Aqueous Chemistry Rules!

Apparently, polyoxometalates have been found to be "very powerful inhibitors of a specific protein kinase, CK2, an enzyme that is overactive in a number of cancers." I say apparently, since it was reported in the journal "Chemistry and Biology," a journal to which I do not have access. I only know of the study because of this press release. Polyoxometalates are large anionic clusters generally consisting of transition metals and oxygen. A good description can be found here. This study is of particular interest to me since I have worked with polyoxometalates of V, Mo, and W in the past. I admit to having lost touch with them over the years, mostly because my work at that time involved aqueous polymetalates (I love aqueous chemistry!) and subsequent research on polymetalates had begun turning to derivatives which were only soluble in organic solvents. So it was with some delight that I discovered that aqueous polyoxometalates had reappeared in the literature. Unfortunately, the press release gives very few details about the particular polyoxometalates involved or what kind of chemistry is occurring. In fact, I am only assuming that these are aqueous species since they are being used in biological systems. In any case, since aqueous chemists seem to be vastly outnumbered by non-aqueous chemists (I was definitely in the minority in the U of Illinois Inorganic Chemistry department), I am always happy to see a paper on aqueous chemistry that is at least somewhat mainstream.

Are there any aqueous inorganic chemists out there reading this blog?
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My family and I will be leaving tomorrow to visit my parents in Springfield, Missouri for 5 days. I've talked about Springfield before, so it's always a fun trip, but I won't be updating the blog until next week. In the meantime, here is the previously promised picture of my garden (or at least a small part of it).

Wii

Well, we finally broke down and bought a Nintendo Wii last weekend. "Broke down" probably isn't the most accurate description since everyone in the family has wanted one since last Christmas. It's just that we had originally planned to wait until the fall. But my wife discovered that a supply had arrived at the local Target and so I was dispatched to grab one before they disappeared. This is our first game console. I spend all my gaming time playing on the PC, in part because I really don't like gamepads. I'll take a mouse/keyboard combo everytime (old school?). But I think the Wii might be a good way for me to become proficient with a gamepad.

Anyway, the kids love it. And my six year old son quickly discovered you don't have to be near the TV to play. The sensor system can pick up the signals from the Wiimote all over our house, so he runs around various rooms throughout the house playing games like "bowling" with no video feedback. It's a little disheartening to watch him get a strike when he's somewhere in the basement while you're standing right there in front of the TV and still haven't gotten a strike all game. Annoyingly, he actually has the nerve to get upset when he loses the game. Oh well, in the meantime, I'll be looking for some good chemistry-based games.

Non-Standard Laboratory Equipment

Over at The Chem Blog, Kyle describes his development of a photochemical light source built out of items purchased at the local Wal-Mart. I'm sure we all have stories about the ingenious use of items obtained from outside the laboratory environment. Years ago, when I was working on "Better Ceramics Through Chemistry" projects in the metallurgy department (yes, I was exiled to the metallurgy department for a while. I'll discuss that in more detail at another time.), my co-worker used a wet isostatic press to compress ceramic materials in preparation for high temperature sintering. Basically, wet isostatic pressing consists of sealing the material in a flexible waterproof container, removing as much air as possible from that container, placing it into the oil reservoir of the press, and then letting the press pressurize the oil until the ceramic material is compacted to the desired density. Unable to find a suitable container from the usual lab catalogs, he eventually took a trip to the drugstore and bought some condoms. Apparently they worked like a charm in the isostatic press. Unfortunately, he ended up paying for them out of his own pocket since he didn't have the nerve to submit an expense report to upper management.

Where Has All the Ammonia Gone?

This weekend, I was filling a bottle with some copper nitrate crystals for display in my office at home. They are a really beautiful shade of blue and as long time readers of this blog know, I love bright, pretty colors. My daughter wanted to dissolve a few crystals in water to make a blue solution, and so we did, but the solution was disappointingly pale. Sure that I could solve the problem, I went to the laundry room where we keep many of our household cleaners, hoping to find some ammonia which we could add, since Cu((NH₃)₆²⁺ is much more intensely colored. To my dismay, I found that we do not carry ammonia any longer (assuming we ever did). So I rummaged through the various cleaners, sure that at least one of them was ammonia-based. The glass cleaning solution looked promising, but the label stated "ammonia free formula" so that was out. Finally I found some Windex with "Ammonia D," what ever that is, and tried adding that to our copper solution. No color change occurred, although a precipitate did form. Acknowledging my defeat, I told my daughter I'd bring something back from the lab on Monday.

Today, a few pinches of ammonium carbonate did the trick and restored my standing as a chemist in our home again.
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Instructors at the University of Nottingham have put together a series of short videos describing each element of the periodic table . I haven't had the chance to go through all the elements yet, but it's definitely worth a look.

Chemophilia - Part II

Continuing in the vein of Wednesday’s chemophilia post, some non-chemists enjoy doing chemical experiments on their own bodies. For example, the LA Times has an article describing the current fad of self-chelation therapies. For those that don’t know, a chelating agent is a molecule that binds to metal ions at multiple sites, generally leading to a very stable metal-chelate complex. Although chelation therapy is performed by doctors intravenously to remove metals from the body in cases of severe metal poisoning, there are various “health” promoters who suggest that ingesting small amounts of these same chelating agents can also remove low levels of toxic metals. There are a variety of reasons why self-chelation is a scam and possible health risk, but that doesn’t stop the websites from selling these concoctions.

A website named "Vibrant Life", for example, describes the benefits of self-chelation. (Sounds pornographic, doesn’t it?). A check of their chelating product ingredient list reveals that it contains a standard mix of vitamins, minerals, amino acids, and 500 milligrams of EDTA as the chelating agent. Considering how poorly EDTA is absorbed through the gastrointestinal tract, you might as well drink Mountain Dew if you want to ingest EDTA. On the other hand, the makers of Chelorex say that oral EDTA chelation is a scam, which is why their self-chelating formula has no EDTA in it. In fact their product doesn’t appear to have much in the way of metal chelators at all – just vitamins, minerals, and amino acids. Hmmm…. Where’s the FDA when you need them?
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Obligatory story from the past about self-chelating… well, sort of, anyway.

A professor back in grad school once told me about a friend of his who was using the old school habit of mouth-pipetting. As you might have guessed, he accidentally swallowed some of the reagent, which turned out to be rather poisonous. (I want to apologize here since I don’t really remember which chemicals were involved, so bear with me.) He immediately began to panic and proceeded to rush from lab to lab yelling for someone to help him. Since no one responded quickly enough for his liking, he ran back to his lab where he had the bright idea of swallowing a second chemical to counteract the first. Again, I don’t remember which chemical it was, but it would have precipitated out the first reagent. Oh, and it was poisonous too. But he drank it anyway.

After calming down a bit, the chemist within began to reassert itself and he wondered if these 2 chemicals would really react at the low pHs present in the stomach. Calmly, he performed the calculations and found that, yes, they would indeed not react under those conditions. So now he had 2 poisons in his system. As far as I know, he ended up suffering no ill effects.

Woo hoo! I made it through an entire post about chemistry and didn't use a single subscript or superscript. Good times, indeed!

Chemophilia

A couple of weeks ago, I posted about Chemophobia, the irrational fear of chemicals (and possibly chemists too, I suppose). Now I’d like to talk about the opposite extreme, Chemophilia, which I define as a non-chemist’s desire to be a chemist. Let’s face it -- who wouldn’t want to be a chemist? One of the simplest methods for fulfilling those types of dreams is by the practice of chemical collecting. I recently read an article about a doctor in Ohio (recently deceased) who had been collecting chemicals in his garage as a hobby. His daughter was totally unaware of this hobby until she found the chemicals and decided to call the fire department, resulting in significant media attention. Element collecting is not an uncommon hobby, and there are plenty of websites devoted to the practice. Here is one example. (I collect elements myself, but then I’m a chemist.) More surprisingly, there are web sites and organizations devoted to the practice of performing chemistry experiments at home. Not just simple experiments with pretty color changes, but major synthetic procedures. Some of these web sites let you order chemicals and chemical equipment, while some will tell you how to obtain the chemicals on your own. There are discussion groups which give step by step instruction for the synthesis of various compounds – some of them rather hazardous. Sciencemadness is one such site, but there are lots more. Since I’ve been toying with the idea of trying some simple experiments at home, I’m glad there are sources like this available. But it worries me when I think about non-chemists attempting some of the procedures I’ve seen online.

Cell Phone Rant

Warning: this is a non-chemistry related rant.

Last year, I switched from a monthly cell phone plan (Verizon) to a fixed rate per minute plan (AT&T). My wife had been tracking my cell phone use patterns and had convinced me I would pay less on a pay per minute plan. So far she has been right, although as more and more people at work are beginning to call my cell, that advantage is beginning to disappear. The increase in work related calls is not totally unexpected since I am currently existing in a hybrid state, as I resonate between 3 different locations and the cell is often the easiest way to catch me.

Pay per minute plans tend to make you acutely aware of the length of your calls, especially since AT&T graciously sends you a note after each call telling you how much you just spent. These plans are also the source of much aggravation as you notice all the little things the phone company does to drain your phone card of money as quickly as possible. I don’t mind that AT&T rounds calls up to the next minute, but how do they manage to make sure my calls always last X minutes and 1 second? Slightly more annoying is the phone’s user interface, which is designed to maximize the number of times one can accidentally sign on to the AT&T web store (for which you are charged). And nothing is more annoying than hanging up the phone, seeing the “call ended” message, and then a second or two later seeing a “call resumed” message as the timer begins counting again. WTF? The other party has already hung up. Why is my phone reinitiating the call?

However, these minor annoyances are not why I am writing today. My rant is directed at the callers themselves -- in particular, two people at work that are most responsible for my phone card drainage. It’s not just that they constantly call with no real purpose in mind (Hello! The company does have email, you know?). The real problem is that these two guys simply don’t know how to end a phone conversation. Seriously, phone calls that should barely last a minute drag out for 5 or 6 minutes because they can’t bring themselves to say goodbye.

Cell Phone Drainer (CPD): “Ken, I’ve got those samples you wanted.”
Me: “Great, I’ll come on over to pick them up.”
CPD: (Pause……) “I didn’t have any trouble making them.”
Me: Were you expecting any trouble? You’ve already made dozens of them.”
CPD: (Pause…..) ”No, I just wanted you to know that I didn’t have any trouble.”
Me: OK, I’ll come on over right now.”
CPD: (Long pause……) “Anything happening over in your area?”
Me: “Uhhh, no. Thanks for making the samples. I really need to start working on them.”
CPD: (Pause…..) ” Do you want to come over and get them now?”
Me: “Yes, I’m on my way. Thanks.
CPD: (Long awkward pause….) ”I’ll be at my cubicle.”
Me: “Yes, I know.”
CPD: “Have you been enjoying the weather lately?”

I start watching the timer on my phone.

Me: “It’s been okay. OK, I’m leaving now.”
CPD: (Pause…..) ”The samples should all be fine, I didn’t have any problems.”
Me: (Coworkers in nearby cubicles begin to notice my desperation) “Ummm, I really need to use the bathroom, so I think I have to go now.”
CPD: “You want me to leave the samples at my cubicle?”
Me: “Yes!”
CPD: (Longer pause….) “How do you think the project is going?”
Me: “I think I just heard an explosion coming from the lab. I should really go.”
CPD: (Pause…..) “Do you want a printout for the samples?”
Me: “I’m sure I hear screaming. I should really go now. Talk to you when I get there.”
CPD: “OK….If there’s nothing else…I’ll be at my cubicle….with the samples. You can pick them up anytime. Are you coming over right now?”
Me: “Bye.”
CPD: (Pause….) ”Uhhh… bye…. I’ll… I’ll talk to you later."
I hang up and my cell phone tells me I've been on for 4 minutes and 1 second. Damn!!!

I tend to ignore his phone calls now but then he just leaves messages which require me to call my voice mail (for a fee) to erase. Anyway, thanks for reading. I feel much better now.
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For all those analytical chemists who managed to make it through that rant, here is a link to a music video for those interested in automated pipetting. Woo hoo!!

Disappearing Elements? - Part II

I’d love to say it’s great to be back home, but I can’t do it with a straight face. Although our vacation only consisted of driving to the other side of the state and staying in Saugatuck (near Lake Michigan) for a few days, it was one of the most relaxing few days I’ve ever spent. Going back to work on Monday was definitely a challenge. Diligent chemist that I am, however, I made sure to practice my chemical techniques throughout the vacation. Examples would include:

1. Oxidizing a fair bit of ethanol with ADH (alcohol dehydrogenase). (Note to self -- consuming ice cream after a bottle of wine is no longer recommended).

2. Altering a large number of my DNA molecules via UV radiation.

3. Witnessing many colorful pyrotechnic explosions. Unfortunately, I’ve noticed that I spend more time trying to guess which elements are being used to generate the colors than I do just ooohing and aaahing like everyone else. At least I’m not trying to make my own fireworks (anymore) like this guy.

So it’s hard enough to get back into the work routine, but now I read over at Practical Transmutations that we may be running out of certain elements. I’ve written about this before, but it seems that the situation is more dire than I originally thought. Apparently, a German chemist has estimated when our supply of certain metals is going to be exhausted. This is not good news for some inorganic chemists. For example, becoming an expert on gallium and indium may not be a good career choice if you plan on working more than 10 years. And as if we aren’t using indium up quickly enough, we now have marketers promoting the use of indium as a promoter of good health. As far as I know, there are no studies demonstrating its efficacy in this area -- only its toxicity. Of course, they used to use arsenic for health reasons too, so who knows?

Anyway, this is not a good way to begin the work week. Stop using up our elements, you swine!

Well Meaning Cheating

Over at The Chem Blog, there have been a series of posts dealing with cheating in science. As this has been discussed in many forums over the years, I really don’t have much to add other than mentioning that there is one aspect which is rarely discussed – the well-intentioned falsification of your data by someone else. Back in grad school, I was determining a reaction mechanism using labeled ⁹⁵Mo. After conversion of the various Mo products into MoO₄^2-, it was easy to measure the isotopic enrichment using ⁹⁵Mo NMR. To test out the technique, I prepared a sample of ⁹⁵MoO₄^2- and gave it to the NMR guy for analysis. The resulting spectrum was beautiful! A nice symmetrical peak with very little noise. Of course, since I wanted to run a fair number of samples (each sample required 2.5 hours) and since the NMR guy was busy, I soon realized I would have to run them myself if I planned on finishing my degree before my advisor retired. So I learned how to run the instrument and eventually analyzed the sample again for practice. The spectrum looked something like this.
(OK, so I added the boat, but you get the idea. The little stick in the water was the Mo signal)

WTF?! How did I screw this up so badly? I asked other grad students for help. I repeated the analysis with another sample. I tried everything I could think of in my rather limited repertoire of NMR tricks. Nothing I tried made the spectrum look any better. Finally I located the NMR guy who had done the original analysis and asked him what he had done to get such a good spectrum. It took me a little while to figure it out, but I eventually realized that he had prettied up the spectrum a little before giving it to me. Looking back at the original data, his original spectrum had looked a lot like mine, but then he had MANUALLY ZEROED OUT THE ROLLING BASELINE, POINT BY POINT, until I had a nice sharp peak with zero noise. Then he had blown up the spectrum until the small blip looked like a giant Gaussian peak. Needless to say, I never let him run a sample for me again.

Of course, it never occurred to him that he was cheating or manipulating the data. He just figured he was doing me a favor. The moral is: If you depend upon someone else collecting data for you, make sure you always see the raw data.