Modification of chemical reactivity by cyclodextrins. Observation of moderate effects on Norrish type I and type II photobehavior

The photochemistry and photophysics of organic molecules in organized assemblies are being studied with great interest in order to understand the features controlling the selectivity in the photoreactions brought about by these media.l These studies have paved the way to an intriguing number of possibilities by which photoreactivity can be modified. In this connection, we have investigated the photobehavior of a number of phenyl alkyl ketones and cu,cu-dimethylphenyl alkyl ketones (Scheme I) incorporated in the hydrophobic interior of cyclodextrin cavities.

Mixed ligand complexes in vinyl polymerization-II: [NN-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)Image and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.

Preparation and properties of nickel(II) complex dyes

The preparation and properties of five new dyes derived from nickel(I1) ions and aromatic azo derivatives of ethylenebls(P-ketoesters) are reported.

Mononitrosated and phenylamido substituted chelate linkage isomers of quadridentate Schiff base copper(II) complexes

The nitrosation of monophenylamido substituted quadridentate Schiff base complexes of copper(II) are observed to adopt N-bonded isonitroso coordination whereas the phenylisocyanation of the corresponding mononitrosated quadridentate complexes are found to prefer O-bonded isonitroso coordination.

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)6(ClO4)3. 2H2O (Ln=La, Sm, Dy and Ho); Ln(CyPO)7 (ClO4)3. 2H2O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)5 (ClO4)3. 2H2O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)6 (ClO4)3 (Ln=La, Pr, Nd and Ho); and Ln (CpicO)5 (ClO4)3 (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)6 (ClO4)3 (Ln=La and Nd); Ln(DMPicO)7 (ClO4)3 (Ln=Gd, Er and Yb); and Ln(DMPicO)8 (ClO4)3 (Ln=Dy and Ho).

Iron(II) and iron(III) complexes of 2,4-dithiobiuret

Ferrous and ferric complexes of 2,4-dithiobiuret (Dtb) of the type Fe(Dtb)m Xn where m, n = 1-3, and X = CI–, Br–, I– and SO 4 2– , and a neutral Fe(Dtb-H)2 complex have been synthesized and characterised by elemental analyses, magnetic susceptibility, i.r., electronic and Mössbauer spectroscopic studies. From its i.r. spectrum Dtb was found to act as a S,S-coordinating bidentate chelate. The magnetic moment, electronic and Massbauer spectra are consistent with a low spin distorted octahedral structure for the ferric complexes and a high spin form for ferrous complexes.

Novel role of the nitrite transporter NirC in Salmonella pathogenesis: SPI2-dependent suppression of inducible nitric oxide synthase in activated macrophages

Activation of macrophages by interferon gamma (IFN- ) and the subsequent production of nitric oxide (NO) are critical for the host defence against Salmonella enterica serovar Typhimurium infection. We report here the inhibition of IFN- -induced NO production in RAW264.7 macrophages infected with wild-type Salmonella. This phenomenon was shown to be dependent on the nirC gene, which encodes a potential nitrite transporter. We observed a higher NO output from IFN- -treated macrophages infected with a nirC mutant of Salmonella. The nirC mutant also showed significantly decreased intracellular proliferation in a NO-dependent manner in activated RAW264.7 macrophages and in liver, spleen and secondary lymph nodes of mice, which was restored by complementing the gene in trans. Under acidified nitrite stress, a twofold more pronounced NO-mediated repression of SPI2 was observed in the nirC knockout strain compared to the wild-type. This enhanced SPI2 repression in the nirC knockout led to a higher level of STAT-1 phosphorylation and inducible nitric oxide synthase (iNOS) expression than seen with the wild-type strain. In iNOS knockout mice, the organ load of the nirC knockout strain was similar to that of the wild-type strain, indicating that the mutant is exclusively sensitive to the host nitrosative stress. Taken together, these results reveal that intracellular Salmonella evade killing in activated macrophages by downregulating IFN- -induced NO production, and they highlight the critical role of nirC as a virulence gene.

Self-assembly of a Pd-II neutral molecular rectangle via a new organometallic Pd-2(II) molecular clip and oxygen donor linker

Two components self-assembly of a Pd-4 neutral molecular rectangle driven by Pd-O bond coordination has been achieved and this pi-electron rich rectangle shows fluorescence quenching in presence of nitroaromatics, which are the chemical signatures of many explosives.

Interfacial structure and crystallographic studies of transformations in betat' and beta Cu---Zn alloys-II. martensitic formation of alpha1' plates in beta'

A TEM study of the interphase boundary structure of 9R orthorhombic alpha1' martensite formed in beta' Cu---Zn alloys shows that it consists of a single array of dislocations with Burgers vector parallel to left angle bracket110right-pointing angle beta and spaced about 3.5 nm apart. This Burgers vector lies out of the interface plane; hence the interface dislocations are glissile. Unexpectedly, though, the Burgers vectors of these dislocations are not parallel when referenced to the matrix and the martensite lattices. This finding is rationalized on published hard sphere models as a consequence of relaxation of a resultant of the Bain strain and lattice invariant shear displacements within the matrix phase.

Optimal simultaneous maximum a posterioriestimation of states, noise statistics and parameters II. Numerical performance

A very general and numerically quite robust algorithm has been proposed by Sastry and Gauvrit (1980) for system identification. The present paper takes it up and examines its performance on a real test example. The example considered is the lateral dynamics of an aircraft. This is used as a vehicle for demonstrating the performance of various aspects of the algorithm in several possible modes.

Non-Abelian monopoles break color. II. Field theory and quantum mechanics

Many grand unified theories (GUT's) predict non-Abelian monopoles which are sources of non-Abelian (and Abelian) magnetic flux. In the preceding paper, we discussed in detail the topological obstructions to the global implementation of the action of the "unbroken symmetry group" H on a classical test particle in the field of such a monopole. In this paper, the existence of similar topological obstructions to the definition of H action on the fields in such a monopole sector, as well as on the states of a quantum-mechanical test particle in the presence of such fields, are shown in detail. Some subgroups of H which can be globally realized as groups of automorphisms are identified. We also discuss the application of our analysis to the SU(5) GUT and show in particular that the non-Abelian monopoles of that theory break color and electroweak symmetries.

Magnetic interactions in the oxide systems LaNi1-xMxO3 (M = Cr, Fe, or Co)

Magnetic susceptibilities of several members of the series of oxides of the general formula LaNi1-xMxO3 (M = Cr, Fe, or Co) are reported. The oxides show evidence for interesting ferrimagnetic (Cr and Co) and antiferromagnetic (Fe) interactions.

Dynamics of dense sheared granular flows. Part II. The relative velocity distributions

The distribution of relative velocities between colliding particles in shear flows of inelastic spheres is analysed in the Volume fraction range 0.4-0.64. Particle interactions are considered to be due to instantaneous binary collisions, and the collision model has a normal coefficient of restitution e(n) (negative of the ratio of the post- and pre-collisional relative velocities of the particles along the line joining the centres) and a tangential coefficient of restitution e(t) (negative of the ratio of post- and pre-collisional velocities perpendicular to line joining the centres). The distribution or pre-collisional normal relative velocities (along the line Joining the centres of the particles) is Found to be an exponential distribution for particles with low normal coefficient of restitution in the range 0.6-0.7. This is in contrast to the Gaussian distribution for the normal relative velocity in all elastic fluid in the absence of shear. A composite distribution function, which consists of an exponential and a Gaussian component, is proposed to span the range of inelasticities considered here. In the case of roughd particles, the relative velocity tangential to the surfaces at contact is also evaluated, and it is found to be close to a Gaussian distribution even for highly inelastic particles.Empirical relations are formulated for the relative velocity distribution. These are used to calculate the collisional contributions to the pressure, shear stress and the energy dissipation rate in a shear flow. The results of the calculation were round to be in quantitative agreement with simulation results, even for low coefficients of restitution for which the predictions obtained using the Enskog approximation are in error by an order of magnitude. The results are also applied to the flow down an inclined plane, to predict the angle of repose and the variation of the volume fraction with angle of inclination. These results are also found to be in quantitative agreement with previous simulations.