Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Synthesis and characterization of mono- and bis-D-pi-A cryptand derivatives for second-order nonlinear optics and its modulation with different metal ion inputs

Two new classes of mono- and bis-D-pi-A cryptand derivatives with a flexible and a rigid cryptand core have been synthesized. The linear and nonlinear optical properties of these molecules are probed. The three dimensional cavity of the cryptand moiety has been utilized to modulate the SHG intensity to different extents in solution with metal ion inputs such as Ni-II,Cu-II,Zn-II, and Cd-II. We also report that decomplexation events can be used to reversibly modulate their NLO responses.

Anomalous Temperature dependence of Fermi-edge Singularity in Modulation-doped AlGaAs/InGaAs/GaAs hetero-structures

The temperature and power dependence of Fermi-edge singularity (FES) in high-density two-dimensional electron gas, specific to pseudomorphic AlxGa1-xAs/InyGa1-yAs/GaAs heterostructures is studied by photoluminescence (PL). In all these structures, there are two prominent transitions E11 and E21 considered to be the result of electron-hole recombination from first and second electron sub-bands with that of first heavy-hole sub-band. FES is observed approximately 5 -10 meV below the E21 transition. At 4.2 K, FES appears as a lower energy shoulder to the E21 transition. The PL intensity of all the three transitions E11, FES and E21 grows linearly with excitation power. However, we observe anomalous behavior of FES with temperature. While PL intensity of E11 and E21 decrease with increasing temperature, FES transition becomes stronger initially and then quenches-off slowly (till 40K). Though it appears as a distinct peak at about 20 K, its maximum is around 7 - 13 K.

Fusion of multi resolution remote sensing data for urban sprawl analysis

Urban population is growing at around 2.3 percent per annum in India. This is leading to urbanisation and often fuelling the dispersed development in the outskirts of urban and village centres with impacts such as loss of agricultural land, open space, and ecologically sensitive habitats. This type of upsurge is very much prevalent and persistent in most places, often inferred as sprawl. The direct implication of such urban sprawl is the change in land use and land cover of the region and lack of basic amenities, since planners are unable to visualise this type of growth patterns. This growth is normally left out in all government surveys (even in national population census), as this cannot be grouped under either urban or rural centre. The investigation of patterns of growth is very crucial from regional planning point of view to provide basic amenities in the region. The growth patterns of urban sprawl can be analysed and understood with the availability of temporal multi-sensor, multi-resolution spatial data. In order to optimise these spectral and spatial resolutions, image fusion techniques are required. This aids in integrating a lower spatial resolution multispectral (MSS) image (for example, IKONOS MSS bands of 4m spatial resolution) with a higher spatial resolution panchromatic (PAN) image (IKONOS PAN band of 1m spatial resolution) based on a simple spectral preservation fusion technique - the Smoothing Filter-based Intensity Modulation (SFIM). Spatial details are modulated to a co-registered lower resolution MSS image without altering its spectral properties and contrast by using a ratio between a higher resolution image and its low pass filtered (smoothing filter) image. The visual evaluation and statistical analysis confirms that SFIM is a superior fusion technique for improving spatial detail of MSS images with the preservation of spectral properties.

Remote detection and distinction of ants using nest-site specific LISS-derived Normalised Difference Vegetation Index

This study in Western Ghats, India, investigates the relation between nesting sites of ants and a single remotely sensed variable: the Normalised Difference Vegetation Index (NDVI). We carried out sampling in 60 plots each measuring 30 x 30 m and recorded nest sites of 13 ant species. We found that NDVI values at the nesting sites varied considerably between individual species and also between the six functional groups the ants belong to. The functional groups Cryptic Species, Tropical Climate Specialists and Specialist Predators were present in regions with high NDVI whereas Hot Climate Specialists and Opportunists were found in sites with low NDVI. As expected we found that low NDVI values were associated with scrub jungles and high NDVI values with evergreen forests. Interestingly, we found that Pachycondyla rufipes, an ant species found only in deciduous and evergreen forests, established nests only in sites with low NDVI (range = 0.015 - 0.1779). Our results show that these low NDVI values in deciduous and evergreen forests correspond to canopy gaps in otherwise closed deciduous and evergreen forests. Subsequent fieldwork confirmed the observed high prevalence of P. rufipes in these NDVI-constrained areas. We discuss the value of using NDVI for the remote detection and distinction of ant nest sites.

Pixel based fusion using IKONOS imagery

Pixel based image fusion entails combining geometric details of a high-resolution Panchromatic (PAN) image and spectral information of a low-resolution Multispectral (MS) image to produce images with highest spatial content while preserving the spectral information. This work reviews and implements six fusion techniques – À Trous algorithm based wavelet transform (ATW), Mulitresolution Analysis based Intensity Modulation, Gram Schmidt fusion, CN Spectral, Luminance Chrominance and High pass fusion (HPF) on IKONOS imagery having 1 m PAN and 4 m MS channels. Comparative performance analysis of techniques by various methods reveals that ATW followed by HPF perform best among all the techniques.