Selectively excited luminescence and magnetic circular dichroism of Cr4+-doped YAG and YGG

Site selective luminescence and magnetic circular dichroism experiments on Cr4+-doped yttrium aluminum garnet and yttrium gallium garnet have been made at low temperature. The spectral assignments for these near-IR lasing materials have been made using experimental data and ligand field calculations guided by the known geometry of the lattices. [S0163-1829(99)07003-4].

Reverse Microemulsion Synthesis, Structure, and Luminescence of Nanosized REPO(4):Ln(3+) (RE = La, Y, Gd, or Yb, and Ln = Eu, Tm, or Er)

A surfactant-mediated solution route for the obtainment of nanosized rare-earth orthophosphates of different compositions (LaPO(4):Eu(3+), (Y,Gd)PO(4):Eu(3+),LaPO(4):Tm(3+), YPO(4):Tm(3+), and YbPO(4):Er(3+)) is presented, and the implications of the morphology control on the solids properties are discussed. The solids are prepared in water-in-heptane microemulsions, using cetyltrimethylammonium bromide and 1-butanol as the surfactant and cosurfactant; the alteration of the starting microemulsion composition allows the obtainment of similar to 30 nm thick nanorods with variable length. The morphology and the structure of the solids were evaluated through scanning electron microscopy and through powder X-ray diffractometry; dynamic light scattering and thermal analyses were also performed. The obtained materials were also characterized through vibrational (FTIR) and luminescence spectroscopy (emission/excitation, luminescence lifetimes, chromaticity, and quantum efficiency), where the red, blue, and upconversion emissions of the prepared phosphors were evaluated.

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).

Monitoring the composition and form of urban environments based on the vegetation-impervious surface-soil (VIS) model by sub-pixel analysis techniques

The majority of the world's population now resides in urban environments and information on the internal composition and dynamics of these environments is essential to enable preservation of certain standards of living. Remotely sensed data, especially the global coverage of moderate spatial resolution satellites such as Landsat, Indian Resource Satellite and Systeme Pour I'Observation de la Terre (SPOT), offer a highly useful data source for mapping the composition of these cities and examining their changes over time. The utility and range of applications for remotely sensed data in urban environments could be improved with a more appropriate conceptual model relating urban environments to the sampling resolutions of imaging sensors and processing routines. Hence, the aim of this work was to take the Vegetation-Impervious surface-Soil (VIS) model of urban composition and match it with the most appropriate image processing methodology to deliver information on VIS composition for urban environments. Several approaches were evaluated for mapping the urban composition of Brisbane city (south-cast Queensland, Australia) using Landsat 5 Thematic Mapper data and 1:5000 aerial photographs. The methods evaluated were: image classification; interpretation of aerial photographs; and constrained linear mixture analysis. Over 900 reference sample points on four transects were extracted from the aerial photographs and used as a basis to check output of the classification and mixture analysis. Distinctive zonations of VIS related to urban composition were found in the per-pixel classification and aggregated air-photo interpretation; however, significant spectral confusion also resulted between classes. In contrast, the VIS fraction images produced from the mixture analysis enabled distinctive densities of commercial, industrial and residential zones within the city to be clearly defined, based on their relative amount of vegetation cover. The soil fraction image served as an index for areas being (re)developed. The logical match of a low (L)-resolution, spectral mixture analysis approach with the moderate spatial resolution image data, ensured the processing model matched the spectrally heterogeneous nature of the urban environments at the scale of Landsat Thematic Mapper data.

Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

Vietnam's strategic hedging vis-à-vis China: the roles of the European Union and Russia

Against the backdrop of China's assertive policies in the South China Sea, the present study evaluates how Vietnam has sought to mitigate the increasingly unequal regional power distribution vis-à-vis China. It argues that Vietnam tends to cope with China mainly by engaging itself in hedging strategies on the basis of diversified and strong relationships with different players. Appraising the roles of Russia and the European Union (EU), the study analyzes the pay-offs of Vietnam's military hedging with Russia and its economic hedging with the EU.

UV-Vis spectroscopic study preferential solvation and intermolecular interactions in methanol/1-propanol/acetonitrile by means of solvatochromic probes

Solvatochromic UV-Vis shifts of four indicators (4-nitroaniline, 4-nitroanisole, 4-nitrophenol and N,N-dimethy-1-4-nitro aniline) have been measured at 298.15 K in the ternary mixture methano1/1-propanol/acetonitrile (MeOH/1-PrOH/MeCN) in a total of 22 mole fractions, along with 18 additional mole fractions for each of the corresponding binary mixtures, MeOH/1-PrOH, 1-PrOH/MeCN and MeOH/MeCN. These values, combined with our previous experimental results for 2,6-dipheny1-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (Reichardt's betaine dye) in the same mixtures, permitted the computation of the Kamlet-Taft solvent parameters, alpha, beta, and pi*. The rationalization of the spectroscopic behavior of each probe within each mixture's whole mole fraction range was achieved through the use of the Bosch and Roses preferential solvation model. The applied model allowed the identification of synergistic behaviors in MeCN/alcohol mixtures and thus to infer the existence of solvent complexes in solution. Also, the addition of small amounts of MeCN to the binary mixtures was seen to cause a significant variation in pi*, whereas the addition of alcohol to MeCN mixtures always lead to a sudden change in a and The behavior of these parameters in the ternary mixture was shown to be mainly determined by the contributions of the underlying binary mixtures. (C) 2014 Elsevier B.V. All rights reserved.

Color and Luminescence stability of selected dental materials in vitro

To study luminescence, reflectance, and color stability of dental composites and ceramics. Materials and Methods: IPS e.max, IPS Classic, Gradia, and Sinfony materials were tested, both unpolished (as-cast) and polished specimens. Coffee, tea, red wine, and distilled water (control) were used as staining drinks. Disk-shaped specimens were soaked in the staining drinks for up to 5 days. Color was measured by a colorimeter. Fluorescence was recorded using a spectrofluorometer, in the front-face geometry. Time-resolved fluorescence spectra were recorded using a laser nanosecond spectrofluorometer. Results: The exposure of the examined dental materials to staining drinks caused changes in color of the composites and ceramics, with the polished specimens exhibiting significantly lower color changes as compared to unpolished specimens. Composites exhibited lower color stability as compared to ceramic materials. Water also caused perceptible color changes in most materials. The materials tested demonstrated significantly different initial luminescence intensities. Upon exposure to staining drinks, luminescence became weaker by up to 40%, dependent on the drink and the material. Time-resolved luminescence spectra exhibited some red shift of the emission band at longer times, with the lifetimes in the range of tens of nanoseconds. Conclusions: Unpolished specimens with a more developed surface have lower color stability. Specimens stored in water develop some changes in their visual appearance. The presently proposed methods are effective in evaluating the luminescence of dental materials. Luminescence needs to be tested in addition to color, as the two characteristics are uncorrelated. It is important to further improve the color and luminescence stability of dental materials.

In situ NIR spectroscopy monitoring of plasmid production processes effect of producing strain, medium composition and the cultivation strategy

BACKGROUNDWhile the pharmaceutical industry keeps an eye on plasmid DNA production for new generation gene therapies, real-time monitoring techniques for plasmid bioproduction are as yet unavailable. This work shows the possibility of in situ monitoring of plasmid production in Escherichia coli cultures using a near infrared (NIR) fiber optic probe. RESULTSPartial least squares (PLS) regression models based on the NIR spectra were developed for predicting bioprocess critical variables such as the concentrations of biomass, plasmid, carbon sources (glucose and glycerol) and acetate. In order to achieve robust models able to predict the performance of plasmid production processes, independently of the composition of the cultivation medium, cultivation strategy (batch versus fed-batch) and E. coli strain used, three strategies were adopted, using: (i) E. coliDH5 cultures conducted under different media compositions and culture strategies (batch and fed-batch); (ii) engineered E. coli strains, MG1655endArecApgi and MG1655endArecA, grown on the same medium and culture strategy; (iii) diverse E. coli strains, over batch and fed-batch cultivations and using different media compositions. PLS models showed high accuracy for predicting all variables in the three groups of cultures. CONCLUSIONNIR spectroscopy combined with PLS modeling provides a fast, inexpensive and contamination-free technique to accurately monitoring plasmid bioprocesses in real time, independently of the medium composition, cultivation strategy and the E. coli strain used.

Geospatial assessment of pest-induced forest damage through the use of UAV-bases NIR imaging and Gi-technology

Dissertation submitted in partial fulfillment of the requirements for the Degree of Master of Science in Geospatial Technologies.

Discrimination of Brazilian propolis according to the seasoning using chemometrics and machine learning based on UV-Vis scanning data

Propolis is a chemically complex biomass produced by honeybees (Apis mellifera) from plant resins added of salivary enzymes, beeswax, and pollen. The biological activities described for propolis were also identified for donor plants resin, but a big challenge for the standardization of the chemical composition and biological effects of propolis remains on a better understanding of the influence of seasonality on the chemical constituents of that raw material. Since propolis quality depends, among other variables, on the local flora which is strongly influenced by (a)biotic factors over the seasons, to unravel the harvest season effect on the propolis chemical profile is an issue of recognized importance. For that, fast, cheap, and robust analytical techniques seem to be the best choice for large scale quality control processes in the most demanding markets, e.g., human health applications. For that, UV-Visible (UV-Vis) scanning spectrophotometry of hydroalcoholic extracts (HE) of seventy-three propolis samples, collected over the seasons in 2014 (summer, spring, autumn, and winter) and 2015 (summer and autumn) in Southern Brazil was adopted. Further machine learning and chemometrics techniques were applied to the UV-Vis dataset aiming to gain insights as to the seasonality effect on the claimed chemical heterogeneity of propolis samples determined by changes in the flora of the geographic region under study. Descriptive and classification models were built following a chemometric approach, i.e. principal component analysis (PCA) and hierarchical clustering analysis (HCA) supported by scripts written in the R language. The UV-Vis profiles associated with chemometric analysis allowed identifying a typical pattern in propolis samples collected in the summer. Importantly, the discrimination based on PCA could be improved by using the dataset of the fingerprint region of phenolic compounds ( = 280-400m), suggesting that besides the biological activities of those secondary metabolites, they also play a relevant role for the discrimination and classification of that complex matrix through bioinformatics tools. Finally, a series of machine learning approaches, e.g., partial least square-discriminant analysis (PLS-DA), k-Nearest Neighbors (kNN), and Decision Trees showed to be complementary to PCA and HCA, allowing to obtain relevant information as to the sample discrimination.

Antibiotic-dependent correlation between drug-induced killing and loss of luminescence in Streptococcus gordonii expressing luciferase.

Measuring antibiotic-induced killing relies on time-consuming biological tests. The firefly luciferase gene (luc) was successfully used as a reporter gene to assess antibiotic efficacy rapidly in slow-growing Mycobacterium tuberculosis. We tested whether luc expression could also provide a rapid evaluation of bactericidal drugs in Streptococcus gordonii. The suicide vectors pFW5luc and a modified version of pJDC9 carrying a promoterless luc gene were used to construct transcriptional-fusion mutants. One mutant susceptible to penicillin-induced killing (LMI2) and three penicillin-tolerant derivatives (LMI103, LMI104, and LMI105) producing luciferase under independent streptococcal promoters were tested. The correlation between antibiotic-induced killing and luminescence was determined with mechanistically unrelated drugs. Chloramphenicol (20 times the MIC) inhibited bacterial growth. In parallel, luciferase stopped increasing and remained stable, as determined by luminescence and Western blots. Ciprofloxacin (200 times the MIC) rapidly killed 1.5 log10 CFU/ml in 2-4 hr. Luminescence decreased simultaneously by 10-fold. In contrast, penicillin (200 times the MIC) gave discordant results. Although killing was slow (< or = 0.5 log10 CFU/ml in 2 hr), luminescence dropped abruptly by 50-100-times in the same time. Inactivating penicillin with penicillinase restored luminescence, irrespective of viable counts. This was not due to altered luciferase expression or stability, suggesting some kind of post-translational modification. Luciferase shares homology with aminoacyl-tRNA synthetase and acyl-CoA ligase, which might be regulated by macromolecule synthesis and hence affected in penicillin-inhibited cells. Because of resemblance, luciferase might be down-regulated simultaneously. Luminescence cannot be universally used to predict antibiotic-induced killing. Thus, introducing reporter enzymes sharing mechanistic similarities with normal metabolic reactions might reveal other effects than those expected.

Use of NIR spectroscopy and multivariate process spectra calibration methodology for pharmaceutical solid samples analysis

Accomplish high quality of final products in pharmaceutical industry is a challenge that requires the control and supervision of all the manufacturing steps. This request created the necessity of developing fast and accurate analytical methods. Near infrared spectroscopy together with chemometrics, fulfill this growing demand. The high speed providing relevant information and the versatility of its application to different types of samples lead these combined techniques as one of the most appropriated. This study is focused on the development of a calibration model able to determine amounts of API from industrial granulates using NIR, chemometrics and process spectra methodology.

White luminescence from Si+ and C+ ion-implanted SiO2 films

The microstructural and optical analysis of SiO2 layers emitting white luminescence is reported. These structures have been synthesized by sequential Si+ and C+ ion implantation and high-temperature annealing. Their white emission results from the presence of up to three bands in the photoluminescence (PL) spectra, covering the whole visible spectral range. The microstructural characterization reveals the presence of a complex multilayer structure: Si nanocrystals are only observed outside the main C-implanted peak region, with a lower density closer to the surface, being also smaller in size. This lack of uniformity in their density has been related to the inhibiting role of C in their growth dynamics. These nanocrystals are responsible for the band appearing in the red region of the PL spectrum. The analysis of the thermal evolution of the red PL band and its behavior after hydrogenation shows that carbon implantation also prevents the formation of well passivated Si/SiO2 interfaces. On the other hand, the PL bands appearing at higher energies show the existence of two different characteristics as a function of the implanted dose. For excess atomic concentrations below or equal to 10%, the spectra show a PL band in the blue region. At higher doses, two bands dominate the green¿blue spectral region. The evolution of these bands with the implanted dose and annealing time suggests that they are related to the formation of carbon-rich precipitates in the implanted region. Moreover, PL versus depth measurements provide a direct correlation of the green band with the carbon-implanted profile. These PL bands have been assigned to two distinct amorphous phases, with a composition close to elemental graphitic carbon or stoichiometric SiC.