Undergraduate Research Opportunities in Chemistry and Physical Sciences

Our research is a part of the Lead-Free Indy Initiative, a collaborative effort focused on reducing and ultimately eliminating lead exposure in Indianapolis communities. Through education, awareness, and community-based remediation, our goal is to create safer environments and healthier futures for all residents. We invite you to incorporate these materials into your curriculum or contact us to schedule customized workshops that meet your specific needs.

https://www.marian.edu/college-of-arts-and-sciences/department-of-chemistry-and-physical-sciences/research-opportunities/lead-poisoning

From the bulk down to a scale of a few hundred nanometers, the properties of materials do not vary much with the size of the particles from which they are composed, but below this scale there are changes that can involve structural preferences and physical and electronic properties: this is the world of nanoparticles, larger than molecules, but smaller than - and different from - bulk matter. Various factors influence these size-dependent phenomena, including structural effects near the particle surface and the transition from bulk-like to molecule-like quantum states. We have experience in making and studying several kinds of nanoparticles, including silica, metal oxide, and compound semiconductor materials.

Carbon compounds are the archetypes of covalently-bonded molecules, and are at the heart of simple views of chemical bonding; carbon atoms in molecules can usually be characterized as sp3 (tetrahedral), sp2 (trigonal), or sp (linear). Allotropes of elemental carbon include the bulk forms diamond (sp3) and graphite (sp2), as well as a proliferation of fullerenes, nanotubes, and other molecular forms where factors such as symmetry, surface curvature, and elimination of dangling bonds play roles in determining the preferred structures.

Currently active projects in this area include:

• Iron oxidation states in superparamagnetic nanoparticles
• Fluorescence studies of quantum dot growth
• Electronic states of elemental carbon nanostructures

Contact Dr. Rod Macrae

Atoms and molecules behave in accordance with the laws of quantum mechanics. Quantum chemistry is the branch of chemistry dedicated to the prediction of molecular structures and physical properties by solving the relevant quantum mechanical equations. This requires highly numerically intensive calculations, and is done with the help of computers. While modern personal computers are capable of carrying out quantum chemical calculations, the intensiveness of the calculations increases rapidly with the size of the molecule and the sophistication of the approach. We use in-house computational resources located within the Simmons-Purdie Data Center at Marian University (including a new GPU-based server), as well as national supercomputing infrastructure (XSEDE) where necessary.

For medium-sized molecules, density functional theory (DFT) is a set of methods that allows molecular structures, energies, and electron density distributions to be calculated with reasonable computational effort.

Currently active projects in this area include:

• Ion-molecule interactions
• Boron complexation equilibria
• Electronic states of elemental carbon nanostructures
• Energetics and spin density distributions in radicals and biradicals
• Exploring GPU-accelerated electronic structure calculations

Contact Dr. Rod Macrae

In our laboratory we use modular spectroscopic equipment to carry out several different types of measurements, including fluorescence spectroscopy with excitation from diode-pumped solid-state lasers of various wavelengths.

One strand of research studies light-induced reactions occurring in solutions containing dyes in the class known as xanthenes (which includes fluorescein, Eosin Y, and Rose Bengal) and molecules containing conjugated carbon chains (polymethines and polyenes). These reactions are thought to be mediated by singlet oxygen generated via spin exchange from the xanthene triplet state. Research on these systems includes rate law measurements and product identification.

Currently active projects in this area include:

• Photoinduced reactions in solutions containing cyanines and xanthenes
• Fluorescence studies of quantum dot growth

Contact Dr. Rod Macrae

Nuclear magnetic resonance spectroscopy is commonly encountered by students of organic chemistry as a technique for qualitative identification of molecules. However, this only scratches the surface of the capabilities of NMR, which has applications ranging from physics to biochemistry. Among the most interesting possibilities offered by the method are the use of different pulse sequences to study sources of spin relaxation including translational diffusion and interactions of the probe spin with paramagnetic species.

As an example, pulsed field-gradient NMR offers a suite of methods for the study of molecular diffusion dynamics in solution. The basic technique is a spin echo sequence in which an additional field gradient pulse along the z axis is applied before and after the 180° pulse. The first pulse generates a position-dependent phase along the z direction which is only exactly reversed by the second pulse if no diffusion of the nuclei has occurred. In the presence of diffusion, the spin echo is weakened by an amount dependent on the field gradient. Mapping the echo intensity as a function of field gradient in a 2D spectrum leads to the form of spectroscopy known as DOSY (“diffusion-ordered spectroscopy”). We apply these methods to the study of molecular transport in self-organized nanoenvironments such as micelles.

Currently active projects in this area include:

• Boron-11 NMR studies of boron complexation equilibria
• NMR relaxometry of MRI contrast agents
• Radiation damping effects in water-dominated systems
• DOSY studies of self-organized nanoenvironments

Contact Dr. Rod Macrae

The purpose of this study is to evaluate the applicability of electrospray laser desorption ionization (ELDI) mass spectrometry imaging (MSI) to interrogate tablet formulations for the spatial distributions of ingredients. ELDI combines laser ablation via an ultraviolet laser with electrospray ionization to create spatially resolved molecular images. The general ablation setup and process of ELDI-MSI can be seen in Figure 1. Mass spectrometry imaging is a non-targeted technique allowing the concurrent detection of different classes of small molecules from a solid sample surface. This is ideal for the analysis of pharmaceutical preparations. Five Marian undergraduate students are working on this project.

While we have previously shown that ELDI-MSI on pills is possible (Figure 2) we are currently working to expand the capabilities of the method to further explore agglomeration of the active ingredient, and the form by which the active ingredient exists in the pill with high accuracy. Here at Marian, we are building our ELDI-MSI setup with a brand new Q-Spark 266 nm nanosecond high-power laser (RPMC Lasers) coupled with our Thermo Scientific LTQ XL linear ion trap mass spectrometer. This is the same instrument used by many pharmaceutical companies for routine analysis. The ultimate goal of this project is to diagnose agglomeration of the active ingredient in tablets with MSI molecular images and determine the percentage of the active ingredient existing in the crystalline versus amorphous forms. This project is funded by AbbVie Inc., North Chicago, IL. All samples are provided by AbbVie.

Figure 1. General setup of ELDI-MSI method. The pill sample is mounted on a glass slide which is rastered by a xyz micro-translational stage under a static laser beam.

Figure 2. ELDI-MSI of acetaminophen tablets. A) “Filler” compound at m/z 112.0844. A steady signal across the entire tablet surface was observed for these filler compounds. The MS-images in B, C, D, and E show the spatial distributions of acetaminophen [M+H]+ at different crystallinity percentages, with the same normalized heat map intensity scale.

Contact Dr. Patrick McVey

This study will look at changes in the spatial distributions of small metabolites in plant leaves due to external stimuli. Sugars, flavonoids, amino acids, and organic acids among other small molecules will be tracked across the study. Past data can be seen in Figure 3 below from the previous publication: https://doi.org/10.3389/fpls.2018.01348. This project will begin in summer 2019.

Figure 3. Four different anthocyanins in a coleus leaf as affected by light exposure after 28 days of one half of the leaf illuminated (left) and the other half shaded (right).

Contact Dr. Patrick McVey

Check back soon for more information about this project!

Contact Dr. Patrick McVey

Research in the Nicholson Group focuses on aspects of organic reaction development and novel experiments for undergraduate teaching labs. Undergraduate research students in my group are focused currently on the applications of 3D printing in the design of small volume lab devices to innovate learning while minimizing waste in the teaching lab. Students are also carying out research aimed at identifying biological systems that can carry out appropriate asymmetric enzymatic reactions to study stereochemistry in the undergraduate organic laboratory as well as reactions that can be carried out to demonstrate transfer or loss of that stereochemistry in a teaching context.

Contact Dr. Chris Nicholson