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.     

Retention models for isocratic and gradient elution in reversed-phase liquid chromatography

One- and multi-variable retention models proposed for isocratic and/or gradient elution in reversed-phase liquid chromatography are critically reviewed. The thermodynamic, exo-thermodynamic or empirical arguments adopted for their derivation are presented and discussed. Their connection to the retention mechanism is also indicated and the assumptions and approximations involved in their derivation are stressed. Special attention is devoted to the fitting performance of the various models and its impact on the final predicted error between experimental and calculated retention times. The possibility of using exo-thermodynamic retention models for prediction under gradient elution is considered from a practical point of view. Finally, the use of statistical weights in the fitting procedure of a retention model and its effect on the calculated elution times as well as the transferability of retention data among isocratic and gradient elution modes are also examined and discussed.     

The inductive dimension of a space by its normal base

Properties of the large inductive dimension of a space by its normal base introduced by S. Iliadis are studied. The proposed dimension-like functions generalize both the classic dimensions Ind, Ind₀ and the relative inductive dimensions I. Properties of the normal base characterizing the fulfillment of basic classic theorems of the dimension theory (sum, subset and product theorems) are found.     

Multilinear gradient elution optimisation in reversed-phase liquid chromatography using genetic algorithms

The treatment presented in a recent paper [P. Nikitas, A. Pappa-Louisi, J. Chromatogr. A, 1068 (2005) 279] is extended to multilinear gradients, i.e. continuous gradients consisting of a certain number of linear portions. Thus, the experimental lnk versus phi curve, where k is the retention factor of a sample solute under isocratic conditions and phi is the volume fraction of the organic modifier in the water-organic mobile phase, is subdivided into a finite number of linear portions resulting in simple analytical expressions for the solute gradient retention time. These expressions of the retention time are directly used in an optimisation technique based on genetic algorithms. This technique involves first the determination of the theoretical dependence of k upon phi by means of gradient measurements, which in turn is used by the genetic algorithm for the prediction of the best gradient profile. The validity of the analytical expressions and the effectiveness of the optimisation technique were tested using fifteen underivatized amino acids and related compounds with mobile phases modified by acetonitrile. It was found that the adopted methodology exhibits significant advantages and it can lead to high quality predictions of the gradient retention times and optimisation results.     

Invariant Manifolds,Nonclassical Normal Modes,and Proper Orthogonal Modes in the Dynamics of the Flexible Spherical Pendulum

It is shown that the flexible spherical pendulum undergoes purely slow motions with master and slaved components. The family of slow motions is realized as a three-dimensional invariant manifold in phase space. This manifold is computed analytically by applying the method of geometric singular perturbations. This manifold is nonlinear and for all energy and angular momentum levels is characterized precisely by three PO (proper orthogonal) modes. Its submanifold of zero angular momentum is a two-dimensional invariant manifold; it is the geometric realization of a nonclassical nonlinear normal mode. This normal mode is characterized precisely by two PO modes. The slaved slow dynamics are characterized precisely by a single PO mode. The stability of the slow invariant manifold as well as interactions between fast and slow dynamics are considered.     

A singular function boundary integral method for elliptic problems with singularities

In this work we present a singular function boundary integral method for elliptic problems with boundary singularities. In this method, the approximation is constructed from the truncated asymptotic expansion for the solution near the singular point and the Dirichlet boundary conditions are weakly enforced by means of Lagrange multiplier functions. The resulting discrete problem is posed and solved on the boundary of the domain, away from the point of singularity. We are able to show that the method approximates the generalized stress intensity factors, i.e. the coe cients in the asymptotic expansion, at an exponential rate. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Switchable photocatalysis for the chemodivergent benzylation of 4-cyanopyridines

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides. The judicious choice of different photocatalyst quenchers allowed us to select at will between mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path proceeding via radical coupling and a Minisci-type addition, enabled selective access to regioisomeric C4 or C2 benzylated pyridines, respectively. Mechanistic investigations shed light on the origin of the chemoselectivity switch.

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides.     

Synthesis and Biological Evaluation of the Novel Growth Inhibitor Streptol Glucoside,Isolated from an Obligate Plant Symbiont

The plant Psychotria kirkii hosts an obligatory bacterial symbiont, Candidatus Burkholderia kirkii, in nodules on their leaves. Recently, a glucosylated derivative of (+)-streptol, (+)-streptol glucoside, was isolated from the nodulated leaves and was found to possess a plant growth inhibitory activity. To establish a structure–activity relationship study, a convergent strategy was developed to obtain several pseudosugars from a single synthetic precursor. Furthermore, the glucosylation of streptol was investigated in detail and conditions affording specifically the α or β glucosidic anomer were identified. Although (+)-streptol was the most active compound, its concentration in P. kirkii plant leaves extract was approximately ten-fold lower than that of (+)-streptol glucoside. These results provide compelling evidence that the glucosylation of (+)-streptol protects the plant host against the growth inhibitory effect of the compound, which might constitute a molecular cornerstone for this successful plant-bacteria symbiosis.     

Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides,Hydroxamic Acids and Esters

A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.     

A discrete event simulation model in the case of managing a software project

The design and development of large-scale software projects is a complex endeavor, often facing problems like cost and schedule overruns as well as low quality. Over the last years the management of software development projects has been recognized as the cornerstone point of seeking improvement and solutions. Simulation modeling of the software project process is gaining interest among academics and practitioners, as a method to tackle the complex questions with which relevant enterprises are confronted. It offers support on several issues, such as defining software product development strategies, decision-making regarding process improvement and training, in a time span ranging from a short portion of the life cycle to long term product evolution, with organization-wide implications. The aim of this work is to implement a model simulating a core part of a software project process, enabling the estimation of several project development details such as delivery times and quality metrics. The purpose of the model is to assist project managers in control and monitoring, but also in identifying the best planning alternatives. The model scope covers a portion of the life cycle of an incremental software development venture.