Instabilities in optically pumped infrared lasers

The unstable emission of an optically pumped FIR gas laser is theoretically analysed through numerical resolution of the associated Maxwell-Bloch equations. The instability domain in the main control parameters space is determined and an example of chaotic behaviour is examined.     

Finding the dominant energy transmission paths in statistical energy analysis

A key issue for noise, vibration and harshness purposes, when modelling the vibroacoustic behaviour of a system, is that of determining how energy is transmitted from a given source, where external energy is being input, to a target where energy is to be reduced. In many situations of practical interest, a high percentage of the transmitted energy is driven by a limited set of dominant paths. For instance, this is at the core of the existence of transmission loss regulations between dwellings. In this work, it is shown that in the case of a system modelled with statistical energy analysis (SEA), the problem of ranking dominant paths can be posed as a variation of the so-called K shortest path problem in graph theory. An algorithm for the latter is then modified and adapted to obtain the sorted set of K dominant energy transmission paths in a SEA model. A numerical example to show its potential for practical applications is included.     

Luminance adaptation model for increasing the dynamic range of an imaging system based on a CCD camera

We propose a luminance adaptation model (LAM) to increase the dynamic range of an imaging system when scenes containing areas of low and high illumination are imaged. The LAM that we developed is based on capturing images at different exposure times to obtain digital levels within the linear response zone for all the pixels in the image. The levels are subsequently transformed to a reference exposure time that is common to all pixels. We use a linear transformation whose coefficients are determined by the digital levels obtained for a set of flat-spectrum samples. In this study, the LAM is applied to a multispectral imaging system that is based on a CCD camera used for color measurements and spectral reconstructions. It is shown to be a very useful method for increasing the dynamic range of the system, whilst maintaining its accuracy.     

A New Porphyrin for the Preparation of Functionalized Water-Soluble Gold Nanoparticles with Low Intrinsic Toxicity

A potential new photosensitizer based on a dissymmetric porphyrin derivative bearing a thiol group was synthesized. 5-[4-(11-Mercaptoundecyloxy)-phenyl-10,15,20-triphenylporphyrin (PR-SH) was used to functionalize gold nanoparticles in order to obtain a potential drug delivery system. Water-soluble multifunctional gold nanoparticles GNP-PR/PEG were prepared using the Brust–Schiffrin methodology, by immobilization of both a thiolated polyethylene glycol (PEG) and the porphyrin thiol compound (PR-SH). The nanoparticles were fully characterized by transmission electron microscopy and ¹H nuclear magnetic resonance spectroscopy, UV/Vis absorption spectroscopy, and X-ray photoelectron spectroscopy. Furthermore, the ability of GNP-PR/PEGs to induce singlet oxygen production was analyzed to demonstrate the activity of the photosensitizer. Cytotoxicity experiments showed the nanoparticles are nontoxic. Finally, cellular uptake experiments demonstrated that the functionalized gold nanoparticles are internalized. Therefore, this colloid can be considered to be a novel nanosystem that could potentially be suitable as an intracellular drug delivery system of photosensitizers for photodynamic therapy.     

Kinetico‐Mechanistic Insights on the Assembling Dynamics of Allyl‐Cornered Metallacycles: The PtNpy Bond is the Keystone

The square‐like homo‐ and heterometallamacrocycles [{Pd(η³‐2‐Me‐C₃H₄)( L ⁿ )₂}₂{M(dppp)}₂](CF₃SO₃)₆ (dppp=1,3‐bis(diphenylphosphino)propane) and [{Pd(η³‐2‐Me‐C₃H₄)( L¹ )₂}₂{M(PPh₃)₂}₂](CF₃SO₃)₆ [py=pyridine, M=Pd, Pt, L ^{n =}4‐PPh₂py ( L¹ ), 4‐C₆F₄PPh₂py ( L² )] containing allyl corners were synthesised by antisymbiotic self‐assembly of the different palladium and platinum metallic corners and the ambidentate N,P ligands. All the synthesised assemblies displayed a complex dynamic behaviour in solution, the rate of which is found to be dependent on the electronic and/or steric nature of the different building blocks. A kinetico‐mechanistic study by NMR line shape analysis of the dynamics of some of these assemblies was undertaken in order to determine the corresponding thermal activation parameters. Both an enhanced thermodynamic stability and slower dynamics were observed for platinum‐pyridine‐containing species when compared with their palladium analogues. Time‐dependent NMR spectroscopy in combination with ESI mass spectrometry was used to study the exchange between the assemblies and their building blocks, as well as that occurring between different metallamacrocycles. Preliminary studies were carried out on the activity of some of the metallamacrocyclic compounds as catalytic precursors in the allylic substitution reaction, and the results compared with that of the monometallic allylic corner [Pd(η³‐2‐Me‐C₃H₄)( L¹ )₂]⁺.     

Synthesis, characterization and electrochemical studies of the heterometallic diclusters [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}2(diphosphine)] (diphosphine=dppm, dppip, dppe, dppp)

Treatment of [(ClAu)₂(diphosphine)] {diphosphine=bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)isopropane (dppip), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp)} with two equivalents of the anion [Fe₂(μ-CO)(CO)₆(μ-PPh₂)]⁻ in the presence of TlBF₄ gives the new heterometallic diclusters [{Fe₂(μ-CO)(CO)₆(μ-PPh₂)Au}₂(diphosphine)] that have been isolated and characterized. Their ³¹P-NMR spectra show different patterns as a function of the diphosphine ligand. The electrochemical behavior of these compounds has been investigated and compared with that of the mono- [Fe₂(μ-CO)(CO)₆(μ-PPh₂)(μ-AuPPh₃)] and tricluster [{Fe₂(μ-CO)(CO)₆(μ-PPh₂)Au}₃(triphos)] derivatives.     

Synthesis and mesogenic properties of four series of polyesters derived from dicarboxylic and dihydroxylic aromatic monomers

Some members of four series of polyesters were synthesized by the direct polycondensation of two types of dicarboxylic acids (4,4′-dicarboxy-α,ω-diphenoxyalkanes and 4,4′-dicarboxy-α,ω-dibenzoyloxyalkanes) with two types of bisphenols (4,4′-dihydroxy-α,ω-diphenoxyalkanes and 4,4′-dihydroxy-α,ω-dibenzoyloxyalkanes) using tosyl chloride in pyridine in the presence of N, N-dimethylformamide. The ¹H-NMR spectra of the polymers synthesized showed that these polymers have an ordenated structure. The mesogenic properties of these polymers were studied by optical microscopy and differential scanning calorimetry. Many of the polymers show nematic mesomorphism.