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At least 253 records · Page 14

Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy

The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.

NASA Discipline Exobiology↗

A magnetic‐directed micro‐particle with near‐ IR light triggered guest‐release property

Abstract In this study, guest carriers, composed of magnetic‐directed hydrogel particles with near‐infrared (NIR)‐light‐triggered guest‐release properties, are prepared via the one‐pot method. The gel particles contain photostable NIR‐responsive polypyrrole nanoparticles with temperature‐sensitive poly(N‐isopropyl acrylamide), the combination of which can induce the accelerated release of encapsulated drugs by 337% upon 5 minutes of NIR light irradiation based on the release profile of NRMG‐1 at 10–15 min. Additionally, with magnetic iron oxide particles crosslinking the polyvinyl alcohol frames, these gel particles can form a physical barrier that decreases the release rate by 20% under an external magnetic field over 24 h. The magnetic iron oxide particles also enable the gel particles to reach their target destination without extra drug losses.

60 APPLIED LIFE SCIENCES↗

Improving Nocturnal Fire Detection with the VIIRS Day-Night Band

Building on existing techniques for satellite remote sensing of fires, this paper takes advantage of the day-night band (DNB) aboard the Visible Infrared Imaging Radiometer Suite (VIIRS) to develop the Firelight Detection Algorithm (FILDA), which characterizes fire pixels based on both visible-light and infrared (IR) signatures at night. By adjusting fire pixel selection criteria to include visible-light signatures, FILDA allows for significantly improved detection of pixels with smaller and/or cooler subpixel hotspots than the operational Interface Data Processing System (IDPS) algorithm. VIIRS scenes with near-coincident Advanced Spaceborne Thermal Emission and Reflection (ASTER) overpasses are examined after applying the operational VIIRS fire product algorithm and including a modified "candidate fire pixel selection" approach from FILDA that lowers the 4-μm brightness temperature (BT) threshold but includes a minimum DNB radiance. FILDA is shown to be effective in detecting gas flares and characterizing fire lines during large forest fires (such as the Rim Fire in California and High Park fire in Colorado). Compared with the operational VIIRS fire algorithm for the study period, FILDA shows a large increase (up to 90%) in the number of detected fire pixels that can be verified with the finer resolution ASTER data (90 m). Part (30%) of this increase is likely due to a combined use of DNB and lower 4-μm BT thresholds for fire detection in FILDA. Although further studies are needed, quantitative use of the DNB to improve fire detection could lead to reduced response times to wildfires and better estimate of fire characteristics (smoldering and flaming) at night.

Day-night band↗

Mid-day photomixotrophy by Roseiflexus spp. and implications for the 13 C content of hot spring cyanobacterial mats

Microbial mats inhabiting extreme environments have been studied as modern analogs of stromatolites. Mats in Octopus Spring and Mushroom Spring, Yellowstone National Park, are predominated by unicellular photoautotrophic cyanobacteria (Synechococcus spp.), which are thought to cross-feed filamentous photoheterotrophic bacteria (mainly Roseiflexus spp.), except under early morning anoxic conditions when Roseiflexus spp. have been shown to fix dissolved inorganic carbon (DIC). Transcription patterns, however, suggest that Roseiflexus spp. may perform photomixotrophy, in which DIC is incorporated together with organic compounds during the daytime. We investigated the roles played by Synechococcus spp. and Roseiflexus spp. in DIC and organic matter uptake in mid-day light and oxic mats. Mass spectrometry was used to show that 13 C-bicarbonate uptake under infrared (IR) light (utilized by anoxygenic phototrophs) or visible-minus-blue light (V-B) (used by cyanobacteria) was about two-thirds and one-third, respectively, of that incorporated in full light. Laser-ablation mass spectrometry analysis demonstrated that 13 C incorporation under V-B light was restricted to the uppermost portion of the mat, whereas 13 C incorporation under IR light was maximal in deeper mat layers. 13 C-acetate, -propionate, -lactate, and -glycolate were incorporated to an equal or greater extent under IR and full light. Incorporation of 13 C into peptides showed that both Synechococcus spp. and Roseiflexus spp. were active in DIC uptake, whereas Roseiflexus spp. exhibited greater uptake of 13 C-organic acids, especially glycolate and lactate, into peptides. Peptides of proteins of the 3-hydroxypropionate pathway were labeled. Thus, Roseiflexus spp. appears to exhibit photomixotrophy throughout the day.

Roseiflexus↗

Noncontact measurement of high temperature using optical fiber sensors

The primary goal of this research program was the investigation and application of noncontact temperature measurement techniques using optical techniques and optical fiber methods. In particular, a pyrometer utilizing an infrared optical light pipe and a multiwavelength filtering approach was designed, revised, and tested. This work was motivated by the need to measure the temperatures of small metallic pellets (approximately 3 mm diameter) in free fall at the Microgravity Materials Processing Drop Tube at NASA Marshall Space Flight Center. In addition, research under this program investigated the adaptation of holography technology to optical fiber sensors, and also examined the use of rare-earth dopants in optical fibers for use in measuring temperature. The pyrometer development effort involved both theoretical analysis and experimental tests. For the analysis, a mathematical model based on radiative transfer principles was derived. Key parameter values representative of the drop tube system, such as particle size, tube diameter and length, and particle temperature, were used to determine an estimate of the radiant flux that will be incident on the face of an optical fiber or light pipe used to collect radiation from the incandescent falling particle. An extension of this work examined the advantage of inclining or tilting the collecting fiber to increase the time that the falling particle remains in the fiber field-of-view. Those results indicate that increases in total power collected of about 15 percent may be realized by tilting the fiber. In order to determine the suitability of alternative light pipes and optical fibers, and experimental set-up for measuring the transmittance and insertion loss of infrared fibers considered for use in the pyrometer was assembled. A zirconium fluoride optical fiber and several bundles of hollow core fiber of varying diameters were tested. A prototype two-color pyrometer was assembled and tested at Virginia Tech, and then tested on the Drop Tube at Marshall Space Flight Center. Radiation from 5 mm diameter niobium drops falling in the Drop Tube was successfully detected, and recorded for later analysis. Subsequent analysis indicated that the imaging of light output from the light pipe onto the detector active areas was not identical for both detectors.

Claus, R. O.↗

Metal Side Reflectors for Trapping Light in QWIPs

Focal-plane arrays of quantum-well infrared photodetectors (QWIPs) equipped with both light-coupling diffraction gratings and metal side reflectors have been proposed, and prototypes are expected to be fabricated soon. The purpose served by the metal side reflectors is to increase quantum efficiency by helping to trap light in the photosensitive material of each pixel. The reasons for using diffraction gratings were discussed in several prior NASA Tech Briefs articles. To recapitulate: In an array of QWIPs, the quantum-well layers are typically oriented parallel to the focal plane and therefore perpendicular or nearly perpendicular to the direction of incidence of infrared light. By virtue of the applicable quantum selection rules, light polarized parallel to the focal plane (as normally incident light is) cannot excite charge carriers and, hence, cannot be detected. Diffraction gratings scatter normally or nearly normally incident light into directions more nearly parallel to the focal plane, so that a significant portion of the light attains a component of polarization normal to the focal plane and, hence, can excite charge carriers. Unfortunately, light scattered in directions parallel or nearly parallel to the focal plane can escape sideways from the QWIP of a given pixel, as illustrated in Figure 1. The escaped light has made only a single pass through the interior photosensitive volume of the QWIP. The quantum efficiency of the QWIP would be increased by trapping light so that it makes multiple passes through the photosensitive volume. As shown in Figure 2, the sides of the QWIP of each pixel would be coated with gold to reflect escaping light back into the interior.

Gunapala, Sarath↗

Defect Termination in the UiO-66 Family of Metal–Organic Frameworks: The Role of Water and Modulator

The defect concentration in the prototypical metal–organic framework UiO-66 can be well controlled during synthesis, leading to precisely tunable physicochemical properties for this structure. However, there has been a long-standing debate regarding the nature of the compensating species present at the defective sites. Here, we present unambiguous spectroscopic evidence that the missing-linker defect sites in an ambient environment are compensated with both carboxylate and water (bound through intermolecular hydrogen bonding), which is further supported by ab initio calculations. In contrast to the prevailing assumption that the monocarboxylate groups (COO – ) of the modulators form bidentate bonding with two Zr 4+ sites, COO – is found to coordinate to an open Zr 4+ site in an unidentate mode. The neighboring Zr 4+ site is terminated by a coordinating H 2 O molecule, which helps to stabilize the COO – group. Lastly, this finding not only provides a new understanding of defect termination in UiO-66, but also sheds light on the origin of its catalytic activity.

36 MATERIALS SCIENCE↗

Infrared upconversion as a means of seeing in the dark

A new approach to seeing in the dark is described which is based on the principles of nonlinear optics employing a crystal such as lithium iodate. A nonlinear optical device capable of producing photons at higher frequencies from lower-frequency incident light is shown to upconvert infrared light directly into visible light. The major advantages of the infrared upconversion process is that it permits the infrared signal to be detected by photon-counting devices presently available for the visible spectral region, and that it can provide sensitivity to infrared radiation without the need for cryogenic cooling of the detector used. Early works on infrared upconversion are reviewed. The development of applications is discussed as to astronomical spectroscopy and infrared image upconversion involving either angular or positional resolution elements. The demonstration of infrared upconversion in rectangular waveguides of single-crystal GaAs by Anderson et al. (1971) indicates future possibilities in upconversion by the use of integrated optics devices.

Gurski, T. R.↗

Mid-infrared photodetection with 2D metal halide perovskites at ambient temperature

The detection of mid-infrared (MIR) light is technologically important for applications such as night vision, imaging, sensing, and thermal metrology. Traditional MIR photodetectors either require cryogenic cooling or have sophisticated device structures involving complex nanofabrication. Here, we conceive spectrally tunable MIR detection by using two-dimensional metal halide perovskites (2D-MHPs) as the critical building block. Leveraging the ultralow cross-plane thermal conductivity and strong temperature-dependent excitonic resonances of 2D-MHPs, we demonstrate ambient-temperature, all-optical detection of MIR light with sensitivity down to 1 nanowatt per square micrometer, using plastic substrates. Through the adoption of membrane-based structures and a photonic enhancement strategy unique to our all-optical detection modality, we further improved the sensitivity to sub–10 picowatt-per-square-micrometer levels. The detection covers the mid-wave infrared regime from 2 to 4.5 micrometers and extends to the long-wave infrared wavelength at 10.6 micrometers, with wavelength-independent sensitivity response. Our work opens a pathway to alternative types of solution-processable, long-wavelength thermal detectors for molecular sensing, environmental monitoring, and thermal imaging.

Li, Yanyan [Yale University, New Haven, CT (United↗

Development of flashlamp-pumped Q-switched Ho:Tm:Cr:YAG lasers for mid-infrared LIDAR application

A flashlamp-pumped 2.1 micron Ho:Tm:Cr:YAG laser was studied for both normal mode and Q-switched operations under a wide variety of experimental conditions in order to optimize performance. Laser output energy, slope efficiency, threshold and pulselength were determined as a function of operating temperature, output mirror reflectivity, input electrical energy and Q-switch opening time. The measured normal-mode laser thresholds of a Ho(3+) (0.45 atomic percent):Tm(3+) (2.5 atomic percent):Cr(3+) (0.8 atomic percent):YAG crystal ranged form 26 to 50 J between 120 and 200 K with slope efficiencies up to 0.36 percent with a 60 percent reflective output mirror. Under Q-switched operation the slope efficiency was 90 percent of the normal-mode result. Development of solid state lasers with Ho(3+), Tm(3+) and/or Er(3+) doped crystals has been pursued by NASA for eye-dafe mid-infrared LIDAR (light detection and ranging) application. As a part of the project, the authors have been working on evaluating Ho(3+):Tm(3+):Cr(3+):YAG crystals for normal-mode and Q-switched 2.1 micron laser operations in order to determine an optimum Tm(3+) concentration under flashlamp pumping conditions. Lasing properties of the Ho(3+) in the mid-infrared region have been studied by many research groups since the early 1960's. However, the technology of those lasers is still premature for lidar application. In order to overcome the inefficiency related to narrow absorption bands of the Ho(3+), Tm(3+) and Er(3+), the erbium has been replaced by chromium. The improvement in flashlamp-pumped Ho(3+) laser efficiency has been demonstrated recently by several research groups by utilizing the broad absorption spectrum of Cr(3+) which covers the flashlamp's emission spectrum. Efficient energy transfer to the Tm(3+) and then the Ho(3+) occurs subsequently. It is known that high Tm(3+) concentration and low Ho(3+) concentration are preferred to achieve a quantum efficiency approaching two and to avoid large reabsorption losses. However, determination of the optimum Tm(3+) concentration required to ensure efficient energy transfer from Cr(3+) to Tm(3+) and from Tm(3+) to Ho(3+) has not been made in the Ho:Tm:CR:YAG crystal. The results obtained so far are given.

Choi, Young S.↗

Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This work uncovers the sub- and above-bandgap emission and absorption characteristics of PEA 2 PbI 4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 μm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation–emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump–probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mie-Resonant Three-Dimensional Metacrystals

Optical metamaterials, engineered to exhibit electromagnetic properties not found in natural materials, may enable new light-based applications including cloaking and optical computing. While there have been significant advances in the fabrication of two-dimensional metasurfaces, planar structures create nontrivial angular and polarization sensitivities, making omnidirectional operation impossible. Although three-dimensional (3D) metamaterials have been proposed, their fabrication remains challenging. In this work, we use colloidal crystal engineering with DNA to prepare isotropic 3D metacrystals from Au nanocubes. We show that such structures can exhibit refractive indices as large as ~8 in the mid-infrared, far greater than that of common high-index dielectrics. Additionally, we report the first observation of multipolar Mie resonances in metacrystals with well-formed habits, occurring in the mid-infrared for sub-micron metacrystals, which we measured using synchrotron infrared microspectroscopy. Finally, we predict that arrays of metacrystals could exhibit negative refraction. The results present a promising platform for engineering devices with unnatural optical properties.

3D metamaterials↗

Ultrabroadband Nanocavity of Hyperbolic Phonon–Polaritons in 1D-Like α-MoO 3

The exploitation of phonon–polaritons in nanostructured materials offers a pathway to manipulate infrared (IR) light for nanophotonic applications. Notably, hyperbolic phonon–polaritons (HP 2 ) in polar bidimensional crystals have been used to demonstrate strong electromagnetic field confinement, ultraslow group velocities, and long lifetimes (up to ~12 ps). Here we present nanobelts of α-phase molybdenum trioxide (α-MoO 3 ) as a low-dimensional medium supporting HP 2 modes in the mid- and far-IR ranges. Through real-space nanoimaging techniques with synchrotron and tunable laser IR light, we observe HP 2 Fabry-Perot resonances that demonstrate distinct anisotropic propagation and frequency dependence. We remark an anisotropic propagation that critically depends on the frequency range. Our findings are supported by the convergence of experiment, theory, and numerical simulations. Our work shows that the low dimensionality of natural nanostructured crystals, like α-MoO 3 nanobelts, provides an attractive platform to study polaritonic light–matter interactions and offers appealing cavity properties that could be harnessed in future designs of compact nanophotonic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

Fast Near-Infrared Photodetection Using III–V Colloidal Quantum Dots

Colloidal quantum dots (CQDs) are promising materials for infrared (IR) light detection due to their tunable bandgap and their solution processing; however, to date, the time response of CQD IR photodiodes is inferior to that provided by Si and InGaAs. It is reasoned that the high permittivity of II–VI CQDs leads to slow charge extraction due to screening and capacitance, whereas III–Vs—if their surface chemistry can be mastered—offer a low permittivity and thus increase potential for high-speed operation. In initial studies, it is found that the covalent character in indium arsenide (InAs) leads to imbalanced charge transport, the result of unpassivated surfaces, and uncontrolled heavy doping. Surface management using amphoteric ligand coordination is reported, and it is found that the approach addresses simultaneously the In and As surface dangling bonds. The new InAs CQD solids combine high mobility (0.04 cm 2 V -1 s -1 ) with a 4× reduction in permittivity compared to PbS CQDs. Finally, the resulting photodiodes achieve a response time faster than 2 ns—the fastest photodiode among previously reported CQD photodiodes—combined with an external quantum efficiency (EQE) of 30% at 940 nm.

36 MATERIALS SCIENCE↗

Reduced Energetic Disorders in Dion–Jacobson Perovskites for Efficient and Spectral Stable Blue LEDs

Metal halide perovskites have witnessed great success in green, red, and near-infrared light-emitting diodes (LEDs), yet blue LEDs still lag behind. Reducing undesired energetic disorders – broad n -phases and halide segregation – is considered as the most critical strategy to further improve the performances. Here, the study reports a newly designed and synthesized di-ammonium ligand with rigid π -conjugated rings and additional methyl groups to construct Dion–Jacobson (DJ) structure. Augmented coordination from the extra ammonium site and increased effective bulkiness from methyl groups lead to better distribution control over conventional mono-ammonium ligands. This enhances the radiative recombination of blue emissions in the film with homogeneous energy landscape and improved surface morphology, as evidenced by a series of imaging and mapping techniques. As a result, it demonstrates DJ perovskite LEDs (PeLEDs) with peak external quantum efficiencies of ≈4% at 484 nm and ≈11% at 494 nm, which are among the top reported for pure DJ phase-based PeLEDs in the corresponding wavelength regions. The results deepen the understanding of regulating energetic disorders in perovskite materials via molecular engineering.

36 MATERIALS SCIENCE↗

Shortwave‐Infrared‐Emitting Nanoprobes for CD8 Targeting and In Vivo Imaging of Cytotoxic T Cells in Breast Cancer

Checkpoint immunotherapy has made great strides in the treatment of solid tumors, but many patients do not respond to immune checkpoint inhibitors. Identification of tumor‐infiltrating cytotoxic T cells (CTLs) has the potential to stratify patients and monitor immunotherapy responses. In this study, the design of cluster of differentiation (CD8 + ) T cell‐targeted nanoprobes that emit shortwave infrared (SWIR) light in the second tissue‐transparent window for noninvasive, real‐time imaging of CTLs in murine models of breast cancer is presented. SWIR‐emitting rare‐earth nanoparticles encapsulated in human serum albumin are conjugated with anti‐CD8α to target CTLs with high specificity. CTL targeting is validated in vitro through binding of nanoprobes to primary mouse CTLs. The potential for the use of SWIR fluorescence intensity to determine CTL presence is validated in two syngeneic mammary fat pad tumor models, EMT6 and 4T1, which differ in immune infiltration. SWIR imaging using CD8‐targeted nanoprobes successfully identifies the presence of CTLs in the more immunogenic EMT6 model, while imaging confirms the lack of substantial immune infiltration in the nonimmunogenic 4T1 model. In this work, the opportunity for SWIR imaging using CD8‐targeted nanoprobes to assess CTL infiltration in tumors for the stratification and monitoring of responders to checkpoint immunotherapy is highlighted.

Shah, Jay V.↗