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Characterization of Gramicidin A in Triblock and Diblock Polymersomes and Hybrid Vesicles via Continuous Wave Electron Paramagnetic Resonance Spectroscopy

Studying membrane proteins in a native environment is crucial to understanding their structural and/or functional studies. Often, widely accepted mimetic systems have limitations that prevent the study of some membrane proteins. Micelles, bicelles, and liposomes are common biomimetic systems but have problems with membrane compatibility, limited lipid composition, and heterogeneity. To overcome these limitations, polymersomes and hybrid vesicles have become popular alternatives. Polymersomes form from amphiphilic triblock or diblock copolymers and are considered more robust than liposomes. Hybrid vesicles are a combination of lipids and block copolymers that form vesicles composed of a mixture of the two. These hybrid vesicles are appealing because they have the native lipid environment of bilayers but also the stability and customizability of polymersomes. Gramicidin A was incorporated into these polymersomes and characterized using continuous wave electron paramagnetic resonance (CW-EPR) and transmission electron microscopy (TEM). EPR spectroscopy is a powerful biophysical technique used to study the structure and dynamic properties of membrane proteins in their native environment. Spectroscopic studies of gramicidin A have been limited to liposomes; in this study, the membrane peptide is studied in both polymersomes and hybrid vesicles using CW-EPR spectroscopy. Lineshape analysis of spin-labeled gramicidin A revealed linewidth broadening, suggesting that the thicker polymersome membranes restrict the motion of the spin label more when compared to liposome membranes. Statement of Significance: Understanding membrane proteins’ structures and functions is critical in the study of many diseases. In order to study them in a native environment, membrane mimetics must be developed that can be suitable for obtaining superior biophysical data quality to characterize structural dynamics while maintaining their native functions and structures. Many currently widely accepted methods have limitations, such as a loss of native structure and function, heterogeneous vesicle formation, restricted lipid types for the vesicle formation for many proteins, and experimental artifacts, which leaves rooms for the development of new biomembrane mimetics. The triblock and diblock polymersomes and hybrid versicles utilized in this study may overcome these limitations and provide the stability and customizability of polymersomes, keeping the biocompatibility and functionality of liposomes for EPR studies of membrane proteins.

59 BASIC BIOLOGICAL SCIENCES

Decoherence dynamics in molecular qubits: Exponential, Gaussian and beyond

In this article, we examine how the structure of system–bath interactions can determine commonly encountered temporal decoherence patterns, such as Gaussian and exponential decay, in molecular and other qubits coupled to a thermal bosonic bath. The analysis, based on a pure dephasing picture that admits analytical treatment, shows that decoherence, in general, is neither purely Gaussian nor exponential but rather the exponential of oscillatory functions, with periods determined by the bath’s frequencies. For initially unentangled qubit-bath states, Gaussian decay is always present at early times. It becomes increasingly dominant with increasing temperature, qubit–bath interaction strength, and bath correlation time. Initial system–bath entanglement that arises due to displacement in the position of the bath states preserves the Gaussian decay. By contrast, strict exponential decay arises only in very specific models that we isolate. However, it becomes dominant for times longer than the bath correlation time or for early times when there is initial entanglement due to momentum displacement of the bath states. For molecular electronic decoherence, the long-time exponential regime plays a limited role as it emerges after most coherence is lost. Thus, the Gaussian decay provides a more suitable (albeit imperfect) model of such decoherence. Furthermore, we discuss the connection between electronic decoherence dynamics and electronic spectroscopic line shape theory, where Gaussian spectral peaks correspond to Gaussian coherence decay and Lorentzian peaks correspond to exponential coherence decay. We find that Gaussian spectral peaks, usually associated with inhomogeneous broadening, can emerge from the entangling unitary system–bath dynamics even when there is no inhomogeneity in the initial conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Scramjet Performance Assessment Using Water Absorption Diagnostics (U)

Simultaneous multiple path measurements of temperature and H2O concentration will be presented for the AIMHYE test entries in the NASA Ames 16-Inch Shock Tunnel. Monitoring the progress of high temperature chemical reactions that define scramjet combustor efficiencies is a task uniquely suited to nonintrusive optical diagnostics. One application strategy to overcome the many challenges and limitations of nonintrusive measurements is to use laser absorption spectroscopy coupled with optical fibers. Absorption spectroscopic techniques with rapidly tunable lasers are capable of making simultaneous measurements of mole fraction, temperature, pressure, and velocity. The scramjet water absorption diagnostic was used to measure combustor efficiency and was compared to thrust measurements using a nozzle force balance and integrated nozzle pressures to develop a direct technique for evaluating integrated scramjet performance. Tests were initially performed with a diode laser tuning over a water absorption feature at 1391.7 nm. A second diode laser later became available at a wavelength near 1343.3 nm covering an additional water absorption feature and was incorporated in the system for a two-wavelength technique. Both temperature and mole fraction can be inferred from the lineshape analysis using this approach. Additional high temperature spectroscopy research was conducted to reduce uncertainties in the scramjet application. The lasers are optical fiber coupled to ports at the combustor exit and in the nozzle region. The output from the two diode lasers were combined in a single fiber, and the resultant two-wavelength beam was subsequently split into four legs. Each leg was directed through 60 meters of optical fiber to four combustor exit locations for measurement of beam intensity after absorption by the water within the flow. Absorption results will be compared to 1D combustor analysis using RJPA and nozzle CFD computations as well as to data from a nozzle metric balance measuring thrust and integrated pressure measurements along the length of the nozzle. Assessment of its value as a combustor performance evaluation tool will be conducted.

Cavolowsky, John A.

Solid state 59 Co NMR study of a Np(VII) compound

Np(VII) compounds with [Co(NH 3 ) 6 ] 3+ cations were synthesized and structurally examined using powder X-ray diffraction. Multiple phases were observed, consisting of octahedral [Co(NH 3 ) 6 ] 3+ cations, discrete tetragonal bipyramidal [NpO 4 (OH) 2 ] 3− anions, and waters of hydration. Electric field gradient tensors at Co sites were measured by solid state 59 Co nuclear magnetic resonance (NMR) spectroscopy and compared with theoretical calculations. The relative contributions of the chemical shift and electric field tensors to the NMR lineshape were determined by recording spectra at field strengths of 7.04 and 11.74 Tesla. Further, the evolution of structure and morphology as a function of sample age and the effects on NMR spectral parameters has also been investigated. These results demonstrate the use of NMR at multiple fields to expand understanding of the stability and electronic structure of high valent neptunium compounds.

heptavalent neptunium

Remote sensing by infrared heterodyne spectroscopy

The use of infrared heterodyne spectrocopy for the study of planetary atmospheres is discussed. Infrared heterodyne spectroscopy provides a convenient and sensitive method for measuring the true intensity profiles of atmospheric spectral lines. Application of radiative transfer theory to measured lineshapes can then permit the study of molecular abundances, temperatures, total pressures, excitation conditions, and dynamics of the regions of line formation. The theory of formation of atmospheric spectral lines and the retrieval of the information contained in these molecular lines is illustrated. Notable successes of such retrievals from infrared heterodyne measurements on Venus, Mars, Jupiter and the Earth are given. A discussion of developments in infrared heterodyne technology is also presented.

Kostiuk, T.

Remote sensing by IR heterodyne spectroscopy

The use of infrared heterodyne spectroscopy for the study of planetary atmospheres is discussed. Infrared heterodyne spectroscopy provides a convenient and sensitive method for measuring the true intensity profiles of atmospheric spectral lines. Application of radiative transfer theory to measured lineshapes can then permit the study of molecular abundances, temperatures, total pressures, excitation conditions, and dynamics of the regions of line formation. The theory of formation of atmospheric spectral lines and the retrieval of the information contained in these molecular lines is illustrated. Notable successes of such retrievals from infrared heterodyne measurements on Venus, Mars, Jupiter and the earth are given. A discussion of developments in infrared heterodyne technology is also presented. Previously announced in STAR as N83-28551

Kostiuk, T.

Single-shot femtosecond laser-induced breakdown spectroscopy in low-density gases

Single-shot fs laser-induced breakdown spectroscopy (LIBS) has been used to interrogate low-density gases of H 2 ⁠, CH 4 ⁠, CO 2 ⁠, and H 2 O ranging from 0.5 × 10 15 to 9.1 × 10 15 cm −3 (15–275 mTorr). Strong spectral signatures were observed above the noise baseline for each test gas at all densities considered. Unique molecular signatures were observed for both CH 4 and CO 2 along with atomic features for each gas. The LIBS intensity response with respect to density was determined for each species using Voigt lineshape fitting or numerical integration. Finally, the collection and analysis of LIBS spectra of composite mixtures of CH 4 –CO 2 and CH 4 –H 2 demonstrates that the extraction of individual densities from gas mixtures is feasible at low densities.

Artificial neural networks

Current status of quantitative rotational spectroscopy for atmospheric research

Remote sensing of rotational transitions in the Earth's atmosphere has become an important method for the retrieval of geophysical temperatures, pressures and chemical composition profiles that requires accurate spectral information. This paper highlights the current status of rotational data that are useful for atmospheric measurements, with a discussion of the types the rotational lineshape measurements that are not generally available in either online repository.

limb sounding

Signatures of fractionalization in the optical phonons of the hyperhoneycomb Kitaev magnet 𝛽−Li 2 ⁢IrO 3

Here, in this study, we propose that the signatures of spin fractionalization in quantum magnets can be identified through a detailed analysis of the temperature dependence of the asymmetric Fano lineshape of optical phonons overlapping with a continuum of spin excitations. We focus on the hyperhoneycomb magnet 𝛽−Li 2 ⁢IrO 3 , a promising candidate for being in proximity to a three-dimensional Kitaev quantum spin liquid. The Raman response in 𝛽−Li 2 ⁢IrO 3 notably displays a distinctive asymmetric Fano lineshape in the 24 meV Raman-active optical phonon. This asymmetry arises from the interaction between the discrete phonon mode and the spin excitation continuum, which could be fractionalized if the material is indeed near a quantum spin-liquid phase. Our theoretical model considers the coupling of this optical phonon to Majorana fermions in the Kitaev model on the hyperhoneycomb lattice. Our findings reveal that the temperature-dependent Fano lineshape is consistent with the fractionalization of spins into Majorana fermions and ℤ ⁢2 fluxes.

Kitaev model

Method and apparatus for enhancing laser absorption sensitivity

A simple optomechanical method and apparatus is described for substantially reducing the amplitude of unwanted multiple interference fringes which often limit the sensitivities of tunable laser absorption spectrometers. An exterior cavity is defined by partially transmissible surfaces such as a laser exit plate, a detector input, etc. That cavity is spoiled by placing an oscillating plate in the laser beam. For tunable diode laser spectroscopy in the mid-infrared region, a Brewster-plate spoiler allows the harmonic detection of absorptances of less than 10 to the -5 in a single laser scan. Improved operation is achieved without subtraction techniques, without complex laser frequency modulation, and without distortion of the molecular lineshape signal. The technique is applicable to tunable lasers operating from UV to IR wavelengths and in spectrometers which employ either short or long pathlengths, including the use of retroreflectors or multipass cells.

Webster, Christopher R.

Studies of the Si/SiO2 interface using synchrotron radiation

Synchrotron radiation photoemission spectroscopy (SRPS) in the 1-4 KeV photon energy range is a useful tool for interface characterization. Results are presented of a series of studies of the near-interface region of Si/SiO2 which confirm that a bond strain gradient exists in the oxide as a result of lattice mismatch. These experiments include measurement of photoemission lineshape changes as a function of photon energy, corresponding changes in the electron escape depth near the interface, and surface extended X-ray absorption fine structure (SEXAFS) measurements directly indicating the shortening of the Si-Si second nearest neighbor distance in the near-interface region of the oxide.

Hecht, M. H.

Development of a Sodium LIDAR for Spaceborne Missions

We are currently developing laser and electro-optic technologies to remotely measure Sodium (Na) by adapting existing lidar technology with space flight heritage. The developed instrumentation will serve as the core for the planning of a Heliophysics mission targeted to study the composition and dynamics of Earths mesosphere based on a spaceborne lidar that will measure the mesospheric Na layer. There is a pressing need in the Ionosphere Thermosphere - Mesosphere (ITM) community for high-resolution measurements that can characterize small-scale dynamics (i.e. Gravity Waves with wavelengths smaller than a few hundred km) and their effects in the Mesosphere-Lower-Termosphere (MLT) on a global basis. This is compelling because they are believed to be the dominant contributors to momentum transport and deposition in the MLT, which largely drive the global circulation and thermal structure and interactions with the tides and planetary waves in this region. We are developing a spaceborne remote sensing technique that will enable acquisition of global Na density, temperature and wind measurements in the MLT with the spatial and temporal resolution required to resolve issues associated with the structure, chemistry, dynamics, and energetics of this regionA nadir-pointing spaceborne Na Doppler resonance fluorescence LIDAR on board of the ISS will essentially make high-resolution, in time and space, Na density, temperature and vertical wind measurements, from 75-115 km (MLT region). Our instrument concept consisted of a high-energy laser transmitter at 589 nm and highly sensitive photon counting detector that allows for range-resolved atmospheric-sodium-temperature profiles. The atmospheric temperature is deduced from the linewidth of the resonant fluorescence from the atomic sodium vapor D2 line as measured by our tunable laser. We are currently developing a high power energy laser that allows for some day time sodium lidar observations with the help of a narrow bandpass filter based on etalon or atomic sodium Faraday filter with 5 to 10 pm optical bandwidth. The current baseline detector for the lidar instrument is a 16-channel Photomultiplier Tube with receiver electronics that has been space-qualified for the ICESat-2ATLAS mission. Our technique uses the 16-channels as a photon-number-resolving single detector to provide the required full-spectroscopic sodium lineshape waveform for recovering Mesospheric temperature profiles. In this paper, we will describe our instrument concept for a future Heliophysics space mission based on board of the International Space Station (ISS).

lidar

Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

Smith, R. L.

Supersonic Mass Flux Measurements via Tunable Diode Laser Absorption and Non-Uniform Flow Modeling

Measurements of mass flux are obtained in a vitiated supersonic ground test facility using a sensor based on line-of-sight (LOS) diode laser absorption of water vapor. Mass flux is determined from the product of measured velocity and density. The relative Doppler shift of an absorption transition for beams directed upstream and downstream in the flow is used to measure velocity. Temperature is determined from the ratio of absorption signals of two transitions (lambda(sub 1)=1349 nm and lambda(sub 2)=1341.5 nm) and is coupled with a facility pressure measurement to obtain density. The sensor exploits wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f) for large signal-to-noise ratios and normalization with the 1f signal for rejection of non-absorption related transmission fluctuations. The sensor line-of-sight is translated both vertically and horizontally across the test section for spatially-resolved measurements. Time-resolved measurements of mass flux are used to assess the stability of flow conditions produced by the facility. Measurements of mass flux are within 1.5% of the value obtained using a facility predictive code. The distortion of the WMS lineshape caused by boundary layers along the laser line-of-sight is examined and the subsequent effect on the measured velocity is discussed. A method for correcting measured velocities for flow non-uniformities is introduced and application of this correction brings measured velocities within 4 m/s of the predicted value in a 1630 m/s flow.

Chang, Leyen S.

The SOHO-Stellar Connection

I discusses practical aspects of the so-called "solar-stellar" connection; namely, the fundamental principles, the tools at the disposal of the stellar astronomer, and a few recent examples of the connection in action. I provide an overall evolutionary context for coronal activity, calling attention to the very different circumstances of low mass main sequence stars like the Sun, which are active mainly early in their lives; compared with more massive stars, whose coronally active phase occurs near the end of their lives, during their brief incursion into the cool half of the Hertzsprung-Russell diagram as yellow and then red giants. On the instrumental slide, I concentrate primarily on spectroscopy, in the ultraviolet and X-ray bands where coronae leave their most obvious signatures. I present an early glimpse of the type of moderate resolution spectra we can expect from the recently launched Chandra observatory, and contemporaneous HST STIS high-resolution UV measurements of the CXO calibration star Capella (alpha Aur; G8 III + G1 III). I compare STIS spectra of solar-type dwarfs-zeta Dor (F7 V), an active coronal source; and alpha Cen A (G2 V), a near twin of the Sun-to a trace obtained with the SOHO SUMER imaging UV spectrometer. I also compare STIS line profiles of the active coronal dwarf to the corresponding features in the mixed-activity "hybrid-chromosphere" bright giant alpha TrA (K2 II) and the archetype "noncoronal" red giant Arcturus (alpha Boo; K2 III). The latter shows dramatic evidence for a "cool absorber" in its outer atmosphere that is extinguishing the "hot lines" (like Si IV lambda1393 and N V lambda1238) below about 1500 A, probably through absorption in the Si I lambda1525 and C I lambda1240 photoionization continua. The disappearance of coronae across the "Linsky-Haisch" dividing line near K1 III thus apparently is promoted by a dramatic overturning in the outer atmospheric structure, namely the coronae of the red giants seem to lie beneath their extended chromospheres, rather than outside as in the Sun. I then discuss an intriguing long-slit STIS low-resolution observation of an X-ray active late-A dwarf in the nearby Hyades cluster: the spatially resolved UV spectroscopy clearly shows that a previously unseen close companion (a dKe or dMe) likely is responsible for the coronal activity, rather than some unexplained departure of the A dwarf from its expected state of X-ray dormancy. Finally, I describe early results from a joint observing campaign involving SOHO SUMER, TRACE, and the Kitt Peak Infrared Imaging Spectrometer, conducted May 1999, to explore the dynamics of the quiet solar atmosphere through the key "magnetic transition zone" that separates the kinetically dominated deep photosphere from the magnetically dominated coronal regime. Linking spatially and temporally resolved solar properties to aspects of the averaged lineshapes (for example: widths, asymmetries, intensity ratios, and Doppler shifts) is a crucial step in carrying any physical wisdom we develop in the solar setting to the distant stars.

Ayres, Thomas R.

Optical fiber spectroscopy: A study of the luminescent properties of the europium ion for thermal sensors

Recently, there has been interest in developing a distributed temperature sensor integrated into an optical fiber. Such a system would allow embedding of the optical fiber within or on a structural material to provide for continuous monitoring of the material's temperature. Work has already begun on the development of a temperature sensor using the temperature dependent emission spectra from the lanthanide rare earths doped into crystalline hosts. The lifetime, the linewidth and the integrated intensity of this emission are each sensitive to changes in the temperature and can provide a basis for thermometry. One concept for incorporating this phenomena into an optical fiber based sensor involves bonding the optically active material to the cladding of an optical fiber and allowing the luminescent light to couple into the the fiber by the evanescent wave. Experimental work developing this concept has already been reported. Measurements of the linewidth of Eu3+:Y2O3, diffused into a fiber, made by Albin clearly show a strong and regular dependence on temperature over the range of 300 to 1000 K. We report here on a study of the temperature dependence of the lineshape of the emission at 611 nm using the data in references. We focus attention on understanding the general behavior of the Eu3+:Y2O3 system. Building upon understanding of this system we will be able to establish the physical criterial for a good optical fiber based temperature sensor and then to examine available data on other lanthanide rare earths and transition metal ions to determine the best luminescent system for temperature sensing in an optical fiber.

Buoncristiani, A. Martin

Multidimensional Coherent Spectroscopy of van der Waals materials and heterostructures (Final Technical Report)

This project advanced multidimensional coherent spectroscopy (MDCS) and related spectroscopic-imaging methods as quantitative probes of many-body optical excitations in two-dimensional (2D) van der Waals (vdW) semiconductors and their heterostructures. Monolayer transition-metal dichalcogenides (TMDs) such as MoSe 2 and WSe 2 provide a uniquely strong platform for excitonic physics due to reduced dielectric screening, which enhances Coulomb interactions and makes higher-order correlated states (e.g., biexcitons and exciton–trion correlations) more prominent than in conventional bulk semiconductors. At the same time, the same sensitivity that enables strong interactions also increases susceptibility to spatial inhomogeneity—e.g., strain gradients, wrinkles, nanoscale disorder potentials, and charge puddling—which can broaden resonances, obscure interaction signatures, and complicate device-to-device reproducibility. The work reported here addressed this dual opportunity and challenge by: (i) developing and deploying coherent multidimensional methods (including double-quantum MDCS) capable of isolating interaction signals with reduced background, (ii) integrating electrostatic control to tune carrier populations and interaction strengths in situ, and (iii) introducing complementary spatially resolved photoluminescence (PL) techniques—hyperspectral PL imaging and polarization-/field-dependent PL lineshape analysis—to directly quantify disorder, strain, and localization that govern the coherent response.

36 MATERIALS SCIENCE

Line Narrowing Parameter Measurement by Modulation Spectroscopy

Accurate Characterization of Oxygen A-Band Line Parameters by Wavelength Modulation Spectroscopy with tunable diode lasers is an ongoing research at Old Dominion University, under sponsorship from NASA Langley research Center. The work proposed here will be undertaken under the guidance of Dr. William Chu and Dr. Lamont Poole of the Aerosol Research Branch at NASA Langley-Research Center in Hampton, Virginia. The research was started about two years ago and utilizes wavelength modulation absorption spectroscopy with higher harmonic detection, a technique that we developed at Old Dominion University, to obtain the absorption line characteristics of the Oxygen A-band rovibronic lines. Accurate characterization of this absorption band is needed for processing of data that will be obtained in experiments such as the NASA Stratospheric Aerosol and Gas Experiment III (SAGE III) as part of the US Mission to Planet Earth. The research work for Summer Fellowship undertook a measurement of the Dicke line-narrowing parameters of the Oxygen A-Band lines by using wavelength modulation spectroscopy. Our previous theoretical results had indicated that such a measurement could be done sensitively and in a convenient fashion by using this type of spectroscopy. In particular, theoretical results had indicated that the signal magnitude would depend on pressure in a manner that was very sensitive to the narrowing parameter. One of the major tasks undertaken during the summer of 1998 was to establish experimentally that these theoretical predictions were correct. This was done successfully and the results of the work are being prepared for publication. Experimental Results were obtained in which the magnitude of the signal was measured as a function of pressure, for various harmonic detection orders (N = 1, 2, 3, 4, 5). A comparison with theoretical results was made, and it was shown that the agreement between theory and experiment was very good. More importantly, however, it was shown that the measurement was yielded a very sensitive technique for obtaining the narrowing parameter that describes the deviation of Oxygen A-band lines from the Voigt profile. In particular, it was seen that the best fits were obtained consistently when the narrowing parameter value used was 0.022 1/cm, 1/Atm, Previous work, upon which the current work was based has resulted in several accurate measurements of properties of particular lines of the Oxygen A band. For example, this work has resulted in the measurement of the collision cross sections of several lines including the RQ(13,14) and the RR(15,15) lines. A major achievement of achievement of the work was also the demonstration that the technique we have developed can accurately probe the structure of the absorption lineshape function. In particular, the method we have developed is very well suited for experimentally probing the characteristics of lines in their wings. This work was accepted for publication in the Journal of Applied Physics, and is scheduled to appear in the December 15, 1998 issue.

Dharamsi, Amin N.