Insights into Spectral Distortion and Nonlinearity in UV-Vis and Fluorescence Spectroscopy of Molecular Fluorophore Solutions: Effects of Cascading Optical Processes (Part IV).

Reproducibility and linearity are crucial benchmarks for any measurement technology. However, UV-vis and fluorescence spectral distortion and nonlinearity are prevalent, even in seemingly simple fluorescent solutions that comprise only one dissolved molecular fluorophore, without exogenous absorbing or scattering species. In this report, we introduce an analytical model for the quantification of fluorescence interference on UV-vis measurements and a conceptual model for mechanistically understanding the impacts of higher-order cascading optical processes on fluorescence measurements.

Multiplexed Surface Protein Detection and Cancer Classification Using Gap-Enhanced Magnetic-Plasmonic Core-Shell Raman Nanotags and Machine Learning Algorithm.

Cancer is the second leading cause of death attributed to disease worldwide. Current standard detection methods often rely on a single cancer marker, which can lead to inaccurate results, including false negatives, and an inability to detect multiple cancers simultaneously. Here, we developed a multiplex method that can effectively detect and classify surface proteins associated with three distinct types of breast cancer by utilizing gap-enhanced Raman scattering nanotags and machine learning algorithm.

Advancing Evidence-Based Data Interpretation in UV-Vis and Fluorescence Analysis for Nanomaterials: An Analytical Chemistry Perspective.

UV-vis spectrophotometry and spectrofluorometry are indispensable tools in education, research, and industrial process controls with widespread applications in nanoscience encompassing diverse nanomaterials and fields. Nevertheless, the prevailing spectroscopic interpretations and analyses often exhibit ambiguity and errors, particularly evident in the nanoscience literature. This analytical chemistry Perspective focuses on fostering evidence-based data interpretation in experimental studies of materials' UV-vis absorption, scattering, and fluorescence properties.

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

Cascading optical processes involve sequential photonmatter 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.

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.

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.

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.

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.

Back to the Drawing Board: A Unifying First-Principle Model for Correlating Sample UV-Vis Absorption and Fluorescence Emission.

The popular textbook and literature model (λ,λ) = or its variants for correlating the sample absorption and fluorescence often fails even for the simplest samples where the fluorophore is the only light absorber. Reported is a first-principle model (λ,λ) = for correlating the sample fluorescence measured with a conventional spectrofluorometer and its UV-vis absorbance quantified with a conventional UV-vis spectrophotometer. This model can be simplified or expanded for a variety of fluorescence analyses.

Colloidal Polydopamine Beads: A Photothermally Active Support for Noble Metal Nanocatalysts.

Polydopamine (PDA) is a unique bioinspired synthetic polymer that integrates broadband light absorption, efficient photothermal transduction, and versatile surface-adhesion functions in a single material entity. Here, we utilize colloidal PDA beads in the submicron particle size regime as an easily processable and photothermally active support for sub-10 nm Pd nanocatalysts to construct a multifunctional material system that allows us to kinetically boost thermal catalytic reactions through visible and near-infrared light illuminations. Choosing the Pd-catalyzed nitrophenol reduction by ammonium formate as a model transfer hydrogenation reaction exhibiting temperature-dependent reaction rates, we demonstrate that interfacial molecule-transforming processes on metal nanocatalyst surfaces can be kinetically modulated by harnessing the thermal energy produced through photothermal transduction in the PDA supports.

Kinetic spectroscopic quantification using two-step chromogenic and fluorogenic reactions: From theoretical modeling to experimental quantification of biomarkers in practical samples.

Kinetic chromogenic (CG) and fluorogenic (FG) quantification deduces analyte concentration based on the reaction rate between the CG/FG probe and its targeted molecule. Little progress has been made in the past half century in either the theory or the applications of the kinetic spectroscopic quantification methods. Current kinetic CG/FG quantification is limited only to a subset of CG/FG reactions that can be approximated as the single-step process, and more problematically, to research samples with no matrix interferences.

Quantification of the Photon Absorption, Scattering, and On-Resonance Emission Properties of CdSe/CdS Core/Shell Quantum Dots: Effect of Shell Geometry and Volumes.

Reliable quantification of the optical properties of fluorescent quantum dots (QDs) is critical for their photochemical, -physical, and -biological applications. Presented herein is the experimental quantification of photon scattering, absorption, and on-resonance-fluorescence (ORF) activities of CdSe/CdS core/shell fluorescent QDs as a function of the shell sizes and geometries. Four spherical QDs (SQDs) with different diameters and four rod-like QDs (RQDs) with different aspect ratios (ARs) have been analyzed using UV-vis, fluorescence, and the recent polarized resonance synchronous spectroscopic (PRS2) methods.

Linear Extrapolation of the Analyte-Specific Light Scattering and Fluorescence Depolarization in Turbid Samples.

Anisotropy and depolarization are two interconvertible parameters in fluorescence and light scattering spectroscopy that describe the polarization distribution of emitted and scattered photons generated with linearly polarized excitation light. Whereas anisotropy is more frequently used in fluorescence literature for studying association/dissociation of fluorophore-bearing reagents, depolarization is more popular in the light-scattering literature for investigating the effect of scatterers' geometries and chemical compositions. Presented herein is a combined computational and experimental study of the scattering and fluorescence depolarization enhancement induced by light scattering in turbid samples.

A Divide-and-Conquer Strategy for Quantification of Light Absorption, Scattering, and Emission Properties of Fluorescent Nanomaterials in Solutions.

Optical properties of fluorescent materials including their UV-vis absorption, scattering, and on-resonance fluorescence activities are strongly wavelength-dependent. Reported herein is a divide-and-conquer strategy for experimental quantification of fundamental optical constants of fluorescent nanomaterials including their UV-vis absorption, scattering, and on-resonance-fluorescence (ORF) cross-section spectra and ORF fluorescence and light scattering depolarization spectra. The fluorophore UV-vis extinction spectrum is first divided into a blue and a red wavelength region.

Efficient and scalable high-quality graphene nanodot fabrication through confined lattice plane electrochemical exfoliation.

Reported is a confined lattice plane electrochemical exfoliation method that exploits the electrochemical reaction of face (basal) or side (edge) planes of highly oriented pyrolytic graphite (HOPG) while other planes are blocked using wax, based on the anisotropy of HOPG for efficient and effective fabrication of graphene nanodots with uniform size distribution.

Surface Plasmon Resonance, Formation Mechanism, and Surface Enhanced Raman Spectroscopy of Ag-Stained Gold Nanoparticles.

A series of recent works have demonstrated the spontaneous Ag adsorption onto gold surfaces. However, a mechanistic understanding of the Ag interactions with gold has been controversial. Reported herein is a systematic study of the Ag binding to AuNPs using several and measurement techniques.

Optical Properties and Kinetics: New Insights to the Porphyrin Assembly and Disassembly by Polarized Resonance Synchronous Spectroscopy.

With their unique photochemical properties, porphyrins have remained for decades the most interested chemicals as photonic materials for applications ranging from chemistry, biology, medicine, to photovoltaic. Porphyrins can self-assemble into higher order structures. However, information has been scant on the kinetics and structural evolution during porphyrin assembly and disassembly.

Scattering and absorption differ drastically in their inner filter effects on fluorescence, resonance synchronous, and polarized resonance synchronous spectroscopic measurements.

The sample inner filter effect (IFE) induces spectral distortion and affects the linearity between intensity and analyte concentration in fluorescence, Raman, surface enhanced Raman, and Rayleigh light scattering measurements. Existing spectrofluorometric-based measurements treat light scattering and absorption identically in their sample IFEs. Reported herein is the finding that photon scattering and absorption differ drastically in inducing the sample IFE in Stokes-shifted fluorescence (SSF) spectrum, resonance synchronous spectrum (RS2), and the polarized resonance synchronous spectrum (PRS2) measurements.

Synthesis of C-Unsubstituted 1,2-Diazetidines and Their Ring-Opening Reactions via Selective N-N Bond Cleavage.

C-Unsubstituted 1,2-diazetidines, a rarely studied type of four-membered heterocyclic compounds, were synthesized through an operationally simple intermolecular vicinal disubstitution reaction. 1,2-Diazetidine derivatives bearing various N-arylsulfonyl groups were readily accessed and studied by experimental and computed Raman spectra. The ring-opening reaction of the diazetidine was explored and resulted in the identification of a selective N-N bond cleavage with thiols as nucleophiles, which stereoselectively produced a new class of N-sulfenylimine derivatives with C-aminomethyl groups.

Quantification of Material Fluorescence and Light Scattering Cross Sections Using Ratiometric Bandwidth-Varied Polarized Resonance Synchronous Spectroscopy.

Presented herein is the ratiometric bandwidth-varied polarized resonance synchronous spectroscopy (BVPRS2) method for quantification of material optical activity spectra. These include the sample light absorption and scattering cross-section spectrum, the scattering depolarization spectrum, and the fluorescence emission cross-section and depolarization spectrum in the wavelength region where the sample both absorbs and emits. This ratiometric BVPRS2 spectroscopic method is a self-contained technique capable of quantitatively decoupling material fluorescence and light scattering signal contribution to its ratiometric BVPRS2 spectra through the linear curve-fitting of the ratiometric BVPRS2 signal as a function of the wavelength bandwidth used in the PRS2 measurements.

Quantification of Gold Nanoparticle Ultraviolet-Visible Extinction, Absorption, and Scattering Cross-Section Spectra and Scattering Depolarization Spectra: The Effects of Nanoparticle Geometry, Solvent Composition, Ligand Functionalization, and Nanoparticle Aggregation.

Using the recent polarized resonance synchronous spectroscopic (PRS2) technique, we reported the quantification of photon extinction, absorption, scattering cross-section spectra, and scattering depolarization spectra for AuNPs of different sizes and shapes. The effects of the solvent composition, ligand functionalization, and nanoparticle aggregation on the AuNP photon absorption and scattering have also been experimentally quantified. The light scattering depolarization is close to 0 for gold nanospheres (AuNSs) crossing the entire UV-vis region but is strongly wavelength-dependent for gold nanorods (AuNRs).

Determining the Liquid Light Scattering Cross Section and Depolarization Spectra Using Polarized Resonance Synchronous Spectroscopy.

Rayleigh scattering is a universal material property because all materials have nonzero polarizability. Reliable quantification of the material light scattering cross section in the liquid phase and its depolarization spectra is, however, challenging due to a host of sample and instrument issues. Using the recently developed polarized resonance synchronous spectroscopic method, we reported the light scattering cross section and depolarization spectra measured for a total of 29 liquids including water, methanol, ethanol, 1-propanol, 1-butanol, dimethylformamide, carbon disulfide, dimethyl sulfoxide, hexane and two hexane isomers (3-methylpentane and 2,3-dimethylbutane), tetrahydrofuran, cyclohexane, acetonitrile, pyridine, chloromethanes including di-, tri, tetrachloromethane, acetone, benzene and eight benzene derivatives (toluene, fluorobenzene, 1,2-, 1,3-, and 1,4-difluorobenzene, chlorobenzene, 1,2- and 1,3-dichlorobenzene, and nitrobenzene).

Facile displacement of citrate residues from gold nanoparticle surfaces.

The stability of citrate-residues on gold nanoparticles (AuNPs) against ligand displacement has been controversial. Using AuNPs synthesized with deuterated citrate in combination with in-situ surface-enhanced Raman spectroscopic (SERS) analysis, we report that both citrate-residues and solution impurities can be simultaneously adsorbed onto citrate-reduced AuNPs in solution. The citrate-residues can be readily displaced from AuNPs by organosulfur such as organothiols (RS-H), organodisuflide (R-S-S-R), and non-specific ligands including halides and adenine.

Quantification of the Depolarization and Anisotropy of Fluorophore Stokes-Shifted Fluorescence, On-Resonance Fluorescence, and Rayleigh Scattering.

Fluorophores are important but optically complicated photonic materials as they are simultaneous photon absorbers, emitters, and scatterers. Existing studies on fluorophore optical properties have been focused almost exclusively on its photon absorption and Stokes-shifted fluorescence (SSF) with scant information on the fluorophore photon scattering and on-resonance fluorescence (ORF). Presented herein is a unified theoretical framework and experimental approach for quantification of the fluorophore SSF, ORF, and scattering depolarization and anisotropy using a combination of fluorophore UV-vis, fluorescence emission, and resonance synchronous spectroscopic spectral measurements.