Enhanced Raman Scattering by Molecular Nanoaggregates

The formation of a molecular aggregate in a confined, nanodimensioned region of space leads to what might be termed a ‘molecular nanoaggregate’. The present review deals with a theoretical formulation termed ‘aggregation-enhanced Raman scattering’ (AERS), and its use in discussion of relative Raman band intensities and selection rules for nanoaggregates. AERs represents a concept for discussion of nanoaggregates that is different from those provided by resonance Raman scattering, surface-enhanced Raman scattering and Mie scattering, all of which ignore the impact of aggregation of molecules on Raman scattering. Beyond the theoretical formulation behind the AERS phenomenon, also outlined in this review are representative samples of the publications of other authors and researchers using AERS to provide explanations for experimental findings. In addition to clarifying issues regarding the use of nanocomposites involving aggregated molecules, it is found that increasing use of AERS concepts is being made to rationalize Raman spectral observations in a range of other disciplines that fall in both the physical sciences and the medical fields

The Non-Native Royal Damsel (Neopomacentrus cyanomos) in the Southern Gulf of Mexico: An Invasion Risk?

A diminutive, non-native damselfish (Neopomacentrus cyanomos) was recently discovered inhabiting coral reefs near Veracruz, Mexico—far removed from where it is native in the Red Sea and the Indo-Pacific. The quantities found in the Gulf of Mexico (GOM) suggest that the fish has already established a self-sustaining population in this new ecosystem. There is understandable concern, therefore, that this new arrival may become invasive and spread, yet the invasion risk imposed by this fish has not been assessed. In this study, a computer model was employed to deliver a forecast of the potential range of incursion of N. cyanomos in the GOM spanning 5 years. The model incorporated oceanic water flow in the region, tolerances of this damselfish to the ocean environment, and their reproductive strategy in order to supply a temporal and spatial forecast of their spread. From this study, targeted early detection and removal of the fish can be directed if the fish is deemed a threat to native fauna. On the basis of this work, it is foreseeable that the reefs presently harboring N. cyanomos will likely see increased abundance of this damsel. Immediate attempts to eliminate the fish, therefore, should be focused in nearshore shallow waters spanning Veracruz to Frontera, Mexico. Further, water flows in the southern GOM are not widely conducive to long-distance transport of marine organisms with pelagic larvae, reducing the risk of this damsel permeating the greater GOM over 5 years. Aside from N. cyanomos, this study implicitly adds to mounting evidence supporting a biogeographic disconnect between the Veracruz reef complex and the greater GOM and the Caribbean

Infrared and Raman Spectroscopic Characterization of Porphyrin and its Derivatives

Density functional theory (DFT) was employed to investigate protonation, deuteration, and substitution effects on the vibrational spectra of porphyrin molecules. The results of the calculations were compared with experimental data. The calculations show that meso‐substitutions produced a substantial shift in frequencies when the meso‐carbons within the parent porphine are involved in the vibrational motion of molecules, while protonation of the N atoms leads to a significant blue shift when the H atoms covalent bonded to the N atoms that are substantially involved in the vibrational motion. Deuteration of N atoms at the porphyrin core is found to result not only in a red shift in the frequencies of the corresponding peaks below 1600 cm-1, but also to generate new Raman bands of frequencies in the range of 2565–2595 cm-1, resulting from N‐D bond stretching. Also, the deuteration of O atoms within the sulfonato groups (‐SO3-) results in a new peak at near 2642 cm-1 due to O‐D bond stretching. Calculated IR spectra of the compounds studied here showed similar differences. Finally, we discuss solvent effects on the IR spectrum of TSPP

Geometric and Electronic Properties of Porphyrin and its Derivatives

In this chapter, we discuss protonation and substitution effects on the absorption spectra of porphyrin molecules based on density functional theory (DFT) and time-dependent DFT calculations. The results of the calculations are compared with experimental data. The calculations show that protonation of core nitrogen atoms of porphyrin and meso-substituted porphyrins produces a substantial shift in Soret and Q-absorption bands, relative to their positions in corresponding nonprotonated and nonsubstituted chromophores. A relaxed potential energy surface (RPES) scan has been utilized to calculate ground and excited state potential energy surface (PES) curves as functions of the rotation of one of the meso-substituted sulfonatophenyl groups about dihedral angles θ (corresponding to Cα─Cm─Cϕ─C) ranging from 40 to 130°, using 10° increments. The ground state RPES curve indicates that when the molecule transitions from the lowest ground state to a local state, the calculated highest potential energy barrier at the dihedral angle of 90° is only 177 cm−1. This finding suggests that the meso-sulfonatophenyl substitution groups are able to rotate around Cm─Cϕ bond at room temperature because the thermal energy (kBT) at 298 K is 207.2 cm−1. Furthermore, the calculations show that the geometric structure of the porphyrin is strongly dependent on protonation and the nature of the meso-substituted functional groups

Superradiant lasing from J-aggregated molecules adsorbed onto colloidal silver

Cataloged from PDF version of article.The picosecond time-resolved emission spectrum of the cyanine dye 1,18-diethyl-3,38- bis-~3-sulfopropyl!-5,58,6,68-tetrachlorobenzimidazolocarbocyanine ~also known as BIC! adsorbed onto colloidal silver was examined as a function of laser pulse energy at room temperature. BIC is found to aggregate on colloidal silver, and the number of coherently responding molecules involved in the one-exciton state ~i.e., the coherence length! was estimated to involve 8–9 molecules. Lasing at a remarkably low incident pulse energy threshold was found for this system and explained in terms of a mechanism involving superradiant states created in coherently coupled adsorbed molecules that emit photons which stimulate emission from other spatially distributed superradiant states. © 1998 American Institute of Physics

Reimagining INFO 101: A Tale of Revisions and New Beginnings

Realized that video you love showing in class is nearly as old as your students now? We’ve been there. Lander University librarians spent this summer collaborating to redesign INFO 101, our 1-credit information literacy course. The goals were to keep the course fresh, useful, effective, and synchronized across instructors and delivery methods. This initiative included reformatting into an eight-week schedule offered twice per semester, moving to a new textbook, establishing a shared Blackboard sandbox in the university’s recommended online course template, and ditching the final project. Results will be discussed from the Fall 2021 sections taught face-to-face and online