[ASAP] Coherent Acoustic Interferometry during the Photodriven Oxygen Evolution Reaction Associates Strain Fields with the Reactive Oxygen Intermediate (Ti–OH*)

Journal of the American Chemical SocietyDOI: 10.1021/jacs.1c04976

Suryansh Singh, Hanna Lyle, Luca D’Amario, Elena Magnano, Ilya Vinogradov, and Tanja Cuk

https://ift.tt/2WaPDRa

👍︎ 3
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📅︎ Sep 24 2021
🚨︎ report
Dissecting the Flash Chemistry of Electrogenerated Reactive Intermediates by Microdroplet Fusion Mass Spectrometry

A novel mass spectrometric method for probing the flash chemistry of electrogenerated reactive intermediates was developed based on rapid collision mixing of electrosprayed microdroplets by using a theta-glass capillary. The two individual microchannels of the theta-glass capillary are asymmetrically or symmetrically fabricated with a carbon bipolar electrode to produce intermediates in situ . Microdroplets containing the newly formed intermediates collide with those of the invoked reactants at sub-10 microsecond level, making it a powerful tool for exploring their ultrafast initial transformations. As a proof-of-concept, we present the identification of the key radical cation intermediate in the oxidative dimerization of 8-methyl-1,2,3,4-tetrahydroquinoline and also the first revealment of previously hidden nitrenium ion involved reaction pathway in the C–H/N–H cross-coupling between N,N’-dimethylaniline and phenothiazine.

https://ift.tt/35EPrLf

👍︎ 2
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📅︎ Jun 16 2021
🚨︎ report
In Situ Stable Generation of Reactive Intermediates by Open Microfluidic Probe for Subcellular Free Radical Attack and Membrane Labeling

An open space microfluidic probe has been developed to stably synthesize reactive intermediates in situ for subcellular chemistry. Reactant systems (A, B) mix and react with each other within a chemical reaction microregion (several μm). The continuously produced free radicals can attack cellular compounds within the microregion before quenching, realizing subcellular radical stimulation.

Abstract

Subcellular stimulation by free radicals is crucial for deeper insight of cell behaviors. However, it remains a tough challenge due to the high spatial precision requirement and short life of radicals. Herein, we report a versatile open microfluidic probe for stable generation of free radical and subcellular stimulation. By optimizing parameters, the chemical reaction can be confined in a microregion with a diameter of several μm, and the real‐time produced reactive radicals can attack the desired subcellular region of a single cell. In order to reveal the attacked region, fluorescent cyanine 3 labeled tyramide free radicals are synthesized, and the target microregion on a single cell is successfully stained by the covalent linking reaction between radicals and membrane proteins, which proves the feasibility of our method. We believe this method will open new avenues for short‐lived reactive intermediates stimulation at the single‐cell/sub‐cell level and selective membrane labeling.

https://ift.tt/3a27k8w

👍︎ 2
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📅︎ Mar 03 2021
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Overall Oxygen Electrocatalysis on Nitrogen‐Modified Carbon Catalysts: Identification of Active Sites and In Situ Observation of Reactive Intermediates

Dynamic evolution of active sites and key oxygen intermediate products during the ORR and OER on N‐doped carbon catalysts are monitored experimentally with in situ ATR‐IR spectra. With the assistance of isotopic labeling, the formation of OOH species from O2− (O2−*+H2O→OOH*+OH−) is suggested to be a possible RDS during the ORR process, whereas the generation of O2 from OOH* species is the most possible RDS during the OER process.

Abstract

The recent mechanistic understanding of active sites, adsorbed intermediate products, and rate‐determining steps (RDS) of nitrogen (N)‐modified carbon catalysts in electrocatalytic oxygen reduction (ORR) and oxygen evolution reaction (OER) are still rife with controversy because of the inevitable coexistence of diverse N configurations and the technical limitations for the observation of formed intermediates. Herein, seven kinds of aromatic molecules with designated single N species are used as model structures to investigate the explicit role of each common N group in both ORR and OER. Specifically, dynamic evolution of active sites and key adsorbed intermediate products including O2 (ads), superoxide anion O2−*, and OOH* are monitored with in situ spectroscopy. We propose that the formation of OOH species from O2− (O2−*+H2O→OOH*+OH−) is a possible RDS during the ORR process, whereas the generation of O2 from OOH* species is the most likely RDS during the OER process.

https://ift.tt/38rIJLd

👍︎ 2
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📅︎ Dec 08 2020
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In a three step endothermic reaction diagram how would I know which of the intermediates is the most reactive?
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👤︎ u/frntc
📅︎ Sep 22 2020
🚨︎ report
Reactive Intermediates in Organic Chemistry
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👤︎ u/AOCisOK
📅︎ Apr 09 2019
🚨︎ report
[ASAP] Unraveling the Mechanism of Catalytic Water Oxidation via Synthesis of Reactive Intermediate

Journal of the American Chemical SocietyDOI: 10.1021/jacs.9b10265

https://ift.tt/2ZZbIQh

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📅︎ Jan 04 2020
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RuV‐Acylimido Intermediate in [RuIV(Por)Cl2]‐Catalyzed C−N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Metal-catalyzed acylnitrene transfer reactions are widely proposed to proceed via M(NCOR) intermediates. In their Research Article (DOI: 10.1002/anie.202100668), Chi-Ming Che and co-workers report [Ru(Por)Cl2]-catalyzed highly selective acylnitrene transfer to alkenes, indoles, silyl enol ethers, and C(sp3)−H bonds to afford aziridines/oxazolines, 3-aminoindoles, α-aminoketones, and N-acyl amines, respectively, and also experimental and computational evidence that porphyrin-supported Ru(NCOR) intermediates, which belong to RuV-imido species, are involved in these reactions.

https://ift.tt/2TRgsZc

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📅︎ Jun 22 2021
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RuV‐Acylimido Intermediate in [RuIV(Por)Cl2]‐Catalyzed C–N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Experimental studies including ESI-MS, EPR spectroscopy and KIE, and also DFT calculations point to the intermediacy of a porphyrin-supported RuV(NCOR) species in [RuIV(Por)Cl2]-catalyzed C−N bond formation reactions with acyl azides N3COR (up to 99 % yield). The [RuIV(Por)Cl2]/N3COR catalytic method is applicable to various substrates, including alkenes, indoles, silyl enol ethers, and C(sp3)−H bonds.

Abstract

Metal-catalyzed C−N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R=aryl or alkyl) species in these reactions poses a formidable challenge. Herein, we report on Ru(NCOR) intermediates in C−N bond formation catalyzed by [RuIV(Por)Cl2]/N3COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α-amino ketone formation from silyl enol ethers, amination of C(sp3)−H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99 % yield). Experimental studies, including HR-ESI-MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a RuV-imido species.

https://ift.tt/3geiGdY

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📅︎ Jun 01 2021
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Base‐Free Cross‐Couplings of Aryl Diazonium Salts in Methanol: PdII–Alkoxy as Reactivity‐Controlling Intermediate

Detailed systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism of the Pd‐catalyzed cross‐coupling of aryldiazonium salts.

Abstract

Pd‐catalyzed cross‐coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic PdII intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (=effective) and Stille (=ineffective) cross‐couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to PdII‐methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki “Pd‐oxy” mechanism with the direct demonstration of transmetalation of a PdII‐alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

https://ift.tt/2MDES51

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📅︎ Feb 24 2021
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[ASAP] Identification and Reactivity of -,--Dihydroxycarbene, a New [CH2O2] Intermediate

Journal of the American Chemical SocietyDOI: 10.1021/jacs.0c09317

Henrik Quanz, Bastian Bernhardt, Frederik R. Erb, Marcus A. Bartlett, Wesley D. Allen, and Peter R. Schreiner

https://ift.tt/3phnLoi

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📅︎ Nov 10 2020
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Born again (again): USS New Jersey (BB-62) as she is towed from Puget Sound Intermediate Maintenance Facility for her third reactivation, July 1981[2925x1957]
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👤︎ u/Taldoable
📅︎ Jan 28 2019
🚨︎ report
Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt‐Catalyzed Hydroformylation

The 18‐electron cobalt hydride (R,R)‐(iPrDuPhos)Co(CO)2H has been synthesized. Despite being coordinatively saturated this compound promotes reversible 2,1‐insertion of styrene and catalytic hydrogenation, raising questions as to the mechanism of action of the modified cobalt catalysts.

Abstract

Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18‐electron (R,R)‐(iPrDuPhos)Co(CO)2H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2/CO gas (1:1) at 100 °C. Deuterium‐labeling studies established reversible 2,1‐insertion of styrene into the Co−D bond of (R,R)‐(iPrDuPhos)Co(CO)2D. Whereas rapid β‐hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)‐(iPrDuPhos)Co(CO)2Cl in the presence of CO enabled the interception of (R,R)‐(iPrDuPhos)Co(CO)2C(O)CH2CH2Ph, which upon hydrogenolysis under 4 atm H2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H−, Cl−), underwent exchange with free 13CO. Under reduced pressure, (R,R)‐(iPrDuPhos)Co(CO)2Cl underwent CO dissociation to form (R,R)‐(iPrDuPhos)Co(CO)Cl.

https://ift.tt/2wgAb8X

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📅︎ Mar 30 2020
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Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt‐Catalyzed Hydroformylation

Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to the catalytic process. Among these, the 18‐electron cobalt carbonyl hydride with a chiral bis(phosphine), ( R , R )‐( iPr DuPhos)Co(CO) 2 H has been structurally characterized. Despite being an analog of rhodium precatalysts widely used in asymmetric hydroformylation, ( R , R )‐( iPr DuPhos)Co(CO) 2 H promoted exclusive hydrogenation of styrene in the presence of 750 psi of H 2 /CO gas (1:1) at 100 ºC. Deuterium labeling studies established reversible 2,1 insertion of styrene into the Co–D bond of ( R , R )‐( iPr DuPhos)Co(CO) 2 D. Whereas rapid β‐H elimination from cobalt alkyls occurred under an atmosphere of N 2 , alkylation of the cobalt chloride ( R , R )‐( iPr DuPhos)Co(CO) 2 Cl in the presence of CO enabled the interception of a cobalt acyl complex, ( R , R )‐( iPr DuPhos)Co(CO) 2 C(O)CH 2 CH 2 Ph. Hydrogenolysis of the cobalt acyl under 4 atm H 2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. While the hydride derivative was inert to CO substitution, the π‐donating chloride ligand in ( R , R )‐( iPr DuPhos)Co(CO) 2 Cl underwent rapid CO dissociation (or exchange) to form a tetrahedral, S = 1 complex, ( R , R )‐( iPr DuPhos)Co(CO)Cl.

https://ift.tt/2wgAb8X

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📅︎ Mar 17 2020
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USS New Jersey (BB-62) being towed from the Puget Sound Intermediate Maintenance Facility to Long Beach Naval Shipyard for reactivation, July 1981[2925x1957]
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👤︎ u/Taldoable
📅︎ May 23 2017
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New Player Guide and Resources

I'll start this post off by welcoming you all, if you are a newer player and you've found your way to this thread, I hope you find everything you need here to get started! If you are an older player/veteran to the game, and want to contribute or feel any information in this post is out of date please let me know and I'll do my best to get it back up to date.

If you are looking for an extensive list of guides and resources, scroll down to the bottom of this post!

The first step is diving into the most frequent topic when it comes to Legends of Runeterra and new players, the economy. Legends of Runeterra is a very free to play game, with multiple ways to obtain and use resources to craft cards. While it is very generous, it can feel a tad overwhelming at first. So, we'll take a moment to break down how it all works.

Cards are crafted or purchased using various currencies in game.
Shards - Shards are the most common currency you will come accross, they are represented by a green gem icon. These can be used to craft any card in the game for varying costs.
Wildcards - Wildcards are sorted by rarity and can craft any card of the same rarity. For example, a common wild card will create any common card of your choice. Each rarity is represented by a color, which will be shown in the table below.
Coins - This is the paid currency in Legends of Runeterra, they can be used to purchase cards or cosmetics.

Rarity Wildcard Shard Cost Coin Cost *Duplicate Shards
Common Green 100 10 15
Rare Blue 300 30 60
Epic Purple 1200 120 250
Champion Orange 3000 300 750

Duplicate Shards - This is how many shards you will receive upon gaining a copy of a card that you already own 3 copies of. Champion and Epic rarity cards have protection, which means upon receiving a 4th copy it will be converted to another random champion or epic card. Once you own every champion/epic card in the game you will start receiving duplicate shards.

So how do we obtain these resources?
The main source will be Capsules and Chests obtained through playing the game. Each chest or capsule in the game has a chance to upgrade to a higher tier upon redemption, if it upgrades it will roll again to see if it upgrades further. This method is repeated for each item in your c

... keep reading on reddit ➡

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👤︎ u/CaptSarah
📅︎ Jan 03 2022
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A few years ago I didn’t know anything about programming. Thanks to you I got a job, and I’ve just launched my dream app

First of all, I want to thank /r/learnprogramming and /r/androiddev. When I had questions you helped me, when I had a bad day - and I had a lot - I read about the journey of people who succeeded in their career change and it kept me motivated.And the mandatory: “Sorry for my English”.

Timeline

- At 28 I didn’t know anything about programming.
- At 30 I got my first job as a developer.
- At 32 I lost my job during the pandemic.
- At 33 I’m launching an app with two friends.

Some advices

  • Languages and frameworks are just tools. Learn broad concepts, read a lot of code and learn to search on Google / Stackoverflow.
  • I didn’t get my first job because I knew all the new trends, nor that I knew perfectly a language syntax and data structures. I got it because I’m always willing to learn, because I enjoy solving problems, because you can’t be more motivated than I am and because sometimes you are in the right place at the right time. The right mindset will get you the skills, eventually. And that’s what a company should look for in a junior developer. So don’t be too hard on yourself, be patient, have discipline, believe in you and believe in others!

Journey

At 24 I graduated with a master degree in marketing and started to work in advertising in Paris. From the beginning I wasn't really excited about it, it was boring and meaningless. From being bored I went to being unhappy and it started to affect my personal life. At 28 I realised it was time for a change. And because I’m not always the sharpest tool in the shed I quit without any plan. PLEASE DO NOT DO THAT, DON'T QUIT YOUR JOB IF YOU DON'T HAVE A SOLID PLAN OR A JOB OFFER. I had enough savings to live for 1 year without income. When I was younger I thought about programming but I felt it was too complicated for me. Truth is I was really lazy back then so I decided to give it a try.

October 2016

I started to learn HTTP and CSS. I had already learned the basics of the basics a few years ago when I decided to change the colors of a WordPress theme to put my resume on. But I soon realized that I didn't want to create websites, for no specific reason, I just didn't feel like it was my thing.

November 2016

I was still attracted to the idea of being a developer, so I looked for a subreddit about programming and went straight to "Which programming language should I start with?". I told myself "well, I already heard about JAVA, I have an Android phone so let's try that". I star

... keep reading on reddit ➡

👍︎ 1k
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👤︎ u/chiracjack
📅︎ Dec 21 2021
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Follow-on AMA is up on the Clover website an hour ago...

LINK: https://investors.cloverhealth.com/news-releases/news-release-details/clover-healths-follow-offering-ama

12/17/2021: Hello everyone. We appreciate your patience on hearing from us during the quiet period connected to our follow-on offering (which was due to the fact that our underwriters had 30 days to purchase additional shares). We are more excited than ever in our long-term vision for Clover, with a goal of generating long-term value for shareholders and incredibly positive and massive impact within healthcare.

Before we get into the specific questions that have been asked of us since the launch of the offering, we wanted to provide a general summary of the outcome:

  • We raised $300 million in gross proceeds through the offering of our Class A Common Stock.
  • We are a technology company that is rapidly growing, and plan to use the proceeds for working capital and general corporate purposes, which includes our continued growth efforts and to have further cushion in the event COVID-19 has a larger impact than we currently expect.
  • Over 40 funds invested in our transaction, and we are very pleased with the quality of the investors who bought shares and the fact that several of our existing investors decided to take part and increase their holdings.
  • This deal raised our awareness with additional institutional investors. We met with about 30 investors and our banks spoke with about 150 in total. We expect to gain three additional research analysts – Deutsche Bank, SVB Leerink and Canaccord – early next year.

We are very excited entering 2022. We expect another year of strong growth, and we’re progressing on making the Clover Assistant even more powerful and extending its capabilities further, while leveraging our platform to drive impressive operating synergies over time.

Thanks for being on this journey with us.

Vivek & Andrew

Why did Clover do a secondary offering?
It’s typical for high-growth companies to raise capital in multiple rounds over time (especially those that require to scale operations and marketing). At the end of the third quarter, we had approximately $589 million of cash, cash equivalents and investments on our balance sheet, and we raised an additional $300 million in gross proceeds from the offering. One of our primary motivators, since we are a health insurer, is that we have to put aside capital for

... keep reading on reddit ➡

👍︎ 241
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👤︎ u/mrbundle
📅︎ Dec 17 2021
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USS New Jersey (BB-62) being towed from the Puget Sound Intermediate Maintenance Facility to Long Beach Naval Shipyard for reactivation, July 1981
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👤︎ u/RPBot
📅︎ May 23 2017
🚨︎ report
6 months old Aussie developing leash frustration?

Hi r/reactivedogs! Coming here for some advice and good training suggestions. Our 6 month old Aussie is developing leash frustration and reactive barking whenever we are close to other dogs. It seems like this is not an uncommon issue and we would love to work on it now to teach our Aussie good long term habits.

We have currently enrolled her in an intermediate dog training after successfully finishing puppy class. The first class went horribly for us with our dog barking loudly and unable to settle when other dogs were there for the whole class. She kept pulling on her harness and essentially choking herself out of frustration of not being able to play and greet. My first reaction was that she is not ready to be leashed in close quarters with other dogs so the training class will only encourage her reactivity. She’s done this at other pet friendly stores, vets office, and especially in her training class.

We have been working on walks a lot with just observing other dogs and not barking so her current safe distance is about 30 feet. I want to pull her out of training and keep working on calm behavior from a distance and slowly get her closer and closer to other dogs. Would you recommend just sticking it out?

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👤︎ u/maroonrice
📅︎ Jan 23 2022
🚨︎ report
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.

👍︎ 17k
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📅︎ Jan 15 2022
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6'0" tall female skier looking for new/used skis. Help?

So I'm currently skiing on my old (2005, looool) Dynastar Pro Model Phil Dion freestyle twin tip skis. The skis are fun and they have served me well. But they're 165cm, which I feel is too short for my ability level and height. And they're ancient.

I typically ski at an intermediate to advanced level on-piste. I will ski at an advanced level for the majority of the day on the mountain, and intermediate when I'm tired. I keep up with my snowboarder friends who love their tree runs and off-piste activity, but I am also content coasting down groomers with my beginner skier friends. I don't do a lot of park these days in fear of reactivating an old knee injury, but I still venture in there for Small park features, and I like going off jumps on the sides of runs. Also like twin tips for spinning around and having fun.

I feel like I'm overworking myself using skis I've grown out of. I'm looking for a twin tip all mountain ski (I think). But because I'm so tall, there aren't a lot of options for me in terms of women's skis. I weigh around 145-150lbs. Boot size 26.5. Would I be OK with a men's ski? Do I have to be concerned about getting an Ultralight ski?

I went to a couple shops around Boxing Week but everyone was obviously cleaned out and I didn't get much help from staff. Saw a nearly-new pair of 2022 Line Sick Day 88 skis on FB Marketplace, 179cm, with Tyrolia Attack2 16 bindings. $625 OBO for the skis with bindings. Would this be a good choice? Should I be concerned about re-mounting bindings?

I've done some research and have a few ideas, and a lot of questions. I'd love to pick the brains of Reddit ski enthusiasts to point me in the right direction. Any help is greatly appreciated!!

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📅︎ Jan 19 2022
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Just because it's a joke, doesn't mean it's a dad joke

Alot of great jokes get posted here! However just because you have a joke, doesn't mean it's a dad joke.

THIS IS NOT ABOUT NSFW, THIS IS ABOUT LONG JOKES, BLONDE JOKES, SEXUAL JOKES, KNOCK KNOCK JOKES, POLITICAL JOKES, ETC BEING POSTED IN A DAD JOKE SUB

Try telling these sexual jokes that get posted here, to your kid and see how your spouse likes it.. if that goes well, Try telling one of your friends kid about your sex life being like Coca cola, first it was normal, than light and now zero , and see if the parents are OK with you telling their kid the "dad joke"

I'm not even referencing the NSFW, I'm saying Dad jokes are corny, and sometimes painful, not sexual

So check out r/jokes for all types of jokes

r/unclejokes for dirty jokes

r/3amjokes for real weird and alot of OC

r/cleandadjokes If your really sick of seeing not dad jokes in r/dadjokes

Punchline !

Edit: this is not a post about NSFW , This is about jokes, knock knock jokes, blonde jokes, political jokes etc being posted in a dad joke sub

Edit 2: don't touch the thermostat

👍︎ 6k
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📅︎ Jan 23 2022
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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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I heard that by law you have to turn on your headlights when it’s raining in Sweden.

How the hell am I suppose to know when it’s raining in Sweden?

👍︎ 10k
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📅︎ Jan 25 2022
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Petition to ban rants from this sub

Ants don’t even have the concept fathers, let alone a good dad joke. Keep r/ants out of my r/dadjokes.

But no, seriously. I understand rule 7 is great to have intelligent discussion, but sometimes it feels like 1 in 10 posts here is someone getting upset about the jokes on this sub. Let the mods deal with it, they regulate the sub.

👍︎ 8k
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👤︎ u/drak0ni
📅︎ Jan 24 2022
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French fries weren’t cooked in France.

They were cooked in Greece.

👍︎ 9k
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📅︎ Jan 20 2022
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This subreddit is 10 years old now.

I'm surprised it hasn't decade.

👍︎ 14k
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📅︎ Jan 14 2022
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When I was a single man, I had loads of free time.

Now that I listen to albums, I hardly ever leave the house.

👍︎ 7k
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📅︎ Jan 25 2022
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You've been hit by
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👤︎ u/mordrathe
📅︎ Jan 20 2022
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My 4 year oldest favourit joke, which he very proudly memorized and told all his teachers.

Two muffins are in an oven, one muffin looks at the other and says "is it just me, or is it hot in here?"

Then the other muffin says "AHH, TALKING MUFFIN!!!"

👍︎ 9k
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📅︎ Jan 22 2022
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I'm sick of you guys posting dumb wordplay in here for awards and upvotes.

Don't you know a good pun is its own reword?

👍︎ 11k
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📅︎ Jan 21 2022
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Dropped my best ever dad joke & no one was around to hear it

For context I'm a Refuse Driver (Garbage man) & today I was on food waste. After I'd tipped I was checking the wagon for any defects when I spotted a lone pea balanced on the lifts.

I said "hey look, an escaPEA"

No one near me but it didn't half make me laugh for a good hour or so!

Edit: I can't believe how much this has blown up. Thank you everyone I've had a blast reading through the replies 😂

👍︎ 20k
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📅︎ Jan 11 2022
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What starts with a W and ends with a T

It really does, I swear!

👍︎ 6k
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📅︎ Jan 13 2022
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My wife left me because I couldn’t stop doing impressions of pasta

And now I’m cannelloni

👍︎ 6k
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📅︎ Jan 23 2022
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Help Selecting My First Bowling Ball

There are thousands of options between companies, different coverstocks, reactive vs. non-reactive, pearl, hybrid or solid options, the list goes on and on.

I would like to buy at least an intermediate ball (I'm a beginner but I don't want to buy a beginner ball only to have to replace it in short order) what I can get fitted to my hand that will do more-or-less everything I need. I'll be in bowling alleys with standard oil patterns and am comfortable using a 14 lb. ball. I am not sure what my rev. rate is, but I bowl often enough so if folks know how to figure it out I'm all ears!

TL;DR I'm looking to buy my first bowling ball but need some help figuring out what I should be looking for.

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📅︎ Jan 11 2022
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Why did Karen press Ctrl+Shift+Delete?

Because she wanted to see the task manager.

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👤︎ u/Eoussama
📅︎ Jan 17 2022
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Steve JOBS would have made a better President than Donald Trump

But that’s comparing apples to oranges

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📅︎ Jan 22 2022
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I just flew in from Chernobyl

And boy are my arms legs.

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👤︎ u/JhopkinsWA
📅︎ Jan 23 2022
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So 2 trees got arrested in the town I live...

Heard they've been doing some shady business.

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📅︎ Jan 18 2022
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In Situ Stable Generation of Reactive Intermediates by Open Microfluidic Probe for Subcellular Free Radical Attack and Membrane Labeling

Subcellular stimulation by free radicals is crucial for deeper insight of cell behaviors. However, it remains a tough challenge due to the high spatial precision requirement and short life of radicals. Herein, we report a versatile open microfluidic probe for stable generation of free radical and subcellular stimulation. By optimizing parameters, the chemical reaction can be confined in a microregion with a diameter of several μm, and the real‐time produced reactive radicals can attack the desired subcellular region of a single cell. In order to reveal the attacked region, fluorescent cyanine 3 labeled tyramide free radicals are synthesized, and the target microregion on a single cell is successfully stained by the covalent linking reaction between radicals and membrane proteins, which proves the feasibility of our method. We believe this method will open new avenues for short‐lived reactive intermediates stimulation at the single‐cell/sub‐cell level and selective membrane labeling.

https://ift.tt/3a27k8w

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📅︎ Jan 26 2021
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Overall oxygen electro catalysis on nitrogen‐modified carbon catalysts: identification of active sites and in situ observation of reactive intermediates

The recent mechanistic understandings including active sites, adsorbed intermediate products and rate‐determining steps (RDS) of  nitrogen ( N ) ‐ modified  carbon catalysts in   electrocatalytic oxygen reduction (ORR) and oxygen evolution reaction  ( OER ) , however, are still rife with controversies  due to the inevitable coexistence of diverse N configurations and the technical limitation for observing  formed   intermediates. In this work, seven kinds of aromatic molecules with designated single N species  are  used as model structures to investigate the explicit role of each common N group in both ORR and OER.  Specifically, dynamic evolution of active sites and key  adsorbed intermediate products including O 2 (ads), superoxide anion O 2 ‐* and OOH*  are  monitored  with  in situ  spectroscopy. We propose that t he formation of OOH species from O 2 ‐ (O 2 ‐+H 2 O→OOH+OH‐) is a possible RDS during the ORR process, whereas the generation of O 2 from OOH* species is the most possible RDS during the OER process.

https://ift.tt/38rIJLd

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📅︎ Nov 05 2020
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RuV‐Acylimido Intermediate in [RuIV(Por)Cl2]‐Catalyzed C–N Bond Formation. Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Metal‐catalyzed C‐N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R = aryl or alkyl) species in these reactions poses a formidable challenge. Herein we report on Ru(NCOR) intermediates in C‐N bond formation catalyzed by [Ru IV (Por)Cl 2 ]/N 3 COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α‐amino ketone formation from silyl enol ethers, amination of C(sp 3 )‐H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99% yield). Experimental studies including HR‐ESI‐MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a Ru V ‐imido species.

https://ift.tt/3geiGdY

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📅︎ Apr 13 2021
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Base‐Free Cross‐Couplings of Aryl Diazonium Salts in Methanol: Pd(II)‐Alkoxy as Reactivity‐Controlling Intermediate

Pd‐catalyzed cross coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic Pd(II) intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (= effective) and Stille (= ineffective) cross‐couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in‐situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to Pd(II)‐ methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki "Pd‐oxy" mechanism with the direct demonstration of transmetalation of a Pd(II)‐alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

https://ift.tt/2MDES51

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📅︎ Feb 05 2021
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Clover AMA on Offering

Hi - Below is the AMA we just published on our offering. We appreciate your patience and support!

-Clover IR Team

LINK: https://investors.cloverhealth.com/news-releases/news-release-details/clover-healths-follow-offering-ama

12/17/2021: Hello everyone. We appreciate your patience on hearing from us during the quiet period connected to our follow-on offering (which was due to the fact that our underwriters had 30 days to purchase additional shares). We are more excited than ever in our long-term vision for Clover, with a goal of generating long-term value for shareholders and incredibly positive and massive impact within healthcare. Before we get into the specific questions that have been asked of us since the launch of the offering, we wanted to provide a general summary of the outcome:

  • We raised $300 million in gross proceeds through the offering of our Class A Common Stock.
  • We are a technology company that is rapidly growing, and plan to use the proceeds for working capital and general corporate purposes, which includes our continued growth efforts and to have further cushion in the event COVID-19 has a larger impact than we currently expect.
  • Over 40 funds invested in our transaction, and we are very pleased with the quality of the investors who bought shares and the fact that several of our existing investors decided to take part and increase their holdings.
  • This deal raised our awareness with additional institutional investors. We met with about 30 investors and our banks spoke with about 150 in total. We expect to gain three additional research analysts – Deutsche Bank, SVB Leerink and Canaccord – early next year.

We are very excited entering 2022. We expect another year of strong growth, and we’re progressing on making the Clover Assistant even more powerful and extending its capabilities further, while leveraging our platform to drive impressive operating synergies over time. Thanks for being on this journey with us. Vivek & Andrew

Why did Clover do a secondary offering? It’s typical for high-growth companies to raise capital in multiple rounds over time (especially those that require to scale operations and marketing). At the end of the third quarter, we had approximately $589 million of cash, cash equivalents and investments on our balance sheet, and we raised an additional $300 million in gross proceeds from th

... keep reading on reddit ➡

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📅︎ Dec 17 2021
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