Nanoh my god I can't believe that got published

It's been blogged about before elsewhere but I can't help but show the following in keeping with this week's theme of nanowtf. It's the graphical abstract from a paper that came out in Inorganic Chemistry a few years ago.


The, uh... thing... on the left is some Ru(bpy) complex and the, uh... thing... on the right is cyclodextrin. (I'm tempted to start calling cyclodextrin "nanovag," but I'm a classy guy, y'know? Real classy. By the way, I'm the future of chemistry, so plan accordingly.)

Oh, and on a side note, Febreze is awesome at getting rid of thiol odors. This person was working near my desk with some nasty stinky thiol, and I just so happened to have a bottle of Febreze and so I sprayed some about. Completely got rid of the odor. It's a lovely staple to have around for some of those more icky-smelling things you work with.

Okay, I'm done with the nanoperversion (for now). ψ*ψ will return soon with, like, something not related to nanocock.

Alternative Nanolifestyles

So a few years back Jim Tour, simultaneous nanogenius and nanopsycho, developed Nanoputians- molecules that look like people- and subsequently made himself the punchline of the organic chemistry community. Tour's done some really good stuff and has been a great innovator in molecular electronics... then he had to go to some crazy-ass shit like make molecules that look like people and get it published in the Journal of Organic Chemistry, of all places, diminishing the journal and Tour's reputation.

I think the most offensive thing, though, is that Tour's Nanoputian community was not represented in whole in that JOC paper. Where were the alternative nanolifestyles? I mean, you had the nanoballerina, which was obviously female, but where were the male nanodancers? Well, I've decided to profile some of them here, because I accept alternative nanolifestyles, unlike some organic chemists, who shall remain nameless. I already introduced you to the Nanobot, scourge of the Nanoputians, but there are many others Tour conveniently left out as well.

First, the Nanoputians' neighbor to the North, the Nanocanadians, eh? Their socialized nanohealthcare makes a mockery out of Nanoputianland's system, and also they beat the Nanoputians at nanohockey every year. But the Nanoputians, at least, know that Nanocanada wouldn't be a country without them.

Next are the Nanohippies. They kinda smell, what with the nanodoobs they're constantly smoking, and their thiol-smelly feet. But they just want to relax man, chill out, get in the ether. They're just asking you to give nanopeace a chance.

Finally, let me introduce you to the Nanoqueers! These, happy, gay fellows are happy to find you the latest fashions in functionalized nanoclothes, and all they ask in return is to be left alone to homocouple in peace. These nanoqueers want to get nanomarried too and be represented just like every other Nanoputian. They're nanohere, they're nanoqueer, get nanoused to it!

And there you have it. A small sampling of the Nanoputians Tour forgot about. My seminar is coming along nicely, but sometimes I need to take a mental break. Some people read books. Some people play frisbee outside. I make ChemDraw images of molecules fucking. Whatever floats your boat, I guess.

(...This might be my most offensive post ever. I hope professors don't read blogs. Well, except for the cool ones.)

EDIT: The crazy kids in the Holland group at Rochester sent this one in, complete with lolnano caption:

And here's Kyle's contribution:

Seriously, if you have some good ones, send 'em in! Make sure they're skeezy though.

Panda-Free Nanobamboo

The wonders of the Internet never cease to amaze me. Just Friday, while reading the Nano Letters ASAP list, I gazed in wonder upon the coolest graphical abstract I've seen yet:


This is a TEM video of a carbon nanotube being born. But not just any carbon nanotube- a bamboo nanotube! I am including a picture of a panda for this reason. Here is a picture of a panda:


Pandas do not eat bamboo-like carbon nanotubes, most likely because they do not grow naturally in China. However, they do grow unnaturally in Singapore, as this group has shown us with their amazing in-situ reaction TEM camera apparatus thingy.

Carbon nanotubes, as I've blagged about before, are renowned for their extraordinary strength and conductivity. Conductive carbon has been a huge thrust in research, particularly in the past five years, due in part to the discovery of monolayer graphene and extensive progresses in nanotube-based devices. Of the latter, two of my favorite nanotube-related discoveries have been putting shit into nanotubes, and grafting nanotubes for use as high aspect ratio AFM tips.

There are basically two kinds of carbon nanotubes: single-wall nanotubes (SWNT) and multi-wall nanotubes (MWNT). Both kinds come in different sizes and MWNTs come in various layer amounts and whatnot. Bamboo-like nanotubes, as opposed to regular nanotubes, are distinguished by graphene-based "knots" that connect one side of the nanotube to the other. Bamboo has knots, too- except instead one or several graphene sheets, panda-approved bamboo is made of plant matter- lots of starches and whatnot. That's why they're called bamboo-like nanotubes.


Granted, imaging of carbon nanotube growth is nothing new. However, this is the first time the growth of bamboo-like nanotubes has been imaged. So how'd they do it? TEM, by necessity, has to operate under ultrahigh vacuum, so ambient growth of nanotubes was out. The process was pretty sneaky. Nanotubes can be grown by heating ethylene gas in the presence of nickel nanoparticles at high temperatures. So they took a sliver of nickel nanoparticles, put it in the TEM, and bled a small amount of ethylene gas into the TEM chamber such that the pressure was kept constant, but still under ultrahigh vacuum. They heated the TEM to 650°C and took several stills of nanotube growth and, through the magic of the internet, put it up for everyone to enjoy.

Videos are one of the more dynamic forms of media on the internet. I hope that more scientists in the future will utilize some of the more non-trivial methods of data presentation, to ensure that things like videos of nanotubes being made are more than just sensory fluff- they can be used as a legitimate, useful form of output.

photoelectrochemical cells, quick & dirty

Alright, already. I wasn't planning on it, but there were enough curious comments on the last post that I'm actually going to tell you guys what that little device was.[1] However, I'm not in the lab now (else, I would be working and not writing, duh) so I'm short on notes and lit references (which are currently lying on my desk, in the lab...where I am not). Soooo...this is the quickie version from off the top of my head. Sadly, I have no pictures for you here. Feel free to correct me. (Especially YOU, Dave. Or YOU, Lakshmi. Or anyone else, really.)
Remember all those posts from a while ago on solar cells?[2] Well, I've been meaning to do a post on Graetzel (dye-sensitized) cells as well. Not that I've ever worked on them, but they're pretty cool. There's a back electrode (read: not transparent), and usually there's a lot of nanocrystalline TiO₂ in them. This functions as an n-type semiconductor. Attached to the nanocrystalline titania is a dye. The "nanocrystalline" bit here is important--it provides a higher surface area for dye adsorption. Since titania's bandgap is too high to have much to do with absorbing sunlight, the dye is rather useful. After all, if it's a dye, it's not white like TiO₂, so it's absorbing something, somewhere in the visible spectrum. Often, the dyes used for this purpose are ruthenium complexes, although price concerns may drive the development of alternatives. Usually there is some carboxylic acid functionality present, which enables the dye to adhere to the titania. Other (frequently oxide-based) semiconductors can be used in place of titania, which has the associated problem (advantage, maybe, elsewhere?) of nibbling on organic things.
So the dye absorbs light, and transfers an electron to the titania. And then...yeah, pretty much nothing, until I mention the electrolyte that is essential to the functioning device. What's generally used is I^-/I₃^-. This, along with the front electrode, provides a cute little redox shuttle to restore the dye to its original state.
As I said, no pictures, since I have never made one of these and am not in the mood to Photoshop a nice little figure for other people to steal.[3] However, if you're interested, there are instructions for DIY dye-sensitized solar cells on the cheap here. Things like this are especially nice for outreach (HINT HINT).
Back to the original purpose of this post (which has thus far been neglected), the nanopopsicle I showed you a few days ago is not, in fact, a Graetzel cell. It is similar, though--the major difference is that the semiconductor used in my little device has a sufficiently low bandgap to absorb light in the visible spectrum.[4] That, and all the materials are completely different. The only appearance carbon makes in the nanopopsicle is in the insulating coat of epoxy.
Speaking of which, epoxy is not such a terrific thing for XPS, so I would be thrilled if someone had other quick & easy ideas for an alternative.

[1] In the early days of CBC, no one said much of anything to a device post. I know many of you are just bored synthetic chemists looking to see neat little structures, but...when there are no comments, we get lonely. And we stop doing device posts. Have the audience members experienced a change of heart?
[2] I'm not terribly satisfied with it, so a follow-up may be in the works. You have been warned.
[3] Not that you would want to, but anything of mine that appears on CBC is free for the taking as long as I am credited (and, yeah, it would be nice if you let me know you were going to use it).
[4] Never mind, y'know, all that infrared light from the sun. Bandgap's not THAT low.

dude, where's my carbon?

Well, I mentioned in my last post that I wasn't doing synthesis, but that doesn't mean I'm not working on exciting new things. Right now, those exciting new things happen to involve a lot of device fabrication. Here's a little something I made last week:




Only one component of this little guy contains my favorite element. Everything else pretty much falls into the "icky metal" (or otherwise inorganic) category. Can you guess where the carbon is? Bonus points if you can guess what the nanopopsicle is actually designed to do.

Pimp My Nanotubes

As far as wacky materials papers go, noone's got anything on RSC journals. The self-cleaning cotton article I discussed earlier was from an RSC journal. I think out of all the journals, the most entertaining to read are Angewandte Chemie and ChemComm, the former for allowing flowery, grandiose language that occasionally makes for entertaining prose- the kind of writing I wish the scientific community would start favoring. One need only read one of one of Nicolaou's excellent reviews in ACIE to know what I mean.

But anywho! This awesome article comes from ChemComm's ASAP I got this morning. ChemComm's articles are always on the fringe of really novel chemistry, sometimes bordering on the simply wacky. This ChemComm from Ma and coworkers can I think best be described in the following theoretical brainstorm session:

Boss: Alright everyone, we want to get aromatics like benzene out of the water supply. Suggestions?
Lackey: Uh, well, activated carbon seems to work pretty well...
Boss: Too messy! Impossible to separate!
Lackey #2: Well what if we use something a little easier to separate, like, I dunno, iron? We could use magnets.
Boss: Iron doesn't get crap out of the water supply!
Lackey #2: What if we adhere it to the carbon?
Boss: Hmm... kay. How do we do that?
Nano-Obsessed Lackey: You know carbon nanotubes are more efficient at adsorbing aromatics than activated carbon is...
Boss: Nanotubes! Everyone loves nanotubes! Instant paper!
Nano-Obsessed Lackey: Yeah! And we can put little iron nanoparticles INSIDE the nanotubes, and functionalize the nanotubes with ionizable groups to make them even MORE soluble! Then, we can just remove the stuff from the water with a magnet!
All: Hurrah! Beer and fellowship money all around!

And thus, these pimped-out nanotubes were born. The group started with some multi-walled nanotubes which they stuffed with iron, reduced under high temperatures to generate pure iron nanoparticles, while simultaneously using a radical-initiated process (with everyone's favorite radical initiator- AIBN) to functionalize the nanotubes with a cyano group which is subsequently hydrolyzed to form water-soluble carboxylates on the nanotube surface.


The result is a pimped-out water-soluble magnetic nanotube that can adsorb benzene with the best of them, be removed easily with a simple bar magnet, washed and reused. Great application of nanocrap for use in cleaning up the environment! Is there nothing these lil' nanotubes can't do?

Have you seen this girl?

A Japanese artist(?) has made a pretty creepy video of what he calls Ferrofluid sculptures. I have to say, this video creeps me out, but it does use ferrofluids, which are pretty awesome. A ferrofluid is a dispersion of iron nanoparticles in (usually) water, which can interact with magnetic fields to generate corrugated patterns that look like this:



Ferrofluids are more than just artsy and freaky-cool. Its magnetic properties have found use in the IT, optics and defense industries. They will probably be partly responsible for this guy looking for Sarah Connor.

And for the truly bored during this Festivus break, here's how to synthesize your very own ferrofluids. Have fun!

Self-cleaning cotton ftw

As Ψ*Ψ showed in the last post, pretty colors are awesome. But sometimes, pretty colors are better off in the flask than, say, on your new white shirt. And ugly colors are frankly never appreciated anywhere. Imagine the following situation: you're in lab, drinking coffee and working, it's midnight, and you spill some coffee on your lucky synthesis shirt- a white shirt you got for free from some hot female (or male) sales rep at PittCon. Well crap, now if you want to clean it, you have to go home and do a load of laundry and you're running a column right now and... well, looks like your lucky shirt is now your lucky coffee-stained shirt. "What if," you think... "What if I never had to clean this shirt again?"

Nanocrap to the rescue! A textile group in Hong Kong has developed a type of fabric they call self-cleaning cotton. In it, cotton is doped with nanocrystalline TiO₂ that act as self-cleaning agents. Upon irradiation with sunlight for a few hours, the titania acts as a photobleaching agent to remove common stains such as red wine and coffee. Furthermore, the titania possessed antibacterial properties, rendering the fabric truly self-cleaning, from both a colorimetric and microbial perspective. However, the casting process to embed these titania crystals in the cotton weakens the structure of the cotton, rendering the cotton more prone to tearing. Furthermore, I'm not sure how titania would react to your skin, so wearable self-cleaning cotton adds a whole new challenge to the mix. Still, this is a pretty awesome start to a interesting field, and one that blends nanocrap with materials with useful properties.

Just think: in a few years you'll have one less reason to go home. This is either a good or a bad thing, depending on your boss' thoughts on the matter.

Don't make me nanocut you

Let's face it: there is really only one reason why nanotechnology is such a hot topic nowadays, and that is because "nano-" is the hippest prefix ever. It's terribly euphonic, its consonant repetition pleasing to our ears. Nano slides off the tongue easily, and the second syllable just sort of hangs there, yearing to be affixed to anything. And that's aside from the dimensions it refers to: just the word nano gives the reader a sense of the impossibly small, and impossibly small, as we've learned from every tech company ever, is awesome. Thus, now just about everything can be nano'd, though not all of it is really useful.

This one might be though. Doods and doodettes at NIST and CU-Boulder have developed the alliterative "Nanoknife," a sort-of cheese slicer that utilizes a material close to my heart as the cutting wire- carbon nanotubes. Carbon nanotubes are only a couple of nanometers wide and are quite durable, thus the exhaustively internetty ranting about using them to build a Space Elevator. Utilizing a single nanotube grafted to tungsten needles, this nanoknife can potentially be used by biologists to cut very small slivers of cells with high accuracy. Have they actually tried to cut stuff with it? Well... no. Engineers as they are, they HAVE done a bunch of pressure tests on them to test their durability (they are weakest, not surprisingly, at the graft points). They plan to cut stuff with one later on, so your nanocheese will have to wait. Nonetheless, this and other nanotools this team has developed might greatly help biologists do... whatever the hell it is they do. Something about life and shit.

(And check out that hot AFM action in the pic! Makes ME wanna la-la. In the kitchen, on the... lab... floor.)

They don't see him rollin'

For my first post (short as it will be), I'd like to pay homage to the most, er, unique proof-of-concept of nanotechnology I've seen to date. out of the Tour group at Rice (the reigning king of proof-of-concepts) comes... Nanocars! Yes, Nanocars. Cars that are about four nanometers in diameter, have Buckyballs for wheels and roll around on gold surfaces, using external voltages for power.

You might ask yourself, "Umm... what? Why?" I don't know. This is what the Tour group does. They take their incredibly sophisticated array of nanoscale techniques and... make nanocars and molecules that look like people. I'm not sure if this is a stroke of genius or if Tour just gets paid a lot of money to fuck around with nanotech, but either way you slice it, they won't be catchin him ridin' dirty. (Unless they had an STM. Which they might.)

Nevertheless, the nanocar's applications, which probably won't have a direct impact per se on society, are definitely a great way to get the public interested in nanotechnology. Tour's rather evangelical nature certainly will help pave the way for other, more potentially useful applications. Like nanoMinivans to haul around nanoKids that are driven by nanoMoms that constantly cut nanoMe off because their nanoLives are that much more nanoImportant. Not like that would ever happen to me in the macroscale, though.