Synthesis and spectral studies of methyl heterocylic systems

2-Carboxy-2?-methyldiphenyl sulfide was prepared by the Ullmann reaction and cyclodehydrated by sulfuric acid to afford 4-methylthioxanthone. 1-Methylthioxanthone was separated from the reaction mixture obtained upon cyclodehydration of 2-carboxy-3f-methyldiphenyl sulfide. In addition, 1-, 2-, 3- and 4-methylthioxanthone 10,10-dioxides were synthesized by oxidation of the corresponding thioxanthones. o-, m- and p-N-Tolylanthranilic acids were prepared by the Ullmann reaction and used as precursors for the preparation of 1-, 2- and 4- methyl-9-chloroacridine and finally 1-, 2-, 3- and 4-methylacridone. High resolution, 60 MHz PMR spectra were obtained on the four monomethyl isomers of xanthone, thioxanthone, thioxanthone 10,10-dioxide and acridone, and on 1-, 2- and 4-methyl-9-chloroacridine. For some compounds, coupling of all three different aromatic protons to the methyl was observed, two of the couplings typically being smaller than the third. With the large (ortho) coupling being on the order of 0.5 to 1.0 Hz, it was necessary to decouple the aromatic part of the spectrum. The magnitude of the ortho benzylic constant may be related to an incomplete Tr-bond delocalization in the molecules.

Optimization of the Mechanical and Optical Properties of Tunable Optical Sensor Arrays (TOSA) for a Nanospectrometer in the Visible and Near Infrared Spectral Range

Tunable Optical Sensor Arrays (TOSA) based on Fabry-Pérot (FP) filters, for high quality spectroscopic applications in the visible and near infrared spectral range are investigated within this work. The optical performance of the FP filters is improved by using ion beam sputtered niobium pentoxide (Nb2O5) and silicon dioxide (SiO2) Distributed Bragg Reflectors (DBRs) as mirrors. Due to their high refractive index contrast, only a few alternating pairs of Nb2O5 and SiO2 films can achieve DBRs with high reflectivity in a wide spectral range, while ion beam sputter deposition (IBSD) is utilized due to its ability to produce films with high optical purity. However, IBSD films are highly stressed; resulting in stress induced mirror curvature and suspension bending in the free standing filter suspensions of the MEMS (Micro-Electro-Mechanical Systems) FP filters. Stress induced mirror curvature results in filter transmission line degradation, while suspension bending results in high required filter tuning voltages. Moreover, stress induced suspension bending results in higher order mode filter operation which in turn degrades the optical resolution of the filter. Therefore, the deposition process is optimized to achieve both near zero absorption and low residual stress. High energy ion bombardment during film deposition is utilized to reduce the film density, and hence the film compressive stress. Utilizing this technique, the compressive stress of Nb2O5 is reduced by ~43%, while that for SiO2 is reduced by ~40%. Filters fabricated with stress reduced films show curvatures as low as 100 nm for 70 μm mirrors. To reduce the stress induced bending in the free standing filter suspensions, a stress optimized multi-layer suspension design is presented; with a tensile stressed metal sandwiched between two compressively stressed films. The stress in Physical Vapor Deposited (PVD) metals is therefore characterized for use as filter top-electrode and stress compensating layer. Surface micromachining is used to fabricate tunable FP filters in the visible spectral range using the above mentioned design. The upward bending of the suspensions is reduced from several micrometers to less than 100 nm and 250 nm for two different suspension layer combinations. Mechanical tuning of up to 188 nm is obtained by applying 40 V of actuation voltage. Alternatively, a filter line with transmission of 65.5%, Full Width at Half Maximum (FWHM) of 10.5 nm and a stopband of 170 nm (at an output wavelength of 594 nm) is achieved. Numerical model simulations are also performed to study the validity of the stress optimized suspension design for the near infrared spectral range, wherein membrane displacement and suspension deformation due to material residual stress is studied. Two bandpass filter designs based on quarter-wave and non-quarter-wave layers are presented as integral components of the TOSA. With a filter passband of 135 nm and a broad stopband of over 650 nm, high average filter transmission of 88% is achieved inside the passband, while maximum filter transmission of less than 1.6% outside the passband is achieved.

Resolution of the uncertainties in the radiative forcing of HFC-134a

HFC-134a (CF3CH2F) is the most rapidly growing hydrofluorocarbon in terms of atmospheric abundance. It is currently used in a large number of household refrigerators and air-conditioning systems and its concentration in the atmosphere is forecast to increase substantially over the next 50–100 years. Previous estimates of its radiative forcing per unit concentration have differed significantly 25%. This paper uses a two-step approach to resolve this discrepancy. In the first step six independent absorption cross section datasets are analysed. We find that, for the integrated cross section in the spectral bands that contribute most to the radiative forcing, the differences between the various datasets are typically smaller than 5% and that the dependence on pressure and temperature is not significant. A “recommended'' HFC-134a infrared absorption spectrum was obtained based on the average band intensities of the strongest bands. In the second step, the “recommended'' HFC-134a spectrum was used in six different radiative transfer models to calculate the HFC-134a radiative forcing efficiency. The clear-sky instantaneous radiative forcing, using a single global and annual mean profile, differed by 8%, between the 6 models, and the latitudinally-resolved adjusted cloudy sky radiative forcing estimates differed by a similar amount.

Infrared filters and coatings for the High Resolution Dynamics Limb Sounder (6-18µm)

This paper describes the spectral design and manufacture of the narrow bandpass filters and 6-18µm broadband antireflection coatings for the 21-channel NASA EOS-AURA High Resolution Dynamics Limb Sounder (HIRDLS). A method of combining the measured spectral characteristics of each filter and antireflection coating, together with the spectral response of the other optical elements in the instrument to obtain a predicted system throughput response is presented. The design methods used to define the filter and coating spectral requirements, choice of filter materials, multilayer designs and deposition techniques are discussed.

Spectral invariant behavior of zenith radiance around cloud edges observed by ARM SWS

The ARM Shortwave Spectrometer (SWS) measures zenith radiance at 418 wavelengths between 350 and 2170 nm. Because of its 1-sec sampling resolution, the SWS provides a unique capability to study the transition zone between cloudy and clear sky areas. A spectral invariant behavior is found between ratios of zenith radiance spectra during the transition from cloudy to cloud-free. This behavior suggests that the spectral signature of the transition zone is a linear mixture between the two extremes (definitely cloudy and definitely clear). The weighting function of the linear mixture is a wavelength-independent characteristic of the transition zone. It is shown that the transition zone spectrum is fully determined by this function and zenith radiance spectra of clear and cloudy regions. An important result of these discoveries is that high temporal resolution radiance measurements in the clear-to-cloud transition zone can be well approximated by lower temporal resolution measurements plus linear interpolation.

Physical interpretation of the spectral radiative signature in the transition zone between cloud-free and cloudy regions

One-second-resolution zenith radiance measure- ments from the Atmospheric Radiation Measurement pro- gram’s new shortwave spectrometer (SWS) provide a unique opportunity to analyze the transition zone between cloudy and cloud-free air, which has considerable bearing on the aerosol indirect effect. In the transition zone, we find a re- markable linear relationship between the sum and difference of radiances at 870 and 1640 nm wavelengths. The intercept of the relationship is determined primarily by aerosol prop- erties, and the slope by cloud properties. We then show that this linearity can be predicted from simple theoretical con- siderations and furthermore that it supports the hypothesis of inhomogeneous mixing, whereby optical depth increases as a cloud is approached but the effective drop size remains un- changed.

The troposphere-to-stratosphere transition in kinetic energy spectra and nonlinear spectral fluxes as seen in ECMWF analyses

Global horizontal wavenumber kinetic energy spectra and spectral fluxes of rotational kinetic energy and enstrophy are computed for a range of vertical levels using a T799 ECMWF operational analysis. Above 250 hPa, the kinetic energy spectra exhibit a distinct break between steep and shallow spectral ranges, reminiscent of dual power-law spectra seen in aircraft data and high-resolution general circulation models. The break separates a large-scale ‘‘balanced’’ regime in which rotational flow strongly dominates divergent flow and a mesoscale ‘‘unbalanced’’ regime where divergent energy is comparable to or larger than rotational energy. Between 230 and 100 hPa, the spectral break shifts to larger scales (from n 5 60 to n 5 20, where n is spherical harmonic index) as the balanced component of the flow preferentially decays. The location of the break remains fairly stable throughout the stratosphere. The spectral break in the analysis occurs at somewhat larger scales than the break seen in aircraft data. Nonlinear spectral fluxes defined for the rotational component of the flow maximize between about 300 and 200 hPa. Large-scale turbulence thus centers on the extratropical tropopause region, within which there are two distinct mechanisms of upscale energy transfer: eddy–eddy interactions sourcing the transient energy peak in synoptic scales, and zonal mean–eddy interactions forcing the zonal flow. A well-defined downscale enstrophy flux is clearly evident at these altitudes. In the stratosphere, the transient energy peak moves to planetary scales and zonal mean–eddy interactions become dominant.

A high-resolution near-infrared extraterrestrial solar spectrum derived from ground-based Fourier transform spectrometer measurements

A detailed spectrally-resolved extraterrestrial solar spectrum (ESS) is important for line-by-line radiative transfer modeling in the near-infrared (near-IR). Very few observationally-based high-resolution ESS are available in this spectral region. Consequently the theoretically-calculated ESS by Kurucz has been widely adopted. We present the CAVIAR (Continuum Absorption at Visible and Infrared Wavelengths and its Atmospheric Relevance) ESS which is derived using the Langley technique applied to calibrated observations using a ground-based high-resolution Fourier transform spectrometer (FTS) in atmospheric windows from 2000–10000 cm-1 (1–5 μm). There is good agreement between the strengths and positions of solar lines between the CAVIAR and the satellite-based ACE-FTS (Atmospheric Chemistry Experiment-FTS) ESS, in the spectral region where they overlap, and good agreement with other ground-based FTS measurements in two near-IR windows. However there are significant differences in the structure between the CAVIAR ESS and spectra from semi-empirical models. In addition, we found a difference of up to 8 % in the absolute (and hence the wavelength-integrated) irradiance between the CAVIAR ESS and that of Thuillier et al., which was based on measurements from the Atmospheric Laboratory for Applications and Science satellite and other sources. In many spectral regions, this difference is significant, as the coverage factor k = 2 (or 95 % confidence limit) uncertainties in the two sets of observations do not overlap. Since the total solar irradiance is relatively well constrained, if the CAVIAR ESS is correct, then this would indicate an integrated “loss” of solar irradiance of about 30 W m-2 in the near-IR that would have to be compensated by an increase at other wavelengths.

Objective determination of feature resolution in two sea surface temperature analyses

Considerable effort is presently being devoted to producing high-resolution sea surface temperature (SST) analyses with a goal of spatial grid resolutions as low as 1 km. Because grid resolution is not the same as feature resolution, a method is needed to objectively determine the resolution capability and accuracy of SST analysis products. Ocean model SST fields are used in this study as simulated “true” SST data and subsampled based on actual infrared and microwave satellite data coverage. The subsampled data are used to simulate sampling errors due to missing data. Two different SST analyses are considered and run using both the full and the subsampled model SST fields, with and without additional noise. The results are compared as a function of spatial scales of variability using wavenumber auto- and cross-spectral analysis. The spectral variance at high wavenumbers (smallest wavelengths) is shown to be attenuated relative to the true SST because of smoothing that is inherent to both analysis procedures. Comparisons of the two analyses (both having grid sizes of roughly ) show important differences. One analysis tends to reproduce small-scale features more accurately when the high-resolution data coverage is good but produces more spurious small-scale noise when the high-resolution data coverage is poor. Analysis procedures can thus generate small-scale features with and without data, but the small-scale features in an SST analysis may be just noise when high-resolution data are sparse. Users must therefore be skeptical of high-resolution SST products, especially in regions where high-resolution (~5 km) infrared satellite data are limited because of cloud cover.

Synergistic angular and spectral estimation of aerosol properties using CHRIS/PROBA-1 and simulated Sentinel-3~data

A method has been developed to estimate Aerosol Optical Depth (AOD), Fine Mode Fraction (FMF) and Single Scattering Albedo (SSA) over land surfaces using simulated Sentinel-3 data. The method uses inversion of a coupled surface/atmosphere radiative transfer model, and includes a general physical model of angular surface reflectance. An iterative process is used to determine the optimum value of the aerosol properties providing the best fit of the corrected reflectance values for a number of view angles and wavelengths with those provided by the physical model. A method of estimating AOD using only angular retrieval has previously been demonstrated on data from the ENVISAT and PROBA-1 satellite instruments, and is extended here to the synergistic spectral and angular sampling of Sentinel-3 and the additional aerosol properties. The method is tested using hyperspectral, multi-angle Compact High Resolution Imaging Spectrometer (CHRIS) images. The values obtained from these CHRIS observations are validated using ground based sun-photometer measurements. Results from 22 image sets using the synergistic retrieval and improved aerosol models show an RMSE of 0.06 in AOD, reduced to 0.03 over vegetated targets.

Derivation of an urban materials spectral library through emittance and reflectance spectroscopy

Recent advances in thermal infrared remote sensing include the increased availability of airborne hyperspectral imagers (such as the Hyperspectral Thermal Emission Spectrometer, HyTES, or the Telops HyperCam and the Specim aisaOWL), and it is planned that an increased number spectral bands in the long-wave infrared (LWIR) region will soon be measured from space at reasonably high spatial resolution (by imagers such as HyspIRI). Detailed LWIR emissivity spectra are required to best interpret the observations from such systems. This includes the highly heterogeneous urban environment, whose construction materials are not yet particularly well represented in spectral libraries. Here, we present a new online spectral library of urban construction materials including LWIR emissivity spectra of 74 samples of impervious surfaces derived using measurements made by a portable Fourier Transform InfraRed (FTIR) spectrometer. FTIR emissivity measurements need to be carefully made, else they are prone to a series of errors relating to instrumental setup and radiometric calibration, which here relies on external blackbody sources. The performance of the laboratory-based emissivity measurement approach applied here, that in future can also be deployed in the field (e.g. to examine urban materials in situ), is evaluated herein. Our spectral library also contains matching short-wave (VIS–SWIR) reflectance spectra observed for each urban sample. This allows us to examine which characteristic (LWIR and) spectral signatures may in future best allow for the identification and discrimination of the various urban construction materials, that often overlap with respect to their chemical/mineralogical constituents. Hyperspectral or even strongly multi-spectral LWIR information appears especially useful, given that many urban materials are composed of minerals exhibiting notable reststrahlen/absorption effects in this spectral region. The final spectra and interpretations are included in the London Urban Micromet data Archive (LUMA; http://LondonClimate.info/LUMA/SLUM.html).

Simple method for sub-diffraction resolution imaging of cellular structures on standard confocal microscopes by three-photon absorption of quantum dots

This study describes a simple technique that improves a recently developed 3D sub-diffraction imaging method based on three-photon absorption of commercially available quantum dots. The method combines imaging of biological samples via tri-exciton generation in quantum dots with deconvolution and spectral multiplexing, resulting in a novel approach for multi-color imaging of even thick biological samples at a 1.4 to 1.9-fold better spatial resolution. This approach is realized on a conventional confocal microscope equipped with standard continuous-wave lasers. We demonstrate the potential of multi-color tri-exciton imaging of quantum dots combined with deconvolution on viral vesicles in lentivirally transduced cells as well as intermediate filaments in three-dimensional clusters of mouse-derived neural stem cells (neurospheres) and dense microtubuli arrays in myotubes formed by stacks of differentiated C2C12 myoblasts.

Synergistic angular and spectral estimation of aerosol properties using CHRIS/PROBA-1 and simulated Sentinel-3 data

We develop a method to derive aerosol properties over land surfaces using combined spectral and angular information, such as available from ESA Sentinel-3 mission, to be launched in 2015. A method of estimating aerosol optical depth (AOD) using only angular retrieval has previously been demonstrated on data from the ENVISAT and PROBA-1 satellite instruments, and is extended here to the synergistic spectral and angular sampling of Sentinel-3. The method aims to improve the estimation of AOD, and to explore the estimation of fine mode fraction (FMF) and single scattering albedo (SSA) over land surfaces by inversion of a coupled surface/atmosphere radiative transfer model. The surface model includes a general physical model of angular and spectral surface reflectance. An iterative process is used to determine the optimum value of the aerosol properties providing the best fit of the corrected reflectance values to the physical model. The method is tested using hyperspectral, multi-angle Compact High Resolution Imaging Spectrometer (CHRIS) images. The values obtained from these CHRIS observations are validated using ground-based sun photometer measurements. Results from 22 image sets using the synergistic retrieval and improved aerosol models show an RMSE of 0.06 in AOD, reduced to 0.03 over vegetated targets.

A mechanism of internal decadal atlantic ocean variability in a high-resolution coupled climate model

The North Atlantic Ocean subpolar gyre (NA SPG) is an important region for initialising decadal climate forecasts. Climate model simulations and palaeo climate reconstructions have indicated that this region could also exhibit large, internally generated variability on decadal timescales. Understanding these modes of variability, their consistency across models, and the conditions in which they exist, is clearly important for improving the skill of decadal predictions — particularly when these predictions are made with the same underlying climate models. Here we describe and analyse a mode of internal variability in the NA SPG in a state-of-the-art, high resolution, coupled climate model. This mode has a period of 17 years and explains 15–30% of the annual variance in related ocean indices. It arises due to the advection of heat content anomalies around the NA SPG. Anomalous circulation drives the variability in the southern half of the NA SPG, whilst mean circulation and anomalous temperatures are important in the northern half. A negative feedback between Labrador Sea temperatures/densities and those in the North Atlantic Current is identified, which allows for the phase reversal. The atmosphere is found to act as a positive feedback on to this mode via the North Atlantic Oscillation which itself exhibits a spectral peak at 17 years. Decadal ocean density changes associated with this mode are driven by variations in temperature, rather than salinity — a point which models often disagree on and which we suggest may affect the veracity of the underlying assumptions of anomaly-assimilating decadal prediction methodologies.

Modelling spectral reflectance of open cork oak woodland: a simulation analysis of the effects of vegetation structure and background

This study analyses the influence of vegetation structure (i.e. leaf area index and canopy cover) and seasonal background changes on moderate-resolution imaging spectrometer (MODIS)-simulated reflectance data in open woodland. Approximately monthly spectral reflectance and transmittance field measurements (May 2011 to October 2013) of cork oak tree leaves (Quercus suber) and of the herbaceous understorey were recorded in the region of Ribatejo, Portugal. The geometric-optical and radiative transfer (GORT) model was used to simulate MODIS response (red, near-infrared) and to calculate vegetation indices, investigating their response to changes in the structure of the overstorey vegetation and to seasonal changes in the understorey using scenarios corresponding to contrasting phenological status (dry season vs. wet season). The performance of normalized difference vegetation index (NDVI), soil-adjusted vegetation index (SAVI), and enhanced vegetation index (EVI) is discussed. Results showed that SAVI and EVI were very sensitive to the emergence of background vegetation in the wet season compared to NDVI and that shading effects lead to an opposing trend in the vegetation indices. The information provided by this research can be useful to improve our understanding of the temporal dynamic of vegetation, monitored by vegetation indices.