Limonene, part 1

November 6, 2008 1:10 pm

We’re starting a new lab in O-Chem this week: Extraction of a Volatile Oil from Orange Peels via Steam Distillation.

In layman’s terms: we’re taking the stuff that smells good out of the orange peels by boiling it off. 

The major compound responsible for the orange smell in peels is a volatile oil called “Limonene”, and is also found in lemons. Interestingly, the enantiomer (more on that in a minute) of this compound is not palatable at all (it has an odor similar to Turpentine).

Briefly, an Enantiomer is a mirror-image of a molecule. These 3-d arrangements behave differently (the case study always used is the Thalidomide tragedy) and thus interact differently with the smell receptors in our noses.

d-limonene l-limonene

The enantiomers of limonene, in stick structure form, are pictured to the left. 

They may not look like mirror images, but I just need you to trust me on this. (If you were to make up a MolyMod model of it, you’d see what I mean) You may think that they look identical except for that the left one has a thick black line towards the bottom and the right one has a dashed line. 

In organic stick structures, thick black lines like that indicate a bond whose subsitiuents are coming TOWARDS you, and dashed lines indicate a bond whose substituents are receding into the paper. So the left side one, imagine that the /\\ part at the bottom is coming towards you.

Side note: “d” and “l” indicate which enantiomer is being referred to, and are necessary for drawing the structure correctly. “d” is from the latin “dextrorotatory”, and “l” from the latin “laevorotatory”. [Read more]

If you’ve ever had a citrusy-flavored alcoholic beverage, you may have seen the  bartender “zest” the orange peel into the drink as a garnish. I always used to wonder why they would zest the PEEL instead of just squeezing some juice into it. 

As it turns out, the peel contains the highest concentration of d-Limonene in the orange, so zesting is the easiest / most effective way to get that volatile oil out. 

Also contained in the orange peel are the compounds “Octanol” (like “Octane” found in gasoline, except with a hydroxyl (-OH) group on the end of the chain, making it an alcohol), and “Carvone“, a compound derived from Limonene (via Oxidation).

Carvone is another interesting case like Limonene: its flavor depends on which enantiomer you consume. Fortunately, they are both non-toxic and (in my opinion) tasty. 

The “R” orientation (For the purposes of this blog post, “R” = “d” and “S” = “l” — pardon the confusion) is a major contributor to the flavor of spearmint oil, and the “S” orientation is a “principal constituent” of caraway seeds.

Through oxidation, we can produce Carvone from d-limonene. (If you compare the structures, you’ll notice that the only difference is that extra “O” doublebonded near the top of the molecule.) I suspect that leaving lemon or orange peel out in the open air will cause it to naturally oxidize (via an SN2 reaction), and we could certainly test for this by leaving the peels out and running an FTIR scan on the extract, looking for ketone peaks (that “O” double bond attached to a secondary carbon).

At this point, we are working on developing the procedure. I’m pretty sure that our lab group will be using a distillation apparatus (the big ol’ macro variety) to try and steam off some of the orange oil. The thing I found interesting was that all the sources I consulted (admittedly: all via google) said that orange oil has a boiling point of 176 C — we’re not going to get temperatures that high with our apparatus. I suspect that the heterogeneous mixture (the orange oil is non-polar, and we’ll be mixing it with water, a very polar solvent) may have a decreased boiling point, or that it will piggy back on over or something. We’ll see. 

If it works, we’ll see a thin film on the distillate beaker, if not, we’ll know to look into the short-flask. I’ve got lab again on Thursday afternoon, so we’ll see what happens!

School: Week 1

January 18, 2008 8:06 am

First week of classes (for me) is over. I’m taking the following courses:

  1. Organic Chemistry II with Lab component
  2. Introduction to Biology (aka “Biology 107″)
  3. Protein Purification / Synthesis

First off this week was Organic II. My professor, Dr. Dhawale (”dah-WAH-leh”) had a medical procedure done at the end of last semester and is still out recovering. So our interim instructor for this class is Prof. Errol Huffman. I had never had Errol before, but he seems like a really neat guy. He’s a taller, skinny fellow, about my height, mostly balding with thin hair around the sides. He wears thin-rimmed glasses and has the kind of smile that  you can see on his mouth and in his eyes and face. He seems very cordial and has an engaging speech pattern.

Our first day of class he passed out an “eye-opener” quiz, designed to remind us of the material we learned in the first semester. Things like SN1/SN2 reactions, stereochemistry, free-radical halogenation, nomenclature etc.  Most of the people in class I recognized from Organic I, although there were one or two new faces. The girl I sat next to, a 20-something brunette with freckles that reminded me of Punky Brewster, was having trouble recalling some of the material from semester 1. She admitted that she’s a “cram-and-forget” student, angling for a Biology major. We compared notes with the two girls sitting in front of us — some of the questions were a bit ambiguous, which could have been caused by Dr. Dhawale’s English-as-second-language idiosyncrasies, or perhaps because of medication he’s on right now, or perhaps some combination of the two.

I chatted with a few other people in class. There was a guy and a girl I recognized from Organic I that talked with me about the Biotechnology program, a major that I’m considering as my next major after I graduate in the fall.

Thursday’s class was a proper class, although we mostly sat in the darkened room gazing at a Powerpoint slideshow reviewing the last chapter we covered in Organic I. The other half was a cursory introduction to Chapter 8, which deals specifically with Alkenes and Alkene synthesis.  Errol peppered the introduction with some interesting side-trivia bits. We learned Markinokov’s Rule, did some practice equations, and then went over to lab.

Organic II Lab is neat, although somewhat intimidating. I partnered up with a woman from my Organic I class; I think her name is Kim, but I don’t know for sure. I hadn’t taken Organic I lab and so I was still quite the greenhorn with respect to the practical material. We chatted for a bit: Kim told me that she was auditing Organic I to refresh on it for Organic II this semester, which she had also already taken. Apparently she and her daughter had a shitstorm of medical problems all hit at once at the end of the semester for Organic II — she withdrew on the last possible day to focus on her other courses, and then retook Organic this semester. So she was very familiar with what we’d be doing, which was reassuring, because I had no farking clue.

The first thing we did was use the “ITFR” [That's "FTIR", kemosabe -- Ed.], which I think stands for “Infrared-Beam-Shooting-Through-Chemicals-Reader.” Basically it’s a large grey device, probably about 2′ on each side and 1′ tall, connected to a computer. You prep this little metal widget with some crystals and a chemical you wish to read, slide it into a compartment in the front of the ITFR, and it shoots Infrared light through the chemical and reads the diffraction. We did Diethylamine (C2H5)2-NH2, I think). The graph prints out a curve that looks sort of like a tremor sensor: lots of squiggles, a few dramatic dips. The dips are apparently what’s important. We’ll use this later on the semester for qualitative analysis of unknowns.

Back in the lab, we posted the Diethylamine (functional group: Amine) on the corkboard, grabbed some lab materials (test tubes, gloves, pipettes, etc.) and started doing some practice qualitative analyses of known chemicals. The lab manual has this binary-tree, kind of a 20-questions for chemicals: “Are you soluble in water? Are you soluble in Sodium Hydroxide (NaOH)? If I  fuse you with sodium, do you produce Nitrogen or Sulfur as a byproduct?” We use known chemicals for practice so we can practice the procedure and see if we get the expected result. It’s pretty tough — checking solubility on two clear chemicals is difficult because the layer isn’t always distinct. (imagine putting clear vegetable oil and water into a testtube, and then trying to locate the layer) I did learn two things though: (1) It’s only insoluble if it’s layered or forms a precipitate. I incorrectly identified 1-Butanol as insoluble in water because it was cloudy for a moment. Errol pointed out that cloudy simply meant it was hydrating, but slowly. Oops! (2) If the concentration is strong enough, a chemical can solvate anything. So using 3M Hydrochloric Acid when it calls for 5% HCl might not accurately reflect solubility.

On Tuesday and Thursday,  I had Biology. This time Errol was the designated Instructor for the class. The classroom is an average sized classroom, with lab benches around the perimeter and several 3 or 4-seater desks facing the front. Diagrams, posters, and a really neat large-scale DNA model adorn the walls. A body shower and eye-wash station are in the back, for those extremely-rare occasions of fire or chemical splash.

The course content seems really cool. It operates in a rather innovative (and apparently experimental) format:

  1. We form into groups (4-5 people each)
  2. Discuss the chapter we just read as groups
  3. Discuss the chapter as a class (still in our groups)
  4. Separate and take a quiz individually
  5. Re-group and take the quiz as a group
  6. Receive graded quizzes and compare with the key, at which point we are allowed to appeal, in writing, any answers where we differ from the key.
  7. Still in groups, do lab work

The appeal process is especially interesting. Errol told me on Thursday that occasionally one of the other Prof’s (Sabine) will intentionally mark an answer on the key incorrectly so that it must be appealed. On Tuesday, I successfully recovered a point by identifying that Proteins are predominantly composed of Carbon, Oxygen, Hydrogen, and Nitrogen where they key identified the fourth element as Sulphur. Go me. :)

Errol counted us off by threes and we all coalesced into our individual groups. Mine was composed of myself with three other people. Gary, an gentleman in his 40’s, is an EMT/First Responder that is taking classes with hopes of getting into the very competitive nursing program. Another fellow, a tall youth whose name escapes me, is dressed in urban garb. He’s as Biology major, is on the basketball team, and missed most of the season so far due to a knee-injury. He said that a good portion of the school’s team has been injured this season. The third person is a young married woman, around my age, although I’m not entirely sure what her major is.

For our first lab, our group had to pick 2 of 6 or 7 listed body traits (height, arm length, etc.) and experimentally determine if they were related. The idea is to get our feet wet with experimental design, procedure, and data collection / presentation. Our group chose height and foot length. Our hypothesis is: Does being tall grant larger feet?

On Thursday evening, we collected our data. When I get it all tabulated and graphed, I’ll post it up here (in case anyone is interested). To be fair, our sample size was 11 people, so the conclusion won’t be terribly conclusive.

The last class I had was Protein Purification, on Thursday midday. The classroom was the same room as my Organic II lab, but was much less populated. Most of the faces were familiar: people from Organic I and II, and there were 1 or 2 others that I didn’t recognize.

This class seemed very intimidating at first. Errol was acting as Dr. Dhawale’s substitute again, and to kind of review over some fundamentals, he did some transparencies and a crash course in protein composition: what proteins are composed of, how they are chemically formed and structured, what elements comprise individual amino acids, etc. It was simultaneously interesting and frightening. The scary aspect was mostly because I had no idea of the context of the course: Is it all independent study? Will we be guided? How much independent research do we need to do? Errol later told me that Dr. Dhawale will be going over the procedures and examples with us, when he returns.

My prognosis of difficulty for the semester:

Organic II > Organic II lab > Protein Synthesis > Biology

We’ll see if I’m correct…

School’s Out!

December 14, 2007 3:05 pm

Yesterday, around 6pm, I finished my last project for one of my classes, meaning that I am now officially done for this semester.

Cholesterol It’s been one helluva semester - first time I’ve done a full-time schedule (12 credit hours) in a few years. Compound that with a baby, and the fact that three of the courses were 300-level courses, and you’ve got a formula for disaster!

This semester I had four classes:

  • Organic Chemistry I (Chem 341, Lecture only)
  • Distributed Computing (Info 320)
  • Information Technology for Management (IIM 300)
  • Linear Data Structures (CompSci 243)

By far, Organic Chem was the hardest of all of them, and I successfully pulled off a B+ in that class. While I wouldn’t have minded an A-grade, I am completely happy with a high B. Distributed Computing & Linear Data structures were both somewhat difficult — in the former I had to learn the Python scripting language on the fly (I had never used it before), which was very frustrating. In the latter, I learned Java, a really awesome object-oriented programming language. The hardest part about that class though was learning the running times for all the algorithms. O(n^2) and O(n log n) and O(2^n), it was a lot of memorization that I only half-did.

The IT for management class was basically a discussion only course. Every class, people would present topics and we all would discuss them. It was pretty interesting — it definitely made the book more entertaining.

In other development, I am now double-majoring: My Bachelor’s degree will be a General Studies degree (or as my wifey calls it, a “degree in nothing”), and I will also be getting an A.S. in Chemistry. I’m considering a minor in Biology as well. I would major in it, but I would be stuck in classes for at least another 2 or 3 years minimum waiting for the classes I need to cycle in.

I saw the degree requirements for the Biotechnology program and became very envious. Genetics? Cell biology? Sign me up! It’s unfortunate it would take me too long to complete it. I suppose I can look into that for my graduate program?

Next semester’s classload, also full-time, is:

  • Organic Chemistry II (Lecture & Lab)
  • Intro to Biology (a pre-req for pretty much every other bio course)
  • Chemistry Topics: Protein Synthesis

Protein Synthesis should be neat - it’s my Chemistry professor that teaches it, and he’s a neat guy. He said we’ll all pick a protein and learn how to artificially create it from other base chemicals and whatnot. It’s strictly lab and should be a light workload compared to the other courses. (fingers crossed)

But for now, I’m going to enjoy a well-deserved break from school.