Giving Up Benzyne

From Rolf Huisgen's highly detailed and comprehensive biography The Adventure Playground of Mechanisms and Novel Reactions comes this rather eyebrow-lifting passage:

"I had several reasons for abandoning benzyne chemistry at the beginning of the 1960s. Many groups were active in the field, and other areas like 1,3-dipolar cycloaddition began to blossom in Munich. In addition, Georg Wittig, my venerated senior colleague, signaled in print and word that he regarded dehydrobenzene as his domain."

Left, benzyne, in one of its (many) accepted resonance forms
Right: Emeritus professor Rolf Huisgen, of dipolar cycloaddition fame

I wonder: Given the advances in benzyne chemistry over the past 112 years, and that up-and-coming groups make its study a central piece of their research portfolios, would this choice be made in today's research landscape? Readers, have you ever been asked to cease your studies in a certain area because someone more prestigious laid claim?

2014 State of the (Scientific) Union

(Adapted from last year's post, with updated data for 2014)

Did you watch President Barack Obama present the 2014 State of the Union address?

Source: Whitehouse.gov

Once again, I downloaded the text to the 2014 S.o.T.U. (Opportunity for All), and compared it against the text from 2011 (Winning the Future), 2012 (An America Built to Last), and 2013 (Unfinished Tasks / Next Chapter). 

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 365 days.

Breakdown (# of each word in full text):

Energy – 2011: 9, 2012: 23, 2013: 18, 2014: 8

Oil – 2011: 2, 2012: 10, 2013: 5, 2014: 6

Gas - 2011: 1, 2012: 9, 2013: 7, 2014: 4

Wind / Solar - 2011: 4, 2012: 3, 2013: 4, 2014: 2

Nuclear – 2011: 5, 2012: 3, 2013: 3, 2014: 5

Batteries - 2011: 0, 2012: 2, 2013: 1, 2014: 0

-----

Biotech / Biomed / Biofuel – 2011: 3, 2012: 0, 2013: 0, 2014: 0

Chemical – 2011: 0, 2012: 1, 2013: 0, 2014: 1

Tech / technology – 2011: 12, 2012: 9, 2013: 8, 2014: 6

Science / scientist – 2011: 7, 2012: 2, 2013: 4, 2014: 1

Engineering – 2011: 3, 2012: 1, 2013: 3, 2014: 1
Math – 2011: 3, 2012: 0, 2013: 2, 2014: 1

Research – 2011: 9, 2012: 4, 2013: 4, 2014: 4

Development – 2011: 1, 2012: 2, 2013: 1, 2014: 0
Carbon – 2011: 0, 2012: 0, 2013: 1, 2014: 3

-----

College / Universities– 2011: 12, 2012: 15, 2013: 8, 2014: 12

Health – 2011: 8, 2012: 5, 2013: 5, 2014: 8

Internet – 2011: 6, 2012: 1, 2013: 1, 2014: 0

Cyber – 2011: 0, 2012: 1, 2013: 2, 2014: 1

Jobs – 2011: 25, 2012: 33, 2013: 32, 2014: 23

Fun 2014 one-offs - "Let's Move!", in-sourcing, "vaccines against drug-resistant bacteria, and paper-thin material stronger than steel," unemployment insurance, STEM!, gender pay inequality, "MyRA," student loan debt, minimum wage, military drones, Iran, Mad Men.

Is there a take-home message here? Does word count relate to the overall direction of the country? Probably not. Each speech is different: 2014 spoke to middle-class unemployment, higher ed, and equality issues, while 2013 spent serious time on fiscal reform, job creation, foreign affairs, and domestic mass shooting incidents.

We've got Obama shilling for more jobs, which is great. It's a bit disheartening, though, to see that, in an era of STEM politics, we're seeing a steady year-to-year decrease for scientific terms in the SoTU. The excitement I once felt about a President who would speak about solar panels and hydrogen fuel cells has substantially dampened. 

Readers: Did I miss anything? Let's discuss it in the comments!

Friday Fun: Who Should be Science Laureate?

Perhaps this little tidbit from ScienceInsider got lost in the shuffle yesterday:

Looks like Washington wants a Science Laureate, a travelling scientist "national spokesman for science" to rove about the country drumming up support and excitement. From Sen. Hirono's (HI) office:

"This new honorary position would be appointed by the President from nominees recommended by the National Academy of Sciences and serve for a term of 1-2 years. Using this national platform, the Science Laureate would be empowered to speak to Americans on the importance of science broadly and scientific issues of the day..."

"So, should we rock-paper-scissors for it, then?"
Credit: Solar San Antonio | Hayden Planetarium

“...Establishing honorary U.S. Science Laureates would send a clear message to young people about the value of science and technology in our society, and the importance of scientific research to both economic progress and our quality of life,” said Alan I. Leshner Chief Executive Officer of the AAAS and Executive Publisher of Science." 

OK, I'm all in favor of increasing exposure and public awareness of science, even if most of the politicians quoted in the article keep beating the STEM STEM STEM horse to death.
So, what does this gig pay, anyway?

"Like the Poet Laureate, the Science Laureate would be an unpaid, honorary post. The scientist would also be encouraged to continue their important scientific work."

Tough break. Guess you'd be expected to write those R01's on the road, then.

Happy Friday!
SAO 

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.

Straight From the Horse's Mouth

That post about corporate euphemisms I wrote the other day? Meant to be informational, but with a ring of sarcastic truth to it; often times these nicknames help exiting employees to cope and offer them an element of control in an otherwise bad situation. 

An alternate reality? Sounds like Pfizer...
Source: briterevolution.com

Survival in the heavily matrixed environment at Pfizer apparently took more than just hard work and pedigree. Over the past few days, I've spoken with some former employees, and I'll briefly paraphrase the conversations (Note: I'm hardly the first to discuss these layoffs...)


All former Pfizerites felt that they had spent a lot of time meeting and politicking, perhaps as much as they did generating new data or discovering new drugs. One said that layoffs were announced as early as six months prior to corporate action, leaving employees wondering if they would have a job next season (I guess they were "lucky" not to be let go over the weekend?!). Another worker alluded to overemphasis of negative traits during performance reviews, such that if you were laid off in the future, the document might seem to presage your departure. 


When layoffs occurred, scientists often abandoned still-running equipment and in-progress experiments. The equipment would sit around for a time, unused, and later be sold at auction to recover costs. Since no one would be hired to replace the outgoing researcher, many data sets were irrevocably lost.


The most shocking sentiment I heard was that of a long-time chemist, who compared negotiating the enormous, post-merger(s) Pfizer to a zero-sum game, where the only way to move ahead was to "bring someone else down." 


To borrow a popular sentiment: Best wishes to all of us.

Petition Expedition – Cancer in Laundry Detergent?

On Facebook and other social media sites, online petitions quickly gather steam. Users see others’ posts, rally to the cause, and spread word to their friends and families using “Likes” and “+1s.” However, this rush to join also belies a lack of judgment; as the petition becomes easier to circulate and sign, critical reading of its content diminishes.

Source: P&G

Take the example of Tide Free & Gentle, a popular laundry detergent advertised as free from dyes and perfumes.  Political site change.org has recently posted a petition titled “Tide: Get Cancer-Causing Chemicals Out of Laundry Detergent.” This petition focuses on one specific compound purportedly isolated from detergent: 1,4-dioxane. As of March 6, it had amassed >68,000 signatures, just under 1 month after going live (I caught it making the rounds on both Facebook and Twitter).

The petition references data from a recent report, published online last November by Women’s Voices for the Earth, an environmental awareness organization based out of Montana. Dubbed Dirty Secrets: What’s Hiding in Your Cleaning Products?, the report aims to expose “hidden toxic chemicals” in household products, cleaners, and air fresheners (see here for P&G’s published Tide F&G ingredient list).

(Disclaimer: I am a chemist by profession, and I’m not advocating corporate secrecy or consumer harm. I’m just trying to critically analyze the data before making decisions.)

I think this post might function better as a Q&A.

 Q1 – What is dioxane, anyway? Can it harm me?

1,4-Dioxane is a cyclic diether (2 oxygens, 4 carbons, 6-membered ring). Chemists use it to dissolve compounds for reactions. It possesses specific properties (chelation, high-boiling, water solubility) that make it attractive for certain reactions over other solvents. According to its MSDS, dioxane can irritate the skin eyes, and nasal passages, but only by acute (large amount in small timeframe) dose.

Q2 – Does it cause cancer?

Dioxane lists as a 2B – Possible Human Carcinogen.  Note the exact wording there. Two other levels exist for compounds known to cause human cancers, 2A (Probable) and 1 (Known Carcinogen). If you enter “dioxane” into TOXNET and browse the carcinogenicity data, you’ll find studies on rats where ~1.0% dioxane in drinking water caused liver tumors in many cases, also squamous cell carcinomas, and a single report of mammary gland tumors over two years’ exposure (Dirty Secrets mentions only breast cancer, and calls dioxane a “known cancer-causing substance”).

Q3 – Well, what did the report actually find?

Good question. Page 10 of the report lists the data for Tide Free & Gentle, which indicates 89.00 ppm dioxane, and 0.8 ppm limonene, a fragrance isolated from citrus peels. Now, ppm? Parts per million, meaning that 89 milligrams are found in each liter of detergent. Put another way, if you round up to 100 ppm, it becomes one part in 10,000, or 0.01%. If you paid 0.01% sales tax, you’d pay $1.00 on a new $10,000 car. Remember the Ivory Soap ad, with “99.44% pure?” Relative to dioxane content, you could still state that Tide F&G was “99.99% pure.”

To compare against the animal data – 1.0% in drinking water – we’re more than two orders of magnitude (100x) off . . .and, last time I checked, most people don’t drink laundry detergent.

Q4 – But these are chronic exposures, so doesn’t it build up over time?

If the entire detected amount were to be absorbed into your body each time, maybe so. However, given dioxane’s high water solubility, and the large amount of water used to wash clothes relative to the tiny volume of detergent added, it’s likely that only a vanishingly small amount ever ends up stuck to your T-shirts.

Q5 – Tell me more about the science.

He wants to know your L.O.D.
Source: P&G / Tide

I thought you’d never ask! To start, the samples were analyzed at Analytical Sciences, LLC, in Petaluma, CA, using selective ion mass spectrometry. Theoretically, this selectively targets the ion of interest and increases the sensitivity of the instrument for this analyte. However, note the Limits of Detection (p. 15) for dioxane = 250 ppm. So, how are they accurately measuring below their L.O.D.? Where are the error bars, or ranges for multiple runs? No analytical chemist ever uses a single data point to prove an argument. Add in pseudo-scientific statements such as “analytical analysis,” and “very specific mass spectral ions,” and you wonder who Q.C.’d this report! The nail in the coffin, however, has to be the asterisks (***) that litter the analysis section, including these statements in tiny font, buried under the data:

*These measurements represent levels detected in laboratory testing, and may not represent actual exposure levels experienced with use of the product in the home… 

***In most cases, research has never been conducted to determine if exposure to the chemical through use of the cleaning product is associated with the health outcome.

Wile E. Chemist
Source: Chuck Jones / Looney Tunes

Despite the obviously inflammatory titles of the petition and the report, and the overwhelmingly negative bias towards all those “dirty chemicals” made by wily chemists, I can empathize: the petition addresses moms, and its message aims to keep children safe. I’m sure the scientists at P&G, many of whom have their own kids, want to keep children safe, too! However, in my opinion, this report should not be the ideological or scientific basis for thousands of social-media-equipped petitioners to vent their frustration.


(Update: 3/8, 2:30AM - Minor grammatical changes)

State of the (Scientific) Union

Pres. Obama presents Peter Stang with Nat. Medal of Science
Source: Getty Images

Did folks tune in to watch President Barack Obama present the 2012 State of the Union tonight?

Out of sheer curiosity, I downloaded the text to both the 2011 SoTU (Winning the Future) and the 2012 speech (An America Built to Last). Now, I’m no political pundit or news analyst - I’m a scientist. So, I thought an interesting game might be to see how certain scientific themes grew or shrunk over the past 365 ¼ days.

Here’s the breakdown I tallied:
(# of mentions per word in the text)

Oil – 2011: 2, 2012: 10

Energy – 2011: 9, 2012: 23

-------

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

Tech / technology – 2011: 12, 2012: 9

Science / scientist – 2011: 7, 2012: 2

Engineering – 2011: 3, 2012: 1

Research – 2011: 9, 2012: 4

Development – 2011: 1, 2012: 2

Nuclear – 2011: 5, 2012: 3

College / Universities– 2011: 12, 2012: 15

Chemical – 2011: 0, 2012: 1 (Unfortunately, it was used in a negative connotation)

Math – 2011: 3, 2012: 0

Health – 2011: 8, 2012: 5

Is there a take-home message to counting up words and relating them to the direction of the country? Perhaps not. Thematically, the two speeches were different: 2011 was more forward-looking and focused on education, business, and terrorism; while 2012 dealt with global politics, congressional reform, and taxes. 

But there exists notable declines in most science-related topics from last year’s speech to this one. Except, of course, on topics where economics and science often cross – substantial mentions of oil and energy.