IR-visible upconversion and thermal effects in Pr3+/Yb3+-codoped Ga2O3 : La2S3 chalcogenide glasses

IR-visible upconversion fluorescence spectroscopy and thermal effects in pr(3+)/Yb3+-codoped Ga2O3:La2S3 chalcogenide glasses excited at 1.064 mum is reported. Intense visible upconversion emission in the wavelength region of 480-680 nm peaked around 500, 550, 620 and 660 nm is observed. Upconversion excitation of the Pr3+ excited-state visible emitting levels is achieved by st combination of phonon-assisted absorption, energy-transfer and phonon-assisted excited-state absorption processes. A threefold upconversion emission enhancement induced by thermal effects when the codoped sample was heated in the temperature range of 20-200 degreesC is demonstrated. The thermal-induced enhancement is attributed to a multiphonon-assisted anti-Stokes process which takes place in the excitation of the ytterbium and excited-state absorption of the praseodymium. The thermal effect is modelled by conventional rate equations considering temperature-dependent effective absorption cross-sections for the F-2(7/2)-F-2(5/2) ytterbium transition and (1)G(4)-P-3(0) praseadymium excited-state absorption, and it is shown to agree very well with experimental results. Frequency upconversion in singly Pr3+-doped samples pumped at 836 nm and 1.064 mum in a two-beam configuration is also examined.

Upconversion fluorescence spectroscopy of Er3+/Yb3+-doped heavy metal Bi2O3-Na2O-Nb2O5-GeO2 glass

Upconversion fluorescence emission of Er3+/Yb3+-doped Bi2O3-Na2O-Nb2O5-GeO2 heavy metal glass samples excited at 1.06 mu m is experimentally investigated. The results reveal the existence of intense emission bands centered around 520, 545, and 655 nm. The germano-niobate based host glass presents high transparency in the region of 400-2700 nm, the capability of incorporating high dopant concentrations, high melting temperature, and large resistance to atmospheric moisture. The observed intensity of the green fluorescence emission, suggested that the niobium based host glass material plays an important role in the efficiency of the upconversion process. Emission lines centered at 425, 483, 503, 608, and 628 nm were also observed. (C) 1997 American Institute of Physics.

Infrared-to-visible upconversion emission in Er3+ doped TeO2-WO3-Bi2O3 glasses with silver nanoparticles

The influence of silver nanoparticles (NPs) on the frequency upconversion luminescence in Er3+ doped TeO2-WO3-Bi2O3 glasses is reported. The effect of the NPs on the Er3+ luminescence was controlled by appropriate heat-treatment of the samples. Enhancement up to 700% was obtained for the upconverted emissions at 527, 550, and 660 nm, when a laser at 980 nm is used for excitation. Since the laser frequency is far from the NPs surface plasmon resonance frequency, the luminescence enhancement is attributed to the local field increase in the proximity of the NPs and not to energy transfer from the NPs to the emitters as is usually reported. This is the first time that the effect is investigated for tellurite-tungstate-bismutate glasses and the enhancement observed is the largest reported for a tellurium oxide based glass. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754468]

Infrared-to-visible upconversion in Yb3+/Er3+ co-doped PbO-GeO2 glass with silver nanoparticles

Enhanced frequency upconversion (UC) emission was studied in Yb3+/Er3+ co-doped PbO-GeO2 glass containing silver nanoparticles (NPs). Optical excitation was achieved with a laser operating at 980 nm in resonance with the Yb3+ transition F-4(5/2)-> F-4(7/2). The intensity of the whole UC spectrum from 400 to 700 nm was intensified due to the influence of silver NPs. The green and red emissions were enhanced by more than 300%. Emission bands centered at 408 nm and 480 nm were also detected corresponding to the H-2(9/2)-> I-4(15/2) and F-4(7/2)-> I-4(15/2) transitions of Er3+ ion. An intensity enhancement of approximate to 150% due to the NPs was measured. For the first time the influence of silver NPs on the blue emission of Yb3+/Er3+ co-doped PbO-GeO2 glass is reported. The large enhancement in the whole UC spectrum is due to the increased local field in the Er3+ ions locations and the proximity between the luminescence wavelengths and the NPs surface plasmon resonance. (C) 2010 Elsevier B.V. All rights reserved.

Time-resolved fluorescence spectroscopy of white-spot caries in human enamel

The objective is to differentiate noncavitated caries enamel through time-resolved fluorescence and to find excitation and emission parameters that can be applied in future clinical practice for detection of caries lesions that are not clearly visible to the professional. Sixteen human teeth with noncavitiated white-spot caries were selected for this work. Fluorescence intensity decay was measured by using an apparatus based on the time-correlated single-photon counting method. An optical fiber bundle was employed for sample excitation (440 nm), and the fluorescence collected by the same bundle (500 nm) was registered. The average lifetime for sound enamel was 7: 93 +/- 0: 09, 2: 46 +/- 0: 04, and 0: 51 +/- 0: 02 ns, whereas for the carious enamel the lifetimes were 4: 84 +/- 0: 06, 1: 35 +/- 0: 02, and 0: 16 +/- 0: 01 ns. It was concluded that it is possible to differentiate between carious and sound regions by time-resolved fluorescence and that, although the origin of enamel fluorescence is still uncertain, the lifetime values seem to be typical of fluorophores like collagen I. (C) 2010 Optical Society of America

Size dependent fluorescence spectroscopy of nanocolloids of ZnO

In this article we present size dependent spectroscopic observations of nanocolloids of ZnO. ZnO is reported to show two emission bands, an ultraviolet (UV) emission band and another in the green region. Apart from the known band gap 380 nm and impurity 530 nm emissions, we have found some peculiar features in the fluorescence spectra that are consistent with the nanoparticle size distribution. Results show that additional emissions at 420 and 490 nm are developed with particle size. The origin of the visible band emission is discussed. The mechanism of the luminescence suggests that UV luminescence of ZnO colloid is related to the transition from conduction band edge to valence band, and visible luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies and by the transition from conduction band to deep acceptor level due to impurities and defect states. A correlation analysis between the particle size and spectroscopic observations is also discussed.

Twentyfold blue upconversion emission enhancement through thermal effects in Pr3+/Yb3+-codoped fluoroindate glasses excited at 1.064 mu m

Infrared-to-visible upconversion emission enhancement through thermal effects in Yb3+-sensitized Pr3+-doped fluoroindate glasses excited at 1.064 mu m is investigated. A twentyfold increase in the 485 nm blue emission intensity as the sample temperature was varied from 20 to 260 degrees C was observed. The visible upconversion fluorescence enhancement is ascribed to the temperature dependent multiphonon-assisted anti-Stokes excitation of the ytterbium sensitizer and excited-state absorption of the praseodymium acceptor. A model based upon conventional rate equations considering a temperature dependent effective absorption cross section for the F-2(7/2)-->F-2(5/2) transition of the Yb3+ and (1)G(4)-->P-3(0) excited-state absorption of the Pr3+, agrees very well with the experimental results. (C) 2000 American Institute of Physics. [S0021-8979(00)08209-8].

Fluorescence spectroscopy for tongue carcinoma detection: Study in an animal model

Fluorescence diagnosis of malignant lesions has been showed as an attractive optical technique due especially to its real-time response and a more objective and quantitative evaluation. Even though the oral cavity allows a direct examination many lesions are diagnosed when it is already in advanced stage, compromising the patient prognosis. In this study, the fluorescence spectroscopy was used to the detection of chemically induced carcinoma at the lateral border of the tongue in a hamster model. Two excitations wavelengths in visible region were applied: 442 and 532 nm. All the spectra results were analyzed comparing with the histopathological diagnosis. The better results were achieved with the 442 nm laser excitation. The spectra from carcinoma showed new emission bands and these were used to determined different ratios for a quantitative analysis. Using the 625-645 nm fluorescence range under 442 nm excitation (A3 coefficient) the percentage of false negative was of 9.1%, however the false positive percentage was of 18.5%. The 532 nm excitation provided a better normal tissue detection compared to 442 nm excitation. The ideal clinical condition is probably the use of multiple wavelengths excitation for a broader tissue fluorescence investigation.

Efficient UV-visible upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate vitroceramic

Cooperative energy-transfer upconversion luminescence in Tb 3+/Yb 3+-codoped PbGeO 3-PbF 2-CdF 2 vitroceramic and its precursor glass under resonant and off-resonance infrared excitation, is investigated. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm, identified as due to the 5D 3( 5G 6 → 7F J(J=6,5,4) and 5D 4 → 7F J(J=6,5,4,3) transitions, respectively, were readily observed. The results indicate that cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The comparison of the upconversion process in a vitroceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.

Comparing Near-infrared Conventional Diffuse Reflectance Spectroscopy And Hyperspectral Imaging For Determination Of The Bulk Properties Of Solid Samples By Multivariate Regression: Determination Of Mooney Viscosity And Plasticity Indices Of Natural Rubber.

Conventional reflectance spectroscopy (NIRS) and hyperspectral imaging (HI) in the near-infrared region (1000-2500 nm) are evaluated and compared, using, as the case study, the determination of relevant properties related to the quality of natural rubber. Mooney viscosity (MV) and plasticity indices (PI) (PI0 - original plasticity, PI30 - plasticity after accelerated aging, and PRI - the plasticity retention index after accelerated aging) of rubber were determined using multivariate regression models. Two hundred and eighty six samples of rubber were measured using conventional and hyperspectral near-infrared imaging reflectance instruments in the range of 1000-2500 nm. The sample set was split into regression (n = 191) and external validation (n = 95) sub-sets. Three instruments were employed for data acquisition: a line scanning hyperspectral camera and two conventional FT-NIR spectrometers. Sample heterogeneity was evaluated using hyperspectral images obtained with a resolution of 150 × 150 μm and principal component analysis. The probed sample area (5 cm(2); 24,000 pixels) to achieve representativeness was found to be equivalent to the average of 6 spectra for a 1 cm diameter probing circular window of one FT-NIR instrument. The other spectrophotometer can probe the whole sample in only one measurement. The results show that the rubber properties can be determined with very similar accuracy and precision by Partial Least Square (PLS) regression models regardless of whether HI-NIR or conventional FT-NIR produce the spectral datasets. The best Root Mean Square Errors of Prediction (RMSEPs) of external validation for MV, PI0, PI30, and PRI were 4.3, 1.8, 3.4, and 5.3%, respectively. Though the quantitative results provided by the three instruments can be considered equivalent, the hyperspectral imaging instrument presents a number of advantages, being about 6 times faster than conventional bulk spectrometers, producing robust spectral data by ensuring sample representativeness, and minimizing the effect of the presence of contaminants.

Optical fiber laser induced fluorescence spectroscopy as a citrus canker diagnostic

Citrus canker is a serious disease caused by Xanthomonas citri subsp. citri bacteria, which infects citrus plants (Citrus spp.) leading to large economic losses in citrus production worldwide. In this work, laser induced fluorescence spectroscopy (LIF) was investigated as a diagnostic technique for citrus canker disease in citrus trees at an orchard using a portable optical fiber based spectrometer. For comparison we have applied LIF to leaves contaminated with citrus canker, citrus scab, citrus variegates chlorosis, and Huanglongbing (HLB, Greening). In order to reduce the noise in the data, we collected spectra from ten leaves with visual symptoms of diseases and from five healthy leaves per plant. This procedure is carried out in order to minimize the environmental effect on the spectrum (water and nutrient supply) of each plant. Our results show that this method presents a high sensitivity (similar to 90%), however it does present a low specificity (similar to 70%) for citrus canker diagnostic. We believe that such poor performance is due to the fact that the optical fiber collects light from only a small part of the leaf. Such results may be improved using the fluorescence imaging technique on the whole leaf. (C) 2010 Optical Society of America

Fluorescence spectroscopy for the detection of tongue carcinoma - validation in an animal model

The efficacy of fluorescence spectroscopy to detect squamous cell carcinoma is evaluated in an animal model following laser excitation at 442 and 532 nm. Lesions are chemically induced with a topical DMBA application at the left lateral tongue of Golden Syrian hamsters. The animals are investigated every 2 weeks after the 4th week of induction until a total of 26 weeks. The right lateral tongue of each animal is considered as a control site (normal contralateral tissue) and the induced lesions are analyzed as a set of points covering the entire clinically detectable area. Based on fluorescence spectral differences, four indices are determined to discriminate normal and carcinoma tissues, based on intraspectral analysis. The spectral data are also analyzed using a multivariate data analysis and the results are compared with histology as the diagnostic gold standard. The best result achieved is for blue excitation using the KNN (K-nearest neighbor, a interspectral analysis) algorithm with a sensitivity of 95.7% and a specificity of 91.6%. These high indices indicate that fluorescence spectroscopy may constitute a fast noninvasive auxiliary tool for diagnostic of cancer within the oral cavity. (C) 2008 Society of Photo-Optical Instrumentation Engineers.

Detection of mechanical and disease stresses in citrus plants by fluorescence spectroscopy

We have investigated the detection of mechanical and disease stresses in citrus plants (Citrus limonia [L.] Osbeck) using laser-induced fluorescence spectroscopy. Due to its economic importance we have chosen to investigate the citrus canker disease, which is caused by the Xanthomonas axonopodis pv. citri bacteria. Mechanical stress was also studied because it plays an important role in the plant's infection by such bacteria. A laser-induced fluorescence spectroscopy system, composed of a spectrometer and a 532 nm 10 mW excitation laser was used to perform fluorescence spectroscopy. The ratio of two chlorophyll fluorescence bands allows us to detect and discriminate between mechanical and disease stresses. This ability to discriminate may have an important application in the field to detect citrus canker infected trees. (c) 2008 Optical Society of America.

Fluorescence spectroscopy of small peptides interacting with microheterogeneous micelles

Many peptides containing tryptophan have therapeutic uses and can be studied by their fluorescent properties. The biological activity of these peptides involves interactions with many cellular components and micelles can function as carriers inside organisms. We report results from the interaction of small peptides containing tryptophan with several microheterogeneous systems: sodium dodecyl sulphate (SDS) micelles; sodium dodecyl sulphate-poly(ethylene oxide) (SDS-PEO) aggregates; and neutral polymeric micelles. We observed that specific parameters, such as wavelength of maximum emission and fluorescence anisotropy, could be used to ascertain the occurrence of interactions. Affinity constants were determined from changes in the intensity of emission while structural modifications in rotameric conformations were verified from time-resolved measurements. Information about the location and diffusion of peptides in the microheterogeneous systems were obtained from tryptophan emission quenching experiments using N-alkylpyridinium ions. The results show the importance of electrostatic and hydrophobic effects, and of the ionization state of charged residues, in the presence of anionic and amphiphilic SDS in the microheterogeneous systems. Conformational stability of peptides is best preserved in the interaction with the neutral polymeric micelles. (C) 2009 Elsevier B.V. All rights reserved.