Supporting process reuse in PROMENADE

Process reuse (the ability to construct new processes by assembling already built ones) and process harvesting (the ability to build generic processes that may be further reused, from existing ones) are two crucial issues in process technology. Both activities involve defining a set of mechanisms, like abstraction, adaptation, composition, etc. which are appropriate to achieve their goals. In this report, we define a general framework to process reuse and harvesting that proposes a complete set of mechanisms to deal with both activities. This general framework is particularized to the context of a process modelling language to model software processes, called PROMENADE. A definition of the identified reuse and harvesting mecha-nisms is proposed in the context of PROMENADE. Finally, two process reuse case studies which composes various reuse mechanisms are presented.Postprint (published version

Diastereoisomerism, Stability, and Morphology of Substituted meso-4-Sulfonatophenylporphyrin J-Aggregates

The comparison between nanoparticle morphologies of the J-aggregates of different meso-4-sulfonatophenylporphyrins showing non-sulfonato groups at some of the meso-positions constitutes an ultimate proof of the 2D crystal-like character of the basic self-assembly motif of this family of J-aggregates. Diastereoisomerism stemming from the tacticity of the relative configurations in relation to the J-aggregate bidimensional sheet is the key factor that determines both the striking monolayer in solution and also the hierarchical pathways leading to different nanoparticle morphologies upon further growth. The unexpected stability of such large monolayered sheets made up of porphyrin units is probably caused by the support originated at both surface faces by the double layer potentials of the peripheral ionic substituents. These double layer potentials play a driving role in the subsequent 3D growth of the monolayers, as deduced herein from the determining role of tacticity both in the stability of the J-aggregate sheet and in its evolution either to monolayered or to bilayered nanoparticles. The stabilizing role of the forces at the electrical double layer of the particle suggests a relationship between these forces and the previously reported detection of racemic biases when shear hydrodynamic forces are in action during the aggregation process

Necessary conditions for the emergence of homochirality via autocatalytic self-replication

We analyze a recent proposal for spontaneous mirror symmetry breaking based on the coupling of first-order enantioselective autocatalysis and direct production of the enantiomers that invokes a critical role for intrinsic reaction noise. For isolated systems, the racemic state is the unique stable outcome for both stochastic and deterministic dynamics when the system is in compliance with the constraints dictated by the thermodynamics of chemical reaction processes. In open systems, the racemic outcome also results for both stochastic and deterministic dynamics when driving the autocatalysis unidirectionally by external reagents. Nonracemic states can result in the latter only if the reverse reactions are strictly zero: these are kinetically controlled outcomes for small populations and volumes, and can be simulated by stochastic dynamics. However, the stability of the thermodynamic limit proves that the racemic outcome is the unique stable state for strictly irreversible externally driven autocatalysis. These findings contradict the suggestion that the inhibition requirement of the Frank autocatalytic model for the emergence of homochirality may be relaxed in a noise-induced mechanism

Mirror symmetry breaking with limited enantioselective autocatalysis and temperature gradients: a stability survey

We analyze limited enantioselective (LES) autocatalysis in a temperature gradient and with internal flow/recycling of hot and cold material. Microreversibility forbids broken mirror symmetry for LES in the presence of a temperature gradient alone. This symmetry can be broken however when the auto-catalysis and limited enantioselective catalysis are each localized within the regions of low and high temperature, respectively. This scheme has been recently proposed as a plausible model for spontaneous emergence of chirality in abyssal hydrothermal vents. Regions in chemical parameter space are mapped out in which the racemic state is unstable and bifurcates to chiral solutions

Structure vs. excitonic transitions in self-assembled porphyrin nanotubes and their effect on light absorption and scattering

The optical properties of diprotonated meso-tetrakis(4-sulphonatophenyl)porphyrin (TPPS4) J-aggregates of elongated thin particles (nanotubes in solution and ribbons when deposited on solid interfaces) are studied by different polarimetric techniques. The selective light extinction in these structures, which depends on the alignment of the nanoparticle with respect to the polarization of light, is contributed by excitonic absorption bands and by resonance light scattering. The optical response as a function of the polarization of light is complex because, although the quasi-one-dimensional structure confines the local fields along the nanotube axis, there are two orthogonal excitonic bands, of H- and J-character, that can work in favor of or against the field confinement. Results suggest that resonance light scattering is the dominant effect in solid state preparations, i.e. in collective groups (bundles) of ribbons but in diluted solutions, i.e. with isolated nanotubes, the absorption at the excitonic transitions remains dominant and linear dichroism spectra can be a direct probe of the exciton orientations. Therefore, by analyzing scattering and absorption data we can determine the alignment of the excitonic bands within the nanoparticle, i.e. of the orientation of the basic 2D porphyrin architecture in the nanoparticle. This is a necessary first step for understanding the directions of energy transport, charge polarization and non-linear optical properties in these materials

Reversible mechanical induction of optical activity in solutions of soft-matter nanophases

Nanophases of J-aggregates of several achiral amphiphilic porphyrins, which have thin long acicular shapes (nanoribbons), show the immediate and reversible formation of a stationary mechano-chiral state in the solution by vortex stirring, as detected by their circular dichroic signals measured by 2-modulator generallized ellipsometry. The results suggest that when a macroscopic chiral force creates supramolecular chirality, it also creates an enantiomeric excess of screw distortions, which may be detected by their excitonic absorption. An explanation on the effect of the shear flow gradients is proposed on the basis of the orientation of the rotating particles in the vortex and the size, shape, and mechanical properties of the nanoparticles

On the mechano-chiral effect of vortical flows on the dichroic spectra of 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin J-aggregates

Phase-modulated ellipsometry of the J-aggregates of the title porphyrin shows that the material gives a true CD signal. This confirms that there is a real chiral transfer by mechanical forces, mediated by shear gradient flows, from the macroscopic to the electronic transition level. Dislocations in the structure of the aggregate could justify the formation of chirality at the level of the electronic transitions once the mesophases can be sculptured by hydrodynamic gradient flows

Structure vs. properties chirality, optics and shapes in amphiphilic porphyrin J-aggregates

The structure of the meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) J-aggregates could be determined by X-ray and electron diffraction methods. A sheet-like architecture reveals the relationship between structure and chirality, optics and shapes of the J-aggregate of the meso 4-sulfonatophenyl- and phenyl- substituted porphyrins. The structure of the J-aggregates of H4TPPS4 belongs to the chiral space group P21 and includes four porphyrin molecules in its unit cell. The intermolecular stabilization of the zwitterionic units by hydrogen bonding and electrostatic interactions between the positively charged central NH groups and the periphery anionic sulfonato groups results in a structure of porphyrins sheets along the [ ] plane direction. The structure of the sheet on the [ ] plane is already chiral and its molecular architecture explains the simultaneous presence of H- and J-aggregate bands in their absorption spectra. This structure also accounts for the high similarity observed between the absorption spectra of different mesophorms of the same substance and even between different members of the series of meso-4-sulfonatophenyl-and-aryl substituted diprotonated porphyrins. The possibility, or not, of the sheet-like structure on [ ] to interact with other layers, either through ionic or hydrophobic interactions, depends on the substitution pattern at the meso-positions of the porphyrin ring. Thus, the different morphologies of the particles [mono- bi- and multilayered] of this series of J-aggregates are explained taking into account the role that the fourth meso-subtituent plays in the interlayer stabilization. The results suggest that supramolecular helicity, previously detected in several J-aggregates, is not the explanation of their chirality but would be the expression of the intrinsic chirality of the packing between building blocks

PROMENADE: a PML intended to enhance standarization, expressiveness and modularity in software process modelling

Some limitations have been identified in current software process modelling languages (SPML) concerning expressiveness, standarization, modularity and flexibility. We present a SPML called PROMENADE which aims at improving the above-mentioned features. Expressiveness is enhanced in PROMENADE by the use of a basic catalogue of precedence relationships (instead of transitions), the ability to define derived precedences using a high-level notation and the existence of dynamic precedences intended for relationships that are not known until process enactment time. Standarization is achieved by the mapping of PROMENADE features into a slightly extended UML. PROMENADE allows also the construction of complex models by the combination of partial ones using high-level operators.Postprint (published version

Supporting process reuse in PROMENADE

Process reuse (the ability to construct new processes by assembling already built ones) and process harvesting (the ability to build generic processes that may be further reused, from existing ones) are two crucial issues in process technology. Both activities involve defining a set of mechanisms, like abstraction, adaptation, composition, etc. which are appropriate to achieve their goals. In this report, we define a general framework to process reuse and harvesting that proposes a complete set of mechanisms to deal with both activities. This general framework is particularized to the context of a process modelling language to model software processes, called PROMENADE. A definition of the identified reuse and harvesting mecha-nisms is proposed in the context of PROMENADE. Finally, two process reuse case studies which composes various reuse mechanisms are presented