Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating

In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g^?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.     

Stacking Gaussian processes to improve $$pK_a$$ p K a predictions in the SAMPL7 challenge

Journal of Computer-Aided Molecular Design - Accurate predictions of acid dissociation constants are essential to rational molecular design in the pharmaceutical industry and elsewhere. There has...     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Eine Schwefelbestimmungsmethode von allgemeiner Anwendbarkeit

Ohne Zusammenfassung     

Gray code for derangements

We give a Gray code and constant average time generating algorithm for derangements, i.e., permutations with no fixed points. In our Gray code, each derangement is transformed into its successor either via one or two transpositions or a rotation of three elements. We generalize these results to permutations with number of fixed points bounded between two constants.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Fluorination of diamond — C4F9I and CF3I photochemistry on diamond (100)

The radiation-induced decomposition of C₄F₉I and CF₃I overlayers at 119 K on diamond (100) surfaces has been shown to be an efficient route to fluorination of the diamond surface. X-ray photoelectron spectroscopy has been used for photoactivation as well as for studying the photodecomposition of the fluoroalkyl iodide molecules, the attachment of the photofragments to the diamond surface, and the thermal decomposition of the fluoroalkyl ligands. Measured chemical shifts agree well with ab initio calculations of both C 1s and F 1s binding energies. It is found that chemisorbed CF₃ groups on diamond (100) decompose by 300 K whereas C₄F₉ groups decompose over the range 300 to 700 K and this reactivity difference is rationalized on steric grounds. Both of these thermal decomposition processes produce surface C---F bonds on the diamond. The surface C---F species thermally decompose over a wide temperature range extending up to 1500 K. Hydrogen passivation of the diamond surface is ineffective in preventing free radical attack from the photodissociated products of the fluoroalkyl iodides; I atoms produced photolytically abstract H from surface C---H bonds to yield hydrogen iodide at 119 K allowing diamond fluorination. The attachment of chemisorbed F species to the diamond (100) surface causes band bending as the surface states are occupied as a result of chemisorption. This results in a shift to higher binding energy of the diamond-related C 1s levels present in the surface and subsurface regions which are sampled by XPS on the diamond. The use of photoactivation of fluoroalkyl iodides for the fluorination of diamond surfaces provides a convenient route compared to other methods involving the action of atomic F, molecular F₂, XeF₂ and F-containing plasmas.     

Regularity of multiwavelets

The motivation for this paper is an interesting observation made by Plonka concerning the factorization of the matrix symbol associated with the refinement equation for B-splines with equally spaced multiple knots at integers and subsequent developments which relate this factorization to regularity of refinable vector fields over the real line. Our intention is to contribute to this train of ideas which is partially driven by the importance of refinable vector fields in the construction of multiwavelets. The use of subdivision methods will allow us to consider the problem almost entirely in the spatial domain and leads to exact characterizations of differentiability and Hölder regularity in arbitrary L _p spaces. We first study the close relationship between vector subdivision schemes and a generalized notion of scalar subdivision schemes based on bi-infinite matrices with certain periodicity properties. For the latter type of subdivision scheme we will derive criteria for convergence and Hölder regularity of the limit function, which mainly depend on the spectral radius of a bi-infinite matrix induced by the subdivision operator, and we will show that differentiability of the limit functions can be characterized by factorization properties of the subdivision operator. By switching back to vector subdivision we will transfer these results to refinable vectors fields and obtain characterizations of regularity by factorization and spectral radius properties of the symbol associated to the refinable vector field. Finally, we point out how multiwavelets can be generated from orthonormal refinable bi-infinite vector fields.     

Correlated polarization propagator calculations of static polarizabilities

We present a systematic comparison of the correlation contribution at the level of the second-order polarization propagator approximation (SOPPA ) and MP 2 to the static dipole polarizability of (1) Be, BeH^?, BH, CH⁺, MgH^?, AIH, SiH⁺, and GeH⁺; (2) BH₃, CH₄, NH₃, H₂O, HF, BF, and F₂; and (3) N₂, CO, CN^?, HCN, C₂H₂, and HCHO . Fairly extended basis sets were used in the calculations. We find that the agreement with experimental values is improved in SOPPA and MP .2 over the results at the SCF level. The signs and magnitudes of the correlation contribution in SOPPA are similar to those obtained in analytical derivative MP 2 calculations. However, it is not possible to say, in general, which method gives the largest correlation contribution or the best agreement with experiment, nor is it possible to make a priori prediction of the sign of the correlation contribution. For the first group of molecules, which have a quasi-degenerate ground state, additional CCDPPA and CCSDPPA calculations were performed and compared with polarizabilities obtained as analytical/numerical derivatives of the CCD and CCSD energies. The CCSDPPA results were found to be in better agreement with other calculations than were the SOPPA results, demonstrating the necessity of using methods based on infinite-order perturbation theory for these systems. © 1994 John Wiley & Sons, Inc.