The UMD Green Chemistry Initiative seeks to introduce green chemistry to undergraduate students through three courses intended to meet the campus goals for sustainability coursework. These courses will serve a wide variety of students, emphasizing the importance of sustainability, environmental initiatives and green chemistry and green engineering to science majors and non-majors alike.

Objective 1 of 7: Develop Course Syllabi
Task 1A: Review Principles of Green Chemistry and Green Engineering
The project group met in early January to review the Principles of Green Chemistry and Green Engineering and discuss how they could be incorporated into coursework at a variety of levels. The group occasionally returns to this topic to ensure they continuing to consider these principles as they move forward with curriculum design for the three courses.

Task 1B: Draft course outlines
Course outlines have been drafted for Chem 1105, From the Industrial Revolution to Green Chemistry, and Chem 2901, Principles of Green Chemistry. The course outline for Chem 2212, Environmental Chemistry has been modified to reflect the inclusion of a green chemistry unit.

Task 1C: Collect printed and online Green Chemistry resources
Copies of the following texts have been purchased to support the development of Chem 1105 and Chem 2901:

• Green Chemistry and the Ten Commandments of Sustainability, by SE Manahan
• Chasing Molecules: Poisonous Products, Human Health, and the Promise of Green Chemistry, by E Grossman
• Green Chemistry: Theory and Practice, by PT Anastas and JC Warner
• Green Chemistry: An Introductory Text, by M Lancaster
• Experiments in Green and Sustainable Chemistry, by HW Roesky and D Kennepohl
• The text Green Chemistry Education: Changing the Course of Chemistry, by PT Anastas, has been acquired by the UMD Library on behalf of the Department of Chemistry & Biochemistry.

The project group continues to identify additional print and online resources to support development of the three courses.

Task 1D: Create course bibliographies
Draft bibliographies have been developed for all three courses. The bibliographies for Chem 1105 and Chem 2901 have been included in the course proposals submitted to the department.

Task 1E: Draft course syllabi
A draft syllabus for Chem 1105 has been created and will be shared with department faculty at the next Undergraduate Studies Committee meeting for review. A draft syllabus for Chem 2901 has also been prepared, though it will undergo some revisions as a result of discussion with the Undergraduate Studies Committee and the department as a whole.

Task 1F: Departmental review of course syllabi
The syllabus for Chem 1105 is scheduled to be reviewed by the department’s Undergraduate Studies Committee. After comments from faculty on the Undergraduate Studies Committee, the course proposal for Chem 2901 is scheduled for review by the department. Based on comments from that meeting, the syllabus will be revised and reviewed at a future meeting of the Undergraduate Studies Committee.

Task 1G: Finalize course syllabi
Course syllabi will be finalized in late April or early May after final feedback from the Undergraduate Studies Committee and the Department.

Objective 2 of 7: New Course Approval
UMD  has been working to convince the department that one of the new courses, formerly referred to as Introduction to Green Chemistry, should be offered as a 2000-level majors specific course designed to fulfill one or more of the requirements of UMD’s new liberal education program. Tasks 2A and 2B have been completed and final revisions are being made prior to submitting the course proposal to the Swenson College of Science and Engineering (SCSE) Curriculum Committee.

Task 2A: Draft new course proposal for Principles of Green Chemistry
The new course proposal for Principles of Green Chemistry, Chem 2901, was completed and presented to the Undergraduate Studies Committee for their review. After some discussion, it was agreed that UMD should pursue designing the course as a 2000-level course for Chemistry, Biochemistry & Molecular Biology, Biology, and Cell & Molecular Biology majors. The committee also strongly encouraged the inclusion of more toxicology material in the course than was originally proposed. With these revisions the proposal was presented to the department.

Task 2B: Departmental review of course proposal
The revised proposal was submitted to the faculty of the Department of Chemistry & Biochemistry for consideration at a department meeting. The course was approved by the faculty with suggestions for some minor changes, primarily more consideration of the timing of the course, i.e., fall semester, spring semester, summer session, etc.

Task 2C: Finalize and submit course proposal to SCSE Curriculum Committee
The course proposal was finalized with input from the Undergraduate Studies Committee, submitted to the SCSE Curriculum Committee, and received final approval as a new course.

Objective 3 of 7: Establish Courses Within the Liberal Education Program
The tasks of Objective 3 have been completed for Chem 1105 and Chem 2212. The project group is in the process of developing the liberal education proposal for Chem 2901, now that the content of the course has been largely approved by the faculty of the Department of Chemistry & Biochemistry. The liberal education proposal will be submitted to the SCSE Curriculum Committee at the same time as the final course proposal.

Task 3A: Draft liberal education course proposals
Liberal education course proposals for Chem 1105 and Chem 2212 have been written. UMD is currently working on the proposal for Chem 2901 now that the topics covered have been approved by the Undergraduate Studies Committee. The proposal is scheduled for review by the committee. 

Task 3B: Departmental review of liberal education proposals
Liberal education proposals for Chem 1105 and Chem 2212 have been approved at the department level. Pending approval of the proposal for Chem 2901 by the Undergraduate Studies Committee, the liberal education proposal for Chem 2901 will be presented to the faculty.

Task 3C: Finalize and submit liberal education proposals to SCSE Curriculum Committee and Liberal Education Implementation Group (LEIG)
Liberal education proposals for Chem 1105 and Chem 2212 have been submitted to the SCSE Curriculum Committee and the LEIG. Both groups have approved the courses for inclusion in the new liberal education program as sustainability courses. The proposal for Chem 2901 will be submitted to the SCSE Curriculum Committee, and will be passed on for consideration in the liberal education program after approval at the college level.

Objective 4 of 7: Develop Lesson Plans
Work is ongoing on task 4A. Significant work has been completed on lesson plans for Chem 1105, though work on Chem 2901 has been slower. In part this is the result of the redesign of the course in March to focus on it being a course for Chemistry and related majors, rather than as a 1000-level introductory course.

Task 4A: Draft lesson plans
Development of lesson plans for Chem 1105 is underway. Based on a highly-detailed course outline, work is being done on collecting and developing materials for discrete units within the course. No progress to report on these tasks: Conduct peer review with Undergraduate Studies committee and department head; finalize lesson plans.

Objective 5 of 7: Develop Green Chemistry Experiments
Task 5A: Draft experimental procedures
Discussions on potential “green” experiments for inclusion in Chem 2212 have begun; drafting new experimental procedures has not yet begun in earnest. No progress to report on these tasks: Purchase necessary supplies; testing and validation of experimental procedures; finalize experimental procedures.

Objective 6 of 7: Reporting
Semi-annual report has been submitted.

Objective 7 of 7: Develop Course Assessment Tools
It is anticipated that most of the work on this objective will occur between May and September of 2012.

The goal of this project is to design a renewable resources polymer experiment suitable for adoption in the sophomore level (and up) organic chemistry laboratory course. Since the purpose of the course is to teach modern chemistry relevant to the daily lives of students, green chemistry principles must be included in the curriculum to illustrate how scientists are aggressively seeking to tackle the issues of sustainability and environmental impact in the chemical industry.

Collaboration was established with Professor Marc Hillmyer in November and a first year graduate student was hired to perform the research. The goal was to modify the recently published polymerization chemistry involving δ -decalactone to conditions suitable for the less stringent environment of the teaching labs. The student began experimental work in January and has accomplished an exceptional amount of research towards the project goals which is summarized below.

Catalyst Studies
The majority of the research has focused on finding a suitable replacement for the TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) catalyst used in the Hillmyer publication. This catalyst is expensive and sensitive to reaction conditions; both exposure to air and water. Attempts to emulate glove box results on the bench top with unpurified commercially purchased δ-decalactone proved detrimental to polymer formation. Therefore a wide range of catalysts both basic (DBU, DMAP, DBU + thiourea, DMAP+DMAP/HCl) and acidic (p-toluenesulfonic acid monohydrate, diphenylphosphate, tartaric acid, HCl in ether, triflic acid, silicon supported propylsulfonic acid) were explored. Those demonstrating the highest potential for flexibility and success are the HCl in ether, (commercially available and inexpensive) and diphenylphosphate (more expensive; but green qualities). Kinetic studies using size exclusion chromatography (SEC) and 1H nuclear magnetic resonance (1H NMR) have shown that HCl in ether polymerizes the δ-decalactone to 85 percent conversion in approximately 48 hours to a viscous liquid that could be characterized by 1H NMR end group analysis. Studies are underway, as described below in using this polymer in the formation of a block copolymer with lactide.

Initiator Studies
Though the 1,4-benzenedimethanol is an efficient initiator for the polymerization reaction, several alternatives were studied with the goal of finding a greener replacement and/or a polymer with physical properties resembling more of a gel, semi-solid, or elastomer. Also, the creation of an experiment with a guided-inquiry component that allowed groups of students to use different initiators and compare the characteristics of the polymers produced would add a valuable pedagogical dimension to the experiment. Towards that end, glycerol (natural, ubiquitous, and biodegradable) and pentaerythritol (also biodegradable) were studied and shown to initiate the δ-decalactone ring-opening polymerization under the glove box conditions. When the reaction conditions for the teaching experiment are finalized, all three initiators will be revisited to evaluate their suitability for incorporation.

Cross-linked or Block Copolymer Formation
The δ-decalactone starting material is a clear, high-boiling liquid having the odor and taste of sweet coconut which, upon polymerization, results in a very viscous, opaque material. Though this transformation is visible and can be quantified by H NMR, the formation of a gel, semi-solid, or rubbery material would add student enjoyment, the ability to test some physical properties, and a visualization of how such a polymer might have commercial application. Therefore, several strategies for increasing the molecular weight and complexity of the end polymer were investigated.

Attempts to react the δ-decalactone polymer with maleic anhydride as a potential crosslinking unit were unsuccessful and abandoned. Next, the reaction of the δ-decalactone polymer with boric acid in hopes of producing trialkylborate coupled polymer chains was attempted, but resulted in polymer degradation. Success was observed with methylene diphenyl diisocyanate (MDI) as a cross-linking agent and an elastic, rubbery material was obtained with malleable properties. However, the toxicity of this reagent is cause for concern in the teaching laboratories.

Refocusing on renewable starting materials, it was decided that preparation of a block copolymer using lactide should be further studied following the preliminary reports in the original paper. It was reconfirmed that a δ-decalactone /PLA coblock polymer could be synthesized using the TBD catalyst conditions. However, the acid catalysts found to be effective for δ-decalactone polymerization, did not catalyze the polymerization of lactide to produce block polymers. Triflic acid, previously reported as an effective catalyst for lactide polymerization, also did not catalyze the addition lactide to telechelic poly δ-decalactone. The current strategy is to attempt the δ-decalactone polymerization using the HCl/ether conditions, remove the HCl, and attempt the block polymerization with lactide by the addition of a basic catalyst known to produce PLA polymer.

To date all objectives and tasks that should have been completed by this time have been done. The green general chemistry lab was implemented during winter semester rather than the spring in order to disseminate the results at spring conferences.

Objective 1: Plan and develop a green chemistry lab for general chemistry focusing on freezing point depression.

Objective 1 has been completed. A lab procedure has been chosen and tested that uses fatty acids instead of halogenated hydrocarbons to test colligative properties. A student procedure and worksheet has been created for this lab along with a pre/post test to test student knowledge of chemical principals. This has been completed before the proposed date so it can be disseminated at local spring chemistry conferences.

Objective 2: Plan a green chemistry project for organic chemistry that requires students to compare the greenness of two reactions.

Guidelines were prepared to help students choose reactions to study for their green chemistry project. Students will do a three step synthesis of their choosing. For one of the steps they will have to use an alternative reagent. For another step they will have to use an alternative solvent. For those reactions that they do two different ways the students will be required to green metrics using the chart below. A rubric was created to evaluate student performance on these independent projects. A pre/post test was also created in order to evaluate the effect this project had on students understanding of green principals.

Objective 3: Execute green general chemistry lab.

The green general chemistry lab planned in Objective 1 has already been implemented in labs during the third week of class of the winter semester. Both the pre and post test were administered.

Objective 4: Execute green organic chemistry project.

A pre test was administered to evaluate student awareness of green principals before undertaking their green synthesis project. Instructor has met with students to discuss the feasibility of their projects and worked with them to make appropriate adjustments. The necessary chemicals have been ordered and the student began week one of the five weeks they have to work on their targets.

This project will introduce the concepts of green chemistry, green engineering, and lifecycle analysis into the General Chemistry (freshman), Analytical Chemistry (junior), and Composite Materials Engineering (freshman, sophomore, junior) curriculum, through lab exercises, lecture material, and student research on biodegradable polymers.

Three students have been recruited to work on this project, one in engineering and two in chemistry. Several different ASTM and ISO methods were tested for their potential to actually see measurable degradation within the constraints of time and equipment present in both the General and Analytical curriculum. Four of these worked very well for measuring the degradation of polylactic acid (PLA), the principal component in “biodegradable trash bags”.  They are: (1) a cumulative measurement respirometric (CMR) system, (2) a gas evolution tests (GET) system, (3) a gravimetric measurement respirometric (GMR) system, and (4) Infrared (IR) signal changes over time. All four systems showed similar trends of biodegradation for PLA films and at the end of the 67th day the mass loss was 22.37±1.9% averagely, the concentration of CO2 (an indicator of conversion of the polymer to its constituent atoms) in a sealed chamber significantly increased, and the IR signal of the hydroxyl bond (indicative of degradation) declined.

Because the loss during an approximately 10 week time period is significant (~22%), it is believed that typical students in a General or Analytical Chemistry course will see degradation despite inexperience and general lab error.  In order for an experiment to be successfully incorporated into the curriculum, it must be robust enough for most students to get the expected results. As far as the techniques employed, the CMR, and GMR tests would both be well suited to be in the General Chemistry curriculum based on the chemistry displayed. Furthermore, reaction rate’s dependence on temperature is a topic covered in the General Chemistry curriculum. It is envisioned that students in the General Chemistry class will do this degradation experiment both at room temperature over the course of seven weeks and at an elevated temperature over a shorter time period so that students can see first-hand how the degradation rate of a biodegradable plastic is dependent on temperature. Work to develop this temperature dependence portion into the General Chemistry lab will begin this quarter.

The GET and IR tests, because of the techniques employed, may be better suited to be in the analytical curriculum. In addition, several ways to monitor changes in molecular weight of the polymer are currently being explored. It is expected that a polymer’s molecular weight will decrease as it degrades.  The primary technique to monitor changes in molecular weight this quarter was a technique based upon changes in refractive index and fluorescence based on the paper “Spectrofluorimeters as Light-Scattering Apparatus: Application to Polymers Molecular Weight Determination” which appeared in the Journal of Chemical Education in March of 1995. There have been some hurdles with adapting this for biodegradable polymers because the polymer needs to be in solution and finding a suitable solvent to dissolve the biodegradable polymer has been a challenge. This quarter this method for measuring molecular weight will continue to be pursued and, as necessary, another technique to measure molecular weight may be explored.

The results of this work were presented at the 6th annual Celebration of Student-Faculty Research and Creative Scholarship, Winona State University, April 12, 2012 in two separate posters. One of the student posters (Li) won an award as one of the best posters at the entire celebration.