Influence of polymer molecular weight on the chemical modifications induced by UV laser ablation

This paper investigates the influence of polymer molecular weight (M(W)) on the chemical modifications of poly(methyl methacrylate), PMMA, and polystyrene, PS, films doped with iodonaphthalene (NapI) and iodophenanthrene (PhenI), following irradiation at 248 nm (KrF excimer laser, 20 ns fwhm and hybrid excimer-dye laser, 500 fs fwhm) and at 308 nm (XeCl excimer laser, 30 ns fwhm). The changes of intensity and position of the polymer Raman bands upon irradiation provide information on cleavage of the polymer bonds. Degradation of PMMA, which is a weak absorbing system at 248 nm, occurs to a higher extent in the case of a larger M(W), giving rise to the creation of unsaturation centers and to degradation products. For highly absorbing PS, no degradation is observed upon irradiation with a KrF laser. Consistently irradiating doped PS at 308 nm, where the absorption is low, induces degradation of the polymer. Results provide direct support for the bulk photothermal model, according to which ejection requires a critical number of broken bonds. In the case of irradiation of doped PMMA with pulses of 248 nm and 500 fs, neither degradation nor dependence with polymer M(W) are observed, indicating that mechanisms involved in the femtosecond laser ablation differ from those operating in the case of nanosecond laser ablation. Participation of multiphoton/avalanche processes is proposed.     

A versatile and general one-pot method for synthesizing bis-spiroketal motifs

[reaction: see text] A versatile and general method for the biomimetic construction of [5,5,5]- and [6,5,6]-bis-spiroketals, starting from easily accessible furan nuclei, by means of a powerful one-pot singlet oxygen-mediated cascade sequence is reported.     

Finite element modeling of the mechanical effects of the UV laser ablation of polymer coatings

Laser ablation constitutes the basis of a number of techniques aiming at the processing and diagnosis of polymeric coatings on a variety of substrates. In all these applications, however, the issue is raised about the mechanical effects of the procedure on the substrate integrity. To this end, we employ finite element modeling for simulating the mechanical effects of UV laser ablation on a polymer specimen, with particular emphasis on the structural modifications that may be induced at areas away from the ablation spot. The cylindrical specimen consists of a poly(methylmethacrylate) (PMMA) film on a silica substrate. The analysis shows that stresses of high enough amplitude may propagate to distances far away from the irradiated spot and may induce deleterious mechanical deformations (e.g., cracks or delaminations). The dependence of the distribution of the tensile stresses on the thickness of the two components, as well as on size of the ablation spot area, is examined. Finally, the possibility of growth of pre-existing defects is shown. The results are overall in very good agreement with experimental observations.     

A study concerning splitting and jointly continuous topologies on C(Y,Z)

Let Y and Z be two fixed topological spaces and C(Y, Z) the set of all continuous maps from Y into Z. We construct and study topologies on C(Y, Z) that w^{e call F}n(τn)-family-open topologies. Furthermore, we find necessary and su?cient conditions such that these topologies to be splitting and jointly continuous. Finally, we present questions concerning a further study on this area.     

A study of the order dimension of a poset using matrices

In every finite poset (X, ≤) we assign the so called order-matrix , where α_ij ∈ {?2, 0, 1, 2}. Using this matrix, we characterize the order dimension of an arbitrary finite poset.     

Using singlet oxygen to synthesise a [6,6,5]-bis-spiroketal in one-pot from a simple 2,5-disubstituted furan

Singlet oxygen (1O2) proves to be a powerful tool in mediating the one-pot synthesis of a salinomycin-type [6,6,5]-bis-spiroketal unit starting from a suitably substituted furan nucleus.     

Identification and Preliminary Structure-Activity Relationship Studies of 1,5-Dihydrobenzo[e][1,4]oxazepin-2(3H)-ones That Induce Differentiation of Acute Myeloid Leukemia Cells In Vitro

Acute myeloid leukemia (AML) is the most aggressive type of blood cancer, and there is a continued need for new treatments that are well tolerated and improve long-term survival rates in patients. Induction of differentiation has emerged as a promising alternative to conventional cytotoxic chemotherapy, but known agents lack efficacy in genetically distinct patient populations. Previously, we established a phenotypic screen to identify small molecules that could stimulate differentiation in a range of AML cell lines. Utilising this strategy, a 1,5-dihydrobenzo[e][1,4]oxazepin-2(3H)-one hit compound was identified. Herein, we report the hit validation in vitro, structure-activity relationship (SAR) studies and the pharmacokinetic profiles for selected compounds.     

Laser assisted removal of synthetic painting-conservation materials using UV radiation of ns and fs pulse duration: Morphological studies on model samples

In an effort to establish the optimal parameters for the cleaning of complex layers of polymers (mainly based on acrylics, vinyls, epoxys known as Elvacite, Laropal, Paraloid B72, among others) applied during past conservation treatments on the surface of wall paintings, laser cleaning tests were performed with particular emphasis on the plausible morphological modifications induced in the remaining polymeric material. Pulse duration effects were studied using laser systems of different pulse durations (ns and fs) at 248 nm. Prior to tests on real fragments from the Monumental Cemetery in Pisa (Italy) which were coated with different polymers, attention was focused on the study of model samples consisting of analogous polymer films cast on quartz disks. Ultraviolet irradiation is strongly absorbed by the studied materials both in ns and fs irradiation regimes. However, it is demonstrated that ultrashort laser pulses result in reduced morphological alterations in comparison to ns irradiation. In addition, the dependence of the observed alterations on the chemical composition of the consolidation materials in both regimes was examined. Most importantly, it was shown that in this specific conservation problem, an optimum cleaning process may rely not only on the minimization of laser-induced morphological changes but also on the exploitation of the conditions that favour the disruption of the adhesion between the synthetic material and the painting.