Enhancement of two-photon absorption cross-section and singlet-oxygen generation in porphyrins upon beta-functionalization with donor-acceptor substituents

The microwave-enhanced synthesis, comparative singlet oxygen sensitization efficiency, and nonlinear optical characterization of a new beta-functionalized porphyrin and its copper complex are described. We show that the introduction of a donor-acceptor push-pull conjugated fragment in the beta position strongly perturbs the porphyrin electronic structure leading to a remarkable one- and two-photon NIR absorption enhancement.     

Exact dynamic stiffness elements based on one-dimensional higher-order theories for free vibration analysis of solid and thin-walled structures

In this paper, an exact dynamic stiffness formulation using one-dimensional (1D) higher-order theories is presented and subsequently used to investigate the free vibration characteristics of solid and thin-walled structures. Higher-order kinematic fields are developed using the Carrera Unified Formulation, which allows for straightforward implementation of any-order theory without the need for ad hoc formulations. Classical beam theories (Euler–Bernoulli and Timoshenko) are also captured from the formulation as degenerate cases. The Principle of Virtual Displacements is used to derive the governing differential equations and the associated natural boundary conditions. An exact dynamic stiffness matrix is then developed by relating the amplitudes of harmonically varying loads to those of the responses. The explicit terms of the dynamic stiffness matrices are also presented. The resulting dynamic stiffness matrix is used with particular reference to the Wittrick–Williams algorithm to carry out the free vibration analysis of solid and thin-walled structures. The accuracy of the theory is confirmed both by published literature and by extensive finite element solutions using the commercial code MSC/NASTRAN^®$\mathrm{MSC}/{\mathrm{NASTRAN}}^{\circledR }$.     

Assessment of water-soluble pi-extended squaraines as one- and two-photon singlet oxygen photosensitizers: design, synthesis, and characterization

Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials.     

Second-order advantage from kinetic-spectroscopic data matrices in the presence of extreme spectral overlapping A multivariate curve resolution--alternating least-squares approach

Multivariate curve resolution coupled to alternating least-squares (MCR-ALS) has been employed to model kinetic-spectroscopic second-order data, with focus on the achievement of the important second-order advantage, under conditions of extreme spectral overlapping among sample components. A series of simulated examples shows that MCR-ALS can conveniently handle the studied analytical problem unlike other second-order multivariate calibration algorithms, provided matrix augmentation is implemented in the spectral mode instead of in the usual kinetic mode. The approach has also been applied to three experimental examples, which involve the determination of: (1) the antiparkinsonian carbidopa (analyte) in the presence of levodopa as a potential interferent, both reacting with cerium (IV) to produce the fluorescent species cerium (III) with different kinetics; (2) Fe(II) (analyte) in the presence of the interferent Zn(II), both catalyzing the oxidation of methyl orange with potassium bromate; and (3) tartrazine (analyte) in the presence of the interferent brilliant blue, both oxidized with potassium bromate, with the interferent leading to a product with an absorption spectrum very similar to tartrazine. The results indicate good analytical performance towards the analytes, despite the intense spectral overlapping and the presence of unexpected constituents in the test samples.     

Strategies for electrooptic film fabrication. Influence of pyrrole-pyridine-based dibranched chromophore architecture on covalent self-assembly, thin-film microstructure, and nonlinear optical response

The new dibranched, heterocyclic "push-pull" chromophores bis{1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (1), 1-(pyrid-4-yl)-2-(N-methyl-5-formylpyrrol-2-yl)ethylene (2), {1-(N-methylpyridinium-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}{(1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (3), N-methyl-2-[1-(N-methylpyrid-4-yl)ethen-2-yl]-5-[pyrid-4-yl]ethen-2-yl]pyrrole iodide (4), bis{1-(N-methyl-4-pyridinio)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane iodide (5), and N-methyl-2,5-[1-(N-methylpyrid-4-yl)ethen-2-yl]pyrrole iodide (6) have been synthesized and characterized. The neutral (1 and 2) and monomethyl salts (3 and 4) undergo chemisorptive reaction with iodobenzyl-functionalized surfaces to afford chromophore monolayers SA-1/SA-2 and SA-3/SA-4, respectively. Molecular structures and other physicochemical properties have been defined by (1)H NMR, optical spectroscopy, and XRD. Thin-film characterization by a variety of techniques (optical spectroscopy, specular X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and angle-dependent polarized second harmonic generation) underscore the importance of the chromophore molecular architecture as well as film growth method on film microstructure and optical/electrooptic response.     

Fractionation of carrier ampholytes for isoelectric focusing.

A simple method for fractionating synthetic carrier ampholytes is reported, based on the principle of continuous-flow isoelectric focusing in gel-stabilized layers. An 8% ampholyte solution, encompassing the pH range 3-9.5, is separated into 12 fractions in a chamber filled with Sephadex G-100 by a continuous-flow technique. We are thus able to obtain ampholytes of narrow pH range, encompassing approximately 2 pH units, whose resolving power is comparable with that obtained with commercial Ampholine covering similar pH ranges.     

Entrapping of Push-Pull Zwitterionic Chromophores in Hybrid Matrices for Photonic Applications

A new class of heterocycle-based push-pull chromophores showing enhanced nonlinear properties characterized by an aromatic and highly zwitterionic ground state and a quinoid/neutral excited state have been synthesized to be incorporated in sol-gel hybrid systems. This class of compounds shows very large first molecular hyperpolarizabilities ( as high as 27000 × 10^–48 esu) and is a promising candidate for photonic applications where large second order non-linearities are required. In spite of their very large hyperpolarizability and chemical and thermal stability, these chromophores are decomposed in presence of light and oxygen (photobleaching) and are sensitive to acidic environments due to the carbanionic nature of the donor moiety. A hybrid matrix, based on N-[(3-trimethoxysilyl)propyl]ethylenediamine and 3-glycidoxypropyltrimethoxysilane, has been specifically designed to allow the incorporation of such zwitterionic compounds assuring at the same time a good temporal stability of the optical properties. Amine functionalisation has been found very effective in reducing the photobleaching by acting on these chromophores via the singlet oxygen. Second harmonic generation has been observed on poled films, and an order parameter, , of 0.17 has been estimated. The nonlinear coefficient d_eff of the samples has been thus estimated at a value two times larger than for d₁₁ of quartz that, from literature data, is about 0.335 pm/V.     

Pyridoneimines and pyridonemethides: substituent- and solvent-tunable intramolecular charge transfer and geometric isomerism.

We have prepared and fully characterized by means of multinuclear NMR and UV-vis spectroscopy a series of pyridoneimines and pyridonemethides in order to show how it is possible to finely tune pi-electron structure properties by properly exploiting substituent and solvent effects. Substituents with different electron-withdrawing capacities were introduced in pyridoneimines 2-4, pyridonemethides 5 and 6, and pyridine sulfonamido derivatives 7-9. The anisochrony of the carbon position of the azinium ring (geometric isomerism) and the exploitation of previously reported (13)C and (15)N shift/pi-electron density relationships allowed the investigation of the extent of intramolecular charge transfer from the donor group to the acceptor pyridinium moiety. By combining different substitutions with the polarity of the surrounding media, we were able to access a whole range of push-pull electron structures in solution, from fully aromatic-zwitterionic to quinoid-neutral, through many possible intermediate situations along the path. Due to the strict correlation between the pi-electron structure of push-pull derivatives and many photonic properties such as nonlinear optical activity, we believe that the achieved results should be valuable for the development of new efficient, tailor-made, heteroaromatic systems with optimized features as advanced organic materials.     

High-performance liquid chromatography of thiazolidinic compounds obtained by condensation of pyridoxal 5'-phosphate or pyridoxal with aminothiols (L- or D-cysteine, cysteamine, L-cysteine ethyl ester).

We investigated six thiazolidine 4-carboxylic acids of biological interest, obtained by condensation of pyridoxal 5'-phosphate or pyridoxal with L- or D-cysteine, cysteamine or L-cysteine ethyl ester. A reversed-phase high-performance liquid chromatographic method, using a C18 column for their separation, was developed by sequential optimization of the pH and the gradient of the mobile phase. Resolution of the compounds was obtained with an analysis time of less than 20 min.     

Improvement of photo-stability of LLDPE-based nanocomposites

LLDPE-based nanocomposites undergo faster photo-oxidation than the unfilled matrix and the extent of their physical properties deterioration, namely elongation at break and tensile strength, is dependent on the organo-nanoclay loading. The observed acceleration is not due to faster photo-oxidation but rather due to a reduction of the oxidation induction time. The presence in the organoclays of trace amounts of metal ions may be promoting catalytic photodegradation. While UV absorbers provide useful protection, use of a metal deactivator has been found to greatly enhance the photo-stability of the LLDPE-based nanocomposites. Combinations of a metal deactivator and UV absorber yield synergistic effects.