More Nanoparticle Bondage

In a previous entry, I mentioned a technique whereby gold nanoparticles could be attached to the exterior of fungal cells to form unusual hybrid materials. Once the gold scaffolding was complete, the fungi could be removed (digested), leaving behind 3 dimensional gold structures. This started me thinking that there might be a rich field of exploration here, finding simple ways of attaching metal nanoparticles like gold to new substrates in the hopes of creating new 3-dimensional structures with unusual properties. Even better, many of these techniques would be based on aqueous chemistry, which make them especially appealing (to me at least).

Of course, within a week or two of that article, two more articles appeared which demonstrated that other research groups are already way ahead of me in this area.

In the first paper, J. P. Hinestroza and coauthors at Cornell University (Ithaca, NY) and the University of California, Davis, described a method of applying silver nanoparticles to porous nylon fibers, resulting in fibers with strong antibacterial properties. By using AQUEOUS chemistry techniques (pH control, isoelectric points, citrate stabilization, etc.), they found they could control the resulting properties of the final material. When you consider the fact that the original gold and silver nanoparticles can be easily produced by reducing aqueous solutions of the metal salts, you begin to realize just how much fun this type of project could be for an aqueous inorganic chemist like myself.

In the second paper, Y. Yin and co-workers at the University of California, Riverside, described the synthesis of gold nanoparticle catalysts supported on silica-encapsulated Fe3O4 spheres and protected by a porous silica shell. The purpose of the silica shell was to fix the gold nanoparticles in place for catalysis. Apparently the resulting material were found to be a good catalyst for the liquid-phase reduction of 4-nitrophenol with NaBH4. Interestingly, the purpose of placing the catalyst onto Fe3O4 cores was to give the researchers a convenient way of separating the catalyst from the reaction mixture. Nice.

I'm predicting a whole slew of papers are going to start appearing which involve placing gold and silver nanoparticles on every material imaginable.

Of course, maybe that's already happened and I just haven't noticed yet.

Ah yes..., it feels good to be blogging again.

Merry Christmas

I naively thought all the extra time I would have available to me during my career transition would translate into my having more time to devote to this blog. I actually do have extra time, despite all the inevitable timesinks (job search, buying presents, rearranging my office at home, etc.). However, I've also discovered that it's a lot harder for me to update this blog if I am not following a regular schedule throughout the day. So I ask you to bear with me as I begin to develop a regular routine.

I hope everyone has a very merry Christmas today.

Update

Well that didn't take long. I am officially a patient now. Damn viruses.

Another Use for Copper

I've just returned from a 5 day visit with my parents in Missouri (which partly explains my recent lack of postings). It was great to visit, but it's always good to come back home again. Unfortunately, "home" is 20 degrees colder, my wife's computer had stopped working, and everyone in the house has some sort of vicious stomach virus. I briefly considered going to a motel, but my wife would have killed me.

Really.

So I spent Monday passing out medicines, cleaning up various messes, mostly eating by myself, and fixing the computer. The computer's working now, which is more than I can say for the rest of the family. I've already resigned myself to the inevitability of becoming a patient myself within the next couple of days. Perhaps I should invest in some copper bedsheets.

Why copper, you ask?

I have previously discussed the anti-bacterial properties of silver and gold. The list of purchasable items containing silver grows daily, and includes bandages, socks, towels, bedsheets, ointments, plastic food containers, soaps, and washing machines. Gold is not at that level of marketability yet, with gold-laced soap being the main use of its anti-bacterial properties. So it only makes sense that copper, the third element in the 1B group, also exhibits some of these same properties. In fact, in Chili, the biggest suppler of copper, copper fibers are being added to socks, towels, pillow cases and underwear. Copper sponge filters are being tested for their ability to purify water. I suspect it won't be long before this becomes a new marketing opportunity.

Despite their anti-fungal properties, these elements may also be used in conjunction with fungi. In a novel approach, fungi are being used as templates for stabilizing gold nanoparticles. Under the right conditions, fungi can absorb microscopic metal particles onto their surfaces, creating unusual clusters of nanoparticles, and resulting in metal-fungus hybrids which are able to catalyze certain reactions. It's certainly a novel way of doing bioinorganic chemistry.

Gotta go. I hear some rather vile noises emanating from my son's bedroom.

Full Circle

Hope everyone had a good Thanksgiving (assuming you live in the US). It was a good time to get together with friends and family.

My last day at work wasn’t as bad as I had expected. Pretty much everyone I knew had taken Wednesday off, so I had done all of my goodbyes the previous day. And since I’ve only been in the new building for about a month, it wasn’t like walking out was all that big a deal. Still, I’ll always remember my last day at work, just as I’ll always remember my first day of work, although for very different reasons. The story I’m about to tell is a lesson on what not to do when leaving school to start a new career….

It was Monday and my PhD still wasn’t finished, despite the fact that it was due in the graduate office on Friday. My thesis advisor had already left town on sabbatical, the movers were showing up in a couple of days, my timetable was inflexible (you’ll see why in a bit), and my fiancée had already made it abundantly clear that I would NOT be missing any of the agreed upon dates. (In the interest of truth, and the fact that my wife might actually read this post, I will point out that this fiancée is not my current wife). The thesis was pretty much done, but I was still fiddling around with the figures, since the thesis examiner was known to be a stickler for thesis formatting rules and if he declined to accept it on Friday, there would be hell to pay.

On Wednesday I discovered my thesis advisor was required to sign my cover page in two different locations. I had had him sign about 10 copies of the cover sheet before he left town (in case I needed backups), but hadn’t noticed the need for the second signature and now he was out of the country. I sweated bullets for a while before I remembered that, as the head of the chemical education program, he had a stamp with his signature on it stored away in his office. After talking with my advisor by phone, and after much practice, I managed to stamp his signature onto the appropriate spot without it obviously appearing to be a stamp. I was hoping the examiner wouldn’t notice.

On Thursday, the movers showed up and after explaining to them which items should be packed and which items should be left alone (I lived in a house with four other people), I went back to working on my thesis. At one point, I left to bring back some fast food, since everything seemed to be going smoothly with the movers. Of course, the instant I left, the movers started packing up my housemates stuff. I spent several hours on Thursday unpacking boxes and returning items which weren’t mine.

After pulling an all-nighter, the thesis was finished by Friday morning and I made all the necessary copies at Kinko’s. I showed up at the thesis examiner’s office with the copies at the designated time, 11:00 am, knowing that the office closed at noon, which meant there would be no time to fix any problems in the thesis should the examiner reject it. I had heard rumors about this guy, who was apparently fond of using rulers to ensure that all formatting rules were followed to the letter.

He accepted the thesis.

Relieved, I drove back to my house, packed up a few things, picked up one of my housemates (who was one of the bridesmaids), and immediately drove 4 hours to southern Illinois for my 5 o’clock wedding rehearsal. Yes, I was trying to squeeze a wedding into the middle of all this. I warned you this was not the way to do things.

Saturday was the wedding, and other than some discomfort in the morning due, I suspect, to a few drinks on Friday night, everything turned out well.

Sunday, picked up a U-Haul trailer and loaded my wife’s things into it.

Monday, left for Detroit, stopping at my house in Urbana to pick up more of my stuff. This made it a 3 day trip, which meant arriving in Detroit on Thursday. Unfortunately, I hadn’t had the time to make hotel reservations, assuming I could just find something on the fly. Not knowing Detroit very well, I ended up stopping at a motel whose reputation turned out to be rather suspect. This suspicion began when, during my check in at the office, some guy appeared, asking if the motel rented rooms by the hour. My suspicion was confirmed when the manager specifically had me park the car so that the doors of the U-Haul would be backed up against a tree, so that no one would be tempted to break open the lock. Needless to say, I must have checked the trailer 10 times over the course of the night.

Friday, I showed up for work on the absolute last day I could have arrived and still been granted vacation days the following year. Thus the rather strict timetable.

Saturday, left for the honeymoon.

That was one hell of a week!

My advice: Make sure to give yourself plenty of time for relaxation before reporting to your new job.

Scary Times, Indeed

Tomorrow -- the 27th day of the 11th month of the 8th year of the 3rd millennium -- is my last day at work.

It's been one hell of a ride. Layoffs, buyouts, spinoffs, promotions, bankruptcy, blue sky research, product development projects. I've seen good times and bad times. And soon, hopefully, I'll be starting it all over again somewhere else.

One of the things you have to deal with in these situations is understanding why YOU had to be (one of) the sacrificial goats. I know WHY the company had to make deep cuts to survive (at least for a while longer), but as I look around at the people who made it past this round of cuts, I'm not sure why I was one of the chosen. For example, one of my coworkers, who was part of my group before a reorganization in January, is now coordinating projects with the national labs. Those were MY projects before the reorganization. Now I'm not trying to take anything away from her, but these projects simply are not in her area of expertise -- they're in mine. They were given to her simply because they needed to find something for her to do. Had I still been working those projects, I might have survived this rounds of cuts. In fact, I can think of several projects I was working on last year which turned out to be safe harbors. Unfortunately, it was my new project assignment which got axed, and me along with it. Apparently it was a matter of being involved on the wrong project at the wrong time. Ironically, the assignment which got me axed involved more chemistry than I had seen in years.

It's also easy to look around and see people just going through the motions, waiting for retirement to come, and wonder why they weren't approached. Part of that is due to having been in their respective business units for a long time. I was originally a part of the R&D labs, which was broken up about 2 years ago and distributed to various parts of the company. Of the 100 of us originally in the R&D labs, only about 5 of us are now left in the company. I had been warned this summer (by someone with connections inside the company) that we R&Ders had targets painted on our backs, and I guess they were right. Needless to say, the company is going to have a difficult time developing new products in the future.

Low level managers also appeared to be particularly immune to the layoffs, even if the product lines in which they were in charge were being dropped, leaving them with no real purpose in the company. Some of these managers are now spending all their time desperately trying to come up with project areas to justify their continued existence. It's not going to be easy.

All this may sound as though I'm somewhat bitter about the whole mess, and a week or two ago, I probably was. But I've come to realize that I was missing the point. As the company has continued to shrink due to a decline in the automotive sector (and unfortunately that target is still continuing to move downwards), it has been forced to shed many of the product areas in which an inorganic chemist (or any kind of chemist for that matter) would be useful. I look over what's left of the company and realize the company didn't really dump me. It's just that the company I joined many years ago no longer exists.

Miscellaneous Monday

A few miscellaneous items today.

A week or so ago, our secretary set up a departmental luncheon for the 5 of us in our group who are being "asked" to leave at the end of the month. This morning she came by to tell me that the going away luncheon has been cancelled for now. There were a variety of reasons, including other commitments by at least 2 of the "honorees", but the first reason she mentioned was "a lack of response/participation" from the rest of the department. Nice way to start a day. We'll probably just all get together informally at a bar somewhere instead.
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Ever wonder what might happen if The Matrix was running on Windows XP? Check out this video.
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I guess it's a sign of the financial crisis this country (and the rest of the world) is going through, but I've received 2 of those "help us give you millions of dollars" scam emails in the last week. Is it too much to ask these guys to do spellchecking? It's pretty hard to get really worked up over the prospect of getting free money when you keep hitting misspelled words. Here's an example....

Mr. ABDUL SAAZ a well known Philanthropist, before he died, he made a Will in our law firm stating that Five Million, Two Hundred Thousand British Pond-Stealing should be donated to Ten Philanthropist each.

Of course, some of the misspellings might actually be Freudian Slips. Too funny.

Of course, I take this all back if these guys turn out to be legit.

Glass -- Not Just For Inorganic Chemists!

Back in the day, we used glass in the lab. Our glassware was glass, our cuvettes were glass, and our eyedroppers were glass. Even our Bunsen burners were glass. And we liked it! Times were good. Having nice, shiny glass equipment on your lab bench made you feel superior to everyone else. And cleaning glass was easy. You just threw everything into a KOH bath for a couple of hours (or weeks) and they came out as good as new.¹ The only reason anyone ever threw glassware away was because of breakage, and even then, if it was only a crack, you kept using it anyway. Or you brought it back to the dorm room/apartment/home office as a showpiece. (Just ask my wife.)

But now you can get almost everything in plastic. Plastic beakers, plastic eyedroppers, plastic volumetric flasks …it’s insidious.² Not only does this practice decrease our valuable reserves of bisphenol A, but it also facilitates the practice of “throwing out” versus “cleaning up”.³ Even worse, it allows the organikers a foothold into the Hallowed Halls of Inorganic chemistry. Dammit! Inorganic reactions should be performed in Inorganic vessels! And silica is about as inorganic as you can get.⁴

But evil always loses out in the end. It’s now been reported that certain organic compounds which tend to leach out of plastic labware can influence (read: screw up) certain experiments. Ha! I always knew those plastic testtubes were releasing nasty organic chemicals! Plastic should only be used to store foods and medicines.

I'll write about this more after I finish repairing a cracked beaker of mine with some epoxy.
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I'd like to take this opportunity to apologize to those readers who have sent me emails asking for information. Although I've been neglecting this site lately due to employment concerns, I've been totally remiss in actually checking out my emails. I'll try to start answering your questions in the future. Thanks again.
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Footnotes – I blame the large number of footnotes on Carbon Based Curiosities and its influence on the blogosphere.

¹KOH/ethanol baths work by slowly dissolving the surface of the glass. It’s an excellent way of dealing with stubborn deposits, although it can trash a fritted glass filter if you leave it in there for too long. There are limitations however. In my attempt to decorate my home office with all sorts of exotic glassware, I’ve discovered that while KOH can make laboratory glassware (borosilicate) look like new, it can mar the finish of regular old antique glass bottles. You have been warned!

²Some of those plastic volumetric flasks have no menisci when holding aqueous solutions. I tell you, that’s damned unnatural.

³I’m actually fairly conflicted about this “throwing out” vs “cleaning up” dilemma. Anyone who knows me knows I’m a hoarder. I rarely throw anything away. Yet, I’m really bad about cleaning, so I tend to find myself surrounded by hoards of dirty, unusable stuff. (Just ask my wife.)

⁴Any evidence (video or otherwise) pertaining to my use of nonglass vessels or equipment is categorically denied.

Attack of the Heavy Metals

As a (mostly) transition metal chemist, I enjoy heavy metals -- the elements, not the bands. Heavy metals should be a part of any self-respecting chemist’s lab. But they shouldn’t be part of our ecosystem, at least not in the levels associated with human use. The health effects can be serious. Industrial waste, residential garbage (you do recycle your Ni-Cd batteries, don’t you?), and certain pesticides all lead to elevated levels of these elements. I now read that heavy metals are a concern in organically grown foods. Not the first place I would have associated with toxic materials. The whole point of organic growing techniques is to be more biofriendly to the environment by using recycled organic matter instead of synthetic fertilizers. Unfortunately, these organic fertilizers, “composted animal manure, rock phosphates, fish emulsions, guano, wood ashes, etc.” can contain significant levels of these metals. Now this does not necessarily mean that heavy metal concentrations are always higher in organically managed soils, but it has been observed and is a concern. Regulations are tightening and research is continuing, but as we release more and more metals into the environment, the differences between organic and nonorganic farming may become smaller and smaller.

Of course, this is an example of unintentional exposure to heavy metals. Some health practitioners actually want you to ingest heavy metals for your own good. For example, Ayurvedic medicine, based on an ancient practice, uses herbal remedies for a wide variety of illnesses. In the practice of Ayurveda, “…a balance of the metals, including lead, copper, gold, iron, mercury, silver, tin, zinc are considered to be essential for normal functioning of the human body and an important component of good health.” So these metals are often added to Ayurvedic medicines. Unfortunately, there have apparently been reports of heavy metal poisoning related to the use of these medicines, especially in the case of lead. Again, regulations are tightening, but it’s hard to control substances you can buy over the Internet.^*

I think I’ll just stick with playing with my metals in the lab.
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^*Why is the Internet always capitalized? Are there religious connotations here?

Back in the Saddle Again

Well, it's been harder to get back into the saddle than I originally expected. Once I stopped my regular routine of web surfing to find snippets of chemistry to post on this blog, it's been too easy to keep putting it off “until tomorrow.” It also doesn’t help that every time I sit down in front of the computer, I feel obliged to visit CareerBuild.com or tweak my resume or search for more companies to whom I can send resumes.

While searching the web for hints on job hunting, I ran into an old post from the “Lamentations on Chemistry” blog. The author describes a rather frightening trip to a recruiter’s office. I read it just a few days before my first interview with a head hunter and I was not sure what to expect. It’s an interesting read.

Obligatory chemistry snippet (It’s about damn time!)
I’m sure you’ve all heard the warnings about cell phones and their possible (but unlikely) harmful side effects due to the small amount of electromagnetic radiation they emit. You’ve probably even seen the amusingly bogus “cell phones pop popcorn” videos on Youtube. (My 8 year old daughter has, and she’s at that age where she’s just coming to grips with the idea that not everything you see on TV or the computer is true). But a new concern over cell phones is showing up as nickel in the phones can result in contact dermatitis for those people with nickel allergies.

I hadn’t heard of nickel allergies before this, although apparently it’s been well known that the presence of nickel in jewelry often causes skin problems for a certain percentage of the population. Since my company (used to) manufacture platinum catalysts, I was aware that Pt could have the same effect. (Hmmm, Ni and Pt are both d⁸ metals. Coincidence?) If a worker in the plant began to show signs of a Pt allergy, they were moved to another location. Besides the dermatological problems, Pt allergies can affect the lungs too, producing symptoms rather similar to asthma. So similar, in fact, that one of the PhDs in charge of that catalyst plant theorized that the use of Pt in automotive exhaust catalysts (starting in the 70’s) may explain the rise in asthma cases in the US at the same time. I haven’t seen any of this verified, so take it with a grain of salt.

I’ve enjoyed working with precious metal (Pt, Pd, Rh) salts over the years and I’m fortunate that I have exhibited no such allergies. I would expect it to be rather disappointing to find that you could no longer work in a certain area of chemistry because you were allergic to chemicals.

Reflections on Job Hunting

Well, it's been exactly 2 weeks since I first got the word about my job status. Since then, I've been sending out resumes, talking to headhunters, scouring the web for job openings in the Detroit area, and networking with people I know. If I didn't have to worry about the future of my family, this would be a pretty exciting time. Surprisingly, I'm fairly upbeat about the whole thing although that might change in a few months if nothing happens. If you've read the intro to this blog, you'll know that I wasn't very happy with the way work had been going. Very little science and even less chemistry. If I land a new job and I'm doing real chemistry again, at roughly the same salary, and without having to move -- it's quite possible this will all have been a blessing. But that's just the optimist in me talking. Or the beer. Not sure which.

Even more surprising is the lack of bitterness over my situation. If the company had been doing well and had just decided to let me go, I'm sure it would be different. But the company is in trouble. Deep trouble. I've never mentioned this before, but my company has been in chapter 11 bankruptcy for about 2 years now. Now originally this was done to allow the company a chance to reorganize itself and shed itself of some money losing contracts and business units. At the time, the future of the company was looking pretty rosy, assuming you were one of the employees who made it through the transition. However, negotiations with labor and the parent company took too long and my company didn't make it out of bankruptcy before the credit crunch hit, and things started going downhill.

As a result, the company was forced to make another round of cuts, much more drastic this time. In this last purge, a lot of really good people were cut. Some of them high performance types who I never would have thought would be released. So my ego didn't take a huge hit. It had nothing to do with performance, but with the job description. Had I started working in the electrochemical sensor group a few months earlier, it might have been someone else in our group who got tapped. So knowing that helps a little.

For that matter, I may still be one of the lucky ones. The severance package is good and I'll be okay for a while. It's generally assumed that the next round of cuts, which might occur early next year based on the company's financials and the general financial state of the country, will have significantly smaller severance packages. At least I have a head start looking for a job in this area.

I was planning on actually discussing chemistry now, but it's late and I'd rather blow up some video game aliens before going to bed.

Enough is Enough!

OK, I think I've spent long enough away from this blog. Between the big lab move at work and working on my resume at night, I've managed to avoid updating this blog for far too long. Yes, the company still wants me to be responsible for making sure the move to our new labs (as well as various aspects of its construction) goes without a hitch, even though I will probably not be around long enough to actually occupy the new lab site. It's tempting to just say "the hell with it" and let someone else work out all the kinks after I'm gone, but I am good friends with some of the people who are going to be occupying the lab and I have no desire to leave them in the lurch. (I'm sure I will never use the work "lurch" again in my lifetime). It is kind of strange though. I'm one of the few chemists they have left in the division and so it's hard to say how much of the new lab will actually be utilized once I'm gone. But the company has much bigger problems to solve, so I suspect this is a rather minor concern for upper management.

I've begun the process of networking, which means meeting people I haven't talked to for a while and letting them know my situation. For example, on Tuesday, I attended my first Michigan Catalysis Society meeting in over a year. I had stopped going to them when I realized I wasn't really performing much science at work anymore. I had forgotten how much fun it can be to talk to other researchers in my field.

I talked to my first headhunter on Friday, and it was an interesting experience. When I finished my doctorate at Illinois, all I needed to do to find a job was to interview with the recruiters who came to the campus, so I've never had to go out and look for a job before. When you talk to a headhunter, you feel obligated to try and sell yourself to them even though they won't be the one to actually hire you and I found that to be a bit surreal. During the course of the interview, I also began to realize I really wasn't ready to describe myself to potential employers in a coherent fashion yet. I'm working on that now.

So besides being a place to discuss aspects of chemistry, this blog will also be an record of my attempts to find new employment. I hope that part of the blog ends rather quickly.

A New Beginning

When I started this blog back in January, one of my reasons for doing so was to compensate for the lack of chemistry in my current job. Well, this will soon not be a problem since, as of December 1st, I will no longer be employed at my current job. The severance package is fairly generous, especially considering the financial condition of the company, so I'll be all right in the near term. But I'm not necessarily looking forward to the prospect of finding another job with similar pay at my current location. Life sure is interesting.

The headcount reduction was pretty severe, and a lot of good people were let go. In our group, it came down to a choice between myself and another guy, and we were both fighting over the same position. In its original incarnation, that spot was tailor-made for my skills and experience, but for reasons I'll probably never know, that position was redefined at the last minute and the other guy was chosen, much to the surprise of the rest of the group.

In any case, I should now have more time to devote to this blog. And if anyone is looking for an inorganic chemist in the general Detroit area, be sure to let me know.

Chemist Ken

Interesting Times

I apologize for not posting anything for the past week, but we are undergoing some major upheavals at work right now. They are downsizing significantly, and the advanced research group is going to get hit. I'll know in about 3 weeks whether I am still employed at this company or not. So my postings may be a bit less frequent for a little while.

Nano-Rods and Sex Videos

Fortunately, my mother doesn't read this blog, or its titles.

In a continuation of what appears to be my rather unhealthy obsession with nanoparticles, I now read that gold nano-rods are useful in the treatment of cancer. If you are interested in the details, you may read about them here. My reason for mentioning these nano-rods has more to do with their synthesis, which utilizes ionic liquids as the solvent. This results in the formation of nano-rods, as opposed to the usual nano-spheres. [1]

Now ionic liquids aren't all that hard to make -- just heat a salt until it melts. In reality though, the term ionic salts is typically used to indicate salts which are liquids at room temperature, or at least below 100C. Ethylammonium nitrate is one example, with a melting point of 34C, but there are lots of them out there.

I’ve always thought ionic liquids were a pretty cool concept. A fluid made up totally of ions just seems so bizarre. As a class, they tend to have certain properties such as high electrical conductivities, low vapor pressures, and high heat capacities that make them excellent coolants. I had a chance to work on a project focusing on ionic liquids a few years ago, which was tempting since I would have been doing real synthetic chemistry again. However, based on reasons which have nothing to do with science, I chose not to work on that project. A decision which I am now very happy with, for reasons which I won't mention. (Never let it be said that the roads through industrial research careers are any less tricky to navigate than academic career paths.)

The use of ionic liquids as solvents is particularly intriguing. I mean, these liquids are more polar than water! Imagine the opportunities in synthesis. Both inorganic and organic chemists can use them, and anything that brings us closer together isn’t a bad thing.
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Just in case you were disappointed with this post after reading the title, consider David Bradley's take on spray-on condoms. The video is particularly amusing.




[1] I never know whether I should use a hyphen after the term "nano," so I tend to be rather random with its use.

Chemical Symbolism

So, they are now making nano particles from volcanic lava.

Yes.

From lava.

Really.

When is this nano madness going to end?

Okay, so perhaps I'm exaggerating here a little bit. It would be more correct to say that Dang Sheng Su and his team are making nano particles using volcanic lava. Lava obtained from Mt. Etna in Sicily contains nanosized Fe2O3 particles, which can be reduced to iron nanoparticles at 700C in the presence of hydrogen. These iron particles are apparently good templates for the production of carbon nanotubes and nanofibers when exposed to ethylene and hydrogen at high temperatures.

I know I tend to rag on nano-technology a bit too much on this blog. My first post on nanoparticles wasn't too complimentary. But I've been coming around lately as I read more and more articles on the subject. Much of the research may eventually just turn out to be hype (which can probably be said about any emerging field), but it certainly seems as if there is a lot of potential in this area. Who knows? Maybe I'll be offered a job in nanotechnology sometime in the future. I wouldn't want my views on this blog to limit my opportunities. :)
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Back in 1803, John Dalton developed a series of atomic symbols for some of the known elements at that time. Here is his representation of the table of elements. It cannot be called a periodic table yet since it doesn't demonstrate the periodicity of the elements.

Picture obtained from Wired

Now it's not like there wasn't already a series of symbols for most of these elements already. Alchemists had been using a set of elemental symbols for centuries before Dalton came along, but a lack of standardization was a significant problem, especially since alchemists often used many different symbols for the same element. Certainly, part of the problem was due to the lack of a central authority (IUPAC hadn’t been invented yet). There are at least 20 different versions of the symbol for gold that I know of, and probably a lot more. But the biggest roadblock to standardization among the alchemists was their need for secrecy. Treatises by alchemists were often ambiguous and confusing, apparently to confuse the competition. For example, alchemists often used the term "mercury" for the element mercury, the element gold, the liquid fraction of certain reactions, and various metaphysical concepts such as spiritual goodness. You really need a course to understand what these alchemists were trying to say.

I'm guessing that Dalton was doing his part to disassociate chemistry from the art of alchemy by refusing to use any of the common alchemical symbols of the time. Ironically, his symbol for hydrogen is the same as (one of) the alchemical symbols for gold. Remove the circle from the symbol for phosphorus and you have the alchemical symbol for phosphorus. His symbol for sulfur is the same as the alchemical planetary symbol of earth. Nevertheless, it was a start. It wasn't until Berzelius started using letters based on the Latin version of the element names that everything became manageable. Can you imagine writing out chemical formulas for large organic molecules using Dalton's symbols? If that wouldn't drive you toward Inorganic chemistry, then nothing would. ;P

Xbox's and Cats

Warning! Very little chemistry in today's post.

How many of you have Xbox 360s? How many of you have had Xbox 360s that have failed? If you're interested, here's a link to an article about what went wrong at Microsoft's Xbox division.
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Yesterday we celebrated the one year anniversary of our cat Sierra. One year ago, we found her as an undernourished 2 month old kitten in my mother-in-law's back yard. Other than destroying a few glass vases, she's turned out to be a great cat. She was apparently weaned off her mother too soon, as her favorite pastime now is to suck on my wife's shirt sleeve whenever she gets a chance (as she is shown doing here).

Several months ago there was an article on the blackest black pigment ever produced, using carbon nanotubes (IIRC). Back when Sierra was a kitten, before her coat became shiny, she probably could have challenged that claim. She was an absolute black hole as far as absorbing visible light. Taking photographs was almost pointless since all you'd see was an amorphous black mass, occasionally with two eyes showing, which let you know which end you were looking at.

Happy first birthday, Sierra!

Nano-gold Catalysts

Reports of nano-gold and its use as a catalytic material are beginning to pile up. Last week I mentioned nanogold particles in stained glass windows and their ability to oxidize organic pollutants. This week, two more articles showed up, here and here. Hmmm…. seems like we’re beginning to reach a critical mass here. Pretty good for a metal that hasn’t been considered a particularly good catalyst over the years. Perhaps I'll start paying more attention to this area. I’ve read articles about nano-particle based catalysts in the past and have generally been underwhelmed, but nano-gold catalysts may be about to change that view. And that’s because of two words that are often found in these reports.

Room temperature.

Or at least, low temperature.

The obvious reason for using nano-particles is their much larger surface area to mass ratio. Higher surface areas generally mean better catalysts, so the drive to make smaller and smaller catalyst particles has been going on for decades. Back before “nano” became a marketing term, I recall at least one set of researchers making platinum nano-particle catalysts to improve the efficiencies of automotive exhaust catalysts. They succeeded, but unfortunately, at the high operating temperatures (generally above 400^oC) to which these catalysts were subjected, the platinum nano-particles tended to move around and coalesce into much larger particles, losing much of their surface area and eventually not looking all that different from more crudely prepared catalysts. In fact, with these types of catalysts, research is focused less on the catalyst itself and more on the substrate which supports the catalyst -- changing its properties so as to limit the movement of the catalyst particles. This is always a bit of a balancing act since too much interaction between the catalyst and substrate can change the properties of the catalyst in undesirable ways. But if the reactions to be catalyzed take place near room temperature, or at least at lower temperatures, you stand a much better chance of maintaining the catalyst nanoparticles and hence their benefits.

Gold has traditionally been the forgotten metal, with all catalyst discussion centering on its neighbors on the periodic table (Pt, Pd, Rh, Re, Ru, and Ag). That looks like it's about to change. The big question to be answered: Why are nanogold particles so much better than bulk gold? Here are some possibilities to consider.

1. Larger surface areas. Well yes, you would expect some benefit here, but gold has been so unremarkable as a catalyst, I don’t believe a simple increase of surface area would account for this big of an effect. If it were that easy, everyone would just have dumped more gold into their catalyst formulations in order to increase the available surface area.

2. More defect sites. In many cases, catalysis only occurs at specific sites on the catalyst surface, such as the so-called "steps" as shown in the figure below. Perhaps nano-gold particles naturally have more of these locations.

3. More of the appropriate crystal faces. Different lattice faces such as (111) or (100) often have significantly different catalytic rate constants. See figure above. Perhaps nano-gold particles have more of the correct lattice orientations at the defect sites than bulk gold.

4. Different surface oxide properties. One of the reasons metals like Pt and Rh make such good catalysts is their ability to maintain surfaces which are relatively clean of oxygen atoms. Whereas the early transition metals tend to form oxides, the late transition metals favor the metallic state. Heat vanadium or molybdenum in air and you form the oxides. Heat platinum or its salts in air and you wind up with platinum metal. Keeping the surface free of oxygen atoms makes the metal more available for catalyzing the desired reactions. Perhaps smaller gold particles tend to have less oxygen on their surface.

Figure obtained from http://www.pnas.org/content/103/28/10577.full.pdf

Fall and Chemistry

It's September and that means the fall semester has begun in most universities. Of course, this also means the start of chemistry classes. If you are currently employed in industry, like me, then you probably didn’t notice this momentous event, at least until you realized the college football season had begun. If you're an undergraduate, or perhaps a first or second year graduate student, you probably noticed it a lot, especially as you paid for this semester's chemistry textbooks. Once they're done with classes, however, grad students usually don't pay much attention to the beginning of semesters either, unless they are required to teach undergraduate courses. Once they make the switch to full research mode, the ebb and flow of university life is often lost to them. I've known grad students who were so oblivious to the change of semesters, they would often wonder out loud why parking was suddenly so difficult to find.

When I was a graduate student at the University of Illinois at Champaign-Urbana, however, it was always easy to notice the start of the fall semester, no matter how deeply involved you were in your research. It wasn’t football fever, or seeing all the wide-eyed newbies milling around in herds, or even the sudden lack of parking. The most obvious sign that classes were about to begin in Urbana was: after going through the entire summer with absolutely no road construction projects, suddenly seeing 4 or 5 road projects spring up around campus during the week before classes. Try to imagine 30,000 students showing up at the same time in cars and vans loaded with all the necessities of life (for a university student) and finding many of the roads blocked off. Seriously, this happened every year I was there and I have no reason to believe that tradition still doesn’t occur today. Correct me if I’m wrong.

By the way, the Illinois football team lost their opener to Missouri. I’m not too particularly bummed out about that since Missouri is where I received my B.S. and M.S. in chemistry. Talk about a no lose situation -- one of my alma mater’s had to win.

Laxatives and Boredom

Catchy title, huh?

My daughter recently discovered she has an in-grown toenail and the doctor recommended she soak her foot in a warm Epsom salt bath. So of course she asked us what the Epsom salts did. My wife thought Epsom salts (essentially MgSO4) kept the bath warm longer, but that didn’t seem very likely to me since you could get the same effect from cheaper salts like NaCl. So of course, I had to look it up.

Apparently, MgSO4 absorbs through the skin and does reduce inflammation. It acts as a calcium channel blocker and relaxes the smooth muscle groups (blood vessel walls, for example). If you absorb enough of it, it can lower your blood pressure. If you consume enough magnesium (for example, Milk of Magnesia or Maalox) you’ll discover it behaves as a laxative. If you consume MgSO4, you'll discover it is a very good laxative since the sulfate group enhances the effect.

Irrelevant fact: MgSO4 was given the name Epsom salts in honor of the town in which it was originally discovered back in the 1500s -- Epsom, England.
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I was looking over the statistics for this website today and noticed that while traffic has been slowly rising over the past several months, a very noticeable periodicity has begun developing. It’s a weekly cycle, with a minimum on the weekends (no surprise there), and (almost) always peaking on Wednesdays. It’s a triangle waveform, with Tuesdays and Thursday roughly equal but lower, and Fridays and Mondays equal but lower still. Not the distribution I would have expected. Does this represent middle of the week inquisitiveness, restlessness or boredom? Perhaps I should save my best posts for Tuesday evening?

Question of the day: Do you find your blog reading habits to be that structured?

Journal Backlog

One of the reasons I started this blog was to bring myself back to feeling like a real chemist again. I do not work at a chemical company, I work at a manufacturing company. There aren't many chemists here and there is no library of chemical journals. Only on rare occasions can I justify going to chemical meetings and I just don't do that much wet chemistry anymore. One of the purposes of this blog was to force me to read the literature again, in order to know what's going on out there in the world of chemistry. So early this year I started subscribing to various journal alert emails. Every time a new issue is released I get an email with all the article titles along with links to their abstracts. Of course, if I find an article I'm interested in, I still have to drive to a nearby university in order to actually read it, but it's a start.

Unfortunately, I have not been very diligent with these alerts. At first, I read them immediately upon arrival, but as various projects began to heat up, I started putting off reading them until later. Eventually I created a "Stuff to Read" folder to store the emails to prevent them from being lost forever. Unfortunately it's gotten to the point where I immediately move them to this folder the instant they show up - whether I'm busy or not. Well today I actually opened the folder and was embarrassed to discover I had 250 unopened email alerts. Perhaps I need to cut back on the number of journals I want to track. Then again, as I think back to grad school, perhaps I wasn't all that good about reading journals then either. Does anyone else have problems keeping up with their journals?

Grad students, be sure to take advantage of your library while you've got it. You may not have it forever.

Edit: I woke up this morning to find 5 more alerts in my mailbox. Crap! I'll never catch up.

MeatWater

Sometimes (like right now), it's late, I'm tired, and I don't have anything relevant to talk about. In that case, I basically have 3 choices:

Choice #1. I can forget about posting tonight and hope that inspiration occurs within the next 24 hours. This is usually the easiest thing to do.

Choice #2. I can imitate those horrible sitcom episodes where the actors sit around and "recall" things that happened in previous episodes so that 25 minutes of old footage can be used to create a 30 minute show. In my case, I would craftily sprinkle links to some of my old blog posts in sentences that had nothing to do those posts. But since that would be demeaning to you, the reader, I refuse to do that.

Choice #3. I can point you to an funny website and hope you are amused. I'm sure you've heard of vitamin water, right? Bottled water with a few vitamins added for marketing purposes? Well, we all need proteins too, so now we have MeatWater. Available in 18 flavors (bacon was just added), now you can get all your amino acids while you're hydrating yourself. Isn't marketing wonderful?













BTW, just in case you were beginning to wonder just how pathetic the human race was becoming, I should point out that this website is a fake.

Old Memories

I hope everyone enjoyed the Labor Day weekend. We spent a lot of it cleaning out our basement, which translated into throwing out a lot of old stuff, most of it mine, and much of it items I didn't even remember having in the first place. One of the items was a desk that I've had since grad school in Missouri. No one was using it anymore, so we gave it to my wife's nephew who is beginning his freshman year at Lawrence Tech, so it's going to a good home. I originally bought the desk from another student who was leaving Missouri after graduating with a B.S. in chemistry. It was painted a rather bizarre looking green color, which meant no one other than another grad student would have felt comfortable bringing it back to their apartment.

While emptying the drawers, I came across some old pictures I had taken early in grad school - in particular, pictures of my old chemistry lab. They certainly brought back some (mostly) fond memories. There were pictures of my old chemistry building, my lab, and the old Nuclide isotope ratio mass spectrometer with which I performed most of my undergraduate and master's thesis work (and which now looks like a prop from a "B" science fiction movie).

Schlundt Hall.

This was the building where I spent much of my life during grad school in Missouri. Schlundt Hall was known as the "old chem building" as opposed to the flashier new chemistry building which housed the organic, analytical, biochemical, and some of the other inorganic groups. Home to the main lecture hall and most of the freshman labs, it also contained several labs in the basement which were under the control of my advisor, R. Kent Murmann, who had no problem setting up undergraduate students in this rooms. Although Schlundt Hall was often looked down upon by some residents of the newer building, it just oozed with atmosphere (the good kind, not the kind generated by chemicals, ... at least I hope). It had that old style fortress/castle look to its architecture, including the crenellations (the notches in the wall from which archers could fire) on the roof (upon which you could walk if you knew how to pick the door locks -- which we did). This place could have been Hogwarts -- minus the magic and about half of the deathtraps. And since we were the only group in that part of the building, we basically had free reign to do as we wished. Perhaps I'll reveal some of the things that went on in that building at night in another post. In any case, the memories were great.

My Desk

If you think this desk is a little messy, you should have seen it before it was cleaned. Amanda over at "A Chemist's Laboratory Notebook" shows pictures of her desk at various times, but believe me, even 2 weeks before her thesis defense, her desk still looked better than mine on average. God knows what most of that stuff on my desk is. Yes, that is a can of diethyl ether sitting on the desk. Having chemicals occupying much of the desktop seemed normal at the time. I can only hope I didn't eat food at my desk very often.

My Lab Bench

What can I say? I can only imagine what the bench looked like before I cleaned it up. The "Accidents Before They Happen" poster taped to the wall was probably placed there by my advisor. I suppose I could have a contest to see how many safety violations could be found in this picture, but that would only destroy the romance of the lab. Damn, I had access to a lot of chemicals back then. I'm lucky if I have more than 10 in my current lab at work. I'm definitely bummed about that.

If you are a graduate student, or an undergraduate with a lab, I suggest you take pictures of it before you leave. You'll be glad you did later.

We're Moving.... Sometime.... Maybe.....

Today we received word that our lab will be moving to the new research site at the end of October. Even though this pronouncement was delivered by upper management, it can be considered nothing more than a rumor until it actually happens. Too many unknowns exist for anyone to even guess at our move date. For one thing, the construction crews haven't even begun work on our lab yet. We are part of the third (and final) phase in the rollout plan and they haven't even finished the first two phases yet. As a further complication, our current building is being taken over by another set of tenants in the near future. If they show up early, we may find ourselves being thrown out early. And of course, knowing how this company works, it would not be surprising if some clueless upper manager somewhere arbitrarily changes the move date with little regard for how it might affect our projects.

I've talked about our move before, and while it will be great to get all of us (chemists, physicists, engineers, purchasing, IT, marketing, etc.) together in one building, I'm still going to have to endure some pain before everything is settled. Our group is not the only group waiting for their new labs to be finished. But those groups have not been given permission to stay in their labs any longer, so they will be moving into our already crowded lab for a few months.

Since I do stop over at the new location occasionally, I've begun to notice some of the annoyances that the new place will have to offer. First, while remodeling the building for our use, it was decided that a wireless intranet was the way to go. We still have network jacks at all our desks, but that's about it. None of the conference rooms had internet jacks installed. This isn't a problem if your laptop is wireless, but mine isn't. Nothing can quite describe the pure horror of having to attend a group meeting without having access to the internet. What the hell are we supposed to do during the boring parts of the meeting? Everyone else uses these meetings to go through their mail, read Dilbert cartoons, and check stock prices. It's just not fair! I've ordered a new laptop computer so hopefully this will not a problem by the time I move to the new location.

Parking is also going to be a problem at the new site. It's not like there aren't plenty of spaces available, it's just a matter of how far away you'll be from the building when you find a spot. This can be a significant issue during Michigan winters.

You have to use your magnetic security badges to unlock doors in order to go anywhere in the new building. No more just sticking it in your pocket and leaving it there all day.

Finally, there is this one guy at the main desk who insists on checking my laptop every time I leave in the evening. He actually checks the serial number on the bottom of the laptop with the number on my security badge. It's not like he hasn't seen me before with a laptop, and it's not like it would take me more than 5 minutes to fake the serial number on the laptop, but he insists on doing it every time. I can bypass this problem by exiting through one of the unmanned, security badge accessible side exits, but that puts me a lot farther from my car and will not be a favored option during the winter.

Additional note: Our old location is located within three miles of the four plant nurseries where I buy most of the flowers I plant every year. The new site has no nurseries anywhere near it. Damn! Obligatory garden picture follows:

Golden Health

Gold has been used for medicinal purposes since the time of the Romans. Rightly or wrongly, gold was often used as a medical treatment for a variety of conditions. It does appear to have anti-bacterial properties, much like silver. In medieval Europe, pills were often coated with gold to "enhance" the benefits of the medicine. Paracelsus, the alchemist, developed a solution of colloidal gold which he named "Aurum Potable". He considered it a powerful elixer capable of curing all sorts of ills.

In recent years, gold has experienced a bit of a renaissance in the form of nano-particles. Gold nano-particles are being used for drug delivery systems, biosensors, optical devices, and catalysts, among other things. It's hard to get through a chemistry journal without seeing at least on paper on nano-gold. In retrospect, gold nano-particles aren't really all that new. First of all, they apparently already existed in nature. They were also used by the Romans to create red stained glass. In bulk form, gold is yellowish since it reflects light at the blue end of the spectrum less efficiently than other colors. However, if the size of the gold particles is significantly smaller than the wavelength of visible light, new interactions occur between the light and the gold surface, resulting in a red color. In aqueous suspensions, purple and yellow colors can also be obtained if the particles are allowed to aggregate. In fact, Paracelsus's purple "Aurum Potable" was a simple suspension of gold nano-particles.

As you can imagine, colloidal gold is now available all over the net (for example, here and here) for boosting your physical and mental health. Don't feel like drinking gold? No worries. They also sell nano-silver, nano-copper, nano-platinum, nano-palladium, nano-iridium, nano-titanium, and nano-zinc too.

Why am I mentioning gold's supposed health benefits? Apparently the Romans were on to something back in the day since it turns out their gold nano-particle based stained glass windows are good at removing volatile organic compounds from the air. Will we be seeing gold-based air purifiers in the stores soon? I can only imagine what the web marketeers are going to do with this information.

Hooray! Aqueous Transition Metal Chemistry Talks

I really miss going to ACS meetings, but with chemistry not being as big a focus at my company anymore, it can be difficult to justify (to upper management) the expense of going to one unless there is a session directly related to my current project. I attended a session on reforming catalysts several years ago, but that’s been it for a while. Besides, my true love is aqueous transition metal chemistry and those types of talks can be few and far between. So imagine my surprise and delight when I ran across blogs discussing, not one, but two such talks being presented at this week’s national ACS meeting.

The first talk was mentioned on the Chemistry Blog, concerning a study to use chelating agents like EDDA to extract actinides from nuclear waste. YES! Good, old-fashioned aqueous transition metal chemistry. Okay, actinides aren't strictly transition metals, but they're close enough. I did find it amusing when Mitch wrote "These types of systems look promising and are a nice upgrade over traditional old-school extractors like tributylphosphate(TBP)." Any reference to classic chelating agents as "new-school" is music to my ears. To be honest though, I would have thought that these chelators, especially EDDA, would have been tested for this application a long time ago. At least it shows there are still applications for this type of chemistry yet to be discovered.

The second talk involved the use of Fe-TAML complexes to facilitate the oxidation of organic pollutants by hydrogen peroxide. Apparently these complexes are good mimcs of peroxidase enzymes. Here is the structure of the compound taken from the Collins group website:


Although I haven't had the chance to read the mechanistic and kinetic work on these reactions yet, this seems like a classic example of the TAML group basically locking the Fe into a square planar configuration and keeping it stable while it’s shuttling back and forth between the +2 and +3 states as it facilitates the transfer of electrons between the H2O2 and the target molecule. I've always had a soft spot for chelating agents that lock themselves around metals in tight, specific configurations, significantly changing the metal's properties in the process. My first undergraduate project used an amine oxime to wrap itself around cobalt in a manner resembling the structure of cobalamin (B12 vitamin). Classic aqueous transition metal chemistry. It brings a tear to my eye.

The Value of Toxic Metals

These's a body of water in Montana known as the Berkeley Pit. This lake is a remnant of an old open-pit copper mine that closed down in 1982 when it was no longer profitable to operate. It has since filled with water, about 37 billion gallons worth, and that's when the real chemistry began. Pyrites and other sulfides dissolved in the water and oxidized, forming sulfuric acid, and lowering the pH of the water to less than 3. This led to the steady leeching of metals out of the surrounding rocks, and after 25 years the Berkeley "Lake" has high levels of arsenic, lead, zinc, manganese, iron, copper, aluminum, and cadmium. It's a place only an inorganic chemist could love. It's also a part of one of the largest Superfund sites in the U.S. Nothing lives there - no fish, no birds, no plants - it's a dead zone, or at least that's what everybody thought. In 1995, someone spotted some green slime on the surface of the lake, which turned out to be a form of green algae.

Organisms which manage to survive extremely harsh conditions are called extremophiles. They have been found under the ice in the Arctic, around deep sea vents, and in the boiling water of hot springs. Their ability to survive these conditions makes them of interest to biologists. In particular, many extremophiles demonstrate a superior ability to repair their DNA, which makes them of great interest to cancer researchers. Andrea and Don Stierle have been studying the organisms which have been living in the pit, looking for new compounds which may have anti-cancer activity. And they have been successful, having discovered berkeleydione, berkeleytrione, and berkeley acid, all of which have shown anti-cancer activity. The structures for berkeleydione and berkeleytrione are shown below.

Thought #1:
Makes you look at toxic metals in the environment a little differently now, doesn't it? Perhaps we should be harvesting more of the toxic waste dumps we have created over the years. It could be one of this country's biggest resources.

Thought #2:
Microorganisms are better at making new and novel organic compounds than grad students. Soon, the only reason why faculty members will continue to hire grad students instead of microorganisms will be because grad students are usually paid less than what microorganisms would accept.

Disappearing Elements? - Part III

In what is shaping up to be a recurring theme, there is yet another report warning of the possible future scarcity of an element. This time it's lithium.

The biggest sources of lithium are salt pans and salt lake deposits, mostly in Chile and Argentina. There is also a large, relatively untapped reserve of lithium salt is in the Bolivia salt pans. The Bolivian reserves are thought to contain 5.4 million tonnes of lithium (nearly 50 per cent of the global lithium salt reserves). Since the annual worldwide production of lithium is about 70,000 tonnes (lithium carbonate), this would seem to indicate we have plenty of lithium for the near future, assuming that demand does not significantly increase. Unfortunately, demand may be about to increase drastically. Lithium ion batteries are becoming all the rage, especially as automakers attempt to mass produce hybrid and electric vehicles.

According to William Tahil, the report's author: "to make 60 million plug-in hybrid vehicles a year containing a small lithium-ion battery would require 420,000 tonnes of lithium carbonate – or six times the current global production annually. But in reality, you'd want a decent-sized battery, so it's more likely you'd have to increase global production 10-fold. And this excludes the demand for lithium in portable electronics." At that rate, lithium is going to run out a lot more quickly.

However, this is not a universally accepted opinion. Keith Evans, a geologist with some expertise in lithium mining, disputes Tahil's conclusions. Evans believes that the available lithium reserves are much larger. His critique of Tahil's report is given here, and additional details can be found at his blog, which is named Lithium Abundance.

I don't use lithium very much in the lab, although I have occasionally used LiAlH4 and LiBH4. Still, I would be rather bummed out if we ever ran out of lithium, or any element for that matter. Let's hope Evans is correct.
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In more lighthearted news, John Swain of Northeastern university has a video demonstrating that the iron which is used to enrich cereals like Total is actually in the metallic form. The link to the story is here and a link to a commercial free version of the video is here. I assume this isn't some sort of joke.

Chemistry Journalism?

I try to spend some time every day browsing through the various science reporting websites so as to receive my daily dose of science. I generally find them informative, but today I was greatly disappointed with the level of their quality. Science Daily reported the discovery of “an unusual molecule that is essential to the atmosphere's ability to break down pollutants, especially the compounds that cause acid rain.” "Okay," I thought, "that sounds interesting. I'll check it out." So I read through the entire article, several times, looking for the new molecule until I finally realized the molecule was never identified.

"Okay," I thought, "the writer screwed up. I'll just google some other articles."

Googling did indeed reveal many, many other sites which had covered this story. Unfortunately, it quickly became obvious that other sites weren't describing the molecule either. In fact, the articles were all identical copies of the original Purdue press release. No additional explanations, no deep dives into the subject matter, nothing but simple copying and pasting.

Now that is just plain laziness. I realize the internet is one huge morass of plagiarism -- it's not uncommon to find the same page duplicated over and over again when googling -- but I expect a little more from science news sites that are updated on a daily basis. At the end of the Science Daily article it reads: "Adapted from materials provided by Purdue University." By adapt, I assume they mean reformatted.

Of course, all this occurred because the Purdue press release had failed to identify the molecule. A full color ball and stick model of the molecule was presented, which the science sites dutifully reproduced, but there was a problem. I present the figure and its caption here.

Image caption: Scientists at Purdue and Pennsylvania universities have discovered an atmospheric molecule that is essential to the breakdown of pollutants in the atmosphere. The molecule, which had not been seen before, is unusual because it has two hydrogen bonds. This image shows the structure of the molecule, with the blue ball being a nitrogen atom, red representing hydrogen atoms, white representing oxygen atoms, and the yellow clouds showing the location of the double hydrogen bonds. (Purdue News Service image/Joseph Francisco)

So the molecule was O-H-NH2? That sure looks like one hell of a reactive molecule. Who cares about a double hydrogen bond? We have a hydrogen with two covalent bonds -- a much bigger story. Or maybe the person writing the caption just got the colors for hydrogen and oxygen switched. I was able to figure out the molecule's identity by looking at the title of the abstract tacked on at the end of the press release. If any of the website writers had actually bothered to read this press release while pasting, this mistake would have easily been caught. BTW, the new molecule is an HONO2 + OH moiety, held together by hydrogen bonding.

I'm not trying to dump on Purdue here, mistakes like this can happen. I’m just disappointed that none of the science sites I frequent picked up on it.

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Note: while writing this I noticed that the Science Daily report did list a link to the paper which included the terms OH and HONO2, so it wasn't totally necessary to go to the Purdue site to figure out what was going on.

Humility is Good for the Soul

One of the reasons I started this blog was to sharpen my chemical skills -- skills which have been steadily declining over the years as my job has required less and less chemistry. I just played the “Can You Name the Elements in the Periodic Table in 15 Minutes” game and was reminded of just how little attention I’ve paid to the periodic table in the last 10 years. I expected that my score was going to be rather poor, and I was not disappointed. I only remembered 70% of the elements. I knew I’d have trouble with the actinides and lanthanides, but I also had trouble with the heavier main group elements. And even though I nailed all the transition metals, it required an embarrassingly long time -- embarrassing because transition metals are supposed to be my area of expertise. And it hasn't been that long since I've worked with the precious metals (Pt, Pd, etc.), so why did it take so long to remember rhodium, dammit? That’s pathetic. I also missed a few elements because I couldn’t remember how to spell them. Damn that praseodymium. Where’s the spell checker when you need one? Try the game at your own risk.

Maltese Water Problems

Reverse osmosis is the technique generally used for the desalination of seawater. Unfortunately, the polyamide-based membranes typically used in these processes are attacked by chlorine, which complicates the purification process (meaning more expensive). Polysulfone-based membranes are resistant to chlorine, but their hydrophobicity means that water does not move well through them. Extra hydrophilic sulfone groups can be added to the polymer, but they tend to attach to the least stable sites, which limits their effectiveness. Now, two research groups have combined to solve these problems -- by using the remarkably simple idea of adding the polysulfone groups to the original monomers before polymerization.


Reaction diagram obtained from patent application

Considering the lack of fresh water at locations around the world, anything that can help lower the cost of desalination can be a big deal. As I read this article, one country immediately came to mind -- Malta. Located 50 miles south of Sicily, the islands of Malta are the home country of my wife's parents. As a result, my wife and I have already visited Malta three times in the past 12 years. And believe me – it is hot! Since I think Michigan summers are too hot, you can only imagine what I think about our summer visits to Malta. Here is a family picture taken last summer in Malta.


Not a lot of greenery around. Mars probably has more water in the soil than Malta. Notice my daughter's T-shirt. Never too early to start influencing them.

It turns out that due to the quantity and quality of their beaches, Malta is a common vacation spot for many Europeans, especially the British and Germans, who tend to spend all day at the beach before showing up later in the evening looking remarkably like broiled lobsters. The water quality was fine 12 years ago during our first visit, but the influx of tourists, along with an increased demand for water by the local residents, has apparently stressed the desalination plants. 5 years ago, during our second trip to Malta, the water was really too salty to drink and we essentially lived off of bottled water for two weeks. Last summer, although the water was getting better, we still stuck with the bottled water. It's weird being surrounded by all that water and yet having to import water from the mainland. I hope this new membrane will allow Malta to build a few more desalination plants before our next visit.

Textbooks Are Becoming Old School

Question. How many of you still have your old chemistry (or physics or whatever) textbooks from your undergraduate years? I think I still have nearly all of mine. And although I'm sure this is at least partly due to my being a packrat who can't throw anything away, it's also due to the fact that I like books. I may still go to the web first if I need some piece of information, but sometimes it's easier to go back to your textbooks for more detailed explanations. Besides, there is just an intrinsically good feeling when holding a book in your hands. But after reading this article, I'm beginning to wonder how much longer this trend will continue. Apparently, it's becoming just as easy to download textbooks illegally as it is to download ripped music and warez. And publishers are beginning to react in various ways. Unfortunately, one of their strategies is to offer the texts in ebook format, with subscriptions that run out at the end of the semester. So much for using that text as a reference a year from now.

Publishers, please let us keep our paper-based books!

BTW, this only applies to real textbooks. Textbooks for classes like psychology or sociology can be burned or thrown into an acid bath for all I care.

MIT Propaganda Machine

No doubt, many of you have heard of the recent “MIT Breakthrough”^TM which provides a dramatic new way to store solar energy. Using a simple catalyst consisting of cobalt and phosphate, Daniel Nocera has supposedly removed the biggest road block holding back mass utilization of solar power. This story has been making its way through the web and the blogosphere for several days now and since I’m not an electrochemist, I’m not sure how much more I could add. However, my first reaction after reading the article was a sense of annoyance, and I found myself becoming more irked every time I read another article on the “breakthrough.” Part of my irkness^TM was due to the authors themselves. I’m not sure how much information MIT released to the press, but several of the writers really had no clue about what the invention really was or why it was novel. Perhaps I'm a poor reader, but it required reading several articles before I was even sure exactly what Nocera had and had not done.

Irksome point #1. The constant references to solar energy, despite the fact that this catalyst has nothing to do with solar energy per se. The invention makes the electrolysis of water more efficient, nothing more. Nocera hopes that one day his invention may work in conjunction with solar power, using electrolytically generated hydrogen as an energy storage material, but right now, it doesn’t really have that much to do with solar energy, despite MIT's press release.

Irksome point #2. Many of the article writers appeared to be unfamiliar with the process of electrolysis, marveling at the novelty of being able to electrolyze water at room temperature. Hmmmm, I vaguely seem to recall hooking up a battery to salt water back in high school. Why wasn’t I referenced in these articles? The problem is that the efficiency of electrolysis is poor under these conditions, which I believe is due to the overpotential required when generating gases. (Please let me know if I am mistaken here.) Commercial electrolysis devices have been around for awhile, although to keep the efficiencies high, they are often run at high temperatures and pressures, using expensive electrodes and basic solutions. The novelty of Nocera’s breakthrough is that the cobalt-phosphate material allows for higher efficiencies at room temperature using cheaper materials.

Irksome point #3. The Scientific American writer who referred to both cobalt and phosphate as metals needs a refresher course in chemistry.

Irksome point #4. The MIT press machine set off the BS (Blatant Statement) meter way too often for my taste. Nocera didn’t do himself any favors either, with quotes like:

“This is the nirvana of what we've been talking about for years"

“I've gotten rid of all the goddamn [power] grids."
Probably not during your lifetime, Daniel.

"Solar power has always been a limited, far-off solution. Now we can seriously think about solar power as unlimited and soon."
Sorry, but as I understand it, one of the big problems with solar power is the low conversion efficiency of sunlight into electricity. This invention does nothing to solve that problem.

Irksome point #5. I don’t really have one, but I really wanted to use “irk” as many times as possible. I’ll probably never use the word again.

Snarkier blog posts on this subject can be found here and here.

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!