Again, I noticed that whenever I tried conducting experiments using Yb(OTf)₃ in the absence of Stas there was never any product.  Finally, I demanded to see some of his samples.  Despite having run many reactions, each of which made multiple gram quantities, Stas was only able to supply me with a couple (ca. 3) samples in small vials (< 1 g).  Upon testing them with a number of analytical techniques including GPC and ¹H NMR I discovered them to be polydimethylsiloxane and not PIB (see files below this paragraph)!  Indeed, I now had positive proof of falsification of data.  Immediately I setup a time to present this evidence to “Kennedy” and when I did the same result occurred.  This time around not only did “Kennedy” tell me he only cared about data but he informed me that I needed to consider if I wanted to continue to work for him.  I was to have a response to him within 1-2 days.  When I met with “Kennedy” the last time I informed him that I would do anything to continue working under him with the exception of falsifying data.  It was then that “Kennedy” called in his secretary at the time, Debbie England, and began to ramble off false allegations about how “Stewart has failed to fulfill his obligations to me.”  I stopped him in mid-sentence and told the two of them that I need not listen to this crap anymore and that I was going to get an attorney.  The very next day, “Kennedy” left the country for Europe.

GPC of Stas’ acutal samples (these are GPC traces for samples supplied by Stas)

1H NMR of Stas’ actual samples (Proton NMR spectra for samples supplied by Stas)

Following the accident (of which U. Akron never supplied me any photos of despite EOHS taking numerous pictures) “Kennedy” had me back to working on polymerizations and requested the construction of a less dangerous cooling bath.  Despite having spent almost one month on the construction of this bath, “Kennedy” decided to not use it.  During this period my relations with both Stas and “Kennedy” continued to deteriorate as I was never able to reproduce any of Stas’ results in the area of the Yb(OTf)₃ polymerization system (please see files below this paragraph).  Likewise, Stas began acting unusual and his physical appearance, odor, and physiological responses began to take a weird turn.  For example, on numerous occasions he acted paranoid during experimentation.  According to him, failure was certain unless I did as he said.  He also appeared to be either drunk or sedated by some sort of drug and his body odor at times had become so unpleasant that people could not stand to be in the same office cube room as him.  While working in complete air conditioning he would begin to sweat profusely as if he was running a marathon.  As I continued to question his previous results threats were being lodged against me, death threats.  These threats were of such a grave nature that I had to begin locking all personal belongings in a filing cabinet to prevent the possibility of being poisoned.  A friend of mine, Mr. S. Carrolla and I approached “Kennedy” about Stas but as per usual “Kennedy” did nothing.

(This is a picture of a master table of experiments Dr. Lewis conducted in an attempt to replicate work originally reported by Stas and Dr. “Kennedy”)

Yb master table summary 4-24-01 (this file contains tabulated data necessary to construct the table shown in the above picture).

I soon began to suspect that “Kennedy” was possibly the mastermind behind the entire fabrication of experimental data.  During several group meetings between the three of us “Kennedy” would make unusual comments.  For example, after Stas started to become somewhat belligerent during one meeting “Kennedy” stated, “You know Stas, Stalin wasn’t a bad guy.  He did many good things.” To which Stas replied, “Dr. ‘Kennedy’ you should not say these things.”  While attending these meetings I kept voicing my concern over the fact that Stas did not possess any physical samples of the polymers he had supposedly made.  “Kennedy’s” reply to me was, “I don’t care about samples.  Go into the lab and make me data.”  It seemed as if my assumptions were true.  To me it would appear that the entire thing was fake from the very beginning and both Stas and “Kennedy” knew it.  Still, I wasn’t sure as “Kennedy” didn’t give me a direct order to falsify data, but what else could “Go into the lab and make me data.” mean if physical samples were not important?  Regardless, my conscious is such that even at that time doing such a thing was impossible for me.  So, I returned to the lab once more (at least for approximately one more week) to conduct some final experimentation.

As my suspicions grew and I became more vocal about them an unusual accident occurred which almost decapitated me.  While working in one of “Kennedy’s” state of the art dry boxes (sarcasm implied) an explosion occurred while I attempted to increase the speed on an electric stirrer.  These boxes were crudely constructed and always possessed such a high moisture content that withdrawal of TiCl₄ from septum sealed bottles always resulted in the generation of so much HCl that it obscured the view from the front window to the back window (these boxes had two sets of gloved windows opposite to one another).  At the time I was overly ignorant about what a proper glove box looked like and obviously what a good versus bad atmosphere behaved like.  In this instance it would appear that oxygen, a contaminant that is difficult to exclude with this sort of glove box was the culprit in starting this explosion (in addition to the obvious glaring safety violation of using a non-explosion proof motor in a dry box containing about 15 L of highly flammable heptane in addition to several mL of even more highly flammable IB and methyl chloride {MeCl})!  I should mention that the collection method used for both IB and MeCl always involved loss of no less than 5-10 mL of condensed liquid (which quickly volatilized to gas) to the glove box atmosphere.  These problems were no doubt compounded by poor techniques that were common practice in the “Kennedy” lab such as the use of only purging to bring in certain items as opposed to the standard pump-refill technique.  Regardless, even though I escaped harm and no one else was injured and furthermore, I was able to prevent a serious fire from developing (despite safety glass being flung about 20+ feet {see pictures and documents below}) the accident did not improve my relationship with “Kennedy.”

 This is a fragment of the window pane and a piece of wire that may have come from the electric motor.

 Dr. Lewis’ accident description, part 1.

 Dr. Lewis’ accident description, part 2.

  UA memo.  UA never investigated this matter to determine if the accident may have resulted from an attempt to kill Dr. Lewis.

Being one of only two Americans in the “Kennedy” group was in some regards a positive experience for me.  It was here that my interest in India and China grew and when Stas arrived a similar desire to learn about Russia emerged.  In fact, my curiosity in these countries is still quite keen these days.  So, for the first couple months I intently learned as much as I could from Stas in both the area of chemistry as well as Russia.  Stas (please refer to files below this paragraph) had been polymerizing IB in eutectic mixtures containing primarily CaCl₂, sometimes in the presence of a surfactant, and always using the Lewis acid ytterbium(III) trifluoromethanesulfonate {Yb(OTf)₃}.  This was a slight departure from the system that emerged from the Sawamoto group as no purposefully added initiator was present in Stas’ system and therefore the common consensus was that water was functioning in this role.  Stas also demonstrated through the use of ¹H NMR and modeling with triflic acid that two different types of PIBs were being formed in these polymerizations.  One type of PIBs had low MWs and according to Stas’ modeling experiments (see files below this paragraph) these were formed by triflic acid impurities present in the Yb(OTf)₃.  The second type of PIBs possessed higher MWs and these were being formed by Yb(OTf)₃, supposedly in conjunction with water (again, refer to files below this paragraph).  IMA experiments by Stas also supposedly showed that these polymerizations possessed living characteristics to them (see files below this paragraph).

Early report by Stas (This report was presented by Stas during the first meeting with Dr. “Kennedy” and Dr. Lewis.  The handwriting on the left is Stas’ the handwriting on the right is Dr. Lewis’.)

Early Stas IMA data set (This is a copy of data that Stas had generated.  The handwriting is Dr. Lewis’.)

Stas 1st ima experiment (Another data set generated by Stas presented during one of the first meetings with Dr. “Kennedy” and Dr. Lewis.)

Another Stas ima experiment (This is yet another data set presented by Stas during a group meeting.)

1H NMR by Stas showing low and high MW PIBS (These are 1H NMR spectra generated by Stas that supposedly showed two types of propagating species.  One being initiated by triflic acid the other being initiated by water in conjunction with Yb(OTf)₃.  Most of the writing is Stas’.)

Second meeting with Kennedy and Stas (These are notes taken by Dr. Lewis from the second meeting with “Kennedy” and Stas.)

Third meeting with Kennedy and Stas (These are notes taken during a third meeting by Dr. “Kennedy” who then passed them to Dr. Lewis.)

The experiments that I conducted with Stas (please see files below this paragraph) were not overly demanding when it came to manipulations; however, most were quite lengthy (many requiring 8 or more hours).  Still, with Stas’ assistance, PIB was being made in aqueous media and “Kennedy” was happy.  Oddly enough, “Kennedy” assigned other side projects.  One involved the polymerization of IB by triflic acid followed by quenching with an amine in order to generate amine functionalized PIBs.  The other involved the attempted polymerization of IB in aqueous media using BF3·OEt₂ (which is again a basic polymerization system reported earlier by Sawamoto’s group).  In all instances, with the exception of BF3·OEt₂ polymerizations, experimentation was initially conducted with Stas (see below this paragraph for scanned copies of my notebook and of reports to “Kennedy” during this period).

Lab notebook Yb(OTf)3 scandal 1 (First section of lab notebook on Yb(OTf)₃ project.)

Lab notebook Yb(OTf)3 scandal 2 (Second section of lab notebook on Yb(OTf)₃ project.)

Lab notebook Yb(OTf)3 scandal 3 (Third section of lab notebook on Yb(OTf)₃ project.)

Progress Report 12-13-00 (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)₃ project much being done in conjunction with Stas.  The corrections on this report were made by Dr. “Kennedy.”)

Progress report late dec into early jan (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)₃ project much being done in conjunction with Stas.)

Progress report 1-13 to 26-00 (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)₃ project much being done in conjunction with Stas.  The corrections on this report were made by Dr. “Kennedy.”)

table amine functionality (This was a report written primarily by Dr. Lewis covering details of work on the triflic acid/amine functionalization project much being done in conjunction with Stas).

As time slowly passed on I began to venture out on my own in order to increase productivity and to hasten the time needed for graduation.  Then I hit a brick wall.  Every time I conducted experimentation on my own with the Yb(OTf)₃ system I was unable to produce more than a few milligrams of product (if any) and in most instances those few milligrams of material were most likely surfactant (please see files below this paragraph).  Stas and “Kennedy” informed me that my technique was to blame and so I returned to working with Stas in order to remedy this.  Oddly enough, with his assistance we continued to make PIB but whenever I tried similar experiments on my own I was unable to generate polymer.  I slowly began to question the previous results and increasingly began pointing out that polymer was only being generated when Stas was involved in experimentation (again, see files below this paragraph).  As I did this, my relationship with both Stas and “Kennedy” progressively went downhill.

early April ca 9th 2001 progress report (Another report generated by Dr. Lewis where he begins to question the validity of the data being generated by Stas.)

Summary of Experimental Data 4-9-01 (Another report generated by Dr. Lewis where he begins to question the validity of the data being generated by Stas.)

While conducting laboratory work on 8-16-00, I experienced a serious injury when the bottom of a four liter beaker collapsed into my right hand while transferring liquids (see pictures below).    As the bottom of the beaker collapsed into my right hand resulting in a severe laceration with arterial spraying of blood, the upper lip portion of the beaker broke into my left hand but somehow this second breakage did not result in a cut to my other hand.  I immediately went to student health services with the assistance of Pious Kurian who was nice enough to fashion a makeshift tourniquet out of a pipe cleaner and who subsequently drove me to the ER of Akron General.  The end result of this visitation was multiple stitches (ca. 10) and I was informed that I almost severed the tendons that control my thumb which would have resulted in permanent loss of movement.  With the assistance of the secretary at the time (Lavern Corn) I submitted an accident report form (see below) and after several days break I was back working.  When I reviewed the portion of the accident report form that was filled out by Dr. “Kennedy,” who was not present during the time of the accident, I noticed that everything he wrote was false.  When I approached Dr. “Kennedy” and informed him that he needed to resubmit this form he told me that he would do so; however, when I subsequently checked with Ms. Corn I found that indeed “Kennedy” never bothered to correct his lies.  Now I had concrete affirmation as to the integrity of “Kennedy.”

Despite my disappointment with “Kennedy’s” lack of integrity and ability to generate useful ideas (or even input) regarding my research project I continued to trudge forward.  As the year began to wind down I had conducted a few introductory experiments concerning POSS-PIB-POSS triblock materials but the physical properties were not up to “Kennedy’s” standards.  It wasn’t until later that I realized how to solve this problem but at the present time “Kennedy” requested that I no longer work on the triblock materials but instead generate yet more project ideas.  Then a stroke of luck seemed to occur.  By chance the new postdoctoral student, Stanislav Yankovski (aka Stas), happened to make an important breakthrough.  Stas had been mimicking work originally conducted by the Sawamoto research group on the aqueous cationic polymerization of reactive styrenic monomes (e.g. para-methoxystyrene) with scandium(III) trifluoromethanesulfonate {Sc(OTf)₃} and was able to polymerize IB in aqueous media using this Lewis acid.  On 11-22-00, Dr. “Kennedy” offered me the option of working with Stas in order to complete the required research necessary for my degree.  I immediately leapt at the chance to do this as “Kennedy” informed me that the bulk of the work had already been conducted by Stas and all I had to do was simply replicate some of his earlier experiments and expand upon them slightly.  “Kennedy” kindly supplied me with a copy of Kotaro Satoh’s dissertation (the cover sheet and TOC below) and Stas gave me journal articles published by the Sawamoto group to read.  I eagerly began digesting this information and within a period of days I was working with Stas.  Unfortunately for me, this would be yet another bizarre twist in attempting to finish my Ph.D. in the “Kennedy” lab.  One that would be life changing…

Satoh Dissertation Cover & TOC

Shortly after delivering my formal talk, scientists from Firestone who had been in attendance approached “Dr. Kennedy” and informed him that the basic chemistry I was working on had recently been patented by Kaneka (see JP 11209702, JP 11209701, WO 19990225, and so on).  Immediately “Kennedy” turned on me stating “It is your fault, it was your responsibility.”  At that time I was surprised by the dramatic change in “Kennedy’s” demeanor.  For many months I received nothing but praise and was told to focus on conducting actual research work.  At that time I had continued to do generalized (keyword) searches on SciFinder Scholar^®; however, none of them produced any hits.  Likewise, “Kennedy” had conducted numerous searches with the assistance of the head science librarian at the time, Ann Bolek, and still nothing relating to the project had been uncovered.  This unusual twist of fate was the first indication to me that “Kennedy” was not a man of his word as he had reneged on his promise to “protect my soft underbelly.”

In response to the finding that much of the chemistry had more or less be patented, focus was shifted to increasing the silica content of the star core through the use of alkoxy silanes (and even titanium alkoxides for hybrid structures) but the primary thrust of my work was temporarily shifted by “Kennedy.”  “Kennedy” informed me that Firestone was going to pay his research group money (according to him, part of which would fund me) and in return I was to teach one of their scientists (Terry Hogan) how to conduct living polymerization of IB.  Starting several days following the visit by Firestone scientists I began to generate new project ideas (see below) that would be related to the work I had been conducting so that I could tie the two together and finish the requirements necessary for my Ph.D. without losing much if any time.  From this point forward Dr. “Kennedy” offered no useful ideas in regards to work I was involved in.  It was in June of 2000 when I officially began a series of interactions with Dr. Hogan at U. Akron and taught him the basic aspects of living polymerization of IB while at the time I continued to work on the PIB silsesquioxane star project.  Dr. Hogan then was able to reduce to practice an invention that he had made involving copolymerization of styrenic monomers bearing reactive siloxy groups with IB to make a moisture curable form of PIB (see US 6838539).  Hogan’s invention was patented and Dr. “Kennedy” somehow got his name listed as a coinventor, despite the fact that Hogan told me personally that “Kennedy” made no inventive contributions whatsoever.  Interestingly, no money through Firestone ever came my way despite Hogan informing me that Firestone had paid “Kennedy” approximately $2,000.  At this point I was beginning to slowly realize what Dr. “Kennedy” was really about when it came to polymer science.

Despite these revelations I continued to work in the area of PIB-silsesquioxanes and transitioned into some of the chemistry I had proposed to “Kennedy” concerning the use of polyhedral oligomeric silsesquioxanes (POSS).  Unbeknownst to me several more twists of fate were about to transpire…

Lewis Ideas 1 Lewis Ideas 2 Lewis Ideas 3 Lewis Ideas 4

With the assistance of Jack and practice I was soon making silyl functionalized PIBs necessary for the research project.  With the exception of holidays or when he was out on travel I submitted monthly reports to Dr. “Kennedy” (see examples below).  As the project progressed I slowly became aware of the fact that Dr. “Kennedy” had very little insightful input to give in regards to problems that I was experiencing in the condensation of these arms into stars.  Another thing that I continued to encounter were issues related to equipment failures, mostly in the dry box that I used but also in instrumentation (e.g. GPC and NMR).  At times progress was hampered by the fact that I was becoming routinely ill with severe difficulty in breathing, something that was abnormal for me.  Regardless of the setbacks, I was able to figure out alternative methods (e.g. nonhydrolytic sol-gel synthesis) that led to improved yields of star polymers and within approximately one year following the beginning of laboratory work I had amassed enough data to deliver my formal talk as required by the polymer science department (see below).

Shortly after this talk (4-15-00) a physician informed me that my health problems were due to severe asthma and it was speculated that a major factor in causing this (which I did not have prior) could have been due to exposure to volatile reagents in the “Kennedy” lab.  Unfortunately, while at U. Akron I never once received any formal safety training and had been exposed to some unsafe practices in the handling of solvents commonly used in the “Kennedy” lab.  From that point forward I began to incrementally implement safer handling procedures when it came to use of reagents; however, I had already suffered the physical damage that they could cause.  Sadly this was but one bit of bad news to occur during this period as the reader will see…

Report Si 4_4_99  Report Si 6_4_99  Report Si 7_8_99  Report Si 8_18_99                Report Si Nov_99  Report Si Dec_99  Report Si 2_5_00

Formal abstract

formal talk

My first (and only mentor at U. Akron) was Zhengjie (aka Jack) Pi.  Jack originated from Claire Tessier’s research group in the adjacent chemistry department at U. Akron.  His background was as an organometallic chemist who specialized in silicon chemistry.  Unbeknownst to me at the time was the fact that Dr. “Kennedy” knew very little about silicon chemistry and that Jack was highly instrumental in helping “Kennedy” catch up to the curve of front running scientists in the field of isobutene (IB) polymerization by mimicking work from a well-known industrial chemist (i.e. Dr. Tim Shaffer).  The reader will soon see that this is a repetitive pattern when it comes to Dr. “Kennedy” and that in many instances patents, research work, and principles described in some of his books are essentially direct copies of other researchers.

During the time I spent with Jack I learned the basics of the living polymerization of IB and very rudimentary air-sensitive manipulations.  I use the adjective “rudimentary” as “Kennedy’s” lab did not contain modern day dry boxes nor did it have anything that could be remotely described as a fully functioning Schlenk line.  Likewise, the techniques I learned were in fact substandard and not what could be termed stringent in terms of such manipulations.  At the time my ignorance of such chemistry prevented me from seeing the obvious fact that besides Jack no one else in the “Kennedy” research group was properly schooled in air-sensitive chemistry.  Despite these limitations, Jack was highly instrumental in getting me versed in the chemistry required to complete the research project assigned to me by Dr. “Kennedy.”  Within a relatively short period of time I was not only able to synthesize the required starting polymer (allylic functionalized PIB) but I was also able to convert it to ~100% silyl functionalized PIB, which was the precursor for the PIB silsesquioxane stars.  During this period Dr. “Kennedy” would routinely comment “just keeping doing lab work, I’ll worry about the literature” and also indicated his pleasure with the progress being made.  Despite his assurances, I continued to do my best in reviewing the scientific literature in context to the ongoing project; however, as the reader will see this was still not enough to prevent a crisis.

When I first set foot into Dr. “Kennedy’s” laboratory at the University of Akron I noticed a stark difference between it and the bulk majority of synthetic laboratories in the polymer science department.  Some of the first things that were obvious included the antiquated pieces of equipment, the limited selection of glassware, and the large quantities of old reagents strewn here and there.  Even more shocking was that the more time I spent in this laboratory I encountered even more deplorable conditions in terms of cleanliness, upkeep, and reagent storage (please refer to photos below).  Due to my limited experience as a chemist I did not fully grasp the dangers that this laboratory actually posed, and later the reader will see that I wish I had been cognizant of the hazards contained in this laboratory.

“Kennedy” Chem Storage 1

Chemical Storage Cabinet of Dr. “Kennedy” 2

Fume hood “Kennedy”

drawer “Kennedy” lab

Preface:

     Some may ask why I am taking the time to write this blog series.  The simple answer to that question is that this will (in part) pave the way to correcting a number of crimes that were committed against me while I studied at this University.  Let me make it clear to the reader that all of the information contained in this blog series is factual and I will stand by it in any court of law.  In this series it is up to the reader to make conclusions based on the evidence presented and as to the integrity (or lack thereof) of the individuals involved as well as the institution that has employed them over these years.

My Beginnings in the “Kennedy” Lab

     In late 1998 (ca. November, 1998) I began working for Dr. “Joseph P. Kennedy” (reader, I put this individual’s “name” in quotations as it is an alias that he picked up apparently sometime in Europe.  I have yet to meet a single person who knows this person’s true name or his true background!).  From the very beginning I realized that this was a unique experience.  Prior to being accepted into the research group he gave me what was in effect an interview which also required submission of a resume and grade transcripts.  When it was decided that I was worthy of inclusion (please see research group photo below) Dr. “Kennedy” delivered a grandiose speech.  During this speech he informed me that he would “protect my soft underbelly, and my research project would be unique.”  Towards the conclusion of his diatribe, I was asked as to whether I knew of the story of Damocles’ sword.  I admitted to my ignorance of this story and Dr. “Kennedy” filled me in on its details.  According to him, Damocles was made the guest of honor at a dinner given by his enemies and they suspended a sword above his head with a human hair.  “Kennedy” told me “this represents the inherent danger that I face when I undertake new students.”  Little did I understand the hidden messages in the statements he was making at the time.

     I have to take an aside here and mention that at the time I was so innocent that I didn’t once think that it was strange for a Hungarian to have the name of an American senator.  Even when some of the postdoctoral students in the laboratory told me that not only was this not his true name but asked me if I understood what side of WWII Hungary was on the message still really didn’t register.  Not only was this man’s name stolen, but “Kennedy’s” Damocles speech was also in fact stolen (almost verbatim) from a speech delivered to congress by President John F. Kennedy!  I found this out while watching a documentary on the History Channel.  Now, back from my digression.

     The first order of business that had to be taken care of was to determine the research project.  During this period I was advised by Dr. “Kennedy” to seek the help of other faculty in the polymer science department.  This included Professors Harwood and Reneker, as well as a visiting scientist Professor Teyssie (please see PDF files below).  At this time I did not have much in the way of inventive skills and many of the ideas that I devised were more or less step change improvements to chemistry described in “Kennedy’s” books or described by others such as Professor Wilkes.  After presenting my ideas and asking them for help, each of these professors submitted additional ideas to me (Harwood making the offhand comment, “why should I give all my ideas to Joe?”).  Another unusual thing happened during this time but again I was too blind or too naïve to see.  Dr. “Kennedy” requested photocopies of all documents that we were to discuss during our group meetings.  Below you can find PDF files for the original copies as well as the photocopies of the originals (which he normally retained), the latter which have Dr. “Kennedy’s” hand writing.  This is one of few instances where I was able to retain the photocopied documents as I soon learned “Kennedy’s” standard modus operandi was to collect these photocopies into cabinetry located directly behind his computer desk that faced the door.

     During the review of these ideas Dr. “Kennedy” shot most of them down.  One humorous comment that “Kennedy” made to me concerning polyisobutene (PIB) based ionomers was “Storey steals my best ideas.”  Although I have never met this individual my guess is that this is far from the truth (i.e. Professor Storey devises his own ideas).  In the end, Dr. “Kennedy” decided that the best project would involve the preparation of PIBs bearing reactive silyl end groups, followed by subsequent hydrolysis/condensation to yield PIB stars with a silsesquioxane core.   Much of this chemistry was derived from work described by a Professor Wilkes whose papers “Kennedy” originally referred me to.  Again, my ignorance got the better of me.  Some years later, while reviewing the chemical literature and remembering that at least one Japanese visiting scientist had been working on somewhat similar chemistry did I realize that this idea was no doubt closely related to work that had been done by this Japanese chemist who had most likely left photocopies of his ideas with Dr. “Kennedy”.  Evidence supporting this will be shown in a subsequent blog posting in this series.

Kennedy 1999 to 2000 Group photo

Example of Meeting Notes with Prof Teyssie

Original Notes of Dr Lewis Prepared for Prof Kennedy

Dr Lewis notes JPK Photocopy with notes from latter