Ambidentate coordination of isonitrosoacetylacetone imines in their nickel(II) and palladium(II) complexes

Nickel(I1) and palladium(I1) complexes of the types Ni(R-IAI)(IAI'), Pd(IAI)(IAI'), and Pd(R-IAI), , where IAI and IAI' represent isonitrosoacetylacetone imine and R-IAI represents its Aralkyl derivative, have been prepared. The molar conductance, molecular weight, magnetic moment, and ir, pmr, and electronic spectra of these com- plexes have been studied. It is suggested that the isonitroso group of R-IAI coordinates through the nitrogen and that of IAI' thiough the oxygen in Ni(R-IAI)(IAI'). In Pd(R-IAI), the isonitroso groups of both ligands coordinate through nitrogen while Pd(IAI)(IAI') has a structure similar to that of Ni(R-IAI)(IAI'). The amine- exchange reactions of nickel(I1) and palladium(I1) complexes are discussed and compared on the basis of their structures.

Complexes of lanthanide iodides with 3-methylpyridine-1-oxide

Complexes of lanthanide iodides with 3-methylpyridine-1-oxide of the formula Ln(3-MePyO)8I3.xH2O where x = 0 for Ln = La and Tb, x = 1 for Ln = Pr, and x = 2 for Ln = Nd, Sm, Dy, Yb, and Y have been prepared and characterized by chemical analyses, conductance, infrared, proton nmr, and DTA data. Infrared and proton nmr data have been interpreted in terms of the coordination of the ligand to the metal ion through the oxygen of the N—O group. Proton nmr spectrum of the Yb(III) complex is indicative of a restricted rotation of the pyridine ring about the N—O bond.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.

Crystal structure and semiconductor-metal transition of the quasi-two-dimensional transition metal oxide, La2NiO4

Abstract is not available.

Homogeneous hydrogenations ofα, β-unsaturated compounds using pentacyanocobaltate (II) anion as catalyst system

Hydrogenation of someα, β-unsaturated carbonyl compounds using potassium pentacyanocobaltate (II), K3Co(CN)5, as a homogeneous catalyst has been investigated. Thus, hydrogenation of 1-carvone (I), mesityl oxide (4), 2-cyclohexenone (8) and benzalacetone (6) afforded the corresponding dihydrocompounds. Hydrogenation ofβ-ionone (10) afforded a mixture of theα, β-dihydrocompounds (14) and (15). In all these cases, it was observed that the reaction proceeded to completion only in the presence of added base. Hydrogenation of 5α-androst-l-en-17β-ol-3-one acetate (19) afforded the saturated compound, 5α-androst-17β-ol-3-one (20) in 60% yield. It was found that other steroid enones and dienones were not reduced by this catalyst system.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

Komplexe von Lanthanidnitraten mit 2-Methylpyridin-1-oxid

Complexes of lanthanide nitrates with 2-methylpyridine-1-oxide of the formuleLn(2-MePyO)3(NO3)3 whereLn=Nd, Sm, Tb, Dy and Yb and La(2-MePyO)3(NO3)3·2H2O have been prepared and characterized by chemical analyses, IR spectral, conductance andDTA data. IR spectral data have been interpreted in terms of the coordination of the ligand to the metal through the oxygen of the N–O group. Conductance and IR spectral data show that all the nitrate groups are bidentate and that two of the nitrate groups are bound to the metal in a different manner than the other.

Activities of daily living in children with developmental coordination disorder: Performance, learning, and participation

Background Children with developmental coordination disorder (DCD) face evident motor difficulties in daily functioning. Little is known, however, about their difficulties in specific activities of daily living (ADL). Objective The purposes of this study were: (1) to investigate differences between children with DCD and their peers with typical development for ADL performance, learning, and participation, and (2) to explore the predictive values of these aspects. Design. This was a cross-sectional study. Methods In both a clinical sample of children diagnosed with DCD (n=25 [21 male, 4 female], age range=5-8 years) and a group of peers with typical development (25 matched controls), the children’s parents completed the DCDDaily-Q. Differences in scores between the groups were investigated using t tests for performance and participation and Pearson chi-square analysis for learning. Multiple regression analyses were performed to explore the predictive values of performance, learning, and participation. Results Compared with their peers, children with DCD showed poor performance of ADL and less frequent participation in some ADL. Children with DCD demonstrated heterogeneous patterns of performance (poor in 10%-80% of the items) and learning (delayed in 0%-100% of the items). In the DCD group, delays in learning of ADL were a predictor for poor performance of ADL, and poor performance of ADL was a predictor for less frequent participation in ADL compared with the control group. Limitations A limited number of children with DCD were addressed in this study. Conclusions This study highlights the impact of DCD on children’s daily lives and the need for tailored intervention.

Development and psychometric properties of the DCDDaily: a new test for clinical assessment of capacity in activities of daily living in children with developmental coordination disorder

Objective To develop the DCDDaily, an instrument for objective and standardized clinical assessment of capacity in activities of daily living (ADL) in children with developmental coordination disorder (DCD), and to investigate its usability, reliability, and validity. Subjects Five to eight-year-old children with and without DCD. Main measures The DCDDaily was developed based on thorough review of the literature and extensive expert involvement. To investigate the usability (assessment time and feasibility), reliability (internal consistency and repeatability), and validity (concurrent and discriminant validity) of the DCDDaily, children were assessed with the DCDDaily and the Movement Assessment Battery for Children-2 Test, and their parents filled in the Movement Assessment Battery for Children-2 Checklist and Developmental Coordination Disorder Questionnaire. Results 459 children were assessed (DCD group, n = 55; normative reference group, n = 404). Assessment was possible within 30 minutes and in any clinical setting. For internal consistency, Cronbach’s α = 0.83. Intraclass correlation = 0.87 for test–retest reliability and 0.89 for inter-rater reliability. Concurrent correlations with Movement Assessment Battery for Children-2 Test and questionnaires were ρ = −0.494, 0.239, and −0.284, p < 0.001. Discriminant validity measures showed significantly worse performance in the DCD group than in the control group (mean (SD) score 33 (5.6) versus 26 (4.3), p < 0.001). The area under curve characteristic = 0.872, sensitivity and specificity were 80%. Conclusions The DCDDaily is a valid and reliable instrument for clinical assessment of capacity in ADL, that is feasible for use in clinical practice.

Lanthanide coordination in dimethyl sulphoxide and antipyrine complexes of rare earth nitrates

Abstract is not available.

Pyridine-1-oxide complexes of lanthanide iodides

Pyridine-1-oxide complexes of lanthanide iodides of the formulaLn(PyO)8I3 whereLn=La, Pr, Nd, Tb, Dy, Er, and Yb have been prepared and characterised by analyses, molecular weight, conductance, infrared and proton NMR data. Proton NMR and IR data have shown the coordination of the ligand to the metal through the oxygen atom of the N–O group. NMR data have been interpreted in terms of a distorted square antiprismatic geometry in solution.

Metal-insulator transition of naxwo3 studied by angle-resolved photoemission spectroscopy

The electronic structure of sodium tungsten bronzes NaxWO3 is investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The ARPES spectra measured in both insulating and metallic phases of NaxWO3 reveals the origin of metal-insulator transition (MIT) in sodium tungsten bronze system. It is found that in insulating NaxWO3 the states near the Fermi level (E-F) are localized due to the strong disorder caused by the random distribution of Na+ ions in WO3 lattice. Due to the presence of disorder and long-range Coulomb interaction of conduction electrons, a soft Coulomb gap arises, where the density of states vanishes exactly at E-F. In the metallic regime the states near E-F are populated and the Fermi level shifts upward rigidly with increasing electron doping (x). Volume of electron-like Fermi surface (FS) at the Gamma(X) point of the Brillouin zone gradually increases with increasing Na concentration due to W 5d t(2g) band filling. A rigid shift of the Fermi energy is found to give a qualitatively good description of the Fermi surface evolution. As we move from bulk-sensitive to more surface sensitive photon energy, we found the emergence of Fermi surfaces at X(M) and M(R) point similar to the one at the Gamma(X) point in the metallic regime, suggesting that the reconstruction of surface was due to rotation/deformation of WO6 octahedra.

Photocytotoxic 3d-Metal Scorpionates with a 1,8-Naphthalimide Chromophore Showing Photoinduced DNA and Protein Cleavage Activity

Ternary 3d-metal complexes of formulation [M(Tp(Ph))(py-nap)](ClO4)(1-3), where M is Co(II) (1), Cu(II) (2), and Zn(II) (3); Tp(Ph) is anionic tris (3-phenylpyrazolyl)borate; and py-nap is a pyridyl ligand with a conjugated 1,8-naphthalimide moiety, have been prepared from the reaction of metal perchlorate with KTp(Ph) and py-nap in CH2Cl2. The complexes have been characterized from analytical and physicochemical data. The complexes are stable in solution as evidenced from the electrospray ionization mass spectrometry data. The complexes show good binding propensity with calf thymus (CT) DNA, giving binding constant (K-b) values of similar to 10(5) M-1 and a molecular ``light-switch'' effect that results in an enhancement of the emission intensity of the naphthalimide chromophore on binding to CT DNA. The complexes do not show any hydrolytic cleavage of DNA. They show poor chemical nuclease activity in the presence of 3-mercaptopropionic acid or hydrogen peroxide (H2O2). The Co(II) and Cu(II) complexes exhibit oxidative pUC19 DNA cleavage activity in UV-A light of 365 rim. The Zn(II) complex shows moderate DNA photocleavage activity at 365 nm. The Cu(II)complex 2 displays photoinduced DNA cleavage activity in red light of 647.1 nm and 676 rim and near-IR light of >750 rim. A mechanistic studyin UV-A and visible light suggests the involvement of the hydroxyl radical as the reactive species in the DNA photocleavage reactions. The complexes also show good bovine serum albumin (BSA) protein binding propensity, giving K-BSA values of similar to 10(5) M-1. Complexes 1 and 2 display significant photoinduced BSA cleavage activity in UV-A light. The Co(II) complex 1 shows a significant photocytotoxic effect in HeLa cervical cancer cells on exposure to UV-A light of 365 nm, giving an IC50 value of 32 mu M. The IC50 value for the py-nap ligand alone is 41.42 mu m in UV-A light. The IC50 value is >200 mu M in the dark, indicating poor dark toxicity of 1. The Cu(II) complex 2 exhibits moderate photocytotoxicity and significant dark toxicity, giving IC50 values of 18.6 mu m and 29.7 mu m in UV-A light and in the dark, respectively.

Synthesis of a one-dimensional coordination polymer containing pendant hydrosulfide groups

In view of the recent interest in compounds containing M-SH units, an organotin hydrosulfide compound, Me2Sn(SH)(O2CMe) (1) was prepared by controlled hydrolysis of the diorganotin thioacetate. Under similar mild hydrolytic conditions the corresponding benzoate could not be isolated. Instead, the thiobenzoate complex, Me2Sn(SOCPh)(2) (3) was obtained in excellent yields indicating that there was no hydrolysis. Both 1 and 3 were characterized by X-ray crystallography. Some properties of the polymeric compound 1, such as spectral, electrical conductivity and NLO response were also studied. The reactivity and properties were explained using density functional calculations.