Hey guys, it's Nate, AKA The Foot Accountant. Welcome back to the channel. Happy Saturday and welcome to Future Stars inside of FIFA 22 Ultimate Team. We're gonna take a look, actually take a look back at yesterday on Friday for a lot of this video because there was a lot of insane stuff that happened yesterday. Of course, Future Stars dropped, team of the year ended, and we had a really weird market crash. I wanna talk about all of that with the new promo, how the EA servers actually caused that market crash before Future Stars came out yesterday, and take a look at some leaks because there are some pretty big leaks for Future Stars content coming in the next couple of days, and it's already starting to impact the market, so that's why we're gonna talk about that today. And yes, as you do see in the title, I had a buzzer beater team in your pack poll yesterday. We crafted some packs to start the stream, and if you wanna see the reaction to me packing this messy, it is down below in the description. I still cannot believe it. There's a link down below in the description to my Twitter, and I'll post the link there where I packed this messy, but that means so freaking much. That pack right there, unbelievable. A buzzer beater, literally 30 minutes before they went out of packs. I still can't believe it. The pack look is beyond absolutely juiced this year, but Future Stars team won a lot of mixed reviews. Some of the cards look insane. Some of them do not look that insane. So we're gonna cover it all today. It might be a little bit of a longer video, but hopefully you guys are having a good weekend, your weekend leagues, even though there was a little bit of server outage yesterday, they didn't make weekend league extended or anything like that. There was really no compensation. I think it was just because it was between the PlayStation and the PC platforms where there was an issue. So we'll talk about all that and what's going on with the market in general as well. So if you're excited for any of these Future Stars cards or the content to come, make sure you hit a thumbs up on it and subscribe if you're new. Now I know the market crash didn't affect everybody, but I wanna talk about it, right? Because if you saw these market movements yesterday in the morning on Friday, you were like, what in the world is going on? And you look at this graph and it looks absolutely wild. But this is what happened, right? There was nothing happened, nothing unusual, right? A normal Friday on FIFA, maybe a little bit of drop in the panic selling right before a new promo. And then all of a sudden the servers went down and it was about for like an hour, I think, hour, hour and a half, the servers went down and the market absolutely died. It was really weird. Again, this was only on PlayStation and only on PC, but you saw so many prices drop because the market was like halfway down, right? What you saw was so many people were able to like access the market in terms of transfer, the transfer list. They were able to sell cards, list cards up and people saw prices dropping. So they kept undercutting, like not sure what was going on and something crazy was happening. People saw the panic and they just kept undercutting each other and foot bin caught the undercut. So then people were seeing foot bin prices undercutting from there. But like, you know, at the same time, people were there were listing cards up, you know, and driving some of these prices down for some of the people that were on the market. People were trying to buy as well. And I was one of those people trying to buy, like Kiesa was down here at a, he was actually at 140K, about two Kiesas yesterday at 140,000 coins. But I literally snagged like 20 or 30 of them, but only two of them registered, right? It was really weird with the servers being down for like this little hour to two hour period in here. And it's just created honestly, one of the most crazy episodes on the market that I've ever seen where a lot of this stuff just died for like an hour and then bounced back. Mostly team of the year honorable mentions, SPC fodder did this. I bought like a Alessane Jirini winter wildcards for 35,000 coins and sold it for 55,000 coins as he bounced back in price. It was honestly one of the most crazy things on the market that I've ever seen. But again, what really happened was the servers went down. Some people were still on the game and able to list their cards, but when the mass amount of users on this game are not able to access the market, and we've seen this happen multiple times before. And this is just something kind of to keep in mind when we have situations like this arise again. If you see the panic selling like that because the servers are down, that is a huge opportunity if you're able to buy, to buy cards because yes, there wasn't like there was a big pack that was released that was supplying honorable mention cards and making their prices drop like crazy. It was purely people selling and panic selling them for whatever reason, and that's why their prices dropped. So the prices basically as you saw on these graphs, they went down like crazy and then rebounded so fast when the servers came back up, everybody was like, oh my goodness, prices are so low. They went back out, bought cards and the market shot back up. So there was a lot of profit to be made, but a lot of people weren't able to make, you know, tons and tons of coins just because the rebounds were so fast, so quick and so sharp. So if you're seeing things about a market crash and stuff like that going on, you know, that's kind of what happened yesterday. And again, it was a really, really wild thing. If you were on the market at that time, like Raheem Sterling, even from a fodder perspective, Raheem Sterling was popping up at 13,000 coins. 13,000 coins for an 88 rated card that right now is 27K. It was ridiculous. The whole entire market just absolutely died and then bounced back. So I don't know if I've ever seen anything like that in that short amount of time, only affecting like two platforms, PC and PlayStation. But the issue was fixed pretty quickly. EA did tweet about it, but then afterwards they didn't say anything else about it. They said that it's been fixed. So yeah, anyways, that's that whole situation. I wanted to talk about that a little bit. And I also want to talk about future stars, right? Because I think the promo yesterday left a decent amount of people just like, man, this future stars, yes, there's some really, really good players in here, but overall, this is not as hype as the future stars promos that we have seen in the past. And you saw the market react accordingly as a lot of the honorable mention cards that we are looking at right here, as we were just looking at Kiesa. A lot of these cards rebounded pretty well. They really did, right? I was a little bit scared about Kunde because we had two French center backs that were gonna be in the new future stars team that were released yesterday. But Kunde still went from 200,000 coins up to about 230, where he is now.  He's now almost 240K, as you can see here. And a lot of these honorable mention cards did rebound pretty well because the content yesterday for future stars was just kind of average. It was just kind of average, right? And that's what I want to look over right now. Now, there's a few of these cards that are not average by any means, right? Take a look at this Chalmeni card, which I bought a few of him just a little bit ago at 1.2 lows and one on snipe at 1.1 mil. But like this card, the upgrade in this Chalmeni is really, really insane.  This card looks like just ridiculous. This is like prime icon, a Hobbit level, and then some four star, four star, high, high work rates. This card looks ridiculous. So the price tag on some of these cards, it's like a really big discrepancy for the future stars. You have these great cards in the upper echelon, the top tier, like over 500K. You've got four cards. You've got Vlahovic. You've got Bellingham, Chalmeni, and Smith Row. Those four cards are really, really hype. And then after that, there's a huge drop-off to Konate at 300,000 coins and Dick is 200K. And then like the whole rest of the team, I guess Mateus Kunia is also about 290. Then you've got, you know, Batman, Gakpo, Trinkau, Pedro Porro, Glankalo Ramos. These guys are basically like discard, right? They're so cheap. They're so low in price. And the stats are just okay, right? And they're not that insane. So we have a very like, very top heavy and very bottom feeder team all at the same time with not very many cards in the middle. And I think that left a lot to be desired for content yesterday on this game. Now, SBCWise, that was another place. We talked about in yesterday's video, the pack weight and the SBC content would really carry the content yesterday on the game. Our talent scout winner, SBC came a bit early, right? We knew we were gonna get a Brazilian striker. We got Arthur Cabral, while he did get a very nice boost, only three star skill moves. And the price tag on this SBC, just being too much. I believe the SBC price tag here is about 170,000 coins for this card, which it is a very nice Brazilian striker. But for most people on the game, it's not gonna be worth the coins that you could spend on this card. You might as well go do, if you need a Serial Striker, you might as well go do Lautaro Martinez's team of the year card, team of the year honorable mention that is, I believe, inside of the SBC section here, somewhere, if I could find it. I'm sure that he's in here, he's still out. He was released for a long time. But that card is definitely better. Here it is. This card, in my opinion, is way better, more usable. He's got the four star, four star. I think he's got better shooting, better dribbling. He's got more traits, better physicality. I think this card is just flat out better than the Arthur Cabral that was released yesterday. But still, Cabral is interesting. It is a future star, and that was the talent scout picked card. Now, this one is actually kind of dope. The Future Stars Academy player pick, Shaloba, Centerback, or CDM. And I think a lot of people are picking the CDM version because it just has way better stats overall. And technically, if you wanted to use Shaloba at Centerback, you could just slap a shadow on him or slap an anchor on his center defensive mid card and move him to Centerback in game. And you would basically have the stats of the Centerback item with better passing, better dribbling, and better shooting, and a four star weak foot on the CDM card. So that's why I think a lot of people, a lot of people, if you look on foot bin, they've upvoted the CDM Shaloba. So it was nice to get the Future Stars Academy player day one. Now, of course, it is a bit of a grind. You're gonna have to play a decent amount of games between foot families, between rivals, squad battles, all three of those modes. You're gonna have to play a decent amount of games to get this card. There's also a swaps token that is hidden in here. And it's kinda hard. It's kinda hard, as you can see. You get a objective reward. It's the climbing the ranks. Score in eight separate squad battles matches on minimum professional difficulty with the 83 overall Future Stars Shaloba in your squad to earn the 85. So if you are trying to get all of your swap tokens, you kinda have to do the Shaloba card to get a swap token. So again, EA is kind of being very sneaky about hiding some of these swap tokens in here. As you can see here, they're hiding one in this climbing the ranks section of Shaloba. So I'm not a huge fan of that. But we also had another swap token, SBC. So there were two. There were two tokens that were available as of yesterday because they released another challenge, SBC. And they released that objective. So that was kind of all of our content yesterday. Now, with the Foot Future Stars items, let's talk market here for a second. The pack weight on these cards is honestly not bad. It's pretty high, 9.8% as you can see from a 100K pack. In my opinion, that's decently high. But again, as you look at this team and as you look at these cards, and we can kinda look over them a little bit closer again if we would like, again you see there's such a, the high tier cards and the low tier cards. There's such a big gap in there. 10% chance of packing one out of a 100K pack. You know, most of that percentage is probably your Guncaloramos, Pedro Poro, Gacpo, Batman and those lower tier cards. So these upper tier cards like Vlahovic, Smith, Rowe, Bellingham, Chalmony, they're pretty rare, right? And you're seeing their prices fluctuate around a lot already on this game and on this market. Now they started off pretty expensive, right? These cards started off pretty expensive. As you can see, I've got some on my transfer targets. I accidentally cleared my transfer list again. We're also gonna show you some of the sale prices that I had. Vlahovic was like 1.2 million coins. Chalmony was like 1.7. Bellingham was about 2 million coins all day until just a couple hours ago. He dropped down under 1.7 mil. He's now rebounding back into the 1.8s. Chalmony, I actually picked up three Chalmonys. I got some really good deals on this card. And the reason why I picked him up is because he was super duper cheap. I got an insane snipe on one of these. 1.23, 1.22 and 1.1 flat. I got a really insane deal on him. And I think he's now rebounding above 1.3. But these cards are gonna be staying pretty rare into this morning as well on Saturday, I would imagine. Because people are gonna wake up and wanna try these cards. Now one annoying thing about these cards in the market right now is of course that there's no search filter. As you're looking here in the quality section, there is no Future Star search filter. So like it has almost become normal on promo Fridays, they've kind of omitted that feature. So hopefully this Chalmony card can bounce back up. I would love to see him. Honestly, I think he can go to about 1.4 mil because he is very rare and he's got a lot of hype. Maybe 1.3 highs, I would love to see that. So we will see if Chalmony can reach those heights this morning. Another card that I flipped, I bought a Smith Row at 825,000 coins. Now Smith Row was one of the more hyped up cards from yesterday because he got a five star weak foot upgrade. And EA, they did some pretty good business here with the weak foot upgrades on a lot of these cards and skill move upgrades. Smith Row, the five star weak foot of four star skills, I bought one at 825, sold it at 977. I got a bit lucky, that was a lazy. And then he went back down. Smith Row went back down to about 830 and now he's rebounding back up. I think he's gonna be over 900,000 coins here in the few hours this morning on the market. Vlahovic, as we talked about yesterday and mispronounced his name of course, that was pretty legendary for the YouTube channel. Vlahovic went down to about 650,000 coins and has rebounded up since over 700,000. There's a decent amount of hype with this card as well because he got that four star, four star upgrade. And just to show you the stat boost that this guy got in the dribbling category, you have to take a look at this because it cannot go without noting. 92 agility and 90 balance on the 92 rated future stars of Vlahovic. From his 87 rated player of the month, plus 21 agility and plus 29 balance. You gotta give credit where credit is due. That is an insane boost, probably the most insane boosted card that we had from the promo team yesterday in my opinion. I know it's just kind of like Team of the Year Leventosky. I know that it's kind of like Holland vibes, right? But brand new transfer to UVA, they actually did give him the UVA card and it's kind of funny because they gave him, it's showing him kissing the badge, right? And this dynamic image of course would have been from him at Fiorentina. So he's like kissing the Fiorentina badge but he made the money move to Juventus. So it's just kind of funny in that, but huge dub to EA on this boost on the Vlahovic. But then when you look at the rest of the team, besides again those top tier cards that we talked about, you know, Pedro Poro, whatever, you know, Batman, no thanks, Gakpo, no thanks, Trinkau, decent, cheap, you know. So I just think that the overall hype for the future stars cards that were released and for the SBC content and objective content yesterday is like a six out of 10. Now, with that being said, there are some more leaks, right? And we've seen this happen during team of the year as well. There was a lot of leaks earlier on at the start of team of the year and there is a huge. And when I mean huge, I mean, this is flashback Varan level of hype, huge. SBC leaked to be coming out very soon. So I'm gonna take a look at a couple leaks again, just a little bit of a warning as we look into some of these. Flashback Gareth Bale has been leaked. It's been shown, it's been confirmed. He is gonna be coming through in SBC pretty soon. Now, I wanna make this clear because I think this leak tweet sounds a bit confusing. It says here, he will be a flashback for Tottenham. Stats and positions are a prediction on this card right here, right? He'll be a flashback for Tottenham. That just means that EA is giving him the flashback card for his days back at Tottenham Hotspur. Probably the first days, right? Where he was at Tottenham Hotspur the first time before he moved and then of course last year he came back, probably that first number of years that he was with Spurs. And this does not mean that his card is going to be a Tottenham card. Because again, just like we saw with the flashback Kante or a flashback Christiane Ronaldo from last year in FIFA 21, they have to use the current club that the player is at for cards that they release in the game. They can't release a Gareth Bale that is at Tottenham Hotspur unless they've got some crazy deal or something that they've never done before and this is going to be an absolutely insane first card ever. I mean, Gareth Bale is expected to be a Real Madrid SBC in this game. So we don't know when this is coming, but this is a big boy SBC. And I mean, hopefully they juice this card up because Gareth Bale does like not have any special cards this year. He really hasn't earned one yet to be completely honest.  That'd be awesome. We would absolutely love that. Maybe it's a left back, right? There's a lot of potential here. And the reason why I'm talking about this too is that there's a lot of hype with this, right? 3,000 likes in the suite, right? Gareth Bale is a big, big name. You've already started to see some of these Real Madrid links go up in price. I bought two Valverde's yesterday at about 400,000 coins. He is 440 and this card is rare, right? 440, you can see only a couple to 500K. That's up like 40,000 coins. The 87 Valverde was 510K. He's up to 542. This Modge was 700K flat and he's actually dropped a little bit. But you've seen some of these Real Madrid links rise up because people are already expecting and investing in the hype of this SBC since it's since. It is such a big name. I think Ed and Hazard, Winter Wildcards, he is up as well. He was like 150. Yeah, now he's about 170. So that card is definitely going up. This Modge, I'm keeping an eye on because he was up at like 740 and he's so, so rare that if I saw one at like 700 flat, I would pull the trigger because that's just really, really cheap for this card, for how rare he is as well with the amount of hype that Gareth Bale will have. So just kind of keep that out there. I don't think that's coming today. I think it's too soon for that to be coming today. But in the next coming days, watch out for a flashback Gareth Bale. Of course, we'll probably be talking about that as we get closer and closer to that date because that's gonna impact the market a lot, right? Another SBC that has leaked, Dominic Calvert Lewin, Premier League striker Everton. This will be one that if EA give him a nice boost, that could be a pretty nice card. Pacey striker, especially if it is cheap. That could be a nice SBC that we see in this game with English links, of course, being very popular. And then this one looks really cool as well. Another player pick for the future stars, Brahim Diaz. These are confirmed stats, left wing and center attacking mid. So kind of similar to the Shaloba player pick. We're gonna have a player pick between two different versions of Brahim. His gold base has four star skills, five star weak foot. So if he were to get five star skills on either of these versions, that would be insane. I think people would be more likely to choose the center attacking mid central version. Yes, the pace is a little bit down, but the passing is up, the dribbling is still good. And if this one were to have like five star skills, if he was five star, five star, that would be a really, really high card. So that'll be a cool SBC that we could see very soon. And again, we talked about the Tomiyasu, right? That is still out there and there's still potential for a Tomiyasu SBC to be coming. I think that that could be sometime either today, later on this weekend. Because usually the stuff that you see leaked earlier on is the stuff that is a little bit better in terms of, or not better, but in terms of dropping in the game, it happens faster. So that's kind of what I would expect to see with that. Now, a couple of other things. Two big Player of the Month SBCs dropped yesterday as well. Angel Corea. This SBC is great value. If you look at footprint, he's got a lot of thumbs up. It's basically very similar and even a little bit better to the versus ice and fire cards that were released a couple of months ago as a part of that promo. And this Angel Corea is like 70,000 coins. He's very cheap to complete. I think he's like an 85-rated squad with an in form, 80 chemistry. So that's kind of high, but that's a W. And then Player of the Month, David Deheya as well. I've already completed this SBC, but David Deheya got himself a Player of the Month and it's coming in at about 32,000 coins. That caused some crazy movements on the market yesterday in terms of goalkeepers like Donnaruma is down because of the hype on that David Deheya. So that's just kind of something to keep in mind as well as that card is pretty hype. And again, since the content yesterday beside those Player of the Month SBCs was just kind of average. Again, like I said, you saw a lot of these cards bounce back, right? As I'm looking at a few of these cards that I see on my transfer list, some of the out-of-packs items that we saw, Robertson was at like 220. He rebounded back to like 240, 250. This Del Piero was down. I flipped him for a nice profit. And if you look across the market, especially on the team of your honorable mentions, some of these cards had really nice rises because again, what happened was people saw the content yesterday and it wasn't that good. So they went out and they bought some of these cards. Muhammad Salah was like 980,000 coins and I believe he was at 1.07 at one point. He's 1.02 with an undercut there, 1.04, 1.05. But a lot of these honorable mention cards rebounded very nicely on the market yesterday. Rutiger rebounded really well. Jonathan David's still kind of working on a rebound. Hasn't gone up too much yet. Phil Foden was like 450, 460,000 coins and he is now upwards of almost 500K. Yeah, 498, 499. Same thing with Bruno, right? Bruno went down to 500K flat and he's now up in like 570, 580K range. So some nice rebounds on those honorable mentions. Now today for content on Saturday, what do I think we can expect? Well, they've been continuously releasing of course these challenges that give out the tokens. I think we'll get another token SBC today for a Future Stars swap token. I think that's one thing that we'll see and I think we'll get an SBC. Whether it's one player for the, you know, like the Tomiyasu player pick, whether it's a player pick SBC or whether it's the Dominic Calvert Lewin or the Burhim Diaz, I think we'll get one of those types of SBCs today on this game, but I think we'll just be lighting rounds and SBC and a token, right? They also dropped this Future Stars Challenge 1. That was the new SBC, not Team There Challenge 9. That's on me. It was the Future Stars Challenge 1 which gave you a rare gold pack on tradeable. That was the brand new SBC from yesterday for a token. So I think we'll get another token SBC today and you'll probably see some more market movements with these Future Stars because again, even though a lot of them don't look that insane, there's still a lot of hype for some of these like top tier cards like the Smith Row. Again, Smith Row has so much hype and he is pretty rare, right? If you take a look at this card, he's literally just gone from 830K to 900,000 coins in the past like not even 30 minutes as I've been watching his card. So keep an eye on these items as they continue to fluctuate. Konate as well had some, these guys had some really big fluctuations in the first hour. Konate was like 400,000 coins. He went all the way up to like 530, 550 even and then went back down to 370 where I picked two of them up, still have those. And hopefully he rebounds back into the 400s. Then of course I bought those Chiamenis. I think Chiamenis can keep rising up as he's got a lot of hype. So hopefully we can see these guys get rare into today, rise nicely in price and it should be a good Saturday. It should be a pretty good Saturday. Hopefully the content is good. Again, it seems like it was a six out of 10 day. It really does. I'm gonna kinda grade it as a six out of 10 day for the Future Stars promo. Really good top tier cards, not so good cards on the bottom tier lower echelon you could say. But with the leaked SBCs that are coming that will maybe see even the first of those today on this game, that's just something to keep in mind that there is more potential content coming. And you know, EA during Future Stars in the past has done a really good job of releasing some sort of upgrade pack, right? 85 plus upgrades, player picks, all that sort of stuff. I would not be surprised if we had those coming out in this next week as well. So just be prepared as EA is gonna keep the content rolling in this game. So that is the video today. If you did enjoy, make sure to smack a thumbs up on it. Of course, comment down below if you have any questions. Let me know what you think about Future Stars and what you think about these cards or more so what you think about the leaks because I think again, there's more hype in some of those leaks and those cards that are coming than some of the items that are in this game right now as a part of Future Stars. And of course, if you're new around here make sure to subscribe if you're new. So happy Saturday, hope your weekend links go well. I'm taking this one off. But next weekend I gotta take Messi for a spin because again, I can't just have this card sitting in the club and not use him, right? We used him in one friendly yesterday.  So I can't wait to use this guy a little bit more. Again, can't believe that even happened. But it's been Nathan Ford Accounting. I will catch you guys later. Peace out.


Can you get there? Oh, hold on. The LED pop. See where my finger is? Put your finger down. Hold that right there. Okay. And I am going to... I don't know if I can take it with one hand. Right there. Bring it back. The LED went on. Oh, there. See? Do it again. Perfect. Can you just put it right here? There you go. It jumped. So, both my kids were recently involved in a science fair. And my son's project was on using sonar to detect blind spots on a car. And as you saw in the video, you know, he did a lot of work himself. He needed a little more assistance than my seven-year-old daughter. He's four. But he really did hook up a lot of that himself. Obviously, I uploaded the code and actually was going to write my own code for that. But the example code I found online worked for exactly what we were doing. And so I uploaded to the Arduino. But as far as creating the thing, as you can see in the video, you know, I basically... I would plug in like three wires and go, look at these. Okay. And I'd unplug them and say, you plug them in now. And he did that. And he did a great job with his little tiny fingers getting them in there. It was painfully slow to watch, but he did it. And then I helped him obviously tape things down. But basically what you saw in the video is what he did. That's why I recorded it to show, you know, even though he needed a lot of assistance through it, he did do it all himself. And as far as his presentation, he did a great job considering he's four up in front of people. The original situation there was going to be people coming around to table to table. And I wanted their projects to be very interactive. In the end, they changed it last minute to be you're up in front of everybody presenting, which was a little different for him. Well, not different for him. He does that quite often at school, but it wasn't what we originally were planning. And he did a wonderful job. Very, very basic explanation. He basically just said, this is a car. It uses sonar, which is sound to detect when something's there and lights up an LED. It's basically what he said in his presentation. It wasn't much more than that. But he did a great job. And I just wanted to share this video of him getting it all ready.


Hello, improvisers. I'm Mary Tiskevich and I'm going to show you how to use your improv superhero skills for good and create heroic communities where you are. Fort Mason is a historical place of embarkation. Isn't that a great place to launch heroes? So many things have been launched here, drama, adventure, ships. So why not heroes? And heroes need to start with the journey. So I just am so grateful to be here today. So I've been thinking about heroic improvisation for a long time, so I see it everywhere. So I'm going to give you an example of a story of something that I saw a year ago on a YouTube video that went viral. Maybe some of you saw it. It was a Logan, Utah, a traffic accident. There was a motorcyclist who got hit by a BMW. And this was all taken on amateur video. So you get to watch the whole thing. So you see it's smoking, the BMW is smoking. You can see that the cycles underneath.   And they decide to lift the car. That's ultimately what happens. And you'll see this in a video in a minute and 30 seconds. And I have a website, heroic-improved.com. And I'm going to put the link up to that. There was clearly no time to wait for any help. I mean, it was smoking. And I watched how these people were solving the problem. So the construction workers were figuring out the physics, the petite college-aged woman was scouting, she was getting down on the ground and looking and giving a report back of where the guy actually was. And so the first, in the short video, you see the whole thing. The first attempt with a dozen people doesn't work. Not enough. So then a dozen more people show up. And they move it. And then as soon as it's safe, someone goes underneath and grabs this guy and pulls him to safety. And the car continues to burn. I mean, it's really super cool to see. And I find this story inspiring. And people moved up to make something happen, even though there was danger. I saw a group of people responding powerfully to catastrophe together. And these are people who never worked together before. They never practiced this particular scenario in real life or in their imaginations. But together, in that moment, they responded in a way that was unexpected but effective. In this story, I say you see the new hero. So the new hero is one who collaborates and helps all of us to be a heroic group together. The new hero is someone who can build a team quickly. The new hero listens, perceives, and focuses the action of the fast-moving situation. The new hero understands fear and uses it as a jumping off point instead of a barrier to action. So what happened in Logan, Utah, I want to happen all over the United States. I want many, many people, citizens, emergency professionals, and elected officials to have the opportunity to practice responding to catastrophe in a group together. I have a PhD in public administration, and I'm fascinated about how government works. So how government works in a crisis is even more interesting. So I've been studying in the last 10 years. I just went right into American emergency management. I wanted to really understand it. And a core concern of emergency managers are, how do you get people to practice disaster and not wait for an actual disaster? How do you do that? And it's not ideal for someone to respond to a catastrophe without any practice. But unfortunately, that's what happens often, especially for elected officials and citizens. For many elected officials, the first time they're learning about disaster response is when they are in charge during an actual disaster. But don't get me wrong, American emergency professionals are really well trained. They have plans, and they exercise them often. Emergency. But even for these three groups, there's a gap in practicing what happens in the very first moments of a catastrophe. In the first moments of a catastrophe, there's a lot of chaos, there's a lot of confusion. Usually in a catastrophic situation, a single person cannot make a large positive impact. It must be a group. So heroic improvisation practices the group effort of people working together to listen and observe what's going on, to choose to trust the group and pick a focus, and then move into action, despite the uncertainty, chaos, and maybe danger. So as a researcher, I've been focusing on how to prepare elected officials better for disaster. And I was working with a collaborator at the Arizona State University's Decision Theater in creating different types of disaster exercises. Our hypothesis was, hey, if we get a lot of modeling and simulation, and put the elected officials in a room with all that data, they'd make better choices. So we had the opportunity to run that exercise. So we put them in a very information rich environment. It's exactly how you would imagine. You know, it's an emergency center, and there's all these screens behind them, the disaster unfolding data feeds, all kinds of stuff. And this particular exercise was about pandemic influenza. So the question of the exercise is, when do we close the K through 12 schools? It's an important choice that has profound implications for pandemic influenza, because the schools are very related for how a pandemic would go through a community. We did this exercise in Phoenix in February 2009. The officials really got into the plan during the exercise. They understood through discussion that there were vulnerabilities and assumptions in the plan that weren't clear. There was a lot of different jurisdictions in the room. There were the medical officers, there was the governor's representative, there were school officials. In the exercise, the officials worked out who made the voices, who communicates those choices. And it wasn't clear in the plans or in the law as written. So they had to work it out and they worked it out in advance during the exercise. Again, this happened in February 2009. Only researchers would be excited about this. But two months later, pandemic influenza shows up in Phoenix, Arizona. And I'm really excited about it. Yeah, disaster research. Oh my gosh. But because of the exercise and the real practice that the elected officials and emergency managers did together, they were confident in their response to put pandemic influenza. One of the assumptions they practiced was, what if pandemic influenza is not virulent? What if it doesn't kill people like the last one did in 1918? What happens then? What if it's more like a seasonal flu event? They practiced this in February 09. So when the pandemic influenza shows up, the elected officials see the data and they're like, Oh, this is really like a seasonal flu event. And we practice this. So they made choices, confident choices, both from a political point of view, and from a public health point of view, to keep the schools open during the pandemic influenza. And it turns out their decision was backed up by the Center for Disease Control, whose own plan was not as well exercised as Phoenix, Arizona's, because they never looked at the option that people wouldn't die. Everyone equated pandemic with a lot of people dying. And that plan was never exercised. But this plan was. So yay, I was very excited about that. So my partner, we really saw that we had a powerful way to get decision makers together. And it turns out that the most difficult hurdle for emergency managers is just to get the elected officials to show up. I mean, it's really a problem. And so this was our exercise was an attractive way to get them to show up, play for real play for four hours, learn things and most importantly become a team. And then when the catastrophe hit, they were ready. So based on this, we found out that yes, modeling and simulation helps. But the most powerful tool to get people ready for catastrophe is to get them together in a room and play for real to get them in a room, and have them play and play for real, like not pretend like you're in a catastrophe right now. And that's what the that was the example of the Phoenix people is that they played for real, they made real political choices, they chose real roles for one another. And then they implemented that when the actual catastrophe showed up. So at the same time, my mother gets back onto the community theater stage in her 70s. I'm a total fangirl for community theater. I'm just like, I'm so amazed by the talent and capability that I saw. A few people are paid, they have a director, they have some technical staff, but everyone else is an amateur. And then they they mount this really credible, entertaining, complex endeavor known as community theater. And it inspired me to think. Why do we need special effects? Why do we need all this virtual reality? Maybe all we really need is people's imagination to be in a situation where the plane for real, and we could use this in disaster exercises.  And so making choices. So I've studied decision making. And I'm always about making the perfect choice. So I tried theater improv 20 years ago. And I had such a paralysis by analysis that I dropped out. I was like, This is too hard. I'm too freaked out. I can't do it. So what drew me back to theater improv is that it's practical for this situation. It's disasters are inherently chaotic. A disaster happens uniquely in a local place and demands high stakes political trades to deliver resources. So these circumstances need flexibility, speed and creativity in the moment. The response choices cannot be modeled by a computer. The better analogy was improvisation is demonstrated in jazz music and theater. So I stepped out of my research comfort zone. And I tried theater improv again. And like Delclose advises, I followed my fear and practice fearlessness with my improv partners. So in my two years study of theater improv, I've come to the insight that theater improv in a group is very related to catastrophic decision making. So and here's how first during a disaster, there's a group of people who are in a lot of confusion and chaos. Just like in the beginning of an improv scene, we start in the middle, we're not exactly sure where we're going. Second, during a disaster, people are scrambling, they're using their brains and their senses to understand what may be happening. Just like in the early moves of an improv performance. Third, during an effective disaster response, people form a team that connects, chooses a direction and then moves into action, just like the guidelines for improv performance. So in regular life, the team is only as strong as its weakest player. But the team is as strong as its strongest player. And anybody could be a strong player. And that's the person who chooses boldly and focuses the action. And then that focus shows a common direction that opens up other possibilities for participation. So one of the glaring missions in emergency management training is neither elected officials nor emergency professionals are actually forced to choose together in an urgent situation. They practice in conference rooms and they flip, they literally flip scripts. They still use paper in planning, disaster planning. So one of the things I noticed in my own experience in theater improv in scenes and showcases and performances is right off. You're in chaos, you're in chaos and uncertainty, which is exactly where we want to put all these citizens, emergency professionals, and elected officials. So my improv collaborator and I have come up with a series of exercises that we call heroic improvisation practice. And we decided that everybody who has a role would start with a foundation of theater improv games. And they would first learn to listen, second to choose to trust and find a focus, and third move into action quickly. So after the first level, we would move them into a second level, which would be creating a spontaneous team, just like Utah. And in the third level, we would help people create a team in a plan. In the fourth level, we would test a team in a plan, which is what I told you happened in Phoenix, Arizona. And then in the fifth level, we would really use theater special effects to test a plan and a very experienced team. So what I love about this is everybody can take this practice into an unimagined situation right away, because we're focusing on a process and building a habit. So I want to thank you for all your improvisation that you've done up till now, because I believe it has the potential for heroism. And I hope through this talk, you can see these opportunities move into them and bring your community with you. Thank you very much.


What kind of full love when I've got feet? You know, this is such a common issue that I see in people with two feet. You're wandering around, you're trying to find love. People say, put one from the other, it's going to be okay. Just keep walking, but your foot always winds up in your mouth. And what is common in all of these scenarios? That's right, feet, which is why I think if you really are looking for love, you should maybe try cutting one of them off, right? Is it possible? Think about it. Is it possible that feet are holding you back in your love life? Yes, it is possible. So maybe it's time to take a leap of faith. Step out, have some courage and try something new.


Hi, this is Brandon Moore. I'm from North Adderborough, Massachusetts, and you're watching DJV Trucker Josh vlogs on YouTube Monday morning everybody. It's a beautiful sunshiney morning. Let's say it's gonna be a beautiful day. Hope you had a good weekend Get back to trucking Got us a tri-axle 53-foot roll tight today Got to bring this up to Woodlands, Manitoba Which is northwest of Northwest of Winnipeg, yeah, up highway six, I believe. Got a whole load of this steel Looks heavy. Just gonna walk around here and check all the straps. Make sure that they're still tight All the way down here to the back Some more space on the other side Probably took the most difficult way, right? Let's check this all out I'm still gonna wash these trailers on the inside tight tight Whoever brought this in was really diligent with the straps. That's good to see Everything is very tight as it should be with a load like this This load's probably pretty heavy. I'll check the paperwork, but it's pretty heavy There we go and usually this load would have to be tarped, right? Hence the roll tight. I love these trailers I really do they can be a real pain in the butt sometimes like they can be a Especially in wintertime and when the rollers aren't working properly and you got to be careful with them because they're really fragile So you can't force them to do anything. They don't want to do you sort of got to sit there and talk them through it and convince them to open and close sometimes or sometimes you need two guys, but Definitely is worth it to me really It's just easier than tarping so much easier.  We still do tarping but compared to what we used to do Rare very rare. So just remember when you hook up to a trailer that somebody else loaded Whoever did this did a fantastic job but Never trust anyone Okay, doesn't matter who tied it down when you hook on to a new trailer go in there and check it all Okay, because I've missed things before too when I'm loading other people miss things to double-check my work I'll double-check yours because now that I'm hooked on to this load this load is mine So if there's anything wrong with it My responsibility can't blame it on the guy before me. Oh, he didn't tie it down, right? So when I tie a low-down, I leave it in the yard here and you hook on to it make sure you double-check it Make sure I didn't miss anything You can see the door behind me there in the in my mirrors I've got a back in there inside the building They're just clearing space right now and making room for me and then I back into the building They close the door I open the trailer and then there's a big overhead crane that rolls along the top of the building and They lift the steel off Off the trailer and put it on the ground beside the trailer and then when I'm done I close up the trailer and I drive out Easy as that and it's all indoors. I really like these receivers and shippers when they do this And it's one of the only ways to unload such heavy and large pieces of steel otherwise you'd need a massive forklift outside and It kind of defeats the purpose because if it's raining you can't unload or load the trailer then because this steel can't get wet That's why it's in a covered trailer And you can't put it in a van trailer because they have to look unload it from the top because there's no way to Unload it from the back and pull it out the back. It's too heavy They could probably create some kind of system for that, but it's just easier this way so once they open that door behind me there they're gonna guide me in and I'm gonna start unloading Shouldn't take too long once I'm in there We're all backed in now.  Not like this would do much to prevent injury from These things they're pretty heavy, but you know just in case oh here comes the crane right now Can you see it already?  It was a little bit different than I thought it that I thought it would be I thought they were gonna unload it right off the truck with the overhead crane They were actually unloading one little bundle at a time with a forklift Putting it on the ground then picking it up with that overhead crane and then putting it away into storage on the other side of the Building over there so lifting it up and over all the other stuff and then putting it behind I guess maybe rotating their stock so that the older stuff gets used sooner Sort of what it looked like anyways, but Pretty neat either way. I get to see that kind of thing all the time Makes the job fun when it's something different every day Now I don't know what the rest of the day has planned. It's About one o'clock or so By the time I get back, it'll be two Maybe we'll do one more thing today and Some pretty big news everybody. I'm gonna try not to get all choked up while I tell you this Because I got pretty choked up when I got the news myself Ah How can I say this? This Peterbilt is soon going to be replaced by a Kenworth W900 In this shop. I just bought the truck I've wanted For 26 years Let's clarify something. We haven't signed the paperwork yet But we have all of the eyes dotted all of the T's crossed. I've gotten my approval I've gotten everything together that I need to have together And we've gotten all green lights as of four o'clock today, I Am buying a 2008 Kenworth W900 L see me flat top sleeper or mid roof what they call it It's blue to match my motorcycle and I've wanted this for 26 years Since I was eight years old when I decided I'm gonna be a truck driver one day I've owned a couple of trucks in the past already, but it's never been the one It's always been a truck of convenience a truck. That's available now I've owned a couple of trucks in the past. I've leased one. I've owned one and I know what headaches await me in the future, but this one's different. This is a headache that I chose hand-picked I Found the truck the truck. I'm so excited to show you guys Hopefully within a week. I can show it to you and do the big reveal Here on my channel But this is a this is big big for me Other than you know getting married and meeting my wife Career-wise as a truck driver This is going to be the biggest day of my life when I take that truck home and I got couches in my shop Have you noticed I almost forgot to tell you that who cares about that right? I'm getting the Kenworth W900, but there's a couch is here who cares about that Kenworth So Yeah, I want to have it up and running by June 1st So we got to get plates. We got to get registration licensing if we got to get decals or as you Americans call it decals They get the truck all All done up with those and I'm going to be running as an owner operator on regional fleet at Keystone Western. So I'll be home every weekend Most likely home one string the week to most weeks Depending on how much money we want to make It's a 2008 It's got a rebuild about 600,000 kilometers ago a full rebuild on the engine everything done That's So it's got about another three four years on the engine before I have to start thinking about rebuilding it again Yeah, I'm Almost speechless right now. I'm I don't know what to say when I got the approval at like four o'clock It was like 402 that will be a time that will live in infamy in my mind at 402. I got the phone call and they said Josh She's yours All you got to do is come in and sign and you can take her home So hopefully next weekend or so. Maybe we can do a tour show you guys the truck I have so many plans for the truck what we're going to be doing with this truck and the reason I'm so excited. We're going to be building it into a show truck I'm gonna take it to as many shows as I can as I can afford to go to because I still got to make money so we're gonna have to pay for it and We're gonna build it from the ground up build it and Stretch the frame We'll worry about all of that later. We can talk about that at a later date right now. Let's just get it here I've got these coaches here not because we've got new coaches coming in the house, right? I've got these coaches here now where we can just sit right here and stare at it as soon as it gets here This Peter built I've shined up quite a bit. I'm actually kind of proud of the work. I've done to it It is better than I found it and the next driver who gets into it will have a better nicer looking truck Then I got into when I got into it. That was my goal leave things better than you found. Always make them better Whatever it is you get given something to use take care of it and make it better in in some way Even if it's just small or if it's bigger like this That's my big news I got through it without choking up so that's good that means I'm doing it Very excited. I'm very excited. We're gonna be back on the road another Big exciting thing is that diesel is gonna be back in the truck with me as soon as that thing's on the road Me and diesel will be back on the road We won't be going as long distance as we did in the beginning long ago. I have a family at home now and we're gonna grow that and we're Looking to have a couple of children as you guys know. We're building a house. That's still on Track we want to build by 2027. Don't worry buying a truck doesn't slow that down. It doesn't affect that at all We're still good because the truck makes you money So that's still on track. We're still gonna be building a house and starting a family And I'm gonna be home every weekend and probably once during the week as well We'll see how it goes, but I'm very very happy Brits happy. There's the big news Surprise, but I am gonna leave you hanging on a few things. I'm not gonna show you any pictures yet My family and close friends have seen it already but I want you to stay tuned because as soon as we sign the paperwork and I take possession of it I'm gonna do a tour of it This is starts a whole new chapter on my channel here as well because we're going to be building this truck into a Show truck together here on this channel.  This is what I'd like to do to the truck. What should we do first? What should we do next? You'll have a say in that we'll have a vote and together we'll build this truck My dad wants to help me build this truck as well. So here in this shop is probably we're all Everything's gonna happen so whatever me and my dad can do together we're gonna do and We'll do it right here on YouTube with you as well And if you guys want us to do stacks first Well, then we go and do the stacks we'll go buy the stacks and I'll take you guys along when we go buy them as we bring Them here and the whole process of installing them and Then we'll do a vote see what we do next. Well, should we do the visor next? Should we do a air ride front suspension next should I do a bumper next fiberglass rear fenders? Next mudflaps the whole rear assembly here Chicken lights and chrome to the moon That's what I'm talking about and so it'll be a whole new step for us as a family here on YouTube and definitely a whole new step for me and my family here in the Manitoba as well That's the big news. That's all I got to tell you. There's the biggest news I have delivered on this channel so far yet I hope you're as excited as I am if you haven't already Subscribe because the future is gonna be a lot of fun. You don't want to miss it. What is this?  So could it be? sunlight So I'm in a good mood Just want to wrap this up. I know my vlogs lately have been Lacking compared to what they have been in the past I've had a lot of things going on. Obviously we bought a truck I'm gonna wait to give you the tour of it though. I'm gonna be trying to release my videos Every day like the next day now cuz right now I'm filming a video this video is from Monday So it would usually be released the following Monday and I really don't like doing that because then It feels very I feel very disconnected You know, especially when I go read the comments that the vlog is new for you guys But for me it happened a week ago already, so I'm reading your comments I'm trying to relate to what you're commenting on I'm got to think back and remember what happened that day and It's confusing for me. It's confusing for you. The only reason I do it is because it's very convenient It's very nice to be able to you know get back at the end of a very long day and not have to edit I still have a video to go up tomorrow because it's last week's video and then I can edit all my videos on the weekend instead of every evening Freeze up my evenings during the week, but it bogs down my weekends So I don't have a full day on the weekend is just gone to Editing videos whereas if I just spent like a couple of hours every day my evenings are gone But then I have my weekend. It's trying to decide what works best for me here And I'm gonna have gone back and forth like this over the last ten years and so we're so quite a few times And I think we're gonna go back to releasing the next day So you're gonna get a vlog dump this long weekend may long weekend I'm when I'm filming this clip right here. It's Sunday of may long weekend. You guys have a may long weekend where you are We do now with the date to May 21st something Beautiful weekend out here though So you're gonna get a vlog dump today and tomorrow from all of last week and then we're gonna start Releasing videos from the day before so when you watch a video on Tuesday that will be my day from the day before Monday you'll watch Tuesday so you get Immediate like that's as quickly as I can do it because I still have to you know Live the day film it and then edit it and then release it at a time when you guys are mostly all of you are awake So that we could watch it and you don't miss it and it doesn't get lost in your feed So that's we're gonna try that it's a little bit more Go go go for me that way, but I think it'll free up my weekends more Either way I got to get these videos edited right neither way. It's a lot of work, but I've been doing this for a long time It's something I really enjoy doing so we're not gonna stop So I just got to decide when when I want to do my work Kind of nice I'm sort of self-employed with this year. Thank you very much for Putting up with all the ads that you see here on YouTube all of the money. We've made from that in the past a Year or so has gone towards our IVF procedure And we're still Waiting on that there's still a few more things we got to go through so there's no news on that yet But the money we've made off that has gone towards that So I appreciate your patience with all of the ads that you've been seeing in my videos. They help us out for that and in the future a lot of that money is going to be going towards this new truck and Getting it ready for shows new accessories. Well, we'll see what happens really The truck is the big news though and right now I'm just waiting to take possession of it everything's done finished and We should have it. I'm thinking by the end of this week. There's just a bunch of work that has to be done to it first They got to get it safety. He's changing the transmission fluid Diff fluid putting a new bumper on the front for me because that one that was on there was bent Polishing the truck Then we got to get it licensed and everything takes a few days Get the decals on there. So Coming soon, but I'm not gonna share what it looks like until I actually have it That's that I'm gonna leave you in suspense and I got to leave some suspense I couldn't keep my mouth shut about buying it, but I got to leave something something for you to wait for, right? Yeah, it's exciting. Let's see how we do with this next day vlog thing if it doesn't work for me We'll just go back to the week a week later But I do like it better Doing it the next day that that is my preferred way It's just a little little more work for me during the week, but it's okay. We'll see what happens. Thanks for tuning in everybody Don't forget to hit that subscribe button, especially now. I really like I said earlier I really do want you guys to be involved in building this truck I think we can find some creative ways to get you in the audience involved in what we're doing and and when and What our projects will be on it and Together we can build it up and then I'll have it a few truck shows Maybe I'll come through through your town to a truck show near you and then you can come and meet us there and see the truck in person and We shake hands hang out for a bit When we were at truck world, I really enjoyed meeting you all of you people who did come out to see see us there And all the people I met there It was a lot of fun and that was part of the reason why I wanted to pull the trigger on this truck now too because I Want to do more stuff like that I want to bring this truck around to the different truck shows and meet you guys hang out and Get to know you a little bit too, you know me pretty well You see me on this side of the camera. I don't see you there So it's nice when we get to actually meet and talk in person Looking forward to that in the future. So stay tuned. Please don't forget to subscribe if you haven't already It's gonna be a lot of fun We'll talk to you later in the next vlog that will probably be about four or five to get released


Okay, I want to start off with, so today we're going to talk about anions and really what we're talking about is proton transfers. It's a way to get to anions and think about proton transfers and maybe the nucleophilicity of the species that you can generate.  This is the kind of reaction that you see in a sophomore organic chemistry textbook. And let's talk about this mechanism because it's not so simple. It's kind of stunning that this is the kind of thing they ask in introductory organic classes.  So you have to think about the things that have to happen here. We've got to get some sort of an oxygen nucleophile to attack water at that carbonyl group. We have to somehow get the phenoxide, the phenoxy group to sudden kind of a state where it's willing to act as a leaving group. And so that relates to proton transfers. So right off the bat we've got a question. What do we do first? Do we protonate the carbonyl first? Like a fissure of stratification? Or do we attack the carbonyl? This is a particularly easy kind of carbonyl to attack, a formate ester, much more reactive than regular esters. And so how do you decide? So notice I've asked you here for the mechanism. I don't do that on the problem sets. I don't say what's the mechanism for this reaction. I've never done that. I always ask you what is a plausible mechanism for this reaction. That's all I'm capable of asking you and that's all I'm capable of evaluating. So how do we decide which of these two starting steps is plausible? If you choose the wrong starting step the rest of your mechanism will be garbage. If you pick the wrong first step. You get to the next stage of the reaction.  Should I come along with my acid and protonate the leaving group like this and then use and then come along and deprotonate the water? Or do I deprotonate the water first, right? Of these two steps that we need to transfer a proton, pull one off, put one on, in what order do we do that? How do you decide that kind of stuff? How do you look at those kinds of proton transfers and decide if they're reasonable or not? So let's talk about proton transfer equilibria. That's how you decide. You know something about the equilibria of those proton transfers. So one of the things we had an earlier lecture where we talked about proton transfers and I tried to get across this idea that you should assume that proton transfers are fast. You should assume that all proton transfers are fast and facile. Any proton transfer I've drawn here, you should assume it's fast and facile. And so it boils down to not is it possible for a phenoxy lone pair to pull a proton off of some acid? Yes, that's possible and yes, it's fast. What you should ponder is the equilibrium for that process good. So now let's talk about how do we estimate the equilibria for a protonation of an ester, for a protonation of an ether? And I'll give you two ways to estimate equilibrium ratios and that's what we care about. It's ratios that are intuitive. I have 10 times more money than I had yesterday. I have 100 times more electricity running through this wire. We think about ratios. That's easy to think about. Okay, so I'm going to give you two scenarios where I expect you to know how to use pKas to estimate ratios of protonated versus deprotonated species. And I'm going to start off with buffered conditions. So if you're a chemical biologist, these are the conditions that should matter most to you. You've got some sort of a buffer that either soaks up or delivers protons in order to keep the pH constant. And those extra ions, your buffering ions are present in large concentrations relative to the substrate. So let me go ahead and take an example. This will be a very organic molecule, not very biological. But the point is that when you're under buffered conditions, you have to pay attention to the pH of the solution. So we'll look at deprotonation of this nitro ketone. Very acidic. So to have this nitro group at the alpha position, which is already acidified by the carbonyl, it becomes way more acidic when we have the nitro group on there. It turns out that these protons here have a pKa of 8. That's the pKa of those protons. And so what's the ratio of protonated to deprotonated in solution? Is it reasonable for me to predict that I'm going to deprotonate to make an enolate anion and that that anion is going to attack? Well, it depends on how much is in solution. If there's a lot of it, then yeah, it's probably reasonable that that's a nucleophile floating around. And if there's very little of it, well, then maybe that's not such a reasonable mechanism. So the way you decide what the ratios of these are is you have to know something about the pH. And here's the way that I do this. I'm going to make a little chart here. And we'll just imagine that I know something about the pH of the solution. Let me make a list of pHs here. And I would expect you to be able to estimate the equilibrium ratios at any of these pHs. But there's one pH at which it is easier to estimate the equilibrium than any other pH. And that's when the pH is equal to the pKa for that proton. When I'm looking at a solution that has the same pH as the pKa for my proton, I know for a fact that the ratio of these two species is one to one at pH8. So if I know the pKa and I know the pH of my solution, I can readily have this sort of intuitive sense for what's going on. Half of my substrate in there is deprotonated. That's a lot of deprotonated stuff that's floating around. What happens at pH9 if I make a pH9 buffer? What happens to this ratio? If I go into the lab and prepare a buffer that's pH9 instead of 8, it's one to 10. When I go up in pH by a factor of one, this is logarithmic here, when I go up in pH by a factor of one, my solution is 10 times more basic. So let's just write that down. It should be totally intuitive of you now that there should be 10 times more of the deprotonated substrate in there. Now what happens if I go to pH10? See, this is the kind of math I know how to do. I expect you guys to be able to do this kind of math. Now it's one to 100. That's about 99 percent. I don't know how to work that math exactly. But I would say that's about 99 percent deprotonated. About 99 percent of my ketone is actually enolated pH10. And now I can go backwards. What happens if I pick neutral solution? Let's suppose that I'm interested in physiological conditions closer to pH7. What's the ratio there? So now it's 10 to 1 disfavoring the deprotonated side and favoring the neutral side. Only about 10 percent of my substrate in there exists as the enolate. And notice I don't care at all about the mechanism for deprotonation. We're assuming all of that stuff is fast. We're assuming proton transfers are fast. Don't get caught up in worrying about whether proton transfer, gee, should I draw that arrow? It's always a good arrow to draw a proton transfer, a curved arrow. And the issue is the equilibrium. And as I become more and more acidic by factors of 10, you can see what's happening to the amount of the protonated species that becomes larger and larger. So I expect you, anytime you know the pKa of a lysine side chain, a cysteine thylate, any sort of species, a phosphate group on DNA, I expect you to be able to estimate the ratio of protonated to deprotonated. Most commonly at physiological conditions but in any buffer that you're given. I expect you to have an intuitive sense for, oh, yeah, at physiological pH about 0.1% of lysine side chains exist as the free amine and have a lone pair that can attack things. That's the kind of intuitive sense that I'd like you to have. So there's some equation called the Henderson-Hosselbach equation. I can't even remember the equation. It's somehow or another you can get these numbers out of that but I don't know how to do that. So if you can work that equation and come up with this intuition, then good. Okay, so that's buffered conditions. That's for chemical biology. And there's some organic reactions where you buffer things, not so common. So now let's talk about unbuffered reactions. This is organic synthesis. Hydrolysis of an ester. You're working up some butylithium addition or a Mukayama-Aldal reaction. These are unbuffered reaction conditions that you set up and put into your round bottom flask and stir. So how do we deal with this? It's totally different now. So let me just give you this simple generic equation for a proton transfer like this. I feel like we've talked about this already but I can't remember whether we've talked about it. And there's a simple equation that I can use to estimate the equilibrium constant for any proton transfer. And I just need two numbers to estimate the equilibrium constant. We're not going to argue about whether it's easy for this to pull a proton off. You should assume that's always fast. What you need to worry about is what are the relative concentrations of these species in solution? Okay, so let's go ahead and be more pre, well I gave you some sort of equation here. And I'm even scared to give you the equation because the equation is so much more complex than the actual math you use to solve it. It looks something like this. The equilibrium constant for any proton transfer is equal to 10 to the pKa of the, how do I do this? The product minus the pKa of the reactant. And that looks so complex it scares me. So let's go ahead and take a real example so I don't get too scared by those, that kind of complex equation. So here's a reaction that wouldn't work under buffered conditions very well. Now we're looking at making an enolate by using a strong base, t-butoxide, to pull off a proton. It should be getting t-butanol as a byproduct. And there's a potassium ion floating around. Don't worry about that. That'll be our next lecture, how to deal with that. So the way I would work this equation, the equilibrium constant, how much of each of these species do I have present at solution? In other words, we're not going to worry about whether it's plausible to draw deprotonation. We're going to worry about how much of that deprotonated species is there. There's some there, how much? And so now we're going to work this equation. The pKa for this particular ketone, and I'm giving you numbers for DMSO. It happened to be the solvent for this reaction. In DMSO, I'm giving you the pKa's for this, or 24.7 for the ketone. And we'll talk about the solvent issue later. And 29.4 for the t-butanol. Those are the pKa's in DMSO. And so when I work this equation, I go like this. The equilibrium constant equals 10 to the 30 minus 25, 10 to the 5th. So what's the ratio of deprotonated to protonated? Is it mostly protonated or deprotonated? So a favorable equilibrium constant like this says it's almost all in this, not almost all. But it tells you that the ratio is 10 to the 5th, I'm going to say 100,000, I want it to 1. That means over 99.99% of this exists in the enolate form. And I get that just from these two pKa numbers here. So again, we're not worrying about whether it's plausible to pull protons off with t-butoxide. We're assuming that's always plausible. But we need this sense that, yeah, 99.99% of my ketone exists as the carbanion enolate. There's lots of it in my solution. Okay, so that's the sense that I'd like you to have. Now there's an issue here that I want to point out. And this equation is completely valid under typical conditions. And that is that your equilibrium constant is only going to be as good as the pKa numbers that you throw in there. So I gave you an example where this reaction was in DMSO. But you very rarely know the pKa's in DMSO. Or THF, or hexanes, or dichloromethane. And so what do we do about this? What do you know? And what will you know? You're going to know the pKa's in water.  There are tables and tables and tables of pKa's in water. Somebody had a burette and they measured in something with phenolphthalein or some indicator. And they did titrations in water. So what I'll tell you is don't worry about the fact that you've mainly only got aqueous pKa's to work with. Use them anyways. You may be a little bit off where we'll talk about where you'll see differences between water and organic solvents. Even though you may not know the pKa and the solvent you're working with, use the water pKa anyways. It'll give you a good estimate and a good starting point. Okay, so I expect you to know ratios of protonated and deprotonated things. At every single stage in your mechanism where you've got a proton transfer step, you've got two species. And I'd like you to have an intuition for the relative amounts of those species and solution. So I'm going to give you a set of pKa's and I want you to memorize them. And there's no simple way around this. You just need to memorize these numbers. And more importantly, I want you to know the trends so that you can predict pKa's for vast numbers of molecules that I'm not going to show you here. So let me give you a set of pKa's. These are all aqueous pKa's relative to aqueous solutions. Some of them are extrapolated. And so let's go ahead and start off. What I'm going to do is I'm going to draw groups of molecules so that we can see trends. I'm going to group these together and I expect you to know these trends. So the first trend I expect you to know is the effect of electronegativity. So let me give you a series of compounds here. I'll start off with ethane and then I'll compare that to, let me draw this the same way, to methylamine and then I'll compare that to methanol. All I'm doing is I'm changing one of the, so forget about the fact there's different numbers of protons on the alcohol versus the methyl. What I really want to focus on is that I'm changing that second row atom from carbon to nitrogen to oxygen. I hope you already have an intuition that this atom becomes more acidic as I replace that with more and more electronegative groups. I hope you already know from your early organic chemistry courses that these are becoming more acidic going down this way and of those this is the most acidic. What you may not know is the numbers and so I want you to know those numbers. The pK for methanol, we're going to use a number 16 for an alcohol so it's actually, that's water, that's most alcohols, it'll range 15 to 17, use 16, it will never hurt you. It won't be a case where you'll be sad you didn't use 15.2 or something. Okay so an amine, the NH on an amine, very hard to pull those off, to pull the, that's LDA, lithium to isopropylamide is pulling the proton off of this. You get an amide anion, nitrogen with a negative charge, very difficult to pull off, 20 orders of magnitude less acidic than an alcohol. Okay finally you get to a simple alkane, there are no reactions that allow you to deprotonate simple alkanes. You should consider that to be the least acidic type of proton that's out there. So pK of 50 relative to water, 34 orders of magnitude harder to deprotonate than an alcohol. Okay so that's electronegativity. So the second type of trend I want you to know about and I want you to remember these numbers would be resonance. How does resonance affect pK? So let me go ahead and start off with that ethane molecule but instead of ethane I'm going to attach a C-C double bond on there. So now if you deprotonate this you'll have this allyl anion. So resonance stabilized allyl anion if you deprotonate that methyl group. And so how would we compare that to an amine versus an alcohol? All right and don't worry about the fact that there's a keto-toddomer that's more stable. You will see exactly the same pK if it's phenol it turns out. You could never have guessed that. Phenol and vinyl alcohol have the same pK. This and aniline same pKa. So the pK is now so I hope you know that this is the most acidic of the bunch the alcohol again there's an electric really we're just changing to more electronegative atoms as we go carbon, nitrogen and oxygen. So now we get over here to this vinyl this enamine is the name of that functional group and the number for that is about 28 so aniline an amino group on a benzene ring will have a pK of about 28. So significantly easier to deprotonate an amino group on a benzene ring than just a simple amino group. Then finally we get to a simple allyl like how easy is it to make an allyl anion? It's a billion times easier to deprotonate allylic CHs than just regular alkane CHs like the ones you have on your hexane solvent. So you're not going to deprotonate your hexane solvent but with the right base you can medilate here on an allyl position. Okay so we can make resonance worth more if I replace this CC double bond with a carbonyl group. That ought to be a better resonance stabilizer for any kind of an anion. I expect you to know the pKa for the alpha positions alpha to a ketone that's what this is. So now we're just talking about the pKa of acetone and I'm going to give you a number of 20 which is a good sort of average value for ketones, alpha to ketones. Okay if we look at an amid, if you're interested in the peptide backbone and understanding how easy is it to deprotonate the NHs on a peptide backbone or a protein backbone it's not easy, it's not impossible but there's a pKa of about 17. So a physiological pH of 7, you know, maybe 1 out of every 10 billion amide backbones is deprotonated. That's not very many. That's a very low concentration. And then finally we come over here and replace this OH or this double bond in this vinyl alcohol with a carbonyl group and we have a carboxylic acid. And that pKa is about 5 for carboxylic acids. It doesn't matter if it's 4.8 or 4.76. Okay so you can see that you see more of an acidity effect with carbonyl groups than with simple Cc double bonds. You should have expected that carbonyl groups are better resonance acceptors for anions. Okay so you need to know those numbers. Those are super common compounds that represent classes of compounds. Let's keep going with our trend. So this is a concept that we've already talked about. So this isn't as many numbers as you might think it is because look I'm giving you the same number. I just gave you this number. What is it for ethane? Fifty, yes, same for hexanes, cyclohexanes, all pretty similar, close enough. So we already talked about 50. But now what happens if we put a double bond in here? It's not the same anymore. Or if we come over and we put a triple bond in between these. So we're changing the hybridization of the atom. And so what happens to the acidity of these? They're going to become more acidic. And it can be quite dramatic here, the effects. Again these are all CHs. There's no resonance, anything going on, atoms with higher P-character. So if you look at the carbanion here, you know the carbanion that you would get by deprotonating this is very nucleophilic, very reactive and very unstable in a way. It's unstable. There's lots of P-character here. But as you reduce the P-character it becomes less reactive, it becomes more stable. So finally when we get down to SP-hybridized carbon, now there's not all that P-character that makes things so unstable and reactive. There's plenty of 50% S-character here in this alkyne lanion. And so that's what's accountable for this and what is the math here? 26 orders of magnitude of acidity. All the same atom, carbon. And we're just changing the hybridization. So I hope by now in this class you respect the effects of hybridization on reactivity, this gives you a sense how that affects acidity. Okay, let's keep going. This won't really make sense unless we walk back and we compare it to the amine way over here. See this methyl amine? PK for methyl amine or diisopropyl amine or any NH on a regular amine is about 36. And so what difference does it make to have a positive charge on the amine? So now I'm talking about a different compound. Not an amine, I'm talking about the PK of an ammonium ion. This is one of the most common mistakes is to confuse an amine for an ammonium. Amine NHs are very hard to pull off. You need butylythium to deprotonate a simple alkylamine. This, anything can deprotonate, well not anything, but just about anything can deprotonate that. And the PK of this is about 11. That's a lysine side chain in a biological context. And so what about a protonated alcohol? Well, protonated alcohol is a little lower, but a protonated ether. You know, it's protonated alcohol is about minus 2, minus 3, protonated ether. Again, the important point is the effect of charge. If we compare this to an alcohol, you know, it's pretty acidic, but when you have a positive charge on the oxygen, it's very acidic. So it's very easy to pull protons off of oxonium ions. That's oxygen with three bonds. We call it an oxonium ion. Okay, so what are some more, let me keep drawing some more species. So I have an ammonium ion. What about an aminium ion? So we talked about aminium ions as reactive intermediates. It's much easier to do nucleophilic attack to aminium ions than carbonyls. The whole field, not the whole field, most of the field of organocatalysis is aminium ions. So these have PKs on the order of about five to, I'll just give you the number of five. And it's not, right, it's not the fact that there's just a simple isolated amine. If you look at the PK for this, for pyridinium, it's five. It's the same. Aminium, pyridinium, it's about five. Okay, protonated oxygen on a carbonyl group. Now it's very, very hard to protonate that. It's extremely hard. If you want to protonate, I'm talking about simple ketones. If you want to put a, protonate a simple ketone, what you see people doing is they add sulfuric acid or hydrochloric acid, serious business acids minus seven. Incredibly hard to protonate the carbonyl of a simple ketone. And let's put these into context. And I, it's like, I don't know why I have this here. I, maybe just you can seem like a no at all. But if, if 16 isn't good enough for you and you somehow need to know exactly the PK for water, you can use 15.7. But I've never had that be any better for me than, than 16. So if you want to use that. The main point here is I want to compare this to hydronium ion. So we know a number for that. And that's minus two, minus 1.7. So remember somewhere here I noted this, oh, this difference. That if you have an, a protonated here with two alcohol groups, it's minus four. Hydronium ion is minus two. And a protonated alcohol where there's just one alcohol is right in between, minus three. But again, I, you know, if you just want to memorize kind of minus three for an oxygen with three bonds and a proton, I'm sure that'll always do you right. Okay, so next trend, the last, no, two more trends to talk about. These are the kinds of numbers where you're going to be in your oral's exam and they'll be at the board drawing something out. And then suddenly you'll hear this question from them in back of you. What do you think is the pKa of that pro, and you'll turn it on and be like, four? And your committee will look at each other, right? They'll wonder why you didn't remember that, that number. So this isn't just for this class. You guys need to know these numbers in perpetuity. Okay, so obviously I'm talking about getting to bigger and bigger atoms as we drop down from second row to third row to fourth row to fifth row atoms. And you'll see a concomitant increase in acidity, aqueous acidity. There's a huge leap when we go from, and this kind of corresponds to leaving groupability. There's a massive leap when we go from fluoride to chloride. So HF is not like hydrochloric acid. It's nothing like hydrochloric acid in terms of acidity. What it has is a nucleophilic counter ion, fluoride. So HBR, and one that's very basic. It's not that different from HCl in terms of acidity. I can't think of in many cases where you get anything in terms of acidity by switching from HCl to HBR, what you get is a more nucleophilic counter ion, bromide. And if you switch to HI, again, if you just want a stronger acid, you're not going to go grab a bottle of hydroiotic acid instead of HCl. You'll go to sulfuric acid. Okay, so finally we're down to, I think, the last important comparison for this series. And that would be thiol versus alcohol. So alcohol has a pK of about 16. What happens when we drop from the second row OH to the third row, SH? So now the pK is about 11. And the pK is actually very considerably depending on what's attached there. So this is getting close to a cysteine side chain. You'll see numbers in the 9s sometimes for the cysteine side chain on protein. pK around 9, so there's considerable variability here. When you start to put polar groups nearby, you'll see that pK drop a little bit more. The important point is it's 100,000 times or more acidic than a regular OH. It is very easy to deprotonate a thiol. If you take any thiol and you put it at physiological pH, there is a substantial concentration of the thiolate anion in solution. And they are super nucleophilic thiolate anions. Yeah, that's a crappy drawn ethyl, badly drawn ethyl. Okay, so now polar effects. You might call these inductive effects would be the term some people would use. Here's a cool number because we have so many tetrahedral intermediates that we're interested in. How easy is it to deprotonate species like this where we have, well, whatever, where we have more than one electronegative atom attached to the same carbon. So when you look at the pK for this, you kind of should expect that it's easier to deprotonate this OH when there's an electronegative atom close by. And what you don't know is how much easier. The nearby electronegative atom should make it easier to deprotonate that. And it turns out the pK is 13.4. So it's the number I keep in mind is 1,000 times more acidic than, but I don't know that the 0.4 really matters. So it's easier. You might have known that. You might not have known how much. Okay, let me redraw a molecule that I've already drawn for you. So what's the pK of this one? Five, yep. I'm trying to understand why I wrote these decimal places because I'm just going to write five. I have 4.8 written in my notes. I don't care whether you memorize 4.8. Okay, now let me give you the number for fluorosidic acid. What happens if we put a fluorine atom here? Right now, if I deprotonate this proton, there's no resonance structure I can draw here in which the fluorine is going to help that. If there's any effect of fluorine, it's kind of like a through space interaction. You know, the nucleus has more protons in the nucleus of fluorine, so it's more positive. That'll help stabilize negative charge way over there on the carboxylate. So that fluorine ought to make it easier to deprotonate here, and it does by this much. So it goes from 4.8 to 2.7. It's 100 times more acidic to have that fluorine close by like that. And as you might guess, to have three fluorines, very electronegative, trifluoroacetic acid is close to zero. It's essentially zero. So 100,000 times more acidic than acetic acid when you see people use TFA, trifluoroacetic acid as a catalyst. Okay, so those are PKAs I expect you to know. You just have to memorize those PKAs. But the trends I expect you, those ought to be much easier. I hope by knowing those PKAs, you'll always be able to rely on some trends that you can extrapolate. Okay, I want to look at some trends here for alkyl lithiums. And let me start off by saying that it is not a bad conceptual tool, especially when you're first starting off. At this point, I don't really expect you to make this jump, but when you first start off in organic chemistry, you take your first year of organic chemistry, this starts to look very bizarre. It's like, what's this lithium carbon bond thing there? And so most books encourage you to think of this as a methyl anion. Trust me, there is no methyl anion in a bottle of methyl lithium. There's no free carbon anion. Every single carbon is bound to at least one lithium and it actually forms aggregates where it's bound to two. So people draw this because they just don't like that. They don't like drawing a nucleophilic sigma bond. But there's nothing you're going to do with this lone pair that you couldn't also do with this carbon lithium. So just think of this alkyl lithium is about the same in terms of nucleophilicity as you might consider that lone pair to be. And the main point I want to make here has to do with the basicity and reactivity of these species. I want to draw a trend here as we increase the size, the number of carbons in each of these species. So I've got a whole set of alkyl lithiums here. And if you think about basicity, what happens if you take a syringe that has methyl lithium in it and you squirt it into the air or into some water? It's not a real show. There's not a lot to see going on there. But if I take a syringe that has T-butylythium in it and I squirt it into the air, it will instantly burst into flames. The second the T-butylythium touches the water vapor in air, it so aggressively deprotonates the water that the heat it generates ignites the solvent and causes a fire. It's instant fire. There's a huge difference in reactivity. So if you look at, and how did I phrase this? This is reactivity, not stability. So if you look at the reactivity of these, the more alkyl groups that you put on a carbon atom increases the solution phase activity. And why am I being so careful about talking about solution phase reactivity? Because if you do calculations, and this is where I'm just pointing out that you have to be careful with calculations, gas phase calculations. If you do a calculation on just a single ethylithium molecule that you've drawn on the computer screen and you compare that, here's what you would find. Or carb anions. I'm going to switch this, instead of talking about this, I'm going to talk about alcohols. Sorry if you've started drawing that. Acidity. So T-butanol acidity, which of these should make a more stable anion as the way you can think about this? Isopropanol versus ethanol, because I think this will be more useful to you, versus methanol. If you look at the gas phase acidity of these, it's the opposite of what you expect in terms of substitution, it turns out that T-butanol is more acidic in the gas phase than isopropanol. And that's more acidic than ethanol and that's more acidic than methanol. It's the reverse of what you see in solution phase. T-butoxide turns out to be more stable than methoxide in the gas phase. In general, I feel like I pointed this out before with cations, in general when you look at the stability of larger molecules in the gas phase by calculations, they seem more stable. And let me give you a way of thinking about why is it that when you do computer calculations, that larger things end up seeming more stable. Let me go ahead and compare for you these two types of molecules here. I'll just start off with methanol or methoxide anion. The thing that will stabilize either of these two molecules is the donation of filled orbitals into unfilled orbitals. So over here, I look at, here's my nucleophilic orbital. What can it donate into? Well, it can donate into this antibonding orbital for the CH bond. So I'm donating now into sigma star for the CH bond. If that were really true, I would expect a little bit of nucleophilicity out of this bond. If I'm really donating into that bond and weakening in it, I would expect it to be slightly nucleophilic. And I'll show you later some reactions where exactly that happens because that donation is real. But now when I come over here and I look at this larger molecule, I can donate with this and that makes this bond more nucleophilic. And if I have another bond here, I can take that, those electrons, and now that nucleophilic orbital can donate into this one. And as I keep going, the more bonds I have, the more anti-bonding empty orbitals I have, and the more empty orbitals I have, the more chance I have to donate filled into unfilled orbitals. So in general, when you do gas phase calculations, you'll see this effect that larger ions, anions or carbocations, look more stable. But when you put them in solution, you don't see, you see almost no effect of that kind. Solvation becomes a more important issue. And we'll talk about salvation in just a moment. Okay, so I'm going to go ahead and, I added some little table here and I'm going to go ahead and skip that. What I want to talk about is the effect of solvents. What effect does solvent have on stuff like this? On chemical reactivity. So I'll give you some rate cons, some relative rates for a Finkelstein reaction. That's just a simple SN2 reaction where you displace a chloride with iodide. And we're just going to look at the effect of solvent on this SN2 reaction. So how does solvent affect this? So I'm going to give you a series of solvents. I'll tell you what the dielectric constant for these are and I'll tell you the relative rates, not the absolute rate constants, but the relative rate constants. As I compare different solvents, I'm going to start off with water, very powerful solvent. Nitromethane, very powerful. And then dimethyl formamide, I'll just write DMF. And then finally acetone. So I'm moving to grease here and I don't have numbers for hexanes. I guess that would be no further down the list here. What I would see is I go to, from polar solvents to less polar solvents is an increase in rate. So I'm going to assign relative rate for SN2 reaction in water as 1. If I simply switch to nitromethane, it's 14,000 times faster. You need to use this kind of thinking in the lab when you set up reactions. What if you could make your PhD 14,000 times faster? Who wouldn't want to do that? I go to DMF. Now it's 800,000 times faster just by switching to a different solvents. I walked over to the shelf, I grabbed a different bottle. And now things are 800,000 times faster. And acetone, that's a 4. So now we're 1.4 million times faster. So instead of talking about why it's faster, let me talk about why these things are getting slower as we go to more polar solvents. It's not all the solvent bulk dielectric constant. So water is the most polar in terms of bulk dielectric constant. There is a trend here. But you get to this stage and there's not an exact trend. There's something else going on here, especially when you look at the nitromethane versus DMF. Let's talk about water. That's the biggest jump. It's like why is water such a sucky reaction? What's such a sucky solvent for this reaction? It's not just polarity for the water. There's another reason why water is not good. So first of all, let me just talk about this. So I have iodide. There's a minus charge. I have a substrate here, chloride. And there's a calomic advantage to having these things get close. There's a partial positive charge on carbon. The closer they get, the more Coulomb's law, and I could calculate this, the more Coulomb's law tells me that it's energetically favorable to bring these closer together. And if you have a dielectric here, the larger the dielectric constant, the bigger this is, the less these charges can see each other. Dielectric, high dielectric hides charges. They can't see each other when the dielectric constant. So that's part of this effect right here. But there's a second major effect here. So dielectric is one origin of this set of differences. But there's a second effect.  And the problem is when you're in a protic solvent, this is, it's the protic solvents that really screw you on this. It's not just this, this ion's not seeing each other effect. The problem is this iodide is already, and I don't know how to draw this. I'll draw this as dashed lines. The iodide is already, in a way, kind of reacting because it hydrogen bonds with the solvent. When you have solvents that are protic that can form hydrogen bonds with nucleophilic species, it's almost like it's already donating into an antibonding orbital. That's what the hydrogen bond is. And with all these distractions around here, you can imagine why it's not so easy for this iodide to get interested in attacking anything. So hydrogen bonds distract nucleophiles. Because most nucleophiles, good ones are anionic or have anionic character. So this is reason number two for the big difference. So there's the charge screening effect of polar solvents and then there's this protic solvent distraction effect. Okay, it's harder to distract bigger atoms.  What you'll find is when you have smaller atoms, it's very easy to form very tight hydrogen bonds. And let's take a look at the practical implication of that as we go to the second row atom, sulfur, ethyl. It's harder to distract bigger atoms and it's easier to distract smaller atoms. So when you put fluoride anion in aqueous solution, this is not very nucleophilic. In organic chemistry, nobody uses aqueous solutions of fluoride anion. Who would do that? The hydrogen bonds between water and fluoride totally shut down their activity of the fluoride. If you're interested in using fluoride as a nucleophile, for example, to attack silicon, what you use is this, tetrabutylammonium fluoride. I'm not going to draw the butyl groups. That can't form hydrogen bonds with the fluoride. If you form any hydrogen bonds with the fluoride, it's over. You've shut down the nucleophilicity. So here's another sort of, I'm not sure what this is. This is just a related factoid. If you're into chemical biology, you should keep this in mind for things like native chemical ligation of proteins. You have cysteine thiols on proteins and amines on proteins. And they're in equilibrium. There's an equilibrium between thiols and thiolate anions, between amines and ammonium. Most lysine side chains are protonated in aqueous solution. Most thiolates are also protonated. But the small amount of thiolate anions that are present in solution, in any aqueous solution, are so nucleophilic that if you have a protein or if you have equal amounts of thiol and amine in a buffered solution, I'll call this pH 7, it doesn't matter what the pH is. You'll find that thiols are more nucleophilic. So you can see what's the problem is if you're under acidic conditions, almost all the amines are protonated. There's no lone pairs on those things to act as nucleophiles. At least there's some thiolate anion. If you try to go to more basic conditions, so at least you have an even playing field, if you go to higher pH to try to get some of your lysine side chains deprotonated, well then you're going to deprotonate even more of the thiols, you'll have even more of the thiols around that can act as a nucleophile. So generally, when you have thiols in aqueous solution, expect them to be way more nucleophilic than lysine side chains. So unless you have 300 times more lysine side chains than thiols, typically it's like 40 to 50, then expect the thiolates to act as a nucleophile, the cysteines. Okay, we're going to stop there. We've got one last little piece that we're going to cover when we get back. I have finished grading about half of those two page proposals and Chris is going to give those back.