Synthesis of a new hyperbranched‐linear‐hyperbranched triblock copolymer and its use as a chemical modifier for the cationic photo and thermal curing of epoxy resins

A new hyperbranched‐linear‐hyperbranched polymer was prepared in a one pot process by reaction of 4,4‐bis(4‐hydroxyphenyl)valeric acid and poly(ethylene glycol) (HPH). After characterization by ¹H and ¹³C NMR, SEC, DSC, and TGA, this polymer was used, in proportions of 5, 10, and 15 phr, as a chemical modifier in the UV and thermal cationic curing of 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexyl carboxylate epoxy resin. The curing process was studied by calorimetry, demonstrating the accelerating effect of the hydroxyl groups present in HPH's structure. The morphology of the resulting thermosets depended on the curing system used, as demonstrated by FE‐SEM microscopy, but in both cases phase separation occurred. Thermosets obtained by thermal curing presented lower thermal stability than UV‐cured materials. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Enantioselective ethylation of aldehydes with 1,3-N-donor ligands derived from (+)-camphoric acid

Derivatives of (+)-camphoric acid were prepared by a short and simple synthetic sequence and proved to be excellent ligands for the enantioselective ethylation of benzaldehyde with diethylzinc, with ees of up to 96% being obtained. The most efficient ligand was tested with several aromatic aldehydes and ees of up to 99% were observed. Structural features of the ligands are determinant for achieving high enantioselectivities.     

Synthesis of a new multiarm star polymer based on hyperbranched poly(styrene) core and poly(ε‐caprolactone) arms and its use as reactive modifier of epoxy thermosets

A well‐defined multiarm star copolymer poly(styrene)‐b‐poly(ε‐caprolactone) (PSOH‐b‐PCL) with an average number of PCL arms per molecule of 60 has been prepared. 4‐Chloromethyl styrene (4‐CMS) was polymerized by means of atom transfer radical polymerization (ATRP) to obtain a hyperbranched poly(styrene) with chlorines as terminal groups. Subsequently, chlorines were substituted by reaction with diisopropanolamine (DIPA) to give the hydroxyl‐ended derivative. Finally, the hydroxyl‐ended hyperbranched poly(styrene) has been used as a macroinitiator core to polymerize ε‐caprolactone by means of cationic ring‐opening polymerization so as to obtain the star copolymer. In a second step, PSOH‐b‐PCL was used as reactive modifier of diglycidylether of bisphenol A formulations cured by 1‐methyl imidazole (1‐MI) obtaining nanostructured thermosets. The curing process was studied by dynamic scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). By rheometry, the effect of this new polymer topology on the complex viscosity (η*) of the reactive mixture and on the gelation process was also analyzed. The thermomechanical characteristics of the modified materials were determined. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Enzyme‐Mediated Preparation of (+)‐ and (−)‐β‐Irone and (+)‐ and (−)‐cis‐γ‐Irone from Irone alpha®

The (−)‐ and (+)‐β‐irones ((−)‐ and (+)‐ 2 , resp.), contaminated with ca. 7 – 9% of the (+)‐ and (−)‐trans‐α‐isomer, respectively, were obtained from racemic α‐irone via the 2,6‐trans‐epoxide (±)‐ 4 (Scheme 2). Relevant steps in the sequence were the LiAlH₄ reduction of the latter, to provide the diastereoisomeric‐4,5‐dihydro‐5‐hydroxy‐trans‐α‐irols (±)‐ 6 and (±)‐ 7 , resolved into the enantiomers by lipase‐PS‐mediated acetylation with vinyl acetate. The enantiomerically pure allylic acetate esters (+)‐ and (−)‐ 8 and (+)‐ and (−)‐ 9 , upon treatment with POCl₃/pyridine, were converted to the β‐irol acetate derivatives (+)‐ and (−)‐ 10 , and (+)‐ and (−)‐ 11 , respectively, eventually providing the desired ketones (+)‐ and (−)‐ 2 by base hydrolysis and MnO₂ oxidation. The 2,6‐cis‐epoxide (±)‐ 5 provided the 4,5‐dihydro‐4‐hydroxy‐cis‐α‐irols (±)‐ 13 and (±)‐ 14 in a 3 : 1 mixture with the isomeric 5‐hydroxy derivatives (±)‐ 15 and (±)‐ 16 on hydride treatment (Scheme 1). The POCl₃/pyridine treatment of the enantiomerically pure allylic acetate esters, obtained by enzymic resolution of (±)‐ 13 and (±)‐ 14 , provided enantiomerically pure cis‐α‐irol acetate esters, from which ketones (+)‐ and (−)‐ 22 were prepared (Scheme 4). The same materials were obtained from the (9S) alcohols (+)‐ 13 and (−)‐ 14 , treated first with MnO₂, then with POCl₃/pyridine (Scheme 4). Conversely, the dehydration with POCl₃/pyridine of the enantiomerically pure 2,6‐cis‐5‐hydroxy derivatives obtained from (±)‐ 15 and (±)‐ 16 gave rise to a mixture in which the γ‐irol acetates 25a and 25b and 26a and 26b prevailed over the α‐ and β‐isomers (Scheme 5). The (+)‐ and (−)‐cis‐γ‐irones ((+)‐ and (−)‐ 3 , resp.) were obtained from the latter mixture by a sequence involving as the key step the photochemical isomerization of the α‐double bond to the γ‐double bond. External panel olfactory evaluation assigned to (+)‐β‐irone ((+)‐ 2 ) and to (−)‐cis‐γ‐irone ((−)‐ 3 ) the strongest character and the possibility to be used as dry‐down note.     

Attractor-Specific and Common Expression Values in Random Boolean Network Models (with a Preliminary Look at Single-Cell Data)

Random Boolean Networks (RBNs for short) are strongly simplified models of gene regulatory networks (GRNs), which have also been widely studied as abstract models of complex systems and have been used to simulate different phenomena. We define the “common sea” (CS) as the set of nodes that take the same value in all the attractors of a given network realization, and the “specific part” (SP) as the set of all the other nodes, and we study their properties in different ensembles, generated with different parameter values. Both the CS and of the SP can be composed of one or more weakly connected components, which are emergent intermediate-level structures. We show that the study of these sets provides very important information about the behavior of the model. The distribution of distances between attractors is also examined. Moreover, we show how the notion of a “common sea” of genes can be used to analyze data from single-cell experiments.     

New calibrations and time stability of the response of the INTERCAST CR-39

We present new calibrations of different production batches (from 1989 to 1999) of the INTERCAST CR-39, using the BNL-AGS 1 A GeV iron beam. The comparison with previous results, obtained with the 158 A GeV lead beam from the CERN-SPS shows that, while each production batch has a different calibration curve (mainly due to minor differences in the production conditions), the aging effect is negligible. We also tested the dependence of the CR-39 response from the time elapsed between exposure and analysis (fading effect). The fading effect, if present, is less then 10%. It may be compatible with the experimental uncertainties on the bulk etching rate v_B.     

Fast Algorithms to Generate Necklaces, Unlabeled Necklaces, and Irreducible Polynomials over GF(2)

Many applications call for exhaustive lists of strings subject to various constraints, such as inequivalence under group actions. A k-ary necklace is an equivalence class of k-ary strings under rotation (the cyclic group). A k-ary unlabeled necklace is an equivalence class of k-ary strings under rotation and permutation of alphabet symbols. We present new, fast, simple, recursive algorithms for generating (i.e., listing) all necklaces and binary unlabeled necklaces. These algorithms have optimal running times in the sense that their running times are proportional to the number of necklaces produced. The algorithm for generating necklaces can be used as the basis for efficiently generating many other equivalence classes of strings under rotation and has been applied to generating bracelets, fixed density necklaces, and chord diagrams. As another application, we describe the implementation of a fast algorithm for listing all degree n irreducible and primitive polynomials over GF(2).     

A Korovkin-type theory for finite Toeplitz operators via matrix algebras

Preconditioned conjugate gradients (PCG) are widely and successfully used methods for solving a Toeplitz linear system [59,9,20,5,34,62,6,10,28,45,44,46,49]. Frobenius-optimal preconditioners are chosen in some proper matrix algebras and are defined by minimizing the Frobenius distance from . The convergence features of these PCG have been naturally studied by means of the Weierstrass–Jackson Theorem [17,36,45], owing to the profound relationship between the spectral features of the matrices , generated by the Fourier coefficients of a continuous function f, and the analytical properties of the symbol f itself. In this paper, we capsize this point of view by showing that the optimal preconditioners can be used to define both new and just known linear positive operators uniformly approximating the function f. On the other hand, by modifying the Korovkin Theorem to study the Frobenius-optimal preconditioning problem, we provide a new and unifying tool for analyzing all Frobenius-optimal preconditioners in any generic matrix algebra related to trigonometric transforms. Finally, the multilevel case is sketched and discussed by showing that a Korovkin-type Theory also holds in a multivariate sense. Received October 1, 1996 / Revised version received May 7, 1998     

Study of the plume generated by Nd:YAG laser ablation of a hydroxyapatite target

The plume generated by Nd:YAG laser ablation of a hydroxyapatite target has been investigated in vacuum and at 0.1 and 0.2 mbar of water vapor. The investigation has been carried out by means of fast intensified CCD imaging with the aid of bandpass interferential filters that allow the following single species to be isolated: neutral calcium, calcium oxide radicals and neutral oxygen. Results obtained in vacuum reveal that expansion takes place at a constant velocity of about 2᎒⁴ m/s for the atomic species and about 3᎒³ m/s for the molecular ones and that emission is completely dominated by emissive neutral calcium. When ablation is carried out in a water atmosphere, the background gas confines the species in the leading edge of the plume, which results in the formation of a planar shock wave at 0.1 mbar and a spherical shock wave at 0.2 mbar. Comparison of the images with those obtained at 0.1 mbar of Ne has revealed the existence of chemical reactions between the plume and the water atmosphere, leading to the formation of calcium oxide radicals. In that case, plume emission is dominated by these molecular species.