K.V. Waynant Research Group

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Waynant Group Research

Organic Synthesis

The group has multiple synthesis projects as Prof. Waynant begins his independent career.  Most of the project center on target driven glycosides and other biologically important natural products and the synthetic methodology along the way.

Host-Guest Coordination Chemistry 

The group has a keen interest in redox-active ligands and the coordination chemistry and binding kinetics involved. Supramolecular coordination complexes and ligand design are leading to coordinative metal dissolution, catalysis, and biological studies.

Polymeric Materials

The group focuses on new polymeric materials for stimuli-responsive and stimuli-reactive polymeric surfaces as well as polymer brush derived sensors. There are also projects on zwitterionic cross-linking materials and diffusion kinetics in modified hydrogels. 

Chemical Education

Many students also work on the design and implementation of Course-based undergraduate research experiences in the freshmen and upper division laboratories.  The group is interested in assessing how guided research projects influence student retention and persistence in STEM degrees and careers.  

2020 Publications

Supramolecular Chemistry, 2020 https://doi.org/10.1080/10610278.2020.1795172

Publication Date: 30 Jul 2020

Substitution effects on the binding interactions of redox-active arylazothioformamide ligands and copper(I) salts

Rabina Pradhan, Vincent M Groner, Kaylaa L Gutman, Zachariah M Heiden, Mark F Roll, James G Moberly, and Kristopher V Waynant

The straightforward synthesis of redox-active arylazothioformamide (ATF) ligands allows for electronic diversity as to measure the weak-binding interactions of transition metal salts in supramolecular coordination complexes. A small library of para-substituted ATFs was created with varied electronic components to evaluate how electron-donating and electron-withdrawing groups alter binding association constants. Following full characterisation, including single-crystal X-ray diffraction, UV-Vis titration studies were performed using copper(I) salts to assess the Host:Guest binding. Simultaneously, substitutions were evaluated computationally by modelling the Gibbs’ Free Energy change of the rotational barriers from ligand crystal structures to the predicted metal coordinating species and the various complexes. The multi-model association calculations and experimental measurements interplay to help limit error propagations and reliably predict the more accurate binding models. Through a thorough investigation it was found that experimentally, each ligand supports a 2:1 binding model yet may employ unique binding mechanisms to achieve that model.

Journal of Chemical Education, 2020, 97,1, 195-99


Publication Date (Web): November 12, 2019

Carbohydrate Characterization through Multidimensional NMR: An Undergraduate Organic Laboratory Experiment

Jacob S Kennedy, Garrett E Larson, Alex Blumenfeld, Kristopher V Waynant

Carbohydrates are an essential group of molecules to the organic chemistry classroom providing molecular relevance to a common ingredient in chemical biology. While the meticulous elucidation of the carbohydrate structures by Fischer and others is an engaging topic in the lecture, there are few laboratory experiments that can emulate carbohydrate complexity. Advanced and multidimensional NMR (2D NMR) techniques such as correlation spectroscopies (COrrelation SpectroscopY (COSY), 13C Distortionless Enhancement by Polarization Transfer (DEPT), and HETeronuclear CORrelation (HETCOR) or Heteronuclear Single Quantum Coherence (HSQC)) have become more routine as they require less time on today’s instruments and are taught more often in lecture. A laboratory experiment is described for second-year introductory undergraduate organic chemistry students that involves the transformation of …

2019 Publications

Acta Crystallographica Section E: Crystallographic Communications 2019, 75(9), 1394-98

The synthesis and crystal structure of bis [3, 3-diethyl-1-(phenylimino-κN) thiourea-κS] silver hexafluoridophosphate

Vincent M Groner, Garrett E Larson, Yuwei Kan, Mark F Roll, James G Moberly, Kristopher V Waynant

Publication Date (Web): 9/1/2019

The structure of the title complex, [Ag(C11H15N3S)2]PF6, has monoclinic (P21/c) symmetry, and the silver atom has a distorted square-planar geometry. The coordination complex crystallized from mixing silver hexafluoridophosphate with a concentrated tetrahydrofuran solution of N,N-diethylphenylazothioformamide [ATF; systematic name: 3,3-diethyl-1-(phenylimino)thiourea] under ambient conditions. The resultant coordination complex exhibits a 2:1 ligand-to-metal ratio, with the silver(I) atom having a fourfold AgN2S2 coordination sphere, with a single PF6 counter-ion. In the crystal, however, one sulfur atom from an ATF ligand of a neighboring complex coordinates to the silver atom, with a bond distance of 2.9884 (14) Å. This creates a polymeric zigzag chain propagating along the c-axis direction. The chains are linked by C—H⋯F hydrogen bonds, forming slabs parallel to the ac plane.

Tetrahedron Letters 2019, 60(44), 1512-3. 

Abdulakeem Osumah, Jakob Magolan, Kristopher V Waynant
Publication Date (web): 10/31/2019
Preparation of mixed carbonates proceeded in one step from ketones and aldehydes via treatment with NaBH4 in dimethyl or diethyl carbonate solvent at elevated temperatures. This is an efficient and convenient alternative to the traditional two-step sequence of carbonyl reduction to alcohol and subsequent carbonate formation by treatment with an alkyl chloroformate. 25 examples are presented from 49 to 92% yield, highlighting the versatility of this reaction.

2018 Publications

Journal of Chemical Education, 2018, 95,7, 1226-1229
DOI: 10.1021/acs.jchemed.7b00969  or here
Publication Date (Web): May 25, 2018
Expanding Evaporation Rate Model Determination of Hand-Rub Sanitizers to the General Freshman and Engineering Chemistry Undergraduate Laboratory: Inquiry-Based Formulations, Viscosity Measurements, and Qualitative Biological Evaluations
Additions to the popular evaporation rate determination laboratory of alcohol-based hand-rub sanitizers are described here. Significantly, inquiry-driven protocols for formulating hand-rub sanitizers, falling-ball viscometry, and sanitizer efficacy are included. Incorporation of familiar substances (“molecular relevance”) enables students to assimilate knowledge and connect to and recognize interrelated disciplines.

Journal of Cheminformatics

Key features and updates for Origin 2018

OriginLab’s newest version update to Origin and OriginPro includes ease-of-use features, like Origin Central updates and creation of an App Center, as well as larger changes like the addition of Unicode charac...

James G. Moberly, Matthew T. Bernards and Kristopher V. Waynant

Journal of Cheminformatics 2018 10:5

Published on: 9 February 2018

2017 Publications  

European Journal of Inorganic Chemistry

DOI: 10.1002/ejic.201701097

Deconvoluting the Innocent vs. Non-Innocent Behavior of N,N-diethylthioformamide Ligands with Copper Sources

Nicolas A. Johnson, Samuel R. Wolfe, Human Kabir, Gabriel A. Andrade, Glenn P.A. Yap, Zachariah M. Heiden, James G. Moberly, Mark F. Roll, and Kristopher V. Waynant

Experimental and computational investigation of reactions involving the redox-active arylazothioformamide ligand with multiple Cu(I) sources is described. Cu(I) halides produce dimeric 1:1 coordination species, while non-coordinating counter ions (BF4 and PF6) gave 2:1 species. Computational comparisons of bond length and angles suggest that the Cu atom remains in the +1 oxidation state.

Journal of Chemical Education

DOI: 10.1021/acs.jchemed.7b00440

UV–Vis Spectrophotometric Analysis and Quantification of Glyphosate for an Interdisciplinary Undergraduate Laboratory

Daniel E. Felton, Martina Ederer, Timothy Steffens, Patricia L. Hartzell and Kristopher V. Waynant

A simple assay to quantify glyphosate concentrations in environmental samples was developed as part of an interdisciplinary effort linking introductory laboratory courses in chemistry, biology, and microbiology.  Regression analysis indicated that the assay is linear up to 20.0 ppm, making it particularly useful for detection of low levels of glyphosate in environmental samples. The assay can be used to quantify the activity of glyphosate-degrading soil microorganisms by comparing glyphosate levels between autoclaved and nonautoclaved soil slurries.

Polymers for Advanced Technologies 
DOI: 10.1002/pat.3861
Volume 28, Issue 1, pgs 73-79.
Qualitative degradation of the pesticide coumaphos in solution, controlled aerosol, and solid phases on quaternary ammonium fluoride polymer brushes (pages 73–79)

Kristopher V. Waynant, Hyung-Jun Koo, Chunjie Zhang and Paul V. Braun

Version of Record online: 6 JUL 2016 | DOI: 10.1002/pat.3861

Quaternary ammonium fluoride polymer brush thin-film surfaces synthesized from surface-initiated atom transfer radical polymerization and post-polymerization modification proved capable of degrading the known pesticide coumaphos. Coumaphos degradation was visualized through detection of known fluorescent by-product chlorferon. Brush surfaces allow for various pesticide delivery methods and could prove useful for detection and degradation of pesticides and chemical threats.

2013-2016 Publications as part of UIUC team:

Hyung-Jun Koo, Kristopher V Waynant, Chunjie Zhang, Richard T Haasch, Paul V Braun

Chemistry of Materials 2014, 26(8) 2678-2683

We report a general diffusion based method to form micrometer-scale lateral chemical
gradients in polymer brushes via selective alkylation. A quaternized brush gradient is
derived from a concentration gradient of alkylating agent formed by diffusion in permeable
media around a microchannel carrying the alkylating agent. Polymer brushes containing
both charge and aromatic gradients are formed using the alkylating agents, methyl iodide
and benzyl bromide, respectively. The gradients are quantitatively characterized by ...

Hyung-Jun Koo, Kristopher V Waynant, Chunjie Zhang, Paul V Braun

ACS applied materials & interfaces 2014 6(16) 14320-14326

We present a facile microfluidic method for forming narrow chemical gradients in polymer
brushes. Co-flow of an alkylating agent solution and a neat solvent in a microfluidic channel
forms a diffusion-driven concentration gradient, and thus a gradient in reaction rate at the
interface of the two flows, leading to a quaternization gradient in the underlying poly (2-
(dimethylamino) ethyl methacrylate) polymer brush. The spatial distribution of the
quaternized polymer brush is characterized by confocal Raman microscopy. The ...

Chunjie Zhang, Amit Sitt, Hyung-Jun Koo, Kristopher V Waynant, Henry Hess, Brian D Pate, Paul V Braun

Journal of the American Chemical Society 2015, 137(15) 5066-5073

Materials which induce molecular motion without external input offer unique opportunities for
spatial manipulation of molecules. Here, we present the use of polyacrylamide hydrogel
films containing built-in chemical gradients (enthalpic gradients) to direct molecular
transport. Using a cationic tertiary amine gradient, anionic molecules were directionally
transported up to several millimeters. A 40-fold concentration of anionic molecules dosed in
aerosol form on a substrate to a small region at the center of a radially symmetric cationic ...

2010-2013 Publications 

Synthesis of β-C-GlcNAc Ser from β-C-Glc Ser

EG Nolen, L Li, KV Waynant
The Journal of organic chemistry 78 (13), 6798-6801

Enhanced shape-selective recognition of anion guests through complexation-induced organization of porphyrin hosts

MJ Wienkers, J Ramos, H Jemal, C Cardenas, P Wiget, A Nelson, S Free, ...
Organic letters 14 (6), 1370-1373

Synthesis of hydronaphthalenes through coupling of enyne-carbonyl compounds that contain pendant alkane groups with Fischer carbene complexes
RK Patti, S Duan, A Camacho-Davila, K Waynant, KA Dunn, JW Herndon
Tetrahedron letters 51 (28), 3682-3684

Publications before 2008