Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Geometry changes induced by negative hyperconjugative interactions involving carbonyl and thiocarbonyl groups

MNDO geometry optimizations have been carried out on a series of acyclic and cyclic unsymmetrically disubstituted carbonyl and thiocarbonyl compounds. The C=X unit shows a consistent and often sizeable tilt towards one of the substituents, following the order O > Snot, vert, similarN > C > B. Reference ab initio calculations and available experimental results support the MNDO results. The effect, which is particularly dramatic in small rings, is attributed primarily to favorable negative hyperconjugative interaction between the lone pair on X and a low lying adjacent σ* orbital. Such an interaction can lead to highly distorted structures, including perhaps to a planar molecule with an inverted sp2 carbon center.

Electronic structure of square planar CuO46− clusters

The results of spin-polarized MSXagr calculations show that the ground state of the CuO 4 6– cluster is essentially non-magnetic in spite of odd number of electrons in the system for short Cu–O distances (1.90 Å) as found in the highT c superconductors. This arises due to the fact that the unpaired electron resides in a molecular orbital with primarily oxygen 3s character. The stability of this molecular orbital is found to be sensitive to the cluster geometry and thus, increase in Cu–O distance (as well as other changes affecting oxygen-oxygen distance) tend to favour a magnetic state. From these calculations we have also estimated the Coulomb correlation strength within the Cu 3d to be about 5.3 eV.

Magnetic susceptibility studies on ternary oxides of copper(II)

The magnetic susceptibilities of a large number of ternary oxides of copper having structural features common to the presently identified phases of high-temperature superconductors have been studied in the temperature range 14-300 K. The systems studied are Ln2CuOP( Ln = La, Pr, Nd, etc.), Sr2CuO2CI2,B i2Cu0,, Ca2Cu03,S r2Cu03,S rCu02, MgCu203,B a2Cu3O4CI2Y, 2Cu205,Y2BaCu0,, BaCu02, Li2Cu02, etc. Cu2+ ions take different coordinations, like isolated square planar, square pyramidal or distorted-tetrahedral and octahedral, in these compounds. These compounds also exhibit different varieties of possible magnetic superexchange interactions like 180' or 90' Cu-0-Cu or Cu-0-0-Cu types as well as direct Cu-Cu interactions. Compounds in which there are extended 180' Cu-0-Cu interactions show a low, nearly temperature-independent susceptibility (100 X lod emu/mol). The estimated value of J for the Cu-0-Cu interaction is between 800 and 1500 K in these compounds. Isolated Cu2+ ions in which there are no 180' or close to 180" Cu-0-Cu interactions show Curie-Weiss susceptibility behavior. Compounds with only Cu-0-0-Cu interaction show evidence for the onset of antiferromagnetic coupling between 30 and 50 K. The superexchange rules are useful for explaining the qualitative features of the results. The possibility of disproportionation of Cu2+ ion when there are short Cu-Cu distances as in Bi2Cu04 is discussed. The extended geometry of the copper-oxygen framework seems to be more important than the local geometry around the Cu2+ ion in determining the magnetic properties.

Electron paramagnetic resonance studies of some ternary oxides of copper (II)

The electron paramagnetic resonance (EPR) of ternary oxides of Cu(II) has been studied between 4.2 and 300 K. The systems include those with 180 degrees Cu-O-Cu interactions (such as Ln2CuO4, Sr2CuO2Cl2, Sr2CuO3 and Ca2CuO3) or 90 degrees Cu-O-Cu interactions (such as Y2Cu2O5 or BaCuO2) as well as those in which the Cu2+ ions are isolated (such as Y2BaCuO5, La1.8Ba1.2Cu0.9O4.8 and Bi2CuO4). The change in the EPR susceptibility as a function of temperature is compared with that of the DC magnetic susceptibility. Compounds with extended 180 degrees Cu-O-Cu interactions which have a low susceptibility also do not give EPR signals below room temperature. For compounds such as Ca2CuO3 with one-dimensional 180 degrees Cu-O-Cu interactions a weak EPR signal is found the temperature dependence of which is very different from that of the DC susceptibility. For Y2BaCuO5 as well as for La1.8Ba1.2Cu0.9O4.8 the EPR susceptibility as well as its temperature variation are comparable with those of the static susceptibility near room temperature but very different at low temperatures. Bi2CuO4 also shows a similar behaviour. In contrast, for Y2Cu2O5, in which the copper ions have a very distorted nonsquare-planar configuration, the EPR and the static susceptibility show very similar temperature dependences. In general, compounds in which the copper ions have a square-planar geometry give no EPR signal in the ground state (0 K) while those with a distortion from square-planar geometry do give a signal. The results are analysed in the light of recent MS Xalpha calculations on CuO46- square-planar clusters with various Cu-O distances as well as distortions. It is suggested that in square-planar geometry the ground state has an unpaired electron in anionic orbitals which is EPR inactive. Competing interactions from other cations, an increase in Cu-O distance or distortions from square-planar geometry stabilise another state which has considerably more Cu 3d character. These states are EPR active. Both these states, however, are magnetic. For isolated CuO46- clusters the magnetic interactions seem to involve only the states which have mainly anionic character.

Cross-field gas breakdown in a coaxial cylinder geometry

Sparking potentials in a coaxial cylinder geometry in oxygen and dry air were measured in crossed electric and magnetic fields. From the data effective collision frequencies were calculated using the equivalent pressure concept. It is shown that the equivalent pressure concept holds good for deriving the effective collision frequencies in non-uniform electric fields.

Heat Shock Protein 90 as a Drug Target against Protozoan Infections Biochemical characterization of HSP90 From plasmodium falciparum and trypanosoma evansi and evaluation of its inhibitor as a candidate drug

Using a pharmacological inhibitor of Hsp90 in cultured malarial parasite, we have previously implicated Plasmodium falciparum Hsp90 (PfHsp90) as a drug target against malaria. In this study, we have biochemically characterized PfHsp90 in terms of its ATPase activity and interaction with its inhibitor geldanamycin (GA) and evaluated its potential as a drug target in a preclinical mouse model of malaria. In addition, we have explored the potential of Hsp90 inhibitors as drugs for the treatment of Trypanosoma infection in animals. Our studies with full-length PfHsp90 showed it to have the highest ATPase activity of all known Hsp90s; its ATPase activity was 6 times higher than that of human Hsp90. Also, GA brought about more robust inhibition of PfHsp90 ATPase activity as compared with human Hsp90. Mass spectrometric analysis of PfHsp90 expressed in P. falciparum identified a site of acetylation that overlapped with Aha1 and p23 binding domain, suggesting its role in modulating Hsp90 multichaperone complex assembly. Indeed, treatment of P. falciparum cultures with a histone deacetylase inhibitor resulted in a partial dissociation of PfHsp90 complex. Furthermore, we found a well known, semisynthetic Hsp90 inhibitor, namely 17-(allylamino)-17-demethoxygeldanamycin, to be effective in attenuating parasite growth and prolonging survival in a mouse model of malaria. We also characterized GA binding to Hsp90 from another protozoan parasite, namely Trypanosoma evansi. We found 17-(allylamino)-17-demethoxygeldanamycin to potently inhibit T. evansi growth in a mouse model of trypanosomiasis. In all, our biochemical characterization, drug interaction, and animal studies supported Hsp90 as a drug target and its inhibitor as a potential drug against protozoan diseases.

A standard reference frame for the description of Nucleic Acid Base-Pair Geometry

A common point of reference is needed to describe the three-dimensional arrangements of bases and base-pairs in nucleic acid structures. The different standards used in computer programs created for this purpose give rise to con¯icting interpretations of the same structure.1 For example, parts of a structure that appear ``normal'' according to one computational scheme may be highly unusual according to another and vice versa. It is thus dif®cult to carry out comprehensive comparisons of nucleic acid structures and to pinpoint unique conformational features in individual structures

HELANAL: A program to characterise helix geometry in proteins,

A detailed analysis of structural and position dependent characteristic features of helices will give a better understanding of the secondary structure formation in globular proteins. Here we describe an algorithm that quantifies the geometry of helices in proteins on the basis of their C-alpha atoms alone. The Fortran program HELANAL can extract the helices from the PDB files and then characterises the overall geometry of each helix as being linear, curved or kinked, in terms of its local structural features, viz. local helical twist and rise, virtual torsion angle, local helix origins and bending angles between successive local helix axes. Even helices with large radius of curvature are unambiguously identified as being linear or curved. The program can also be used to differentiate a kinked helix and other motifs, such as helix-loop-helix or a helix-turn-helix (with a single residue linker) with the help of local bending angles. In addition to these, the program can also be used to characterise the helix start and end as well as other types of secondary structures.

Nature of Cl center dot center dot center dot Cl Intermolecular Interactions via Experimental and Theoretical Charge Density Analysis:Correlation of Polar Flattening Effects with Geometry

The experimental charge density distribution in three compounds, 2-chloro-3-quinolinyl methanol, 2-chloro-3-hydroxypyridine, and 2-chloro-3-chloromethyl-8-methylquinoline, has been obtained using high-resolution X-ray diffraction data collected at 100 K based on the aspherical multipole modeling of electron density. These compounds represent type I (cis), type I (trans), and type II geometries, respectively, as defined for short Cl center dot center dot center dot Cl interactions. The experimental results are compared with the theoretical charge densities using theoretical structure factors obtained from a periodic quantum calculation at the B3LYP/6-31G** level. The topological features derived from the Bader's theory of atoms in molecules (AIM) approach unequivocally suggest that both cis and trans type I geometries show decreased repulsion, whereas type II geometry is attractive based on the nature of polar flattening of the electron density around the Cl atom.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

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]

Lattice embedding and equilibrium geometry of metal-halogen chains in the two-band extended Hubbard model

Two-band extended Hubbard model studies show that the shift in optical gap of the metal-halogen (MX) chain upon embedding in a crystalline environment depends upon alternation in the site-diagonal electron-lattice interaction parameter (epsilon(M)) and the strength of electron-electron interactions at the metal site (U(M)). The equilibrium geometry studies on isolated chains show that the MX chains tend to distort for alternating epsilon(M) and small U(M) values.

Geometry of proline-containing alpha-helices in proteins

Crystal structure analysis of proline-containing alpha-helices in proteins has been carried out. High resolution crystal structures were selected from the Protein Data Bank. Apart from the standard internal parameters, some parameters which are specifically related to the bend in the helix due to proline have been developed and analyzed. Finally the position and nature of these helices and their interactions with the rest of the protein have been analyzed.

Post-transcriptional Repair of a Split Heat Shock Protein 90 Gene by mRNA trans-Splicing

Heat shock protein 90 participates in diverse biological processes ranging from protein folding, cell cycle, signal transduction and development to evolution in all eukaryotes. It is also critically involved in regulating growth of protozoa such as Dictyostelium discoideum, Leishmania donovani, Plasmodium falciparum, Trypanosoma cruzi, and Trypanosoma evansi. Selective inhibition of Hsp90 has also been explored as an intervention strategy against important human diseases such as cancer, malaria, or trypanosomiasis. Giardia lamblia, a simple protozoan parasite of humans and animals, is an important cause of diarrheal disease with significant morbidity and some mortality in tropical countries. Here we show that the G. lamblia cytosolic hsp90 ( glhsp90) is split in two similar sized fragments located 777 kb apart on the same scaffold. Intrigued by this unique arrangement, which appears to be specific for the Giardiinae, we have investigated the biosynthesis of GlHsp90. We used genome sequencing to confirm the split nature of the giardial hsp90. However, a specific antibody raised against the peptide detected a product with a mass of about 80 kDa, suggesting a post-transcriptional rescue of the genomic defect. We show evidence for the joining of the two independent Hsp90 transcripts in-trans to one long mature mRNA presumably by RNA splicing. The splicing junction carries hallmarks of classical cis-spliced introns, suggesting that the regular cis-splicing machinery may be sufficient for repair of the open reading frame. A complementary 26-nt sequence in the ``intron'' regions adjacent to the splice sites may assist in positioning the two pre-mRNAs for processing. This is the first example of post-transcriptional rescue of a split gene by trans-splicing.