Spectral Window Research Articles

Rapid Primary Sulfate Aerosol Generation Observed With OP‐FTIR in the Eruptive Plume of the Fagradalsfjall Basaltic Eruption, Iceland, 2021

AbstractOpen‐Path Fourier‐Transform Infrared (OP‐FTIR) absorption spectroscopy is a powerful method for remote characterization of volcanic plume composition from safe distances. Many studies have used it to examine the composition of volcanic gas emitted at the surface, which is influenced by initial volatile contents and magma ascent/storage processes, and help to reveal the dynamics controlling surface activity. However, to evaluate the health hazard threats associated with volcanic emissions and their potential impact on wider atmospheric conditions, near‐source particle measurements are also key. Here we present a forward model and fitting algorithm which allows quantification of particle size and abundance. This was successfully applied to radiometrically uncalibrated OP‐FTIR spectra collected with a highly dynamic radiation source during the Fagradalsfjall eruption, Iceland, on 11 August 2021. Quantification of plume temperatures ranging from 350 to 650 K was essential to characterize the emission‐absorption behavior of SO2, enabling retrievals of particulate matter in the thermal infrared spectral window (750–1250 cm−1) in each spectrum. For the first time, we observe the rapid formation of primary aerosols in young plumes (only a few seconds old) with OP‐FTIR. Temperature‐dependent SO2/SO42− molar ratios range from 100 to 250, consistent with a primary formation mechanism controlled by cooling and entrainment of atmospheric gases. This novel aerosol spectrum retrieval opens new frontiers in field‐based measurements of sulfur partitioning and volcanic plume evolution, with the potential to improve volcano monitoring and quantification of air quality hazard assessments.

Development of Optical Nanosensors for Detection of Potassium Ions and Assessment of Their Biocompatibility with Corneal Epithelial Cells.

Imbalance of potassium-ion levels in the body can lead to physiological dysfunctions, which can adversely impact cardiovascular, neurological, and ocular health. Thus, quantitative measurement of potassium ions in a biological system is crucial for personal health monitoring. Nanomaterials can be used to aid in disease diagnosis and monitoring therapies. Optical detection technologies along with molecular probes emitting within the near-infrared (NIR) spectral range are advantageous for biological measurements due to minimal interference from light scattering and autofluorescence within this spectral window. Herein, we report the development of NIR fluorescent nanosensors, which can quantitatively detect potassium ions under biologically relevant conditions. The optical nanosensors were developed by using photoluminescent single-walled carbon nanotubes (SWCNTs) encapsulated in polymers that contain potassium chelating moieties. The nanosensors, polystyrene sulfonate [PSS-SWCNTs, nanosensor 1 (NS1)] or polystyrene-co-polystyrene sulfonate [PS-co-PSS-SWCNTs, nanosensor 2 (NS2)], exhibited dose-dependent optical responses to potassium ion level. The nanosensors demonstrated their biocompatibility via the evaluation of cellular viability, proliferation assays, and expression of cytokeratin 12 in corneal epithelial cells (CEpiCs). Interestingly, the nanosensors' optical characteristics and their responses toward CEpiCs were influenced by encapsulating polymers. NS2 exhibited a 10 times higher fluorescence intensity along with a higher signal-to-noise ratio as compared to NS1. NS2 showed an optical response to potassium ion level in solution within 5 min of addition and a limit of detection of 0.39 mM. Thus, NS2 was used for detailed investigations including potassium ion level detection in serum. NS2 showed a consistent response to potassium ions at the lower millimolar range in serum. These results on optical sensing along with biocompatibility show a great potential for nanotube sensors in biomedical research.

H2CO and CS in diffuse clouds: Excitation and abundance

Context. Diffuse interstellar clouds present an active chemistry despite their relatively low density and the ubiquitous presence of far-UV radiation. Aims. To provide constraints on the chemical processes responsible for the observed columns of organic species, we used the NOEMA interferometer to observe the sight line toward NRAO150 (B0355+508) in the 2 mm spectral window. Methods. We targeted the low excitation lines of ortho H2 CO (21,1–11,0) and para H2 CO (20,2–10,1) as well as the nearby transitions of CS (3–2) and c-C3H2 (31,2–22,1), (41,4–30,3), and (22,0–11,1). We combined these data with previous observations of the same sight line to determine the excitation conditions, column densities, and abundances relative to H2 in the different velocity components. We performed non-LTE radiative transfer calculations including collision cross sections with ortho and para H2 and with electrons. New collision cross sections with electrons were computed for ortho and para formaldehyde. Results. All targeted lines were detected. The c-C3H2 line profiles are very similar to those of HCO+ and CCH, while the CS absorption features are narrower and mostly concentrated in two main velocity components at VLSR = −17.2 and −10.4 km s−1. H2CO absorption lines present an intermediate pattern with absorption in all velocity components but larger opacities in the two main velocity components. The ortho-to-para ratios of H2CO and c-C3H2 are consistent with the statistical value of three. While the excitation temperature of all c-C3H2 velocity components is consistent with the Cosmic Microwave Background (CMB), the two strong components detected in CS show a clear excess over the CMB indicating that CS resides at higher densities than other species along this particular sightline, n(H2) ~ 2500 cm−3 while n(H2) < 500 cm−3 for the other velocity components. We detected faint absorption from o-H213CO and C34S allowing us to derive isotopic ratios: o-H2CO/o-H213CO = 61 ± 12 and C32S/C34S = 24 ± 6. The excitation of the 11,0−11,1 line of formaldehyde at 4.8 GHz is sensitive to the electron fraction and its excitation temperature is predicted to be lower than the CMB at low and moderate electron fractions (x(e) < 6 × 10−5), and to rise above the CMB at high electron fractions (x(e) > 10−4).

Reabsorption‐Free Scintillating Hetero‐Ligand MOF Crystals Activated by Ultrafast Energy Transfer

AbstractFast photoluminescence and scintillation with a Stokes shift larger than 1 eV is achieved in hetero‐ligand metal–organic framework (MOF) crystals comprising inorganic linking nodes and fluorescent conjugated ligands. By finely engineering the MOF composition with the use of ligands with strictly complementary emission and absorption properties and highly delocalized molecular electronic orbitals, the singlet excitons diffusion is enhanced through the ligand framework, fully exploiting both Förster and Dexter energy transfer mechanisms. This allows for the sensitization of energy acceptor ligand fluorescence by ultrafast non‐radiative energy transfer with a rate up to the THz range. This efficient antenna effect instantly activates the MOF scintillation with a Stokes shift as large as 1.3 eV in the blue spectral range, matching the highest sensitivity spectral window of the best photodetector available. This is obtained using a minimal doping level of the energy acceptor species, with a consequent elimination of emission re‐absorption that allows the achievement of a 500% increment of the MOFs scintillation efficiency and the detection of the radioactive krypton isotope 85Kr from the gas phase with an improved sensitivity compared with the reference material.

Heterointerface Effects on Carrier Dynamics in Colloidal Quantum Dots and Their Application to Light-Emitting Diodes.

Colloidal quantum dots (QDs) are promising candidates for next-generation display technology because of their unique optical properties and have already appeared in the market as a high-end product. On the basis of their extraordinary properties, QD emissions with a given chemical composition can be tailored in a wide spectral window due to quantum size effects, which constitutes a key advantage of QDs in the display field. Specifically, investigations of structure-dependent and composition-dependent characterizations outside the quantum confinement effect have become an important part of practical applications. Therefore, from the perspective of designing nanostructures with well-defined heterointerfaces, strong quantum confinement effects with effective carrier confinement are desirable. Our results show that the photoluminescence (PL) intensity of CdSe/CdZnS core-shell QDs was enhanced 5.7 times compared with that of the CdSe core QDs. Supplementary analytical techniques involving transmission electron microscopy revealed the heterointerface configuration and composition distribution of the core and shell materials. The effects of the heterointerface on carrier dynamics in core-shell QDs were revealed by monitoring wavelength-dependent time-resolved PL. To further develop the QD light-emitting diodes (QD-LEDs), we produced an all-solution processed inverted QD-LEDs using CdSe/CdZnS core-shell QDs as the emitter. The electroluminescence spectrum of deep-red emissive QD-LEDs with CIE chromaticity coordinates of (0.68, 0.32) exhibited a peak at 638 nm.

High‐Efficiency Single‐Photon Upconversion Photoluminescence of Perovskite Quantum Dots via Intragap State Regulation

AbstractLead halide perovskite quantum dots (PQDs) have shown remarkable single‐photon upconversion photoluminescence (SPUC‐PL) bringing them a brilliant perspective as the active media for biological imaging, optiag, and upconversion photovoltaics. However, the mechanism of SPUC in PQDs is still in dispute, and the specific strategy for optimizing PQDs toward a higher SPUC performance has yet to be established, which impedes the application of PQDs‐based SPUC‐PL in practice. In this work it is revealed that the PL quantum yield is declined by surface trap states, while the SPUC efficiency is promoted by Urbach tail states. These two types of intragap states can be chemically manipulated by engineering the surface ligand and the growth kinetics of perovskite nanocrystals, bringing on the improvement of light emission efficiency and the promotion of subgap low‐energy photon absorption, respectively. As a proof of concept, utilizing the synergistic effect of the proposed chemical manipulation method, the SPUC‐PL efficiency of PQDs is boosted by more than 40%, which gives rise to a spectral window of optical refrigeration gain as broad as ≈130 meV.

The JWST Early Release Science Program for Direct Observations of Exoplanetary Systems. V. Do Self-consistent Atmospheric Models Represent JWST Spectra? A Showcase with VHS 1256–1257 b

The unprecedented medium-resolution (R λ ∼ 1500–3500) near- and mid-infrared (1–18 μm) spectrum provided by JWST for the young (140 ± 20 Myr) low-mass (12–20 M Jup) L–T transition (L7) companion VHS 1256 b gives access to a catalog of molecular absorptions. In this study, we present a comprehensive analysis of this data set utilizing a forward-modeling approach applying our Bayesian framework, ForMoSA. We explore five distinct atmospheric models to assess their performance in estimating key atmospheric parameters: T eff, log(g), [M/H], C/O, γ, f sed, and R. Our findings reveal that each parameter’s estimate is significantly influenced by factors such as the wavelength range considered and the model chosen for the fit. This is attributed to systematic errors in the models and their challenges in accurately replicating the complex atmospheric structure of VHS 1256 b, notably the complexity of its clouds and dust distribution. To propagate the impact of these systematic uncertainties on our atmospheric property estimates, we introduce innovative fitting methodologies based on independent fits performed on different spectral windows. We finally derived a T eff consistent with the spectral type of the target, considering its young age, which is confirmed by our estimate of log(g). Despite the exceptional data quality, attaining robust estimates for chemical abundances [M/H] and C/O, often employed as indicators of formation history, remains challenging. Nevertheless, the pioneering case of JWST’s data for VHS 1256 b has paved the way for future acquisitions of substellar spectra that will be systematically analyzed to directly compare the properties of these objects and correct the systematics in the models.

Near-infrared hyperspectral imaging and robust statistics for in vivo non-melanoma skin cancer and actinic keratosis characterisation.

One of the most common forms of cancer in fair skinned populations is Non-Melanoma Skin Cancer (NMSC), which primarily consists of Basal Cell Carcinoma (BCC), and cutaneous Squamous Cell Carcinoma (SCC). Detecting NMSC early can significantly improve treatment outcomes and reduce medical costs. Similarly, Actinic Keratosis (AK) is a common skin condition that, if left untreated, can develop into more serious conditions, such as SCC. Hyperspectral imagery is at the forefront of research to develop non-invasive techniques for the study and characterisation of skin lesions. This study aims to investigate the potential of near-infrared hyperspectral imagery in the study and identification of BCC, SCC and AK samples in comparison with healthy skin. Here we use a pushbroom hyperspectral camera with a spectral range of ≈ 900 to 1600 nm for the study of these lesions. For this purpose, an ad hoc platform was developed to facilitate image acquisition. This study employed robust statistical methods for the identification of an optimal spectral window where the different samples could be differentiated. To examine these datasets, we first tested for the homogeneity of sample distributions. Depending on these results, either traditional or robust descriptive metrics were used. This was then followed by tests concerning the homoscedasticity, and finally multivariate comparisons of sample variance. The analysis revealed that the spectral regions between 900.66-1085.38 nm, 1109.06-1208.53 nm, 1236.95-1322.21 nm, and 1383.79-1454.83 nm showed the highest differences in this regard, with <1% probability of these observations being a Type I statistical error. Our findings demonstrate that hyperspectral imagery in the near-infrared spectrum is a valuable tool for analyzing, diagnosing, and evaluating non-melanoma skin lesions, contributing significantly to skin cancer research.

Ultrabroadband Near-Infrared Transient Absorption Spectrometer with Simultaneous 900-2350 nm Detection.

In this work, we detail an ultrafast pump-probe transient absorption (TA) spectrometer capable of probing the near-infrared (NIR) spectral region from 900 to 2350 nm simultaneously. Two key advances were required to overcome previous spectral window limitations, which typically result from constrained supercontinuum ranges (e.g., 1700 nm) and/or InGaAs detector line rates, especially those with >1700 nm range. First, we generated a broadband NIR supercontinuum using the 1980 nm idler beam of an optical parametric amplifier and implement a unique spectral filtering scheme to balance the detected spectrum. Second, we used a prism-based spectrometer system equipped with high speed InGaAs cameras having ∼2500 nm sensitivity cutoffs. To the best knowledge of the authors, such an extended probe range was previously inaccessible because the combination of two optical geometries either using different supercontinuum crystal materials for generating the NIR and shortwave infrared (SWIR) regions, or using differing pump wavelengths, were required. Finally, we demonstrate the performance and capabilities of the ultrabroadband TA spectroscopy system by presenting data showing ultrafast charge photogeneration in a polymer : fullerene blend thin-film and comparing the results to the literature with a complete agreement.

Silicon-Nanowire-Based 100-GHz-Spaced 16λ DWDM, 800-GHz-Spaced 8λ LR-8, and 20-nm-Spaced 4λ CWDM Optical Demultiplexers for High-Density Interconnects in Datacenters

Several types of silicon-nanowire-based optical demultiplexers (DeMUXs) for use in short-reach targeted datacenter applications were proposed and their spectral responses were experimentally verified. First, a novel 100-GHz-spaced 16λ polarization-diversified optical DeMUX consisting of 2λ delayed interferometer (DI) type interleaver and 8λ arrayed waveguide gratings will be discussed in the spectral regimes of C-band, together with experimental characterizations showing static and dynamic spectral properties. Second, a novel 800-GHz-spaced 8λ optical DeMUX was targeted for use in LR (long reach) 400 Gbps Ethernet applications. Based on multiple cascade-connected DIs, by integrating the extra band elimination cutting area, discontinuous filtering response was analytically identified with a flat-topped spectral window and a low spectral noise of &lt;−20 dB within an entire LR-8 operating wavelength range. Finally, a 20-nm-spaced 4λ coarse wavelength division multiplexing (CWDM)-targeted optical DeMUX based on polarization diversity was experimentally verified. The measurement results showed a low excessive loss of 1.0 dB and a polarization-dependent loss of 1.0 dB, prominently reducing spectral noises from neighboring channels by less than −15 dB. Moreover, TM-mode elimination filters were theoretically analyzed and experimentally confirmed to minimize unwanted TM-mode-oriented polarization noises that were generated from the polarization-handling device. The TM-mode elimination filters functioned to reduce polarization noises to much lower than −20 dB across the entire CWDM operating window.

Coronagraphic Observations of Si x 1430 nm Acquired by DKIST/Cryo-NIRSP with Methods for Telluric Absorption Correction

We report commissioning observations of the Si x 1430 nm solar coronal line observed coronagraphically with the Cryogenic Near-Infrared Spectropolarimeter at the National Science Foundation’s Daniel K. Inouye Solar Telescope. These are the first known spatially resolved observations of this spectral line, which has strong potential as a coronal magnetic field diagnostic. The observations target a complex active region located on the solar northeast limb on 2022 March 4. We present a first analysis of these data that extracts the spectral line properties through a careful treatment of the variable atmospheric transmission that is known to impact this spectral window. Rastered images are created and compared with extreme-UV observations from the Solar Dynamics Observatory (SDO) Atmospheric Imaging Assembly (AIA) instrument. A method for estimating the electron density from the Si x observations is then demonstrated that makes use of the forbidden line density-sensitive emissivity and an emission-measure analysis of the SDO/AIA bandpass observations. In addition, we derive an effective temperature and nonthermal line width across the region. This study informs the calibration approaches required for more routine observations of this promising diagnostic line.

Monolithically integrated multimode interference coupler-based master oscillator power amplifier with dual-wavelength emission around 830 nm

A monolithically integrated dual-wavelength multimode interference coupler-based master oscillator power amplifier is presented. It consists of two shallowly etched, laterally separated ridge waveguide laser cavities as master oscillators with individual distributed Bragg reflector gratings as cavity mirrors. A deeply etched coupling section containing S-bend shaped waveguides and a multimode interference coupler is used to couple the laser emission of the master oscillators into a shallowly etched single waveguide serving as power amplifier. Changing the etch depth for the coupling section enables a compact device layout. In addition, increased radiation angles of modes not coupled into the power amplifier help to suppress beam steering, otherwise indicated by laterally separated far-field intensity distributions. The device provides 0.5 W of dual-wavelength emission around 830 nm in individual and common operation. As designed, both emission wavelengths are separated by 0.5 nm with spectral widths below 20 pm, limited by the spectral resolution of the spectrometer. Both peak wavelengths remain within spectral windows of 50 pm within the available power range. This enables full flexibility selecting operating points for applications such as shifted excitation Raman difference spectroscopy and the generation of THz emission by photomixing. The emission wavelengths can additionally be non-continuously tuned by applying a heater current to resistors implemented next to the distributed Bragg reflector gratings. As an example, selected spectral distances of 0.5 nm, 1.0 nm, 1.5 nm, and 2.0 nm are demonstrated. Near field widths of 5 μm and far field angles of 17° result in beam propagation ratios of 1.4 (1/e2) in all operation modes and enable easy beam shaping or optical single-mode fiber coupling.

Stimulated emission does not radiate in a pure dipole pattern

Stimulated emission (StE) remains relatively unused as an image-forming signal despite having potential advantages over fluorescence in speed, coherence, and ultimately resolution. Several ideas for the radiation pattern and directionality of StE remain prevalent, namely, whether a single molecule would radiate StE itself in a pure dipole pattern, or whether its emission direction depends on the driving field. Previous StE imaging has been carried out in transmission, which would collect signal either way. Here, we introduce the StE driving field (the probe) at an angle, using total internal reflection to avoid incident probe light and its specular reflections in our detection path. In this non-collinear detection configuration that also collects some fluorescence from the sample, we observe fluorescence depletion even in the spectral window where an increase in detected signal from StE would be expected if StE radiated like a simple classical dipole. Because simultaneous direct measurement of the fluorescence represents a calibration of the potential size of StE were it spatially patterned like a classical dipole emitter, our study clarifies a critical characteristic of StE for optimal microscope design, optical cooling, and applications using small arrays of emitters.

Teaming up Radio and Sub-mm/FIR Observations to Probe Dusty Star-Forming Galaxies

In this paper, we investigate the benefits of teaming up data from the radio to the far-infrared (FIR) regime for the characterization of dusty star-forming galaxies (DSFGs). These galaxies are thought to be the star-forming progenitors of local massive quiescent galaxies and to play a pivotal role in the reconstruction of the cosmic star formation rate density up to high redshift. Due to their dust-enshrouded nature, DSFGs are often invisible in the near-infrared/optical/UV bands. Therefore, they necessitate observations at longer wavelengths, primarily the FIR band, where dust emission occurs, and the radio band, which is not affected by dust absorption. Combining data from these two spectral windows makes it possible to characterize even the dustiest objects, enabling the retrieval of information about their age, dust temperature, and star-formation status, and facilitates the differentiation between various galaxy populations that evolve throughout cosmic history. Despite the detection of faint radio sources being a challenging task, this study demonstrates that an effective strategy to build statistically relevant samples of DSFGs would be reaching deep sensitivities in the radio band, even restricted to smaller areas, and then combining these radio observations with FIR/submm data. Additionally, this paper quantifies the improvement in the spectral energy distribution (SED) reconstruction of DSFGs by incorporating ALMA band measurements, in particular, in its upgraded status thanks to the anticipated Wideband Sensitivity Upgrade.

Abstract 4167: Selective imaging of cancer-associated fibroblasts in the breast cancer microenvironment with near-infrared fluorescent probes

Abstract Tumors consist of a complex mixture of resident and infiltrating cells that can support their survival and evasion of treatment. Selective detection of genetically stable cells in the tumor microenvironment (TME) offers insight into tumor biology beyond the malignant cells, which are the focus of most molecular imaging approaches to cancer detection. Motivated by the goal of non-invasively understanding the primary breast TME, we have developed fluorescent molecular probes that target cancer-associated fibroblasts (CAFs), a major component of the stromal compartment of many tumors, and emit light in the near-infrared (NIR) spectral window, providing access to deeper tissues than visible probes. We synthesized and characterized a series of CAF-targeted antibody- and small molecule-based fluorescent imaging agents utilizing a highly hydrophilic NIR dye and ligands that target Fibroblast Activation Protein (FAP). FAP is a key cell-surface marker of breast cancer CAFs with an S1 phenotype, which are modulators of immunosuppression, metastatic spread, and are associated with worse outcomes, especially in HER2+ and triple-negative breast cancer. Modifications to the chemical structure of the linker and targeting ligands allowed us to alter the specificity and brightness of the CAF-probes in cellulo. Imaging of a co-implanted tumor model of SKBR3 human breast cancer cells and FAP expressing fibroblasts after administering our lead small-molecule CAF imaging agent revealed selective tumor targeting of CAF-rich tumors compared to cancer cell predominant tumors with favorable pharmacokinetics and tumor-to-background ratio (TBR) greater than 2. Similar imaging studies with MMTV-PyMT transgenic mice, an established murine model of breast cancer, showed analogous enhanced uptake in mammary tumors (TBR &amp;gt; 2) and clearance over 24 hours. NIR fluorescence also correlated with CAFs isolated from PyMT tumor tissue via flow cytometry, consistent with our hypothesis that this agent can specifically detect endogenous CAFs. This study identified a novel, bright, and water-soluble FAP-specific NIR agent for in vivo imaging, setting the stage for simultaneous optical imaging of malignant cells and activated fibroblasts in the TME to elucidate cancer-host interactions. Citation Format: Megan S. Michie, Junwei Du, Jiayu (Jennifer) Ye, Kathleen Duncan, Mikhail Y. Berezin, Samuel Achilefu. Selective imaging of cancer-associated fibroblasts in the breast cancer microenvironment with near-infrared fluorescent probes [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 4167.

Spectrally resolved nonlinearities within a laser pulse in a single-scan and spectrometer-based nonlinear optical probing.

The intricate spectrally resolved optical nonlinearities resulting from a spectrally broad femtosecond Gaussian laser pulse have been unraveled using a single-scan and spectrometer-based nonlinear optical probing technique. The interaction of the broad femtosecond laser pulse with a strongly absorbing organic dye has unveiled a remarkably distinct nonlinear absorption behavior across the broad spectral window. The nonlinear absorption behavior unveils an unusual transition from the reverse saturation absorption (RSA) to the saturation absorption (SA) as we sweep the wavelength on both sides of the central wavelength of the excitation laser pulse. A competition between the band-filling and excited-state absorption results in such a dramatic switch-over from the RSA to the SA due to the variation of the intensity distribution across the Gaussian pulse spectrum. On the other hand, the nonlinear refraction studies dictate more over the constant Kerr-type positive nonlinear refractive indices across the entire laser pulse, with a pronounced contribution from the nonlinear absorption phase dominating at the center of the pulse. The presented technique establishes a robust and simple spectrometer-based technique that offers new, to the best of our knowledge, avenues for estimating optical nonlinearities for rapid nonlinear optical measurements.

L2 to Lp bounds for spectral projectors on the Euclidean two-dimensional torus

AbstractWe consider spectral projectors associated to the Euclidean Laplacian on the two-dimensional torus, in the case where the spectral window is narrow. Bounds for their L2 to Lp operator norm are derived, extending the classical result of Sogge; a new question on the convolution kernel of the projector is introduced. The methods employed include $\ell^2$ decoupling, small cap decoupling and estimates of exponential sums.

Triple para-Functionalized Cations and Neutral Radicals of Enantiopure Diaza[4]helicenes.

Modulation of absorbance and emission is key for the design of chiral chromophores. Accessing a series of compounds absorbing and emitting (circularly polarized) light over a wide spectral window and often toward near-infrared is of practical value in (chir)optical applications. Herein, by late-stage functionalization on derivatives bridging triaryl methyl and helicene domains, we have achieved the regioselective triple introduction of para electron-donating or electron-withdrawing substituents. Extended tuning of electronic (e.g., E1/2red -1.50 V → -0.68 V) and optical (e.g., emission covering from 550 to 850 nm) properties is achieved for the cations and neutral radicals; the latter compounds being easily prepared by mono electron reductions under electrochemical or chemical conditions. While luminescence quantum yields can be increased up to 70% in the cationic series, strong Cotton effects are obtained for certain radicals at low energies (λabs ∼ 700-900 nm) with gabs values above 10-3. The open-shell electronic nature of the radicals was further characterized by electron paramagnetic resonance revealing an important spin density delocalization that contributes to their persistence.

Photo-Induced Charge State Dynamics of the Neutral and Negatively Charged Silicon Vacancy Centers in Room-Temperature Diamond.

The silicon vacancy (SiV) center in diamond is drawing much attention due to its optical and spin properties, attractive for quantum information processing and sensing. Comparatively little is known, however, about the dynamics governing SiV charge state interconversion mainly due to challenges associated with generating, stabilizing, and characterizing all possible charge states, particularly at room temperature. Here, multi-color confocal microscopy and density functional theory are used to examine photo-induced SiV recombination - from neutral, to single-, to double-negatively charged - over a broad spectral window in chemical-vapor-deposition (CVD) diamond under ambient conditions. For the SiV0 to SiV- transition, a linear growth of the photo-recombination rate with laser power at all observed wavelengths is found, a hallmark of single photon dynamics. Laser excitation of SiV‒, on the other hand, yields only fractional recombination into SiV2‒, a finding that is interpreted in terms of a photo-activated electron tunneling process from proximal nitrogen atoms.

Exploiting the entire near-infrared spectral range to improve the detection of methane plumes with high-resolution imaging spectrometers

Abstract. Remote sensing emerges as an important tool for the detection of methane plumes emitted by so-called point sources, which are common in the energy sector (e.g., oil and gas extraction and coal mining activities). In particular, satellite imaging spectroscopy missions covering the shortwave infrared part of the solar spectrum are very effective for this application. These instruments sample the methane absorption features at the spectral regions around 1700 and 2300 nm, which enables the retrieval of methane concentration enhancements per pixel. Data-driven retrieval methods, in particular those based on the matched filter concept, are widely used to produce maps of methane concentration enhancements from imaging spectroscopy data. Using these maps enables the detection of plumes and the subsequent identification of active sources. However, retrieval artifacts caused by particular surface components may sometimes appear as false plumes or disturbing elements in the methane maps, which complicates the identification of real plumes. In this work, we use a matched filter that exploits a wide spectral window (1000–2500 nm) instead of the usual 2100–2450 nm window with the aim of reducing the occurrence of retrieval artifacts and background noise. This enables a greater ability to discriminate between surface elements and methane. The improvement in plume detection is evaluated through an analysis derived from both simulated data and real data from areas including active point sources, such as the oil and gas (O&amp;amp;G) industry from San Joaquin Valley (US) and the coal mines from the Shanxi region (China). We use datasets from the Precursore IperSpettrale della Missione Applicativa (PRISMA) and the Environmental Mapping and Analysis Program (EnMAP) satellite imaging spectrometer missions and from the Airborne Visible/Infrared Imaging Spectrometer – Next Generation (AVIRIS-NG) instrument. We find that the interference with atmospheric carbon dioxide and water vapor is generally almost negligible, while co-emission or overlapping of these trace gases with methane plumes leads to a reduction in the retrieved concentration values. Attenuation will also occur in the case of methane emissions situated above surface structures that are associated with retrieval artifacts. The results show that the new approach is an optimal trade-off between the reduction in background noise and retrieval artifacts. This is illustrated by a comprehensive analysis in a PRISMA dataset with 15 identified plumes, where the output mask from an automatic detection algorithm shows an important reduction in the number of clusters not related to CH4 emissions.