Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Influence lines for bending under a ring load of a free shell, a shell embedded in a soft medium and a shell containing a soft core

Theoretical expressions for stresses and displacements have been derived for bending under a ring load of a free shell, a shell embedded in a soft medium, and a shell containing a soft core. Numerical work has been done for typical cases with an Elliot 803 Digital Computer and influence lines are drawn therefrom.

Studies in bubble formation — III

Bubble formation from single horizontal orifices submerged in Newtonian liquids has been investigated for such chamber volumes that both the pressure inside the chamber and flow rate into the bubble are time dependent. The data collected show that under these conditions the bubble volume decreases exponentially with increase in orifice submergence. The equations for the generalized two stage model of bubble formation, taking the variation of gas flow rate with time into account, have been derived. These equations reduce to the cases of constant gas flow rate and constant pressure when adequate constraints are imposed. The results obtained under intermediate conditions have been quantitatively explained on the basis of these equations.

Nucleotidases in plants *1, , *2: III. Effect of metabolites on the enzyme hydrolyzing flavine adenine dinucleotide (FAD) from Phaseolus radiatus

The highly purified enzyme from mung bean seedlings hydrolyzing FAD at pH 9.4 and temperature 49 °, functioned with an initial fast rate followed by a second slower rate. The activity was linear with enzyme concentration over a small range of concentration and was dependent on the time of incubation. Inhibition of enzyme activity with increasing concentrations of AMP was sigmoid;concentrations less than 1 × 10−6 M were without effect, concentrations between 1 × 10−6 and 8 × 10−5 M inhibited by 20% and concentrations beyond 8 × 10−5 Image caused progressive inhibition. Concentrations beyond 1 × 10−3 Image inhibited the activity completely. Preincubation of the enzyme with PCMB or NEM, or aging, or reversible denaturation with urea abolished the inhibitory effect of AMP at concentrations lower than 8 × 10−6 Image . The aged enzyme could be reactivated by ADP.

Interrelations of micro-organisms and mulberry III. The beneficial influence of certain heterotrophs on the nitrifiers in rhizosphere

Evidence has been presented to show that the autotrophic nitrifying organisms get stimulated in the mulberry rhizosphere. Three species of Pseudomonas, one each of Achromobacter and Bacillus capable of degrading methionine were shown to be stimulated in the rhizosphere. These bacteria were capable of reversing the inhibitory effect of methionine on soil nitrification. Two of them were able to form nitrite from methionine. The possibility that the increased nitrifying activity in the mulberry rhizosphere in the presence of methionine found in mulberry root exudations was the result of the activity of these organisms was suggested.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Dimethyl sulphoxide and dimethyl formamide complexes of Mn(III) perchlorate

Dimethyl sulphoxide (DMSO) and dimethyl formamide (DMF) complexes of Mn(III) perchlorate have been prepared and their conductivity, magnetic susceptibility and i.r. and electronic spectra studied. The complexes behave as uni-trivalent electrolytes in acetonitrile. Their magnetic moments of 5·1 B.M. show them to be of high spin type. Infra-red spectra show that oxygen is the donor atom in both complexes. The spin allowed electronic transition for d4 system, around 20,000 cm−1, ascribable to the 5Eg → 5T2g transition, suggests an octahedral configuration for these complexes

Metabolism of Plasmodium bergheistar, open: III. Carbon dioxide fixation and role of pyruvate and dicarboxylic acids

Formation of C4 dicarboxylic acids in Plasmodium berghei by carbon dioxide fixation reaction has been demonstrated by the use of labeled NaH14CO3. The reactions require glucose, which may be required not only as an energy source but also to contribute to the formation of pyruvate in the process of carbon dioxide fixation. Intracellular concentration of pyruvate may play an important role in the metabolism of P. berghei; an increased intracellular level of pyruvate seems to be a prerequisite before some of these reactions could be detected. The distribution of the label indicates extensive randomization of amino acids and suggests an extensive cycling of the amino acid and organic acid pools of the parasites. This investigation formed part of the thesis submitted in 1965 for the doctoral degree at the Indian Institute of Science, Bangalore 12, India, and was supported in part by the Council of Scientific and Industrial Research, India.

A novel fibre-coated sorbent for rapid removal of heavy metals from wastewater. Sorption of Zinc(II) from dilute aqueous solutions in the presence of high concentrations of common salts

The commercial acrylic fibre "Cashmilon" was partially hydrolyzed to convert a fraction of its nitrile (-CN) groups to carboxylic acid (-COOH) groups and then coated with polyethylenimine (PEI) resin and cross-linked with glutaraldehyde to produce a novel gel-coated fibrous sorbent with multiple functionalities of cationic, anionic and chelating types, and significantly faster sorption kinetics than bead-form sorbents. The sorption properties of the fibrous sorbent were measured using Zn(II) in aqueous solution as the sorbate to determine the effects of pH and the presence of common ions in the solution on the sorption capacity. The rate of sorption on the gel-coated fibre was measured in comparison with that on Amberlite IRA-68 weak-base resin beads, to demonstrate the marked difference between fibre and bead-form sorbents in their kinetic behaviour.

Ring loading of a long, thin, circular cylindrical shell enclosing a soft, solid core: A recalculation by the love function method of elasticity.

The problem is solved using the Love function and Flügge shell theory. Numerical work has been done with a computer for various values of shell geometry parameters and elastic constants.

Temperature dependence of g values in tetragonal ionic Cu++ salts

A temperature dependence has been observed in the spin-Hamiltonian parameters of the Cu++ ion in a tetragonal crystal field and the variation has been interpreted in terms of vibronic effects.

Reactions of tetrahalogeno-1,2-benzoquinones. Part III. Reaction of tetrachloro-1,2-benzoquinone with tetralones and naphthols: Pathway to the condensates

With a view to understanding the mechanism of the formation of 6-methoxy-2,2-(tetrachloro--phenylenedioxy)-naphthalen-1 (2H)-one (IIIa) in the reaction of 6-methoxy-1-tetralone (Ia) with tetrachloro-1,2-benzoquinone (II), the reaction of (II) with various tetralones and naphthols has been studied. Reaction with either α-tetralone or α-naphthol gives 2,2-(tetrachloro-o-phenylenedioxy)naphthalen-1 (2H)-one (IIIb), whereas reaction with either β-tetralone or β-naphthol gives a mixture of (IIIb) and ,1-(tetrachloro-o-phenylenedioxy)-naphthalen-2 (1H)-one (IX), with the former predominating. Further, reactions of (II) with 7-methoxy-3,4-dihydrophenanthren- 1 (2H)-one and m-methoxyphenol gave respectively 7-methoxy- ,2-(tetrachloro-o- phenylenedioxy)phenanthren-1 (2H)-one (VII) and 3-methoxy-6,6-(tetrachloro-o- phenylenedioxy)cyclohexa-2,4-dien-1-one (VIII). Structures of all these compounds have been proved on the basis of i.r. and n.m.r. data. The pathway to the formation of the condensates (III) is discussed.