Experimental and quantum-chemical studies of 1H, 13C and 15N NMR coordination shifts in Pd(II) and Pt(II) chloride complexes with methyl and phenyl derivatives of 2,2'-bipyridine and 1,10-phenanthroline

1H, 13C and 15N NMR studies of platinide(II) (M=Pd, Pt) chloride complexes with methyl and phenyl derivatives of 2,2'-bipyridine and 1,10-phenanthroline [LL=4,4'-dimethyl-2,2'-bipyridine (dmbpy); 4,4'-diphenyl-2,2'-bipyridine (dpbpy); 4,7-dimethyl-1,10-phenanthroline (dmphen); 4,7-diphenyl-1,10-phenanthroline (dpphen)] having a general [M(LL)Cl2] formula were performed and the respective chemical shifts (delta1H, delta13C, delta15N) reported. 1H high-frequency coordination shifts (Delta1Hcoord=delta1Hcomplex-delta1Hligand) were discussed in relation to the changes of diamagnetic contribution in the relevant 1H shielding constants. The comparison to literature data for similar [M(LL)(XX)], [M(LL)X2] and [M(LL)XY] coordination or organometallic compounds containing various auxiliary ligands revealed a large dependence of delta1H parameters on inductive and anisotropic effects. 15N low-frequency coordination shifts (Delta15Ncoord=delta 15Ncomplex-delta15Nligand) of ca 88-96 ppm for M=Pd and ca 103-111 ppm for M=Pt were attributed to both the decrease of the absolute value of paramagnetic contribution and the increase of the diamagnetic term in the expression for 15N shielding constants. The absolute magnitude of Delta15Ncoord parameter increased by ca 15 ppm upon Pd(II)-->Pt(II) transition and by ca 6-7 ppm following dmbpy-->dmphen or dpbpy-->dpphen ligand replacement; variations between analogous complexes containing methyl and phenyl ligands (dmbpy vs dpbpy; dmphen vs dpphen) did not exceed+/-1.5 ppm. Experimental 1H, 13C, 15N NMR chemical shifts were compared to those quantum-chemically calculated by B3LYP/LanL2DZ+6-31G**//B3LYP/LanL2DZ+6-31G*, both in vacuo and in DMSO or DMF solution.     

Dialkylaminopyridine-functionalized mesoporous silica nanosphere as an efficient and highly stable heterogeneous nucleophilic catalyst

A new nucleophilic catalytic system comprised of dialkylaminopyridine-functionalized mesoporous silica nanosphere (DMAP-MSN) has been synthesized and characterized. We have demonstrated that this material is an efficient heterogeneous catalyst for Baylis-Hillman, acylation, and silylation reactions with good reactivity, product selectivity, and recyclability. We envision that this DMAP-functionalized mesoporous silica material can also serve as an effective heterogeneous catalyst for many other catalytic nucleophilic reactions.     

Remarkable influence of surface composition and structure of oxidized iron layer on orange I decomposition mechanisms

Although the decomposition of water pollutants in the presence of metallic iron is known, the reaction pathways and mechanisms of the decomposition of azo-dyes have been meagerly investigated. The interface phenomena taking place during orange I decomposition have been investigated with the use of infrared external reflection spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The studies presented in this paper establish that there are close relationships between the composition and structure of the iron surface oxidized layers and the kinetics and reaction pathway of orange decomposition. The influence of the molecular structure of azo-dye on the produced intermediates was also studied. There are remarkable differences in orange I decomposition between pH 3 and pH 5 at 30 degrees C. Decomposition at pH 3 is very fast with pseudo-first-order kinetics, whereas at pH 5 the reaction is slower with pseudo-zero-order kinetics. At pH 3, only one amine, namely 1-amino-4-naphthol, was identified as an intermediate that undergoes future decomposition. Sulfanilic acid, the second harmful reduction product, was not found in our studies. At pH 3, the iron surface is covered only by a very thin layer of polymeric Fe(OH)(2) mixed with FeO that ensures orange reduction by a combination of an electron transfer reaction and a catalytic hydrogenation reaction. At pH 5, the iron surface is covered up to a few micrometers thick, with a very spongy and porous layer of lepidocrocite enriched in Fe(2+) ions, which slows the electron transfer process. The fastest decomposition reaction was found at a potential near -300 mV (standard hydrogen electrode). An addition of Fe(2+) ions to solution, iron preoxidation in water, or an increase of temperature all result in an increasing decomposition rate. There is no single surface product that would inhibit the decomposition of orange. This information is crucial to perform efficient, clean and low cost waste water treatment. The findings presented here make the treatment of wastewater in the presence of metallic iron a very promising solution.     

Naravelia zeylanica [corrected] occurrence of primary benzamides in flowering plants

Extract of Naravelia zeylanica (Ranunculaceae) yielded three simple benzamides, 3,4-methylenedioxybenzamide, 4-methoxybenzamide and 4-hydroxy-3-methoxybenzamide. These simple C6C1 metabolites have been encountered as natural products for the first time. The compounds were identified by direct comparison of their spectral (1H- and 13C-NMR) and chromatographic (GCMS) data with those of authentic samples. Authentic 4-hydroxy-3-methoxybenzamide was synthesized in one step by treatment of 4-hydroxy-3-methoxybenzonitrile with sodium perborate. Authentic 3,4-methylenedioxybenzamide was synthesized from the corresponding acid.     

Photoinduced intramolecular charge transfer to meta position of benzene ring in 6-aminophthalides

Substitution of non-fluorescent phthalide (Pd) with amino group at meta (6) position in relation to the electron-accepting part of the lactone ring completely changes Pd photophysics: a new long-wavelength absorption band arises and the molecule becomes highly fluorescent. The experimental data and the analysis of vertical electronic transitions with TDDFT method indicate that the first absorption band in 6-aminophthalides (6-APds) comprises a single CT transition to the S1 state. Almost equal absorption and emission transition dipole moments indicate that S0 <--> S1 transition in all 6-APds is not affected by any mixing with other electronic states, the excited-state vibrational relaxation is not accompanied by significant conformational changes and the Stokes shifts reflect mainly solvation energetics of these molecules. Excited state dipole moments obtained from solvatochromic plots and from CASSCF calculations confirm large charge displacement from amino group towards the meta position of the benzene ring upon excitation of 6-APds to S1 state. Long fluorescence lifetimes and high fluorescence quantum yields demonstrate efficient and stable excited state charge separation in 6-APds. Taken together with sensitivity of 6-APds to polarity and proticity of the environment these properties make them good candidates for fluorescent probes of long-time scale molecular dynamics.     

The behavior on fundamental group of a free pro-homotopy equivalence

We study the question: given a morphism $\text{?{(X}{}_{\mathrm{n}}\text{, x}{}_{\mathrm{n}}\text{)}→{(Y}{}_{\mathrm{n}}\text{, y}{}_{\mathrm{<mtext>n</mtext>}}\text{)}}$ in the category pro-(Poi nted. Homotopy) where the domain and range are inverse sequences of well-pointed CW complexes, and given that ? induces an isomorphism {X_n}→{Y_n} in pro-(Homotopy), what additional hypotheses force ? to be an isomorphism in pro-(Pointed Homotopy)? Conjecture. If the dimensions of the Y_n's are bounded, then ? is an isomorphism in pro-(Pointed Homotopy). We first prove the special case of this conjecture in which dim Y_n?d<∞ for all n, and $\text{lim}\text{{H}{}_{\mathrm{d}}\text{Y}{}_{\mathrm{n}}\text{}≠0}$, Y_n being the universal cover of Y_n. Then we deal with the general case: we show that there are certain elements of each π₁Y_n with the properties: (i) these elements commute if and only if ? is an isomorphism in pro-(Pointed Homotopy); (ii) if dim Y_n?d<∞ for all n, then powers of these elements commute. While (i) and (ii) are not incompatible, this result puts severe restrictions on the nature of any possible counter-example to the conjecture.Our method also gives pro-homotopy analogues of the well-known fact that if a K(π, 1) is N-dimensional, then π is torsion-free and contains no abelian subgroup of rank>N. The latter theorems apply to inverse sequences {Y_n} of CW complexes where dim Y_n is finite but not necessarily bounded, hence in particular to infinite-dimensional shape-aspherical compacta.     

Locally optimal rank tests for independence

The problem of testing the hypothesis of independence against multiparametrical set of alternatives is considered. Rank tests, having some locally maximin property are studied and a certain characterization of these tests is given. Finite sample and asymptotic test statistics in a restricted class of tests are derived.     

Synthesis and Photochemical Properties of Luminescent Eu(III) Complexes with Macrocyclic and Macropolycyclic Ligands Incorporating 3,3′-Biisoquinoline-2,2-dioxide Units

Three novel ligands incorporating two, or three 3,3-biisoquinoline-2,2-dioxide units have been synthesized using modified standard methods of cyclization. These ligands formed photoactive mononuclear complexes with a Eu(III) cation. The ligand with two photoactive units displayed a better quantum yield for the Eu(III) emission (0.064) upon UV excitation than the other two complexes incorporating three units, whose luminescence quantum yields have been estimated to be below 0.01. The luminescence of the Eu(III) complex with two sensitizing units was not stable in aqueous solution, whereas with the two other complexes, their luminescence in solution remained for a couple of days.