The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made approximately 50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity.
Second order nonlinear optical imaging of chiral crystals (SONICC) is a promising new method for the sensitive and selective detection of protein crystals. Relevant general principles of second harmonic generation, which underpins SONICC, are reviewed. Instrumentation and methods for SONICC measurements are described and critically assessed in terms of performance trade-offs. Potential origins of false-positives and false-negatives are also discussed.
Second harmonic generation (SHG) has developed into a powerful tool for characterizing oriented thin films, surfaces, and interfaces. Furthermore, the nonlinear optical nature of wave-mixing processes typically results in the generation of a coherent signal beam with a well-defined polarization state. This coherence offers unique opportunities for the extraction of detailed molecular and surface properties from polarization analysis. In previous studies, nonlinear optical ellipsometry (NOE) has been developed as a means to retain sign and phase information between the different nonzero χ
(2) tensor elements present in a given sample. However, those previous methods and related approaches for polarization analysis have all relied on the physical movement of optical elements to perform the analysis. The time required to physically move the appropriate optical elements ultimately dictates the fastest analysis time possible in a given technique. Such long acquisition times have limited NOE analyses to systems exhibiting excellent photostability and have precluded the feasibility of NOE imaging. Development of nonlinear optical Stokes ellipsometry (NOSE) was shown to address many of these problems. By increasing the repetition rate of the laser system and replacing previously slow rotating polarization optics with a rapid photoelastic modulator, the acquisition time with full polarization analysis was reduced from several hours to less than a second. This technique was validated against established NOE techniques using z-cut quartz as a reference sample and then demonstrated on a dye thin film. Additionally, an orientation analysis of the thin film was performed. These studies resulted in an order of magnitude improvement in precision relative to previous NOE techniques, while simultaneously accompanied by a reduction in acquisition time of more than four orders of magnitude.
A symmetry-additive ab initio model for second-harmonic generation (SHG) activity of protein crystals was applied to assess the likely protein-crystal coverage of SHG microscopy. Calculations were performed for 250 proteins in nine pointgroup symmetries: a total of 2250 crystals. The model suggests that the crystal symmetry and the limit of detection of the instrument are expected to be the strongest predictors of coverage of the factors considered, which also included secondary-structural content and protein size. Much of the diversity in SHG activity is expected to arise primarily from the variability in the intrinsic protein response as well as the orientation within the crystal lattice. Two or more ordersof-magnitude variation in intensity are expected even within protein crystals of the same symmetry. SHG measurements of tetragonal lysozyme crystals confirmed detection, from which a protein coverage of $84% was estimated based on the proportion of proteins calculated to produce SHG responses greater than that of tetragonal lysozyme. Good agreement was observed between the measured and calculated ratios of the SHG intensity from lysozyme in tetragonal and monoclinic lattices.
When implementing anion exchange (AEX) for perand polyfluoroalkyl substances treatment, temporal drinking water quality changes from concurrent inorganic anion (IA) removal can create unintended consequences (e.g., corrosion control impacts). To understand potential effects, four drinking water-relevant IAs (bicarbonate, chloride, sulfate, and nitrate) and three gel-type, strong-base AEX resins were evaluated. Batch binary isotherm experiments provided estimates of IA selectivity with respect to chloride (K x/C ) for IA/resin combinations where bicarbonate < sulfate ≤ nitrate at studied conditions. A multi-IA batch experiment demonstrated that binary isotherm-determined K x/C values predicted competitive behavior. Subsequent column experiments with and without natural organic matter (NOM) allowed for the validation of a new ion exchange column model (IEX-CM; https://github.com/USEPA/Water_Treatment_Models). IA breakthrough was well-simulated using binary isotherm-determined K x/C values and was minimally impacted by NOM. Initial AEX effluent water quality changes with corrosion implications included increased chloride and decreased sulfate and bicarbonate concentrations, resulting in elevated chloride-to-sulfate mass ratios (CSMRs) and Larson ratios (LRs) and depressed pH until the complete breakthrough of the relevant IA(s). IEX-CM utility was further illustrated by simulating the treatment of low-IA source water and a change in the source water to understand the resulting duration of changes in IAs and water quality parameters.
It has been suggested that fluorescence from amine-containing dendrimer compounds could be the result of a charge transfer between amine groups and molecular oxygen [Chu, C.-C.; Imae, T. Macromol. Rapid Commun.
2009, 30, 89.]. In this paper we employ equation-of-motion coupled cluster computational methods to study the electronic structure of an ammonia–oxygen model complex to examine this possibility. The results reveal several bound electronic states with charge transfer character with emission energies generally consistent with previous observations. However, further work involving confinement, solvent, and amine structure effects will be necessary for more rigorous examination of the charge transfer fluorescence hypothesis.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.