Transformation of mixed anionic coordination polymers of lead

The coordination polymerization from lead(II) nitrate on reaction with 4-nitrobenzoic acid and pyridine N-oxide at room temperature passes through stepwise ligand substitution reaction. An intermediate polymer [Pb(NB)(PyO)₂(NO₃)]_n (where NB = 4-nitrobenzoate, PyO = Pyridine N-oxide) is formed to give the final polymer [Pb(NB)₂(PyO)]_n. A hydrated mononuclear complex [Pb(NB)₂(PyO)(H₂O)] is also formed if rigorous anhydrous condition is not maintained. The reaction is extended to 4,4′-bipyridyl N-oxide (BPNO), which initially gives a coordination polymer [Pb₂(NO₃)(NB)₃(BPNO)₂]_n which gets converted to another coordination polymer [Pb(NB)₂(BPNO)₂]_n. All these complexes are structurally characterized.     

Synthesis and characterization of three covalently linked porphyrin-phthalocyanine pentamers with nucleophilic substitution

In this paper the synthetic methods of three covalently linked porphyrin-phthalocyanine heteropentamers, containing four units of porphyrin linked to a central phthalocyanine (Mpor-LPc; M = 2H, Fe, L = Zn, Fe), are described. The synthetic strategy is on the basis of nucleophilic substitution reactions between [1,8,15,22-tetra nitro phthalocyanines] and [5-(4-hydroxy phenyl)-10,15,20-triphenyl porphyrins] as the phenolic alcohols. Porphyrins are linked with oxygen as spacer through meso position of phenyl group to phthalocyanines. These macromolecules were characterized by ¹H NMR, UV-Vis, IR, fluorescence and mass spectroscopy. The electronic absorption spectrums of the hetero-dyad systems changed significantly upon coupling and showed a great red shift in the phthalocyanine Q-bands. These changes confirm the electron-donating effects of the porphyrin units and the extension of conjugated п-systems. The emission spectra of the products supports intramolecular energy and charge transfer between the sub-units.     

Discovery of dual ZAP70 and Syk kinases inhibitors by docking into a rare C-helix-out conformation of Syk

The non-receptor tyrosine kinase Syk (spleen tyrosine kinase) is a pharmaceutical relevant target because its over-activation is observed in several autoimmune diseases, allergy, and asthma. Here we report the identification of two novel inhibitors of Syk by high-throughput docking into a rare C-helix-out conformation published recently. Interestingly, both compounds are slightly more active on ZAP70 (Zeta-chain-associated protein kinase 70), which is the kinase closest to Syk in the phylogenetic tree of human kinases. Taken together, the docking pose and experimental results suggest that the higher affinity of the inhibitors for ZAP70 than Syk originates from a more populated C-helix-out conformation in ZAP70. The latter observation is congruent with the 100-fold lower intrinsic activity of ZAP70 than Syk, as the C-helix-out conformation is inactive. The pharmacophore features of DFG-in, C-helix-out compounds are analyzed in relation to DFG-out inhibitors.     

Ultrastructural aspects of the hyphal tip ofSclerotium rolfsii preserved by freeze substitution

Summary The hyphal tip ofSclerotium rolfsii was examined after fixation by freeze substitution. The Spitzenkörper consisted of a dense mass of apical vesicles and microvesicles surrounding a vesicle-free zone. Linear arrangements of microvesicles were occasionally observed within the Spitzenkörper. Abundant microfilaments were seen within the Spitzenkörper region, often in close association with apical vesicles and microvesicles. Microtubules passed through the Spitzenkörper and terminated at the plasmalemma at the extreme hyphal apex. Filasomes were mostly observed within the apical region and were in close proximity to the plasmalemma. Rough ER, mitochondria, microtubules, and vacuoles were abundant in the subapical region and were usually oriented parallel to the long axis of the hypha. Ribosomes were aligned on the outer surfaces of mitochondria. Golgi body equivalents were observed throughout the subapical region and appeared as inflated cisternae of varying shapes and electron opacities. Relationships to other basidiomycetous hyphal tip cells are discussed.Abbreviations AV apical vesicle - C Celsius - diam diameter - f filasome - G Golgi body equivalent - h hour - nm nanometer - M mitochondria - ME membranous elements; min minute - MV microvesicle - MVB multivesicular body - N nucleus - OsO₄ osmium tetroxide - R ribosome - ER endoplasmic reticulum - S Spitzenkörper - Va vacuole - m micrometer     

Ultrastructural immunolocalization of actin in a fungus

Summary We have successfully localized fungal actin for the first time using immuno-electron microscopy and hyphal tips of the rice blast pathogenMagnaporthe grisea. Following ultrarapid freezing, samples were processed in a novel substitution fluid of 10% acrolein in anhydrous ethanol and embedded in LR White resin. A monoclonal anti-actin antibody, previously shown to recognizeM. grisea actin, bound specifically to filasomes concentrated in the peripheral cytoplasm of subapical regions, and to the core-region of the Spitzenkörper.Abbreviations IEM immuno-electron microscopy - TEM transmission electron microscopy     

Microfilaments in the preprophase band of freeze substituted tobacco root cells

Summary The organization and distribution of microfilaments (MFs) in the preprophase bands (PPBs) of tobacco (Nicotiana tabacum L. var. Maryland Mammoth) root tip cells were studied with high pressure freezing and freeze-substitution methods. MFs were present predominantly as single filaments interspersed among microtubules (MTs) throughout the PPB. Some MFs appeared to be associated with MTs, whereas others were not. This is the first time that MFs have been demonstrated in the PPB at the electron microscope level.     

Foundations of vectorial metabolism and osmochemistry

Chemical transformations, like osmotic translocations, are transport processes when looked at in detail. In chemiosmotic systems, the pathways of specific ligand conduction are spatially orientated through osmoenzymes and porters in which the actions of chemical group, electron and solute transfer occur as vectorial (or higher tensorial order) diffusion processes down gradients of total potential energy that represent real spatially-directed fields of force. Thus, it has been possible to describe classical bag-of-enzymes biochemistry as well as membrane biochemistry in terms of transport. But it would not have been possible to explain biological transport in terms of classical transformational biochemistry or chemistry. The recognition of this conceptual asymmetry in favour of transport has seemed to be upsetting to some biochemists and chemists; and they have resisted the shift towards thinking primarily in terms of the vectorial forces and co-linear displacements of ligands in place of their much less informative scalar products that correspond to the conventional scalar energies. Nevertheless, considerable progress has been made in establishing vectorial metabolism and osmochemistry as acceptable biochemical disciplines embracing transport and metabolism, and bioenergetics has been fundamentally transformed as a result.     

Effects of DNA binding and metal substitution on the dynamics of the GAL4 DNA-binding domain as studied by amide proton exchange.

Backbone amide proton exchange rates in the DNA-binding domain of GAL4 have been determined using 1H-15N heteronuclear correlation NMR spectroscopy. Three forms of the protein were studied-the native Zn-containing protein, the Cd-substituted protein, and a Zn-GAL4/DNA complex. Exchange rates in the Zn-containing protein are significantly slower than in the Cd-substituted protein. This shows that Cd-substituted GAL4 is destabilized relative to the native Zn-containing protein. Upon DNA binding, global retardation of amide proton exchange with solvent was observed, indicating that internal fluctuations of the DNA-recognition module are significantly reduced by the presence of DNA. In all forms of the protein, the internal dyad symmetry of the DNA-recognition module of GAL4 is reflected by the backbone amide proton exchange rates.