{"version":"1.0.0","segments":[{"speaker":null,"startTime":1.014,"endTime":2.694,"body":"Kevin: welcome to Innovate and React."},{"speaker":null,"startTime":2.834,"endTime":8.034,"body":"In today's episode, we will lookinto catalyst research and how DFT"},{"speaker":null,"startTime":8.044,"endTime":9.724,"body":"calculations can help with that."},{"speaker":null,"startTime":10.089,"endTime":14.126,"body":"It's always interesting to seehow we can improve conventional"},{"speaker":null,"startTime":14.216,"endTime":19.216,"body":"petrochemical pathways and find moresustainable options with new catalysts."},{"speaker":null,"startTime":20.366,"endTime":23.466,"body":"For this discussion, I'm very happyto welcome back Thomas Bouveyron."},{"speaker":null,"startTime":24.856,"endTime":30.786,"body":"He's a PhD candidate at the RWTHAachen, uh, in cooperation with"},{"speaker":null,"startTime":30.826,"endTime":36.878,"body":"the TH K\u00f6ln University of AppliedSciences in the field of catalysis"},{"speaker":null,"startTime":37.385,"endTime":38.135,"body":"hi, Thomas."},{"speaker":null,"startTime":38.508,"endTime":38.992,"body":"Thomas: Hi, Kevin."},{"speaker":null,"startTime":39.429,"endTime":40.081,"body":"Great to be back."},{"speaker":null,"startTime":40.309,"endTime":44.179,"body":"Kevin: Yeah, I'm, uh, looking forwardto this discussion and, uh, learn more"},{"speaker":null,"startTime":44.179,"endTime":47.179,"body":"about your, uh, catalyst research."},{"speaker":null,"startTime":47.199,"endTime":52.049,"body":"Maybe let's start with the goalmolecule of the reaction you're"},{"speaker":null,"startTime":52.079,"endTime":54.549,"body":"looking into and what that is used for."},{"speaker":null,"startTime":55.109,"endTime":55.359,"body":"Thomas: Yeah."},{"speaker":null,"startTime":55.362,"endTime":59.78,"body":"So we chose one goal moleculein particular, and that's the"},{"speaker":null,"startTime":59.81,"endTime":66.412,"body":"N-decanal, but it could also beum, non-substituted, aldehyde."},{"speaker":null,"startTime":67.98,"endTime":72.702,"body":"But yeah, we chose this one becauseit has great value in the, in the"},{"speaker":null,"startTime":72.702,"endTime":75.122,"body":"fragrance industry and as a pesticide."},{"speaker":null,"startTime":75.191,"endTime":80.212,"body":"It's, uh, I think it's used as afungicide and in the food industry as"},{"speaker":null,"startTime":80.212,"endTime":85.132,"body":"a flavoring agent, and yeah, its, itsconventional route is quite interesting"},{"speaker":null,"startTime":85.132,"endTime":87.952,"body":"to look at and maybe to improve."},{"speaker":null,"startTime":88.521,"endTime":88.841,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":89.101,"endTime":91.081,"body":"How is it made industrially?"},{"speaker":null,"startTime":91.344,"endTime":93.364,"body":"Thomas: Industrially, so far"},{"speaker":null,"startTime":93.533,"endTime":95.423,"body":"Kevin: it's like almost all"},{"speaker":null,"startTime":95.434,"endTime":100.214,"body":"Thomas: chemicals, starts withcrude oil, where ethene is then,"},{"speaker":null,"startTime":100.294,"endTime":105.704,"body":"um, further synthesized SHOP processto an octene and through further"},{"speaker":null,"startTime":105.714,"endTime":111.134,"body":"steps, then, uh, hydroformylation toN-nonanol, dehydration to N-nonene,"},{"speaker":null,"startTime":111.574,"endTime":117.074,"body":"and at the end, through anotherhydroformylation step, you get n-decanal."},{"speaker":null,"startTime":117.074,"endTime":123.511,"body":"So all in all, every step is basedon petrol chemistry and, well, the"},{"speaker":null,"startTime":123.511,"endTime":129.532,"body":"waste is high \u2026and it's very longand not very ecological or economical."},{"speaker":null,"startTime":130.051,"endTime":130.071,"body":"Kevin: Yeah."},{"speaker":null,"startTime":130.071,"endTime":134.941,"body":"Ve-very many steps because, uh,in the conventional route where"},{"speaker":null,"startTime":134.941,"endTime":139.941,"body":"the hydroformylation is used,hydroformylation always is a C1"},{"speaker":null,"startTime":140.261,"endTime":145.891,"body":"extension and, uh, it's difficultto get the aldehyde without that."},{"speaker":null,"startTime":146.081,"endTime":147.051,"body":"And, uh, yeah."},{"speaker":null,"startTime":147.551,"endTime":152.571,"body":"Here you start with the twocarbons less because you get those"},{"speaker":null,"startTime":152.571,"endTime":153.781,"body":"from the Shell process, right?"},{"speaker":null,"startTime":153.952,"endTime":154.962,"body":"Thomas: Yeah, exactly."},{"speaker":null,"startTime":155.502,"endTime":158.382,"body":"And, uh, because we start fromethene and then through the"},{"speaker":null,"startTime":158.442,"endTime":163.865,"body":"hydroformylation, you always get uh,even numbered aldehyde at the end."},{"speaker":null,"startTime":163.865,"endTime":168.335,"body":"So for example, if you wantedto get a odd numbered aldehyde,"},{"speaker":null,"startTime":168.595,"endTime":170.459,"body":"it would be Quite more difficult"},{"speaker":null,"startTime":171.05,"endTime":171.14,"body":"Kevin: Yeah."},{"speaker":null,"startTime":171.34,"endTime":172.01,"body":"Yeah, exactly."},{"speaker":null,"startTime":172.57,"endTime":178.79,"body":"And, um, these aldehydes, uh, aswe discussed, they are used in the"},{"speaker":null,"startTime":178.79,"endTime":184.44,"body":"industry as a fragrance, becausethey have a nice lemony flavor or a-"},{"speaker":null,"startTime":184.44,"endTime":185.28,"body":"Thomas: Yeah \u2026 smell."},{"speaker":null,"startTime":185.55,"endTime":191.159,"body":"Right \u2026 a citrusy and decanal inparticular, and that's one reason why we"},{"speaker":null,"startTime":191.159,"endTime":197.169,"body":"chose it, is, um, one of the scents inperfumes like- Yeah for example chanel No."},{"speaker":null,"startTime":197.203,"endTime":197.913,"body":"5."},{"speaker":null,"startTime":198.18,"endTime":198.69,"body":"Kevin: Interesting."},{"speaker":null,"startTime":198.69,"endTime":202.652,"body":"Yeah, that's, uh, thenalready a pricey product."},{"speaker":null,"startTime":202.712,"endTime":203.462,"body":"Yeah, exactly."},{"speaker":null,"startTime":203.702,"endTime":212.012,"body":"Um, but with many reaction steps, andideally we could use less when, um,"},{"speaker":null,"startTime":212.022,"endTime":217.002,"body":"according to the principles of greenchemistry, it's always best to, uh,"},{"speaker":null,"startTime":217.022,"endTime":220.422,"body":"reduce reaction steps, use catalysts."},{"speaker":null,"startTime":221.022,"endTime":224.022,"body":"Um, what other principlesdid you apply in the-"},{"speaker":null,"startTime":224.401,"endTime":224.861,"body":"Thomas: So-"},{"speaker":null,"startTime":225.028,"endTime":225.728,"body":"Kevin: of the reaction?"},{"speaker":null,"startTime":225.798,"endTime":226.228,"body":"One"},{"speaker":null,"startTime":226.351,"endTime":227.931,"body":"Thomas: thing is, uh, always"},{"speaker":null,"startTime":228.051,"endTime":230.231,"body":"to try and substitute the,"},{"speaker":null,"startTime":230.928,"endTime":231.468,"body":"Kevin: the petrochemicals."},{"speaker":null,"startTime":231.971,"endTime":232.321,"body":"Thomas: petrochemicals."},{"speaker":null,"startTime":232.331,"endTime":233.331,"body":"So we- Mm-hmm."},{"speaker":null,"startTime":233.411,"endTime":235.721,"body":"If-- The conventional routestarts from crude oil."},{"speaker":null,"startTime":236.171,"endTime":241.091,"body":"And it would be nice if we could,uh, start with bio-based chemicals,"},{"speaker":null,"startTime":241.461,"endTime":246.621,"body":"and, uh, that's exactly what wedid with the help of, Verbio GmbH."},{"speaker":null,"startTime":246.621,"endTime":250.421,"body":"Uh, they provided us withthe terminal alkene\u2026 Uh,"},{"speaker":null,"startTime":250.591,"endTime":256.801,"body":"yes, alkene and decane- Mm-hmm whichgot from, the ethanolysis of oleic"},{"speaker":null,"startTime":257.111,"endTime":259.291,"body":"acid methyl ester from a plant."},{"speaker":null,"startTime":259.784,"endTime":263.134,"body":"Kevin: So there youdirectly get the C10, um-"},{"speaker":null,"startTime":263.174,"endTime":263.667,"body":"Thomas: Yes, exactly"},{"speaker":null,"startTime":264.017,"endTime":269.383,"body":"\u2026  Kevin: the C10 building block,and now you want to attach"},{"speaker":null,"startTime":269.383,"endTime":271.193,"body":"an aldehyde function to that."},{"speaker":null,"startTime":271.203,"endTime":271.223,"body":"Yeah."},{"speaker":null,"startTime":271.343,"endTime":273.93,"body":"What reaction, did you look into then?"},{"speaker":null,"startTime":274.17,"endTime":280.35,"body":"Thomas: So we, as you said, uh, wehave the C10 alkene- Mm-hmm \u2026 and"},{"speaker":null,"startTime":280.58,"endTime":284.817,"body":"it's basically just a directoxidation at the end the double bond."},{"speaker":null,"startTime":285.16,"endTime":290.16,"body":"So first thing that comes to mindis the Wacker oxidation, which"},{"speaker":null,"startTime":290.16,"endTime":294.331,"body":"is, well-known reaction that hasbeen used for quite some times."},{"speaker":null,"startTime":294.331,"endTime":296.421,"body":"I think it's over 100 years now."},{"speaker":null,"startTime":296.881,"endTime":297.331,"body":"Mm-hmm."},{"speaker":null,"startTime":297.341,"endTime":303.091,"body":"But, uh, yeah, direct oxidation atthe terminal carbon of a double bond"},{"speaker":null,"startTime":303.101,"endTime":307.971,"body":"is always difficult because there isa rule that most chemists know, and"},{"speaker":null,"startTime":308.001,"endTime":309.761,"body":"it's called the Markovnikov rule."},{"speaker":null,"startTime":309.761,"endTime":310.301,"body":"Yeah."},{"speaker":null,"startTime":310.301,"endTime":314.791,"body":"And, um, yeah, that's one of the mainchallenge we tried to face in this"},{"speaker":null,"startTime":314.801,"endTime":321.772,"body":"project because the second carbon, sothe higher substituted carbon, would"},{"speaker":null,"startTime":321.982,"endTime":323.442,"body":"be preferred in the direct oxidation"},{"speaker":null,"startTime":324.149,"endTime":325.629,"body":"Kevin: in- That is the Markovnikov"},{"speaker":null,"startTime":325.712,"endTime":327.192,"body":"Thomas: And that's the markovnikov rule."},{"speaker":null,"startTime":327.232,"endTime":327.709,"body":"Exactly."},{"speaker":null,"startTime":327.75,"endTime":332.83,"body":"Kevin: And, um, your goal isto have the linear one, which"},{"speaker":null,"startTime":333.46,"endTime":338.12,"body":"has to be the anti-Markovnikov,so the non-favorable product."},{"speaker":null,"startTime":338.18,"endTime":338.74,"body":"Exactly."},{"speaker":null,"startTime":339,"endTime":342.994,"body":"And how did you manage to- changethe odds for this reaction?"},{"speaker":null,"startTime":343.377,"endTime":349.637,"body":"Thomas: Well, so first of all, we lookedinto literature because it is known"},{"speaker":null,"startTime":349.937,"endTime":355.607,"body":"and it has been tried before, not withthe linear, uh, unsubstituted alkane so"},{"speaker":null,"startTime":355.607,"endTime":359.137,"body":"far, or not in this extent as we did."},{"speaker":null,"startTime":359.827,"endTime":364.668,"body":"Um, there are in literature someexperiments that used, aryl-substituted,"},{"speaker":null,"startTime":365.658,"endTime":371.818,"body":"um, alkenes such as, uh, styrene, forexample, and there the styrene group would"},{"speaker":null,"startTime":371.828,"endTime":375.138,"body":"direct the anti-Markovnikov selectivity."},{"speaker":null,"startTime":375.578,"endTime":381.158,"body":"But for us, there is nothing in themolecule that can help with that, so we"},{"speaker":null,"startTime":381.158,"endTime":386.018,"body":"have to look at the catalysts and theconditions of the reaction themselves."},{"speaker":null,"startTime":386.788,"endTime":392.768,"body":"And, um, so we started off with theone factor at a time optimization."},{"speaker":null,"startTime":392.768,"endTime":396.568,"body":"So we took literature experimentsand tried to replicate"},{"speaker":null,"startTime":396.588,"endTime":398.668,"body":"that for our substrates."},{"speaker":null,"startTime":399.258,"endTime":404.388,"body":"And, uh, yeah, we found onecatalyst that worked pretty nicely."},{"speaker":null,"startTime":404.395,"endTime":408.635,"body":"Kevin: Uh- So you started withthe, um, reaction conditions from"},{"speaker":null,"startTime":408.645,"endTime":410.755,"body":"like a styrene paper or- Yeah,"},{"speaker":null,"startTime":410.756,"endTime":411.136,"body":"Thomas: basically."},{"speaker":null,"startTime":411.136,"endTime":413.926,"body":"And so there are more than these styrenes."},{"speaker":null,"startTime":413.936,"endTime":419.586,"body":"There is, um, a few literature about theWacker, the modified Wacker oxidation,"},{"speaker":null,"startTime":419.586,"endTime":425.366,"body":"and they're all in agreement with eachother that, um, this, uh, catalyst,"},{"speaker":null,"startTime":425.366,"endTime":430.926,"body":"the palladium chloride bisacetonitrileworks pretty good for that in,"},{"speaker":null,"startTime":431.026,"endTime":435.596,"body":"uh, the highly substituted alcoholtert-butanol as the solvent- Mm-hmm"},{"speaker":null,"startTime":435.666,"endTime":440.816,"body":"in comparison to water and,hydrochloric acid used in the"},{"speaker":null,"startTime":441.086,"endTime":442.786,"body":"conventional Wacker oxidation."},{"speaker":null,"startTime":443.035,"endTime":443.375,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":444.255,"endTime":444.445,"body":"Yeah."},{"speaker":null,"startTime":444.445,"endTime":450.405,"body":"The, the conventional one I think is,uh, done with ethene, where you basically"},{"speaker":null,"startTime":450.455,"endTime":452.395,"body":"don't really have a different product."},{"speaker":null,"startTime":452.395,"endTime":455.735,"body":"You always get one productbecause both carbons are the same."},{"speaker":null,"startTime":455.796,"endTime":456.216,"body":"Thomas: Yeah."},{"speaker":null,"startTime":456.236,"endTime":460.946,"body":"So there is, there is an example thatmost people would know that, uh, is"},{"speaker":null,"startTime":460.956,"endTime":466.016,"body":"used in the Wacker oxidation, and thatwould be the synthesis of, um, acetone."},{"speaker":null,"startTime":466.295,"endTime":466.575,"body":"Mm-hmm"},{"speaker":null,"startTime":466.676,"endTime":470.816,"body":"where it is the Markovnikov product atthe end where you start with propylene."},{"speaker":null,"startTime":471.225,"endTime":471.415,"body":"Kevin: Yeah."},{"speaker":null,"startTime":471.545,"endTime":472.245,"body":"Yeah, exactly."},{"speaker":null,"startTime":472.415,"endTime":479.235,"body":"And, um, then you apply this reactionconditions to the new substrate,"},{"speaker":null,"startTime":479.275,"endTime":482.235,"body":"which is the n-decanal and\u2026"},{"speaker":null,"startTime":482.625,"endTime":482.945,"body":"Yeah."},{"speaker":null,"startTime":482.995,"endTime":487.925,"body":"But from the theory to a workingreaction, that always takes"},{"speaker":null,"startTime":488.035,"endTime":489.795,"body":"time, as, uh, we all know."},{"speaker":null,"startTime":490.115,"endTime":496.437,"body":"Um, how did you proceed to start withyour reaction and with the new substrate?"},{"speaker":null,"startTime":497.599,"endTime":499.809,"body":"To then basically have aworking reaction in the end."},{"speaker":null,"startTime":500.341,"endTime":500.631,"body":"Thomas: Yeah."},{"speaker":null,"startTime":500.631,"endTime":507.341,"body":"So I, I took literature, as I said-Mm \u2026 and just tried it at first, see"},{"speaker":null,"startTime":507.341,"endTime":513.551,"body":"if it even was possible or if I hadto change basically my whole PhD idea."},{"speaker":null,"startTime":514.141,"endTime":516.491,"body":"Uh, lucky for me, it worked."},{"speaker":null,"startTime":516.551,"endTime":518.011,"body":"The reaction was nice to me."},{"speaker":null,"startTime":518.159,"endTime":520.519,"body":"but it didn't work very well."},{"speaker":null,"startTime":520.529,"endTime":520.849,"body":"Mm-hmm."},{"speaker":null,"startTime":521.017,"endTime":526.749,"body":"So I started off with, uh, selectivitytowards my, um, desired aldehyde of\u2026"},{"speaker":null,"startTime":526.779,"endTime":529.669,"body":"I think they were 8% or"},{"speaker":null,"startTime":529.676,"endTime":529.856,"body":"Kevin: something."},{"speaker":null,"startTime":529.856,"endTime":530.196,"body":"Mm-hmm."},{"speaker":null,"startTime":530.529,"endTime":534.799,"body":"Thomas: So not very good, and theconversion was also not very good."},{"speaker":null,"startTime":535.219,"endTime":540.339,"body":"So I started to change in"},{"speaker":null,"startTime":540.899,"endTime":546.277,"body":"one factor at a time manner allthe, the reaction conditions."},{"speaker":null,"startTime":546.839,"endTime":552.289,"body":"And found some trends that, thatI could not explain quite yet."},{"speaker":null,"startTime":552.911,"endTime":558.756,"body":"After that, I turned myself to,to statistics and tried to find a"},{"speaker":null,"startTime":558.756,"endTime":561.837,"body":"more, organized approach to, um,"},{"speaker":null,"startTime":562.273,"endTime":565.372,"body":"reaction optimization,and that's what we did."},{"speaker":null,"startTime":566.312,"endTime":571.122,"body":"We used, uh, design of experimentand found even more questions"},{"speaker":null,"startTime":571.532,"endTime":575.202,"body":"and, uh, even more problems thanwe expected at the beginning."},{"speaker":null,"startTime":575.212,"endTime":580.452,"body":"But that helped us to, to get inthe right direction to optimize"},{"speaker":null,"startTime":580.482,"endTime":581.932,"body":"the reaction even further."},{"speaker":null,"startTime":582.303,"endTime":582.613,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":583.063,"endTime":586.403,"body":"Let's, uh, recap real quickwhat is, uh, the design of"},{"speaker":null,"startTime":586.413,"endTime":588.13,"body":"experiments in this, context."},{"speaker":null,"startTime":588.643,"endTime":588.824,"body":"Thomas: Yeah."},{"speaker":null,"startTime":588.824,"endTime":593.304,"body":"So I used, uh, Minitab as aprogram, and, um, I had\u2026"},{"speaker":null,"startTime":594.146,"endTime":594.286,"body":"Kevin: I,"},{"speaker":null,"startTime":594.324,"endTime":596.746,"body":"Thomas: I chose seven different factors."},{"speaker":null,"startTime":597.674,"endTime":601.694,"body":"Uh, so the catalyst amount, theco-catalyst amount, substrate"},{"speaker":null,"startTime":601.694,"endTime":605.934,"body":"amount, water content, reactiontime, and reaction temperature."},{"speaker":null,"startTime":605.944,"endTime":605.974,"body":"Mm-hmm."},{"speaker":null,"startTime":606.166,"endTime":606.396,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":606.674,"endTime":610.714,"body":"Thomas: And the outcome of mystatistical design was the selectivity"},{"speaker":null,"startTime":610.714,"endTime":614.954,"body":"and, uh, um, towards the aldehydeand the conversion of the alkene."},{"speaker":null,"startTime":615.126,"endTime":615.316,"body":"Kevin: alkene."},{"speaker":null,"startTime":616.024,"endTime":620.419,"body":"Thomas: And basically, the, theprogram gives you an experimental"},{"speaker":null,"startTime":620.419,"endTime":626.849,"body":"plan, depending on what you choseas a difficulty or an precision."},{"speaker":null,"startTime":627.669,"endTime":631.669,"body":"And, um, then it tells you whatexperiments you should do at what corner"},{"speaker":null,"startTime":631.669,"endTime":637.609,"body":"points of those factors, and it looksat the best outcome you want to give"},{"speaker":null,"startTime":637.609,"endTime":639.972,"body":"him or the, the reaction gives you."},{"speaker":null,"startTime":639.972,"endTime":644.005,"body":"And then it, tells you wherethe optimum of your reaction is"},{"speaker":null,"startTime":644.365,"endTime":646.055,"body":"based on the outcome you got."},{"speaker":null,"startTime":646.437,"endTime":646.737,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":647.077,"endTime":654.317,"body":"So a statistical approach that, usesnot only the exact points you measure,"},{"speaker":null,"startTime":654.347,"endTime":659.107,"body":"like, uh, you mentioned before,the classical, uh, one point at a"},{"speaker":null,"startTime":659.107,"endTime":664.007,"body":"time reaction, you can only catchwhat is in the points you measure."},{"speaker":null,"startTime":664.047,"endTime":664.197,"body":"Yeah."},{"speaker":null,"startTime":664.747,"endTime":669.217,"body":"But with this, as I also used thedesign of experiments in my PhD, is"},{"speaker":null,"startTime":669.217,"endTime":674.127,"body":"that you can also find optimal pointsin between the points you measure"},{"speaker":null,"startTime":674.127,"endTime":680.182,"body":"because there are some curves in theprogram that gives you an local optimum."},{"speaker":null,"startTime":680.25,"endTime":680.55,"body":"Thomas: Yeah."},{"speaker":null,"startTime":680.55,"endTime":683.9,"body":"And you also can find the,"},{"speaker":null,"startTime":685.164,"endTime":685.494,"body":"Kevin: You can"},{"speaker":null,"startTime":685.502,"endTime":689.952,"body":"Thomas: find, uh, co-dependencies in thedifferent factors between one another."},{"speaker":null,"startTime":689.964,"endTime":695.462,"body":"Mm. So, maybe your temperatureand your substrate amount, are"},{"speaker":null,"startTime":696.242,"endTime":701.422,"body":"together influencing your reaction,and you cannot have the effect of"},{"speaker":null,"startTime":701.432,"endTime":703.092,"body":"one without having the other one."},{"speaker":null,"startTime":703.102,"endTime":706.942,"body":"So that's also nice to havebecause a one factor at a you"},{"speaker":null,"startTime":706.942,"endTime":709.122,"body":"would never see such dependencies."},{"speaker":null,"startTime":709.284,"endTime":709.584,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":710.394,"endTime":710.564,"body":"And"},{"speaker":null,"startTime":710.564,"endTime":714.354,"body":"you also can find, uh, factors thatdon't have an influence at all, and then-"},{"speaker":null,"startTime":714.354,"endTime":720.783,"body":"Yeah \u2026 in future experiments, more orless set them at one point and then test"},{"speaker":null,"startTime":720.813,"endTime":721.773,"body":"with others to- And leave, leave them."},{"speaker":null,"startTime":721.781,"endTime":722.061,"body":"Thomas: Yeah."},{"speaker":null,"startTime":722.33,"endTime":726.5,"body":"Kevin: To also reduce the amount ofexperiments necessary to find the optimum."},{"speaker":null,"startTime":726.807,"endTime":727.087,"body":"Thomas: Yeah."},{"speaker":null,"startTime":727.087,"endTime":731.266,"body":"That's, that's also a good pointbecause, we chose a, a model where we"},{"speaker":null,"startTime":731.266,"endTime":736.592,"body":"only had to do, I think it was about 50experiments, which is quite a lot when"},{"speaker":null,"startTime":736.592,"endTime":738.602,"body":"you think about the palladium catalyst."},{"speaker":null,"startTime":739.162,"endTime":739.182,"body":"Yeah."},{"speaker":null,"startTime":739.192,"endTime":741.922,"body":"Uh, but it could have been way more."},{"speaker":null,"startTime":741.954,"endTime":742.274,"body":"Kevin: Yeah."},{"speaker":null,"startTime":742.814,"endTime":747.414,"body":"Yeah, with seven parameters,when you combine each parameter"},{"speaker":null,"startTime":747.414,"endTime":750.144,"body":"with each, that's way more."},{"speaker":null,"startTime":750.687,"endTime":751.067,"body":"Thomas: That's a lot, yeah."},{"speaker":null,"startTime":752.295,"endTime":753.465,"body":"Kevin: Quick break for two things."},{"speaker":null,"startTime":754.095,"endTime":756.725,"body":"First of all, a bigthank you for tuning in."},{"speaker":null,"startTime":756.855,"endTime":758.315,"body":"This really means a lot to me."},{"speaker":null,"startTime":758.828,"endTime":762.226,"body":"And the other thing is, pleasefollow Innovate and React on"},{"speaker":null,"startTime":762.236,"endTime":764.116,"body":"whatever app you're listening."},{"speaker":null,"startTime":764.176,"endTime":768.656,"body":"This really helps to grow the showand get new guests on to continue."},{"speaker":null,"startTime":769.009,"endTime":770.219,"body":"Thank you so much for your time."},{"speaker":null,"startTime":770.499,"endTime":771.179,"body":"Back to the episode"},{"speaker":null,"startTime":772.047,"endTime":777.517,"body":"You mentioned new challenges that youfound from this design ex-experiments."},{"speaker":null,"startTime":777.537,"endTime":777.967,"body":"Yeah."},{"speaker":null,"startTime":778.245,"endTime":778.745,"body":"What were those?"},{"speaker":null,"startTime":779.119,"endTime":784.274,"body":"Thomas: So what we found is andthat what we observed also in our"},{"speaker":null,"startTime":784.284,"endTime":788.992,"body":"first, preliminary test is thatwe need too much of the catalyst."},{"speaker":null,"startTime":788.992,"endTime":794.76,"body":"So we are not, uh, in a catalytic,environment, but in-- rather in"},{"speaker":null,"startTime":794.76,"endTime":796.46,"body":"a stoichiometric environment."},{"speaker":null,"startTime":796.46,"endTime":801.94,"body":"So we needed way more catalyst and alsoco-catalyst, the copper chloride with--"},{"speaker":null,"startTime":801.94,"endTime":806.204,"body":"uh, which is supposed to, re-oxidizethe palladium chloride at the end."},{"speaker":null,"startTime":807.044,"endTime":811.704,"body":"Mm. And we needed too much of those,so that was a big problem and a"},{"speaker":null,"startTime":811.704,"endTime":813.494,"body":"big question we had to answer."},{"speaker":null,"startTime":814.214,"endTime":819.222,"body":"And, surprisingly enough, the reactionrequired very low temperatures."},{"speaker":null,"startTime":819.232,"endTime":823.422,"body":"So- Mm-hmm \u2026 um,between sixty and eighty."},{"speaker":null,"startTime":823.422,"endTime":825.132,"body":"So we chose seventy, basically."},{"speaker":null,"startTime":825.582,"endTime":827.692,"body":"Seventy-five was the optimal point."},{"speaker":null,"startTime":828.242,"endTime":831.711,"body":"And also, water was a critical factor."},{"speaker":null,"startTime":831.811,"endTime":837.251,"body":"So basically we found that we needless water or actually no water at"},{"speaker":null,"startTime":837.251,"endTime":842.021,"body":"all for the reaction to work in termsof selectivity towards the aldehyde."},{"speaker":null,"startTime":842.581,"endTime":846.221,"body":"which is quite surprising ifyou think of the original Wacker"},{"speaker":null,"startTime":846.221,"endTime":850.492,"body":"oxidation where water is thenucleophile attacking the double bond."},{"speaker":null,"startTime":851.251,"endTime":857.251,"body":"So, water acts as the nucleophileand the oxygen from the water"},{"speaker":null,"startTime":857.261,"endTime":858.311,"body":"attacks the double bond."},{"speaker":null,"startTime":858.771,"endTime":861.051,"body":"And for us, that wasn't the case."},{"speaker":null,"startTime":861.061,"endTime":864.961,"body":"So where, where does thenucleophile come from?"},{"speaker":null,"startTime":864.971,"endTime":866.651,"body":"Where is the oxygen coming from?"},{"speaker":null,"startTime":867.061,"endTime":869.171,"body":"And there is also literature for that."},{"speaker":null,"startTime":869.491,"endTime":874.631,"body":"And, basically, they suggested thatit comes from the, the tert-butanol,"},{"speaker":null,"startTime":874.631,"endTime":877.091,"body":"so the alcohol, the solvent itself."},{"speaker":null,"startTime":878.001,"endTime":882.772,"body":"So that was also a, a subject thatwe had to look into afterwards."},{"speaker":null,"startTime":883.002,"endTime":888.152,"body":"Kevin: So that the solvent is, directlyinvolved in the catalytic mechanism."},{"speaker":null,"startTime":888.162,"endTime":888.59,"body":"Thomas: Yes."},{"speaker":null,"startTime":889.541,"endTime":894.521,"body":"And that, uh, is chemically speakinga big challenge because it's, it"},{"speaker":null,"startTime":894.531,"endTime":900.481,"body":"rewrites the whole Wacker cyclewhere water needs to first activate"},{"speaker":null,"startTime":900.521,"endTime":902.981,"body":"the catalytic complex, and then is,"},{"speaker":null,"startTime":903.082,"endTime":908.052,"body":"Being released afterwards in the cycleand reenters the cycle and everything."},{"speaker":null,"startTime":908.352,"endTime":912.072,"body":"So that was also a bigmechanistic question that was"},{"speaker":null,"startTime":912.082,"endTime":914.692,"body":"opened due to the DOE finding."},{"speaker":null,"startTime":915.534,"endTime":915.704,"body":"Kevin: Hmm."},{"speaker":null,"startTime":915.934,"endTime":916.474,"body":"Interesting."},{"speaker":null,"startTime":916.734,"endTime":925.004,"body":"And then, um, with your results fromthe DOE, you knew which parameters are"},{"speaker":null,"startTime":925.004,"endTime":930.034,"body":"critical for the reaction, and you had aoptimal point for direction conditions."},{"speaker":null,"startTime":930.314,"endTime":930.414,"body":"Mm-hmm."},{"speaker":null,"startTime":930.574,"endTime":937.604,"body":"But the, the mechanism of a reactionis always, uh, something to look at to"},{"speaker":null,"startTime":937.614,"endTime":943.574,"body":"really understand what to improve and whatto change to get better results, right?"},{"speaker":null,"startTime":943.722,"endTime":944.112,"body":"Thomas: Yes."},{"speaker":null,"startTime":944.182,"endTime":949.282,"body":"So, and that is quite surprisingor, yeah, with, with the Wacker"},{"speaker":null,"startTime":949.294,"endTime":950.104,"body":"Kevin: Wacker oxidation"},{"speaker":null,"startTime":950.114,"endTime":951.864,"body":"Thomas: because it is"},{"speaker":null,"startTime":952.042,"endTime":958.572,"body":"a rather old reaction, and it is usedcommonly or was used commonly in the"},{"speaker":null,"startTime":958.572,"endTime":965.424,"body":"industry, but not all its steps in, inthe cycle are really well understood."},{"speaker":null,"startTime":965.742,"endTime":965.812,"body":"Mm-hmm."},{"speaker":null,"startTime":965.822,"endTime":970.462,"body":"So there is a lot of debate, forexample, at the end if the, the last"},{"speaker":null,"startTime":970.462,"endTime":975.062,"body":"step is a beta-hydride eliminationor a reductive elimination."},{"speaker":null,"startTime":975.482,"endTime":981.047,"body":"And for us also the nucleophilic attackcan happen in two different pathways."},{"speaker":null,"startTime":981.047,"endTime":986.597,"body":"So the water, as I mentioned before,can come from inside the complex."},{"speaker":null,"startTime":986.657,"endTime":989.757,"body":"So the complex was activatedwith water before, and then"},{"speaker":null,"startTime":989.767,"endTime":991.177,"body":"the attack happens from inside."},{"speaker":null,"startTime":991.687,"endTime":997.527,"body":"This would be an, syn attack, or itcan happen from outside of the catalyst"},{"speaker":null,"startTime":997.527,"endTime":1003.357,"body":"where water directly attacks the doublebond being an anti sphere attack."},{"speaker":null,"startTime":1003.707,"endTime":1003.737,"body":"Mm-hmm."},{"speaker":null,"startTime":1003.847,"endTime":1006.987,"body":"And this is also a subject of some debate."},{"speaker":null,"startTime":1007.027,"endTime":1013.077,"body":"And yeah, as, as you can tell, the--it is not very easy to, to get everyone"},{"speaker":null,"startTime":1013.107,"endTime":1017.429,"body":"under one roof- Yeah \u2026 and agreeabout the mechanistics of the reaction."},{"speaker":null,"startTime":1017.768,"endTime":1018.038,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1018.508,"endTime":1023.388,"body":"Yeah, maybe to also, I think, uh, withthis mechanisms especially it's sometimes"},{"speaker":null,"startTime":1023.388,"endTime":1025.538,"body":"difficult to just explain them with words."},{"speaker":null,"startTime":1025.548,"endTime":1026.758,"body":"So- um,"},{"speaker":null,"startTime":1026.808,"endTime":1033.158,"body":"I will put in the show notes a link toa picture of the different, mechanisms."},{"speaker":null,"startTime":1033.728,"endTime":1038.708,"body":"Yeah, coming back to the water, uh,is one option, but you also said that,"},{"speaker":null,"startTime":1038.708,"endTime":1041.548,"body":"uh, solvent, uh, can interact there."},{"speaker":null,"startTime":1041.558,"endTime":1043.688,"body":"How, how is that different?"},{"speaker":null,"startTime":1044.04,"endTime":1044.35,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1044.35,"endTime":1048.92,"body":"So we did different testswith different solvents."},{"speaker":null,"startTime":1049.167,"endTime":1053.617,"body":"we did different testing withmethanol, ethanol, pentanol, and"},{"speaker":null,"startTime":1053.617,"endTime":1055.377,"body":"then highly substituted alcohols."},{"speaker":null,"startTime":1056.707,"endTime":1062.847,"body":"And in the first phase, we only went totert-butanol because it is the highest"},{"speaker":null,"startTime":1062.857,"endTime":1065.847,"body":"substituted alcohol at the, the relevant"},{"speaker":null,"startTime":1065.857,"endTime":1066.257,"body":"group,"},{"speaker":null,"startTime":1066.907,"endTime":1068.377,"body":"and it worked quite well."},{"speaker":null,"startTime":1068.897,"endTime":1075.567,"body":"And later on, we found that thissolvent has a few disadvantages"},{"speaker":null,"startTime":1075.577,"endTime":1080.357,"body":"because, um, aliphatic alcoholscan undergo, dehydration."},{"speaker":null,"startTime":1081.367,"endTime":1087.127,"body":"Um, building a carbonyl ion, and then,be turned into either in the presence"},{"speaker":null,"startTime":1087.147,"endTime":1093.397,"body":"of halogens in, the halogen can attackthe carbonyl group, or it can turn into"},{"speaker":null,"startTime":1093.417,"endTime":1099.017,"body":"the alkane itself, and those have aboiling point way below our reaction"},{"speaker":null,"startTime":1099.017,"endTime":1100.607,"body":"temperature, and that's actually what"},{"speaker":null,"startTime":1100.609,"endTime":1101.359,"body":"we observed."},{"speaker":null,"startTime":1101.647,"endTime":1106.737,"body":"We had a big loss inrelevant solvent- Mm-hmm"},{"speaker":null,"startTime":1106.747,"endTime":1110.487,"body":"which, as you said also before,participates in the reaction."},{"speaker":null,"startTime":1110.834,"endTime":1111.124,"body":"Kevin: Yeah \u2026 that"},{"speaker":null,"startTime":1111.15,"endTime":1113.53,"body":"would be the way you don'twant it to participate."},{"speaker":null,"startTime":1113.57,"endTime":1118.37,"body":"You want it to just have thereaction but then stay the solvent."},{"speaker":null,"startTime":1118.93,"endTime":1119.82,"body":"Thomas: Yeah, exactly."},{"speaker":null,"startTime":1119.825,"endTime":1120.605,"body":"But it's"},{"speaker":null,"startTime":1120.625,"endTime":1124.345,"body":"a double-edged sword because-Yeah \u2026 it's nice that the solvent"},{"speaker":null,"startTime":1124.515,"endTime":1129.015,"body":"is there and helps the reaction,but also that means that, uh, the"},{"speaker":null,"startTime":1129.015,"endTime":1131.885,"body":"reaction is consuming itself basically."},{"speaker":null,"startTime":1132.405,"endTime":1134.355,"body":"So that is one thing."},{"speaker":null,"startTime":1135.325,"endTime":1135.785,"body":"And,"},{"speaker":null,"startTime":1135.855,"endTime":1137.055,"body":"um, yeah."},{"speaker":null,"startTime":1137.64,"endTime":1137.82,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1137.82,"endTime":1142.09,"body":"That would also lead to other sideproducts and, uh, probably more difficult"},{"speaker":null,"startTime":1142.1,"endTime":1148.25,"body":"separation, and you lose, uh, solvent,and that all is when you want to"},{"speaker":null,"startTime":1148.32,"endTime":1152.92,"body":"scale up such a reaction to industriallevels, uh, not really beneficial."},{"speaker":null,"startTime":1152.94,"endTime":1153.34,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1153.34,"endTime":1159.164,"body":"It's also funny that you mentionthe, uh, separation because we get\u2026"},{"speaker":null,"startTime":1159.814,"endTime":1165.66,"body":"Of course, we get the ketone as well,and, decanal and decanone are quite"},{"speaker":null,"startTime":1165.66,"endTime":1168.1,"body":"difficult to separate from one another."},{"speaker":null,"startTime":1168.1,"endTime":1171.16,"body":"So that's also an issue thatwe are currently looking into,"},{"speaker":null,"startTime":1171.55,"endTime":1176.5,"body":"and that will probably takea longer time to- to perfect."},{"speaker":null,"startTime":1176.875,"endTime":1180.895,"body":"Kevin: So a a perfect selectivitywould be also great for that purpose"},{"speaker":null,"startTime":1180.895,"endTime":1185.319,"body":"because then you can- You don't haveheadaches, uh, for that separation."},{"speaker":null,"startTime":1185.45,"endTime":1185.76,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1185.76,"endTime":1190.54,"body":"So that's, that's the thing that'sso difficult is, um\u2026 So we know"},{"speaker":null,"startTime":1190.8,"endTime":1195.11,"body":"which parameters are, relevant,so the use of those alcohols."},{"speaker":null,"startTime":1195.11,"endTime":1195.66,"body":"Now we are trying tert-amylalcohol, which is which is"},{"speaker":null,"startTime":1199.15,"endTime":1204.23,"body":"basically tert-butanol with one methylgroup more, so one chain length more,"},{"speaker":null,"startTime":1204.89,"endTime":1209.47,"body":"and it already worked way betterwith an improvement in selectivity"},{"speaker":null,"startTime":1209.47,"endTime":1209.96,"body":"also."},{"speaker":null,"startTime":1210.72,"endTime":1213.93,"body":"So, um, that's one aspectwe are looking into."},{"speaker":null,"startTime":1214.48,"endTime":1219.14,"body":"And, um, the catalyst itself, so the,the complex, the bisacetonitrile,"},{"speaker":null,"startTime":1219.84,"endTime":1221.48,"body":"is also very important."},{"speaker":null,"startTime":1221.56,"endTime":1226.63,"body":"The copper chloride, uh, takes alsopart because there are literature that"},{"speaker":null,"startTime":1226.63,"endTime":1232.79,"body":"suggests that the copper itself isforming a bimetallic complex, that also"},{"speaker":null,"startTime":1232.79,"endTime":1238.81,"body":"reduces the activation energy for thedesired reaction towards the aldehyde."},{"speaker":null,"startTime":1239.23,"endTime":1245.15,"body":"So there are a lot of factors takingplace that all need to work very"},{"speaker":null,"startTime":1245.16,"endTime":1249.77,"body":"well together for the selectivityto be high and the reaction to work."},{"speaker":null,"startTime":1250.169,"endTime":1250.479,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1251.619,"endTime":1259.659,"body":"And, um, yeah, for this you would need amuch better understanding of the catalytic"},{"speaker":null,"startTime":1259.709,"endTime":1262.089,"body":"mechanisms and to see where you can tweak."},{"speaker":null,"startTime":1262.63,"endTime":1266.309,"body":"Where it's decided whether you getthe Markovnikov product and the"},{"speaker":null,"startTime":1266.409,"endTime":1269.379,"body":"anti-Markovnikov product, to tweakthose positions in the catalytic"},{"speaker":null,"startTime":1269.489,"endTime":1272.724,"body":"complex to favor one more, right?"},{"speaker":null,"startTime":1272.874,"endTime":1273.234,"body":"Yeah."},{"speaker":null,"startTime":1273.234,"endTime":1273.404,"body":"Yes."},{"speaker":null,"startTime":1273.404,"endTime":1274.834,"body":"And how did you look into this?"},{"speaker":null,"startTime":1275.223,"endTime":1275.723,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1275.723,"endTime":1276.503,"body":"So"},{"speaker":null,"startTime":1276.718,"endTime":1277.988,"body":"because we were"},{"speaker":null,"startTime":1278.222,"endTime":1282.352,"body":"spending a lot on catalysts andon reactions and everything,"},{"speaker":null,"startTime":1282.692,"endTime":1288.212,"body":"we turned to modeling, to, uh,computational chemistry, and, uh,"},{"speaker":null,"startTime":1288.222,"endTime":1290.622,"body":"more precisely to DFT calculations."},{"speaker":null,"startTime":1291.027,"endTime":1292.077,"body":"Kevin: Maybe a quick recap."},{"speaker":null,"startTime":1292.087,"endTime":1294.367,"body":"What, what does DFT stand for?"},{"speaker":null,"startTime":1294.537,"endTime":1294.567,"body":"It,"},{"speaker":null,"startTime":1294.585,"endTime":1298.005,"body":"Thomas: DFT stands fordifferential functional theorem."},{"speaker":null,"startTime":1298.645,"endTime":1303.265,"body":"So basically what the program doesis, um, calculating the state of"},{"speaker":null,"startTime":1303.285,"endTime":1305.395,"body":"all the electrons in your system."},{"speaker":null,"startTime":1305.825,"endTime":1310.935,"body":"So, uh, the system has a database ofhow many electrons carbon and all the"},{"speaker":null,"startTime":1310.935,"endTime":1316.913,"body":"elements have, and, it looks at anenergetic minimum, depending on what"},{"speaker":null,"startTime":1316.973,"endTime":1318.823,"body":"you want him-- the program to do."},{"speaker":null,"startTime":1319.463,"endTime":1319.783,"body":"Uh,"},{"speaker":null,"startTime":1319.833,"endTime":1323.613,"body":"but yeah, basically it goes throughall the states of all the electrons"},{"speaker":null,"startTime":1323.633,"endTime":1326.453,"body":"and looks for a minimum in energy."},{"speaker":null,"startTime":1326.873,"endTime":1333.183,"body":"And then you can optimize your,your geometries or find transition"},{"speaker":null,"startTime":1333.183,"endTime":1334.643,"body":"states for your reaction."},{"speaker":null,"startTime":1335.053,"endTime":1336.913,"body":"And basically that's what we did."},{"speaker":null,"startTime":1336.913,"endTime":1342.806,"body":"So we looked at,  dissoci-dissociativeligand exchange uh, for the minimal"},{"speaker":null,"startTime":1343.086,"endTime":1345.156,"body":"geometries of the different steps."},{"speaker":null,"startTime":1345.606,"endTime":1349.827,"body":"And then we looked at the transitionstates of the different types of reaction."},{"speaker":null,"startTime":1350.327,"endTime":1355.128,"body":"And we, compared the classicalPdCl4 catalyst with our new"},{"speaker":null,"startTime":1355.158,"endTime":1360.911,"body":"catalyst for two products intwo different reaction pathways."},{"speaker":null,"startTime":1360.923,"endTime":1362.146,"body":"So yeah."},{"speaker":null,"startTime":1362.146,"endTime":1365.156,"body":"The, the\u2026 It were a lot of calculation"},{"speaker":null,"startTime":1365.158,"endTime":1365.728,"body":"Kevin: involved."},{"speaker":null,"startTime":1366.298,"endTime":1366.518,"body":"Yeah."},{"speaker":null,"startTime":1367.188,"endTime":1373.742,"body":"And the, then, um, to break it downmaybe a bit, so you, take these complexes"},{"speaker":null,"startTime":1374.179,"endTime":1376.606,"body":"and then you do a virtual reaction,"},{"speaker":null,"startTime":1377.646,"endTime":1383.716,"body":"or do you just take different states thatyou configure and then you compare those?"},{"speaker":null,"startTime":1383.878,"endTime":1384.798,"body":"Thomas: S- a bit of both,"},{"speaker":null,"startTime":1384.839,"endTime":1385.479,"body":"Kevin: I would say, Mm-hmm."},{"speaker":null,"startTime":1385.939,"endTime":1386.399,"body":"because,"},{"speaker":null,"startTime":1386.569,"endTime":1391.049,"body":"Thomas: we take the, theoptimized geometries of the"},{"speaker":null,"startTime":1391.089,"endTime":1392.909,"body":"different states of the reaction."},{"speaker":null,"startTime":1393.409,"endTime":1398.469,"body":"So i-if you look at the cycle,there are different stable steps,"},{"speaker":null,"startTime":1399.099,"endTime":1402.459,"body":"And there is a transition statein between all of those steps."},{"speaker":null,"startTime":1402.519,"endTime":1407.72,"body":"And what we did is we used, um,Gaussian And, um, a special thing"},{"speaker":null,"startTime":1407.72,"endTime":1409.33,"body":"in Gaussian is that you can use a"},{"speaker":null,"startTime":1409.332,"endTime":1409.542,"body":"Kevin: a QST2"},{"speaker":null,"startTime":1411.582,"endTime":1413.43,"body":"Thomas: type of, uh, calculation."},{"speaker":null,"startTime":1413.46,"endTime":1419.64,"body":"So you give the program the firstoptimized geometry of the, the educt"},{"speaker":null,"startTime":1419.98,"endTime":1425.99,"body":"and then the geometry of product, andthen it moves along all the different,"},{"speaker":null,"startTime":1426.794,"endTime":1428.684,"body":"Kevin: and finds the pathway from"},{"speaker":null,"startTime":1429.123,"endTime":1430.723,"body":"Thomas: the first one to the second one."},{"speaker":null,"startTime":1430.733,"endTime":1430.763,"body":"Mm-hmm."},{"speaker":null,"startTime":1431.133,"endTime":1433.533,"body":"And gives you the energyof the transition state."},{"speaker":null,"startTime":1433.563,"endTime":1434.513,"body":"And that's what I"},{"speaker":null,"startTime":1434.524,"endTime":1434.984,"body":"Kevin: looked at"},{"speaker":null,"startTime":1435.373,"endTime":1439.668,"body":"Thomas: to find the lowestenergy for the, best pathway"},{"speaker":null,"startTime":1439.67,"endTime":1441.618,"body":"with the best catalyst for the"},{"speaker":null,"startTime":1441.65,"endTime":1441.66,"body":"Kevin: AEM"},{"speaker":null,"startTime":1442.1,"endTime":1442.72,"body":"Thomas: product."},{"speaker":null,"startTime":1443.12,"endTime":1446.617,"body":"Kevin: And, what differenttransition states did you find?"},{"speaker":null,"startTime":1446.617,"endTime":1448.157,"body":"What were the conclusions of those?"},{"speaker":null,"startTime":1448.397,"endTime":1454.107,"body":"Thomas: we chose or we identifiedthe, the, the nucleophilic attack"},{"speaker":null,"startTime":1454.127,"endTime":1458.957,"body":"as the critical in the reaction,either if it's this\u2026 Uh, if for"},{"speaker":null,"startTime":1458.977,"endTime":1463.513,"body":"the decision, if it's going to be,Markovnikov or anti-Markovnikov."},{"speaker":null,"startTime":1463.814,"endTime":1464.174,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1464.174,"endTime":1464.194,"body":"So"},{"speaker":null,"startTime":1464.553,"endTime":1467.703,"body":"Thomas: logically, where thenucleophile attacks is where,"},{"speaker":null,"startTime":1467.739,"endTime":1469.297,"body":"the oxygen will be at the end."},{"speaker":null,"startTime":1469.994,"endTime":1476.672,"body":"we looked closely at that and did thecalculation for the different solvents."},{"speaker":null,"startTime":1476.682,"endTime":1482.162,"body":"So we also used water as a possiblenucleophile for the two catalysts."},{"speaker":null,"startTime":1482.162,"endTime":1488.716,"body":"We used tert-butanol, tert-amylalcohol, and, compared the energetic"},{"speaker":null,"startTime":1488.756,"endTime":1494.236,"body":"difference of the activation barrierbetween the, the different transition"},{"speaker":null,"startTime":1494.236,"endTime":1496.276,"body":"states to, uh, ground states."},{"speaker":null,"startTime":1496.878,"endTime":1497.228,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1497.988,"endTime":1504.698,"body":"And, um, you found that the, the biggerthe nucleophile is, the better it works?"},{"speaker":null,"startTime":1504.788,"endTime":1509.058,"body":"I mean, in-- if you look at thenucleophiles you just described,"},{"speaker":null,"startTime":1509.078,"endTime":1512.068,"body":"it's like they get more bulky."},{"speaker":null,"startTime":1512.208,"endTime":1512.618,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1512.688,"endTime":1519.007,"body":"And- So interestingly, what we found isthat for our it's very well aligned with"},{"speaker":null,"startTime":1519.007,"endTime":1526.547,"body":"the experiments the palladium chloridebisacetonitriles lower the activation, uh,"},{"speaker":null,"startTime":1526.579,"endTime":1527.129,"body":"Kevin: barrier"},{"speaker":null,"startTime":1527.177,"endTime":1528.747,"body":"Thomas: for the desired product."},{"speaker":null,"startTime":1529.187,"endTime":1535.499,"body":"But w- we were quite frustrated untilrecently because the Markovnikov"},{"speaker":null,"startTime":1535.549,"endTime":1539.229,"body":"pathway was logically always Mm-hmm."},{"speaker":null,"startTime":1539.849,"endTime":1544.759,"body":"So we could only argue with the, thelowering of the activation barriers why we"},{"speaker":null,"startTime":1544.759,"endTime":1550.749,"body":"would observe what we did in the lab andin-- compared to, uh, the calculations."},{"speaker":null,"startTime":1551.082,"endTime":1558.362,"body":"Until recently where I did, uh, all thecalculations for the two where not only"},{"speaker":null,"startTime":1558.372,"endTime":1561.062,"body":"the activation barrier got way lower,"},{"speaker":null,"startTime":1561.602,"endTime":1562.682,"body":"Kevin: but also the gap"},{"speaker":null,"startTime":1562.782,"endTime":1568.712,"body":"Thomas: between the two differentproduct pathways was lowered quite"},{"speaker":null,"startTime":1568.932,"endTime":1575.062,"body":"substantially, explaining why moreof the other product would also be"},{"speaker":null,"startTime":1575.062,"endTime":1576.822,"body":"formed in comparison to the other."},{"speaker":null,"startTime":1576.822,"endTime":1576.835,"body":"Mm-hmm."},{"speaker":null,"startTime":1576.928,"endTime":1582.181,"body":"And for the bigger alcohols,the bigger the alcohols got, the"},{"speaker":null,"startTime":1582.181,"endTime":1585.541,"body":"better the, the energy was forthe anti-Markovnikov product."},{"speaker":null,"startTime":1586.071,"endTime":1586.211,"body":"Mm-hmm."},{"speaker":null,"startTime":1586.461,"endTime":1591.091,"body":"And starting with the amyl, tert-amylalcohol, we firstly observed an"},{"speaker":null,"startTime":1591.091,"endTime":1597.11,"body":"inversion the energies f- andthat would prefer anti-Markovnikov"},{"speaker":null,"startTime":1597.19,"endTime":1599.081,"body":"after the first relevant transition"},{"speaker":null,"startTime":1599.091,"endTime":1599.501,"body":"state."},{"speaker":null,"startTime":1600.281,"endTime":1604.244,"body":"So not only is it,energetic effect due to the,"},{"speaker":null,"startTime":1604.774,"endTime":1606.974,"body":"Kevin: the catalyst, but also"},{"speaker":null,"startTime":1607.454,"endTime":1608.184,"body":"Thomas: probably"},{"speaker":null,"startTime":1608.244,"endTime":1608.384,"body":"Kevin: a steric effect-"},{"speaker":null,"startTime":1608.384,"endTime":1612.064,"body":"Thomas: effect- Mm-hmm \u2026 of thenucleophile itself, because a big"},{"speaker":null,"startTime":1612.064,"endTime":1618.084,"body":"nucleophile when the, the catalyst is onone carbon, then the bigger nucleophile"},{"speaker":null,"startTime":1618.104,"endTime":1621.594,"body":"would prefer being at the end of-Yeah \u2026 a molecule rather than in the"},{"speaker":null,"startTime":1621.604,"endTime":1621.894,"body":"middle."},{"speaker":null,"startTime":1622.594,"endTime":1625.334,"body":"Kevin: Yeah, I think that's,uh, often, a way to go."},{"speaker":null,"startTime":1625.334,"endTime":1629.684,"body":"That's also in the hydroformylation,how you can also improve"},{"speaker":null,"startTime":1629.724,"endTime":1632.951,"body":"the n to iso products."},{"speaker":null,"startTime":1633.471,"endTime":1635.851,"body":"Uh, I think it, it's a bit similar here."},{"speaker":null,"startTime":1636.201,"endTime":1641.261,"body":"Um, but you also mentioned theacetonitrile, uh, ligands in this complex."},{"speaker":null,"startTime":1641.861,"endTime":1643.911,"body":"Did you try other ligandsor just these, uh?"},{"speaker":null,"startTime":1643.942,"endTime":1646.322,"body":"Thomas: Oh, we, we tried a lot actually."},{"speaker":null,"startTime":1646.382,"endTime":1652.512,"body":"Um, so in the first phase, uh, Ihad students synthesize a bunch"},{"speaker":null,"startTime":1652.581,"endTime":1653.001,"body":"Kevin: of"},{"speaker":null,"startTime":1653.072,"endTime":1657.312,"body":"Thomas: different ligands, and Ibought all the kinds that I could"},{"speaker":null,"startTime":1657.312,"endTime":1661.502,"body":"get, also th- those ones who werealready finished on the palladium."},{"speaker":null,"startTime":1661.532,"endTime":1662.022,"body":"Palladium."},{"speaker":null,"startTime":1662.812,"endTime":1670.568,"body":"And, we tested ylides, uh, ferrites andall bis\u2026 phosphonates phosphosphonates"},{"speaker":null,"startTime":1670.588,"endTime":1675.728,"body":"and everything and we found that, uh,the, the connection between nitrogen"},{"speaker":null,"startTime":1675.728,"endTime":1678.538,"body":"and palladium was the most important."},{"speaker":null,"startTime":1678.598,"endTime":1683.568,"body":"Because we-- in comparison toacetonitrile and benzonitrile."},{"speaker":null,"startTime":1684.298,"endTime":1691.338,"body":"Uh, we also tried cyanides, so where the,the carbon and not the nitrogen is on the"},{"speaker":null,"startTime":1691.338,"endTime":1694.118,"body":"palladium, and those worked, uh, not as"},{"speaker":null,"startTime":1694.128,"endTime":1694.488,"body":"Kevin: well."},{"speaker":null,"startTime":1694.568,"endTime":1694.838,"body":"Mm-hmm."},{"speaker":null,"startTime":1694.858,"endTime":1695.218,"body":"Or,"},{"speaker":null,"startTime":1695.308,"endTime":1697.658,"body":"Thomas: and I don't, I don'tremember quite well, but I"},{"speaker":null,"startTime":1697.658,"endTime":1699.138,"body":"think they didn't work at all."},{"speaker":null,"startTime":1699.148,"endTime":1699.158,"body":"Mm."},{"speaker":null,"startTime":1699.488,"endTime":1701.428,"body":"So that's one thing."},{"speaker":null,"startTime":1701.602,"endTime":1705.846,"body":"The other thing is, um, maybe wecan talk about that later, um,"},{"speaker":null,"startTime":1705.876,"endTime":1708.466,"body":"that these ligands have a problem."},{"speaker":null,"startTime":1709.296,"endTime":1712.706,"body":"They work well, but they getlost in the process also."},{"speaker":null,"startTime":1712.726,"endTime":1717.846,"body":"So another factor to take, uh, intoaccount, and that is also one thing"},{"speaker":null,"startTime":1717.856,"endTime":1724.306,"body":"that we found in our DFT calculation,is that chloride as a ligand always"},{"speaker":null,"startTime":1724.346,"endTime":1726.496,"body":"preferred to be on the palladium."},{"speaker":null,"startTime":1727.39,"endTime":1731.196,"body":"So we have, uh, catalyst fatigue,and that would also explain one of"},{"speaker":null,"startTime":1731.216,"endTime":1736.846,"body":"the factors we saw in the design ofexperiment, uh, that lower temperatures"},{"speaker":null,"startTime":1736.846,"endTime":1741.886,"body":"and lower reaction times especiallyare better for the reaction because"},{"speaker":null,"startTime":1742.136,"endTime":1748.766,"body":"after half an hour, we could only seein the MS the chloride type palladium"},{"speaker":null,"startTime":1748.776,"endTime":1750.726,"body":"catalysts and none of the acetonitrile."},{"speaker":null,"startTime":1751.862,"endTime":1757.408,"body":"But the acetonitrile being the mostimportant thing because it directs the"},{"speaker":null,"startTime":1757.418,"endTime":1759.778,"body":"reaction towards the AEM product, so."},{"speaker":null,"startTime":1759.788,"endTime":1759.808,"body":"Yeah."},{"speaker":null,"startTime":1761.049,"endTime":1761.218,"body":"the,"},{"speaker":null,"startTime":1761.228,"endTime":1762.958,"body":"Kevin: the chloride comesfrom the copper chloride"},{"speaker":null,"startTime":1763.248,"endTime":1763.333,"body":"? Thomas: Chloride or"},{"speaker":null,"startTime":1763.333,"endTime":1764.009,"body":"where Uh, yes"},{"speaker":null,"startTime":1764.009,"endTime":1764.161,"body":"\u2026  Kevin: Yes."},{"speaker":null,"startTime":1764.161,"endTime":1769.343,"body":"And, did you then try other- copperspecies or, or what- Yeah, so-"},{"speaker":null,"startTime":1769.343,"endTime":1770.4,"body":"What, what's the solution for that?"},{"speaker":null,"startTime":1770.67,"endTime":1775.93,"body":"Thomas: That, that's basically ourthought process is we saw, okay, the, the"},{"speaker":null,"startTime":1775.95,"endTime":1779.06,"body":"nucleophile is important, thecatalyst is important, but we lose"},{"speaker":null,"startTime":1779.139,"endTime":1780.039,"body":"Kevin: both of those."},{"speaker":null,"startTime":1780.309,"endTime":1780.419,"body":"Mm-hmm."},{"speaker":null,"startTime":1780.469,"endTime":1784.599,"body":"Thomas: And one big problem would bethe co-catalyst, because the co-catalyst"},{"speaker":null,"startTime":1784.619,"endTime":1789.739,"body":"regenerates the catalyst species thatwe don't want, and that is always"},{"speaker":null,"startTime":1789.739,"endTime":1790.909,"body":"energetically preferred."},{"speaker":null,"startTime":1791.269,"endTime":1791.429,"body":"Mm-hmm."},{"speaker":null,"startTime":1791.439,"endTime":1795.729,"body":"So we tried without copperchloride to begin with."},{"speaker":null,"startTime":1795.844,"endTime":1796.484,"body":"Didn't work."},{"speaker":null,"startTime":1796.616,"endTime":1801.734,"body":"We tried ligand itself asregenerative, um, additive."},{"speaker":null,"startTime":1801.874,"endTime":1804.534,"body":"So acetonitrile in thereaction didn't work."},{"speaker":null,"startTime":1804.746,"endTime":1808.636,"body":"In literature, there's alsobenzoquinone as a co-oxidant."},{"speaker":null,"startTime":1810.628,"endTime":1812.771,"body":"okay-ish, I would say."},{"speaker":null,"startTime":1813.331,"endTime":1817.921,"body":"So we tested also different coppersources and different chloride sources,"},{"speaker":null,"startTime":1818.401,"endTime":1823.951,"body":"and, um, the results of those testsshow that copper is quite important."},{"speaker":null,"startTime":1824.881,"endTime":1829.241,"body":"And that is probably due tothis bimetallic, um, complex"},{"speaker":null,"startTime":1829.241,"endTime":1831.211,"body":"forming that lowers the energy."},{"speaker":null,"startTime":1831.451,"endTime":1835.541,"body":"We didn't look far into thatbecause we had to, look at all"},{"speaker":null,"startTime":1835.551,"endTime":1837.261,"body":"the other factors before that."},{"speaker":null,"startTime":1837.611,"endTime":1842.281,"body":"But Based on those observationsI would say that we agree"},{"speaker":null,"startTime":1842.301,"endTime":1843.801,"body":"with what literature tells"},{"speaker":null,"startTime":1844.781,"endTime":1848.031,"body":"Kevin: And, um, what was then the key?"},{"speaker":null,"startTime":1848.491,"endTime":1849.501,"body":"To solve this problem?"},{"speaker":null,"startTime":1849.501,"endTime":1856.611,"body":"I mean, if the copper chloridemakes you lose ligand and solvent."},{"speaker":null,"startTime":1857.397,"endTime":1857.957,"body":"Thomas: Yeah."},{"speaker":null,"startTime":1857.987,"endTime":1863.037,"body":"So that's not where we're at right now."},{"speaker":null,"startTime":1863.437,"endTime":1867.257,"body":"Uh, we don't have the solution right now."},{"speaker":null,"startTime":1867.747,"endTime":1873.587,"body":"So we are still trying to figureout where we can, optimize the"},{"speaker":null,"startTime":1873.587,"endTime":1878.697,"body":"reaction and where optimization wouldmaybe influence another thing that"},{"speaker":null,"startTime":1878.697,"endTime":1880.607,"body":"would then lower the selectivity."},{"speaker":null,"startTime":1880.617,"endTime":1881.237,"body":"Mm-hmm."},{"speaker":null,"startTime":1881.337,"endTime":1887.677,"body":"And, I would say our big success inthis project so far is that we did"},{"speaker":null,"startTime":1887.747,"endTime":1893.357,"body":"understand the mechanisms, we didunderstand what is important in the"},{"speaker":null,"startTime":1893.357,"endTime":1899.147,"body":"complex and how the complex, uh,activates the alkene and how the"},{"speaker":null,"startTime":1899.157,"endTime":1901.457,"body":"nucleophile takes part in the reaction."},{"speaker":null,"startTime":1902.357,"endTime":1906.927,"body":"Um, and that was, uh, a bit difficultto come to this point and-- of"},{"speaker":null,"startTime":1906.997,"endTime":1912.977,"body":"understanding, and now we are trying to,um, to see what we can do about those."},{"speaker":null,"startTime":1913.412,"endTime":1915.182,"body":"I think that will not be me."},{"speaker":null,"startTime":1915.652,"endTime":1918.432,"body":"Because I'm at the endof my, uh, PhD right now."},{"speaker":null,"startTime":1918.872,"endTime":1924.842,"body":"But, uh, the group where I'm at right noww-will continue the project and hopefully"},{"speaker":null,"startTime":1924.852,"endTime":1928.354,"body":"find, um, a solution to all of those."},{"speaker":null,"startTime":1928.704,"endTime":1929.034,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1929.624,"endTime":1930.544,"body":"Yeah, that would be great."},{"speaker":null,"startTime":1930.689,"endTime":1935.493,"body":"One other thing that I find alsointeresting about this reaction especially"},{"speaker":null,"startTime":1935.493,"endTime":1939.086,"body":"is that you have two catalysts, basically."},{"speaker":null,"startTime":1939.086,"endTime":1943.266,"body":"The, the main catalyst and theco-catalyst, they have to work together."},{"speaker":null,"startTime":1943.726,"endTime":1950.663,"body":"And in the main Wacker oxidation,When you use it for ethene."},{"speaker":null,"startTime":1950.983,"endTime":1954.903,"body":"I remember from, uh, when we did the,in the practical course, we also used"},{"speaker":null,"startTime":1954.923,"endTime":1960.003,"body":"this reaction as an example with thebubble columns and then the- Yeah"},{"speaker":null,"startTime":1960.393,"endTime":1964.866,"body":"um, there were two separatereaction chambers, basically."},{"speaker":null,"startTime":1964.866,"endTime":1970.314,"body":"One where there's the oxidationof the alkene happening, and one"},{"speaker":null,"startTime":1970.324,"endTime":1975.204,"body":"where there's the regeneration ofthe catalyst happening with oxygen."},{"speaker":null,"startTime":1975.684,"endTime":1979.354,"body":"Um, but what was your reaction setup?"},{"speaker":null,"startTime":1979.364,"endTime":1982.454,"body":"Did you also have two reactionchambers, or did you have just one?"},{"speaker":null,"startTime":1982.984,"endTime":1987.884,"body":"Thomas: So we did all of ourtesting in one chamber, so one,"},{"speaker":null,"startTime":1988.06,"endTime":1992.627,"body":"\u2026 very simple setup with a, aflask and, a cooler on top."},{"speaker":null,"startTime":1992.72,"endTime":1997.51,"body":"And, uh, left it at thatbecause, um, we needed to see"},{"speaker":null,"startTime":1997.52,"endTime":1999.43,"body":"what was happening altogether."},{"speaker":null,"startTime":2000,"endTime":2004.29,"body":"And there is another problem forusing the reaction in, the setup you"},{"speaker":null,"startTime":2004.36,"endTime":2009.68,"body":"described because the classical Wackeroxidation has the advantage that the"},{"speaker":null,"startTime":2009.68,"endTime":2016.17,"body":"products that are being generated- havea lower boiling point than all the rest"},{"speaker":null,"startTime":2016.27,"endTime":2016.82,"body":"Kevin: of- Yeah"},{"speaker":null,"startTime":2017.16,"endTime":2018.25,"body":"Thomas: The components."},{"speaker":null,"startTime":2018.96,"endTime":2025.704,"body":"And so if you get acetone, for example,in the, the reactor , you, you described,"},{"speaker":null,"startTime":2026.024,"endTime":2030.984,"body":"then the acetone would evaporate and thenall the reaction mixture with the catalyst"},{"speaker":null,"startTime":2030.984,"endTime":2036.034,"body":"and everything can be transferred intothe second reactor, be regenerated, and"},{"speaker":null,"startTime":2036.034,"endTime":2039.524,"body":"then be, uh, reused in the first one."},{"speaker":null,"startTime":2040.234,"endTime":2045.664,"body":"For us, that's not an option, so that'salso a challenge that we face and that's"},{"speaker":null,"startTime":2045.674,"endTime":2051.783,"body":"also a reason why higher substitutedalcohols would be better because our"},{"speaker":null,"startTime":2051.804,"endTime":2056.994,"body":"products have a boiling point, sothe n-decanal, I think it's 207 to"},{"speaker":null,"startTime":2059.463,"endTime":2067.113,"body":"nine and the ketone is 211, which is wayhigher than anything else in the reaction."},{"speaker":null,"startTime":2067.114,"endTime":2070.993,"body":"So there needs to be anotherseparation step for us."},{"speaker":null,"startTime":2071.172,"endTime":2071.422,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2071.422,"endTime":2073.981,"body":"Do you have, some inmind that you would try"},{"speaker":null,"startTime":2073.981,"endTime":2074.281,"body":"or, or no?"},{"speaker":null,"startTime":2074.371,"endTime":2077.062,"body":"Thomas: Uh, we did afew testings for that."},{"speaker":null,"startTime":2077.062,"endTime":2082.212,"body":"So were hopeful that we could getaround, uh, protecting groups."},{"speaker":null,"startTime":2082.925,"endTime":2085.964,"body":"And, um, that would not be the case."},{"speaker":null,"startTime":2085.964,"endTime":2091.044,"body":"So we, we tried flash chromatography,so we tested different kinds of, um,"},{"speaker":null,"startTime":2091.096,"endTime":2093.216,"body":"solvents to try and separate those."},{"speaker":null,"startTime":2093.502,"endTime":2099.112,"body":"Interestingly enough, only methanolor methanol-containing solvent"},{"speaker":null,"startTime":2099.282,"endTime":2105.132,"body":"mixture worked for, uh, theseparation of ketone to aldehyde."},{"speaker":null,"startTime":2105.672,"endTime":2111.906,"body":"And what we think, we did not look in\u2026that far into that, but what we think is"},{"speaker":null,"startTime":2111.916,"endTime":2118.232,"body":"that, the column and the methanol are,reacting and forming this, this sludge,"},{"speaker":null,"startTime":2118.232,"endTime":2121.722,"body":"uh, that, uh, protects the aldehyde group."},{"speaker":null,"startTime":2121.972,"endTime":2124.712,"body":"And then therefore separating the two."},{"speaker":null,"startTime":2124.713,"endTime":2130.147,"body":"But yeah, that's not a great optionbecause then you have to, unprotect the"},{"speaker":null,"startTime":2130.387,"endTime":2135.567,"body":"aldehyde to regain it, and that wouldadd a lot of steps that are not very"},{"speaker":null,"startTime":2135.567,"endTime":2140.387,"body":"welcome if you think of the, uh, theconventional route that we start at, uh,"},{"speaker":null,"startTime":2140.407,"endTime":2142.397,"body":"we, uh, talked about at the beginning."},{"speaker":null,"startTime":2142.397,"endTime":2146.267,"body":"So you want to keep all thesteps fairly easy and, uh,"},{"speaker":null,"startTime":2146.717,"endTime":2149.137,"body":"simple and not a lot, and yeah."},{"speaker":null,"startTime":2149.466,"endTime":2149.606,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2149.606,"endTime":2152.446,"body":"Well, there, there is a reasonwhy this, uh, conventional"},{"speaker":null,"startTime":2152.506,"endTime":2154.666,"body":"method is still applied, I"},{"speaker":null,"startTime":2154.666,"endTime":2155.036,"body":"guess."},{"speaker":null,"startTime":2155.106,"endTime":2155.506,"body":"Yes."},{"speaker":null,"startTime":2155.516,"endTime":2162.454,"body":"But, uh, chromatography is also, yeah,in, industrial context difficult."},{"speaker":null,"startTime":2162.844,"endTime":2168.239,"body":"Maybe with these higher priced, uh,products it could be worth it, but"},{"speaker":null,"startTime":2168.629,"endTime":2171.299,"body":"usually one would try to avoid that."},{"speaker":null,"startTime":2171.349,"endTime":2171.689,"body":"Yeah."},{"speaker":null,"startTime":2171.693,"endTime":2177.733,"body":"Thomas: That's, that's why we leftthis, uh, section to the side for now"},{"speaker":null,"startTime":2177.753,"endTime":2182.673,"body":"because we first want the reaction towork before we think about separation"},{"speaker":null,"startTime":2182.683,"endTime":2184.673,"body":"and, uh, process development."},{"speaker":null,"startTime":2185.243,"endTime":2189.413,"body":"It is possible, and we're verypositive that it will be possible."},{"speaker":null,"startTime":2189.413,"endTime":2189.903,"body":"Yeah."},{"speaker":null,"startTime":2189.903,"endTime":2190.373,"body":"And"},{"speaker":null,"startTime":2190.399,"endTime":2191.829,"body":"Kevin: even- But it's a different problem."},{"speaker":null,"startTime":2191.883,"endTime":2192.693,"body":"Thomas: But it's a different problem."},{"speaker":null,"startTime":2192.693,"endTime":2193.303,"body":"But it's a different problem, yeah."},{"speaker":null,"startTime":2193.303,"endTime":2198.583,"body":"And even for the chemicals we have,so, uh, the decanal is a fine chemical-"},{"speaker":null,"startTime":2198.933,"endTime":2204.033,"body":"Mm \u2026that is, very high pricedand sold in low amounts, so- could"},{"speaker":null,"startTime":2204.093,"endTime":2206.953,"body":"be worth it to do it that way."},{"speaker":null,"startTime":2207.273,"endTime":2212.933,"body":"But I'm sure someone will find somethingand, uh, solve that problem too."},{"speaker":null,"startTime":2213.367,"endTime":2214.467,"body":"Kevin: Yeah, definitely."},{"speaker":null,"startTime":2214.517,"endTime":2218.17,"body":"That's some also engineering,problems for later."},{"speaker":null,"startTime":2218.23,"endTime":2218.5,"body":"Yes."},{"speaker":null,"startTime":2219.52,"endTime":2222.28,"body":"And, um, yeah."},{"speaker":null,"startTime":2222.65,"endTime":2223.66,"body":"Thomas: wasn't built in a day."},{"speaker":null,"startTime":2225.44,"endTime":2226.33,"body":"Kevin: Yeah, exactly."},{"speaker":null,"startTime":2227.24,"endTime":2232.048,"body":"yeah, I think then, uh, we can cometo an, uh, end to this discussion."},{"speaker":null,"startTime":2232.058,"endTime":2236.718,"body":"And I think since, um, our lastdiscussion here in the podcast was, uh,"},{"speaker":null,"startTime":2236.738,"endTime":2243.518,"body":"before I, uh, started, uh, this closingtradition of, uh, the question, what is"},{"speaker":null,"startTime":2243.518,"endTime":2245.348,"body":"your favorite discovery in chemistry?"},{"speaker":null,"startTime":2245.898,"endTime":2247.198,"body":"You may answer it now."},{"speaker":null,"startTime":2247.558,"endTime":2253.597,"body":"Thomas: My favorite discovery inchemistry I- it's, it's very basic"},{"speaker":null,"startTime":2253.597,"endTime":2255.567,"body":"and maybe a bit childish, I think."},{"speaker":null,"startTime":2255.887,"endTime":2261.527,"body":"But, uh, I always found the storyof phosphorus very interesting."},{"speaker":null,"startTime":2261.537,"endTime":2262.047,"body":"Mm-hmm."},{"speaker":null,"startTime":2262.057,"endTime":2268.057,"body":"Um, because when I was a child, I watcheda lot of, videos on YouTube of these"},{"speaker":null,"startTime":2268.067,"endTime":2271.789,"body":"theatrical, uh, chemists', uh, lectures."},{"speaker":null,"startTime":2272.247,"endTime":2276.097,"body":"And there was one where they explainedhow white phosphorus was found, and"},{"speaker":null,"startTime":2276.097,"endTime":2281.527,"body":"they, um, they lit the thing on fire, andit, Yeah \u2026illuminated the whole room."},{"speaker":null,"startTime":2281.987,"endTime":2288.317,"body":"And, uh, it came from alchemiststhat distilled, I think it was, urine"},{"speaker":null,"startTime":2288.327,"endTime":2291.799,"body":"from horses to try and find gold."},{"speaker":null,"startTime":2293.099,"endTime":2299.359,"body":"uh, they so happened to find phosphorusand, uh, with that, the oxidation"},{"speaker":null,"startTime":2299.369,"endTime":2304.369,"body":"reaction of phosphorus on air whereit lets itself on fire, and that's"},{"speaker":null,"startTime":2304.379,"endTime":2308.739,"body":"where, also where the no- name comesfrom, from Greek, phosphorus, with,"},{"speaker":null,"startTime":2308.819,"endTime":2310.849,"body":"which means, uh, light bringer."},{"speaker":null,"startTime":2310.849,"endTime":2311.329,"body":"Mm-hmm."},{"speaker":null,"startTime":2311.369,"endTime":2312.709,"body":"And I find that quite"},{"speaker":null,"startTime":2312.721,"endTime":2313.251,"body":"Kevin: poetic."},{"speaker":null,"startTime":2313.991,"endTime":2314.681,"body":"Yeah, definitely."},{"speaker":null,"startTime":2314.681,"endTime":2320.841,"body":"That's, uh\u2026 Also the whole discoveryof the element is, uh, interesting story."},{"speaker":null,"startTime":2320.869,"endTime":2324.019,"body":"Thomas: It's, it-- I thinkit shows how science worked."},{"speaker":null,"startTime":2324.029,"endTime":2329.029,"body":"It\u2026 You, you try one thing, even ifit's very absurd, and you end up finding"},{"speaker":null,"startTime":2329.049,"endTime":2333.601,"body":"a whole other thing that will have,uh, use and understanding later on."},{"speaker":null,"startTime":2334.051,"endTime":2334.361,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2334.551,"endTime":2339.931,"body":"And that's also, I think, like back inthe days when they really started to"},{"speaker":null,"startTime":2340.261,"endTime":2346.579,"body":"discover one element by the other, itwas really that even one person could"},{"speaker":null,"startTime":2346.639,"endTime":2352.099,"body":"make major discoveries, which is notreally that easily possible anymore."},{"speaker":null,"startTime":2352.099,"endTime":2352.849,"body":"No, no."},{"speaker":null,"startTime":2352.849,"endTime":2354.439,"body":"Yeah, def- You need teams of researchers."},{"speaker":null,"startTime":2354.539,"endTime":2355.619,"body":"Thomas: Definitely, yeah."},{"speaker":null,"startTime":2355.709,"endTime":2359.089,"body":"And to find an element nowadays,I think you have to be, uh,"},{"speaker":null,"startTime":2359.189,"endTime":2363.851,"body":"some kind of physicist, uh, withaccess to very expensive tech."},{"speaker":null,"startTime":2364.081,"endTime":2364.321,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2364.748,"endTime":2370.198,"body":"But, uh, still, there are very interestingdiscoveries in chemistry still to make."},{"speaker":null,"startTime":2370.198,"endTime":2374.938,"body":"And, uh, yeah, I'm looking forward to, um,these new discoveries that will come up."},{"speaker":null,"startTime":2374.948,"endTime":2375.666,"body":"Yeah, that will come up."},{"speaker":null,"startTime":2375.666,"endTime":2375.956,"body":"Thomas: Yeah, me too."},{"speaker":null,"startTime":2376.982,"endTime":2377.181,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2377.181,"endTime":2379.538,"body":"Thanks for this great discussion"},{"speaker":null,"startTime":2379.638,"endTime":2380.509,"body":"Thomas: Thank you for having me."},{"speaker":null,"startTime":2381.559,"endTime":2383.509,"body":"Kevin: also, thank youso much for listening."},{"speaker":null,"startTime":2384.119,"endTime":2387.469,"body":"Check out the show notes to learnmore about Thomas's research."},{"speaker":null,"startTime":2387.837,"endTime":2392.167,"body":"Let me know if you would like totalk about your own research in"},{"speaker":null,"startTime":2392.267,"endTime":2397.626,"body":"Innovate and React, and send me anemail to contact@innovateandreact.com"},{"speaker":null,"startTime":2397.626,"endTime":2398.506,"body":"or find me on LinkedIn."},{"speaker":null,"startTime":2399.016,"endTime":2401.766,"body":"Again, a follow would really help as well."},{"speaker":null,"startTime":2402.238,"endTime":2405.188,"body":"Until next time, staycurious and keep innovating."}]}