Advanced surface functionalization of periodic mesoporous silica: Kinetic control by trisilazane reagents

The surface reactions of mesoporous silica MCM-41 with a series of new trisilylamines (trisilazanes) (SiHMe2)2NSiMe2R and (SiMe2Vin)2NSiMe2R (R = indenyl, norpinanyl, chloropropyl, 3-(N-morpholin)propyl; Vin = vinyl), disilylalkylamine (SiHMe2)iPrNSiMe2(CH2)3Cl, and monosilyldialkylamines Me2NSiMe2R (R = indenyl, chloropropyl, 3-(N-morpholin)propyl) were investigated. 1H, 13C, and 29Si MAS NMR spectroscopy, nitrogen adsorption/desorption, infrared spectroscopy, and model reactions with calix[4]arene as a mimic for an oxo surface were used to clarify the chemical nature of surface-bonded silyl groups. The trisilylamines exhibited a comparatively slow surface reaction, which allowed for the adjustment of the amount of silylated and nonreacted SiOH groups and led to a stoichiometric distribution of surface functionalities. The 2:1 integral ratio of SiHMe2 and SiMe2R moieties of such trisilazanes was found to be preserved on the silica surface as indicated by microanalytical as well as 13C and 29Si MAS NMR spectroscopic data of the hybrid materials. For example, the reaction of MCM-41 with (SiHMe2)2NSiMe2(CH2)3Cl, (SiHMe2)iPrNSiMe2(CH2)3Cl, and Me2NSiMe2(CH2)3Cl provided bi- and monofunctional hybrid materials with one-third, one-half, or all chemically accessible silanol groups derivatized by chloropropyl groups, respectively. Thus, a molecular precursor strategy was developed to efficiently control the relative amount of three different surface species, SiHMe2 (or SiVinMe2), SiMe2R, and SiOH, in a single reaction step. The reaction behavior of indenyl-substituted monosilazanes and trisilazanes (R = Ind) with calix[4]arene proved that the indenyl substituent can act as a leaving group forming a dimethylsilyl species, which is anchored bipodally on the silica surface, that is, via two Si-O bonds.     

Molecular interaction in some polymeric additive solutions containing styrene-hydrogenated butadiene copolymer

The miscibility of styrene-hydrogenated butadiene copolymer (SHB) with different constituents of polymer additives for lubricating mineral oils was studied in dilute solution regime, using xylene as model solvent, at 30 °C, in a wide range of polymer blend compositions. The systems studied were SHB/poly(ethylene-co-propylene) (EPC), SHB/poly(methyl methacrylate) (PMMA), SHB/poly(dodecyl methacrylate) (PDDMA) and SHB/polystyrene (PS). The viscometric interaction parameters were calculated according to the Krigbaum–Wall and Catsiff–Hewett models of ideal viscometric behavior. Strong repulsive interactions were found in SHB/PMMA and SHB/PDDMA systems pointing to immiscibility. SHB/EPC and SHB/PS deviated much less from ideality. The results were compared to the theoretical estimation of interaction in polymer blends in the absence of solvent, using the Coleman–Graf–Painter approach. No correlation was observed between the interaction in the bulk and in solution.     

Heteronuclear and homonuclear high-spin alkali trimers on helium nanodroplets

The electronic excitation spectra of all possible homo- and heteronuclear high-spin (quartet) trimers of K and Rb (KxRb(3-x), x=0...3) assembled on the surface of superfluid helium droplets, are measured in the spectral range from 10,600 to 17,400 cm(-1). A regular series of corresponding bands is observed, reflecting the similar electronic structure of all these trimers. For the assignment and separation of overlapping bands, we determine x directly, with mass-selected beam depletion, and indirectly with a V-type double-resonance scheme. The assignment is confirmed by high-level ab initio calculations of the electronic structure of the bare trimers. The level structure is rationalized in terms of harmonic-oscillator states of the three valence electrons in a quantum-dot-like confining potential. We predict that three should be a magic number for high-spin alkali clusters.     

Harnack Inequalities for some Lévy Processes

In this paper we prove Harnack inequality for nonnegative functions which are harmonic with respect to random walks in ℝ ^d . We give several examples when the scale invariant Harnack inequality does not hold. For any α ∈ (0,2) we also prove the Harnack inequality for nonnegative harmonic functions with respect to a symmetric Lévy process in ℝ ^d with a Lévy density given by $c|x|^{-d-\alpha}1_{\{|x|\leq 1\}}+j(|x|)1_{\{|x|>1\}}$c|x|^{-d-\alpha}1_{\{|x|\leq 1\}}+j(|x|)1_{\{|x|>1\}}, where 0 ≤ j(r) ≤ cr ^{− d − α} , ∀ r > 1, for some constant c. Finally, we establish the Harnack inequality for nonnegative harmonic functions with respect to a subordinate Brownian motion with subordinator with Laplace exponent ϕ(λ) = λ ^α/2ℓ(λ), λ > 0, where ℓ is a slowly varying function at infinity and α ∈ (0,2).     

Hydrogen‐bonding and C—H⋯π interactions in 7‐hydroxy‐3‐methoxy‐4‐methyl‐5,6,7,8‐tetrahydro­pyrido­[1,2‐c]pyrimidin‐1(9H)‐one

In the title compound, C₁₀H₁₄N₂O₃, a pyrimidine ring is fused with a piperidine ring. The pyrimidine ring is planar, whereas the piperidine ring adopts a half‐chair conformation. The molecules of the title compound are connected via O—H⋯O intermolecular hydrogen bonds into infinite zigzag chains. The pyrimidine ring is involved in three C—H⋯π interactions, which link the hydrogen‐bonded chains into a three‐dimensional framework.     

A novel non photochemical ring contraction of 4-pyrones to cyclopent-2-enones

Unlike comenic acid or most other 4-pyrones, methyl or ethyl comenate reacts with aromatic amines under mild conditions in the sense of ring contraction to 3-arylamino-2,4-dihydroxy-2-cyclopentenone-4-carboxylates. The structure of the new cyclopentenone derivatives were determined from their characteristic spectroscopic behaviour and was confirmed by X-ray crystallographic studies of compound Vb .     

Pion photoproduction and T> versus < analog states in N>Z nuclei

The T_> and T_< components of giant resonance levels in N>Z nuclei cannot be unambiguously identified in photonuclear reactions. In charged pion photoproduction, their analogs may be so identified (at least for the spinflip levels), as illustrated here with a ¹³C target.