Vibration and two-photon absorption

The rigorous and transparent treatment of the effects of nuclear vibrational motion in two-photon absorption (TPA) was discussed. Perturbation formula for diatomic molecules were developed and applied to the X¹Σ+–A¹Π transition in CO. The analysis showed that the vibrations played an important role in TPA, just as their role in the calculation of conventional nonlinear optical (NLO) hyperpolarizabilities

Two and three nucleon induced photon absorption

We have investigated the mechanisms leading to two and three body photon absorption in nuclei. At photon energies around the pion production threshold we obtain a fraction of three body absorption of less than 10% of the total, contradicting previous theoretical claims that it dominates the absorption process. The strength of the three body channel grows smoothly with the photon energy reaching a maximum of about 60% of the total direct absorption at energies of the photon around 400 MeV.

Propietats d'absorció bifotònica del tetrafenilporficè i el seu complex de palladi: potencials sensibilitzadors per a Teràpia Fotodinàmica bifotònica.

Estudi elaborat a partir d’una estada a la Universitat de Aarhus, Dinamarca, durant juliol 2006. En el present treball s’investiguen, per primer cop, les propietats de absorció bifotòniques del fotosensibilitzador 2,7,12,17-tetrafenilporficè (TPPo) i del seu complex de pal•ladi (II) (PdTPPo). Ambos compostos han rebut molta atenció com a possibles otosensibilitzadors per a Teràpia Fotodinàmica (TFD). S’utilitza la detecció de la fosforescència de l’oxigen singlet, centrada a 1270 nm i produïda per l’absorció de dos fotons, per quantificar la magnitud de la secció d’absorció bifotònica, "delta", dels porficèns estudiats. Els experiments se han dut a terme en el marge espectral 750-850 nm i a l’infraroig proper a 1100nm. Aquestes longituds d’ona corresponen a les zones d’absorció bifotònica en les bandes de Soret i Q. Les propietats bifotòniques obtingudes es comparen i contrasten amb les dades conegudes de la tetrafenilporfirina (TPP), isòmer estructural del tetrafenilporficè però amb més gran simetria, i es troba que en la banda de Soret (que coincideix amb la regió de la pell més transparent) els valors de delta per el TPPo i PdTPPo son aproximadament 2000 GM en el màxim, pràcticament cent vegades més grans que per la TPP. A més a més, aquestos valors son dos ordres de magnitud més grans que els obtinguts a l’irradiar a 1100 nm (bandes Q). Aquestes observacions es poden explicar mitjançant la amplificació per ressonància deguda a la presència de transicions monofotòniques ressonants en la regió de les bandes Q. Els elevats valors de "delta" obtinguts per els tetrafenilporficèns estudiats junt a les principals característiques que aquestos presenten (elevat rendiment de formació d’oxigen singlet, estabilitat química i fotoquímica, absència de citotoxicitat,...) qualifiquen al TPPo y PdTPPo com a possibles fotosensibilitzadors per a Teràpia Fotodinàmica Bifotònica.

On the multiwavelength spectrum of the microquasar 1E1740.7-2942

The microquasar 1E 1740.7-2942 is a source located in the direction of the Galactic Center. It has been detected at X-rays, soft gamma-rays, and in the radio band, showing an extended radio component in the form of a double-sided jet. Although no optical counterpart has been found so far for 1E 1740.7-2942, its X-ray activity strongly points to a galactic nature. Aims.We aim to improve our understanding of the hard X-ray and gamma-ray production in the system, exploring whether the jet can emit significantly at high energies under the light of the present knowledge. Methods.We have modeled the source emission, from radio to gamma-rays, with a cold-matter dominated jet model. INTEGRAL data combined with radio and RXTE data, as well as EGRET and HESS upper-limits, are used to compare the computed and the observed spectra. Results.From our modeling, we find out that jet emission cannot explain the high fluxes observed at hard X-rays without violating at the same time the constraints from the radio data, favoring the corona origin of the hard X-rays. Also, 1E 1740.7-2942 might be detected by GLAST or AGILE at GeV energies, and by HESS and HESS-II beyond 100 GeV, with the spectral shape likely affected by photon-photon absorption in the disk and corona photon fields.

Control of optical fields and single photon emitters by advanced nanoantenna structures

The control of optical fields on the nanometre scale is becoming an increasingly important tool in many fields, ranging from channelling light delivery in photovoltaics and light emitting diodes to increasing the sensitivity of chemical sensors to single molecule levels. The ability to design and manipulate light fields with specific frequency and space characteristics is explored in this project. We present an alternative realisation of Extraordinary Optical Transmission (EOT) that requires only a single aperture and a coupled waveguide. We show how this waveguide-resonant EOT improves the transmissivity of single apertures. An important technique in imaging is Near-Field Scanning Optical Microscopy (NSOM); we show how waveguide-resonant EOT and the novel probe design assist in improving the efficiency of NSOM probes by two orders of magnitude, and allow the imaging of single molecules with an optical resolution of as good as 50 nm. We show how optical antennas are fabricated into the apex of sharp tips and can be used in a near-field configuration.

Gated Geiger mode avalanche photodiode pixels with integrated readout electronics for low noise photon detection

Avalanche photodiodes operated in the Geiger mode offer a high intrinsic gain as well as an excellent timing accuracy. These qualities make the sensor specially suitable for those applications where detectors with high sensitivity and low timing uncertainty are required. Moreover, they are compatible with standard CMOS technologies, allowing sensor and front-end electronics integration within the pixel cell. However, the sensor suffers from high levels of intrinsic noise, which may lead to erroneous results and limit the range of detectable signals. They also increase the amount of data that has to be stored. In this work, we present a pixel based on a Geiger-mode avalanche photodiode operated in the gated mode to reduce the probability to detect noise counts interfering with photon arrival events. The readout circuit is based on a two grounds scheme to enable low reverse bias overvoltages and consequently lessen the dark count rate. Experimental characterization of the fabricated pixel with the HV-AMS 0.35µm standard technology is also presented in this article.

Absorption and pharmacokinetics of grapefruit flavanones in beagles

The present study evaluated the pharmacokinetics of three different grapefruit flavanone forms in dog plasma and demonstrated their absorption after an oral intake of a grapefruit extract; pharmacokinetic parameters of these forms were also determined. Ten healthy beagles were administered 70 mg citrus flavonoids as a grapefruit extract contained in capsules, while two additional dogs were used as controls and given an excipient. The grapefruit flavanone naringin, along with its metabolites naringenin and naringenin glucuronide, was detected in dog plasma. Blood samples were collected between 0 and 24 h after administration of the extract. Naringin reached its maximun plasma concentration at around 80 min, whereas naringenin and naringenin glucuronide reached their maximun plasma concentrations at around 20 and 30 min, respectively. Maximum plasma concentrations of naringin, naringenin and naringenin glucuronide (medians and ranges) were 0·24 (0·05 2·08), 0·021 (0·001 0·3) and 0·09 (0·034 0·12) mmol/l, respectively. The areas under the curves were 23·16 l (14·04 70·62) min £ mmol/for nariningin, 1·78 (0·09 4·95) min £ mmol/l for naringenin and 22·5 (2·74 99·23) min £ mmol/l for naringenin glucuronide. The median and range values for mean residence time were 3·3 (1·5 9·3), 2·8 (0·8 11·2) and 8·0 (2·3 13·1) h for naringin, naringenin and naringenin glucuronide, respectively. The results of the present study demonstrate the absorption of grapefruit flavanones via the presence of their metabolites in plasma, thus making an important contribution to the field since the biological activities ascribed to these compounds rely on their specific forms of absorption.

Absorption and pharmacokinetics of green tea catechins in beagles

The present study evaluates for the first time in dogs, the kinetics of green tea catechins and their metabolic forms in plasma and urine. Ten beagles were administered 173 mg (12·35 mg/kg body weight) of catechins as a green tea extract, in capsules. Blood samples were collected during 24 h after intake and urine samples were collected during the following periods of time: 02, 26, 68 and 824 h. Two catechins with a galloyl moiety and three conjugated metabolites were detected in plasma. Most of the detected forms in plasma reached their maximum plasma concentration (Cmax) at around 1 h. Median Cmax for (2)-epigallocatechin-3-gallate (EGCG), (2)-epicatechin-3-gallate (ECG), (2)-epigallocatechin glucuronide (EGCglucuronide), (2)-epicatechin glucuronide (EC-glucuronide), (2)-epicatechin sulphate (EC sulphate) were 0·3 (range 0·11·9), 0·1 (range 00·4), 0·8 (range 0·23·9), 0·2 (range 0·1 1·7) and 1 (range 0·33·4) mmol/l, respectively. The areas under the plasma concentration v. time curves (AUC0!24) were 427 (range 1021185) mmol/l £ min for EGC-glucuronide, 112 (range 53919) mmol/l £ min for EC-sulphate, 71 (range 26306) mmol/l £ min for EGCG, 40 (range 12258) mmol/l £ min for EC-glucuronide and 14 (range 0·1124) mmol/l £ min for ECG. The values of mean residence time (MRT0!24) were 5 (range 216), 2 (range 111), 10 (range 213), 3 (range 216) and 2·4 (range 118) h for EGCG, ECG, EGC-glucuronide, EC-glucuronide and EC sulphate, respectively. In urine, catechins were present as conjugated forms, suggesting bile excretion of EGCG and ECG. Green tea catechins are absorbed following an oral administration and EGC-glucuronide is the metabolic form that remains in the organism for a longer period of time, suggesting that this compound could suffer an enterohepatic cycle.

Absorption and pharmacokinetics of grapefruit flavanones in beagles

The present study evaluated the pharmacokinetics of three different grapefruit flavanone forms in dog plasma and demonstrated their absorption after an oral intake of a grapefruit extract; pharmacokinetic parameters of these forms were also determined. Ten healthy beagles were administered 70 mg citrus flavonoids as a grapefruit extract contained in capsules, while two additional dogs were used as controls and given an excipient. The grapefruit flavanone naringin, along with its metabolites naringenin and naringenin glucuronide, was detected in dog plasma. Blood samples were collected between 0 and 24 h after administration of the extract. Naringin reached its maximun plasma concentration at around 80 min, whereas naringenin and naringenin glucuronide reached their maximun plasma concentrations at around 20 and 30 min, respectively. Maximum plasma concentrations of naringin, naringenin and naringenin glucuronide (medians and ranges) were 0·24 (0·05 2·08), 0·021 (0·001 0·3) and 0·09 (0·034 0·12) mmol/l, respectively. The areas under the curves were 23·16 l (14·04 70·62) min £ mmol/for nariningin, 1·78 (0·09 4·95) min £ mmol/l for naringenin and 22·5 (2·74 99·23) min £ mmol/l for naringenin glucuronide. The median and range values for mean residence time were 3·3 (1·5 9·3), 2·8 (0·8 11·2) and 8·0 (2·3 13·1) h for naringin, naringenin and naringenin glucuronide, respectively. The results of the present study demonstrate the absorption of grapefruit flavanones via the presence of their metabolites in plasma, thus making an important contribution to the field since the biological activities ascribed to these compounds rely on their specific forms of absorption.

Absorption and pharmacokinetics of green tea catechins in beagles

The present study evaluates for the first time in dogs, the kinetics of green tea catechins and their metabolic forms in plasma and urine. Ten beagles were administered 173 mg (12·35 mg/kg body weight) of catechins as a green tea extract, in capsules. Blood samples were collected during 24 h after intake and urine samples were collected during the following periods of time: 0-2, 2-6, 6-8 and 8-24 h. Two catechins with a galloyl moiety and three conjugated metabolites were detected in plasma. Most of the detected forms in plasma reached their maximum plasma concentration (Cmax) at around 1 h. Median Cmax for (2)-epigallocatechin-3-gallate (EGCG), (2)-epicatechin-3-gallate (ECG), (2)-epigallocatechin glucuronide (EGCglucuronide), (2)-epicatechin glucuronide (EC-glucuronide), (2)-epicatechin sulphate (EC sulphate) were 0·3 (range 0·1-1·9), 0·1 (range 0-0·4), 0·8 (range 0·2-3·9), 0·2 (range 0·1 1·7) and 1 (range 0·3-3·4) mmol/l, respectively. The areas under the plasma concentration v. time curves (AUC0!24) were 427 (range 102-1185) mmol/l £ min for EGC-glucuronide, 112 (range 53-919) mmol/l £ min for EC-sulphate, 71 (range 26-306) mmol/l £ min for EGCG, 40 (range 12-258) mmol/l £ min for EC-glucuronide and 14 (range 0·1-124) mmol/l £ min for ECG. The values of mean residence time (MRT0!24) were 5 (range 2-16), 2 (range 1-11), 10 (range 2-13), 3 (range 2-16) and 2·4 (range 1-18) h for EGCG, ECG, EGC-glucuronide, EC-glucuronide and EC sulphate, respectively. In urine, catechins were present as conjugated forms, suggesting bile excretion of EGCG and ECG. Green tea catechins are absorbed following an oral administration and EGC-glucuronide is the metabolic form that remains in the organism for a longer period of time, suggesting that this compound could suffer an enterohepatic cycle.

Absorption and pharmacokinetics of green tea catechins in beagles

The present study evaluates for the first time in dogs, the kinetics of green tea catechins and their metabolic forms in plasma and urine. Ten beagles were administered 173 mg (12·35 mg/kg body weight) of catechins as a green tea extract, in capsules. Blood samples were collected during 24 h after intake and urine samples were collected during the following periods of time: 0-2, 2-6, 6-8 and 8-24 h. Two catechins with a galloyl moiety and three conjugated metabolites were detected in plasma. Most of the detected forms in plasma reached their maximum plasma concentration (Cmax) at around 1 h. Median Cmax for (2)-epigallocatechin-3-gallate (EGCG), (2)-epicatechin-3-gallate (ECG), (2)-epigallocatechin glucuronide (EGCglucuronide), (2)-epicatechin glucuronide (EC-glucuronide), (2)-epicatechin sulphate (EC sulphate) were 0·3 (range 0·1-1·9), 0·1 (range 0-0·4), 0·8 (range 0·2-3·9), 0·2 (range 0·1 1·7) and 1 (range 0·3-3·4) mmol/l, respectively. The areas under the plasma concentration v. time curves (AUC0!24) were 427 (range 102-1185) mmol/l £ min for EGC-glucuronide, 112 (range 53-919) mmol/l £ min for EC-sulphate, 71 (range 26-306) mmol/l £ min for EGCG, 40 (range 12-258) mmol/l £ min for EC-glucuronide and 14 (range 0·1-124) mmol/l £ min for ECG. The values of mean residence time (MRT0!24) were 5 (range 2-16), 2 (range 1-11), 10 (range 2-13), 3 (range 2-16) and 2·4 (range 1-18) h for EGCG, ECG, EGC-glucuronide, EC-glucuronide and EC sulphate, respectively. In urine, catechins were present as conjugated forms, suggesting bile excretion of EGCG and ECG. Green tea catechins are absorbed following an oral administration and EGC-glucuronide is the metabolic form that remains in the organism for a longer period of time, suggesting that this compound could suffer an enterohepatic cycle.

Nanoantenna enhanced emission of lightharvesting complex 2: the role of resonance, polarization, and radiative and non-radiative rates

Nanoantennae show potential for photosynthesis research for two reasons; first by spatially confining light for experiments which require high spatial resolution, and second by enhancing the photon emission of single light-harvesting complexes. For effective use of nanoantennae a detailed understanding of the interaction between the nanoantenna and the light-harvesting complex is required. Here we report how the excitation and emission of multiple purple bacterial LH2s (light-harvesting complex 2) are controlled by single gold nanorod antennae. LH2 complexes were chemically attached to such antennae, and the antenna length was systematically varied to tune the resonance with respect to the LH2 absorption and emission. There are three main findings. (i) The polarization of the LH2 emission is fully controlled by the resonant nanoantenna. (ii) The largest fluorescence enhancement, of 23 times, is reached for excitation with light at λ = 850 nm, polarized along the long antenna-axis of the resonant antenna. The excitation enhancement is found to be 6 times, while the emission efficiency is increased 3.6 times. (iii) The fluorescence lifetime of LH2 depends strongly on the antenna length, with shortest lifetimes of [similar]40 ps for the resonant antenna. The lifetime shortening arises from an 11 times resonant enhancement of the radiative rate, together with a 2–3 times increase of the non-radiative rate, compared to the off-resonant antenna. The observed length dependence of radiative and non-radiative rate enhancement is in good agreement with simulations. Overall this work gives a complete picture of how the excitation and emission of multi-pigment light-harvesting complexes are influenced by a dipole nanoantenna.

A mechanistic approach to methylene blue sorption on two vegetable wastes: Cork bark and grape stalks

Two vegetable wastes, cork bark and grape stalks, were investigated for the removal of methylene blue from aqueous solution. The effects of contact time, dye concentration, pH, and temperature on sorption were studied relative to adsorption on a commercially-activated carbon. The highest adsorption yield was obtained within the pH range 5 to 10 for grape stalks and 7 to 10 for cork bark. The sorption kinetics of dye onto activated carbon and grape stalks was very fast. Kinetics data were fitted to the pseudo-first and second order kinetic equations, and the values of the pseudo-second-order initial rate constants were found to be 1.69 mg g-1 min-1 for activated carbon, 2.24 mg g-1 min-1 for grape stalks, and 0.90 mg g-1 min-1 for cork bark. Langmuir maximum sorption capacities for activated carbon, grape stalks, and cork bark for methylene blue estimated by the Orthogonal Distance Regression method (ODR) were 157.5 mg g-1, 105.6 mg g-1, and 30.52 mg g-1, respectively. FTIR spectra indicated that carboxylic groups and lignin play a significant role in the sorption of methylene blue. Electrostatic forces, n-p interactions, cation-p, and p-p stacking interactions contribute to methylene blue sorption onto grape stalks and cork bark. Grape stalks can be considered an efficient biosorbent and as a viable alternative to activated carbon and ion-exchange resins for the removal of methylene blue