up until it hits its feasibility limit, and then iteratively restarted with a significantly reduced subset of the execution plans currently under consideration. The experimental evaluation of IDP indicated that by appropriate choice of algorithmic parameters, it was possible to almost always obtain "good" (within a factor of twice of the optimal) plans, and in the few remaining cases, mostly "acceptable" (within an order of magnitude of the optimal) plans, and rarely, a "bad" plan. While IDP is certainly an innovative and powerful approach, we have found that there are a variety of common query frameworks wherein it can fail to consistently produce good plans, let alone the optimal choice. This is especially so when star or clique components are present, increasing the complexity of th- e join graphs. Worse, this shortcoming is exacerbated when the number of relations participating in the query is scaled upwards.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

Peptide-lanthanide interactions. Crystal structure of a europium(III)-triglycine complex

Crystals of Eu-(Gly-Gly-Gly).(H2O)5.(ClO4)3 are triclinic, spacegroup P1BAR with a = 9.123 (2), b = 11.185 (5), c = 11.426 (2) angstrom; alpha = 90.79 (2), beta = 98.08 (1), gamma = 98.57 (2)-degrees; Z = 2. The europium cation is surrounded by four oxygens from three different peptide units and four oxygens from water molecules. The geometry around the metal is a distorted bi-capped trigonal prism. The peptide backbone conformation in this complex is compared with those in the free peptide and in various metal complexes. Considerable differences are observed between Eu(III) and Ca(II) complexes of triglycine. (C) Munksgaard 1994.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

Analysis of connectivity map: Control to glutamate injured and phenobarbital treated neuronal network

We study the responses of a cultured neural network when it is exposed to epileptogenesis glutamate injury causing epilepsy and subsequent treatment with phenobarbital by constructing connectivity map of neurons using correlation matrix. This study is particularly useful in understanding the pharmaceutical drug induced changes in the neuronal network properties with insights into changes at the systems biology level. (C) 2010 American Institute of Physics. [doi:10.1063/1.3398025]

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

Stabilisation and characterisation of N,N′-dibenzylidene-o-phenylenediamine as a copper(I) perchlorate complex

QUITE OFTEN, metal ions profoundly affect the condensation of carbonyl compounds with primary amines to form Schiff bases as well as their subsequent reactions[I-4]. Condensation of benzaldehyde with o-phenylenediamine (opd) in glacial acetic acid[5] or in absolute alcohol[6] gives benzimidazole derivative, 1-benzyl-2-phenylbenzimidazole (bpbi). In this reaction, the Schiff base N,N'-dibenzylidene-o-phenylenedianfme (dbpd) has been postulated as an intermediate, which cyclises to give bpbi. It was found that the reaction of opd in presence of copperO1) perchlorate with benzaldehyde gave dbpd complex of copper(l) perchlorate instead of bpbi.

Studies on phosphorus oxychloride and aluminium chloride complex

1. Anhydrous aluminium chloride reacts with phosphorus oxychloride to give a complex with a composition AlCl3.2 POCl3 which can be prepared in the form of a free flowing powder. 2. The phosphorus oxychloride-aluminium chloride complex in nitrobenzene dissociates into AlCl3.POCl3 and POCl3 as indicated by the cryoscopic measurements. 3. The solution of the complex in nitrobenzene has a higher specific conductivity than the corresponding electrical conductivities of individual components. Similar higher electrical conductance is observed when the two components are mixed in nitrobenzene in different proportions. 4.When a solution of anhydrous aluminium chloride in nitrobenzene is titrated conductometrically against a solution of phosphorus oxychloride in nitrobenzene, a limiting value in the conductivity is reached at point corresponding to the molecular composition, the components in the ratio of 1:2 AlCl3: POCl3 in solution. 5. The absorption maxima of the complex in nitrobenzene solution differ from the absorption maximum of the individual components.

Crystal structure of an intermolecular 2:1 complex between adenine and thymine.Evidence for both Hoogsteen and `quasi-Watson-Crick' interactions

The titled complex, obtained by co-crystallization (EtOH/25 degrees C),is apparently the only known complex of the free bases. Its crystal structure, as determined by X-ray diffraction at both 90 K and 313 K, showed that one A-T pair involves a Hoogsteen interaction, and the other a Watson-Crick interaction but only with respect to the adenine unit. The absence of a clear-cut Watson-Crick base pair raises intriguing questions about the basis of the DNA double helix. (C) 2010 Elsevier Ltd. All rights reserved.

Crystal And Molecular Structure Of A Dimethyl Sulphoxide Complex With Lanthanum Nitrate, La(No3)34.(Ch3)2so

The crystal structure of the complex La(NO3)3.4(CH3)2SO has been solved by the heavy-atom method. The complex crystallizes in the monoclinic space group C2/e with four formula units in a unit cell of dimensions a= 14.94, b= 11.04, c= 15.54 A and fl= 109 ° 10'. The parameters have been refined by threedimensional least-squares procedures with anisotropic thermal parameters for all atoms except hydrogen. The final R index for 1257 observed reflexions is 0.094. The La 3 + ion is coordinated by ten oxygen atoms with La-O distances varying from 2.47 to 2.71 A. The geometry of the coordination polyhedron is described.