2016 Montana ACS

Spring Meeting

Saturday, April 9, 2016

Helena College, Donaldson Campus

Helena, MT

Welcome!

Welcome to the Spring 2016 meeting of the American Chemi-cal Society’s Montana Section! Helena College is proud to con-tinue to support the ACS by welcoming its members back to our campus, and we extend our most heartfelt hospitality to you—one and all—as you visit our wonderful part of the great state of Montana.

The mission of the ACS is part of the mission of Helena College, as well—to advance the broader chemistry enterprise and its practitioners for the benefit of Earth and its people. The ACS and Helena College both advocate for chemistry and support future chemists, but we also share the broader goals of advancing science, enabling career development, educating the public, and promoting diversity.

Helena College has been providing higher education and work-force development to the people of Helena since 1939. We continue that tradition today by engaging with our community, including the ACS, to provide the education and training that our vibrant local, regional, and state-wide economy requires. We are thrilled to have the ACS on our campus, and we wish you the very best experience here in Helena at the Spring 2016 meeting.

Sincerely,

Chad E. Hickox, Ph.D.

Helena College Chief Academic Officer

Upcoming National and

Regional Meetings…

252nd ACS National Meeting & Exposition

”Chemistry of the people, by the people,

for the people”

August 21 – 25, 2016 Philadelphia, PA

Northwest Regional Meeting (NORM) 2016

“Chemistry Under the Midnight Sun”

June 26 – 29, 2016 Anchorage, AK

Montana Section email address:

MontanaSectionACS@gmail.com

Montana Section Website:

http://montana.sites.acs.org/

Montana Section Facebook page:

https://www.facebook.com/Montana-ACS-

275145155836505/

Mark Your Calendars and Save the Date!!

2016 Fall Social and Meeting

Montana Section ACS

Fairmont Hot Springs Resort

October 15 – 16, 2016

This year includes: Poster Session

Beer & Wine Social

Awards & Recognition

Catered Dinner

Special Guest Speaker

Dance & D.J.

Poolside Social

And More!

Welcome to Helena College and the

2016 Spring Meeting of the Montana

Section ACS! It is a pleasure to host

this event once again, to share our

explorations in the chemical sciences,

and to network with friends old and

new. We especially welcome our

Keynote Speaker Christina Anderson

who will open our eyes to the

application of chemical methods in

photography.

We know very well how chemistry is

integral to every facet of our lives; clothes, food, transportation,

the environment, and even interactions with each other (colognes,

perfumes, pheromones, and more!). So it’s safe to say that

chemistry doesn’t just have an impact on everything… it IS every-

thing! And we come together at conferences like this to share

even more the deeper understanding we have for “everything”.

Enjoy your time here at Helena College and take advantage of the

opportunities provided by your Montana Section to gather

together, advance appreciation for and understanding of

chemistry, and be better prepared for careers in chemistry.

“Chemistry for Life” is not just an ACS motto but rather a

statement of fact during this meeting and beyond.

John W. Hartman, PhD,

Chair, Montana Section

Meeting Agenda

8:00 – 9:00 am Registration/Check-In & Continental Breakfast

9:00 – 9:10 am Opening Remarks

9:10 – 9:30 am Andrew Hill (Montana State University)

9:30 – 9:50 am Victoria Kong (Carroll College)

9:50 – 10:10 am Abdul Goni (University of Montana)

10:10 – 10:30 am Arianna Celis (Montana State University)

10:30 – 10:40 am Break

10:40 – 11:00 am William Pardis (Flathead Valley Community College)

11:00 – 11:20 am Jasmine Phan (Carroll College)

11:20 – 11:40 am Tacey Hicks (Montana State University)

11:45 – 12:30 pm Lunch

12:30 – 1:30 pm Keynote Speaker — Christina Z. Anderson

1:40 – 2:00 pm Eric Massaro (Montana State University)

2:00 – 2:20 pm Julie McGettrick (University of Montana)

2:20 – 2:40 pm Melodie Machovina (Montana State University)

2:40 – 3:00 pm Inderbir Bains (Carroll College)

3:00 – 3:20 pm Dr. David Long (Flathead Valley Community College)

3:20 – 3:30 pm Break

3:30 – 3:45 pm Awards for best student presentation

3:45 – 4:30 pm Montana ACS Board Meeting

3:00 pm Undergraduate Research as Pedagogy: Global

Chemistry for a Global Perspective

David M. Long* (Flathead Valley Community College)

It is widely recognized that undergraduate research has consid-

erable impact on student skills and abilities germane to problem

solving in science and engineering. At Flathead Valley Communi-

ty College (FVCC), STEM faculty engage students in research pro-

jects in carefully considered formats that constitute teaching

methodology, or pedagogy. The strategies and tactics we em-

ploy directly expose students to the types of environments and

experiences they are likely to encounter as working scientists.

While classroom lecture is an important component of all STEM

programs at FVCC, great emphasis is placed upon authentic re-

search experiences early in students’ studies so they are better

able to evaluate for themselves if a career in STEM might be

right for them. We design research projects and control the re-

search environment in ways that bear as close a relationship as

possible to the types of environments students will find them-

selves working within, should they choose to become profes-

sional scientists or engineers. We are not bound by conditions

typical of a true academic research environment, and thus we

are in an excellent position to manage student research in ways

that maximally benefit the students’ development- as opposed

to making scientific progress. I present a research project in

chemistry that embodies the elements we consider essential to

this educational model.

2:40 pm The effect of 6-ruthenium arene complexes as

electron-withdrawing dienophile substituents in Diels-Alder re-

actions

Inderbir Bains, David M. Hitt* (Carroll College)

6-Ruthenium arene complexes have proven to be valuable inter-

mediates in organic synthesis due to the metal’s ability to act as

an electron-withdrawing group (EWG) making reactions such as

nucleophilic aromatic substitution and deprotonation of benzylic

and aromatic positions very facile. These complexes are also able

to impart stereoselectivity by blocking incoming electrophiles /

nucleophiles from one face of the aromatic ring due to steric hin-

drance created by the metal-ligand environment. Despite being

a known EWG, there has been very little research investigating

these complexes ability to modulate reactivity of alkenes pen-

dent to the complexed arene. In particular, only two examples

has been reported using an eta6-ruthenium arene complex as an

accelerating group for a Diels-Alder (DA) reaction, which is

known to be facilitated by electron-withdrawing dienophile sub-

stituents when reacted with an electron rich diene. Herein, we

report our initial findings into using the electron-withdrawing (5

-cyclopentadienyl )Ru+ (CpRu+) metal fragment as a potential

mediator for DA reactions. Currently, we have successfully syn-

thesized a model dienophile substrate, [CpRu(6-(ethyl trans-

cinnamate))]PF6 and isolated a DA adduct ruthenium complex

that has been characterized by H-1 NMR spectroscopy. Rate

comparison studies using H-1 NMR and GC-MS were also con-

ducted to determine the extent of rate enhancement of the ru-

thenium-bound dienophile compared to the free arene dieno-

phile under non-catalyzed and Lewis acid catalyzed conditions.

Where Chemistry Meets Art: Contemporary Chemical Methods of Photographic Practice

Christina Z. Anderson Associate Professor

Montana State University School of Film and Photography

Montana State University, Bozeman, 59717

Today there is no question that the prevalent form of photographic practice is digital photography, yet in the background is a growing movement of fine art photographers who are returning to the roots of chemical photographic practice. In the 1960s when this niche movement began, it was termed “alternative process photography” because it was an alternative to filling the coffers of big corporations like Kodak. Although a bit outmoded, this term is still used today in the absence of a comparatively enormous company like Kodak to rebel against anymore, and, in fact, B&W photography has now joined in as yet one more alternative process. This movement without a clear name and even less clear delineation with hybrid digital-chemical methods also employed, has one characteristic: photographers who enjoy getting their hands “wet” in the making of fine art prints. Anderson will use fine art examples of a number of contemporary processes such as cyanotype, platinum, mordançage, chromoskedasic sabbatier, chemigram, gum bichromate, and salted paper and show how chemistry is alive and well in the fine art field. While most photographers who practice these methods have no idea what chemical reactions are taking place, Anderson will discuss the chemistry involved with hopes of furthering more dialogue and collaboration between artists and chemists in the future.

Keynote Presentation:

Student Presentations:

9:10 am Ultrafast Microscopy of Methylammonium Lead

Iodide Perovskites

Andrew Hill, Eric Massaro, Kori Smyser, Erik Grumstrup*

(Montana State University)

While organometal halide perovskites exhibit many functional

properties typically associated with high-performance inorganic

semiconductors the solution processing conditions typically used

to fabricate these materials can introduce significant structural

and compositional heterogeneities. Here we report characteriza-

tion of methylammonium lead iodide perovskite thin films using

nonlinear microscopy. The spatial resolution afforded by this

technique reveals extensive spatial heterogeneity in excited

state decay and mobility both within and between individual

crystalline domains. We employ a technique known as lifetime

mapping to directly image spatial heterogeneity in excited state

decay across a single crystalline grain revealing half-lives that

vary over an order of magnitude. Photogenerated charge carrier

diffusion constants are also found to vary substantially from do-

main to domain but are seen to reach values comparable to

diffusivities in single-crystalline nanostructures. Together, these

results suggest the importance of precisely correlating measure-

ments of optoelectronic functionality with specific structural and

compositional properties so as to optimally engineer perovskite-

based devices.

2:20 pm Cofactorless Dioxygen Catalysis by an Antibiotic

Biosynthesis Monooxygenase: Testing the Flavin Hypothesis

Melodie M. Machovina, Robert J. Usselman, Jennifer L

Dubois* (Montana State University)

Members of the antibiotics biosynthesis monooxygenase (ABM) family catalyze O2-dependent oxidations and oxygenations in the absence of any metallo- or organic cofactor. How they surmount the kinetic barrier to reactions between singlet substrates and triplet O2 is unclear. ABM reactions have been proposed to occur via a flavin-like mechanism, where the substrate acts in lieu of the flavin cofactor. To test this model, the uncatalyzed and enzy-matic reactions of dithranol/ O2 were examined, using the nogalamycin monooxygenase (NMO) from treptornyces nogalater. Similar to reactions between flavin and O2, dithranol oxidation was faster at higher pH, with pKas of 6.9 (NMO kcat, kcat/Km) and 8.5 (free substrate), though the reaction did not appear to be base-catalyzed. Rather, conserved asparagines N63 and N 18 contributed to the suppression of the substrate’s pKa. The same residues were critical for enzymatic catalysis which, consistent with the flavoenzyme model, occurred via an O2-dependent slow step. Evidence for a superoxide/substrate radi-cal pair came from detection of enzyme-bound superoxide dur-ing turnover. Both chemical and enzymatic traps (1 -hydroxy-3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine, CMH; superox-ide dismutase) suppressed formation of the oxygenation (dithranone) product under uncatalyzed conditions; however, only CMH had an effect in the presence of NMO. This suggested that NMO both accelerated the formation and directed the re-combination of a superoxide/dithranyl radical pair. These cata-lytic strategies are in many ways flavin-like and stand in sharp contrast to the mechanisms of urate oxidase and (1 H)-3-hydroxy-4-oxoquinaldine 24-dioxygenase (HOD), both cofactor-independent enzymes that surmount the barriers to direct sub-strate/ O2 reactivity via markedly different means.

2:00 pm Separation of Anions and Nitroaromatics by

Electrokinetic Chromatography

Julie McGettrick, Chris Palmer* (University of Montana)

Explosives residues are complex mixtures that can contain both

neutral organic molecules and inorganic ions. Most forensic pro-

tocols use two techniques for explosives analysis: ion chroma-

tography for ions and HPLC for organic compounds. Electroki-

netic chromatography (EKC) is a powerful analytical technique

that combines the instrumentation of capillary electrophoresis

with the principles of chromatography and makes it possible to

analyze both anions and neutral organic compounds in the same

analytical run. In this study AB diblock copolymers that form

latex nanoparticles with a cationic shell and hydrophobic core in

aqueous solutions were synthesized and used as pseudostation-

ary phases. EKC analyses were performed on an Agilent 3DCE

system with on-column contactless conductivity and UV detec-

tion, and quantified with CE ChemStation software. Capillaries

were dynamically coated with a poly([(2-acryloyloxy)ethyl]

trimethylammonium chloride) cationic polymer to create anodic

electroosmotic flow. The effect of different cationic shell and

hydrophobic core chemistries on the separation was investigat-

ed. Both anions and neutral compounds were separated in less

than ten minutes.

9:30 am Ideal and Non- Ideal Temperature- Dependent

Mixing and Solute Partitioning of Coumarin 152 in a Mixed

Phospholipid Bilayer System

Victoria Kong, Christine Gobrogge, Dr. Robert A. Walker*

(Carroll College)

Within every cell of the human body resides a natural barrier,

the lipid bilayer. Though perceived as impermeable, scattered

with various biological gates and protein- specific receptors, this

membrane is actually semi- permeable, and incredibly sensitive

to the movement of solutes residing within the cell and the sur-

roundings. The real- life application of analyzing the interaction

between lipids in mixed lipid systems is that it allows for better

comprehension of the ideal or non- ideal conditions in which

these bilayers are related. In particular, looking at how this ideal

or non- ideal mixing of lipid systems allows for examination of

how solute partitioning is affected, a critical mechanism that

contributes to bio- accumulation.

In order to monitor the interactions of these lipids, Coumarin152

(C152), a fluorescent molecule, is employed. Because the various

lifetimes of C152 in the two distinct aqueous exterior/ cellular

interior and the non- aqueous, non- polar lipid bilayer interior is

known, Time- Correlated Single Photon Counting (TCSPC) tech-

nology can be employed. As the surrounding temperature of the

lipid bilayer system is increased, the various lifetimes, and thus

locations, of C152 can be recorded, and it can be deduced if the

lipids are continuing to act in an ideal or non- ideal way.

9:50 am Immobilization of pyridine based pincer metal

complexes on silica polyamine composites for catalytic applica-

tions

Abdul Goni, Edward Rosenberg* (University of Montana)

Pyridine based pincer metal complexes have received considera-

ble attention in recent years for their interesting catalytic activi-

ties in a wide range of chemical transformations. We have immo-

bilized ruthenium complexes with pyridine based pincer ligands

on silica polyamine composites (SPC-BP1). The pincer complexes

loaded on SPC have been analyzed by solid-state NMR, FT-IR,

elemental analysis, and metal digestion study. The silica polyam-

ine composite surfaces provide amine functionality to generate

active pincer catalysts from the corresponding complexes. Cata-

lytic reactivity of the immobilized ruthenium pincer complexes on

SPC have been investigated in the alcohol dehydrogenation reac-

tions. They successfully converted alcohols to corresponding es-

ters with the liberation of hydrogen.

1:40 pm Ultrafast Super Resolution Spectroscopy by

Structured Pump-Probe Microscopy

Eric S. Massaro, Andrew H. Hill, Erik M. Grumstrup* (Montana

State University)

Pump-Probe microscopy has become a powerful tool for investi-

gating electron dynamics in complex materials systems with sub-

micron spatial resolution and femtosecond temporal resolution.

While the spatial resolution of pump-probe microscopy exceeds

most conventional spectroscopic methods, it is still limited to

~200 nm by the diffraction limit. We have developed Structured

Pump Probe Microscopy (SPPM), which can provide ~114 nm

spatial resolution through the use of a diffraction limited probe

field and a spatially modulated excitation field. The two-fold

resolution increase over the diffraction limit is made possible by

extracting additional high (spatial) frequency information typi-

cally filtered by the optical system. Additionally, SPPM retains

the time-dependent spectroscopic capabilities of pump-probe

microscopy. We demonstrate the ability of SPPM to resolve

unique time-dependent data from two separate objects that are

indistinguishable using diffraction limited pump-probe microsco-

py. Further development of SPPM will further enhance the tech-

niques capabilities for probing sub-wavelength domains of het-

erogeneous materials while remaining within the perturbative

limit.

11:20 am Modeling the Structure and Reactivity of Al(III)/

Fe(III) Substitution in Kaolinite

Tacey L. Hicks, Robert K. Szilagyi* (Montana State University)

Clays are a rapidly emerging group of materials because of their

wide industrial applications. Many of these applications however

greatly depend on the surface chemistry of these minerals. Cur-

rently, surface modifications are designed and optimized primar-

ily on the basis of trial-and-error, empirical procedures. We pro-

pose that computational modeling can assist in rationalizing

these experimental modifications by providing a quantitative

image of the characteristics and reactivity of these surfaces and

their properties. The goal of our study is to develop an accurate

molecular cluster model for the octahedral surface of kaolinite,

which can be used to examine the reactivity and surface charac-

teristics for both the pure Al(III) and Fe(III) substituted models at

the atomic level. A computational model containing 130 atoms

was constructed to capture the complete chemical coordination

environment of a central Al(III) ion site of interest. This model

included the inner sphere coordination environment, outer

sphere and the outer peripheral layer of atoms. All structural

optimizations and reactivity studies were carried out using the

B3LYP density functional theory and def2TZVP converged basis

set with polarizable continuum model and dispersion correction.

The specific surface reactivity study here focuses on successive

reactions of the Fe3+ substituted octahedral layer with H2S mol-

ecules, resulting in the replacement of the surface and inner hy-

droxide groups coordinated to the central Fe(III) ion with a thiol

group. The results obtained from our theoretical models are be-

ing used to rationalize experimental conditions for synthetic

work conducted in our laboratory, providing new ideas for the

specific future projects.

10:10 am The Last Stop On a New Road to Heme

Arianna I. Celis, Bennett Streit, Garrett C. Moraski,

George Gauss, John W. Peters, Jennifer L Dubois* (Montana

State University)

Nature has devised at least three routes for the biosynthesis of

heme b, one of which appears to be common to many gram-

positive bacteria. This recently proposed pathway has the con-

version of two of the four propionate groups on coproheme Ill to

vinyl groups as its final step. The reaction is H2O2 dependent and

catalyzed in a cofactor-independent manner by the enzyme

HemQ. Using the HemQ from Staphylococcus aureus (SaHemQ)

we aimed to determine whether a specific three-propionate

harderoheme isomer could be identified as a reaction intermedi-

ate and to narrow down on possible iron intermediates in order

to propose a possible reaction mechanism. In addition, we have

interrogared the active site environment that accomodates the

two reactive propionate groups in coproheme and obtained a

preliminary view of the first coproheme-bound HemQ structure.

10:40 am Building a Photometeric pH Measuring Device

for Field Studies of Ocean Acidification

William Alexander Pardis, Rachel Sanders, Jim Boger,

and David M. Long* (Flathead Valley Community College)

Precise and accurate measurement of sea water pH is critical for

studies of ocean acidification caused by rising levels of anthropo-

genic atmospheric carbon dioxide. Although there are multiple

methods for measuring pH of seawater, most are imprecise, in-

accurate, and costly. We are building cost-effective, portable,

precise, and accurate pH measurement devices for field meas-

urements.

Subtle changes in seawater chemistry can lead to substantial

changes in ecosystem function. Atmospheric carbon dioxide dis-

solves in seawater forming carbonic acid which reduces pH.

Ocean pH has dropped about 0.1 units in the last 20 years. This

corresponds to a 30% increase in proton concentration. Ready

availability of precise and accurate pH measurement technology

is critical for furthering our understanding of this important

change in marine chemistry.

In this presentation I describe the construction and operation of

a pH measuring device based upon photometry of the sul-

phonephthalein indicator meta-cresol purple (mCP). Although

this chemistry has been developed by previous investigators, we

are adapting it to more challenging field conditions and broaden-

ing it applicability through design improvements. Late this spring

we will travel to French Polynesia under the auspices of Flathead

Valley Community College for extensive evaluation of our instru-

ments and chemistry. Our intent is to employ our instruments in

efforts to quantify and understand acidification of the Pacific

Ocean.

11:00 am Synthesis of 6 Chloro Arene Ruthenium Com-

pounds & Stereoselective Binding Study

Jasmine Phan, David Hitt* (Carroll College)

Planar chiral (6-arene)Cr(CO)3 and ferrocene based complexes

have demonstrated some use as chiral ligands in enantioselec-

tive metal catalysis. Enantioselective transition metal catalyzed

reactions have incredible value in synthesis. It has recently been

suggested by Amouri and coworkers that 6-ruthenium chloroa-

rene compounds may serve as a synthetic stepping stone to simi-

lar complex chiral ligands due to the chlorine substituent’s pro-

pensity to undergo nucleophilic aromatic substitution with a

wide variety of nucleophiles. These researchers used a prece-

dent set by Uemura and coworkers to prepare highly enantioen-

riched samples of an 6– ruthenium complex derived from an

ortho-chlorobenzylic alcohol. This compound was converted to

an 6– ruthenium ortho-phosphinobenzylic alcohol and subse-

quently bound in a monodentate fashion to a gold(I) metal cen-

ter through the phosphine, but was not used for catalysis. In the

current study, we plan to study the stereoselectivity resulting

from 6– complexation of ortho-chloro -substituted benzyl

amines. The resulting complexes could serve as valuable syn-

thetic intermediate for construction of planar chiral ortho-

phosphino -substituted benzyl amines 6 – ruthenium complex-

es similar to those used with related chromium tricarbonyl and

ferrocene systems. Currently, 1-chloro-2-(1-propylaminoethyl)-

benzene has been synthesized and mostly purified. The associ-

ated 6– ruthenium complex has been synthesized,mostly puri-

fied, and an x-ray structure has been obtained supporting Uemu-

ra’s model for stereoselective metal complexation.