Fatal Occupational Exposure to Trimethylsilyl-Diazomethane
Murphy NG,1 Varney SM,2 Tallon JM,1 Thompson JR,1 Blanc PD.3
1IWK Regional Poison Centre, Halifax, NS, Canada; 2Rocky Mountain Poison & Drug Center-Denver Health, Denver, CO, USA; 3Division of Occupational and Environmental Medicine, UCSF, San Francisco, CA, USA.
Background: Diazomethane (DM) is a highly explosive, toxic methylating reagent causing severe pulmonary injury. Trimethylsilyl-diazomethane (TSDM) is a less explosive analogue that may not be less toxic. We describe the first documented case of a fatality following TSDM exposure.
Case report: A 46 year-old male pharmaceutical chemist presented to the ED with progressive dyspnea. At noon on the prior day, as part of a chemical analysis, he had mixed 2 mL of acetone with 25 mL of L-Malic acid to which was added TSDM dissolved in n-hexane. After 1 hour this mix was combined with an inert gas and a small amount of methylene chloride under a fume hood that was later reported to be nonfunctioning.
Although he experienced no immediate mucous membrane irritation, 8 hours post-exposure he developed cough, pleuritic chest pain, hemoptysis, and progressive shortness of breath; by 15 hours, he presented to the ED in respiratory distress, hypoxic (PaO2 67), hypercarbic (PaCO2 46), and acidemic (pH 7.26). A chest radiograph showed an acute lung injury pattern. By 23 hours he required intubation.
At 26 hours postexposure he developed profound bradycardia, refractory hypotension, and asystole.
Case discussion: DM inhalation is known to cause fatal pulmonary edema without an immediate irritant prodrome and with a similar time course to this case. Structural modification of DM with an added trimethylsilyl group makes TSDM less explosive, but its propensity for lung injury is unclear. The chemical admixture as described in this case may have liberated nitrogen gas, but this should not have led to pulmonary injury; nitrogen dioxide should not have evolved. The toxicity may stem from residual DM present in the reagent or a direct effect of TSDM, its metabolites or breakdown products, or potential intracellular formaldehyde formation.
Conclusion: The temporal relationship to exposure with inadequate ventilation and clinical effects similar to the analogue toxicant DM support a causal relationship between TSDM and acute lung injury. Additional safety data for this chemical is warranted, including experimental inhalation testing in animals.The conclusion that I draw from this is not that chemists should not use TMS-diazomethane, but that they should exercise due caution with respect to the potentially fatal consequences of inhaling it. Work practices, engineering controls and PPE are all a part of that.
The drug analyst who was fired for misstating her credentials allegedly falsely testified in federal court as recently as August that she has a degree in chemistry and possibly did so in dozens of state court cases as well, opening the door for a flood of new legal challenges related to the Hinton drug lab scandal.The explanation is somewhat tragic, really:
The analyst, Kate Corbett, was fired by the State Police Friday for allegedly asserting that she holds a degree in chemistry from Merrimack College, though investigators determined that her degree is in sociology.
Corbett has not been accused of tampering with evidence, a charge that led to the conviction of Annie Dookhan, the woman at the center of the lab scandal.
But Corbett’s declarations in court that she is an expert with a chemistry degree could potentially derail convictions in those cases, say legal analysts, who say her testimony would be tainted.
However, State Police conducted background checks on the chemists’ education to ensure that the analysts met the agency’s standards for accreditation, and superiors learned of the discrepancies with Corbett’s education.
According to a State Police report obtained by the Globe, Corbett earned a bachelor of arts degree in sociology from Merrimack College in 2001, though she claimed on her resume that she obtained a degree in chemistry in 2003.
A State Police investigation concluded that, in the two years after she first earned the sociology degree, she took enough credits that she believed would satisfy a chemistry degree. However, according to the State Police report, Corbett assumed she had earned a second degree without confirming it with Merrimack College.
Also, according to the report, she would not have qualified for a second degree because she would have had to take an additional set of coursework to meet bachelor of science requirements.I think her dismissal was the right response from an organization that is being seen as less than competent, charitably speaking. It's fairly apparent to me that her management is (yet again) at fault -- she started working for the lab in 2005. If her credentials were important (and it sure sounds like they were), then they should have been examined by her superiors.
I'm [22-28], BS in chemistry, graduated with GPA < 3.0. I've had personal circumstances that prevented me from actually focusing on school during my whole undergrad. I'm at a much better place in life, considering further education.
As of today, I'm at my first "real" job-- [redacted] chemist at [redacted] -- been here almost one year... I do a lot of [synthesis.]
...I've had some chances to tinker and work with analytical instruments here. I loved it, even though it was only working with IC and GC/MS.
My ideal career would involve studying these instruments, coming up with better methods and improvements to the instrument, and generally be around them 24/7. Would I be able to gain this sort of knowledge/experience via M.S or Ph.D? I was around a few organic, inorganic grad students while in undergrad so I know what their work consists of, but I don't really have a clue on what analytical chemistry grad students do, or what sort of angle they tackle this big umbrella term, "analytical chemistry".Personally, I think WD is eminently eligible for graduate school in analytical chemistry, perhaps a master's program? I would think that WD would need to do some independent study and do well on the chemistry GRE in order to shore up their case. A nice letter from one of WD's analytical colleagues would probably be helpful, or perhaps a letter from an analytical chemistry professor at their old school (one that has reviewed WD's current work experience and has positive comments.)
Annie Dookhan, the drug analyst who tampered with evidence and jeopardized tens of thousands of criminal convictions, was sentenced Friday to three to five years in state prison, closing a sorrowful chapter for the woman at the center of a scandal that continues to plague the state’s criminal justice system. The 36-year-old mother of a disabled child, whose marriage fell apart in the months after the scandal, softly pleaded guilty to 27 counts of misleading investigators, filing false reports, and tampering with evidence. She must also serve two years of probation and undergo mental health counseling, if needed.
After the sentence was handed down, Dookhan struggled to hold back tears as she whispered with her lawyer before being led away in handcuffs by court officers. Two family members, believed to be her parents, watched from the courtroom gallery. Attorney General Martha Coakley, whose office prosecuted the case, said in an interview later that the conviction of Dookhan was only one part of an ongoing investigation into the quality of drug testing at the Hinton drug lab, but she said it was needed to bring some accountability for her crimes.
“Certainly one of the victims in this case, and the actions of Annie Dookhan, is the public trust,” Coakley said.
Dookhan’s lawyer, Nicolas A. Gordon, would not comment after Friday’s hearing. He had asked Suffolk Superior Court Judge Carol S. Ball to sentence Dookhan to no more than a year in prison. Dookhan admitted to filing false test results and mixing drug samples, and to later lying under oath about her job qualifications, but she said it was only to boost her work performance.
Prosecutors had asked that Dookhan serve 5 to 7 years in prison, but Ball kept to her earlier decision that she would sentence the chemist to 3 to 5 years, finding that, while Dookhan was a “broken person who has been undone by her own ambition,” the consequences of her crimes were still “nothing short of catastrophic.”Considering how many people were sent to prison without proper due process (well into the dozens or hundreds, I suspect), her sentence is comically insufficient. Harry Elston is on record (on Twitter) saying that she should be serving the sum total of time served by the innocent people that she sent to prison; can't say I disagree with him.
Wellington Laboratories Inc. is an internationally known supplier of environmental reference standards for use in environmental analysis and toxicological research (http://www.well-labs.com). The company is comprised of a Reference Standards Division, a Research Division, and an Analytical Division operating in a modern technical facility in Guelph, Ontario. The company’s foundation is in its staff which provide a strong combination of synthetic/organic and environmental/analytical backgrounds. We currently have an opening for a Synthetic Organic Chemist in the Reference Standards Division.M.S./Ph.D., looks to be entry-level. Click here for details.
The National Council on Aging (NCOA) has a position available at the U.S. EPA in Cincinnati. This position is with a government grant specifically for seniors over the age of 55. The position applies knowledge of general methods for organic and inorganic analysis of environmental samples, including chromatographic, electrochemical and wet chemical methods. DUTIES: Operate lab instruments, ensure lab equipment is in working order and properly calibrated, analyze drinking water samples and data record keeping. REQUIRED: To be eligible for this government grant you must be over 55, B.A. /B.S. degree in Chemistry, and 10 years related experience in organic (GC. LC) analytical instrumentation. Word processing and spreadsheet skills are highly desired. Send resume to: see.hr@ncoa.org. No phone calls please.What in the heavens is this about?
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| As you can see, the directors don't get paid. |
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| Not so for the officers of ACS, which are all firmly in the 1-2%. |
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| How their pay is structured, regarding bonuses and regular compensation. |
Still, “the vast majority of us are not getting Parkinson’s, and the vast majority of people who work with pesticides don’t get Parkinson’s,” Goldman says. “So there’s obviously something else at play.”
That “something,” today’s scientists believe, is genetic susceptibility. Along with Tanner and Kamel, Goldman explored this gene-environment interaction recently by surveying a group of male farmers. The researchers genotyped the participants’ DNA to determine which subjects had mutations in a gene coding for glutathione S-transferase T1. This type of enzyme is responsible for cleansing cells of foreign substances such as pesticides and protecting against oxidative stress.
Men who were exposed to paraquat and who had nonfunctional glutathione S-transferase were 11 times more likely to have Parkinson’s disease than nonexposed men who had functional enzymes (Mov. Disord. 2012, DOI: 10.1002/mds.25216).
Another recent study examined the association of pesticides, Parkinson’s, and mutations to a protein pump called P-glycoprotein. This macromolecule sits on cells lining blood vessels in the brain, defending a person’s gray matter by pushing out molecular intruders.
Agricultural workers in France who were exposed to organochlorine insecticides and who had gene mutations affecting P-glycoprotein’s performance were three to seven times more likely to have Parkinson’s than those who weren’t exposed (Arch. Neurol. 2010, DOI: 10.1001/archneurol.2010.101).I am always looking for the mechanism behind chemical/epidemiological studies. Genetic variation in how we deal with xenobiotics makes sense to me; when I say to my non-chemist friends, "you have a liver and it does its job well", there's something to the thought that well, different people have different livers.
If technology was no barrier, what sort of mobile (or other) technologies would we want for science - either in research or even in education?This is a great question, and one that I’ve wrestled with for a while now. In my personal life, I’m a bit of a Luddite. I don’t own a smartphone (yet) and it wasn’t until earlier this year that I owned a tablet. In my professional life, I still use a pen and paper quite a bit, and it’s been a while since I’ve used an electronic notebook for work.
Director of Device Analytical Development, Allergan (Santa Barbara, CA):
The Director is responsible for leading the Device Analytical Development department of Allergan Device R&D organization to provide high quality analytical support for the development of biomaterials, medical devices and related drug device combination products for global market meeting worldwide regulatory requirements.
Education and Experience: Ph.D. in Analytical Chemistry or a related scientific field, plus 10-15+ years experience in physical and chemical measurement methodology development and applications for medical devices and pharmaceuticals in support of product development and characterization.
Interested folks can contact Holly McArthur at hmcarthur -at- beaker/dot/comAnd another one, for the (somewhat) younger crowd
Senior Research Associate, CooperVision (Pleasanton, CA):
Performs research and/or development in collaboration with others to support contact lens and ophthalmic materials projects. GMP/GLP experience a plus.
EDUCATION: Bachelor of Science with 5+ years industry experience or Masters of Science with 2+ years industry experience. EXPERIENCE: 2-5 years industry experience depending on level of degreeHere's the ad on LinkedIn. Thanks to those who e-mailed this in!
Then Martin Karplus, a Harvard University chemist, interjected, “ “What understanding of the stock market do you really have?”
Economics – “if one wants to call it a science” – seemed unable to explain the oscillations of the market, he said.
“I see these fluctuations and they make zero sense to me,” Professor Karplus declared. “Maybe they make sense to you.”
Professor Fama dismissed the question as unsophisticated, declaring its premise “factually incorrect.”
The hard scientists, more amused than chastened, turned to mocking the economists.
“You’re asking about a very fundamental question, on what the nature of life is,” James Rothman, a professor of cell biology at Yale University and one of the three newly minted laureates in medicine, told one questioner. “I don’t think there’s anyone here — even the economists – who would have an opinion on that for sure.”It's always interesting for me to see hard scientists dog economics -- I think there's a kernel of truth in there (i.e. economics does seem different than physics or chemistry), but it bothers me in the sense that someone has to think about the intersection of society and money and find some principles in there. Oh, well.
Dear Admitted Aggie PETE Applicant,
The Harold Vance Department of Petroleum Engineering, Texas A&M University, is pleased that you applied and were admitted to our top ranked petroleum engineering program. If you pursue a degree in petroleum engineering, our program is committed to providing the highest quality education available.
Recent data suggests that some concern about the sustainability of the entry level job market during a time of explosive growth in the number of students studying petroleum engineering in U.S. universities may be prudent.
Our advice is that you become aware of graduation projections and petroleum industry employment outlook for people with petroleum engineering degrees. For example, between fall 2011 and fall 2012, the number of freshmen in petroleum engineering programs in the U.S. increased from 1,388 to 2,153, a 55% jump in one year. Based on the many inquiries and applications TAMU is receiving for the petroleum engineering major, the number of U.S. students in petroleum engineering will probably continue a strong upward trend, as long as the employment market remains stable. These days, a very large number of people are already studying in petroleum engineering programs (see attachment, showing data made available through the Society of Petroleum Engineers, SPE), at a time when: the number of recent graduates, who began their studies several years ago, is already at about historical highs and growing rapidly (see attachment); our program’s board of industry advisors are recommending that we “do not grow” our undergraduate program at this time; and oil and natural gas price projections and expectations of U.S. governmental policy influences are viewed as not particularly encouraging by the U.S. petroleum industry.
We are not trying to discourage you from a career that we think is among the most fascinating, dynamic, challenging careers that exist. However, we also want you to know that the Aggie PETE program is doing the right thing by providing you with information that could end up being important to your future.First, does anyone know if this letter is actually true? It's found in a number of places online, but it all leads back to the blog "Cost of College." I suspect that it IS true, in the sense that if someone was e-mailing around a false letter from a Texas A&M department, they'd be quick to respond and deny authorship.
MIT professor Ofer Sharone hopes to solve a dark problem that few even want to discuss: how to help the long-term unemployed.
More than four years after the last recession ended, long-term unemployment remains near record levels, with 4.1 million Americans out of work for more than six months and still struggling to find jobs. What makes the problem so vexing, Sharone said, is these workers, typically older, have qualifications that should provide the path to employment, namely experience, accomplishment, and college degrees.
“You can’t just say go get an education because these people are often educated.” he said. “It’s scary because there’s not an obvious, easy solution.”
Sharone, however, is daring to try to find one. Later this month, he will launch a project called the Institute for Career Transitions, an organization to help the long-term unemployed, focusing on 40- to 65-year-old workers with college degrees. The institute will begin by pairing them with career counselors or job coaches, free of charge, for three months.
Sharone and his researchers will also try to build a better understanding of long-term unemployment and approaches that might help overcome its challenges and barriers. They will study the moods, health, and levels of depression among participants, examining how long-term unemployment — and repeated disappointments — affect them, their motivation, and ability to get back to work.I think the problem of the long-term unemployed will only become more problematic in the future. Best wishes to Professor Sharone and his project, and best wishes to all of us.
