{"version":"1.0.0","segments":[{"speaker":null,"startTime":3.237,"endTime":5.307,"body":"Kevin: Welcome to Innovate and React."},{"speaker":null,"startTime":5.667,"endTime":11.277,"body":"I'm Kevin Hares, and in today's episodewe will talk about how we can turn methane"},{"speaker":null,"startTime":11.277,"endTime":14.727,"body":"into value chemicals via Photocatalysis."},{"speaker":null,"startTime":15.207,"endTime":20.997,"body":"I'm here with Dr. Andres AlvarezConstantino, who is currently a postdoc"},{"speaker":null,"startTime":20.997,"endTime":27.417,"body":"at the Institute of Organic Chemistry inRWTH Aachen welcome Andres, how are you?"},{"speaker":null,"startTime":28.754,"endTime":29.224,"body":"Andres: Thank you."},{"speaker":null,"startTime":29.324,"endTime":31.154,"body":"Thank you so much, uh, Kevin for your, uh."},{"speaker":null,"startTime":31.754,"endTime":32.564,"body":"Kind introduction."},{"speaker":null,"startTime":33.044,"endTime":36.144,"body":"Uh, also thank you for inviting me, here"},{"speaker":null,"startTime":36.144,"endTime":36.504,"body":"today."},{"speaker":null,"startTime":36.817,"endTime":37.777,"body":"Kevin: Yeah, I am happy to have you."},{"speaker":null,"startTime":38.544,"endTime":42.084,"body":"Andres: it's a, it's a big pleasureand always it's a big pleasure to"},{"speaker":null,"startTime":42.084,"endTime":44.514,"body":"discuss about, uh, about cool chemistry."},{"speaker":null,"startTime":44.724,"endTime":45.804,"body":"So thank you."},{"speaker":null,"startTime":45.804,"endTime":46.499,"body":"Thank, thank you so much."},{"speaker":null,"startTime":47.317,"endTime":52.217,"body":"Kevin: Yeah, I'm, uh also excited aboutlearning more about this photocatalysis."},{"speaker":null,"startTime":52.637,"endTime":58.907,"body":"So maybe let's start, uh,with why do we want to."},{"speaker":null,"startTime":59.957,"endTime":67.217,"body":"Turn methane and these, low functionalizedmolecules into value chemicals."},{"speaker":null,"startTime":67.217,"endTime":69.047,"body":"And why is that not done already?"},{"speaker":null,"startTime":70.864,"endTime":77.854,"body":"Andres: Well, um, in fact, this, um, uh,light hydrocarbon methane, Ethan, uh,"},{"speaker":null,"startTime":77.884,"endTime":84.124,"body":"propane and, and so on, uh, we, we need topoint that those are naturally occurring."},{"speaker":null,"startTime":84.664,"endTime":91.384,"body":"They are, uh, present in natural gas, sowe don't need to, to synthesize them and"},{"speaker":null,"startTime":91.444,"endTime":93.754,"body":"we could, uh, just use them directly."},{"speaker":null,"startTime":94.234,"endTime":97.534,"body":"To the synthesis of, uh, complexstructures in organic chemistry."},{"speaker":null,"startTime":97.812,"endTime":98.232,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":99.004,"endTime":104.064,"body":"Andres: Uh, however, currently themain use of this, uh hydrocarbons"},{"speaker":null,"startTime":104.214,"endTime":109.489,"body":"is, um, most of the times is just,uh, they are burned to produce energy"},{"speaker":null,"startTime":110.017,"endTime":114.607,"body":"Kevin: Yeah, I guess that's whereeveryone knows the methane from, like the"},{"speaker":null,"startTime":114.607,"endTime":116.797,"body":"natural gas and the gas stove at home."},{"speaker":null,"startTime":116.797,"endTime":116.857,"body":"Yeah."},{"speaker":null,"startTime":117.964,"endTime":118.479,"body":"Andres: Yes, yes, yes."},{"speaker":null,"startTime":118.779,"endTime":120.699,"body":"The main, the main big application."},{"speaker":null,"startTime":121.089,"endTime":126.069,"body":"And it's a pity because during the, itsextraction, we are consuming energy."},{"speaker":null,"startTime":126.219,"endTime":129.129,"body":"We are, uh, producing a greenhouse gas."},{"speaker":null,"startTime":130.209,"endTime":131.949,"body":"And then when we have this, uh."},{"speaker":null,"startTime":132.444,"endTime":133.224,"body":"Enrich it."},{"speaker":null,"startTime":133.224,"endTime":138.324,"body":"Um, carbon source, we are burningthem again to produce energy and"},{"speaker":null,"startTime":138.374,"endTime":140.654,"body":"release, uh, greenhouse gases again."},{"speaker":null,"startTime":140.834,"endTime":146.213,"body":"So it's little bit, it's a cycle, butthose compounds are not transforming"},{"speaker":null,"startTime":146.213,"endTime":150.023,"body":"something really, let's say, uh, useful."},{"speaker":null,"startTime":150.486,"endTime":151.736,"body":"Kevin: Yeah, exactly."},{"speaker":null,"startTime":152.036,"endTime":157.045,"body":"And I think also in terms of thetransformation of the chemical"},{"speaker":null,"startTime":157.045,"endTime":158.89,"body":"industry where we want to."},{"speaker":null,"startTime":160.015,"endTime":165.595,"body":"Go away from these fossil fuelsin general, but we need to"},{"speaker":null,"startTime":165.595,"endTime":167.035,"body":"get the carbon from somewhere."},{"speaker":null,"startTime":167.125,"endTime":172.375,"body":"And, uh, in my opinion, we should, asmuch as possible, go away from fossil"},{"speaker":null,"startTime":172.375,"endTime":175.345,"body":"fuels in like the energy sector."},{"speaker":null,"startTime":175.915,"endTime":181.705,"body":"But for chemicals, well, we can still needthe carbon source and then it's better"},{"speaker":null,"startTime":181.705,"endTime":183.805,"body":"to use all the carbon sources we have."},{"speaker":null,"startTime":183.805,"endTime":185.965,"body":"So methane would be a great addition."},{"speaker":null,"startTime":187.703,"endTime":189.353,"body":"Andres: yes, I agree completely."},{"speaker":null,"startTime":189.743,"endTime":194.798,"body":"Uh, organic chemistry, luckily,or sadly, depends on carbons."},{"speaker":null,"startTime":194.938,"endTime":198.358,"body":"So we need to get thecarbon from, from somewhere."},{"speaker":null,"startTime":199.018,"endTime":206.558,"body":"But, uh, apart from, uh, fossil fuels, wecould also obtain a methane from, what is"},{"speaker":null,"startTime":206.558,"endTime":213.048,"body":"called the bio methane from wastewater or,um, diverse amount of, uh, of, uh, trash."},{"speaker":null,"startTime":213.053,"endTime":218.148,"body":"And just with the proper anaerobicdigestion we could get, uh,"},{"speaker":null,"startTime":218.328,"endTime":219.65,"body":"as well, those hydrocarbons"},{"speaker":null,"startTime":220.191,"endTime":221.056,"body":"Kevin: Yeah, definitely."},{"speaker":null,"startTime":221.396,"endTime":221.616,"body":"And"},{"speaker":null,"startTime":222.248,"endTime":225.458,"body":"Andres: The green alternative forthe sustainable alternative exists,"},{"speaker":null,"startTime":225.518,"endTime":227.108,"body":"but it's still very underdeveloped."},{"speaker":null,"startTime":227.481,"endTime":227.691,"body":"Kevin: yeah."},{"speaker":null,"startTime":228.831,"endTime":233.841,"body":"Also those biogas is used asa fuel usually, and then we"},{"speaker":null,"startTime":233.888,"endTime":234.818,"body":"Andres: Yes, as well."},{"speaker":null,"startTime":235.011,"endTime":237.861,"body":"Kevin: It to make muchhigher value chemicals."},{"speaker":null,"startTime":238.581,"endTime":245.481,"body":"And um, well there are already someplants who use these ethane and"},{"speaker":null,"startTime":245.481,"endTime":251.121,"body":"stuff for making chemicals, but,um, what's the problem with those?"},{"speaker":null,"startTime":251.121,"endTime":256.821,"body":"Like, I think they're natural gascrackers, uh, that should replace."},{"speaker":null,"startTime":257.151,"endTime":262.351,"body":"Steam crackers with mineral oil,but uh, what's the problem there?"},{"speaker":null,"startTime":263.015,"endTime":267.005,"body":"Andres: Yes, in those processes,the energy consumption is huge."},{"speaker":null,"startTime":267.606,"endTime":272.166,"body":"It's not just an extra step, but it'san extra time consumption, extra energy"},{"speaker":null,"startTime":272.166,"endTime":274.536,"body":"consumption, extra waste generation."},{"speaker":null,"startTime":275.016,"endTime":278.556,"body":"And, uh, at the end is extra money,"},{"speaker":null,"startTime":279.036,"endTime":281.759,"body":"which the, the, the, companyneeds to waste in this, uh."},{"speaker":null,"startTime":282.379,"endTime":283.399,"body":"Transformations."},{"speaker":null,"startTime":283.999,"endTime":291.379,"body":"So it could be ideal if you can justget your, uh, methane, remove the"},{"speaker":null,"startTime":291.469,"endTime":298.579,"body":"hydrogen and attach it to a organicmolecule, rather than just, uh,"},{"speaker":null,"startTime":298.639,"endTime":303.439,"body":"inserting an, uh, an iodine or achlorine or de liquidation to methanol."},{"speaker":null,"startTime":303.739,"endTime":307.399,"body":"And from there, startingdiverse, uh, routes."},{"speaker":null,"startTime":307.817,"endTime":309.378,"body":"Kevin: Yeah, so."},{"speaker":null,"startTime":309.378,"endTime":310.947,"body":"Directly use it."},{"speaker":null,"startTime":311.187,"endTime":314.997,"body":"And then for example, alsothe workup steps in between."},{"speaker":null,"startTime":314.997,"endTime":319.697,"body":"They usually involve all kinds of solventsand the energy consumption is high."},{"speaker":null,"startTime":319.697,"endTime":324.947,"body":"And then you could save all this ifyou use the methane directly in your"},{"speaker":null,"startTime":324.947,"endTime":326.807,"body":"reaction in the synthesis steps."},{"speaker":null,"startTime":326.967,"endTime":333.957,"body":"But um, as we said before, thealkanes are not really reactive."},{"speaker":null,"startTime":334.047,"endTime":335.487,"body":"Like that's what they known for."},{"speaker":null,"startTime":335.487,"endTime":336.237,"body":"They can burn,"},{"speaker":null,"startTime":337.137,"endTime":340.917,"body":"but to start this, theyalso need a lot of energy."},{"speaker":null,"startTime":341.217,"endTime":345.337,"body":"Um, but there are also some otherprocesses , which use alkanes"},{"speaker":null,"startTime":345.357,"endTime":350.277,"body":"for the functionalization,um, what are options there?"},{"speaker":null,"startTime":350.959,"endTime":355.759,"body":"Andres: I think the most commonones is the, are the oxidation."},{"speaker":null,"startTime":356.404,"endTime":361.224,"body":"To corresponding alcohols like methaneto methanol or methane to formic acid."},{"speaker":null,"startTime":361.224,"endTime":365.244,"body":"I think that those can be the,the, the most common ones."},{"speaker":null,"startTime":365.274,"endTime":369.514,"body":"Also the chlorination, directchlorination of, uh, methane with"},{"speaker":null,"startTime":369.604,"endTime":371.839,"body":"chlorine gas under very harsh conditions."},{"speaker":null,"startTime":372.299,"endTime":374.679,"body":"So at the end you have, uh, chlor methane."},{"speaker":null,"startTime":374.989,"endTime":375.079,"body":"And"},{"speaker":null,"startTime":377.089,"endTime":379.909,"body":"potentially some overhalogenation products."},{"speaker":null,"startTime":380.222,"endTime":380.642,"body":"Kevin: Yeah."},{"speaker":null,"startTime":381.439,"endTime":386.689,"body":"Andres: But yes, these proceduresrequire, usually require, uh, very"},{"speaker":null,"startTime":386.689,"endTime":395.144,"body":"harsh conditions and sometimes notvery, um, safe chemicals, oxidation."},{"speaker":null,"startTime":395.254,"endTime":397.333,"body":"Most of the times you need, peroxides."},{"speaker":null,"startTime":398.173,"endTime":399.053,"body":"In the halogenation."},{"speaker":null,"startTime":399.073,"endTime":402.523,"body":"You need a chlorine gas,which is not easy to handle."},{"speaker":null,"startTime":403.063,"endTime":409.138,"body":"And also these, uh, reduction conditionsare not compatible with the presence"},{"speaker":null,"startTime":409.158,"endTime":411.578,"body":"of any other, uh, organic molecule."},{"speaker":null,"startTime":411.862,"endTime":416.602,"body":"Kevin: So you make the methanemore reactive, but then you need"},{"speaker":null,"startTime":416.602,"endTime":422.812,"body":"additional steps to use this activatedcarbon chain, then to attach it to"},{"speaker":null,"startTime":422.812,"endTime":424.287,"body":"whatever you're trying to synthesize."},{"speaker":null,"startTime":425.365,"endTime":426.415,"body":"Andres: Yes, yes."},{"speaker":null,"startTime":426.415,"endTime":433.195,"body":"It's like I said before, every extra stepyou introduce to make me more reactive."},{"speaker":null,"startTime":433.945,"endTime":440.875,"body":"Yes, it will be, uh, at the end will be,uh, easier or you can just use more, uh,"},{"speaker":null,"startTime":440.995,"endTime":443.005,"body":"traditional or straightforward chemistry."},{"speaker":null,"startTime":443.575,"endTime":449.725,"body":"But it's again, extra time, extra,uh, energy, extra waste generation."},{"speaker":null,"startTime":449.91,"endTime":450.75,"body":"Kevin: Yeah, of course."},{"speaker":null,"startTime":451.23,"endTime":456.02,"body":"And then, you looked at,uh, allylation chemistry."},{"speaker":null,"startTime":456.53,"endTime":460.04,"body":"So why did you choose thatkind of, uh, chemistry?"},{"speaker":null,"startTime":460.536,"endTime":465.216,"body":"Andres: This, um, reaction we, wedeveloped in the group where I did a PhD"},{"speaker":null,"startTime":465.556,"endTime":468.276,"body":"in the group of Martinas at, in Spain."},{"speaker":null,"startTime":468.786,"endTime":471.966,"body":"And in our, uh, group, we have an."},{"speaker":null,"startTime":472.881,"endTime":476.151,"body":"Important background onallylation, uh, chemistry."},{"speaker":null,"startTime":476.901,"endTime":483.711,"body":"So, uh, for us was quite evident thatin the literature, um, there was a"},{"speaker":null,"startTime":483.711,"endTime":490.741,"body":"big gap about the allylation or thedirect ation of, uh, gaseous alcanes."},{"speaker":null,"startTime":491.151,"endTime":492.681,"body":"Now in the literature you can find."},{"speaker":null,"startTime":493.126,"endTime":499.25,"body":"Plenty of, Giese additions, whichyou generate the radical of your"},{"speaker":null,"startTime":499.73,"endTime":503.36,"body":"hydrocarbon and it's directlyadd over a Michael acceptor."},{"speaker":null,"startTime":504.26,"endTime":507.71,"body":"And this reaction worksreally, really nice."},{"speaker":null,"startTime":508.248,"endTime":509.773,"body":"Kevin: What is that usually used for?"},{"speaker":null,"startTime":510.883,"endTime":512.053,"body":"This Giese edition?"},{"speaker":null,"startTime":512.965,"endTime":517.165,"body":"Andres: Well, a Giese edition is thesame as some Michael addition, but with,"},{"speaker":null,"startTime":517.165,"endTime":520.105,"body":"um, radical, uh, nucle files, let's say."},{"speaker":null,"startTime":520.338,"endTime":520.798,"body":"Kevin: Oh, okay."},{"speaker":null,"startTime":520.952,"endTime":521.222,"body":"Andres: Yes."},{"speaker":null,"startTime":522.092,"endTime":528.02,"body":"But if we compare the products ofallylation and in the giese, we have,"},{"speaker":null,"startTime":528.08,"endTime":530.81,"body":"uh, double bond, which is highly"},{"speaker":null,"startTime":530.81,"endTime":531.35,"body":"activated."},{"speaker":null,"startTime":532.13,"endTime":536.54,"body":"With electron withdrawing groupssuch as, uh, esters or cyano groups."},{"speaker":null,"startTime":536.96,"endTime":540.525,"body":"So the radical addition of thehydrocarbon, which is a very"},{"speaker":null,"startTime":540.555,"endTime":545.335,"body":"neutrophilic radical, uh, addsvery easily to a double bond."},{"speaker":null,"startTime":545.775,"endTime":549.435,"body":"And then this, uh, double bond is deleted."},{"speaker":null,"startTime":550.065,"endTime":555.735,"body":"So at the end you, you insert your, um,uh, alkyl fragment, which is so cool."},{"speaker":null,"startTime":556.425,"endTime":558.495,"body":"But the, the other thing is gone"},{"speaker":null,"startTime":558.563,"endTime":558.983,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":559.768,"endTime":564.328,"body":"And that you want for further stepsbecause the double point usually"},{"speaker":null,"startTime":564.453,"endTime":567.598,"body":"can, can be functionalized easier."},{"speaker":null,"startTime":567.628,"endTime":567.898,"body":"Yeah."},{"speaker":null,"startTime":568.402,"endTime":570.887,"body":"Andres: that's the main pointfrom synthetic point of view"},{"speaker":null,"startTime":571.637,"endTime":573.707,"body":"and in the, in the elevation."},{"speaker":null,"startTime":574.362,"endTime":579.942,"body":"We have the ole thing, uh,alpha to our living group."},{"speaker":null,"startTime":579.972,"endTime":583.302,"body":"So we have the addition ofour, uh, neutrophilic radical."},{"speaker":null,"startTime":584.172,"endTime":587.592,"body":"Then the ole thing migrates andthe living group is gone, but we"},{"speaker":null,"startTime":587.592,"endTime":590.572,"body":"still have the olefin thing, andthat's the thing, the only thing."},{"speaker":null,"startTime":591.507,"endTime":594.327,"body":"You can still doing a he reaction."},{"speaker":null,"startTime":594.567,"endTime":600.247,"body":"Oxidation, oxidative cleavage,epoxidation, uh, halogenation."},{"speaker":null,"startTime":600.387,"endTime":605.577,"body":"So we still have this very versatile,functional group to make further"},{"speaker":null,"startTime":605.577,"endTime":607.857,"body":"organic, uh, organic transformations."},{"speaker":null,"startTime":608.615,"endTime":608.735,"body":"Kevin: Yeah."},{"speaker":null,"startTime":608.735,"endTime":613.475,"body":"You also have, uh, shown that in thepaper, and we come back to that later."},{"speaker":null,"startTime":613.475,"endTime":617.225,"body":"How you further usethis, uh, compound then."},{"speaker":null,"startTime":617.647,"endTime":618.367,"body":"Quick break."},{"speaker":null,"startTime":618.836,"endTime":620.276,"body":"Two things I want to tell you."},{"speaker":null,"startTime":620.652,"endTime":623.262,"body":"First of all, a bigthank you for tuning in."},{"speaker":null,"startTime":623.532,"endTime":624.732,"body":"This really means a lot to me."},{"speaker":null,"startTime":625.512,"endTime":629.682,"body":"And secondly, if you likechemistry and learn something"},{"speaker":null,"startTime":629.682,"endTime":633.732,"body":"from this show, please subscribeon whatever app you're listening."},{"speaker":null,"startTime":634.025,"endTime":637.165,"body":"It'll help me to get new guests on."},{"speaker":null,"startTime":637.165,"endTime":638.125,"body":"To continue."},{"speaker":null,"startTime":638.341,"endTime":639.151,"body":"Thank you so much."},{"speaker":null,"startTime":639.241,"endTime":640.111,"body":"Back to the episode."},{"speaker":null,"startTime":640.628,"endTime":647.159,"body":"Um, but first you also usedphotocatalysis to mediate the reaction."},{"speaker":null,"startTime":647.238,"endTime":647.838,"body":"Andres: Yes."},{"speaker":null,"startTime":648.689,"endTime":649.494,"body":"Kevin: why not?"},{"speaker":null,"startTime":650.279,"endTime":655.439,"body":"Other catalysts, like a transition metal,catalyst that I'm very familiar with, or,"},{"speaker":null,"startTime":655.685,"endTime":657.23,"body":"other organic catalysts."},{"speaker":null,"startTime":657.597,"endTime":658.047,"body":"Andres: Yes."},{"speaker":null,"startTime":658.047,"endTime":663.507,"body":"Um, transition metal catalysiswould be amazing because you can"},{"speaker":null,"startTime":663.507,"endTime":668.267,"body":"just know, put the organ metalliccatalyst in your, in reactor."},{"speaker":null,"startTime":668.267,"endTime":671.297,"body":"Then you close the system and theorgan metallic catalyst is doing"},{"speaker":null,"startTime":671.297,"endTime":676.652,"body":"the chemistry and the scalabilityproblems of photochemistry."},{"speaker":null,"startTime":677.456,"endTime":680.316,"body":"Are not present 'cause youdon't need to to irradiate."},{"speaker":null,"startTime":680.336,"endTime":683.066,"body":"So everything will bemore straightforward."},{"speaker":null,"startTime":684.296,"endTime":690.886,"body":"But what we have with, um, gaseoushydrocarbons is that they don't, have any"},{"speaker":null,"startTime":690.886,"endTime":694.506,"body":"kind of linkage to the metallic complex."},{"speaker":null,"startTime":694.506,"endTime":701.391,"body":"They don't have an like a loan electronpair maybe directing group has,"},{"speaker":null,"startTime":701.841,"endTime":707.961,"body":"which can anchor the organo metalliccomplex to direct the activation or"},{"speaker":null,"startTime":707.961,"endTime":714.386,"body":"any, um, double bond, which can alsocoordinate the metallic core and"},{"speaker":null,"startTime":714.628,"endTime":720.698,"body":"assist the introduction or theactivation of the H and in, in this"},{"speaker":null,"startTime":720.698,"endTime":727.278,"body":"case, the, the light hydros doesn'thave none of these,  anchoring sites."},{"speaker":null,"startTime":727.373,"endTime":727.613,"body":"Kevin: Yeah."},{"speaker":null,"startTime":727.793,"endTime":731.453,"body":"They cannot really coordinateto the metal and then."},{"speaker":null,"startTime":732.128,"endTime":733.058,"body":"Interact with it."},{"speaker":null,"startTime":733.568,"endTime":736.568,"body":"Also, they're very, in thecase of methane, they're very"},{"speaker":null,"startTime":736.958,"endTime":743.288,"body":"symmetrical and it's, it's difficultto attack in, in the carbon."},{"speaker":null,"startTime":744.418,"endTime":747.378,"body":"Andres: Just at the end we only havebasically carbons and hydrogens,"},{"speaker":null,"startTime":748.018,"endTime":748.228,"body":"Kevin: Yeah."},{"speaker":null,"startTime":748.923,"endTime":750.383,"body":"And those bonds are quite strong."},{"speaker":null,"startTime":751.456,"endTime":755.013,"body":"But I think also the beautyof Photocatalysis is that it's"},{"speaker":null,"startTime":755.466,"endTime":758.046,"body":"very mild conditions, right?"},{"speaker":null,"startTime":758.106,"endTime":759.636,"body":"You, you don't need a lot of heat."},{"speaker":null,"startTime":759.726,"endTime":763.116,"body":"You have your, uh, lightsource, and that's, uh."},{"speaker":null,"startTime":763.754,"endTime":763.934,"body":"Yeah."},{"speaker":null,"startTime":763.934,"endTime":767.654,"body":"Performing the reaction, whereasotherwise you need to heat usually"},{"speaker":null,"startTime":767.654,"endTime":768.944,"body":"to quite high temperatures."},{"speaker":null,"startTime":769.802,"endTime":772.052,"body":"Andres: Yes, but also the light."},{"speaker":null,"startTime":772.292,"endTime":775.187,"body":"It depends which wavelength,uh, are you using?"},{"speaker":null,"startTime":776.071,"endTime":779.831,"body":"That could be also, a drawbackif you're using red light."},{"speaker":null,"startTime":779.861,"endTime":780.221,"body":"Okay."},{"speaker":null,"startTime":780.221,"endTime":785.091,"body":"That's very, uh, fiendly  it'scompatible even with live cells."},{"speaker":null,"startTime":785.391,"endTime":788.991,"body":"But when you go to ultravioletlight, then we have a lot of,"},{"speaker":null,"startTime":789.081,"endTime":793.701,"body":"issues with also with compatibilitywith certain functional groups."},{"speaker":null,"startTime":794.181,"endTime":796.791,"body":"Which, uh, might beactive forcing UV light."},{"speaker":null,"startTime":796.791,"endTime":800.211,"body":"So that in that aspectis a little bit tricky."},{"speaker":null,"startTime":801.109,"endTime":801.469,"body":"Kevin: Okay."},{"speaker":null,"startTime":801.469,"endTime":807.169,"body":"So maybe not for the very latestage functionalization when"},{"speaker":null,"startTime":807.169,"endTime":809.719,"body":"you have a lot of stuff there."},{"speaker":null,"startTime":809.901,"endTime":810.141,"body":"Andres: Hmm."},{"speaker":null,"startTime":811.131,"endTime":813.561,"body":"For later stage functionalization,there's actually a lot of"},{"speaker":null,"startTime":813.771,"endTime":815.841,"body":"protocols using UV light."},{"speaker":null,"startTime":816.261,"endTime":819.561,"body":"I mean, it can be an issue withcertain functional groups, but"},{"speaker":null,"startTime":819.561,"endTime":822.441,"body":"usually it works, uh, quite well."},{"speaker":null,"startTime":822.524,"endTime":822.944,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":824.029,"endTime":831.749,"body":"And, um, now for your reaction, howdid you use, um, the photo catalyst"},{"speaker":null,"startTime":831.749,"endTime":838.649,"body":"and how did you overcome this problemof the really, uh, yeah, almost inert"},{"speaker":null,"startTime":838.649,"endTime":842.369,"body":"C-H bond and those, uh, alkanes."},{"speaker":null,"startTime":843.331,"endTime":843.631,"body":"Andres: Yes."},{"speaker":null,"startTime":843.661,"endTime":849.241,"body":"Um, in the last uh, years, uh, itwas very, uh, became very popular."},{"speaker":null,"startTime":849.271,"endTime":852.031,"body":"These hydrogen atom extraction protocols."},{"speaker":null,"startTime":852.826,"endTime":859.666,"body":"And what we are using is, photo catalyst,which under light radiation generates"},{"speaker":null,"startTime":859.666,"endTime":862.396,"body":"a highly active chlorine radical."},{"speaker":null,"startTime":863.026,"endTime":867.346,"body":"And this chlorine radical has the,the, the power to abstract the"},{"speaker":null,"startTime":867.346,"endTime":869.196,"body":"hydrogen from the, gas cell gain."},{"speaker":null,"startTime":869.946,"endTime":873.456,"body":"So you form HCL and the alki radical."},{"speaker":null,"startTime":874.339,"endTime":874.909,"body":"Kevin: Oh, okay."},{"speaker":null,"startTime":875.689,"endTime":876.319,"body":"Interesting."},{"speaker":null,"startTime":876.499,"endTime":879.619,"body":"Then, uh, maybe for, thelisteners, quickly introduce"},{"speaker":null,"startTime":879.619,"endTime":881.299,"body":"your, uh, catalyst system."},{"speaker":null,"startTime":881.359,"endTime":885.974,"body":"I think then it's also easier tounderstand where the chlorine comes from."},{"speaker":null,"startTime":886.931,"endTime":891.876,"body":"Andres: Yes our catalytic systemis, uh, irontrichloride hexa aqua"},{"speaker":null,"startTime":892.866,"endTime":896.936,"body":"in combination with, with collidine,and it, that is the catalytic system."},{"speaker":null,"startTime":896.936,"endTime":900.586,"body":"So we irradiate and thenthe iron is excited too."},{"speaker":null,"startTime":901.596,"endTime":903.066,"body":"It's, it's excited."},{"speaker":null,"startTime":903.156,"endTime":907.986,"body":"And then the homolytic cleavage betweenthe iron and the chlorine takes place"},{"speaker":null,"startTime":908.016,"endTime":911.826,"body":"and you generate an iron two, andthen the, the, the chlorine radical."},{"speaker":null,"startTime":912.554,"endTime":916.744,"body":"Kevin: And then the chlorineradical reacts with the akene"},{"speaker":null,"startTime":917.294,"endTime":919.034,"body":"to abstract the,  the proton."},{"speaker":null,"startTime":919.304,"endTime":922.304,"body":"What happens then after with the proton?"},{"speaker":null,"startTime":924.271,"endTime":928.836,"body":"Andres: Uh, this proton,uh, remains in the HCL form."},{"speaker":null,"startTime":929.084,"endTime":929.414,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":930.181,"endTime":932.681,"body":"Andres: Which is Quench by the collidine."},{"speaker":null,"startTime":933.121,"endTime":936.821,"body":"Which the collidne has uh, I don'tknow if we are going to, to come back"},{"speaker":null,"startTime":936.821,"endTime":938.921,"body":"again to this, but it has a dual role."},{"speaker":null,"startTime":939.401,"endTime":945.571,"body":"It has a role there as a base, as usuallyit has, but also a role of, of ligand"},{"speaker":null,"startTime":946.151,"endTime":949.061,"body":"and that's, uh, that'ssomething very cool."},{"speaker":null,"startTime":949.061,"endTime":950.551,"body":"We found in this work."},{"speaker":null,"startTime":951.121,"endTime":955.051,"body":"And without calling in thereaction, it's barely working."},{"speaker":null,"startTime":955.694,"endTime":958.784,"body":"Kevin: Yeah, I was wondering whyyou did use two equivalents of"},{"speaker":null,"startTime":958.784,"endTime":961.844,"body":"the collidine, but then, uh, yeah."},{"speaker":null,"startTime":961.904,"endTime":965.654,"body":"If it accepts the, the protonlater on, then that makes sense."},{"speaker":null,"startTime":965.684,"endTime":965.744,"body":"Yeah."},{"speaker":null,"startTime":966.466,"endTime":966.781,"body":"Cool."},{"speaker":null,"startTime":967.078,"endTime":972.808,"body":"you also looked at the mechanismand, uh, the collidine is the"},{"speaker":null,"startTime":972.838,"endTime":978.118,"body":"proton acceptor in the end, but,uh, how does it also interact  with"},{"speaker":null,"startTime":978.118,"endTime":979.498,"body":"the catalyst in the reaction?"},{"speaker":null,"startTime":980.31,"endTime":981,"body":"Andres: Yes."},{"speaker":null,"startTime":982.095,"endTime":988.365,"body":"Um, we found, uh, I don't know ifby serendipity, but the truth is"},{"speaker":null,"startTime":988.365,"endTime":991.215,"body":"that we explore a lot of conditions."},{"speaker":null,"startTime":991.425,"endTime":993.375,"body":"In fact, we start optimization."},{"speaker":null,"startTime":993.375,"endTime":997.665,"body":"Correction just first of all, evaluatingvery carefully all the reported, uh,"},{"speaker":null,"startTime":998.025,"endTime":1000.595,"body":"protocols for activating gaseous alkanes."},{"speaker":null,"startTime":1001.505,"endTime":1002.225,"body":"None of them work."},{"speaker":null,"startTime":1003.725,"endTime":1011.135,"body":"And after a lot of, uh, screening ofbase, uh, ligands, uh, additives, we"},{"speaker":null,"startTime":1011.135,"endTime":1016.355,"body":"found that the specific addition oftri equivalent of collidine was the"},{"speaker":null,"startTime":1016.355,"endTime":1020.765,"body":"optimal and was crucial for the reactionworking as as, as it is working."},{"speaker":null,"startTime":1021.065,"endTime":1027.355,"body":"So, uh, we were wonderingwhy, why collidine?"},{"speaker":null,"startTime":1027.423,"endTime":1027.723,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1028.615,"endTime":1031.615,"body":"Andres: What is doing in thecollidine, which cannot do other"},{"speaker":null,"startTime":1031.715,"endTime":1035.755,"body":"pyridinic base like pyridine 'causepyridine is working the reaction."},{"speaker":null,"startTime":1035.995,"endTime":1040.485,"body":"But no, as nicer as, as, uh, collidine."},{"speaker":null,"startTime":1041.665,"endTime":1046.605,"body":"And we were very, very lucky ourcolleague, uh, Paul could obtain an"},{"speaker":null,"startTime":1046.605,"endTime":1054.855,"body":"x-ray quality crystal, and we, uh,found that the collidine is, uh, is"},{"speaker":null,"startTime":1054.855,"endTime":1060.505,"body":"establishing a dense network of hydrogenbonding between well, actually it's"},{"speaker":null,"startTime":1060.555,"endTime":1061.78,"body":"colling hydrochloride"},{"speaker":null,"startTime":1062.843,"endTime":1063.143,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1063.85,"endTime":1067.6,"body":"Andres: establishing a dense networkof, of, uh, hydrogen bonding between,"},{"speaker":null,"startTime":1068.17,"endTime":1073.29,"body":"uh, these, uh, units and accord of,uh, iron Tera tetrachloride anion."},{"speaker":null,"startTime":1074.23,"endTime":1078.092,"body":"So we have an, an accord of,uh, iron tetrachloride anion."},{"speaker":null,"startTime":1078.753,"endTime":1082.781,"body":"Interacting with three, eh, collidiniumcations by hydrogen bonding."},{"speaker":null,"startTime":1083.021,"endTime":1088.278,"body":"And then the two remaining chlorineanions are just in the, in the"},{"speaker":null,"startTime":1088.278,"endTime":1090.068,"body":"lattice of the x-ray structure."},{"speaker":null,"startTime":1090.381,"endTime":1095.736,"body":"And this supramolecular, uh,uh, ensemble helps to, uh."},{"speaker":null,"startTime":1096.226,"endTime":1102.261,"body":"Stabilize the complex, we are increasingthe photo stability, but also we are,"},{"speaker":null,"startTime":1102.351,"endTime":1104.926,"body":"um, shutting down side reactivity."},{"speaker":null,"startTime":1105.676,"endTime":1108.031,"body":"Kevin: What side reactionscan occure there?"},{"speaker":null,"startTime":1108.88,"endTime":1113.71,"body":"Andres: When you generate, um, ahighly active, uh, radical like"},{"speaker":null,"startTime":1113.71,"endTime":1121.06,"body":"this alkyl Radicals, it's known thatthose radicals can attack to, um,"},{"speaker":null,"startTime":1121.9,"endTime":1127.03,"body":"metal hallogen bond and which iscalled, uh, radical ligand transfer."},{"speaker":null,"startTime":1128.17,"endTime":1133.15,"body":"So what we were observing, a lot of,uh, the times when collidine was not"},{"speaker":null,"startTime":1133.15,"endTime":1137.97,"body":"used is the formation of big amountsof the corresponding alkane chloride."},{"speaker":null,"startTime":1138.153,"endTime":1143.793,"body":"Kevin: So basically the, um, radicalis stealing the chlorine from the."},{"speaker":null,"startTime":1144.213,"endTime":1145.113,"body":"Iron chloride?"},{"speaker":null,"startTime":1145.895,"endTime":1146.315,"body":"Andres: Yes."},{"speaker":null,"startTime":1146.598,"endTime":1151.668,"body":"And that was leading to lowconversions, uh, very low yields"},{"speaker":null,"startTime":1151.998,"endTime":1156.818,"body":"because the active, uh, catalyst wasengaging in inside the activities."},{"speaker":null,"startTime":1157.238,"endTime":1160.838,"body":"But when we have this, uh,supramolecular, complex."},{"speaker":null,"startTime":1162.723,"endTime":1166.913,"body":"We have the central core of theiron tetrachloride, which is, uh, te"},{"speaker":null,"startTime":1167.961,"endTime":1168.161,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1169.128,"endTime":1174.473,"body":"Andres: And the we, and only oneof the chlorines is, uh, is free."},{"speaker":null,"startTime":1175.073,"endTime":1176.663,"body":"Let's say it's, it's free."},{"speaker":null,"startTime":1176.753,"endTime":1178.613,"body":"It's in the actual position and it's free."},{"speaker":null,"startTime":1178.613,"endTime":1182.863,"body":"It's ready to make the homolyticcleavage after the excitation and"},{"speaker":null,"startTime":1182.863,"endTime":1184.213,"body":"generate the chlorine radical."},{"speaker":null,"startTime":1184.903,"endTime":1185.593,"body":"The other three."},{"speaker":null,"startTime":1186.048,"endTime":1188.792,"body":"Are interacting withthe collidinium cations,"},{"speaker":null,"startTime":1189.402,"endTime":1191.947,"body":"through the hydrogen bonding, so."},{"speaker":null,"startTime":1193.467,"endTime":1198.597,"body":"Those, uh, chlorines are not,um, available for any kind of"},{"speaker":null,"startTime":1198.867,"endTime":1200.692,"body":"reactivity, not for the LMC,"},{"speaker":null,"startTime":1201.21,"endTime":1201.5,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1201.912,"endTime":1205.137,"body":"Andres: Um, and not for theseradical ligand transfer."},{"speaker":null,"startTime":1205.527,"endTime":1211.197,"body":"So, and when we don't have, uh, thecollidine, the active, uh, species,"},{"speaker":null,"startTime":1211.197,"endTime":1215.907,"body":"which is the Iron Tera Tetrachloridejust itself in the media has the four."},{"speaker":null,"startTime":1216.042,"endTime":1222.102,"body":"Chlorine's exposed to the reactionmedia, so the probability of some"},{"speaker":null,"startTime":1222.252,"endTime":1229.452,"body":"alkyl radical doing the attacking,this chlorine, uh, iron uh, bond is"},{"speaker":null,"startTime":1229.452,"endTime":1232.332,"body":"much more higher than in our case."},{"speaker":null,"startTime":1232.6,"endTime":1233.02,"body":"Kevin: Hmm."},{"speaker":null,"startTime":1233.23,"endTime":1233.59,"body":"Okay."},{"speaker":null,"startTime":1234.19,"endTime":1238.93,"body":"Yeah, that's, uh, interestinghow basically the structure of"},{"speaker":null,"startTime":1238.93,"endTime":1244.78,"body":"the whole complex then makes orprotects somehow this, uh, catalyst"},{"speaker":null,"startTime":1244.78,"endTime":1247.96,"body":"because the active catalyst itselfis just then the iron chloride."},{"speaker":null,"startTime":1249.01,"endTime":1252.94,"body":"So it would also work with verylow conversions on, with just"},{"speaker":null,"startTime":1252.94,"endTime":1256.16,"body":"iron chloride, but it would notwork with just the collidine."},{"speaker":null,"startTime":1257.217,"endTime":1257.877,"body":"Andres: Yes."},{"speaker":null,"startTime":1258.747,"endTime":1264.562,"body":"And that's yes, just the active, uh,species in this chemistry, in this"},{"speaker":null,"startTime":1264.562,"endTime":1269.842,"body":"photochemistry of, uh, for iron,tetra iron chloride actually is the"},{"speaker":null,"startTime":1269.847,"endTime":1272.189,"body":"iron tetrachloride ion in solution."},{"speaker":null,"startTime":1272.474,"endTime":1277.284,"body":"Two molecules of iron, tri chlorideform, iron tetrachloride anion,"},{"speaker":null,"startTime":1277.664,"endTime":1279.219,"body":"and an iron dichloride cation."},{"speaker":null,"startTime":1279.561,"endTime":1285.298,"body":"And what we have in our systemis, Radical receptor, which is"},{"speaker":null,"startTime":1285.298,"endTime":1290.818,"body":"the allylchloride, which is not asactivated as the Giese receptors."},{"speaker":null,"startTime":1292.121,"endTime":1292.541,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1293.528,"endTime":1296.498,"body":"Andres: If we go to thegiese uh, chemistry."},{"speaker":null,"startTime":1297.258,"endTime":1303.258,"body":"We can see that all the chemistry withiron trichloride is just iron trichloride"},{"speaker":null,"startTime":1303.768,"endTime":1306.238,"body":"radical receptor and gaseous alkane."},{"speaker":null,"startTime":1306.498,"endTime":1311.258,"body":"They don't need any kind of basebecause the radical receptor, the"},{"speaker":null,"startTime":1311.258,"endTime":1314.473,"body":"Giese receptor is extremely activated."},{"speaker":null,"startTime":1314.893,"endTime":1319.383,"body":"So once you form the methane radical,it'll directly add on the radical."},{"speaker":null,"startTime":1321.126,"endTime":1324.546,"body":"Kevin: And then also the, the protondoesn't need to go elsewhere, then"},{"speaker":null,"startTime":1324.548,"endTime":1328.105,"body":"Andres: And then the, the proton is,is also quench resulting product."},{"speaker":null,"startTime":1328.465,"endTime":1328.795,"body":"Yes."},{"speaker":null,"startTime":1329.695,"endTime":1338.125,"body":"In our system, the arides are not as mucha activated, so we need to compensate"},{"speaker":null,"startTime":1338.125,"endTime":1345.685,"body":"this lower activity of the, of our, uh,radical acceptors with the higher activity"},{"speaker":null,"startTime":1346.015,"endTime":1350.645,"body":"of the, uh, iron chloride and, uh, bondstoward the radical ligand transfer."},{"speaker":null,"startTime":1351.215,"endTime":1353.54,"body":"So it was a balance?"},{"speaker":null,"startTime":1353.963,"endTime":1354.293,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1355.283,"endTime":1360.383,"body":"When, what I also saw, when I looked atthe different yields you got, because"},{"speaker":null,"startTime":1360.383,"endTime":1367.313,"body":"you also looked at other alkanes,ethane, propane, and it seemed to, the"},{"speaker":null,"startTime":1367.313,"endTime":1373.943,"body":"yield seemed to increase with the chainlength, and in the introduction you"},{"speaker":null,"startTime":1373.943,"endTime":1379.943,"body":"also mentioned that there are alreadyprotocols for the liquid alkanes."},{"speaker":null,"startTime":1380.423,"endTime":1386.183,"body":"So why it that, uh, the shorter thechain length, the lower the reactivity?"},{"speaker":null,"startTime":1386.959,"endTime":1387.349,"body":"Andres: Yes."},{"speaker":null,"startTime":1387.349,"endTime":1391.759,"body":"Uh, when we, talk about, thestrength of carbon SP three."},{"speaker":null,"startTime":1392.479,"endTime":1393.439,"body":"H bonds."},{"speaker":null,"startTime":1394.369,"endTime":1400.709,"body":"The smaller the molecule, uh, moredifficult is to abstract this hydrogen."},{"speaker":null,"startTime":1401.549,"endTime":1407.419,"body":"And this is because the first of allor mainly the, the radical stability"},{"speaker":null,"startTime":1408.107,"endTime":1408.327,"body":"Kevin: Oh,"},{"speaker":null,"startTime":1408.619,"endTime":1412.309,"body":"Andres: in the methane, we are goingto form a carbon center radical."},{"speaker":null,"startTime":1412.854,"endTime":1415.554,"body":"Which only has three hydrogensto stabilize the radical."},{"speaker":null,"startTime":1416.214,"endTime":1419.947,"body":"So it's not the most stableand radical in the universe."},{"speaker":null,"startTime":1420.157,"endTime":1421.987,"body":"But when we have, uh."},{"speaker":null,"startTime":1423.332,"endTime":1430.667,"body":"Isobutane, for instance, we, uh, stillhave an alkyilc chain, which can, uh,"},{"speaker":null,"startTime":1430.697,"endTime":1433.707,"body":"stabilize the radical or cyclohexane."},{"speaker":null,"startTime":1433.727,"endTime":1437.781,"body":"This radical is a secondaryradical, so the obstruction of this"},{"speaker":null,"startTime":1437.781,"endTime":1442.791,"body":"hydrogen is much easier and canbe performing milder conditions."},{"speaker":null,"startTime":1443.151,"endTime":1449.331,"body":"That's also why we need to go for, um,higher pressures of, uh, of methane."},{"speaker":null,"startTime":1449.838,"endTime":1450.138,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1450.956,"endTime":1452.726,"body":"Andres: Like, I thinkwe're using a 50 bar."},{"speaker":null,"startTime":1453.206,"endTime":1456.446,"body":"For Ethan, which is, uh,easier to, to activate."},{"speaker":null,"startTime":1456.476,"endTime":1460.736,"body":"We use eight and then propaneand isobutane is one bar."},{"speaker":null,"startTime":1461.071,"endTime":1464.311,"body":"That's why, because we needhigher concentration of the, of"},{"speaker":null,"startTime":1464.311,"endTime":1469.925,"body":"the alkane to promote efficientlythe, the ch uh, activation."},{"speaker":null,"startTime":1470.128,"endTime":1470.488,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1470.878,"endTime":1474.843,"body":"Because then radicalis not as easy to form."},{"speaker":null,"startTime":1475.023,"endTime":1476.673,"body":"And so basically this."},{"speaker":null,"startTime":1477.483,"endTime":1483.423,"body":"Very basic organic chem lecture stuffwith the stabilization of the radicals."},{"speaker":null,"startTime":1483.603,"endTime":1484.143,"body":"Oh, interesting."},{"speaker":null,"startTime":1484.693,"endTime":1484.883,"body":"yeah."},{"speaker":null,"startTime":1484.883,"endTime":1489.023,"body":"And then, um, talking aboutthe scope of the reaction."},{"speaker":null,"startTime":1489.083,"endTime":1497.633,"body":"You used all kinds of, uh, differentallylic chlorides, which is great"},{"speaker":null,"startTime":1497.633,"endTime":1499.313,"body":"to have, uh, this versatility."},{"speaker":null,"startTime":1500.438,"endTime":1502.448,"body":"In the beginning we talked about that."},{"speaker":null,"startTime":1502.448,"endTime":1507.848,"body":"Uh, other protocols which use harshchemicals, they have a bit of a"},{"speaker":null,"startTime":1507.848,"endTime":1513.378,"body":"problem with other functional groupsand you could show quite a big scope."},{"speaker":null,"startTime":1513.718,"endTime":1514.738,"body":"What were the limits?"},{"speaker":null,"startTime":1515.238,"endTime":1520.546,"body":"Andres: Of course, the best ones arethe electro deficient, uh, allylic"},{"speaker":null,"startTime":1520.561,"endTime":1526.716,"body":"chlorides because, um, no, this, theradical is a neutrophilic radical."},{"speaker":null,"startTime":1527.861,"endTime":1532.296,"body":"So if we have a very electronpoor, uh, radical trap."},{"speaker":null,"startTime":1533.766,"endTime":1537.351,"body":"The recommendation would be very fast."},{"speaker":null,"startTime":1537.561,"endTime":1541.725,"body":"That's the, the, the situation wehave with the, uh, Giese additions."},{"speaker":null,"startTime":1541.936,"endTime":1546.526,"body":"So, uh, we, we observed that, uh, whenwe have electron withdrawing groups."},{"speaker":null,"startTime":1547.036,"endTime":1549.046,"body":"The reaction is, is really, really fast."},{"speaker":null,"startTime":1549.076,"endTime":1552.136,"body":"In fact, we are gettingalmost quantitative yields,"},{"speaker":null,"startTime":1552.479,"endTime":1552.809,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1553.516,"endTime":1557.056,"body":"Andres: But, um, while in theother cases the reaction still"},{"speaker":null,"startTime":1557.386,"endTime":1562.636,"body":"proceeds, but the yields decreasesa little bit to seventies, uh,"},{"speaker":null,"startTime":1562.666,"endTime":1564.921,"body":"60% of yields, which are still."},{"speaker":null,"startTime":1566.171,"endTime":1571.421,"body":"Good, good talking within thiscontext of gaseous, alkanes."},{"speaker":null,"startTime":1572.111,"endTime":1573.191,"body":"But uh, yes."},{"speaker":null,"startTime":1573.191,"endTime":1579.168,"body":"I think that could be a little bit the,let's say the limitations of the method."},{"speaker":null,"startTime":1579.726,"endTime":1580.596,"body":"Kevin: Would be, yeah."},{"speaker":null,"startTime":1580.866,"endTime":1582.396,"body":"Very electron rich."},{"speaker":null,"startTime":1582.846,"endTime":1584.916,"body":"Uh, chlorides"},{"speaker":null,"startTime":1586.068,"endTime":1587.067,"body":".  Andres: Yes That, that, that could be, uh."},{"speaker":null,"startTime":1587.884,"endTime":1589.514,"body":"For sure a problem."},{"speaker":null,"startTime":1589.694,"endTime":1595.274,"body":"I mean, we didn't evaluate, I guessany very, very electron rich one."},{"speaker":null,"startTime":1595.702,"endTime":1596.122,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1596.826,"endTime":1597.066,"body":"Yeah."},{"speaker":null,"startTime":1597.096,"endTime":1599.016,"body":"But still it's, uh, the."},{"speaker":null,"startTime":1599.811,"endTime":1604.746,"body":"It doesn't have to be super electronpoor to work, which is quite good"},{"speaker":null,"startTime":1604.763,"endTime":1610.454,"body":"Andres: no, no, Just in fact, I thinkthat the, we use, a arylrings associated"},{"speaker":null,"startTime":1610.454,"endTime":1616.42,"body":"with a Methoxy group, which is a strong,electron donating, substitute and"},{"speaker":null,"startTime":1616.42,"endTime":1619.18,"body":"direction proceeds, uh, from fifties."},{"speaker":null,"startTime":1619.9,"endTime":1621.66,"body":"But still, it, works"},{"speaker":null,"startTime":1621.733,"endTime":1622.153,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1622.434,"endTime":1622.713,"body":"Yeah."},{"speaker":null,"startTime":1622.853,"endTime":1628.488,"body":"So this is again, when the, acceptorin this case, uh, is more reactive."},{"speaker":null,"startTime":1628.518,"endTime":1631.728,"body":"You have less side reactionsprobably because then the radical"},{"speaker":null,"startTime":1632.628,"endTime":1636.528,"body":"really readily reacts with this,uh, acceptor and not other places."},{"speaker":null,"startTime":1637.235,"endTime":1637.745,"body":"Andres: yes."},{"speaker":null,"startTime":1639.318,"endTime":1644.738,"body":"Kevin: And then, in case of, uh,application or in, in, yeah, you already"},{"speaker":null,"startTime":1644.798,"endTime":1650.978,"body":"showed some nice, uh, applicationof this in a larger synthesis route."},{"speaker":null,"startTime":1652.103,"endTime":1655.903,"body":"Andres: Yes, we, we demonstratedthe synthesis of the Demestrol,"},{"speaker":null,"startTime":1656.003,"endTime":1661.913,"body":"which is a non-steroidal estrogenusing, uh, hormonal therapies."},{"speaker":null,"startTime":1661.985,"endTime":1662.405,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1662.993,"endTime":1666.998,"body":"Andres: And, to the best of our knowledge."},{"speaker":null,"startTime":1667.118,"endTime":1671.498,"body":"As we also say this on the work,this is the first synthesis"},{"speaker":null,"startTime":1671.558,"endTime":1675.278,"body":"of a bioactive compound usingmethane as a starting material."},{"speaker":null,"startTime":1675.805,"endTime":1675.985,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1676.838,"endTime":1681.218,"body":"Andres: So we are demonstratingthat we can use this a small"},{"speaker":null,"startTime":1681.338,"endTime":1686.983,"body":"little hydrocarbons to build somebigger and complex molecules."},{"speaker":null,"startTime":1687.613,"endTime":1689.683,"body":"And we have around at."},{"speaker":null,"startTime":1689.773,"endTime":1695.473,"body":"20% of the overall yield,which is actually great if"},{"speaker":null,"startTime":1695.473,"endTime":1696.733,"body":"you are talking about methane."},{"speaker":null,"startTime":1697.183,"endTime":1699.793,"body":"'cause sometimes you're doingchemistry in your lab, very"},{"speaker":null,"startTime":1701.083,"endTime":1702.433,"body":"traditional organic chemistry."},{"speaker":null,"startTime":1702.673,"endTime":1707.443,"body":"And after few steps you, you're alsoin the 20% of yield you don't that."},{"speaker":null,"startTime":1709.335,"endTime":1709.455,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1709.455,"endTime":1713.445,"body":"I think in that reaction, the methane isso cheap that if you lose some of that,"},{"speaker":null,"startTime":1713.475,"endTime":1715.905,"body":"it's, it doesn't really matter, right?"},{"speaker":null,"startTime":1716.265,"endTime":1718.365,"body":"You need to convert."},{"speaker":null,"startTime":1719.34,"endTime":1722.64,"body":"The other reagent that,that's more important."},{"speaker":null,"startTime":1722.64,"endTime":1722.97,"body":"Right."},{"speaker":null,"startTime":1723.39,"endTime":1727.65,"body":"Did you also look into the conversionof the other side of direction?"},{"speaker":null,"startTime":1729.478,"endTime":1731.393,"body":"Andres: Eh, usually."},{"speaker":null,"startTime":1732.443,"endTime":1739.973,"body":"The allylic chloride in most of thecases, we still recover some of them."},{"speaker":null,"startTime":1741.053,"endTime":1744.053,"body":"So, and we can isolateback from the column"},{"speaker":null,"startTime":1744.053,"endTime":1744.503,"body":"so we,"},{"speaker":null,"startTime":1744.893,"endTime":1749.543,"body":"ideally we can get it and rerun,rerun again the, the reaction."},{"speaker":null,"startTime":1749.903,"endTime":1753.833,"body":"So we are not just destroying theliquid chlorate, which is great"},{"speaker":null,"startTime":1753.833,"endTime":1756.953,"body":"from the atom economy point of view."},{"speaker":null,"startTime":1757.37,"endTime":1758.18,"body":"Kevin: And you can just."},{"speaker":null,"startTime":1758.885,"endTime":1762.605,"body":"Do the cycle again, and thenit's, uh, not really a problem."},{"speaker":null,"startTime":1762.815,"endTime":1768.135,"body":"And also in terms of the end product,uh, which is quite a complicated"},{"speaker":null,"startTime":1768.135,"endTime":1774.495,"body":"molecule, it's then yeah, verygreat that you can, uh, use such"},{"speaker":null,"startTime":1774.495,"endTime":1776.565,"body":"a simple molecule to start with."},{"speaker":null,"startTime":1777.094,"endTime":1777.244,"body":"Andres: Yeah."},{"speaker":null,"startTime":1777.294,"endTime":1779.914,"body":"And also, from the, uh, point of methane."},{"speaker":null,"startTime":1780.874,"endTime":1781.144,"body":"Okay."},{"speaker":null,"startTime":1781.504,"endTime":1787.819,"body":"Of course, we are using 50 bar ofmethane, which is a lot, and we are only,"},{"speaker":null,"startTime":1787.869,"endTime":1793.719,"body":"in this example, we're only, uh using0.1 millimole, which I don't have the"},{"speaker":null,"startTime":1793.719,"endTime":1799.539,"body":"numbers in my, my head, but maybe thatis like 1% of the 50 bars or even lower."},{"speaker":null,"startTime":1800.259,"endTime":1804.804,"body":"But from a bigger scale pointof view, the, the main thing"},{"speaker":null,"startTime":1804.804,"endTime":1806.184,"body":"is still in the atmosphere."},{"speaker":null,"startTime":1807.074,"endTime":1811.064,"body":"Of the reactor, so it could beeasily just re and recovered to, uh,"},{"speaker":null,"startTime":1811.454,"endTime":1813.734,"body":"again, to, to the methane reactor."},{"speaker":null,"startTime":1813.877,"endTime":1814.237,"body":"Kevin: yeah,"},{"speaker":null,"startTime":1814.814,"endTime":1819.219,"body":"Andres: And could be, and actuallyyou, you're not losing methane."},{"speaker":null,"startTime":1819.487,"endTime":1820.627,"body":"Kevin: yeah, yeah, exactly."},{"speaker":null,"startTime":1820.927,"endTime":1826.237,"body":"I mean, in the industry it's oftentimesyou don't have full conversion"},{"speaker":null,"startTime":1826.237,"endTime":1830.317,"body":"anyway because you want the highestselectivity as possible, so you"},{"speaker":null,"startTime":1830.317,"endTime":1835.927,"body":"create less waste and you just,methane is very easy to cycle around."},{"speaker":null,"startTime":1835.927,"endTime":1839.077,"body":"You can just, uh, keep it in the reactor."},{"speaker":null,"startTime":1839.467,"endTime":1844.417,"body":"Um, I assume if you would scale upyour reaction, you need some kind of"},{"speaker":null,"startTime":1844.417,"endTime":1851.197,"body":"flow reactor to have the efficient,light, uh, distribution, right?"},{"speaker":null,"startTime":1851.527,"endTime":1853.237,"body":"Or how would you scale up this reaction?"},{"speaker":null,"startTime":1854.429,"endTime":1860.804,"body":"Andres: With scale up the reactionfor, uh, for Ethane and for propane we"},{"speaker":null,"startTime":1860.934,"endTime":1867.894,"body":"scale up from 0.2 millimole to threemillimole, which is, uh, approx from"},{"speaker":null,"startTime":1867.984,"endTime":1875.574,"body":"eight milliliters reaction to, I thinkit was, uh, 30 something at the end, or,"},{"speaker":null,"startTime":1875.677,"endTime":1876.097,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1876.594,"endTime":1877.314,"body":"Andres: yes."},{"speaker":null,"startTime":1877.884,"endTime":1881.394,"body":"And we just use some bigger reactor."},{"speaker":null,"startTime":1882.264,"endTime":1885.164,"body":"And instead of one lampsidiating, two lamps"},{"speaker":null,"startTime":1885.187,"endTime":1885.607,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1886.524,"endTime":1888.75,"body":"Andres: And also, a larger reaction time."},{"speaker":null,"startTime":1888.96,"endTime":1893.88,"body":"We went from 16 hours to,I guess, uh, 32 hours."},{"speaker":null,"startTime":1894.513,"endTime":1894.733,"body":"Kevin: No."},{"speaker":null,"startTime":1894.808,"endTime":1895.168,"body":"Okay."},{"speaker":null,"startTime":1896.04,"endTime":1897.81,"body":"Andres: The yield decreased a little bit,"},{"speaker":null,"startTime":1897.838,"endTime":1898.138,"body":"Kevin: yeah."},{"speaker":null,"startTime":1899.405,"endTime":1899.625,"body":"Andres: but."},{"speaker":null,"startTime":1900.268,"endTime":1900.748,"body":"Kevin: Okay."},{"speaker":null,"startTime":1900.868,"endTime":1905.788,"body":"So the, the larger scale alsoimproves the reaction in that sense."},{"speaker":null,"startTime":1905.878,"endTime":1909.528,"body":"I mean, it gets slower, but more yield."},{"speaker":null,"startTime":1910.768,"endTime":1911.338,"body":"Interesting."},{"speaker":null,"startTime":1911.398,"endTime":1917.668,"body":"But then, yeah, if you would scaleit up even bigger, you set that, um."},{"speaker":null,"startTime":1918.208,"endTime":1923.798,"body":"With larger erectors, it's, uh,sometimes a problem for the light to"},{"speaker":null,"startTime":1923.858,"endTime":1926.678,"body":"really go into the reaction mixture."},{"speaker":null,"startTime":1927.82,"endTime":1928.42,"body":"Andres: Yes."},{"speaker":null,"startTime":1928.81,"endTime":1929.17,"body":"Yes."},{"speaker":null,"startTime":1929.44,"endTime":1931.45,"body":"In that sense, yes."},{"speaker":null,"startTime":1931.72,"endTime":1937.06,"body":"Ideally, yes, flow a a flow reactorwould be ideal for, for this application."},{"speaker":null,"startTime":1937.9,"endTime":1945.47,"body":"I'm not 100% sure, but I guesssomebody else in my previous"},{"speaker":null,"startTime":1945.47,"endTime":1946.815,"body":"group was working on that."},{"speaker":null,"startTime":1948.785,"endTime":1952.535,"body":"And also there's a lot of ofresearch in this scale up of,"},{"speaker":null,"startTime":1952.535,"endTime":1954.515,"body":"photo, uh, chemistry reactions."},{"speaker":null,"startTime":1955.235,"endTime":1959.155,"body":"And, uh, there's some, I don'tknow if they're already used, but"},{"speaker":null,"startTime":1959.155,"endTime":1961.335,"body":"there are some kind of light balls."},{"speaker":null,"startTime":1961.775,"endTime":1964.895,"body":"Which can be introduced insideof the, of the big reactors."},{"speaker":null,"startTime":1965.375,"endTime":1968.765,"body":"So the radiation takes place fromthe interior of the reaction."},{"speaker":null,"startTime":1969.545,"endTime":1970.055,"body":"And this,"},{"speaker":null,"startTime":1970.415,"endTime":1974.405,"body":"uh, luminous and wallsare also spinning inside."},{"speaker":null,"startTime":1974.405,"endTime":1976.205,"body":"So you have direct irradiation inside."},{"speaker":null,"startTime":1976.205,"endTime":1981.47,"body":"You don't have this problem of, uh, uh,having lamps outside and going through"},{"speaker":null,"startTime":1981.515,"endTime":1983.075,"body":"the solvent and through the reaction."},{"speaker":null,"startTime":1984.005,"endTime":1989.255,"body":"But yes the scalability of photochemicalreactions is, uh, a big research field."},{"speaker":null,"startTime":1989.718,"endTime":1994.723,"body":"Kevin: Yeah, so that would bedefinitely one way to improve."},{"speaker":null,"startTime":1994.863,"endTime":2000.818,"body":"But this is not really on thelike reaction optimization side."},{"speaker":null,"startTime":2000.843,"endTime":2001.613,"body":"It's more on the."},{"speaker":null,"startTime":2002.378,"endTime":2006.188,"body":"Engineering side on how to getlight into, into the sample."},{"speaker":null,"startTime":2006.788,"endTime":2012.018,"body":"Um, what other, uh, improvements do youthink will come with this, uh, reaction?"},{"speaker":null,"startTime":2012.756,"endTime":2018.996,"body":"Andres: We believe that our findingof, um, our finding with this."},{"speaker":null,"startTime":2019.821,"endTime":2026.373,"body":"Photo catalyst is, uh, supramolecularphoto catalyst in which we can in some way"},{"speaker":null,"startTime":2026.403,"endTime":2033.483,"body":"attenuate these li to metal chart transferreactivity, but also suppress the side"},{"speaker":null,"startTime":2033.633,"endTime":2035.433,"body":"activity of the radical ligand transfer."},{"speaker":null,"startTime":2036.043,"endTime":2044.233,"body":"Um, we believe that this, uh, mayopen new doors to use even less"},{"speaker":null,"startTime":2044.233,"endTime":2046.243,"body":"activated, uh, radical acceptors."},{"speaker":null,"startTime":2048.883,"endTime":2054.023,"body":"We believe that 'cause, until thedate most of the radical acceptors"},{"speaker":null,"startTime":2054.023,"endTime":2056.098,"body":"used were, uh, highly activated."},{"speaker":null,"startTime":2056.19,"endTime":2056.61,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2057.778,"endTime":2062.518,"body":"Andres: Also because, uh, most of thegroups were doing an excellent research"},{"speaker":null,"startTime":2062.578,"endTime":2068.308,"body":"on just developing new catalytic systemto demonstrate, okay, I have this"},{"speaker":null,"startTime":2068.308,"endTime":2072.928,"body":"catalytic system and this catalyticsystem is capable to activate the"},{"speaker":null,"startTime":2072.958,"endTime":2074.638,"body":"hydrogen bonds from the hydrocarbons."},{"speaker":null,"startTime":2075.508,"endTime":2079.408,"body":"And most of the research groupswere a focus on that direction."},{"speaker":null,"startTime":2079.978,"endTime":2083.548,"body":"And to be honest, whenyou want to prove that."},{"speaker":null,"startTime":2083.978,"endTime":2085.988,"body":"Your new photo catalyst is working."},{"speaker":null,"startTime":2086.708,"endTime":2090.638,"body":"You're going to choose the, most,uh, reactive substrate because it's"},{"speaker":null,"startTime":2090.638,"endTime":2092.978,"body":"the most straightforward to demonstr."},{"speaker":null,"startTime":2093.033,"endTime":2097.623,"body":"Kevin: But the challenge then is reallyto use those who would not really react."},{"speaker":null,"startTime":2097.683,"endTime":2101.373,"body":"Like what would be an examplethat would be the dream reaction"},{"speaker":null,"startTime":2101.373,"endTime":2102.963,"body":"in this case that you could use."},{"speaker":null,"startTime":2106.325,"endTime":2110.435,"body":"Andres: The dream reaction whereI could use, uh, gases gains?"},{"speaker":null,"startTime":2110.918,"endTime":2111.208,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2111.725,"endTime":2113.291,"body":"Andres: Hmm, that's a difficult question."},{"speaker":null,"startTime":2113.891,"endTime":2115.871,"body":"Uh, I don't know."},{"speaker":null,"startTime":2115.871,"endTime":2118.331,"body":"Uh, maybe, um,"},{"speaker":null,"startTime":2118.785,"endTime":2123.061,"body":"a radical addition over, um,non activated, all the thing."},{"speaker":null,"startTime":2125.101,"endTime":2125.796,"body":"I think that will be."},{"speaker":null,"startTime":2127.201,"endTime":2130.741,"body":"One of the, the, the hardestone without, of course, the, the"},{"speaker":null,"startTime":2130.741,"endTime":2136.081,"body":"assistance of any second methyl thatmay trap the, the radical and then"},{"speaker":null,"startTime":2136.081,"endTime":2139.051,"body":"insert the, the, the fragment in the"},{"speaker":null,"startTime":2139.051,"endTime":2139.471,"body":"ole thing."},{"speaker":null,"startTime":2140.791,"endTime":2143.841,"body":"Just the, the, the di radicaladdition of the radical."},{"speaker":null,"startTime":2144.849,"endTime":2146.589,"body":"Kevin: Yeah, that sounds very challenging."},{"speaker":null,"startTime":2148.699,"endTime":2149.059,"body":"Okay."},{"speaker":null,"startTime":2149.059,"endTime":2154.159,"body":"And, uh, what I also thought when Iwas, uh, looking in this direction,"},{"speaker":null,"startTime":2154.159,"endTime":2160.729,"body":"currently I'm dealing a lot with,uh, power to X processes and there"},{"speaker":null,"startTime":2160.879,"endTime":2164.899,"body":"one of the ways to go is using, um."},{"speaker":null,"startTime":2165.604,"endTime":2171.874,"body":"CO2 from, uh, direct air capture andthen converting it to methane, and then"},{"speaker":null,"startTime":2171.874,"endTime":2177.784,"body":"you could use that methane also in yourreaction and basically use CO2 as the"},{"speaker":null,"startTime":2177.784,"endTime":2180.124,"body":"starting material in your synthesis route."},{"speaker":null,"startTime":2180.204,"endTime":2184.764,"body":"Well, very many steps, butstill it's interesting concept."},{"speaker":null,"startTime":2185.986,"endTime":2189.761,"body":"Andres: It's a very interinteresting, uh, concept, uh, as well."},{"speaker":null,"startTime":2189.761,"endTime":2194.471,"body":"And actually there's a lot ofresearch groups doing huge efforts"},{"speaker":null,"startTime":2194.471,"endTime":2201.596,"body":"on using CO2 as well because it'salso a. Uh, a greenhouse gas and"},{"speaker":null,"startTime":2202.016,"endTime":2204.056,"body":"that could be a another alternative."},{"speaker":null,"startTime":2204.806,"endTime":2210.416,"body":"You are still adding intermediatesteps in this case to reach methane"},{"speaker":null,"startTime":2210.926,"endTime":2213.721,"body":"with, I don't know, honestly."},{"speaker":null,"startTime":2214.516,"endTime":2218.686,"body":"I don't know if could be the,the best choice to transform"},{"speaker":null,"startTime":2218.686,"endTime":2221.746,"body":"CO2 in something very, uh, inert"},{"speaker":null,"startTime":2221.914,"endTime":2222.604,"body":"Kevin: Yeah, yeah."},{"speaker":null,"startTime":2223.126,"endTime":2230.406,"body":"Andres: Such as methane, but, uh, well,nowadays with a toolbox of gas alkins,"},{"speaker":null,"startTime":2230.406,"endTime":2236.736,"body":"we have to, to activate them couldbe a useful transformation for sure."},{"speaker":null,"startTime":2237.479,"endTime":2237.779,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2238.139,"endTime":2238.289,"body":"Yeah."},{"speaker":null,"startTime":2238.289,"endTime":2238.829,"body":"But you're right."},{"speaker":null,"startTime":2238.829,"endTime":2244.859,"body":"Probably it's easier to use something likemethanol or other, more activated, uh,"},{"speaker":null,"startTime":2244.949,"endTime":2250.079,"body":"C one structures and then use those forthe further chemistry than the methane."},{"speaker":null,"startTime":2250.619,"endTime":2257.309,"body":"It it just a theory thought thento close this, uh, discussion."},{"speaker":null,"startTime":2257.399,"endTime":2260.999,"body":"I always ask in the end, uh,the question, what's your"},{"speaker":null,"startTime":2260.999,"endTime":2262.394,"body":"favorite discovery in chemistry?"},{"speaker":null,"startTime":2263.304,"endTime":2265.014,"body":"Andres: We have a lot of them."},{"speaker":null,"startTime":2266.154,"endTime":2270.894,"body":"Uh, and, and that's a difficultquestion because no matter which"},{"speaker":null,"startTime":2271.909,"endTime":2273.834,"body":"one will choose, uh, somebody will."},{"speaker":null,"startTime":2275.109,"endTime":2277.389,"body":"Will, uh, complain about it."},{"speaker":null,"startTime":2278.74,"endTime":2283.398,"body":"probably structuralelucidation of Ferrocene."},{"speaker":null,"startTime":2284.271,"endTime":2284.351,"body":"Kevin: Hmm."},{"speaker":null,"startTime":2284.621,"endTime":2284.911,"body":"Okay."},{"speaker":null,"startTime":2286.653,"endTime":2290.233,"body":"Andres: Which was, um, uh,important, inflection, uh,"},{"speaker":null,"startTime":2290.293,"endTime":2291.913,"body":"point on the ergonomic metallic"},{"speaker":null,"startTime":2291.913,"endTime":2292.453,"body":"chemistry."},{"speaker":null,"startTime":2293.533,"endTime":2299.593,"body":"And it open a lot of, uh, doorsto synthesize and to design."},{"speaker":null,"startTime":2299.873,"endTime":2302.263,"body":"Novel organo metallic complexes."},{"speaker":null,"startTime":2302.473,"endTime":2303.703,"body":"Metallic reagents."},{"speaker":null,"startTime":2304.453,"endTime":2307.098,"body":"I think that will be one of my favorites."},{"speaker":null,"startTime":2308.321,"endTime":2311.351,"body":"Kevin: Yeah, that's, uh,very impactful for Catalysis."},{"speaker":null,"startTime":2311.351,"endTime":2312.011,"body":"Definitely."},{"speaker":null,"startTime":2312.731,"endTime":2313.121,"body":"Okay."},{"speaker":null,"startTime":2313.331,"endTime":2317.861,"body":"Thank you very much for this, uh,discussion and sharing your research."},{"speaker":null,"startTime":2318.106,"endTime":2319.426,"body":"Andres: Thank you very much, Kevin."},{"speaker":null,"startTime":2322.061,"endTime":2323.201,"body":"Kevin: Yeah, was a pleasure."},{"speaker":null,"startTime":2325.47,"endTime":2327.27,"body":"Thank you very much for listening."},{"speaker":null,"startTime":2327.72,"endTime":2332.16,"body":"If you like chemistry and don'twant to miss a future episode, don't"},{"speaker":null,"startTime":2332.16,"endTime":2334.5,"body":"forget to hit the follow button."},{"speaker":null,"startTime":2334.59,"endTime":2336.78,"body":"This already helps the show to grow."},{"speaker":null,"startTime":2337.41,"endTime":2343.47,"body":"You can now also support the show on BuyMe a Coffee to help me keeping it running."},{"speaker":null,"startTime":2344.97,"endTime":2346.62,"body":"The link is in the show notes."},{"speaker":null,"startTime":2347.88,"endTime":2351.795,"body":"You can find the link in theshow notes if you would like."},{"speaker":null,"startTime":2352.605,"endTime":2356.595,"body":"To be part of a future episode andtalk about your research, send me an"},{"speaker":null,"startTime":2356.595,"endTime":2359.745,"body":"email to contact@innovateandreact.com."},{"speaker":null,"startTime":2360.525,"endTime":2363.675,"body":"And until next time, keepinnovating and stay curious."}]}