Studies on 3,5-diaminopyrazole derivatives

The behaviour of 3,5-diamino-4-phenylazopyrazole toward a variety of reagents is reported. Several new 3,5-diaminopyrazole derivatives as well as amino derivatives of fused pyrazoles have been prepared.

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Untersuchungen an 3,5-Diaminopyrazol-Derivaten

Zusammenfassung Es wird über das Verhalten von 3,5-Diamino-4-phenylazopyrazol gegenüber verschiedenen Agentien berichtet. Es wurden sowohl einige neue 3,5-Diaminooyrazol-Derivate als auch einige Aminoderivate von kondensierten Pyrazolen dargestellt.

     

Control of the morphology of linear and cyclic PS-b-PI block copolymer micelles via PS addition

We have studied the effect of polystyrene (PS) homopolymer addition on the morphology of self-assembled block copolymer micelles made from linear or cyclic poly(styrene-b-isoprene), PS-b-PI, in a selective solvent for the PI block (heptane). Both copolymers have the same composition: the degree of polymerization is 290 for the PS block, and 110 for the PI block, and we focused on the influence of the addition of small amounts of PS homopolymer on the micellar morphology. For the copolymer concentrations considered, the linear copolymer self-organizes into spherical micelles while the cyclic copolymer forms cylindrical micelles. PS and PI chains constitute the core and the corona of these micelles, respectively, due to the different affinity of the blocks for heptane. Consequently, the PS homopolymer added is "solubilized" into the micellar core. Dynamic light scattering (DLS) data combined with atomic force microscopy (AFM) results show that the addition of PS homopolymer induces a drastic change in the micellar organization. Indeed, a morphological transition, from spheres to cylinders for the linear copolymer, and from cylinders to vesicles for the cyclic copolymer, is observed. These results highlight the fact that a small incorporation of PS homopolymer is clearly sufficient to modify the morphology (size and shape) of the micelles. This approach could be a key parameter for the design/control of micelles for specific applications in nanotechnology.     

Vibrational spectra and structure of CH3Cl:NO complex: IR matrix isolation and DFT study

Infrared spectra of the CH(3)Cl:NO complex isolated in solid neon have been investigated. Most of the vibrational modes of the complex have been detected. The weak interaction between NO and CH(3)Cl in CH(3)Cl:NO is responsible for small shifts of the vibrational mode frequencies of both CH(3)Cl and NO molecules. The measured shifts range between -3.2 and + 3.8 cm(-1). On the basis of DFT calculations, different geometries have been explored for the complex, and it has been shown that the most stable structure is of C(1) symmetry. The calculated frequency shifts match well the experimental data.     

Dioxomolybdenum(VI) and dioxotungsten(VI) complexes supported by an amido ligand

Stepwise addition of one equivalent of n-butyllithium and trimethylsilyl chloride to 2-tert-butylmercaptoaniline affords the new ligand 1-(Me3SiNH)-2-(t-BuS)C6H4 (LH), that reacts with one equivalent of butyllithium to its lithium salt LLi. Dioxodichloromolybdenum [MoO2Cl2] and dioxodichlorotungsten dimethoxyethane [WO2Cl2(dme)] react in tetrahydrofuran solution at low temperature with two equivalents LLi to monomeric dioxomolybdenum(VI) [MoO2L2] (1) and dioxotungsten(VI) complex [WO2L2] (2) employing two bidentate amido thioether ligands. The crystallographic determination of the molecular structures of 1 and 2 show evidence for M...S contacts. The reaction of [MoO2Cl2] with LLi in tetrahydrofuran solution at room temperature leads next to 1 to two compounds where silyl group migration from nitrogen to oxygen atoms occurs forming [Mo(=NL')2(OSiMe)2] (3) and [Mo(=NL')2(OSiMe3)L] (4, L' = N-2-t-BuSC6H4) as determined by NMR spectroscopy. Compound 4 was isolated in low yield and its molecular structure determined by X-ray crystallography. Higher yields of a bisimido complex can be obtained by the direct reaction of one equivalent of LLi with [Mo(NAr)2Cl2(dme)] (Ar = 2,6-Me2C6H4) forming [Mo(NAr)2LCl] (5).     

PAMAM dendrimers for efficient siRNA delivery and potent gene silencing

Genuine, nondegraded PAMAM dendrimers self-assemble with siRNA into nanoscale particles that are efficient for siRNA delivery and induce potent endogenous gene silencing.     

Vibrational spectra and structures of H2O-NO, HDO-NO, and D2O-NO complexes. An IR matrix isolation and DFT study

The IR spectra of H2O+NO, HDO+NO, and D2O+NO, isolated in solid neon at low temperature have been investigated. Concentration effects and detailed vibrational analysis of deuterated and partially deuterated species allowed identification of three 1:1 HDO-NO species, two 1:1 D2O-NO species, and only one 1:1 H2O-NO complex. From comparison between the experimental spectra and the results of DFT calculations, it appeared that two different types of weakly bound complexes between water and nitric oxide can be formed in a neon matrix. The first species is a 1:1 complex where bonding occurs between water hydrogen and nitric oxide nitrogen, in which OH-N and OD-N intermolecular bonds are engaged. For this complex only DOD-NO, HOD-NO, and DOH-NO isotopic species have been experimentally detected and no IR bands of HOH-NO were observed. This result could be explained by the fact that the dissociation energy of HOH-NO is lower than those of DOD-NO, HOD-NO and DOH-NO. For the second detected 1:1 H2O-NO complex and its isotopic variants, the H2O-NO potential surface was explored systematically at the B3LYP level, but no stable species corresponding to the complex could be calculated. The structure of the second observed 1:1 H2O-NO complex results from columbic attractions between water and nitric oxide and could be stabilized only in matrix, probably by interaction between NO, water and (Ne)n.     

Frequency polygons for continuous random fields

We study the frequency polygon investigated by Scott (J Am Stat Assoc 80: 348–354, 1985) as a nonparametric density estimate for a continuous and stationary real random field \({\left( X_{\mathbf{t}},\mathbf{t}\in\mathbb{R}^{N}\right)}\). We establish the asymptotic expressions for the integrated pointwise squared bias and the integrated pointwise squared variance of the estimate when the field is observed over a rectangular domain of \({\mathbb{R}^{N}}\). Under mild mixing conditions, we show that the estimate achieves the same rate of convergence to zero of the integrated mean squared error as kernel estimators and it can also attain the optimal uniform strong rate of convergence \({\left(\widehat{\mathbf{T}}^{-1} \log \widehat{\mathbf{T}}\right)^{1/3}}\) for appropriate choices of the bin widths.     

Isometric Equivalence of Integration Operators

We are interested in the isometric equivalence problem for the Cesàro operator C(f) (z) = \frac1z ò₀^zf(x) \frac11-xd x{C(f) (z) =\frac{1}{z} \int_{0}^{z}f(\xi) \frac{1}{1-\xi}d \xi} and an operator T_g(f)(z)=\frac1zò₀^zf(x) g^￠(x) d x{T_{g}(f)(z)=\frac{1}{z}\int_{0}^{z}f(\xi) g^{\prime}(\xi) d \xi}, where g is an analytic function on the disc, on the Hardy and Bergman spaces. Then we generalize this to the isometric equivalence problem of two operators T_g1{T_{g_{1}}} and T_g2{T_{g_{2}}} on the Hardy space and Bergman space. We show that the operators T_g1{T_{g_{1}}} and T_g2{T_{g_{2}}} satisfy T_g1U₁=U₂T_g2{T_{g_{1}}U_{1}=U_{2}T_{g_{2}}} on H ^p , 1 ≤ p < ∞, p ≠ 2 if and only if g₂(z) = lg₁(e^iqz){g_{2}(z) =\lambda g_{1}(e^{i\theta}z) }, where λ is a modulus one constant and U _i , i = 1, 2 are surjective isometries of the Hardy Space. This is analogous to the Campbell-Wright result on isometrically equivalence of composition operators on the Hardy space.     

Bounded-degree polyhedronization of point sets

In 1994 Grünbaum showed that, given a point set S in ${\mathbb{R}}^3$, it is always possible to construct a polyhedron whose vertices are exactly S. Such a polyhedron is called a polyhedronization of S. Agarwal et al. extended this work in 2008 by showing that there always exists a polyhedronization that can be decomposed into a union of tetrahedra (tetrahedralizable). In the same work they introduced the notion of a serpentine polyhedronization for which the dual of its tetrahedralization is a chain. In this work we present a randomized algorithm running in $O(n{\log }^{6}n)$ expected time which constructs a serpentine polyhedronization that has vertices with degree at most 7, answering an open question by Agarwal et al.