Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases

Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts.     

Line Narrowing of a Tunable High Pressure CO2 Laser by Means of an Improved Non-Littrow Cavity

A model is reported to foresee ,for different mirror choices, the spectral properties of a high pressure, frequency tunable, CO₂ laser, operating with a non-Littrow grating mounting. The calculations show a larger frequency selectivity for not collimated plane cavities. The model is experimentally verified in a suitable high pressure laser. In particular narrowed linewidths less than 300MHz ( FWHM) are obtained.     

Some remarks on the identity between a variational integral and its relaxed functional

Summary Letf: (x, z)∈R ⁿ×Rⁿ→f(x, z)∈[0, +∞] be measurable inx and convex inz. It is proved, by an example, that even iff verifies a condition as|z| ^p≤f(x, z)≤Λ(a(x)+|z|^q) with 1<p<q,a∈L _loc ^s (R ⁿ),s>1, the functional that isL ¹(Ω)-lower semicontinuous onW ^1,1(Ω), does not agree onW ^1,1(Ω) with its relaxed functional in the topologyL ¹(Ω) given by inf

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Riassunto Siaf: (x, z)∈R ⁿ×Rⁿ→f(x, z)∈[0, +∞] misurabile inx e convessa inz. Si mostra con un esempio che anche sef verifica una condizione del tipo|z| ^p≤f(x, z)≤Λ(a(x)+|z|^q) con 1<p<q,a∈L _loc ^s (R ⁿ),s>1, il funzionale , che èL ¹(Ω)-semicontinuo inferiormente suW ^1,1(Ω), non coincide suW ^1,1(Ω) con il suo funzionale rilassato nella topologiaL ¹(Ω) definito da inf

     

Quantum field theories of vortices and anyons

We develop the quantization of topological solitons (vortices) in three-dimensional quantum field theory, in terms of the Euclidean region functional integral. We analyze in some detail the vortices of the abelian Higgs model. If a Chern-Simons term is added to the action, the vortices turn out to be anyons, i.e. particles with arbitrary real spin and intermediate () statistics. Localization properties of the interpolating field, scattering theory and spin-statistics connection of anyons are discussed. Such analysis might be relevant in connection with the fractional quantum Hall effect and two-dimensional models of HighT _csuperconductors.     

New pi-extended water-soluble squaraines as singlet oxygen generators

[graph: see text] Condensation of squaric acid with a number of differently substituted 2-pyrrolyl derivatives afforded three new classes of squaraines. Their sharp and intense absorption bands in the biological window (700-900 nm), inherent singlet oxygen generation capabilities, together with proper functionalization allowing good water solubility make them suitable candidates as new non-porphyrinic singlet oxygen photosensitizers for photodynamic therapy (PDT).     

Neue β-Lactam-Antibiotika. Zur Funktionalisierung von 3-Hydroxy-3-cephem-4-carbonsäureestern durch die Wittig-Reaktion. Modifikationen von Antibiotika. 16. Mitteilung [1]

New β-lactam antibiotics. Functionalisation of 3-hydroxy-3-cephem-4-carboxylic esters through the Wittig reaction The 3-hydroxy-ceph-3-em-esters 1a, b reacted smoothly with stabilized phosphor-ylids to give a series of derivatives which were converted into the microbiologically active acids 14a, c, 15c and 20 by known procedures. The synthesis of the amides 23, 24, 26 and of the ester 28 from the 3-carboxymethyl-derivative 19 is also reported.     

Are ring currents still useful to rationalize the benzene proton magnetic shielding?

[structure: see text] The conventional interpretation of proton NMR chemical shifts is supported by large basis set ab initio quantum mechanical calculations. The benzene protons are predicted to lie within the deshielding zone defined in terms of the out-of-plane magnetic shielding domain. However, ring currents by themselves are not sufficient to account quantitatively for the observed benzene proton downfield chemical shift. sigma-Electron contributions must also be taken into account. The conventional explanation for the ethyne proton chemical shift is valid.     

Stability boundaries, percolation threshold, and two-phase coexistence for polydisperse fluids of adhesive colloidal particles

We study the polydisperse Baxter model of sticky hard spheres (SHS) in the modified mean spherical approximation (mMSA). This closure is known to be the zero-order approximation C0 of the Percus-Yevick closure in a density expansion. The simplicity of the closure allows a full analytical study of the model. In particular we study stability boundaries, the percolation threshold, and the gas-liquid coexistence curves. Various possible subcases of the model are treated in details. Although the detailed behavior depends upon the particularly chosen case, we find that, in general, polydispersity inhibits instabilities, increases the extent of the nonpercolating phase, and diminishes the size of the gas-liquid coexistence region. We also consider the first-order improvement of the mMSA (C0) closure (C1) and compare the percolation and gas-liquid boundaries for the one-component system with recent Monte Carlo simulations. Our results provide a qualitative understanding of the effect of polydispersity on SHS models and are expected to shed new light on the applicability of SHS models for colloidal mixtures.     

Homolytic substitutions in indolinone nitroxide radicals—I: Reaction with aroyloxyl radicals

Indolinone nitroxides undergo a homolytic substitution with aroyl oxyl radicals, leading to two isomers, 7-aroyloxy- and 5-aroyloxy-derivative, respectively, whose structures were assigned on the basis of the ESR hfccs and of the ¹H NMR spectra of the corresponding amines. The presence of aroyl oxyl radicals in the reaction medium was demonstrated by thermal decomposition of benzoyl peroxide in the presence of aromatic acids.