Effects of Cascading Optical Processes: Part III. Impacts on Spectroscopic Measurements of Fluorescent Samples.

Cascading optical processes involve sequential photon-matter interactions triggered by the same individual excitation photons. Parts I and II of this series explored cascading optical processes in scattering-only solutions (Part I) and solutions with light scatterers and absorbers but no emitters (Part II). The current work (Part III) focuses on the effects of cascading optical processes on spectroscopic measurements of fluorescent samples. Four types of samples were examined: (1) eosin Y (EOY), an absorber and emitter; (2) EOY mixed with plain polystyrene nanoparticles (PSNPs), which are pure scatterers; (3) EOY mixed with dyed PSNPs, which scatter and absorb light but do not emit; and (4) fluorescent PSNPs that are simultaneous light absorbers, scatterers, and emitters. Interference from both forward scattered and emitted photons can cause nonlinearity and spectral distortion in UV-vis extinction measurements. Sample absorption by nonfluorogenic chromophores reduces fluorescence intensity, while the effect of scattering on fluorophore fluorescence is complicated by several competing factors. A revised first-principles model is developed for correlating the experimental fluorescence intensity with the sample absorbance in solutions containing both scatterers and absorbers. The optical properties of fluorescent PSNPs of three different sizes were systematically investigated by using integrating-sphere-assisted resonance synchronous spectroscopy, linearly polarized resonance synchronous spectroscopy, UV-vis, and fluorescence spectroscopy. The insights and methodology provided in this work should help improve the reliability of spectroscopic analyses of fluorescent samples, where the interplay among light absorption, scattering, and emission can be complex.

Effects of Cascading Optical Processes: Part I: Impacts on Quantification of Sample Scattering Extinction, Intensity, and Depolarization.

Light scattering is a universal matter property that is especially prominent in nanoscale or larger materials. However, the effects of scattering-based cascading optical processes on experimental quantification of sample absorption, scattering, and emission intensities, as well as scattering and emission depolarization, have not been adequately addressed. Using a series of polystyrene nanoparticles (PSNPs) of different sizes as model analytes, we present a computational and experimental study on the effects of cascading light scattering on experimental quantification of NP scattering activities (scattering cross-section or molar coefficient), intensity, and depolarization. Part II and Part III of this series of companion articles explore the effects of cascading optical processes on sample absorption and fluorescence measurements, respectively. A general theoretical model is developed on how forward scattered light complicates the general applicability of Beer's law to the experimental UV-vis spectrum of scattering samples. The correlation between the scattering intensity and PSNP concentration is highly complicated with no robust linearity even when the scatterers' concentration is very low. Such complexity arises from the combination of concentration-dependence of light scattering depolarization and the scattering inner filter effects (IFEs). Scattering depolarization increases with the PSNP scattering extinction (thereby, its concentration) but can never reach unity (isotropic) due to the polarization dependence of the scattering IFE. The insights from this study are important for understanding the strengths and limitations of various scattering-based techniques for material characterization including nanoparticle quantification. They are also foundational for quantitative mechanistic understanding on the effects of light scattering on sample absorption and fluorescence measurements.

Effects of Cascading Optical Processes: Part II: Impacts on Experimental Quantification of Sample Absorption and Scattering Properties.

In Part I of the three companion articles, we reported the effects of light scattering on experimental quantification of scattering extinction, intensity, and depolarization in solutions that contain only scatterers with no significant absorption and photoluminescence activities. The present work (Part II) studies the effects of light scattering and absorption on a series of optical spectroscopic measurements done on samples that contain both absorbers and scatterers, but not emitters. The experimental UV-vis spectrum is the sum of the sample absorption and scattering extinction spectra. However, the upper limit of the experimental Beer's-law-abiding extinction can be limited prematurely by the interference of forward scattered light. Light absorption reduces not only the sample scattering intensity but also the scattering depolarization. The impact of scattering on sample light absorption is complicated, depending on whether the absorption of scattered light is taken into consideration. Scattering reduces light absorption along the optical path length from the excitation source to the UV-vis detector. However, the absorption of the scattered light can be adequate to compensate the reduced light absorption along such optical path, making the impacts of light scattering on the sample total light absorption negligibly small (<10%). The latter finding constitutes a critical validation of the integrating-sphere-assisted resonance synchronous spectroscopic method for experimental quantification of absorption and scattering contribution to the sample UV-vis extinction spectra. The techniques and general guidelines provided in this work should help improve the reliability of optical spectroscopic characterization of nanoscale or larger materials, many of which are simultaneous absorbers and scatterers. The insights from this work are foundational for Part III of this series of work, which is on the cascading optical processes on spectroscopic measurements of fluorescent samples.

Integrating-Sphere-Assisted Resonance Synchronous Spectroscopy for the Quantification of Material Double-Beam UV-Vis Absorption and Scattering Extinction.

Integrating spheres (IS) have been used extensively for the characterization of light absorption in turbid samples. However, converting the IS-based sample absorption coefficient to the UV-vis absorbance quantified with a double-beam UV-vis spectrophotometer is challenging. Herein, we report an integrating-sphere-assisted resonance synchronous (ISARS) spectroscopy method performed with conventional spectrofluorometers equipped with an integrating-sphere accessory. Mathematical models and experimental procedures for quantifying the sample, solvent, and instrument-baseline ISARS intensity spectra were provided. A three-parameter analytical model has been developed for correlating the ISARS-based UV-vis absorbance and the absorbance measured with double-beam instruments. This ISARS method enables the quantitative separation of light absorption and scattering contribution to the sample UV-vis extinction spectrum measured with double-beam UV-vis spectrophotometers. Example applications of this ISARS technique are demonstrated with a series of representative samples differing significantly in their optical complexities, from approximately pure absorbers, pure scatterers, to simultaneous light absorbers, scatterers, and emitters under resonance excitation and detection conditions.

Total Luminescence Spectroscopy for Quantification of Temperature Effects on Photophysical Properties of Photoluminescent Materials.

Quantification of the temperature effects on the optical properties of photoluminescent (PL) materials is important for a fundamental understanding of both materials optical processes and rational PL materials design and applications. However, existing techniques for studying the temperature effects are limited in their information content. Reported herein is a temperature-dependent total photoluminescence (TPL) spectroscopy technique for probing the temperature dependence of materials optical properties. When used in combination with UV-vis measurements, this TPL method enables experimental quantification of temperature effects on fluorophore fluorescence intensity and quantum yield at any combination of excitation and detection wavelengths, including the fluorophore Stokes-shifted and anti-Stokes-shifted fluorescence. All model polyaromatic hydrocarbon (PAH) and xanthene fluorophores exhibited a strong excitation- and emission-wavelength dependence in their temperature effects. However, the heavy-atom effects used for explaining the strong temperature dependence of brominated anthracenes are not operative with xanthene fluorophores that have heavy atom substitutions. The insights from TPL measurements are important not only for enhancing the fundamental understandings of the materials photophysical properties but also for rational measurement design for applications where the temperature sensitivity of the fluorophore fluorescence is critical. An example application is demonstrated for developing a sensitive and robust ratiometric fluorescence thermometric method for in situ real-time monitoring of sample temperatures inside a fluorescence cuvette placed in a temperature-controlled sample holder.

Effect of acid modified tea-waste biochar on crop productivity of red onion (Allium cepa L.).

Biochar has widely been utilized as an agricultural soil amendment owing to its enhanced surface properties and cost-effectiveness. In the present work, the influence of tea waste biochar (TWBC) upon acid modification on Allium cepa L. (red onion) growth has been studied. Its effect as a soil amendment has also been studied by assessing the nutrient retention, microbial population growth and immobilization of potentially toxic metal ions. A greenhouse experiment was carried out by applying different biochar (BC) ratios (2% and 5% w/w) to soil as the growth media for onion plants. A 2.4 times (2.4 × ) reduction of phosphate from leaching was observed upon BC application at a ratio of 2% than that of 5%. Moreover, red onion plants that grew in the BC-fertilizer amended soil at a 2% ratio showed higher growth compared to that of 5%. A ∼1.3 × and ∼1.2 × increment of total dry weight was observed upon amendment of soil fertilizer system with nitric and sulfuric acid-modified TWBC, respectively. An analysis of the potentially toxic metal ion uptake by the respective plant parts showed that lead uptake by the roots of red onion was ∼8.3 × less in BC amended soil compared to that in contaminated soil. Thus, acid-modified TWBC can be considered a potential soil amendment for an enhanced red onion growth. Employing TWBC as a soil amendment in tropical countries, where tea-waste is in abundance, will boost sustainable agriculture.

Microwave and open vessel digestion methods for biochar.

Digestion of biomass derived carbonaceous materials such as biochar (BC) can be challenging due to their high chemical recalcitrance and vast variations in composition. Reports on the development of specific sample digestion methods for such materials remain inadequate and thus require considerable attention. Nine different carbonaceous materials; slow-pyrolyzed tea-waste and king coconut BC produced at 300 °C, 500 °C and 700 °C, sludge waste BC produced at 700 °C, wet fast-pyrolyzed Douglas-Fir BC and steam activated coconut shell BC have been tested to evaluate a relatively fast and convenient open-vessel digestion method using seven digestion reagents including nitric acid (NA), fuming nitric acid (FNA), sulfuric acid (SA), NA/SA, FNA/SA, NA/H2O2 and SA/H2O2 mixtures. From the tested digestion reagents, SA/H2O2 mixture dissolved low temperature produced BC (LTBC) within 2 h with occasional shaking and no external heating. Except peroxide mixtures, the other reagents were used to evaluate microwave digestion (MWD) efficiency. Nitric acid mixture was capable of only completely digesting LTBC in the MWD procedure whereas FNA, NA/SA and FNA/SA mixtures resulted in the successful dissolution of all tested carbonaceous materials. Amongst them, FNA provided the least matrix effect in the quantification of the four metals tested using flame atomic absorption spectrophotometry. Tested recoveries for FNA were satisfactory as well. It was concluded that FNA is a preferable reagent for microwave digestion of BC.