Photochemistry of anthocyanins and their biological role in plant tissues

Anthocyanins, the major red, purple, and blue pigments of plants, absorb visible as well as UV radiation and are effective antioxidants and scavengers of active oxygen species. In plant leaves, one of the functional roles proposed for anthocyanins is protection of the photosynthetic apparatus from the effects of excess incident visible or UV-B radiation and photooxidative stress. In essence, a photoprotective role requires that the excited singlet states of both complexed and uncomplexed anthocyanins deactivate back to the ground state so quickly that intersystem crossing, photoreaction, and diffusion-controlled quenching processes cannot compete. Studies of the photochemical properties of synthetic analogs of anthocyanins and of several naturally occurring anthocyanins show that this is indeed the case, uncomplexed anthocyanins decaying back to the ground state via fast (subnanosecond) excited-state proton transfer (ESPT) and anthocyanin-copigment complexes by fast (sub-picosecond) charge-transfer-mediated internal conversion.

Coupling of a Jahn-Teller pseudorotation with a hindered internal rotation in an isolated molecule: 9-hydroxytriptycene

The irregular vibronic structure in the S-1<--S-0 resonant two-photon ionization (R2PI) spectrum of supersonically cooled triptycene is a result of a classic Exe Jahn-Teller effect [A. Furlan et al., J. Chem. Phys. 96, 7306 (1992)]. This is well characterized and can be used as an effective probe of intramolecular perturbations. Here we examine the S-1<--S-0 R2PI spectrum of 9-hydroxytriptycene and the fluorescence from various excited state vibronic levels. In this system the pseudorotation of the Jahn-Teller vibration is strongly coupled to the torsional motion of the bridgehead hydroxy group. This torsional motion results in a tunneling splitting in both the ground and excited states. The population of the upper level in the ground electronic state results in additional vibronic transitions becoming symmetry allowed in the R2PI spectrum that are forbidden in the bare triptycene molecule. The assignment of the R2PI and fluorescence spectra allows the potential energy surfaces of these vibrational modes to be accurately quantified. The full C-3v vibronic point group must be used to interpret the spectra. The time scale of the internal rotation of the-OH group and the butterfly flapping of the Jahn-Teller pseudorotation are of similar magnitude. The tunneling between the nine minima on the three dimensional potential energy surface is such that the Jahn-Teller pseudorotation occurs in concert with the-OH internal rotation. The Berry phase that is acquired during this motion is discussed. The simple physical picture emerges of the angle between two of the three benzene moieties opening in three equivalent ways in the S-1 electronic state. This geometry follows the position of the hydroxy group, which preferentially orients itself to point between these two rings. (C) 1998 American Institute of Physics. [S0021-9606(98)02348-4].

Geometric and electronic information from the spectroscopy of six-coordinate copper(II) compounds

The ground and excited state geometry of the six-coordinate copper(II) ion is examined in detail using the CuF64- and Cu(H2O)(6)(2+) complexes as examples. A variety of spectroscopic techniques are used to illustrate the relations between the geometric and electronic properties of these complexes through the characterization of their potential energy surfaces.

Non-Markovian homodyne-mediated feedback on a two-level atom: a quantum trajectory treatment

Quantum feedback can stabilize a two-level atom against decoherence (spontaneous emission), putting it into an arbitrary (specified) pure state. This requires perfect homodyne detection of the atomic emission, and instantaneous feedback. Inefficient detection was considered previously by two of us. Here we allow for a non-zero delay time tau in the feedback circuit. Because a two-level atom is a non-linear optical system, an analytical solution is not possible. However, quantum trajectories allow a simple numerical simulation of the resulting non-Markovian process. We find the effect of the time delay to be qualitatively similar to chat of inefficient detection. The solution of the non-Markovian quantum trajectory will not remain fixed, so that the time-averaged state will be mixed, not pure. In the case where one tries to stabilize the atom in the excited state, an approximate analytical solution to the quantum trajectory is possible. The result, that the purity (P = 2Tr[rho (2)] - 1) of the average state is given by P = 1 - 4y tau (where gamma is the spontaneous emission rate) is found to agree very well with the numerical results. (C) 2001 Elsevier Science B.V. All rights reserved.

Reversible luminescence thermochromism in dipotassiumsodium tris[dicyanoargentate(I)] and the role of structural phase transitions

As a function of temperature, the layered compound K2Na[Ag(CN)213 displays dramatic variations in luminescence thermochromism with major trend changes occurring around 80 K. In order to understand these interesting optical properties, high-resolution neutron diffraction investigations were performed on a polycrystalline sample of this material in the temperature range from 1.5 to 300 K, and previous synchrotron X-ray data of Larochelle et al. (Solid State Commun. 114, 155 (2000)) were reinterpreted. The corresponding significant structural changes were found to be continuous with an anomalous increase of the monoclinic c-lattice parameter with decreasing temperature, associated with slight reorientations of two inequivalent, approximately linear N-C-Ag-C-N units. In the whole temperature range, the crystal structure is monoclinic with the space group C2/m. Based on the structural results, the major luminescence thermochromism changes around 80 K are attributed to the dominance of a back energy transfer process from low- to high-energy excitons at high temperatures. (E) 2002 Elsevier Science (USA).

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Novos receptores moleculares baseados em calix[4]arenos: aplicação à química sensorial

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

Novos polímeros conjugados baseados em calixarenos contendo fontes quirais de origem natural: síntese, propriedades e aplicações sensoriais

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Search for new phenomena in events with three or more charged leptons in pp collisions at TeV with the ATLAS detector

A generic search for anomalous production of events with at least three charged leptons is presented. The data sample consists of pp collisions at s√=8 TeV collected in 2012 by the ATLAS experiment at the CERN Large Hadron Collider, and corresponds to an integrated luminosity of 20.3 fb−1. Events are required to have at least three selected lepton candidates, at least two of which must be electrons or muons, while the third may be a hadronically decaying tau. Selected events are categorized based on their lepton flavour content and signal regions are constructed using several kinematic variables of interest. No significant deviations from Standard Model predictions are observed. Model-independent upper limits on contributions from beyond the Standard Model phenomena are provided for each signal region, along with prescription to re-interpret the limits for any model. Constraints are also placed on models predicting doubly charged Higgs bosons and excited leptons. For doubly charged Higgs bosons decaying to eτ or μτ, lower limits on the mass are set at 400 GeV at 95% confidence level. For excited leptons, constraints are provided as functions of both the mass of the excited state and the compositeness scale Λ, with the strongest mass constraints arising in regions where the mass equals Λ. In such scenarios, lower mass limits are set at 3.0 TeV for excited electrons and muons, 2.5 TeV for excited taus, and 1.6 TeV for every excited-neutrino flavour.

Silicon nanocluster sensitization of erbium ions under low-energy optical excitation

The sensitizing action of amorphous silicon nanoclusters on erbium ions in thin silica films has been studied under low-energy (long wavelength) optical excitation. Profound differences in fast visible and infrared emission dynamics have been found with respect to the high-energy (shortwavelength) case. These findings point out to a strong dependence of the energy transfer process on the optical excitation energy. Total inhibition of energy transfer to erbium states higher than thefirst excited state (4I13/2) has been demonstrated for excitation energy below 1.82 eV (excitation wavelength longer than 680 nm). Direct excitation of erbium ions to the first excited state (4I13/2)has been confirmed to be the dominant energy transfer mechanism over the whole spectral range of optical excitation used (540 nm¿680 nm).

O comportamento Fotoquímico dos Complexos Pentaaminas de Rutênio(II) com Ligantes π Insaturados

A general overview on the photochemical behaviour of [Ru(NH3)5L]2+ complexes (where L is a p ligand) is presented. The proposed mechanisms and techniques employed for the study of these reactions are discussed. Emphasis is made on the mechanisms that allow the identification of the reactive excited state of the [Ru(NH3)5py]2+ complex.

Quimiluminescência orgânica: alguns experimentos de demonstração para a sala de aula

The generation of "cold light", visible to the human eye, by chemical reactions has attracted the attention of the scientific community since the beginning of this century. Besides the academic interest in the elucidation of the mechanisms of excited state formations, many chemiluminescence reactions have found widespread analytical applications. Moreover, the phenomenon of chemiluminescence can also be used as a tool in undergraduate and college teaching. In this article, we describe several known chemiluminescence demonstrations, which are suitable for school teaching. The main objective of this work is to produce didactic material in Portuguese to stimulate Brazilian secondary and high school teachers to use these experiments in the classroom. The demonstrations include singlet oxygen emission, the luminol reaction, oscillating chemiluminescence and the peroxyoxalate reaction.

Fotoiniciação de polimerização vinílica

The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.

Utilização de endoperóxidos de derivados de naftaleno como fontes químicas de oxigênio singlete em sistemas biológicos

Molecular oxygen, in the first excited state (singlet oxygen, ¹O2), has a substantial reactivity towards electron-rich organic molecules, such as biological targets, including unsaturated fatty acids, proteins, RNA and DNA. Considering the complexity of biological systems and the great variety of reactive species generated by photochemistry, efforts have been devoted to develop suitable ¹O2 generators based on the thermolysis of water soluble naphthalene endoperoxides. These compounds are chemically inert and have been employed as versatile sources of ¹O2. The synthesis is based on structural modifications in position 1,4 of dimethylnaphtalene, grafting hydrophilic substituents. The correspondent endoperoxide can be generated using photochemical method, or molybdate-catalyzed disproportionation of hydrogen peroxide.

Quimiluminescência de peróxidos orgânicos: geração de estados eletronicamente excitados na decomposição de 1,2-dioxetanos

In this review article, we give a general introduction on the mechanisms involved in organic chemiluminescence, where three basic models for excited state formation are presented. The chemiluminescence properties of 1,2-dioxetanes - four membered ring peroxides - are briefly outlined in the second part. In the main part, the mechanisms involved in the decomposition of 1,2-dioxetanes and analogous peroxides are discussed: (i) the unimolecular decomposition of 1,2-dioxetanes; (ii) the electron transfer catalyzed decomposition of peroxides by an intermolecular CIEEL (Chemically Initiated Electron Exchange Luminescence) mechanism; (iii) 1,2-dioxetane decomposition catalyzed by an intramolecular electron transfer mechanism (intramolecular CIEEL). Special emphasis is given to the latter subject, where recent examples with potential analytical applications are presented.