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.     

Measurement of the working parameters of an air-post vertical-cavity surface-emitting laser

We present a complete experimental evaluation of the effective parameters necessary to describe the dynamical behavior of an air-post vertical-cavity surface-emitting lasers, on the basis of theoretical equations which are also derived in this paper. The experimental investigation is composed of several steps, including power versus current measurement, noise spectrum analysis, linewidth evaluation. The complete set of parameters derived, in particular the linewidth-enhancement factor and the spontaneous emission factor, is particularly important for accurate comparisons of theoretical models on the laser dynamics with experiments.     

Dynamics of kinks in biological membranes

kinks created in a biological membrane by the interaction with a movable bead. We arrive at the evolution equations for both the bead and the membrane, whence we conclude that the force exerted on the bead by a fixed membrane points in the direction along which the curvature of the membrane is more concentrated. This is the first step towards understanding the basic mechanism behind the dynamics of protein aggregation which takes place on biological membranes. Received November 6, 2001 / Published online February 4, 2002     

Segregation of concurrent sounds. II: Effects of spectral envelope tracing, frequency modulation coherence, and frequency modulation width

The research presented here concerns the simultaneous grouping of the components of a vocal sound source. McAdams [J. Acoust. Soc. Am. 86, 2148-2159 (1989)] found that when three simultaneous vowels at different pitches were presented with subaudio frequency modulation, subjects judged them as being more prominent than when no vibrato was present. In a normal voice, when the harmonics of a vowel undergo frequency modulation they also undergo an amplitude modulation that traces the spectral envelope. Hypothetically, this spectral tracing could be one of the criteria used by the ear to group components of each vowel, which may help explain the lack of effect of frequency modulation coherence among different vowels in the previous study. In this experiment, two types of vowel synthesis were used in which the component amplitudes of each vowel either remained constant with frequency modulation or traced the spectral envelope. The stimuli for the experiment were chords of three different vowels at pitch intervals of five semitones (ratio 1.33). All the vowels of a given stimulus were produced by the same synthesis method. The subjects' task involved rating the prominence of each vowel in the stimulus. It was assumed that subjects would judge this prominence to be lower when they were not able to distinguish the vowel from the background sound. Also included as stimulus parameters were the different permutations of the three vowels at three pitches and a number of modulation conditions in which vowels were unmodulated, modulated alone, and modulated either coherently with, or independently of, the other vowels. Spectral tracing did not result in increased ratings of vowel prominence compared to stimuli where no spectral tracing was present. It would therefore seem that it has no effect on grouping components of sound sources. Modulated vowels received higher prominence ratings than unmodulated vowels. Vowels modulated alone were judged to be more prominent than vowels modulated with other vowels. There was, however, no significant difference between coherent and independent modulation of the three vowels. Differences among modulation conditions were more marked when the modulation width was 6% than when it was 3%.     

tert‐Butyl (6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxo‐1,2,5,6‐tetra­hydropyridine‐1‐carboxyl­ate and tert‐butyl (4R,6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxopiperidine‐1‐carboxyl­ate

X‐ray studies reveal that tert‐butyl (6S)‐6‐iso­butyl‐2,4‐dioxo­piperidine‐1‐carboxyl­ate occurs in the 4‐enol form, viz. tert‐butyl (6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxo‐1,2,5,6‐tetra­hydropyri­dine‐1‐carboxyl­ate, C₁₄H₂₃NO₄, when crystals are grown from a mixture of di­chloro­methane and pentane, and has an axial orientation of the iso­butyl side chain at the 6‐position of the piperidine ring. Reduction of the keto functionality leads predominantly to the corresponding β‐hydroxy­lated δ‐lactam, tert‐butyl (4R,6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxo­piperidine‐1‐car­boxyl­ate, C₁₄H₂₅NO₄, with a cis configuration of the 4‐hydroxy and 6‐iso­butyl groups. The two compounds show similar molecular packing driven by strong O—H⋯O=C hydrogen bonds, leading to infinite chains in the crystal structure.     

Assessment of filtered gas–solid momentum transfer models via a linear wave propagation speed test

The propagation speeds of linear waves in gas–solid suspensions depend strongly on the solids volume fraction and the wave frequency. The latter is due to gas–solid momentum transfer and allows a simple test on filtered gas–solid momentum transfer models. Such models may predict linear wave propagation speeds different from those obtained with the non-filtered model at wave frequencies higher than the filter frequency, but not at wave frequencies lower than the filter frequency.     

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