Mid-infrared trace detection with parts-per-quadrillion quantitation accuracy: Expanding frontiers of radiocarbon sensing.

Detection sensitivity is a critical characteristic to consider during selection of spectroscopic techniques. However, high sensitivity alone is insufficient for spectroscopic measurements in spectrally congested regions. Two-color cavity ringdown spectroscopy (2C-CRDS), based on intra-cavity pump-probe detection, simultaneously achieves high detection sensitivity and selectivity. This combination enables mid-infrared detection of radiocarbon dioxide ([Formula: see text]CO[Formula: see text]) molecules in room-temperature CO[Formula: see text] samples, with 1.4 parts-per-quadrillion (ppq, 10[Formula: see text]) sensitivity (average measurement precision) and 4.6-ppq quantitation accuracy (average calibrated measurement error for 21 samples from four separate trials) demonstrated on samples with [Formula: see text]C/C up to [Formula: see text]1.5[Formula: see text] natural abundance ([Formula: see text]1,800 ppq). These highly reproducible measurements, which are the most sensitive and quantitatively accurate in the mid-infrared, are accomplished despite the presence of orders-of-magnitude stronger, one-photon signals from other CO[Formula: see text] isotopologues. This is a major achievement in laser spectroscopy. A room-temperature-operated, compact, and low-cost 2C-CRDS sensor for [Formula: see text]CO[Formula: see text] benefits a wide range of scientific fields that utilize [Formula: see text]C for dating and isotope tracing, most notably atmospheric [Formula: see text]CO[Formula: see text] monitoring to track CO[Formula: see text] emissions from fossil fuels. The 2C-CRDS technique significantly enhances the general utility of high-resolution mid-infrared detection for analytical measurements and fundamental chemical dynamics studies.

Ferromagnetically Coupled Chromium(III) Dimer Shows Luminescence and Sensitizes Photon Upconversion.

There has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono- or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both complexes, entailing comparatively short excited-state lifetimes in the range of 400 to 800 ns in solution at room temperature and making photoluminescence essentially oxygen insensitive. The two chromium(III) ions in the dimer experience ferromagnetic exchange interactions that result in a high spin (S=3) ground state with a coupling constant of +9.3 cm-1. Photoinduced energy transfer from the luminescent ferromagnetically coupled dimer to an anthracene derivative results in sensitized triplet-triplet annihilation upconversion. Based on these proof-of-principle studies, dinuclear chromium(III) complexes seem attractive for the development of fundamentally new types of photophysics and photochemistry enabled by magnetic exchange interactions.

Singlet Oxygen Quantum Yields of Pyrogenic Dissolved Organic Matter from Lab-Prepared and Wildfire Chars.

Wildfires or prescribed fires release pyrogenic dissolved organic matter (pyDOM) into the environment, which can photochemically produce singlet oxygen (1O2) in sun-lit surface waters. 1O2 quantum yields (ΦΔ) are well-studied for non-pyrogenic DOM, but little is understood about the 1O2 generation from pyDOM, especially the ΦΔ values from real wildfire samples and their wavelength dependence. In this study, time-resolved 1O2 phosphorescence was used to determine the wavelength-dependent ΦΔ values for pyDOM generated from wildfire char and a series of lab-prepared chars produced by combusting oak and pine wood. Wildfire and most lab-prepared pyDOM generally had similar ΦΔ values (2.1-2.7%) at 365 nm compared to the reference Suwannee River Natural Organic Matter (SRNOM) isolate (2.4%). Interestingly, pyDOM from the highest combustion temperature char was found to possess extremely low ΦΔ values compared to SRNOM and other pyDOM at all excitation wavelengths. In addition, it was revealed that the predicted steady-state concentration of 1O2 from pyDOM was similar to that from SRNOM, indicating that the addition of pyDOM from wood chars may not strongly impact surface water photochemistry.

Specificity of Photochemical Energy Conversion in Photosystem I from the Green Microalga Chlorella ohadii.

Primary excitation energy transfer and charge separation in photosystem I (PSI) from the extremophile desert green alga Chlorella ohadii grown in low light were studied using broadband femtosecond pump-probe spectroscopy in the spectral range from 400 to 850 nm and in the time range from 50 fs to 500 ps. Photochemical reactions were induced by the excitation into the blue and red edges of the chlorophyll Qy absorption band and compared with similar processes in PSI from the cyanobacterium Synechocystis sp. PCC 6803. When PSI from C. ohadii was excited at 660 nm, the processes of energy redistribution in the light-harvesting antenna complex were observed within a time interval of up to 25 ps, while formation of the stable radical ion pair P700+A1- was kinetically heterogeneous with characteristic times of 25 and 120 ps. When PSI was excited into the red edge of the Qy band at 715 nm, primary charge separation reactions occurred within the time range of 7 ps in half of the complexes. In the remaining complexes, formation of the radical ion pair P700+A1- was limited by the energy transfer and occurred with a characteristic time of 70 ps. Similar photochemical reactions in PSI from Synechocystis 6803 were significantly faster: upon excitation at 680 nm, formation of the primary radical ion pairs occurred with a time of 3 ps in ~30% complexes. Excitation at 720 nm resulted in kinetically unresolvable ultrafast primary charge separation in 50% complexes, and subsequent formation of P700+A1- was observed within 25 ps. The photodynamics of PSI from C. ohadii was noticeably similar to the excitation energy transfer and charge separation in PSI from the microalga Chlamydomonas reinhardtii; however, the dynamics of energy transfer in C. ohadii PSI also included slower components.

In vivo assessment of bladder cancer with diffuse reflectance and fluorescence spectroscopy: A comparative study.

OBJECTIVES: The aim of this work is to assess the performance of multimodal spectroscopic approach combined with single core optical fiber for detection of bladder cancer during surgery in vivo. METHODS: Multimodal approach combines diffuse reflectance spectroscopy (DRS), fluorescence spectroscopy in the visible (405 nm excitation) and near-infrared (NIR) (690 nm excitation) ranges, and high-wavenumber Raman spectroscopy. All four spectroscopic methods were combined in a single setup. For 21 patients with suspected bladder cancer or during control cystoscopy optical spectra of bladder cancer, healthy bladder wall tissue and/or scars were measured. Classification of cancerous and healthy bladder tissue was performed using machine learning methods. RESULTS: Statistically significant differences in relative total haemoglobin content, oxygenation, scattering, and visible fluorescence intensity were found between tumor and normal tissues. The combination of DRS and visible fluorescence spectroscopy allowed detecting cancerous tissue with sensitivity and specificity of 78% and 91%, respectively. The addition of features extracted from NIR fluorescence and Raman spectra did not improve the quality of classification. CONCLUSIONS: This study demonstrates that multimodal spectroscopic approach allows increasing sensitivity and specificity of bladder cancer detection in vivo. The developed approach does not require special probes and can be used with single-core optical fibers applied for laser surgery.

Technology Selection for Inline Topography Measurement with Rover-Borne Laser Spectrometers.

This work studies enhancing the capabilities of compact laser spectroscopes integrated into space-exploration rovers by adding 3D topography measurement techniques. Laser spectroscopy enables the in situ analysis of sample composition, aiding in the understanding of the geological history of extraterrestrial bodies. To complement spectroscopic data, the inclusion of 3D imaging is proposed to provide unprecedented contextual information. The morphological information aids material characterization and hence the constraining of rock and mineral histories. Assigning height information to lateral pixels creates topographies, which offer a more complete spatial dataset than contextual 2D imaging. To aid the integration of 3D measurement into future proposals for rover-based laser spectrometers, the relevant scientific, rover, and sample constraints are outlined. The candidate 3D technologies are discussed, and estimates of performance, weight, and power consumptions guide the down-selection process in three application examples. Technology choice is discussed from different perspectives. Inline microscopic fringe-projection profilometry, incoherent digital holography, and multiwavelength digital holography are found to be promising candidates for further development.

A Novel LIBS Sensor for Sample Examinations on a Crime Scene.

In this work, we present a compact LIBS sensor developed for characterization of samples on a crime scene following requirements of law enforcement agencies involved in the project. The sensor operates both in a tabletop mode, for aside measurements of swabbed materials or taken fragments, and in handheld mode where the sensor head is pointed directly on targets at the scene. The sensor head is connected via an umbilical to an instrument box that could be battery-powered and contains also a color camera for sample visualization, illumination LEDs, and pointing system for placing the target in focus. Here we describe the sensor's architecture and functionalities, the optimization of the acquisition parameters, and the results of some LIBS measurements. On nano-plotted traces at silica wafer and in optimized conditions, for most of the elements the detection limits, in term of the absolute element masses, were found to be below 10 picograms. We also show results obtained on some representative materials, like fingerprints, swabbed soil and gunshot residue, varnishes on metal, and coated plastics. The last, solid samples were used to evaluate the depth profiling capabilities of the instrument, where the recognition of all four car paint layers was achieved.

Comparative Investigation of Ultrafast Excited-State Electron Transfer in Both Polyfluorene-Graphene Carboxylate and Polyfluorene-DCB Interfaces.

The Photophysical properties, such as fluorescence quenching, and photoexcitation dynamics of bimolecular non-covalent systems consisting of cationic poly[(9,9-di(3,3'-N,N'-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and anionic graphene carboxylate (GC) have been discovered for the first time via steady-state and time-resolved femtosecond transient absorption (TA) spectroscopy with broadband capabilities. The steady-state fluorescence of PFN is quenched with high efficiency by the GC acceptor. Fluorescence lifetime measurements reveal that the quenching mechanism of PFN by GC is static. Here, the quenching mechanisms are well proven via the TA spectra of PFN/GC systems. For PFN/GC systems, the photo electron transfer (PET) and charge recombination (CR) processes are ultrafast (within a few tens of ps) compared to static interactions, whereas for PFN/1,4-dicyanobenzene DCB systems, the PET takes place in a few hundreds of ps (217.50 ps), suggesting a diffusion-controlled PET process. In the latter case, the PFN+•-DCB-• radical ion pairs as the result of the PET from the PFN to DCB are clearly resolved, and they are long-lived. The slow CR process (in 30 ns time scales) suggests that PFN+• and DCB-• may already form separated radical ion pairs through the charge separation (CS) process, which recombine back to the initial state with a characteristic time constant of 30 ns. The advantage of the present positively charged polyfluorene used in this work is the control over the electrostatic interactions and electron transfers in non-covalent polyfluorene/quencher systems in DMSO solution.

Iminothioindoxyl Donors with Exceptionally High Cross Section for Protein Vibrational Energy Transfer.

Various protein functions are related to vibrational energy transfer (VET) as an important mechanism. The underlying transfer pathways can be experimentally followed by ultrafast Vis-pump/IR-probe spectroscopy with a donor-sensor pair of non-canonical amino acids (ncAAs) incorporated in a protein. However, so far only one donor ncAA, azulenylalanine (AzAla), exists, which suffers from a comparably low Vis extinction coefficient. Here, we introduce two novel donor ncAAs based on an iminothioindoxyl (ITI) chromophore. The dimethylamino-ITI (DMA-ITI) and julolidine-ITI (J-ITI) moieties overcome the limitation of AzAla with a 50 times higher Vis extinction coefficient. While ITI moieties are known for ultrafast photoswitching, DMA-ITI and J-ITI exclusively form a hot ground state on the sub-ps timescale instead, which is essential for their usage as vibrational energy donor. In VET measurements of donor-sensor dipeptides we investigate the performance of the new donors. We observe 20 times larger signals compared to the established AzAla donor, which opens unprecedented possibilities for the study of VET in proteins.

Understanding Spin-Triplet Excited States in Carbene-Metal-Amides.

Carbene-metal-amides (CMAs) are emerging delayed fluorescence materials for organic light-emitting diode (OLED) applications. CMAs possess fast, efficient emission owing to rapid forward and reverse intersystem crossing (ISC) rates. The resulting dynamic equilibrium between singlet and triplet spin manifolds distinguishes CMAs from most purely organic thermally activated delayed fluorescence emitters. However, direct experimental triplet characterization in CMAs is underutilized, limiting our detailed understanding of the ISC mechanism. In this work, we combine time-resolved spectroscopy with tuning of state energies through environmental polarity and metal substitution, focusing on the interplay between charge-transfer (3CT) and local exciton (3LE) triplets. Unlike previous photophysical work, we investigate evaporated host : guest films of CMAs and small-molecule hosts for increased device relevance. Transient absorption reveals an evolution in the triplet excited-state absorption (ESA) consistent with a change in orbital character between hosts with differing dielectric constants. Using quantum chemical calculations, we simulate ESAs of the lowest triplet states, highlighting the contribution of only 3CT and donor-moiety 3LE states to spectral features, with no strong evidence for a low-lying acceptor-centered 3LE. Thus, our work provides a blueprint for understanding the role of triplet excited states in CMAs which will enable further intelligent optimization of this promising class of materials.

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis.

Organic photocatalysts frequently possess dual singlet and triplet photoreactivity and a thorough photochemical characterization is essential for efficient light-driven applications. In this article, the mode of action of a polyazahelicene catalyst (Aza-H) was investigated using laser flash photolysis (LFP). The study revealed that the chromophore can function as a singlet-state photoredox catalyst in the sulfonylation/arylation of styrenes and as a triplet sensitizer in energy transfer catalysis. The singlet lifetime is sufficiently long to exploit the exceptional excited state reduction potential for the activation of 4-cyanopyridine. Photoinduced electron transfer generating the radical cation was directly observed confirming the previously proposed mechanism of a three-component reaction. Several steps of the photoredox cycle were investigated separately, providing deep insights into the complex mechanism. The triplet-excited Aza-H, which was studied with quantitative LFP, is formed with a quantum yield of 0.34. The pronounced triplet formation was exploited for the isomerization reaction of (E)-stilbene to the Z-isomer and the cyclization of cinnamyl chloride. Catalyst degradation mainly occurs through the long-lived Aza-H triplet (28 µs), but the photostability is greatly increased when the triplet efficiently reacts in a catalytic cycle such that turnover numbers exceeding 4400 are achievable with this organocatalyst.

Gas-Phase Characterization of Hypervalent Carbon Compounds Bearing 7-6-7-Ring Skeleton: Penta- versus Tetra-Coordinate Isomers.

In this study, we afford explicit characterizations of the electronic and geometrical structures of recently reported hypervalent penta-coordinate carbon compounds by using gas-phase characterization techniques: photodissociation spectroscopy (PDS) and ion mobility-mass spectrometry (IM-MS). In particular for a compound with moderately electron-donating ligands, bearing p-methylthiophenyl substituents, the coexistence of tetra- and penta-coordinate isomers is confirmed, consistent with solution characterizations. It is in sharp contrast to the exclusive tetra-coordinate form (with normal valence of the central carbon atom) in the single crystal. This suggests that a non-polar environment makes the penta-coordinate structure thermodynamically most stable. This delicate difference between the tetra- and penta-coordinate structures, which depends on the environment, is a close reflection of the lower activation barrier of the SN 2 reaction found in neutral solvent or gas-phase reactions.

Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability.

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O- …H+ …- OCO) features a single local minima, with the proton localized on the O- group (OH…- OCO). However, the structure with the proton localized on the - OCO group (O- …HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…- OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…- OCO isomer decarboxylate without barrier, while the radicals produced from the O- …HOCO isomer are stable.

Femtosecond Dynamics of Excited States of Chlorophyll Tetramer in Water-Soluble Chlorophyll-Binding Protein BoWSCP.

The paper reports on the absorption dynamics of chlorophyll a in a symmetric tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP. It was measured by a broadband femtosecond laser pump-probe spectroscopy within the range from 400 to 750 nm and with a time resolution of 20 fs-200 ps. When BoWSCP was excited in the region of the Soret band at a wavelength of 430 nm, nonradiative intramolecular conversion S3→S1 was observed with a characteristic time of 83 ± 9 fs. When the complex was excited in the region of the Qy band at 670 nm, relaxation transition between two excitonic states of the chlorophyll dimer was observed in the range of 105 ± 10 fs. Absorption spectra of the excited singlet states S1 and S3 of chlorophyll a were obtained. The delocalization of the excited state between exciton-coupled Chl molecules in BoWSCP tetramer changed in time and depended on the excitation energy. When BoWSCP is excited in the Soret band region, an ultrafast photochemical reaction is observed. This could result from the reduction of tryptophan in the vicinity of chlorophyll.

Photon-level broadband spectroscopy and interferometry with two frequency combs.

We probe complex optical spectra at high resolution over a broad span in almost complete darkness. Using a single photon-counting detector at light power levels that are a billion times weaker than commonly employed, we observe interferences in the counting statistics with two separate mode-locked femtosecond lasers of slightly different repetition frequencies, each emitting a comb of evenly spaced spectral lines over a wide spectral span. Unique advantages of the emerging technique of dual-comb spectroscopy, such as multiplex data acquisition with many comb lines, potential very high resolution, and calibration of the frequency scale with an atomic clock, can thus be maintained for scenarios where only few detectable photons can be expected. Prospects include spectroscopy of weak scattered light over long distances, fluorescence spectroscopy of single trapped atoms or molecules, or studies in the extreme-ultraviolet or even soft-X-ray region with comb sources of low photon yield. Our approach defies intuitive interpretations in a picture of photons that exist before detection.

Localization and chemical speciation of europium(III) in Brassica napus plants.

For the reliable safety assessment of repositories of highly radioactive waste, further development of the modelling of radionuclide migration and transfer in the environment is necessary, which requires a deeper process understanding at the molecular level. Eu(III) is a non-radioactive analogue for trivalent actinides, which contribute heavily to radiotoxicity in a repository. For in-depth study of the interaction of plants with trivalent f elements, we investigated the uptake, speciation, and localization of Eu(III) in Brassica napus plants at two concentrations, 30 and 200 µM, as a function of the incubation time up to 72 h. Eu(III) was used as luminescence probe for combined microscopy and chemical speciation analyses of it in Brassica napus plants. The localization of bioassociated Eu(III) in plant parts was explored by spatially resolved chemical microscopy. Three Eu(III) species were identified in the root tissue. Moreover, different luminescence spectroscopic techniques were applied for an improved Eu(III) species determination in solution. In addition, transmission electron microscopy combined with energy-dispersive X-ray spectroscopy was used to localize Eu(III) in the plant tissue, showing Eu-containing aggregates. By using this multi-method setup, a profound knowledge on the behavior of Eu(III) within plants and changes in its speciation could be obtained, showing that different Eu(III) species occur simultaneously within the root tissue and in solution.

Reactive oxygen species creation by laser-irradiated indocyanine green as photodynamic therapy modality: an in vitro study.

Applications of lasers in phototherapy have been the trend for the last few decades. The photodynamic therapy process normally depends on photosensitizers and laser beams. Through this study, indocyanine green has been used as a photosensitizer, which is normally activated using laser lines between 750 and 805 nm. The activity of the indocyanine green to do fluorescence by other pulsed laser sources has been tested by fluorescence technique, and it has been proven that the laser lines at 810, 940, and 980nm are able to excite the indocyanine green with different extents. The indocyanine green activation has been tested by several laser lines (810, 940, and 980 nm) commonly used as surgical lasers. The generated oxygen has been measured after irradiating the indocyanine green with the different laser lines. A comparison has been made between laser irradiation as a pinpoint and a broad beam. It is found that the wide beam is more effective in activating oxygen production. In the end, it is concluded that lines 810 and 940nm were effective in activating the used dye, while the 980nm activity did not show enough efficiency.

Research on Small-Scale Detection Instrument for Drinking Water Combined Laser Spectroscopy and Conductivity Technology.

In order to realize rapid and accurate evaluation of drinking water quality, a small-scale water quality detection instrument is designed in this paper that can detect two representative water quality parameters: the permanganate index and total dissolved solids (TDS). The permanganate index measured by the laser spectroscopy method can achieve the approximate value of the organic matter in water, and the TDS measured by the conductivity method can obtain the approximate value of the inorganic matter in water. In addition, to facilitate the popularization of civilian applications, the evaluation method of water quality based on the percent-scores proposed by us is presented in this paper. The water quality results can be displayed on the instrument screen. In the experiment, we measured the water quality parameters of the tap water as well as those after the primary and secondary filtration in Weihai City, Shandong Province, China. The testing results show that the instrument can quickly detect dissolved inorganic and organic matter, and intuitively display the water quality evaluation score on the screen. The instrument designed in this paper has the advantages of high sensitivity, high integration, and small volume, which lays the foundation for the popularity of the detection instrument.

Development of a Rapid Measurement Method for Analysis of the NOx Conversion Process Based on Quantum Cascade Laser Absorption Spectroscopy.

In this study, a method for double-beam quantum cascade laser absorption spectroscopy (DB-QCLAS) was developed. Two mid-infrared distributed feedback quantum cascade laser beams were coupled in an optical cavity for the monitoring of NO and NO2 (NO at 5.26 µm; NO2 at 6.13 µm). Appropriate lines in the absorption spectra were selected, and the influence of common gases in the atmosphere, such as H2O and CO2, was avoided. By analyzing the spectral lines under different pressure conditions, the appropriate measurement pressure of 111 mbar was selected. Under this pressure, the interference between adjacent spectral lines could be effectively distinguished. The experimental results show that the standard deviations for NO and NO2 were 1.57 ppm and 2.67 ppm, respectively. Moreover, in order to improve the feasibility of this technology for detecting chemical reactions between NO and O2, the standard gases of NO and O2 were used to fill the cavity. A chemical reaction instantaneously began, and the concentrations of the two gases were immediately changed. Through this experiment, we hope to develop new ideas for the accurate and rapid analysis of the process of NOx conversion and to lay a foundation for a deeper understanding of the chemical changes in atmospheric environments.

A Portable Laser Spectroscopic System for Measuring Nitrous Oxide Emissions on Fertilized Cropland.

Nitrous oxide (laughing gas, N2O) is a relevant greenhouse gas. Agriculture contributes significantly to its emissions. As nitrogen fertilization has been identified as one of the main sources of N2O, controlled application and reduction of the amount of fertilizer adapted to crop demand is essential to reduce N2O emissions. This requires detailed studies of the local distribution of the N2O emission fluxes on different croplands. Consequently, frequent spatially resolved field measurements of N2O concentrations are needed. A precision in the ppb range close to the ambient N2O level of 333 ppb is necessary. Tunable laser absorption spectroscopy using quantum-cascade lasers (QCL) as a light source is an established technique for the measurement of N2O traces. We present the development and validation of a compact portable setup for on-site measurement of N2O emissions from the soil. The setup differs from previous solutions by using an interband cascade laser (ICL), which has significantly lower power consumption compared to a QCL. The portable measurement setup allows N2O emission fluxes to be determined with a precision of 3.5% with a measuring duration of 10 min. The developed system enables the detection of increased N2O emissions because of the fertilization of fields. High N2O emission fluxes are indicators of the overfertilization of the field. Directly after fertilization, N2O fluxes between 2.9 and 5.3 µL m-2 min-1 depending on the gas acquisition site are measured during the field tests. Over time, the fluxes decrease. The obtained results compare well with data from more precise but also more complex and maintenance-intensive instruments for atmospheric research. With this system, the soil moisture as well as the air humidity and air temperature are recorded. Strong influences on N2O fluxes by soil moisture were observed. The presented measurement system is a contribution to the establishment of mobile N2O screening systems that are robust in the field and suitable for comprehensive and routine detection of N2O emissions from soil.