Near-infrared Absorption Band Research Articles

An Expeditious Synthesis of Near‐Infrared‐Absorbing Imide‐Based Graphene Nanoribbons and Their Photothermal Properties

Graphene nanoribbons (GNRs) with low band gap and strong near‐infrared (NIR) absorption are potential candidates for optoelectronic and biomedical applications. In this context, imide‐based GNRs are promising, but there are no rational design principles that yield these robust GNRs with strong NIR absorption. Here, we demonstrate a rational synthesis route to achieve NIR‐absorbing imide‐based robust GNRs by exploring the bay region of polyperylene (PP). Using the oxidative Diels‐Alder reaction, we have successfully introduced mono and diimide functional groups on PP. After cyclodehydrogenation, the resultant GNRs, benzoperylene imide GNR (BPI‐GNR) and coronene diimide GNR (CDI‐GNR), show oscillatory edge geometry with strong NIR absorption (up to 1000 nm) and optical band gap of ~1.3 eV. Computational studies also indicate that imide substituents play an important role in fine‐tuning the optoelectronic properties of GNRs. Moreover, these GNRs are solution‐processable and can be made into thin films via spray coating. Owing to the strong NIR absorption and imide substitutions, BPI and CDI‐GNRs show good photothermal conversion with excellent cyclic stability.

An Expeditious Synthesis of Near-Infrared-Absorbing Imide-Based Graphene Nanoribbons and Their Photothermal Properties.

Graphene nanoribbons (GNRs) with low band gap and strong near-infrared (NIR) absorption are potential candidates for optoelectronic and biomedical applications. In this context, imide-based GNRs are promising, but there are no rational design principles that yield these robust GNRs with strong NIR absorption. Here, we demonstrate a rational synthesis route to achieve NIR-absorbing imide-based robust GNRs by exploring the bay region of polyperylene (PP). Using the oxidative Diels-Alder reaction, we have successfully introduced mono and diimide functional groups on PP. After cyclodehydrogenation, the resultant GNRs, benzoperylene imide GNR (BPI-GNR) and coronene diimide GNR (CDI-GNR), show oscillatory edge geometry with strong NIR absorption (up to 1000 nm) and optical band gap of ~1.3 eV. Computational studies also indicate that imide substituents play an important role in fine-tuning the optoelectronic properties of GNRs. Moreover, these GNRs are solution-processable and can be made into thin films via spray coating. Owing to the strong NIR absorption and imide substitutions, BPI and CDI-GNRs show good photothermal conversion with excellent cyclic stability.

Bowl-Shaped Anthracene-Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion.

The synthesis of bowl-shaped antiaromatic molecules represents a formidable challenge, because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report the synthesis and properties of bowl-shaped fused anthrylnorcorroles that exhibit near-infrared (NIR) absorption reaching 1900 nm. The oxidation of meso-anthryldibromodipyrrin provides fused anthryldibromodipyrrin, which was converted to the fused mono- and bisanthrylnorcorroles through Ni(0)-mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single-crystal X-ray diffraction analyses revealed bowl-shaped structures for the fused mono- and bisanthrylnorcorroles, which enables them to act as suitable receptors for C60 with bonding constants of 2.89 × 103 M-1 and 1.59 × 103 M-1, respectively. The formation of a 1:1 complex between the fused monoanthrylnorcorrole and C60 was confirmed by single-crystal X-ray diffraction analysis. The effective expansion of the π-conjugation through the triple fusion of the norcorrole with the anthracene units substantially enhances the near-infrared absorption bands, which endows these anthrylnorcorroles with effective photothermal conversion.

Oxidation of Weakly Interacting Diradicals: An Approach for Strong and Tunable Near-Infrared-Absorbing Dyes Based on Small Chromophores.

Near-infrared (NIR)-absorbing dyes are valuable for various applications, such as bioimaging and electronic devices. This work introduces a novel approach for designing NIR dyes, oxidation of weakly coupled diradicals. Our approach features a weak exchange interaction in diradicals, which potentially leads to bonding/antibonding molecular orbitals with a small energy gap. We found that removing one of two singly occupied molecular orbital electrons of the diradicals results in an exceptionally narrow frontier orbital energy gap. We examined a series of Blatter radical dimers, and the most weakly coupled diradical prepared in this work (ΔEST ∼ 0.12 eV) with a molecular weight of 590 Da exhibited a strong NIR absorption band reaching 2200 nm upon one-electron oxidation. The optical band gaps of the radical cations strongly correlate to the exchange interaction in the precursor neutral species, offering prediction and fine-tuning of the optical band gap in the NIR region.

Helically Chiral π-Expanded Azocines Through Regioselective Beckmann Rearrangement and Their Charged States.

We report a synthetic approach to π-expanded [6]helicenes incorporating tropone and azocine units in combination with a 5-membered ring, which exhibit intriguing structural, electronic, and chiroptical properties. The regioselective Beckmann rearrangement allows the isolation of helical scaffolds containing 8-membered lactam, azocine, and amine units. As shown by X-ray crystallographic analysis, the incorporation of tropone or azocine units leads to highly distorted [6]helicene moieties, with distinct packing motifs in the solid state. The compounds exhibit promising optoelectronic properties with considerable photoluminescence quantum yields and tunable emission wavelengths depending on the relative position of the nitrogen center within the polycyclic framework. Separation of the enantiomers by chiral high-performance liquid chromatography (HPLC) allowed characterization of their chiroptical properties by circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy. The azocine compounds feature manifold redox chemistry, allowing for the characterization of the corresponding radical anions and cations as well as the dications and dianions, with near-infrared (NIR) absorption bands extending beyond 3000 nm. Detailed theoretical studies provided insights into the aromaticity evolution upon reduction and oxidation, suggesting that the steric strain prevents the azocine unit from undergoing aromatization, while the indene moiety dominates the observed redox chemistry.

Detection of moisture content of polyester fabric based on hyperspectral imaging and BP neural network

To validate the feasibility and improve the accuracy of water content detection in polyester fabrics using hyperspectral imaging, 150 sets of hyperspectral images of polyester fabrics with varying thicknesses and moisture contents were obtained, and the characteristics of the spectral curves and impact of moisture content were elucidated. In addition, the area and full width at half maximum of the characteristic peaks around 1363 and 1890 nm were determined as spectral characteristic variables. Furthermore, the models of polyester fabric moisture content detection were developed using backpropagation neural networks, and their accuracy was evaluated using correlation coefficient and mean squared error. It was observed that the change in the moisture content of polyester fabrics not only affected the reflectance of the overall spectral curve of polyester fabrics but also altered the position and overall shape of the characteristic peaks. As the moisture content increased, the proportion of pure water spectra in the mixed spectra of water-containing polyester fabrics also increased, leading to a change in the overall shape of the characteristic peaks of polyester fabrics. Because of the overlap between the near-infrared absorption bands of pure water and the polyester fabric around 1363 and 1890 nm, the area and full width at half maximum of the characteristic peaks were considered to be more representative than the reflection for modeling. The established backpropagation neural network–based moisture content quantitative detection model has shown extremely high detection accuracy, with the correlation coefficient for the test set being higher than 0.999 and the root mean square error being lower than 0.3 %, indicating that the detection error of moisture content was only about 0.3 wt%.

Identification and quantification of adulteration in frozen-thawed meat of different breeds by NIR spectroscopy and chemometrics

This work aims to compare the characteristic near-infrared absorption bands of different breeds of meats and to develop a qualitative and semi-quantitative method for the detection of adulteration in various types of frozen meat based on near-infrared spectroscopy and chemometrics methods. The adulterated samples were in various combinations of pork, beef and mutton adulterated with different proportions of pork, beef, lamb, duck and chicken. The results showed that the accuracy of the PLS-DA model that identified all adulteration types together was the lowest (AUCP= 0.8265), while the accuracy of the PLS-DA model of lamb-chicken and beef-chicken was the highest (AUCP= 1). AUCP of other adulteration types was higher than 0.92. And the PLSR model constructed by all the adulteration types together had the worst result (Rp2= 0.5348, RMSECV=0.1895, RPD=1.48). The results of PLSR prediction models constructed by the adulteration types separately all reached the expectation (Rp2= 0.8707–0.9703，RMSECV= 0.0637–0.1089，RPD= 2.78–5.80). The results of the PLS-DA models and PLSR models using characteristic band spectral information are basically the same or slightly improved compared with those results of the models using full-band spectral information. Therefore, NIR spectroscopy and chemometrics methods can directly qualitatively identified all adulteration types, but it is more accurate to semi-quantitatively predict the proportion of adulteration according to different adulteration types. The near-infrared absorption of moisture and fat contributed more to the detection of meat adulteration.

Multienzyme cascades analysis of α-glucosidase by oxygen deficient MoO3-x

BackgroundRecently, the enzymatic cascade reactions during the cellular process are widely used for fabricating robust biosensors and they have attracted extensive attention in analyzing various clinical biomarkers. The enzymatic cascades analysis is commonly based on the peroxidase (POD)/oxidase coupled system. However, the requirement of harsh acidic environment, poor stability and interference from the oxidase further limit their analytical practicability. Herein, novel chromogenic nanomaterials with H2O2 sensitive features are urgently required to replace the POD nanozyme in enzymatic cascades based bioanalysis. ResultsHerein, oxygen deficient MoO3-x with H2O2 sensitive features and near-infrared (NIR) absorption band have been ultra-fast synthesized and utilized for the enzymatic cascades analysis of α-Glucosidase's activity, and inhibitors screening. With the addition of 4-nitrophenyl-α-d-glucopyranoside, the simultaneous presence of α-Glucosidase and glucose oxidase (GOx) would fade their dark blue color and decrease the NIR absorption. The α-Glucosidase's activity can be analyzed by the absorption at 770 nm, and their limit of detection is 8 × 10−5 U/mL, indicating the superior performance of the proposed colorimetric assay. Moreover, this proposed α-Glucosidase assay is further utilized for inhibitors screening. Moreover, the activity of α-Glucosidase can also be analyzed by the smartphone and microplate reader through the agarose-based colorimetric portable kit. SignificanceThis MoO3-x involved enzymatic cascades assay would facilitate for the development of bio-analysis related to H2O2 generation or consumption. Moreover, this bio-analysis strategy will contribute to the development of other H2O2 sensitive chromogenic nanomaterials for the analysis of certain biomolecules and biological enzymes.

Syntheses and coordination of linear and macrocyclic pentapyrroles possessing a fused moiety: Confusion modulated structural diversity

Porphyrinoids have attracted wide interest because of their vital roles in biological processes and fascinating structural and functional characters. In this work, a doubly N-confused pentapyrrane precursor N2C–P5 has been synthesized with terminal pyrrole ring A and middle pyrrole C incorporated in the N-confused mode. On this basis, pentapyrrin 1 and sapphyrin 2 have been synthesized by oxidizing N2C–P5 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Both 1 and 2 possess a [5.5.5]-tricyclic fused ring involving pyrrole B and the neighboring confused pyrrole C. Meanwhile, the formation of 2 involves ring closure between the terminal rings A and E. Notably, 2 exists as a diradical showing a half-field signal in the electron paramagnetic resonance (EPR) spectrum and a singlet ground state with a negative singlet-triplet energy gap of −0.50 kcal/mol. Excellent thermal stability has been observed for 2, which may be related to its large π-conjugated framework involving the fused structure. On this basis, 1 and 2 were treated with Cu(acac)2 to afford Cu(II) complexes 3 and 4, respectively. As a result, an acetylacetonyl moiety is attached at the terminal pyrrole ring E to afford an NNNO coordination environment for complex 3, and the sapphyrin macrocycle of 2 has been cleaved between rings A and B to afford a fused pentapyrrin ligand, furnishing an NNNN coordination environment for complex 4, in which a pentafluorophenyl-ketal group generated during the ring cleavage reaction is attached to ring A, and it can be hydrolyzed to the corresponding pentafluorobenzoyl substituent to afford complex 5. Compared with free bases 1 and 2, complexes 3−5 show more intense low-energy near-infrared (NIR) absorption bands at ca. 791, 926 and 907 nm, respectively. This work provides an effective approach for the syntheses of linear and macrocyclic oligopyrroles with intriguing structures and properties by oxidizing oligopyrranes with precisely designed numbers and positions of N-confused pyrroles.

Pseudo-doping effect on structural and electrical properties of polyaniline-camphorsulfonic acid

Electroconductive polymers (ECP) are critical for the design of soft electronic and bioelectronic devices. Polyaniline:camphorsulfonic acid (PANI:CSA) is an example of a biocompatible and affordable ECP, whose electroconductivity is highly dependent on chain organization/conformation. PANI:CSA aggregation ordering is overlooked in most works, but it can greatly impact the performance of PANI:CSA-based devices and limit their applicability. A simple and cheap method to avoid random coil aggregation of PANI:CSA is to select solvents with pseudo-doping properties. This work presents a novel alternative solvent system, based on trifluoroethanol (TFE) and hexafluoropropanol (HFP) mixtures, capable of being removed without hampering the structural and electrical properties of PANI:CSA. For the first time, we present a systematic study that compares the performance of solvent systems containing different amounts of TFE and HFP, which, unlike m-cresol, the golden-standard of pseudo-doping, are easy to remove without compromising the ECP’s electroconductivity and biocompatibility. We also evaluate the influence of the processing method, drop-casting vs spin-coating, on the structural and electrical properties of the obtained samples. Samples obtained by spin-coating show a more consistent improvement in electroconductivity (σ(TFE) = 61 S cm−1, σ(TFE:HFP (50:50 vol)) = 70 S cm−1) and more intense near-infrared (NIR) absorption bands. Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) indicate that samples processed with HFP and m-cresol have higher benzenoid content, lower random coil aggregation and more efficient CSA doping. The solvent system comprised of equal parts of TFE and HFP was found to simultaneously enhance the electrical properties and structural ordering of PANI:CSA. We believe our results are critical for the fabrication of PANI-based next generation bioelectronic devices.

Reversible Electrochromic/Electrofluorochromic Dual Switching in Zn(II)-Based Metallo-Supramolecular Polymer Films.

The introduction of novel materials with multifunctional chromogenic properties, such as electrochromic/electrofluorochromic (EC/EFC) properties, has recently attracted prospective interest in the development of various optoelectronic devices and smart windows. In this study, a novel Zn(II)-based metallo-supramolecular polymer (polyZn) has been developed as an ON/OFF switchable EFC application with prominent EC behavior. In this regard, the polymeric chain of polyZn was first synthesized by 1:1 complexation in a zigzag manner with Zn(II) ions at the metal center and 4,4'-[bis(2,2':6',2″-terpyridinyl)benzene]triphenylamine (LTPY-TPA) as the redox-active ditopic ligand. The polyZn exhibits excellent solubility in organic solvents and can form a very good uniform thin film on an indium tin oxide/glass substrate by spin-coating. In a neutral state, transparent polyZn exhibits a bright yellow color to the naked eye (absorption at ∼325 nm). The electroactive triphenylamine (TPA) core of LTPA-TPY, however, undergoes reversible single-electron oxidation when a positive bias of +1.6 V vs Ag/Ag+ is applied, generating radical cations (TPA ↔ TPA•+) with a significant drop in transparency (77%). A noticeable chromic shift in the hue of the film from brilliant yellow to green was observed with the appearance of a near-infrared absorption band at ∼897 nm with a tail of 1300-1600 nm. Interestingly, in addition to this EC phenomenon, the fabricated solid-state polyZn film exhibits intense, high-contrast reddish-orange photoluminescence with λem = 650 nm, which is significantly desired as a molecular probe for bioimaging. Both the TPA core and the redox-inactive Zn(II)-terpyridine core emit orange-red photoluminescence in polyZn, which is significantly quenched upon the oxidation of the film and is re-emitted at 0.0 V vs Ag/Ag+. This ON/OFF EFC transition was sustained for several cycles. This study should motivate to design and create distinctive new unique materials with combined EC/EFC behavior for the fabrication of optoelectronic devices by combining a metal-fluorescent core with a redox-active spacer.

Constructing Oxygen-related Defects in Carbon Nanodots with Janus Optical Properties: Noninvasive NIR Fluorescent Imaging and Effective Photocatalytic Therapy.

Noninvasive fluorescence (FL) imaging and high-performance photocatalytic therapy (PCT) are opposing optical properties that are difficult to combine in a single material system. Herein, we report a facile approach to introducing oxygen-related defects in carbon dots (CDs) via post-oxidation with 2-iodoxybenzoic acid (IBX), in which some nitrogen atoms were substituted by oxygen atoms. Unpaired electrons in these oxygen-related defects rearranged the electronic structure of the oxidized carbon dots (ox-CDs), resulting in an emerging near-infrared (NIR) absorption band. These defects not only contributed to enhanced NIR bandgap emission but also acted as trappers for photoexcited electrons to promote efficient charge separation on the surface, leading to abundant photo-generated holes on the ox-CDs surface under visible-light irradiation. Under white LED torch irradiation, the photo-generated holes oxidized hydroxide to hydroxyl radicals in the acidification of the aqueous solution. In contrast, no hydroxyl radicals were detected in the ox-CDs aqueous solution under 730nm laser irradiation, indicating noninvasive NIR FL imaging potential. Utilizing the Janus optical properties of the ox-CDs, the in vivo NIR FL imaging of sentinel lymph nodes around tumors and efficient photothermal enhanced tumor PCT were demonstrated. This article is protected by copyright. All rights reserved.

Near-Infrared Spectroscopic Analysis─Formation of Ca(OH)2 and Ca(OD)2 by Hydration of CaO with H2O and D2O

The dehydration behavior of Ca(OH)2 was analyzed using near-infrared (NIR) and mid-infrared spectroscopy, with typical absorption bands attributed to the surface and interlayer hydroxyl groups of Ca(OH)2 being observed at 7260 and 7083 cm–1 in the NIR region, respectively. The dehydration reaction of Ca(OH)2 proceeded at approximately 470 °C, resulting in the disappearance of the interlayer hydroxyls of Ca(OH)2 and the formation of isolated hydroxyls of the CaO surface (7231 cm–1). The hydration behavior of CaO with H2O was also investigated using NIR spectroscopy, revealing that upon contact with H2O vapor at 50 °C [relative humidity (RH), 55%], CaO was immediately hydrated to form the interlayer hydroxyls of Ca(OH)2 after several minutes. Furthermore, since the difference between Ca(OH)2 and Ca(OD)2 could not be distinguished by X-ray diffraction measurements, the hydration behavior of CaO upon exposure to D2O vapor at room temperature was examined using NIR spectroscopy. This revealed the NIR absorption bands at 5357 and 5259 cm–1, corresponding to the surface and interlayer OD groups of Ca(OD)2, respectively. However, it should be noted that since the dehydration of Ca(OH)2 and the hydration of CaO were evaluated under atmospheric conditions, the formation of CaCO3 due to CO2 adsorption on the CaO surface could not be disregarded.

A Switchable Near‐Infrared‐Absorbing Dye Based on Redox‐Bistable Benzitetraazaporphyrin

AbstractActivatable near‐infrared (NIR) dyes responsive to external stimuli are used in medical and other applications. Here, we describe the design and synthesis of bench‐stable 18π‐ and 20π‐electron benzitetraazaporphyrins (BzTAPs) possessing redox‐switchable NIR properties. X‐Ray, NMR, and UV/Visible‐NIR analyses revealed that 20π‐electron BzTAP 1 exhibits NIR absorption and antiaromaticity with a paratropic ring‐current, while 18π‐electron BzTAP 2 shows weakly aromatic character with NIR inertness. Notably, the NIR‐silent BzTAP 2 was readily converted to the NIR‐active BzTAP 1 in the presence of mild reducing agents such as amine. The intense NIR absorption band of BzTAP 1 is in sharp contrast to the very weak absorption bands of previously reported antiaromatic porphyrinoids. Molecular orbital analysis revealed that symmetry‐lowering perturbation of the 20π‐electron porphyrinoid skeleton enables the HOMO–LUMO transition of 1 to be electric‐dipole‐allowed. BzTAPs are expected to be useful for constructing activatable NIR probes working in reductive environments.

A Switchable Near-Infrared-Absorbing Dye Based on Redox-Bistable Benzitetraazaporphyrin.

Activatable near-infrared (NIR) dyes responsive to external stimuli are used in medical and other applications. Here, we describe the design and synthesis of bench-stable 18π- and 20π-electron benzitetraazaporphyrins (BzTAPs) possessing redox-switchable NIR properties. X-Ray, NMR, and UV/Visible-NIR analyses revealed that 20π-electron BzTAP 1 exhibits NIR absorption and antiaromaticity with a paratropic ring-current, while 18π-electron BzTAP 2 shows weakly aromatic character with NIR inertness. Notably, the NIR-silent BzTAP 2 was readily converted to the NIR-active BzTAP 1 in the presence of mild reducing agents such as amine. The intense NIR absorption band of BzTAP 1 is in sharp contrast to the very weak absorption bands of previously reported antiaromatic porphyrinoids. Molecular orbital analysis revealed that symmetry-lowering perturbation of the 20π-electron porphyrinoid skeleton enables the HOMO-LUMO transition of 1 to be electric-dipole-allowed. BzTAPs are expected to be useful for constructing activatable NIR probes working in reductive environments.

Constructing ultra-stable photothermal plastics assisted by carbon dots with photocaged reactivity

Constructing ultra-stable photothermal plastics assisted by carbon dots with photocaged reactivity

Toward Strong Near‐Infrared Absorption/Emission from Carbon Dots in Aqueous Media through Solvothermal Fusion of Large Conjugated Perylene Derivatives with Post‐Surface Engineering

Carbon dots (CDs) have attracted significant interest as one of the most emerging photoluminescence (PL) nanomaterials. However, the realization of CDs with dominant near‐infrared (NIR) absorption/emission peaks in aqueous solution remains a great challenge. Herein, CDs with both main NIR absorption bands at 720 nm and NIR emission bands at 745 nm in an aqueous solution are fabricated for the first time by fusing large conjugated perylene derivatives under solvothermal treatment. With post‐surface engineering, the polyethyleneimine modified CDs (PEI‐CDs) exhibit enhanced PL quantum yields (PLQY) up to 8.3% and 18.8% in bovine serum albumin aqueous and DMF solutions, which is the highest PLQY of CDs in NIR region under NIR excitation. Density functional theory calculations support the strategy of fusing large conjugated perylene derivatives to achieve NIR emissions from CDs. Compared to the commercial NIR dye Indocyanine green, PEI‐CDs exhibit excellent photostability and much lower cost. Furthermore, the obtained PEI‐CDs illustrate the advantages of remarkable two‐photon NIR angiography and in vivo NIR fluorescence bioimaging. This work demonstrates a promising strategy of fusing large conjugated molecules for preparing CDs with strong NIR absorption/emission to promote their bioimaging applications.

Unfused Acceptors Matching π-Bridge Blocks with Proper Frameworks Enable Over 12% As-Cast Organic Solar Cells.

Emerging unfused-ring acceptors (UFAs) have been explored in pursuit of low-cost high-efficient organic solar cells (OSCs). Assembling unfused building blocks into proper frameworks are challenging for the molecular design of UFAs. The authors report herein four UFAs adopting either dithiophene cyclopentadiene (DTC) or dithieno[3,2-b:2',3'-d]pyrrole (DTP) as π-bridge units with different molecular frameworks for high-efficient as-cast OSCs. All these acceptors exhibit strong near-infrared absorption and narrow optical band gap (Eg opt <1.50eV).DTC-bridged symmetric and DTP-bridged asymmetric UFAs exhibit higher planar conformation as well as suitable miscibility and homogeneous phase separation when blending with polymer donor PBDB-T to promote efficient charge transport in the blends. Their blends with PBDB-T contribute optimal PCE of 12.17% and 11.92% in as-cast OSCs, among the highest values for UFAs based as-cast devices in the literature. Experimental and theoretical simulations systematically reveal the impact of manipulating the molecular framework of UFAs on their conformation, optoelectronic, and photovoltaic performance. The results indicate the matching π-bridge units with molecular frameworks as an attractive approach to design UFAs for high-performance as-cast OSCs.

Longitudinal Variation of H2O Ice Absorption on Miranda

Many tidally locked icy satellites in the outer solar system show leading/trailing hemispherical asymmetries in the strength of near-infrared (NIR) H2O ice absorption bands, in which the absorption bands are stronger on the leading hemisphere. This is often attributed to a combination of magnetospheric irradiation effects and impact gardening, which can modify grain size, expose fresh ice, and produce dark contaminating compounds that reduce the strength of absorption features. Previous research identified this leading/trailing asymmetry on the four largest classical Uranian satellites but did not find a clear leading/trailing asymmetry on Miranda, the smallest and innermost classical moon. We undertook an extensive observational campaign to investigate variations of the NIR spectral signature of H2O ice with longitude on Miranda’s northern hemisphere. We acquired 22 new spectra with the TripleSpec spectrograph on the ARC 3.5 m telescope and four new spectra with GNIRS on Gemini North. Our analysis also includes three unpublished and seven previously published spectra taken with SpeX on the 3 m IRTF. We confirm that Miranda has no substantial leading/trailing hemispherical asymmetry in the strength of its H2O ice absorption features. We additionally find evidence for an anti-Uranus/sub-Uranus asymmetry in the strength of the 1.5 μm H2O ice band that is not seen on the other Uranian satellites, suggesting that additional endogenic or exogenic processes influence the longitudinal distribution of H2O ice band strengths on Miranda.

Measurement of absorption cross sections of Co2+:MgAl2O4 crystals with transition of Co2+ ions along two orthogonal directions.

The nonlinear transmission curves of the Co2+:MgAl2O4 crystal at 1.5 µm are experimentally measured by the pump-probe technique. The measurement results demonstrate that the transition into the near-infrared absorption band is polarized not only along the C3 local symmetry axis, but also along the direction perpendicular to the C3 axis, arising from the distortion of oxygen tetrahedrons about the Co2+ ions along the four C3 local symmetry axes. The obtained saturation curves are analyzed using a theoretical model taking into account the transition of Co2+ ions along two orthogonal directions. The ground-state absorption cross sections for polarization parallel and perpendicular to the C3 axis are calculated to be 3.4×10-19cm2 and 2.6×10-20cm2, respectively. The excited-state absorption cross section for polarization parallel to the C3 axis is estimated to be4.2×10-20cm2.