TaxLOL

A cute campaign came up on Twitter to make some Lolcats-style memes for science. Michelle and Ed Yong have weighed in already, and I thought I'd make a play for total synthesis:

Cheat sheet

Friday Fun: John Hartwig, 2.0

Did I just see a GQ model pop up in my Inbox?

Source: Yale University

The email just dropped in to announce Prof. John Hartwig's receipt of the 2013 ACS Catalysis Lectureship. Kudos to him, he certainly deserves it! Over the past few years, I've truly enjoyed reading his explorations of Ir and Ni catalysis to achieve challenging transformations.

But the shocking part was the photo crop in the upper left corner...what a change! The "Hartwig" I have in my head, circa 2004, was this guy (right). Suit, tie, some distinguished grey in the temples, a demure smile.

But who's this, now? Check out the older, wiser Hartwig, stolen off his new group page at UC-Berkeley (left). What a change!

Source: UC-Berkeley

Gone are the glasses, the bookshelves, and the formal tie. Now we have a slightly more grizzled, more wistful JH, hair scattered by the wind, looking like he could take on the world.

I fully approve.

Happy Friday,
SAO

Friday Fun: Chemistry Craigslist

Most folks these days have moved around some - whether for school, jobs, or family - thus buying and selling furniture and appliances on the cheap = required skill. 

Enter Craigslist, the online "Wanted Ads" for the grad student who just needs to find a $50 couch.

Many of the raucous online discussions our community has had over the past few days (plagiarism, checking preps, #chemjobs) would probably benefit from better communication amongst ourselves, and with the larger world. Well, what if we had a little piece of digital property over on CL? What might that look like?

Help Wanted

Needed: Dissertation Typist. Must have encyclopedic knowledge of p-chem terminology, command of stereochemical language, enjoy ramen noodles for lunch. 130 wpm / minimum. 

Please bring own laptop if possible.

LOST: VOLATILE PRODUCT

Dag! While uzing rotovap on teh third-floor labz, heard mah cell go off, rushed too take call. Came back to nuthin'! Anyone emptee the trap l8tley? 

Missed Connections. You: Tall, gangly chemist in need of a shave with thick glasses and a slightly stained lab coat. Me: Passed you by on an OSHA inspection, petite brunette, business suit, designer  goggles. I thought we shared a glance, but you may have just been nervous when you saw my badge. Perhaps a drink might help? Call 555-8G13

Plagiarism Party

We're meeting down in the conference room at 7:00PM tonight for drinks and text-searching. Up your alley?

                          - Location: Cambridge, MA

                                 - Just kidding, it's BYOB. But we'll have pizza (I think)

                                 - Scratch that, we're broke. But come anyway!

Happy Friday, everyone!

-SAO

A Very Important Point

Driving home tonight, I happened upon a fascinating story on All Things Considered. This latest installment of Julie Rovner's series on women's reproductive health analyzes the debate between supporters and opponents of Plan B (levonorgestrel) and ella (ulipristal), two controversial emergency contraceptive measures. I'm hardly well-versed enough to take sides, but something said by one of the scientists Ms. Rovner interviewed really resonated with me (at 4:32):

"Chemically related is not chemically identical." - Dr. Diana Blithe, Contraceptive Program Director, NICHD

Well, in a word: yes! As a career medicinal chemist, I completely concur that tiny changes - say, a methyl here or a deuterium there - can have huge effects on drug potency, targeting, clearance, recognition, plasma concentration, etc, etc.

Dr. Blithe's statement rebuffed a remark made by another researcher, who said that since abortifacient RU-486 (mifepristone) and ella contained similar core skeletal structures ("chemical cousins"), they must function similarly at the same dose.

Actually, are those two drugs really that similar?

Here's ella and RU-486 side-by-side. You'll notice that the "Western" fragment (left) is identical. This probably underlies the two drugs' similar mechanisms of action (progesterone receptor competitive inhibitor) and similar active metabolites (amine demethylation).

But what about at C-17? For one, they're locally diastereomeric - the alcohol points "up" (beta) for RU-486, but the related acetate "down" (alpha) for ella. The various moieties dangling off the right side subtly change drug targeting, explains Dr. Blithe, directing effects toward the ovary (ella) or the uterine lining (RU-486). Finally, different uses (delayed ovulation vs. pregnancy termination) combined with different pharmacokinetics result in different dosing: ella sells in 30 mg tablets, while RU-486 utilizes 200 mg of active ingredient...quite a large dose for a steroid.

Podcast: CJ and SAO Talk Plagiarism

After the latest Xi Yan / Dalton story broke, Chemjobber was gracious enough to sit down with me to hash out our feelings about plagiarism, peer review, and what we hoped might happen when the next batch of purloined text comes around.

Timepoints:

0:02 - Introduction
0:56 - You say "incensed," I say "attracted"
2:29 - Bogus!
3:09 - CJ steals my Great Idea
3:40 - Playing 'Editor' with SAO
5:32 - Is it true? Is it new?
7:01 - Entering the 'gray area'
8:12 - Azaspiracids: Three papers, three different intros
9:30 - Doris Kearns Goodwin
10:44 - Please don't copy word-for-word!
12:23 - Being an Asst. Professor is hard
13:55 - We need a cultural context guidebook...
15:05 - World Science - Impact Factor 35.0
16:20 - Language / Science Barriers
18:09 - Peer Review - Get 'em while they're young!
19:57 - $$ Entrepreneurial Idea! $$
21:33 - How much time do you spend reviewing?
22:45 - CJ's Dangerous Game
23:07 - Conclusions

24:32 - Bonus track

Thanks, as always, to CJ for some stimulating conversation!

Thin Layer Consternation

Earlier today, I was involved in a minor dust-up with some commenters over at Derek's blog. A central issue concerned my (admittedly quick'n'dirty) TLC, which meant to indicate the complete consumption of the acrylate starting material for Blog Syn #002.

Well, since I was already running another entry for #003, I decided to pause and take stock of my TLC tool-box: yes, I should use a ruler, and yes, a classic TLC would have lots more info (solvent system, stain, clearer labels, etc).

So, I took a sample from my IBX oxidation of methylnaphthalene to 2-naphthaldehyde (12 h timepoint, set up in straight DMSO with 0.1 volume of H2O). Results below:

Before anyone goes crazy, that's DMSO / H2O on the baseline, and the SM at Rf ~0.8. It's stained in potassium permanganate, which forms pale yellow spots upon heating. I circled the "UV-only" spots with a pencil before staining.

I'm guessing that the tiny new spot (Rf ~0.45) represents trace aldehyde. But, as you can tell, we're still a long, long way away from completion. Sad, because it was a lot more homogeneous this time!

Readers: How's my technique? Have any more pointers?

Please Pluck Out My Eyes

Regular readers of the blog may know my one-man campaign to eradicate "coloring book" abstract graphics. Of course color helps out - when applied sparingly and to 'draw the eye' - but why the MSPaint-fill backgrounds? Especially those with similar structure colors, which obfuscate more than help?

I ask, of course, because these two abstracts just showed up back-to-back in my RSS feed:

Abe Group, JACS ASAP

Jia Group, JACS ASAP

Readers: Do these colors help you to understand something specific about the chemistry? Or are they just too much?

Was Justice Served?

Source: PrariePastor, Wordpress

What should happen to serial plagiarists?*

Regular readers may recall that I posted back-to-back on suspicious swaths of text in two peer-reviewed papers by Xi Yan, a chemistry professor at Beijing Normal University. Along with others (including the authors of both original papers), I concluded that the huge blocks of essentially unchanged text in Yan's papers merited action by the respective Editors of Chemistry and Dalton Transactions.

So, what happened?

Check out the Dalton paper - there's now an "Addition" listed, off to the bottom right of your screen. It reads (emphasis mine):

"After the publication of our article, it was brought to our attention that an earlier publication containing related work to that described in the article should have been referenced:  'Dynamic copper(I) imaging in mammalian cells with a genetically encoded fluorescent copper(I) sensor', Seraphine V Wegner, Hasan Arslan, Murat Sunbul, Jun Yin and Chuan He, Journal of the American Chemical Society, 2010, 132, 2567-2569. 

The authors apologise for this oversight."

Oversight? "Related work?!" A cowardly, measly, long-overdue REFERENCE?!?!?

Fact: Xi Yan has been caught twice with duplicated text and re-hashed science.
Fact: He has now been given a "pass" for bad behavior by RSC Editors.

I cannot accept this decision. Simply put, it flies in the face of everything I know as an honest scientist. Papers are hard to write! Original science doesn't come easy! I sympathize, but that doesn't condone taking another person's work as your own. This failure to discipline permits not just Xi Yan's folly, but opens the door for future plagiarism.

Hypothetical: Playing under these rules, what's to stop me from re-publishing all of E.J. Corey's papers under my name? I'll just subtly alter the substrates, and make sure to bury his name is my References section! Does anyone else realize how ridiculous that sounds???

Another wrinkle: a friend of the blog mentions that the RSC, along with several other publishers, belong to COPE, a publication ethics group. From COPE's own Code of Conduct (emphasis mine):

"Best practice for editors would include: 

• adopting systems for detecting plagiarism (e.g. software, searching for similar titles) in submitted items (either routinely or when suspicions are raised) 

• supporting authors whose copyright has been breached or who have been the victims of plagiarism 

• being prepared to work with their publisher to defend authors’ rights and pursue offenders (e.g. by requesting retractions or removal of material from websites) irrespective of whether their journal holds the copyright"

Following ChemBark's example, I'll lay out my recommendations:

1. The half-hearted "Addition" should be taken down, and Yan's paper retracted.
2. Xi Yan should issue a massive mea culpa to his university, Dalton, and its Editors.
3. Dalton should take steps to ensure that future plagiarised papers are screened out prior to publication.

Failure to take these steps will result in a severe lack of confidence for all future journal publications. I have reached out to the Editorial staff at Dalton for comment, and will update this post if/when I receive a response.

Update (2/17/13) - Try this at home: Friend of the blog S.C. passes along DOC Cop, an online manuscript comparison tool. I uploaded the two texts, and received a match report of 19%. Although, a quick look-down indicates it's likely much higher than that (the software misses one-off substitutions and different reference numbering). I would estimate ~35% duped text.

*To everyone who comes here for fun chemical adventures and light-hearted content: I'm sorry. I don't mean to be the chemistry Internet Police, but I strongly, strongly believe that science needs a level playing field. More fun to come, I promise.

Friday Fun: All Your Base Are Belong to MOBBs

(With apologies to Ohio)...What's round in the middle and "I" on both ends?

It's a twist!
How does that biaryl bond survive?
Source: OL | ICIQ

If you guessed the newly-reported mu-oxo bridged bisiodones (MOBBs?) reported in Org. Lett., you win. We're all familiar with famous mono-hypervalent iodine reagents: IBX, Togni reagents, iodosobenzene, Dess-Martin, etc., but I'll admit this is the first time I've seen them 'doubled up' like this.

So, aside from a mangled crystal structure - which, if you believe it, almost folds the biaryl in half -  this reagent seems predisposed to rearrange itself in situ, forming a charged pair: [O=I-biaryl-I-NTs2(+)] NTs2(-). Thus, the same molecule decomposes into electrophilic and nucleophilic bis-tosylimides, which can be used to diaminate simple olefins.

Pretty schnazzy.

Now, that's a load of atomic mass to drag around for just two simple C-N bonds. Can we do better? Sure - the researchers demonstrate some early catalytic runs, and along the way swap out the biaryl for a chiral binaphthyl (c'mon, you saw that coming), which induces a proof-of-concept 32% ee.

I'll admit it: when I first saw this abstract pass by, I thought not of reactions but of...invaders. Specifically, Space Invaders, the formative 1978 Atari arcade game where your blocky white tank takes aim at dozens of 8-bit baddies falling from the sky. To me, the fully-formed reagent looks just like the "middle" guy in that picture (see below).

Credit: Atari

Happy synthesizing, happy gaming, and happy Friday!
-SAO

Academic Geneology: "ChemisTree"

Source: Chemistry Tree

Have I been living under a rock? How has the Chemistry Tree escaped me for so long?

Apparently, there's a crowd-sourced, Creative Commons-enabled effort to catalog everyone's academic* genealogy in one easy location. Looks like it spouted from the (much larger) Neurotree, which started up in 2005 and boasts some 38,000 members!

Now, I've seen departments do this for their own faculty - which always seems to trace everyone back to Liebig - but never to this extent. There's a "Closest Nobel" button, so you can see how far removed you are from the Prize, and you can view the "Academic Canopy," which gives a birds-eye overview of all the fields currently cataloged.

Far as I can tell, there's a lot of the "big wheels" already plugged in, but several young up-and-comers are missing. Can you help fill in the branches?

*Nature abhors a vaccum, and I don't see anyone creating an "Industry Tree" (LinkedIn, perhaps?), though it would be fun to see where all the non-academics end up, and who they mentor.

Making Time

Do you ever feel like you don't have enough time?

That seems to be a popular topic today, with two pieces in the popular press exploring that concept, albeit from very different viewpoints.

The first, from Wired writer (and Mythbusters host par excellence) Adam Savage relates the value of deadlines. He claims that he usually allows projects to languish on his workbench when given open-ended timelines, but while 'under the gun' performs at a high level and (in his words) finds solutions that are "innovative, elegant, and shockingly simple."

Of course, there's always that third option...
Credit: BBC | Wikipedia

The second, from the Times' Opinion Pages, tells a very different story: how to relax in order to increase one's productivity. Author Tony Schwartz, CEO of the consulting firm The Energy Project, argues that 'more is less' in the long run - we push to try and fill up work days with actual work, which results in tired, nonproductive employees. He recommends 90-minute 'sessions,' where one focuses solely on the task at hand, followed by breaks, exercise, or even - gasp! - naps.

Chemistry Angle: I like both approaches, but find they work best at different times in project cycles. While you're slogging through, trying to find those optimized conditions or exploring new leads, it's best to follow the '90-minute sessions' approach. Take a break! Nearly every scientific autobiography I've read suggests that problems get solved when the authors step away and do something completely unrelated for a while (Kekule, Feynman, Newton, Watson, Fleming, etc.)

Adam's approach (Hurry! Time running out!) fits best when you have a specific goal in mind - getting that paper out, presenting at the conference, filing that patent. Though I hate to admit it, the 48 hours leading up to submission often produce the bulk of such efforts. Sometimes it's worth the extra stress - and extra coffee - to get a superior final result.

2013 State of the (Scientific) Union

(Adapted from last year's post, with updated data for 2013)

Did you watch President Barack Obama present the 2013 State of the Union address?

Source: Whitehouse.gov

Once again, I downloaded the text to the 2013 S.o.T.U. (Unfinished Tasks / Next Chapter), and compared it against the text from 2011 (Winning the Future) and 2012 (An America Built to Last). Now, I’m not a political pundit or a news analyst - I’m a scientist. So let's see how certain scientific themes grew or shrunk over the past 366 days (leap year!).

Breakdown (# of each word in full text):

Energy – 2011: 9, 2012: 23, 2013: 18

Oil – 2011: 2, 2012: 10, 2013: 5

Gas - 2011: 1, 2012: 9, 2013: 7

Wind / Solar - 2011: 4, 2012: 3, 2013: 4

Nuclear – 2011: 5, 2012: 3, 2013: 3

Batteries - 2011: 0, 2012: 2, 2013: 1

-----

Biotech / Biomed / Biofuel – 2011: 3, 2012: 0, 2013: 0

Chemical – 2011: 0, 2012: 1, 2013: 0

Tech / technology – 2011: 12, 2012: 9, 2013: 8

Science / scientist – 2011: 7, 2012: 2, 2013: 4

Engineering – 2011: 3, 2012: 1, 2013: 3

Research – 2011: 9, 2012: 4, 2013: 4

Development – 2011: 1, 2012: 2, 2013: 1

-----

College / Universities– 2011: 12, 2012: 15, 2013: 8

Math – 2011: 3, 2012: 0, 2013: 2

Health – 2011: 8, 2012: 5, 2013: 5

Internet - 2011: 6, 2012: 1, 2013: 1

Cyber - 2011: 0, 2012: 1, 2013: 2

Jobs: 2011: 25, 2012: 33, 2013: 32

Exciting 2013 "one-offs" - Human Genome, drug development, battery materials, 'Space Race',  human brain, IBM, networks, climate change, NASA 'Mohawk Guy' (guest of the First Lady)

Is there a take-home message here? Does word count relate to the overall direction of the country? Probably not. Each speech is different: 2013 spent serious time on fiscal reform, job creation, foreign affairs, and domestic mass shooting incidents, while 2011 focused on education, business, and terrorism, and 2012 dealt with global politics, Congressional reform, and taxes.

Still, science and scientific policy seem to be waning in recent Presidential politics. Ironically, energy production and storage now garner increased mentions while R&D, education, and biofuel fall away.

Readers: Did I miss anything? How'd you react to the speech? Let me know in the comments.

Elsewhere...

Chemophobia got you down? Need a laugh? Call the Chemistry Avengers!

Hey, check it out: Blog Syn #002 is live!
(And I hear that #003 is well on its way...)

More to come at JLC in the next few days. Stay tuned!

Obituary: T. Occsic Wastrel, 95

For Immediate Release:

Professor T. Occsic Wastrel, "Ollie" to his friends, passed away after a short illness Tuesday. A member of the National Academy and Chair of the Presidential Chemistry Outreach Committee, Dr. Wastrel mentored several doctoral students now ensconced in the highest echelons of chemical industry and 'Big Pharma.'

Born in Bonn, Germany in 1918, Ollie studied at the prestigious Arbeitsschuppen, from whence he received his Diplom in 1936. Nurturing a natural proclivity for synthesis (perhaps spurred on by his well-stocked basement lab), Dr. Wastrel enrolled at Harvard in 1937, earning a B.A. in 1940. His lone publication "On the Hydrolysis of Various Acid Esters" with Distinguished Professor H. Slavedriver, garnered him a Ph.D. in 1942, followed by a 6-month postdoctoral stint at MIT studying seawater gold extraction.

A "gentlemen's agreement" between his former advisor and the hiring committee resulted in Dr. Wastrel's immediate appointment at Princeton in 1943. Associations with future Manhattan Project scientists led to a life-long association with the Atomic Energy Commission (later the NRC), and thus a veritable wellspring of guaranteed future funding. Combined with the G.I. Bill and the scientific expansions of Dr. Vannevar Bush, Prof. Wastrel had a sure path to academic glory for the ensuing five decades.

During his 50+ years of active research, Prof. Wastrel would direct his learned eye towards whatever seemed reasonably likely to be funded. Later life found him traveling the world as a special guest lecturer, consulting for tobacco and mining concerns, and collecting royalties for a pivotal patent concerning the dusty residue found in cathode ray tubes. He would eventually amass 30+ peer-reviewed papers, 2 patents, and train 10 doctoral candidates.

Friends of Ollie recall his jaunty devil-may-care attitude, whether sharing a smoke by the fume hoods, or catching up with a scotch at the Faculty Club. "On Friday evenings, we would pour our synthetic waste down the sinks, incinerate our Bakelite vessels and paper trash, and head off for a spirited round of badminton," remarked E.Z. Tenyoor, who occupied the office down the hall.

In lieu of flowers, donations may be sent to the T. Occsic Wastrel Community Cleanup Fund.

Note for the serious: This is satire, based on this tweet from CJ.

"Tons" of Snow?

Three feet is a lot of snow. Heavy, wet snow.

How much, exactly? Here's a thought exercise: We have some friends in the deeply-affected area of the '013 Blizzard. Their driveway is about 100 ft. long x 6 ft. wide, and is currently covered in 36" (three feet!) of snow.

Quick assumptions: let's assume it's a regular rectangle, and let's say a cubic foot of heavy snow weighs about 15 lbs (7 kg). Thus, we have (100 x 6 x 3) = 1800 cubic feet, which weighs (1800 x 15) = 27,000 lbs. That's 12,000 kilograms, or 12 metric tons.

That's as much weight as five Ford F-150 pickup trucks, or about 10 elephants. Really.
(Time to call for a plow, maybe?)

Best wishes for safety and fast utilities service to those affected in the Northeastern U.S.
-SAO

Friday Fun: Timing = Everything

Looks like a snowy weekend for those in the Northeastern U.S. Predictions for the New York-to-Boston area, which includes a large swath of the biotech / pharma corridor, expect anywhere from 8 to 24+ inches of snow over the next 2 days. 

Well, to paraphrase one of my Twitter colleagues, Pharma 'laughs at snow the way it laughs at stable jobs.' Thus, many of you will still be venturing out into the Snowpochaosalypsemageddisaster. Hopefully, you're already stocked up on salt, sand, and dry goods. 

If you're one of the 'lucky few' who've already closed up for the day, Nature has you covered: a perfectly-timed Top Ten list for future ice and snow research! Author Thorsten Bartels-Rausch says it best on his research page: "Snow and ice are chemically active." From trapped gases to metal reduction, there's a fascinating molecular interplay within frozen water matrices. Go have a look!

Happy Friday. Stay safe!
-SAO

Idol Dreams, Dashed

Fresh from the Inbox:

"Thank you for applying to be part of our America’s Science Idol workshop at the AAAS 2013 Annual Meeting.  We had many quality applications which made choosing extremely difficult.  Unfortunately, you were not chosen." 

"I mean, a talking, blogging dog? You gotta be kidding us, right?"* 

[single tear]

My congratulations to all who were selected, it looks like it'll be a fun time.

*P.S. This was not part of the original rejection email.

Football Pain? Solve it with Solvent

A friend pointed me towards ESPN's recent interview with former Dallas Cowboys defensive lineman Tony Casillas. When asked about the recent hullabaloo regarding deer antler spray, Casillas reportedly answered: "That's nothing. We used to use this stuff called DMSO..."

DMSO? Dimethyl sulfoxide? Like, the polar aprotic solvent we all know and love from the Swern oxidation?

The very same.*

I hadn't realized that the compound had such a long history in medicine. Suppose I should have remembered hearing Breslow once talk about DMSO as his inspiration for the development of SAHA (vorinostat). Still, after the heated warnings I've always received from tox folks while handling DMSO stock solutions (Double gloves! Wipe up spills ASAP!), I'm hesitant to try it myself.

*A note of caution: I'm not endorsing rubbing DMSO on your balky knee or tennis elbow. You should always ask a medical professional before trying something like that. Please don't say "I read this on a blog..."

I Wish...

...that I could make complex science sound simple like Deborah Blum or Carl Zimmer.

...that I could write confidently, yet personably, like Stu Cantrill or Derek Lowe.

When you wish upon a blog...

...that I could mine data and use it to better support my statements and defend against trolls like Chemjobber (can).*

...that I could scribe long-form drafts with overarching structure like Ash or Vinylogous.

...that I could come at subjects with passion and fire like ScienceGeist, Dr. Rubidium, or Paul.

...that I could organize like Bora.

...that my writing sounded 'fresh' and exciting like Carmen or BRSM.


*Update: CJ is not a troll. Poor sentence structure. I blame my second-grad grammar teacher.

Should Chemists 'Dress for Success?'

Chemists: Does your workplace have a dress code? Should it?

Long-time readers may remember that I opined on this very subject waaay back in the early days, noting that long-term bench work does a number on nice duds. Well, I've since switched jobs, and in my current role I'm often called upon to meet vendors, interact with inspectors, and strike up academic collaborations. So, jeans and beat-up T-shirts are decidedly out for me.

I've found that thrift stores (Goodwill, Salvation Army) tend to offer reasonably nice business casual clothes for 20-30% of the original items' costs. And, as Chemjobber has pointed out, proper lab PPE certainly helps to protect any investment you make on the sartorial front.

But out of sheer curiosity, I wonder: does anyone get to wear jeans and T-shirts past grad school?

Let me know in the comments. Thanks!
-SAO

Slow Down, Bob

An open letter to R.B. Woodward (RIP):
(Playfully adapted from Dr. Freddy's post)

Dear Bob,

Listen, I know you can't hear me right now, but I feel like this post may be overdue. Back in your day, the closest thing to "blogs" were the Editorial pages of the newspaper and (actual, cork) bulletin boards. Thus, I'll ask on behalf of all struggling grads and bench chemists: could you please stop being so darn productive?

Someone recently pointed me in the direction of your dual MIT theses. That doctoral title, what chutzpah!

I know, I know, things were different back then. You didn't have a single NMR in your dissertation; after all, it wasn't invented yet! Ditto mass spec or HPLC traces. You characterize everything by mp, bp, and elemental, and yet I can't believe you finished your Ph.D. in a year. 

Dissertation Stats: 64 (typewritten) pages, 23 (hand-drawn) structures, 27 references

Of course, we all know what happened next. You postdoc'd at Illinois for maybe two weeks, and jumped over to Harvard for a 40-year stint. You (almost) single-handedly applied UV and IR to molecular characterization, you made strychnine, chlorophyll, and B12, and you won a single-scientist Nobel at the ripe old age of 48. Some folks even thought you might have deserved (at least) one more! 

Your personality still towers over us today - legends of blue suits, chain smoking, and three-hour lectures abound in roughly 58.8%* of recent blog posts. Even your fashion sense is back in vogue, (perhaps) influenced** by your invisible hand.

While you were making quinine and cortisone in your 30s, we're now just trying to find good, stable jobs. So Bob, please enjoy your well-earned rest, and stop reminding us of how life could have been a few generations ago. We just can't bear the comparison.

*Studies show that roughly 95% of statistics are made up on the spot

**And Mad Men

Friday Fun: [Title Goes Here]

Catchy caption!
Source I 'borrowed' from so I could
avoid drawing it

Wonky offbeat lede!

So, did you hear about Publication X / News Article Y*? Superlative, exclamation! (attempted witty aside). Reminds me of [mostly unrelated event], which I'll support with links. (Jump-backs to Chemjobber or Derek here.)

But wait, there's also [theoretically novel wrinkle] that I'll compare to the first thing, with more links. Boring support text nobody reads gets stuffed in the middle. Tangential relation to Study Z, which I'll forget to link later. [Self-referential in-joke]

Thesis re-hash, leading to BOLD STATEMENT** with overpunctuation‽‽‽ Italicized background option in case I need an out. More filler text. More filler text. A few soon-to-be-broken links for posterity. [Inspirational shout-out to Ash, Carmen, or Paul]. Pop culture reference to obscure band/movie/book for random chuckles.

One-sentence wrap-up.

Readers: Desperate comment solicitation to validate blog's existence.

*Asterisks are bad! Didn't my Editors teach me anything?
**Apparently the lessons didn't stick.

Happy [Day], Everyone!
Talking Dog Avatar

Pd Bites Back! Isopropyl Surprise

Although we don't always admit it, we chemists love a good surprise.

That's the feeling I got reading through a recent JACS ASAP, from the Chen group at PSU. They've been playing with an easy-to-remove C-H activation auxiliary (PA) first developed by Daugulis back in 2005. They've taught it some pretty neat tricks thus far: C-H amination, alkoxylation, and even alkylation reactions using simple primary iodides.

Their latest extends the chemistry to methyl iodide, which, when combined with some silver salts and a phosphate additive, usually plunks a new CH3 on an unhindered, kinetically-accessible gamma-methyl (i.e. the chain grows by one). However, in the case of norbornene, something wild happens: the Pd catalyst activates a secondary C-H bond, sticks a methyl on, but doesn't stop there; it "bites" into the newly formed methyl and adds on two more, to produce an isopropyl group. Sweet!

     
       Source: JACS ASAP 2013 | Chen group, PSU

Chen's group shows that the position of the new i-Pr depends upon exo ("up") or endo ("down") relationships of the initial amine, but doesn't speculate much on mechanism.

O Norbornene Tree, O Norbornene Tree;
I do not grok your sterics.

Well, allow me! I wonder what happens if you keep feeding iodomethane into the system. I'm sure there's a limit (likely steric) that prohibits additional branching past a certain point, but currently nothing completely rules out a dendrimeric "norbornene tree" compound, right?

Readers, can someone disabuse me of this crazy notion?