The first copper(I) complex of tris(hydroxymethyl)phosphine

The first copper(I) complex of tris(hydroxymethyl)phosphine (THP) has been synthesized from a reaction with [Cu(CH3CN)4]ClO4. The crystal structure and spectroscopic properties of this complex showing the tetrahedral coordination around copper and a deprotonated THP coordinated to Cu through P are presented.

Synthesis and characterization of monometallic rhenium(I) complexes and their application as selective sensors for copper(II) ions

Novel imine functionalized monometallic rhenium(I) polypyridine complexes (1-4) comprising two phenol moieties attached to 2,20-bipyridine ligands L1-L4 have been synthesized and characterized. These complexes exhibit selective and sensitive detection towards copper(II) ions and this is observed through changes in UV-visible absorption, luminescence and time-resolved spectroscopic techniques. An enormous enhancement is observed in emission intensity, quantum yield and luminescence lifetime with the addition of copper(II) ions, and this can be attributed to the restriction of C=N isomerization in the Re(I) complexes. The strong binding between copper(II) ions and these complexes reveals that the binding constant values are in the range of 1.1 x 10(3)-6.0 x 103 M-1. The absorption spectral behavior of the complexes is supported by DFT calculations.

Cyclic porphyrin dimers as hosts for coordinating ligands

Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H4A) and adjacent (cisoid, H4B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H8A4+/H8A4+ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H4A/H4B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1: I complex. The Zn2A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 Å. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 Å. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.

Asymptotically-good, multigroup decodable space-time block codes

For a family of Space-Time Block Codes (STBCs) C-1, C-2,..., with increasing number of transmit antennas N-i, with rates R-i complex symbols per channel use, i = 1, 2,..., we introduce the notion of asymptotic normalized rate which we define as lim(i ->infinity) R-i/N-i, and we say that a family of STBCs is asymptotically-good if its asymptotic normalized rate is non-zero, i. e., when the rate scales as a non-zero fraction of the number of transmit antennas. An STBC C is said to be g-group decodable, g >= 2, if the information symbols encoded by it can be partitioned into g groups, such that each group of symbols can be ML decoded independently of the others. In this paper we construct full-diversity g-group decodable codes with rates greater than one complex symbol per channel use for all g >= 2. Specifically, we construct delay-optimal, g-group decodable codes for number of transmit antennas N-t that are a multiple of g2left perpendicular(g-1/2)right perpendicular with rate N-t/g2(g-1) + g(2)-g/2N(t). Using these new codes as building blocks, we then construct non-delay-optimal g-group decodable codes with rate roughly g times that of the delay-optimal codes, for number of antennas N-t that are a multiple of 2left perpendicular(g-1/2)right perpendicular, with delay gN(t) and rate Nt/2(g-1) + g-1/2N(t). For each g >= 2, the new delay-optimal and non-delay- optimal families of STBCs are both asymptotically-good, with the latter family having the largest asymptotic normalized rates among all known families of multigroup decodable codes with delay T <= gN(t). Also, for g >= 3, these are the first instances of g-group decodable codes with rates greater than 1 reported in the literature.

A composition-dependent ``re-entrant'' crystallographic phase transition in the substitutional metal acetylacetonate complex (Cr1-xGax)(acac)(3)

The formation of a complete solid solution between acetylacetonate (acac) complexes of chromium and gallium, (Cr1-x,Ga-x)(acac)(3) for 0.1 complex. Whereas the pure complexes (i.e. the end members of the solid solution, x = 0 and x = 1) are both centro-symmetric, a composition-dependent crystallographic phase transition to a non-centrosymmetric structure is found to occur for compositions with 0.4 < x < 0.9. Such a ``re-entrant'' crystallographic transition is interpreted to be due to the drive to overcome the disorder present in certain centrosymmetric chromium-rich compositions, by going over to a non-centrosymmetric structure with a doubling of the unit cell. The substitutional complex is shown to lead to a substitutional oxide with the beta-gallate structure. (C) 2014 Elsevier Ltd. All rights reserved.

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.

Japanese Encephalitis Virus Utilizes the Canonical Pathway To Activate NF-kappa B but It Utilizes the Type I Interferon Pathway To Induce Major Histocompatibility Complex Class I Expression in Mouse Embryonic Fibroblasts

Flaviviruses have been shown to induce cell surface expression of major histocompatibility complex class I (MHC-I) through the activation of NF-kappa B. Using IKK1(-/-), IKK2(-/-), NEMO-/-, and IKK1-/- IKK2-/- double mutant as well as p50(-/-) RelA(-/-) cRel(-/-) triple mutant mouse embryonic fibroblasts infected with Japanese encephalitis virus (JEV), we show that this flavivirus utilizes the canonical pathway to activate NF-kappa B in an IKK2- and NEMO-, but not IKK1-, dependent manner. NF-kappa B DNA binding activity induced upon virus infection was shown to be composed of RelA: p50 dimers in these fibroblasts. Type I interferon (IFN) production was significantly decreased but not completely abolished upon virus infection in cells defective in NF-kappa B activation. In contrast, induction of classical MHC-I (class 1a) genes and their cell surface expression remained unaffected in these NF-kappa B-defective cells. However, MHC-I induction was impaired in IFNAR(-/-) cells that lack the alpha/beta IFN receptor, indicating a dominant role of type I IFNs but not NF-kappa B for the induction of MHC-I molecules by Japanese encephalitis virus. Our further analysis revealed that the residual type I IFN signaling in NF-kappa B-deficient cells is sufficient to drive MHC-I gene expression upon virus infection in mouse embryonic fibroblasts. However, NF-kappa B could indirectly regulate MHC-I expression, since JEV-induced type I IFN expression was found to be critically dependent on it.

Role of lipid peroxidation in impairment of mitochondrial function at complex I by methyl isocyanate treatment of rats in vivo

The subcutaneous administration of methyl isocyanate (MIC) in 1.0 LD50 dose in rats caused a significant effect on hepatic mitochondrial function only at complex I region of the respiratory chain. MIC administration at 1.0 LD50 dose also resulted in significant increases in malondialdehyde and ferrous ion concentration in liver mitochondria. It is suggested that the augmented lipid peroxidation in hepatic mitochondria, catalyzed by iron, possibly mobilized from intracellular stores leads to the inhibition of enzymes of mitochondrial respiration at complex I region, in vivo, in rats receiving a lethal dose of MIC subcutaneously.

Electron donor-acceptor complex of ICl with diethyl ether - He I photoelectron spectroscopy and ab initio molecular orbital study

The He I photoelectron spectrum of the diethyl ether-ICl complex has been obtained. The oxygen orbitals are shifted to higher binding energies and that of ICl to lower binding energies owing to complex formation. Ab initio molecular orbital (MO) calculations of the complex molecule showed that the bonding is between the sigma-type lone pair of oxygen and the I atom and that the complex has C-2v symmetry. The binding energy of the complex is computed to be 8.06 kcal mol(-1) at the MP2/3-21G* level. The orbital energies obtained from the photoelectron spectra of the complex are compared and assigned with orbital energies obtained by MO calculations. Natural bond orbital analysis (NBO) shows that charge transfer is from the sigma-type oxygen lone pair to the iodine atom and the magnitude of charge transfer is 0.0744 e.

Structural characterization of angiotensin I-converting enzyme in complex with a selenium analogue of captopril

Human somatic angiotensin I-converting enzyme (ACE), a zinc-dependent dipeptidyl carboxypeptidase, is central to the regulation of the renin-angiotensin aldosterone system. It is a well-known target for combating hypertension and related cardiovascular diseases. In a recent study by Bhuyan and Mugesh [Org. Biomol. Chem. (2011) 9, 1356-1365], it was shown that the selenium analogues of captopril (a well-known clinical inhibitor of ACE) not only inhibit ACE, but also protect against peroxynitrite-mediated nitration of peptides and proteins. Here, we report the crystal structures of human testis ACE (tACE) and a homologue of ACE, known as AnCE, from Drosophila melanogaster in complex with the most promising selenium analogue of captopril (SeCap) determined at 2.4 and 2.35 angstrom resolution, respectively. The inhibitor binds at the active site of tACE and AnCE in an analogous fashion to that observed for captopril and provide the first examples of a protein-selenolate interaction. These new structures of tACE-SeCap and AnCE-SeCap inhibitor complexes presented here provide important information for further exploration of zinc coordinating selenium-based ACE inhibitor pharmacophores with significant antioxidant activity.

Deciphering complex patterns of class-I HLA-peptide cross-reactivity via hierarchical grouping

T-cell responses in humans are initiated by the binding of a peptide antigen to a human leukocyte antigen (HLA) molecule. The peptide-HLA complex then recruits an appropriate T cell, leading to cell-mediated immunity. More than 2000 HLA class-I alleles are known in humans, and they vary only in their peptide-binding grooves. The polymorphism they exhibit enables them to bind a wide range of peptide antigens from diverse sources. HLA molecules and peptides present a complex molecular recognition pattern, as many peptides bind to a given allele and a given peptide can be recognized by many alleles. A powerful grouping scheme that not only provides an insightful classification, but is also capable of dissecting the physicochemical basis of recognition specificity is necessary to address this complexity. We present a hierarchical classification of 2010 class-I alleles by using a systematic divisive clustering method. All-pair distances of alleles were obtained by comparing binding pockets in the structural models. By varying the similarity thresholds, a multilevel classification was obtained, with 7 supergroups, each further subclassifying to yield 72 groups. An independent clustering performed based only on similarities in their epitope pools correlated highly with pocket-based clustering. Physicochemical feature combinations that best explain the basis of clustering are identified. Mutual information calculated for the set of peptide ligands enables identification of binding site residues contributing to peptide specificity. The grouping of HLA molecules achieved here will be useful for rational vaccine design, understanding disease susceptibilities and predicting risk of organ transplants.

Synthesis, crystal structure and DNA cleavage activity of (aqua)bis(dipyridophenazine)copper(II) complex

A copper(II) complex of dipyridophenazine, viz., [Cu(dppz)(2)(H2O)](ClO4)(2) (I), has been prepared and structurally characterized by X-ray crystallography. The crystal structure of the complex shows a five-coordinate structure in which two N,N-donor dipyridophenazine (dppz) and one aqua ligand bind to the copper(II) center giving Cu-O and Cu-N bond distances in the range of 1.981(6) to 2.043(6) angstrom. The ESI-MS spectrum of 1 in MeCN shows a peak at m/z value of 313 (100%) indicating the dissociation of the aqua ligand in the solution phase. The complex is one-electron paramagnetic (mu(eff), 1.86 mu(B)). It displays a quasi-reversible Cu(II)/Cu(I) redox process at 0.096 V. The complex is an avid binder to CT DNA giving a binding constant value of 3.5 x 10(5) M-1. It shows significant hydrolytic cleavage of supercoiled pUC19 DNA in dark ill the absence of any external agents. The complex exhibits chemical nuclease activity oil treatment with 3-mercaptopropionic acid as a reducing agent forming hydroxyl radicals. Complex 1 is a model synthetic nuclease and hydrolase showing both modes of DNA cleavage under different reaction conditions. The DNA cleavage activity of 1 is significantly better than its phen analogue but similar to that of the bis-dpq complex.

Reversible Insertion of Methyl Isothiocyanate into Copper(I)Aryloxides

MeNCS undergoes insertion into the copper(I)-aryloxide bond to form [N-methylimino(aryloxy)methanethiolato]-copper(I) complexes. This insertion occurs in the absence of ancillary ligands unlike the analogous insertion of PhNCS. The reaction with 4-methylphenoxide results in the formation of hexakis[[N-methylimino(4-methylphenoxy) methanethiolato]copper(I)] (1), which has been characterized by X-ray crystallography. Crystal data for 1: hexagonal , a = 12.365(3) Angstrom, c = 36.734(16) Angstrom, gamma = 120 degrees, Z = 3, V = 4863(3) Angstrom(3), R = 0.0306. Reactions of 2,6-dimethyl- and 4-chlorophenoxides also result in analogous copper(I) complexes 2 and 3. Addition of stochiometric amounts of PPh(3) to the oligomeric complexes typically results in the extrusion of MeNCS. The ease of extrusion is dependent on the substituents on the aryloxide, and this deinsertion is accelerated by water. However, the extrusion reaction is slow enough in the case of the N-methylimino(2,6-dimethylphenoxy)-methanethiolate complex and the isolation of an intermediate monomeric product bis(triphenylphosphine)[N-methylimino(2, 6-dimethylphenoxy)methanethiolato] copper(I) (4) is possible. Crystal data for 4: triclinic , a = 10.088(2) Angstrom, b = 11.302(1) Angstrom, c = 17.990(2) Angstrom, alpha = 94.06(1)degrees, beta = 95.22(2)degrees, gamma = 103.94(1)degrees, Z = 2, V = 1974.4(7) Angstrom(3), R = 0.0361. In the presence of of PPh(3), the insertion reaction becomes reversible. This allows the exchange of the heterocumulene MeNCS or the aryloxy group in these molecules with another heterocumulene or a phenol, respectively, when catalytic amounts of PPh(3) are added. Oligomers with exchanged heterocumulmes and phenols could be characterized by independent synthesis.

Studies on glass transition and starch re-crystallization in wheat bread during staling using electrical impedance spectroscopy

Bread staling is a very complex phenomenon that is not yet completely understood. The present work explains how the electrical impedance spectroscopy technique can be utilized to investigate the effect of staling on the physicochemical properties of wheat bread during storage. An instrument based on electrical impedance spectroscopy technique is developed to study the electrical properties of wheat bread both at its crumb and crust with the help of designed multi-channel ring electrodes. Electrical impedance behavior, mainly capacitance and resistance, of wheat bread at crust and crumb during storage (up to 120 h) is investigated. The variation in capacitance showed the glass transition phenomenon at room temperature in bread crust after 96 h of storage with 18% of moisture in it. The resistance changes at bread crumb showed the starch recrystallization during staling.

Quantum-Ohmic Resistance Fluctuation In Disordered Conductors - An Invariant Imbedding Approach

It is now well known that in extreme quantum limit, dominated by the elastic impurity scattering and the concomitant quantum interference, the zero-temperature d.c. resistance of a strictly one-dimensional disordered system is non-additive and non-self-averaging. While these statistical fluctuations may persist in the case of a physically thin wire, they are implicitly and questionably ignored in higher dimensions. In this work, we have re-examined this question. Following an invariant imbedding formulation, we first derive a stochastic differential equation for the complex amplitude reflection coefficient and hence obtain a Fokker-Planck equation for the full probability distribution of resistance for a one-dimensional continuum with a Gaussian white-noise random potential. We then employ the Migdal-Kadanoff type bond moving procedure and derive the d-dimensional generalization of the above probability distribution, or rather the associated cumulant function –‘the free energy’. For d=3, our analysis shows that the dispersion dominates the mobilitly edge phenomena in that (i) a one-parameter B-function depending on the mean conductance only does not exist, (ii) an approximate treatment gives a diffusion-correction involving the second cumulant. It is, however, not clear whether the fluctuations can render the transition at the mobility edge ‘first-order’. We also report some analytical results for the case of the one dimensional system in the presence of a finite electric fiekl. We find a cross-over from the exponential to the power-low length dependence of resistance as the field increases from zero. Also, the distribution of resistance saturates asymptotically to a poissonian form. Most of our analytical results are supported by the recent numerical simulation work reported by some authors.