VIPEr

Intermolecular interactions

Learning Goals:

After completing this literature discussion, students will be able to:

provide examples of supramolecular systems in nature that use reversible, weak noncovalent interactions
define terms in supramolecular chemistry such as host, guest, and self-complementary
identify the number and location of hydrogen bonds within the "tennis ball" assembly
draw common organic reaction mechanisms for the synthesis of the "tennis ball" subunits
describe the physical and spectroscopic/spectrometric techniques used to provide evidence for assembly of a host-guest system
explain the observed thermodynamic parameters that are important for encapsulation of small molecule guests by the "tennis ball"

Topics Covered:

Molecular structure

Supramolecular Chemistry Videos

Reaction mechanisms

Synthesis and reactivity

Visualization

Related activities:

Nanomaterials Chemistry

Energy Nuggets: MOF’s for CO<sub>2</sub> Sequestration

Implementation Notes:

This LO could be used at the end of a traditional 2-semester organic chemistry sequence as an introduction to organic supramolecular systems, as an organic chemistry example within a discussion about inorganic supramolecular chemistry, or in an upper-division elective course about supramolecular chemistry. The LO topic, the "tennis ball," has a published laboratory experiment in J. Chem. Educ. (found here). Time permitting, instructors could have students read the article and complete the literature discussion before executing the experiment in the lab.

As usual, instructors may wish to mix-and-match questions to suit their learning goals.

Time Required:

depends upon implementation; minimum of 20-30 minutes for the literature discussion if students read an d answer questions outside of class

Web Resources:

Rebek "tennis ball" laboratory experiment

3 Mar 2019

Supramolecular Chemistry Videos

Submitted by Shirley Lin, United States Naval Academy

Additional Authors:

Shirley Lin, United States Naval Academy

Evaluation Methods:

I have yet to use this resource with students and therefore have no assessment of student learning to share at this time.

Evaluation Results:

I have yet to use this resource with students.

Description:

The Rebek Laboratory homepage contains information on and molecular visualizations of a variety of host-guest systems developed by the research group over several decades. The theme behind this set of examples is the use of hydrogen-bonding to achieve self-assembly. Under the "Research" tab, one can find four videos with narration: an introduction to molecular assembly and three videos of specific examples of self-assembled host systems (the cavitand, the cylinder and the volleyball). In addition, at the bottom of the tab, there are links to JSmol files for 5 host systems (tennis ball, jelly donut, cylindrical capsule, softball, and tetrameric capsule) that allow the assemblies to be visualized interactively.

This is a great resource for faculty looking for ways to incorporate the new ACS Committee on Professional Training guidelines to discuss macromolecular, supramolecular, mesoscale and nanoscale systems within the framework of their existing curricula.

Prerequisites:

Corequisites:

Course Level:

Topics Covered:

Intermolecular interactions

Visualization

Learning Goals:

I have not yet used this resource with students but here are some possible relevant learning goals.

After viewing the Rebek Laboratory Homepage web source, students will be able to:

1) classify various self-assembled host-guest systems by the number of molecular components forming the assembly

2) identify the number and position of the hydrogen bonds that are responsible for the assembly of each host

3) identify the functional groups on the components of the host systems that are responsible for hydrogen bonding

4) state the experimentally determined percent volume of space generally occupied by guests that are encapsulated in these host systems

Subdiscipline:

Energy Nuggets: MOF’s for CO<sub>2</sub> Sequestration

Related activities:

Education Resources at Beloit College - Materials Chemistry, Nanoscience and Solid State Chemistry

Implementation Notes:

I have yet to use this website in my teaching but I hope that it may be a resource in expanding our curriculum in supramolecular chemistry.

Time Required:

depends on use

Web Resources:

Rebek Laboratory Homepage

3 Jan 2019

Venn Diagram activity- What is inorganic Chemistry?

Submitted by Sheila Smith, University of Michigan- Dearborn

Evaluation Methods:

I did not assess this piece, except by participation in the discussion

Evaluation Results:

I asked my students to write an open ended essay to answer the question (asked in that first day exercise): What is Inorganic Chemistry.

Interestingly, 2 of my 15 students drew a version of this Venn Diagram to accompany their essays.

Description:

This Learning Object came to being sort of (In-)organically on the first day of my sophomore level intro to inorganic course. As I always do, I started the course with the IC Top 10 First Day Activity. (https://www.ionicviper.org/classactivity/ic-top-10-first-day-activity). One of the pieces of that In class activity asks students- novices at Inorganic Chemistry- to sort the articles from the Most Read Articles from Inorganic Chemistry into bins of the various subdisciplines of Inorganic Chemistry. As the discussion unfolded, I just sort of started spontaneously drawing a Venn Diagram on the board.

I think Venn diagrams are an excellent logic tool, one that is too little applied these days for anything other than internet memes. This is a nice little add-on activity to the first day.

Your Venn diagram will likely look different from mine. You're right.

Learning Goals:

The successful student should be able to:

identify the various sub-disciplines of inorganic chemistry.
apply the rules of logic diagrams to construct overlapping fields of an Venn diagram.

Prerequisites:

No Prerequisites

Corequisites:

No Corequisites

Equipment needs:

colored chalk may be handy but not required.

Topics Covered:

Bioinorganic chemistry

Coordination chemistry

Descriptive chemistry

Materials chemistry

Organometallic chemistry

Solids & solid state chemistry

Course Level:

First year

Second year

Upper Division

Subdiscipline:

Bioinorganic Chemistry

Coordination Chemistry

f-block Chemistry

Introductory Chemistry

Main Group Chemistry

Organometallic Chemistry

IC Top 10 first day activity

Related activities:

Cool first day activities?

Introducing Inorganic Chemistry - First Day Activities

Implementation Notes:

I used this activity in conjuction with a first day activity LO (also published on VIPEr).

I shared a clean copy (this one) with the students after the class where we discussed this.

Time Required:

10-15 minutes

15 Jun 2018

Developing methodology to evaluate nanotoxicology: Use of density.

Submitted by Tori Forbes, University of Iowa

Evaluation Methods:

I typically evaluate this activity through class participation although the answer key is posted after class to let the students evaluate their own understanding of concepts. The students do know that they will be tested on the material within the activity and usually I have a density problem on the exam.

Evaluation Results:

This activity is designed to give the students more freedom as they move from the first density calculation to the last set of calculations. Within the last set of calculations, they encounter a hexagonal unit cell so that may require some additional intervention to get them to think about how to calculate the volume of a hexagonal unit cell.

Description:

This activity is designed to relate solid-state structures to the density of materials and then provide a real world example where density is used to design a new method to explore nanotoxicity in human health. Students can learn how to calculate the density of different materials (gold, cerium oxide, and zinc oxide) using basic principles of solid state chemistry and then compare it to the centrifugation method that was developed to evaluate nanoparticle dose rate and agglomeration in solution.

Learning Goals:

A student should be able to calculate a unit cell volume from structural information, determine the mass of one unit cell, and combine these two parameters to calculate the density for both cubic and hexagonal structures. In addition, students will have an opportunity to read a scientific article and summarize the major findings, place data in a table, and explain the similarities and differences between the densities calculated in the activity and the experimental values that are reported in the literature.

Corequisites:

No Corequisites

Subdiscipline:

Course Level:

Second year

Equipment needs:

None

Topics Covered:

Extended structure

Materials chemistry

Solids & solid state chemistry

Prerequisites:

No Prerequisites

Related activities:

Will it Float? Density of a Bowling Ball Activity

Investigating the structures of close packed solids in metal sulfide nanocrystals

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Implementation Notes:

I have used this activity in our first semester inorganic chemistry course when we cover solid-state materials. One thing to note is that I do use 2-D projections to describe structures and we cover that in a previous activity. You could remove 2-D projections from this activity if it is not something that you previously covered.

Time Required:

This activity usually takes about 40 to 45 minutes.

Web Resources:

DeLoid et al, 2014, Nature Communications

13 Jun 2018

The Preparation and Characterization of Nanoparticles

Submitted by Kyle Grice, DePaul University

Evaluation Methods:

Students are evaluated on their participation in lab, lab safety, lab notebook pages, and a lab report turned in a week after the last day of the experiment.

Evaluation Results:

This lab was first run in spring of 2016, and again in spring of 2017 and 2018 (a different instructor carried out the lab in 2018).

In general, students do well on the lab report and seem to enjoy the experiment.They often need guidance when interpreting the Analytical Chemistry article and selecting the correct equations. Discussing their values with them in office hours ("does that make sense?") helps them understand their calculations.

A sample lab report that scored above 90% is included in the faculty-only files.

Description:

This is a nanochemistry lab I developed for my Junior and Senior level Inorganic Chemistry course. I am NOT a nano/matertials person, but I know how important nanochemistry is and I wanted to make something where students could get an interesting introduction to the area. The first time I ran this lab was also the first time I made gold nanoparticles ever!

We do not have any surface/nano instrumentation here (AFM, SEM/TEM, DLS, etc... we can access them at other universities off-campus but that takes time and scheduling), so that was a key limitation in making this lab.

While it was made for an upper-division course, I think It could be adapted and implemented at many levels, including gen chem. I do not spend much time on nano in the lecture (none in fact), so this lab was made to have students learn a bit about nanochemistry somewhere in inorganic chemistry. We have one 10-week quarter of inorganic lecture and lab, offered every spring quarter.

This lab takes approximately 2-3 hours if students are well prepared and using their time well, but is usually spread over 2 days. Students are concurrently doing experiments for another lab or two because we have a lab schedule that overlaps multiple labs, and can do these during one day or across two days. The lab space is an organic chemistry laboratory, so we have access to the usual lab synthetic equipment

Students in thelaboratory write lab reports,which are the due the week after the last day of the lab experiment. In the lab report they use their UV-Vis data to calculate information about the AuNP.

The lab has been posted, as well two photos from students' ferrofluids (these were posted with permission on our departmental blog). A rubric has been posted as a faculty-only file. I have also included a student submission that received over 90% on the lab with their identifying information removed. Students write and introduction and need to cite journal articles in their report, so they are expected to do reading on nanochemistry topics outside of the lab period as they write their reports.

I am sure the lab can be improved, this was what i came up with the materials and time I had. I plan on continuing to revise and edit it as time goes on. Any suggestions are very welcome!

Course Level:

Prerequisites:

Corequisites:

Subdiscipline:

Spectroscopy and Structural Methods

Learning Goals:

A student should be able to perform a chemical laboratory experiment safely and follow proper lab notebook protocol.

A student should be able to determine the average size of AuNPs from spectroscopic data and primary literature.

A student should determine atomic and nano-scale information from physical properties.

A student should be able to construct a lab report in the style of an ACS article (Students in my lab wrote lab reports for each experiment).

Topics Covered:

Bonding models: Extended systems

Chemical literature

Descriptive chemistry

Materials chemistry

Quantum Dot Growth Mechanisms

Equipment needs:

For this experiment, you need

The chemical materials - HAuCl4, trisodium citrate,

Heating/stirring plates

Glassware

UV-Vis spectrometer (mainly Vis)

A laser pointer

Strong magnets (the stronger and larger the better)

Related activities:

A Schaaking development of colloidal hybrid nanoparticles

Colloidal Hybrid Nanoparticles

Brief introduction to local surface plasmons (LSPRs) for nanoparticle color

Implementation Notes:

The syntheses are relatively straightforward, although we've had some problems getting "spikes" for the ferrofluid. Anecdotally, adding the reagents and doing the steps faster tends to give better "spiking". Some students just see a blob moving around in response to the magnet, which was fine in terms of their report.

The AuNP synthesis can also be done with an ultrasonicator or by addition of sodium borohydride, among other methods. We don't have them make a calibration curve of chloride addition, but that could be a possibility.

I like having a pre-made solution of a red oroganic dye to shine the laser pointer through to compare versus the laser shining through the AuNP solution.

One year, the AuNP synthesis was going very slow. We realized it was because the Au(III) was diluted in acid, so it was protonating the citrate. Boiling for a while before adding the citrate solution helped fix this problem.

KAuCl3 is also a good source of Au(III) for this lab.

Time Required:

2 hours

Web Resources:

Analytical Chemistry paper relating AuNP size to UV-Vis

3 Jun 2017

Investigating the structures of close packed solids in metal sulfide nanocrystals

Submitted by Eric Villa, Creighton University

Additional Authors:

Barbara Reisner, James Madison University

Catherine McCusker, East Tennessee State University

Janet Schrenk, University of Massachusetts Lowell

Meng Zhou, Lawrence Technological University

Evaluation Methods:

Evaluation methods could include grading as an in-class worksheet, trading with a partner for peer grading or turned in as an out-of-class graded homework assignment.

Evaluation Results:

Currently, this activity has not been tested in a classroom. Please post how your students did!

Description:

This in-class activity is designed to assist students with the visualization of solid-state close-packed structures, using metal-sulfide nanocrystalline materials as a an example system. Students will be asked to visualize and describe both hexagonal closest packed (hcp) and cubic closest packed (ccp) structure types, and isolate the tetrahedral and octahedral holes within each structure type. Lasty, students will be asked to compare and contrast four metal-sulfide unit cells discussed in the paper below.

Powell, A.E., Hodges J.M., Schaak, R.E. Preserving Both Anion and Cation Sublattice Features during a Nanocrystal Cation-Exchange Reaction: Synthesis of a Metastable Wurtzite-Type CoS and MnSJ. Am. Chem. Soc. 2016, 138, 471-474.

http://pubs.acs.org/doi/abs/10.1021/jacs.5b10624

Learning Goals:

In answering these questions, a student will…

...develop stronger visualaztion skills for extended, solid state materials;
...compare the packing sequence of close packed structures;
...locate tetrahedral and octahedral holes in close packed systems;
...count the number of tetrahedral / octahedral holes relative to the lattice ions; and
…determine the number of atoms in a unit cell.

Equipment needs:

The use of software - such as the demo version of CrystalMaker (http://www.crystalmaker.co.uk) or StudioViewer (Esko - app stores) - will be really helpful. StudioViewer can be run on cell phones, tablets, or MacOS devises. CrystalMaker is available for both Mac and PC.

Instructions on using Studio Viewer to visualize structures on mobile devices are available in the learning object, Visualizing solid state structures using CrystalMaker generated COLLADA files.

Subdiscipline:

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Course Level:

Corequisites:

Prerequisites:

Topics Covered:

Related activities:

Visualizing solid state structures using CrystalMaker generated COLLADA files

Solid State Models with ICE Solid State Model Kits

Solid State Stoichiometry Online

X-ray Crystallography

Close Packing Activity

Introduction to Miller Indices

Implementation Notes:

This learning object was developed at the 2017 MARM IONiC workshop on VIPEr and Literature Discussions. It has not yet been implemented.

This could be assigned for homework, but would likely work better in class with guidance.

Time Required:

This will probably take 50 minutes depending on how much work with models you do.

Web Resources:

J. Am. Chem. Soc. 2016, 138, 471-474

3 Jun 2017

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Submitted by Janet Schrenk, University of Massachusetts Lowell

Additional Authors:

Barbara Reisner, James Madison University

Catherine McCusker, East Tennessee State University

Eric Villa, Creighton University

Meng Zhou, Lawrence Technological University

Evaluation Methods:

Evaluation methods are at the discretion of the instructor. For example, you may ask students to provide written answers to the questions, evaluate whether they participated in class discussion, or ask students to present their answers to specific questions to the class.

Description:

In this literature discussion, students use a paper from the literature to explore the synthesis, structure, characterization (powder XRD, EDS and TEM) and energetics associated with the production of a metastable wurtzite CoS phase. Students also are asked define key terms and acronyms used in the paper; identify the goal of the experiments and determine if the authors met their goal. They examine the fundamental concepts around the key crystal structures available.

Preserving Both Anion and Cation Sublattice Features during a Nanocrystal Cation-Exchange Reaction: Synthesis of a Metastable Wurtzite-Type CoS and MnS

Powell, A.E., Hodges J.M., Schaak, R.E. J. Am. Chem. Soc. 2016, 138, 471-474.

http://pubs.acs.org/doi/abs/10.1021/jacs.5b10624

There is an in class activitiy specifically written for this paper.

Corequisites:

Course Level:

Topics Covered:

Electronic spectroscopy

Extended structure

Kinetics

Physical methods / analytical techniques

Reaction mechanisms

Synthesis and reactivity

Thermodynamics

Prerequisites:

General Chemistry

Learning Goals:

In answering these questions, a student will be able to…

define important scientific terms and acronyms associated with the paper;
describe the rocksalt, NiAs, wurtzite, and zinc blende in terms of anion packing and cation coordination;
differentiate between the structure types described in the paper;
explain the difference between thermodynamically stable and metastable phases and relate it to a free energy diagram; and
describe the structural and composition information obtained from EDS, powder XRD, and TEM experiments.

Subdiscipline:

Spectroscopy and Structural Methods

Related activities:

Investigating the structures of close packed solids in metal sulfide nanocrystals

Thinking about Mechanisms of Metal Ion Exchange

Solid State Models with ICE Solid State Model Kits

Visualizing solid state structures using CrystalMaker generated COLLADA files

Solid State Stoichiometry Online

X-ray Crystallography

Close Packing Activity

Introduction to Miller Indices

Implementation Notes:

This learning object was created at the 2017 IONiC Workshop on VIPEr and Literature Discussion. It has not yet been used in class.

Time Required:

50 minutes

Web Resources:

J. Am. Chem. Soc. 2016, 138, 471-474

3 Jun 2017

Quantum Dot Growth Mechanisms

Submitted by Chi Nguyen, United States Military Academy

Additional Authors:

Brian Smith, Bucknell University

Kate Plass, Franklin & Marshall College

Roxy Swails, Lafayette College

Evaluation Methods:

The question document attempted by students in preparation for the literature discussion will be due prior to the in-class discussion. In particular, students' performance on the particle-in-a-box question will be evaluated to assess retention from the previously covered course material. The next exam following the discussion will contain specific question(s) (data/figure analysis) addressing these topics. Students' performance difference between the two will be evaluated. The extent to which students improve their post-discussion understanding of the concepts will direct future implementation.

Evaluation Results:

To be determined. This is a newly proposed literature discussion.

Description:

This literature article covers a range of topics introduced in a sophomore level course (confinement/particle-in-a-box, spectroscopy, kinetics, mechanism) and would serve as a an end-of-course integrated activity, or as a review activity in an upper level course. The authors of the article employ UV-vis absorption spectroscopy of CdSe quantum dots as a tool to probe the growth mechanism of the nanoparticles, contrasting two pathways.

Reference: DOI 10.1021/ja3079576 J. Am. Chem. Soc. 2012, 134, 17298-17305

Corequisites:

Course Level:

Topics Covered:

Electronic spectroscopy

Electronic structure

Kinetics

Physical methods / analytical techniques

Physical properties

Reaction mechanisms

Prerequisites:

General Chemistry

Learning Goals:

Apply the particle in a box model to interpret absorbance spectra with respect to nanoparticle size.

Analyze the step-growth and living chain-growth mechanisms proposed in this paper.

Evaluate the kinetics as it applies to the step-addition.

Recognize and apply multiple scientific concepts in an integrative manner.

Subdiscipline:

Spectroscopy and Structural Methods

Related activities:

Building hybrid nanoparticles

Colloidal Hybrid Nanoparticles

Education Resources at Beloit College - Materials Chemistry, Nanoscience and Solid State Chemistry

Materials Chemistry course

Band Structures, Electronic and Optical Properties of Metals, Semiconductors, and Insulators

Inorganic Chemistry Spectroscopy Tutorial: Theoretical Principles and Applications

Implementation Notes:

Sophomore level implementation: Recommend focusing on select portions (e.g. Figures 1b, 2, 5 with corresponding text) of the paper rather than having students read the entire document. The learning objects focus on select topics, such as particle-in-a-box, reaction mechanism, and kinetics in conjunction with absorbance spectroscopy. This would be a good literature discussion resource for an end-of-course integrative experience that encompasses multiple topics from general chemistry and inorganic chemistry.

Advance level implementation: For an upper division course, incorporate the paper in its entirety early in the course as an assessment on students’ ability to integrate multiple concepts that they should have learned in general chemistry, organic chemistry, and physical chemistry. To enhance the experience, accompanying the literature discussion on this paper with a laboratory experience by repeating the experimental and characterization procedures presented in the paper, and having students' compare their results with published results. This also serves to enhance students’ scientific literacy by critically assessing the quality of the paper.

Excerpts of the paper and questions can be used on a graded event, or as lesson preparation for in class discussion.

Time Required:

In-class discussion takes approximately 50 minutes with students having already read the paper and submitted their responses to the questions.

Web Resources:

J. Am. Chem. Soc. 2012, 134, 17298-17305

27 Mar 2017

Nanomaterials for Carbon Dioxide Reduction

Submitted by Anne Bentley, Lewis & Clark College

Evaluation Methods:

The problems presented here represented half the points on the final exam – I have included point totals to give an idea of the weight assigned to each problem.

Evaluation Results:

Twelve students were enrolled in my course in the fall 2016. The average overall score for these problems was 78%.

For problem 1b, I calculated the oxidation numbers using the familiar general chemistry method of assigning oxygen as –2 and hydrogen as +1. Students recently coming through organic may have some other way to do it, and you may need to provide directions for your students about your preferred method. I think I could have worded part (c) better to try to emphasize the redox processes involved. I wanted them to think of combustion, but I think they needed to be specifically prompted, such as "Give an example of the combustion processes that generate CO2 and trace the oxidation state of carbon through the reaction." Overall my students scored 86% on problem 1.

The second problem (about another method that could be used to measure d-spacing) was fairly hit or miss. Five students got full credit, six students got 3 points, and one got zero. Eleven out of twelve did answer part (a) correctly. I realized as I made this LO that the article says the carbon-based material doesn’t diffract X-rays, but doesn’t actually directly explain whether or not the Cu nanoparticles diffracted X-rays, so you may need to adjust the question to be technically accurate.

Question three (re: surfactants in nanoparticle synthesis) referred back to knowledge from earlier in the course. The overall score was 61%.

Question 4 (define and describe electrodes) was fairly straightforward, and students scored 85%.

Question 5 caused some confusion, as some students missed that I was looking for “carbon-containing” products only. I didn’t count off for that mistake, but it made the problem harder for students who included hydrogen in each box. Overall, students did very well on this problem (89% correct).

Question 6 – again, not too much trouble here (84% correct).

Question 7 – I was surprised that students didn’t do better on this question, as I thought that water reduction was mentioned often in the article. Only three (of 12) students scored 5 points on this problem, and the average score was 53%. This was probably my favorite question, as it foreshadows electrochemistry topics I cover in my inorganic course.

Description:

This literature discussion is based on an article describing the use of copper nanoparticles on an N-doped textured graphene material to carry out the highly selective reduction of CO₂ to ethanol (Yang Song et al., “High-Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle / N-Doped Graphene Electrode” ChemistrySelect 2016, 1, 6055-6061. DOI: 10.1002/slct.201601169). The article provides a good introduction to the concepts of electrochemical reduction, selectivity and recycling of fossil fuels. The literature discussion assignment shared here was used as half of the final exam in a half-credit nanomaterials chemistry course, but could be adapted for use as a take-home or in-class assignment.

Topics Covered:

Chemical literature

Electron transfer

Physical methods / analytical techniques

Corequisites:

Prerequisites:

Course Level:

Learning Goals:

After reading this paper and working through the problems, a student will be able to:

assign oxidation states to carbon and trace the oxidation and reduction of carbon through fossil fuel combustion and CO₂ conversion
describe the role of control experiments in studying the CO₂ conversion presented in the article
define the word “selective” in the context of this research
use the proposed mechanism to explain why the electrode studied produces ethanol in such a high proportion
identify the primary reaction competing with CO₂ reduction for available electrons

Subdiscipline:

Electrochemistry

Main Group Chemistry