Lewis Base–Brønsted Acid–Enzyme Catalysis in Enantioselective Multistep One‐Pot Syntheses

Combining organo‐, bio‐, and metal‐catalyst for up to six synthetic steps allowed the one‐pot production line towards (enantiopure) key building blocks for natural product synthesis as well as polymer science in gram‐scale. The basis was set by an in‐depth investigation of the initial steps of the sequence and investigating the central role of the organocatalyst {Org: 1,4‐diazabicyclo[2.2.2]octane (DABCO)} as well as benzoic acid.

Abstract

Establishing one‐pot, multi‐step protocols combining different types of catalysts is one important goal for increasing efficiency in modern organic synthesis. In particular, the high potential of biocatalysts still needs to be harvested. Based on an in‐depth mechanistic investigation of a new organocatalytic protocol employing two catalysts {1,4‐diazabicyclo[2.2.2]octane (DABCO); benzoic acid (BzOH)}, a sequence was established providing starting materials for enzymatic refinement (ene reductase; alcohol dehydrogenase): A gram‐scale access to a variety of enantiopure key building blocks for natural product syntheses was enabled utilizing up to six catalytic steps within the same reaction vessel.

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Enzyme‐like Supramolecular Iridium Catalysis Enabling C−H Bond Borylation of Pyridines with meta‐Selectivity

“Like an enzyme” best describes the supramolecular catalyst reported by Rafael Gramage-Doria et al. in their Research Article (DOI: 10.1002/anie.202101997). The remotely-located Zn…N interactions within an iridium borylating catalyst are responsible for the unique selectivity and reactivity patterns observed for pyridine C−H bond functionalization. The pyridine approaches the substrate recognition pocket like a Perseid shooting star. Artwork: Romain Baloche.

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📅︎ Jun 22 2021
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Lewis Base–Brønsted Acid–Enzyme Catalysis in Enantioselective Multistep One‐Pot Syntheses

Playfully easy! The targeted combination of organo- and biocatalysts enables the scalable conversion of inexpensive commercial substrates into a library of highly valuable enantiomerically pure synthetic building blocks for natural product synthesis. The approach included newly designed monomers for radical polymerization, as described by Jörg Pietruszka et al. in their Research Article (DOI: 10.1002/anie.202103406). Graphic design: Irene Küberl.

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[ASAP] Phosphodianion Activation of Enzymes for Catalysis of Central Metabolic Reactions

Journal of the American Chemical SocietyDOI: 10.1021/jacs.0c13423

Patrick L. Fernandez, Richard W. Nagorski, Judith R. Cristobal, Tina L. Amyes, and John P. Richard

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📅︎ Feb 10 2021
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Enzyme‐like Supramolecular Iridium Catalysis Enabling C−H Bond Borylation of Pyridines with meta‐Selectivity

An iridium‐based supramolecular catalyst has been designed to selectively recognize pyridine‐like derivatives via secondary Zn⋅⋅⋅N interactions. Owing to the distance between the substrate binding site and the active site as well as the geometrically constraints, meta‐selective borylation reactions were accomplished displaying catalytic behaviors typically encountered in enzymes.

Abstract

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom‐economy C−H bond functionalization. The most powerful catalysts are found via trial‐and‐error screening due to the low association constants between the substrate and the catalyst in which small stereo‐electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn⋅⋅⋅N interactions that binds to pyridine‐like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta‐selective iridium‐catalyzed C−H bond borylations with enzymatic Michaelis–Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns.

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📅︎ May 01 2021
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[ASAP] Loop Dynamics and Enzyme Catalysis in Protein Tyrosine Phosphatases

Journal of the American Chemical SocietyDOI: 10.1021/jacs.0c11806

Rory M. Crean, Michal Biler, Marc W. van der Kamp, Alvan C. Hengge, and Shina C. L. Kamerlin

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[BOOK] Structure And Mechanism In Protein Science: A Guide To Enzyme Catalysis And Protein Folding (Structural Biology) Reprint Edition
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👤︎ u/borednerd7
📅︎ Jul 19 2020
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[ASAP] Single-Chain Nanoparticle Delivers a Partner Enzyme for Concurrent and Tandem Catalysis in Cells

Journal of the American Chemical SocietyDOI: 10.1021/jacs.9b13997

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Machine Learning Identifies Chemical Characteristics That Promote Enzyme Catalysis pubs.acs.org/doi/full/10.…
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👤︎ u/perocarajo
📅︎ May 04 2019
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“Seeing” hydrogen atoms to unveil enzyme catalysis ornl.gov/ornl/news/featur…
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👤︎ u/Vailhem
📅︎ Jan 09 2015
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Dispelling the effects of a sorceress in enzyme catalysis pnas.org/content/113/9/23…
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👤︎ u/trot-trot
📅︎ Mar 08 2016
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Computational Study of a Model System of Enzyme-Mediated [4+2] Cycloaddition Reaction. Enzyme catalysis energy profile with only one transition state dx.doi.org/10.1371/journa…
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👤︎ u/ring42
📅︎ Apr 09 2015
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Enzyme Catalysis Lab (Need Help)

Alright so I have a biology lab and we need to find: Factors Affecting Rate of Enzyme.

The factors are: Temperature, pH, and Concentration

For data, we need to create a point graph, but I don't have a "rate"

I tried watching this video but I dont understand what he means by "Floats per second"

http://www.youtube.com/watch?feature=player_detailpage&v=hs75JmgGW5Y#t=209

Any help would be greatly appreciated :)

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👤︎ u/Temporaryy
📅︎ Sep 27 2013
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DNA nanotechnology places enzyme catalysis within an arm's length phys.org/news/2014-05-dna…
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👤︎ u/agril
📅︎ May 26 2014
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Scientists Provide Novel Tools to Study Enzyme Catalysis scitechdaily.com/scientis…
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👤︎ u/Vailhem
📅︎ Apr 25 2015
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ALT FL 5 BB #44

Question asks: For an enzyme catalyzed reaction, initial reaction velocity is linearly related to which variable?

Answer choices: a) Solution pH b) Enzyme concentration c) Temperature d) Substrate concentration

The answer is b) [E] I put d) [S] because during the initial phase on MM plot, doesn’t it start off as first order kinetics (rate= k[S]) and the rate is approximately linear as more [S] binds?

Chemlibre website states “The variable, V, is also referred to as the rate of catalysis of an enzyme. For different enzymes, V varies with the concentration of the substrate, S. At low S, V is linearly proportional to S, but when S is high relative to the amount of total enzyme, V is independent of S.”

But ALT’s explanation is this:

“Answer B is correct. The relationship between product formation and initial enzyme concentration is proportional, while the relationship between product formation and initial substrate concentration is not. In the Michaelis-Menten Equation, the numerator includes a product of [S] and the denominator includes a sum of [S], which means the relationship between velocity and [S] cannot be linear.”

Now i’m really confused.

https://chem.libretexts.org/Bookshelves/Biological_Chemistry/Supplemental_Modules_(Biological_Chemistry)/Enzymes/Enzymatic_Kinetics/Michaelis-Menten_Kinetics#:~:text=The%20variable%2C%20V%2C%20is%20also,V%20is%20independent%20of%20S.

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👤︎ u/yinsani
📅︎ Dec 22 2021
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SERIOUS: This subreddit needs to understand what a "dad joke" really means.

I don't want to step on anybody's toes here, but the amount of non-dad jokes here in this subreddit really annoys me. First of all, dad jokes CAN be NSFW, it clearly says so in the sub rules. Secondly, it doesn't automatically make it a dad joke if it's from a conversation between you and your child. Most importantly, the jokes that your CHILDREN tell YOU are not dad jokes. The point of a dad joke is that it's so cheesy only a dad who's trying to be funny would make such a joke. That's it. They are stupid plays on words, lame puns and so on. There has to be a clever pun or wordplay for it to be considered a dad joke.

Again, to all the fellow dads, I apologise if I'm sounding too harsh. But I just needed to get it off my chest.

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Loving Leon - Chapter 13

Chapter 12

I woke up before Leon the next morning. I was a restless sleeper so of course I wasn't still in the same position I had fallen asleep in. But given the size of my mattress we were still very close to each other. Leon was still asleep, looking utterly peaceful and also a little bit weird wearing one of my threadbare, washed-out t-shirts instead of the colourful ones he usually wore. I tried to shift away from him as best as I could – after a few seconds of tired blinking I had become aware of the fact that I had a pretty noticeable erection and I didn't want Leon to wake up with that touching his hip. As comfortable as he apparently was with me being gay, there were still limits. But my movement disturbed Leon's sleep and he began to move as well, stretching his arms for a moment before he opened those beautiful blue eyes. God, the boy was barely awake and he was already smiling.

“Good morning Danny.” he said, stifling a yawn.

“Good morning.” I replied awkwardly, still making sure to keep my body far enough away from him and covered by the blanket. For a while we just lay there in a slightly awkward but still surprisingly comfortable silence. Leon shifted around a bit and pulled the blanket over his hips as well. I was acutely aware just how close our bodies were underneath it and tried to shift my hips a little bit further away from him. It wasn't like I woke up hard every morning, why did it have to be today? Maybe because masturbation had been the furthest thing from my mind in the last two weeks and I was currently sharing a bed with an extremely attractive guy.

“What time is it?” Leon asked after a while.

“10 in the morning.” I said after a glance at my alarm clock. “Want some coffee?”

“I wouldn't say no to that.” Leon grinned and stretched again, then quickly adjusted the blanket. “I could also go for some breakfast.”

“I'll see what I can do.” I said with a smile. “But you'll have to let me get out of bed first.”

“But then I'd have to move.” Leon complained. “And I'm comfy right now.”

“Leon, I know what your bed feels like and I know what my bed feels like so stop lying.” I sat up, making sure I was still covered by the blanket. “Now let me out because I don't want to climb over you.”

“Fine.” Leon sat up and I climbed out of my bed behind his back, making sure he wouldn't see. Once I had gotten out of bed I put on the jeans that were still lying on

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!BOOK SUMMARY! Probability's Nature and Nature's Probability: A Call to Scientific Integrity. By: Donald E. Johnson. (Reading Difficulty level: Very Advanced)

Book Cover

https://preview.redd.it/bxiswlgn9dk71.jpg?width=433&format=pjpg&auto=webp&s=29739ad739027dd09e51e60a31a52ee3140de511

About the Author

Earned Ph.D.s in both Computer & Information Sciences and Chemistry. Senior research scientist for 10 years in pharmaceutical and medical/scientific instrument fields. Served as president and technical expert in an independent computer consulting firm for many years. Taught 20 years in universities in the US and Europe.

Prof. Dr. Donald E. Johnson

Introduction

  1. This book will show that undirected naturalism lacks known scientific facts in several critical areas, and that some intelligent agent better accounts for many observations. [Donald E. Johnson: Probability's Nature and Nature's Probability (A Call to Scientific Integrity), Booksurge Publishing 2009, p4.]
  2. Over time, the author began to doubt the natural explanations that had been so ingrained. It was science, and not his religion, that caused his disbelief in the explanatory powers of undirected nature in a number of key areas including the origin and fine-tuning of mass and energy, the origin of life with its complex information content, and the increase in complexity in living organisms. [Donald E. Johnson: Probability's Nature and Nature's Probability (A Call to Scientific Integrity), Booksurge Publishing 2009, p4, 5.]
  3. The fantastic leaps of faith required to accept the undirected natural causes in these areas demand a scientific response to the scientific-sounding concepts that in fact have no known scientific basis. Scientific integrity needs to be restored so that ideas that have no methods to test or falsify are not considered part of science. [Donald E. Johnson: Probability's Nature and Nature's Probability (A Call to Scientific Integrity), Booksurge Publishing 2009, p5.]
  4. For example, one should not be able to get away with stating "it is possible that life arose from non-life by ... " without first demonstrating that it is indeed possible (defined in the nature of probability) using known science. One could, of course, state "it may be speculated that ... ," but such a statement wouldn't have the believability that its author intends to convey by the pseudoscientific pronouncement. [Donald E. Johnson: Probability's Nature and Nature's Probability (A Call to Scienti
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📅︎ Aug 29 2021
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Blind Girl Here. Give Me Your Best Blind Jokes!

Do your worst!

👍︎ 5k
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📅︎ Jan 02 2022
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Enzyme‐Like Supramolecular Iridium Catalysis Enabling C‐H Bond Borylation of Pyridines with meta‐Selectivity

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom‐ economy C‐H bond functionalizations. Unfortunately, the most powerful catalysts are still found via trial‐and‐error screening due to the low association constants between the substrate and the catalyst in which small stereo‐electronic modifications in the catalyst (and/or the substrate) can lead to completely different reactivity patterns. In order to circumvent these limitations and to increase the level of reactivity prediction in this type of important reactions, we report herein a supramolecular catalyst harnessing Zn…N interactions that bind to pyridine‐like substrates as tight as it could be found in some enzymes. Furthermore, the distance and spatial geometry between the catalytically active site and the substrate binding site is ideal to target unprecedented meta ‐selective iridium‐catalyzed C‐H bond borylations with enzymatic Michaelis‐Menten kinetics, besides unique substrate‐selectivity and dormant reactivity patterns.

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📅︎ Mar 12 2021
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Lewis Base‐Brønsted Acid‐Enzyme Catalysis in Enantioselective Multistep One‐Pot Syntheses

Establishing one‐pot, multi‐step protocols combining different types of catalysts is one important goal for increasing efficiency in modern organic synthesis. In particular, the high potential of biocatalysts still needs to be harvested. Based on an in‐depth mechanistic investigation of a new organocatalytic protocol employing two catalysts {1,4‐diazabicyclo[2.2.2]octane (DABCO); benzoic acid (BzOH)}, a sequence was established providing starting materials for enzymatic refinement (ene reductase; alcohol dehydrogenase): A gram‐scale access to a variety of enantiopure key‐building blocks for natural product syntheses was enabled utilizing up to six catalytic steps within the same reaction vessel.

https://ift.tt/3e6iZVz

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📅︎ Apr 15 2021
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Loving Leon - Chapter 12

Chapter 11

“You wanna come over to my place after school? Study together?”

Leon looked as if I had dumped a bucket of water on his head. He said nothing for a few agonizing seconds. I almost expected him to tell me to fuck off for a second.

“S... sure!” he said. “Just gotta text my mum but she won't mind.”

“Awesome.” I tried my best to smile. “I can't offer you a lake or anything but I'm pretty sure we have cookies somewhere. Good enough?”

“I'll survive.” Leon said with a grin.

And just like that, the tension was gone, at least somewhat. We spent most of our classes that day doodling on each other's notepads and trying to make each other crack up in class – at one point during maths I made Leon laugh so loud that he earned one of Mr. Myers infamous stern looks and we tried to keep it a little more subtle after that. The lack of connection in the last ten days had been brutal, but I only realized how much I had truly missed it now that it was back. However, all of that was of course overshadowed by the knowledge that I still owed him an explanation and it was not going to be easy. Still, I tried to enjoy it – this might be the last time we would be like this around each other and I wanted to savour it. Once I told him what was going on he might not be comfortable around me anymore and I wanted to enjoy it as long as I could. I felt guilty as hell but I couldn't help it.

We walked home together that afternoon. Leon had texted his mum that he would stay at my place to study and that he'd let her know as soon as he knew which bus he was going to take home. It was early autumn now and although it wasn't cold by any means I was wearing a light jacket. The afternoon sun was half hidden behind clouds and the wind tousled Leon's hair – it was getting quite long at this point, regular haircuts apparently not being high on his list of priorities.

When we entered the apartment I realized that I hadn't actually told my mum that Leon was coming over. I'd have to text her before she got home. We took off our shoes in the hallway and Leon followed me to my room. I didn't show him the rest of the apartment – it wasn't like there was much to see after all.

“Well, here we are.” I said, awkwardly gesturing at my cramped room. “You did say you wanted to see my place.” I rarely cared about the fact that we weren't exactly well off. I didn't need a big room, the same way I didn't need

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📅︎ Aug 31 2021
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Loving Leon - Chapter 17

Chapter 16

Much as we would have liked to, we couldn't stay at the lake all day. My mum texted me, asking me to come home soon, which rarely was a good sign. She would probably want to talk about something and leaving behind Leon and his affection for that kind of conversation was not exactly tempting. Still, it wasn't like I had much of a choice. Thankfully, Leon offered to drive me home. We spent the trip listening to BANGERRRS and I tried my best to sing along with Leon. I didn't know the songs very well yet, but he seemed to appreciate my efforts. Somehow the trip seemed a lot shorter than I had expected and before I knew it, Leon parked the car in front of my apartment building.

“I... guess I'll see you tomorrow then.” he said, smiling uncertainly.

“Yeah.” I said. “I better go up soon.”

“Can I get another kiss before you go?”

“You really do seem to like kissing me lately.”

“Sorry, can't help it.” Leon said with a grin. “You're just too adorable.” He leaned over and kissed me softly. I closed my eyes and tried to enjoy but as soon as our lips touched, I felt fear creeping through my body, fear that my parents or one of the neighbours would see and I pulled back.

“So... before I go upstairs...” I said, leaning back in the passenger seat, “how do you want to handle this? Us, I mean.”

“I don't really know yet.” Leon said thoughtfully. “To be honest, I think, I'd prefer if we kept things low-key at school for now. Not because I'm afraid of the school homophobes, but because I'd like you to meet my friends before they find out we're boyfriends. And I don't want you to have to deal with any shit because of me.”

“Yeah, I'd prefer that.” I said. I knew Leon wasn't exactly ready to come out at school yet, but I realized that it would almost certainly take him a lot less time than it would take me and that he'd have to hold back on my account – God he really deserved better.

“What about your parents?” I asked.

“Good question.” Leon sighed. “I mean, I'm not afraid to tell them I think, they won't mind... They think you're lovely, so they'll probably be happy about it. But I'd rather wait with that a bit.” Then he gave me a look. “What about yours?”

“No idea.” I said, trying to ignore the comment about what his parents thought of me. “But honestly, I'm probably not telling them anytime soon.”

“Alright.” Leon said. Somehow this felt weird. I was pretty sure most strai

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