so actually this will be about the result what happens in architecture when you have to push down your feelings after you paid your taxes to the Holy Roman Emperor and you've still got to pay your taxes to the Ottoman Sultan so it's about you know wine but to start we're going to be in Central Europe in Slovakia in the vicinity or actually in the in the downtown of the town Kruppina which is located on the very northern edge of Carpathian Bezin. The location was settled slowly from the Carpathian Bezin by the prospector searching for ores like silver, gold and copper which was in abundance here. It was colonized in different waves each somehow after the ores were vanished or couldn't be not produced by the temporary technology so it was in a later age it was colonized from a new this is a micro scale colonization by in the in the Middle Ages where the Slavic tribes came from the south obtaining the silver ores from the mountains of Štelnica here and the process ended up with establishing a Romanesque settlement from 12th century here but it wasn't very much it declined because pretty early to these verbats sex and colonization has established another settlement right here in 1238 which is very early because the sex and colonization in Hungary usually appears after the Mongol raids which was 1241 when the country was almost almost settlement less left so it was because because of the presence of the silver ore because Kruppina is situated on the strategic position between the mining towns and the southern agricultural background for the which supplied the mining towns the country the town evolved into a fortress well it wasn't fortified until until 16th century because it was an interior town in deep inside of the country but after the Mohawk battle of 1526 when the Hungarian army was made by the Ottoman forces it so became a frontier fortress so and very one more important date is a year 1523 when the Ottomans took over the 3m region in Serbia which was the main product of wine in Eastern and Central Europe and actually they occupied most of the regions in Eastern Central Europe where wine could be grown here so reconstruction of ecological limits of wine production in the 18th century which was made according to the first military of Habsburg Empire which depicts different kind of environment including many arts and we are right here on the very edge so that's why before this Ottoman invasion into the central part of Hungary it wasn't too much economically important to grow wine here although it was done but wasn't too much of a thing here here but as you see here during the frontier ages very very big part of the state of the town was used as vineyards which are all the purple areas so to so we decided to work with this Pro-Matico to deeper we went into the terrain for a survey to find some remnants of the wine production and to somehow find out if this map is accurate and we visited a couple of sites which were not destroyed by later agriculture and other other works and we discovered except for the old trading room between mining towns which is in all these historical maps and was found there and we found relics of old vineyards in different sites and on this one side there was a single single single rock cut storage cellar which was almost impossible to somehow survey because it was later redone with concrete and just right here there's a railway track so there's nothing no place for any excavation or anything but these are the types of vineyards but inside inside the town inside the both city we found out that there are there's lots of storage rooms for the wine which was in this time the the basic of the economy of the town and for this is responsible the geology geology where it is green areas represent the rock into which the architecture was cut it is it is actually volcanic soft volcanic rock okay so here here we see the distribution of the the red the red areas are the rock cut cellars and the green vines are the extended modified modified areas where the rugged soil is is there so as we see there are there they're mostly in the in the in this part because this part is located on on the fluol sediments so there was no place to to make any rock art rock art architecture basic pattern of the rock Rensen source is so like this they're always accessible from the street with on street level or slightly going down then there is a rock built entrance entrance hall which is followed by staircase into a long or shorter gallery which could be somewhere divided into side galleries or as you see here here's a three-level it's so it's pretty deep under the street level it's from four to nine meters under the level of the street and it does not respect the pots of the of the city or the town the common features the staircases which are often made of stone slabs or wooden wooden slabs which only in this one single case were preserved on the other wooden vernal preserved there are present ventilation shafts which are in the in the more more in the bigger sellers connected from different galleries into one single ventilation shaft less common features are water resources like wells or or systems of this system is the biggest one which is so some four and four meters in the ground plan and there is only one single solar there's there's something like a niche or something another on the wall because there are all of them are plain with no details just in the single one there are there are small candle niches for them some of the sellers are pretty complicated in in the ground plan some some in some in some instances two separate original separate systems were intentionally merged into one because we have two original entrances into two original systems which were later on merged by cutting through this part and they indicate that this today single town hall was originally house originally two different houses on two different plots but later on it was merged together in some instances there was some of the systems were merged unintentionally like in this case where you can see a very narrow place where they were merged together and to be the residue of the of the way that they were made that there was some beginning there was made a narrow low reconnaissance gallery which were to check out the geology and if there is not there's no another seller in the front and even after after it was okay the whole gallery was made to its full width and height the all the all the galleries I have a almost uh identical width and height which is uh from 60 160 to 180 centimeters only this one is almost double as wide as wide but still the height is still the same uh one one system is unique this this one which has double two levels which the blue one is the higher level which is stone built and underneath is the liberal level which is a stone cut only in a few instances were preserved with technology marks which is due to the material which is pretty fragile and it's and it's only falling apart so only in these three instances the marks were preserved and it shows that it was made by possible hand hand tools of middle ages and for instance like iron iron mining iron and hammer which comes to the which comes to the conclusion that it was made by miners of those called by mining towns which were in trade with with this town the closest mining town is actually only some 15 kilometers away so they're actually they were in close touch there are also some other type of salars in the town in the in the place where where those google deposits are and there's no rock to pad into they're just normal stone will build stone will build single or double spaced or or in this one instead triple spaced sellers the purpose of all of these sellers is is clear it was for storage of wine and other goods just because the architecture of the town didn't allow any other storage storage places you can see it so very very densely built and comparing it to other town from this region where you have plenty of plenty of sorry space so here's the historical context and you will see that this is only place which was never very good wine and have economical profit from that which was never inside of the Ottoman empire so that helps us to date the the expense of the economic potential of the wine we have for dating some of these only these architectural details can help us for some dating because this uniform portal right here and to this one portal is from the now already collapsed town hall it is designed with wine grape motif which from 1545-48 which shows the that the wine grape was very important for the for the citizens we can try to date the analogy we know that but it doesn't help too much because we have the data from 1558 until 20th century with the surrounding localities with similar technology marks yes we have another system like this from the western part of Hulaki in least from 16th to 17th century and so that's thank you for your attention


This triggers the narcissist more than anything else. The narcissist will always end up hating you They will always end up mad and full of rage Because there are things that trigger them more than anything else and These things cause them to feel upset and frightened Which then causes a narcissistic injury Which will be followed by narcissistic rage But there isn't much you can do about that Because these are things that you don't want to change The things that trigger a narcissist more than anything else are your happiness and contentment your pleasure and satisfaction Your state of well-being But it's not just that you're enjoying someone's company or that you're enjoying an event Or enjoying doing something what triggers them more than anything else Is how you're able to generate your happiness from within Because even if you didn't have anyone or anything You'd still be happy and they know it because you're an empath You have the ability to understand the experiences and feelings of other people outside of your own perspective Which is why when you experience happiness and joy it's very intense It's a very strong feeling for you It's not like a fake smile because when you smile you smile from your eyes and When you laugh you laugh from your belly It's a genuine and authentic emotion It's real and although it may feel good for you It actually irritates and avenges the narcissist It causes them to feel upset annoyed and resentful To where they feel like they have been treated unfairly and Then they want to lash out at you. They become vengeful Even though they know you never intended to hurt them Even though they know it was completely innocent Because they see their feelings as facts So if they're hurt then someone must be the blame and Because they lack self-awareness They never look at themselves to see that they are the issue But when they have to witness your excitement it intimidates them It immediately gives them an inferiority complex and then they just can't be around it Your happiness and joy triggers the narcissist more than anything else They can't be around it But if they have to witness it they will try to find something wrong with it They will criticize it or they will try to put a stop to it or they may just go through completely They don't like to see it because they know their happiness isn't like that Because they know that your happiness isn't just dependent on other people or things. It's generated from within It's generated from how you feel about yourself You're confident in your own qualities and abilities You're confident in how you look But even if you were the most beautiful person in the world They would still find a way to put you down And it's not just your beauty on the outside It's also your beauty on the inside Because both things will trigger the narcissist Which is why they will always criticize you and make comments about it But you can also see the beauty in other people both on the inside and outside And it may often overwhelm you it may produce a strong emotional effect It may give you a very intense feeling Which is another thing that narcissists can't stand Because that is real intimacy It's a deep emotional connection Which is something that they will never get to experience Which is why they will often go out of their way to put on a show To try to prove to you and to themselves that they can experience it But the truth is that they will never be able to experience something like that Because they're self-absorbed that they lack empathy So the only thing that they can experience is narcissism They can only experience you experiencing them Which is why they don't attach to you They only want you to attach to them Because that is the only thing that gives them satisfaction But once the relationship is meant to move past that point and they're meant to attach to you They can't do it because they're missing that component Which is why any relationship they get into will never last Because they can't experience true intimacy or an emotional connection When if you're a normal healthy person That's exactly what you crave and desire in a relationship But the only thing they know how to do is to manipulate you and make you attach to them Which doesn't really satisfy them Because it's not even a fraction of the feeling that you get to experience when you're intimately involved with someone Which is why they can't stand you And it's why they're actually deeply envious and jealous of you Because they know they will never get to experience that Which is why they end up hating anything positive or good that you get to experience It's why they will criticize you and put you down It's why they will try to distract you and get you to focus on something else Because they want to make it seem less impressive or valuable They want to take away its significance and importance to you Because they want to take away your desire to do or achieve something They want to take away your desire and determination to achieve success They want to destroy your goals and dreams Because they hate your confidence They hate that you have little doubt about yourself and your abilities They hate your certainty They hate that you're self assured Deep down they actually respect and admire But they can't acknowledge it because it's not them And they know that it's never going to be them Which is why instead of investing their time into themselves and their own lives They will spend their time trying to destroy your confidence By calling your names and insulting you Because they want to show you you're not as intelligent important or attractive as you think Which is why they hate your confidence Because that gives you power When they want to be the ones who have power and control over you So they need you to hope or expect to get help or advice from them They need you to hope that they will provide them and for you They need you to depend on them Which is why they will try to reduce your confidence to your own beliefs and opinions Because they don't want you to be independent They don't want you to have everything you need without them Because if that was to happen then they wouldn't have a foot in the door They wouldn't have any ability to control you Which is why they hate it when you think for yourself And when you do something different than what they expect you to do They need you to always agree with them Because they're very insecure They have no control over their own emotions Which is why they hate that you have an independent mind They hate that you are inclined to decide for yourself what to believe and do Rather than simply accept things because they say that you should So everything that you are triggers the narcissist Everything that you don't want to change Everything that is good Everything that is positive and progressive about you Your happiness, excitement and joy It all triggers the narcissist But it's not something that you can change It's not a problem that you can resolve Because they just can't accept your qualities They can't accept that those qualities belong to you and not them It irritates them because they want to control you Which is why the only thing you can do is disengage Because you need to be around someone Someone who is going to appreciate your qualities Someone who is going to respect you Someone who has the quality of knowing and doing what is morally right Someone who is going to love everything about you Someone who isn't going to try to control you Because that is not love Love has nothing to do with control Love is about freedom Love is about letting go Thank you for watching If you found this video helpful please give it a thumbs up Share your thoughts in the comment section Hit the subscribe button to receive the notifications If you would like to support the channel You can donate at paypal.me slash narksurvivor You can book a one-on-one with me on my website It's narksurvivor the code at UK Thank you for watching and I'll talk to you soon


The other semi-final match in that one, Lake of the Woods and BGMR and the Yaters came out chomping at the bit, McKenna bursally with the ace. They take set one, but the Bears come crawling back. Their go-to in the middle, Marissa Johnson puts it away, we're all tied at one. After BGMR took the third Lake of the Woods answers, Jakaya Thompson says, not in my house. We're going to a fifth set and it goes back and forth, but the Bears grind it out, Johnson from the outside for the win. What a match, Lake of the Woods wins three-two. They play Aida Board, Norman County West Saturday for the section championship. If you've enjoyed this segment of Lakeland News, please consider making a tax-deductible contribution to Lakeland Public Television.


Hey everyone this video is about how the narcissist will leave you when you need them the most. I know many of you are holding on hoping that things are going to change. You think that if you just give them another chance maybe things will improve but that's just never gonna happen. They're not just gonna suddenly be everything that you want them to be. They're not just suddenly gonna act normal around you and even if they do it's just an act it's never real all they can do is play pretend they're never about it for real but one of the tactics they use is future faking where they make you believe that one day you're gonna get everything you want from them everything's gonna be okay and then that's what makes you stick around just hoping that maybe this time they tell the truth. You really need to let go of that hope though because the longer you stay with them the worse it's gonna get the more your health is going to deteriorate the more you're just gonna not even remember who you are anymore. You're not gonna remember what you like because they'll just turn you into a copy of them. Narcissists just get involved with you to use you up to use everything that you have to offer. They don't get involved with you to give anything to you. It's all about what you can do for them and they will drain your health, your finances, your enthusiasm for life.  When you need them the most, when they've drained everything out of you and you've got nothing left that's when they will leave and they will leave you with nothing because the truth is they never really cared about you. They never really loved you.  How you made them feel but they never even saw you as a real person.  They never really cared about you. So yeah this is my advice to you. Don't hold on waiting for things to change. Just look back in the past to remember how long you waited and how much progress they made if any but even if they did make some progress over the last year, five years, ten years are you really gonna wait that much longer again to see the same amount of progress? You could end up waiting the rest of your life for these types of people to change but they're not gonna change. It's not like one day they're just gonna have this epiphany and then realize everything they've done wrong. They already know that what they're doing is wrong. That's why they hide it.  There would be no need to hide what they're doing and not just that but you can tell that their behavior is very different when they're outside in public, when there's a chance of them ruining their image in front of other people. They act very differently then so they do know exactly how to act. They do know what is wrong. They just don't care. All they care about is themselves using you for their own selfish needs and when they've used everything up they're out of there. They're not gonna stick around to help you. All they care about is themselves and when you're in a time of distress or need you're gonna remember back to the false character. You're gonna remember the fantasy that they showed you in the beginning.  Where are they when I need them the most and you know where they're gonna be. They're gonna be displaying that character that they displayed to you in the beginning to someone else. Well you're left alone in the dark with no one, with no hope and you don't even know what's gonna happen next. You don't even know how you're gonna get through the day. That's how they will leave you. You think that you're sticking around for something better to happen or for things to change. It's only gonna get worse. They never change. It only escalates. Just a quick message that I wanted to share with you today. They will leave you when you need them the most and although in some situations they might come back that's only to manipulate you. That's only if they think they can get something more out of you. They're not coming back to give anything to you other than an illusion, a fantasy. That's all they've got for you. Other than that they have nothing to invest and that's why they were never serious about you. That's why they never tried to really make anything develop because they already know narcissists, they are rather stupid at times especially in their behaviors but we all know really what it takes to build a relationship. It takes two people. It can't just be one person invests in everything. It's never gonna build that way. It's never gonna sustain itself. A narcissist know this and they know that since they have nothing to invest with you it's only a matter of time until it all falls apart and that's why they move so quickly and try and get as much out of you as they can in that short amount of time and then they leave you with nothing because they already knew it was doomed from the start. They already knew they never had a chance with you. When you're invest in everything you've got and they've got nothing to bring to the table they know it's only a matter of time until you realize that you deserve so much more. You deserve so much better. So yeah they will leave you when you need them the most. If you're going for a difficult time don't expect them to stick around. They won't. They only care about themselves. I hope this video was helpful to you. Check out the new website www.narksurvivor.co.uk. You can also contact me at coaching at narksurvivor.co.uk or on my Instagram narksurvivor YouTube. There will be two premieres later today from 6 30 p.m. GMT London time so I hope you can join me there. So thank you all for watching and I'll talk to you soon.


In this video, we're going to cover how to set up USB pass-through and PCI pass-through in XCPNG to the virtual machines that are running on that host. Something of note, they recently added the USB pass-through to the web UI, so that one's going to be really simple. And it's not too much command line work to set up the PCI pass-through, but I will have all the commands I use linked down below that you'll find on my forums, as well as a link to the documentation for XCPNG, which has a lot of these in there as well, so let's get started. Are you an individual or forward-thinking company looking for expert assistance with network engineering, storage, or virtualization projects? Perhaps you're an internal IT team seeking help to proactively manage, monitor, or secure your systems. We offer comprehensive consulting services tailored to meet your specific project needs. Whether you require fully managed or cool managed IT services, our experienced team is ready to step in and help. We specialize in supporting businesses that need IT administration or IT team seeking an extra layer of support to enhance their operations. To learn more about any of our services, head over to our website and fill out the higher-ups form at laurancesystems.com. Let us start crafting the perfect IT solution for you. If you want to show some extra love for our channel, check out our swag store and affiliate links down below that will lead you to discounts and deals for products and services we've discussed on this channel. With the ad read out of the way, let's get you back to the content that you really came here for. Now we're going to start by showing the USB Pass True. I'm running the latest version of Zen Orchestra that is up to date as of February 29th of 2024, so it is the self-compiled version, so this is completely the open source you can do this yourself at home version. I've got a link to a video on how to compile this. We're going to go over here to home and then host. From the host, we can go here to advanced and we can see what USBs are available on this host. So I have a sand disk and this is a Z-Wave adapter that I plugged in. Let's go back over here and look at the different VMs we have running. We have the U2 demo one. We can go to the console and we can see that there's currently nothing plugged in here. Let's go to advanced and plug in each of those devices. So if we create a VUSB, we're going to go ahead and plug in the Z-Wave device and we'll plug in the sand disk. Both these are plugged in, but it will let you know the VUSB was not going to work until you start and stop this VM. So if we go into the console, still nothing here. So let's go ahead and just stop it.  If we go over here to advanced and scroll down, you'll see that both of these are connected. So let's go back over to the console, go here, this PC and there's my sand disk that I have. If we go to the device manager, there is the ZigBee and Z-Wave USB device that I have plugged in. It's pretty straightforward to attach these. And if you would like to detach them, they can be detached without shutting it down. So if we go here and just remove them, go back over to the console, it's gone there. And so is the other one. One thing I want to make note of is if you have them attached, this will prohibit your snapshots from working. They will not work with a USB attach. You'll have to detach them to get the snapshot to work. But in the case of doing a backup, the backups can be done provided you do them in offline mode. They're aware that when the system is in offline mode, they can be backed up. So if we were to look at one of the backups, we'll scroll down here. You scroll down under advanced, you choose the offline backup. This will allow you to back these up while leaving those USBs attached if you need to. Now let's talk about how to pass through any PCI devices attached to this host. We're going to SSH into the host.  And I'm going to put a capital D. You don't have to. I'll show you without the D. You get a list of devices. But we want to use a dash D just to make it a little bit easier because I'm really in the habit of copying, pasting things to make sure I get it right. And we need the entirety, including these four zeros that prefix this. So we need to find the devices now that we want. And we have a couple of them. We have a real tech ethernet control that I want to pass through. And then I also have this ever media device that I want to pass through. This is the video capture card that I plugged in just to show you how to pass these devices through. So we have this one at this address here. And then we have the real tech ethernet right here. So these are the two addresses we need in their entirety. And I can show you the command that's actually going to pass them through. But before you pass them through, you're actually hiding them from the host to use because by default, the host is going to boot and then assume those devices. So in order to allow those devices to be passed through, we need to hide them from what they refer to as DOM zero. The command we use for that is opt slash zen source, lib exact command line, set DOM zero, zen PCI back hide. And then there is that number that we had from the PCI device name, the four zeros, colon two a colon zero zero dot zero. So exactly like this. And as I said, these will be in the forums. This is now told DOM zero, it's not allowed to use that device. Now I said there's two of them, but I want to show you how this works. This command will show devices that are hidden from DOM zero. We can see that we have that one on there, which is the real tech adapter. But if we run this command and we hide 10 colon zero zero, this is the average media device. And then we run the command again to show the list of devices that are being hidden from DOM zero, you'll see there's only one. It overwrites it each time you do this. So you actually need to put them all in one command for each device that you want on listed. So let me go ahead and show you the full command for that, which it's still the Zen PCI back hide. And we just put the second device or third or fourth, so on and so forth, all within this one command. So we run the command like this. And then we show them, you can now see that both devices are going to be hidden. Now these are not activated until you reboot. So from here, we're just going to go ahead and reboot this server. Now that we've added those commands. And by doing that, this will restart the server with those parameters at boot. So DOM zero will not be able to use these devices and we'll be able to assign them to a virtual machine. Okay, now the system's been rebooted, we're going to run Excel space PCI assignable list. This shows us what's available to be assigned to a VM. If you don't have anything here, go back to the other steps because you may have missed it or you didn't reboot your server. Now for the next steps, we're going to have to pick a virtual machine to assign it to. So let's go back over to Zen Orchestra. And I want to assign these to this Windows VM. The first thing you need is this UUID. And we're just going to hit copy to clipboard because all the parameters you assign are all done so via UUID, which is how internally Zen identifies that virtual machine. Now I will note you should be adding these while the virtual machine is off. But if you do add them when it's on, they won't show up until you start and stop that virtual machine. Now we can go through the full command, which is XE VM dash param set other config colon PCI equals zero slash the name of the device, and then the UUID of that virtual machine. Now we can go up and start this virtual machine, go into our device manager. And there's our ever media controller that we pass through. Well, let's go ahead and pass the real tech through now. So if we hit stop, go back over to the command line, issue the same command again, but we're going to add a comma a zero slash or zeros to a and this is the real tech device in the same UUID. If we were to omit this and let's just do it as a demonstration here and we only added the real tech device. It's not cumulative. This will only add the real tech, but now the average media wouldn't be there. This command VM param get, then the param name other config and then the UUID will show which devices are attached. And you can see them right here is the first line where it says PCI and we're only seeing the real tech. So we want to do that full command that has both the devices in here. So press enter up arrow twice so I can get to this other one and do the get config. Now you can see that both devices have been added right here. So now if we go back and start our VM, go back into the device manager or network adapters, we'll see the real tech and then there's our average media adapter. So we've added both. Something I want to note is probably people are wondering what happens if you add it to want more than one virtual machine, but I've actually already done that in the background. That's why I have this other one here. So if we try to start this virtual machine, we're going to get an error and it tells us what devices are matching. And this one happens to match the average media device. So that means I have that assigned to here. So if you try to start multiple VMs with that same assignment, it won't work. So let's go back over here to home and stop this VM. And I'll show you how to remove devices from a virtual machine. The next of the command XC VRM param set other config PCI, we're just omitting the rest of the information after the PCI that lists the devices. And if we do the get parameters, you can see that they're now missing. Now one last thing of note is if you would like to get rid of all of the devices that you hid, you can actually run that same tool we showed earlier, the Zen command line delete dom zero, and then Zen PCI back hide, this command will actually clear them all out. Of course, you'll still have to reboot and it'll remove them from the availability to be assigned to host. Now I do recommend you read through the XC PNG documentation on this, just so you can get the concept. If you want to go a little further and they have some of those commands in there, as well as my forum post, which has all the commands that I used for this video. So you didn't have to try to read them off the screen, although I tried to make it as concise and clear by zooming in as I can. But yes, those commands are a little bit long. Something you should know though is that all these parameters are stored within the VM. So when you use the Zen Orchestra backup tools, it does back up all those parameters as well. And if you start shuffling or moving PCI devices and you get any of those device not available, that is why I made sure you were clear on how to remove any of the devices. I didn't want to cover adding them. And then when you restore this VM to maybe another host that doesn't have those and you run into some errors, you'll want to make sure you go through and remove those because it tells you that device is not available if that device is not on another host. Obviously, something always to consider when you're doing this is the fact that this binds that VM to the host. There actually is an option if you have this inside of a resource pool to set an affinity host where you want that VM to start on that host, because well, it's the one that you've passed through the devices. So there are methods by which you can handle this. But as I noted, you are going to be binding that VM to start only on the host where that PCI device that you've passed through is available. Now, I did this demo with my evermedia card and with a real tech card that was on board. But yes, this should work really with any PCI device. So any graphics system should work. I don't know if there's any catches on that. Jeff from Craft Computing certainly has a lot of videos about NVIDIA catches on certain ones when you do pass through. But functionally, the PCI device will pass through. It comes down to some of the driver issues you may run into with certain devices. But the device will work. And this does include if you wanted to virtualize TrueNAS and you want to pass through a controller card. This is that same methodology you would follow. Or if you want to virtualize your firewall, such as PF Sense, and you didn't want to deal with the Zen adapters, you wanted to pass through a network card, such as maybe a four port network card that's PCI, or maybe whatever you have, this is the same idea. The best way to do is to pass it through where you can virtualize the OS, but still allow that underlying VM to have full access to the hardware. This is definitely the way to do that. Like and subscribe if you want to see more content from this channel, head over to my forums, forums.lordsystems.com, to engage with me on this and other topics, and head over to lordsystems.com to connect with me on whatever socials you can find me on there. Thanks.


We are talking about how to implement the DEX and how to continue to study the city as well. And currently the President has quite a lot of plans in the area of education and the logistics. And also there are some other areas. He has quite a strong intention to develop and enhance the DEX capability in India in order to improve the DEX capability in India. So we are very happy to contribute to this area. Such kind of discussion we have.


Jim Belushi has done so many things.  He has a farm in Oregon and it's a cannabis farm. So Jim, you've kind of been in the cannabis industry for a while as an advocate. You've certainly been active in speaking about the plant. What prompted you to decide to get into the farming business because you had to have known by being on the fringe of the cannabis industry that the farming is really, really tough? Well, it actually happened the other way. I got into the farming industry and then got into the cannabis business through that. And it is very tough. The industry has its own challenges, but farming. Farming, I am Elmer Fudd and Bill Murray in Caddyshack. I'm chasing gophers, digger squirrels, russet mites, aphids. I see a grasshopper and I just like panic.  Farming is a whole different thing and I am in this from seed to soil to dispensary to patient. So I'm experiencing all of that. And along with that are conventions where I speak and I've been in the business now for about four or five years, but it all came by accident. I just happened to be in the best growing section in Oregon in the banana belt. And I bought a little place on the river and the farm came up behind me and I bought that and I was like, what am I gonna grow? And cannabis became legal that year and I went, oh, new agriculture, let's just grow cannabis. And then these ladies, these female plants have led me to where I believe I'm supposed to be right here talking to you. Well, it's a beautiful farm. I've seen it on the show on your new Discovery Channel show which I watched the other night and it was hilarious. That's the thing. It was entertaining and for being someone like me who has been very familiar with the farms and the cultivation, I thought it was a very realistic example of what happens when you're dealing with these plants. Well, it's not a stoner show. No. It's not a show about people getting stoned and the humor is real humor. It's based on the relationships that I have.  But as the episode's like tonight's episode is really great because Danny Hackeridge's in it, we're the blues brothers in it and then we go to Columbia in search for the Santa Marta Gold. So it's an exotic travel. It's called growing Belushi and it's not just about growing cannabis, it's about growing the business. It's about my growth in my family and mainly it's about me growing up and understanding the traumas that have happened in my life like losing my brother. Because I think the collapse of family is the number two fear in a person's life. And trauma collapses families. Whether it's losing a sibling, losing a father, a severe illness, epilepsy, Alzheimer's, whether it's divorce, losing a job and we all need medicine to help us through it and the most readily available medicine is alcohol and Xanax and Ambien and the list goes on. And I think cannabis helps, doesn't cure but it helps manage the screaming inside of us that we all carry. So how bad did you feel when you ruined those Captain Jack plants? Because you left the lights on and burned them.  That was very real, right?  Oh my God.  Stupid, but real. All those events that happened in this show are real things that happen on the farm and some of those things we recreated because it's like you know well remember when you burned the plants I don't want to film that. I don't want to show the world that. So it's a real journey. Well and I think what was interesting from a business point of view is that those plants from what I understood were kind of spoken for and that there were you know there was somebody at the end of that supply chain. Stop it right now. Stop it right now. Stop shaming me. You are shaming me. But I'm leading into that you have a deal with grassroots and you know your product is in demand and so now it's not just you know a passion project or or hey I want to go play farmer. This is this is a real business now with somebody at the end of that supply chain saying you know where's my where's my stuff. Yeah it is a real business and like I said the last four years have been like oh well it's been like a kind of bachelor's of science in it right now my master's thesis is this growing Belushi this TV show and now I'm moving to grassroots which is you know Mitch Khan is one of the beautiful men in our industry that we see eye to eye on the deeper mission and we're opening up in Illinois September 3rd with the Blues Brothers brand because branding is isn't just a pretty box branding has to have some emotion and context to the Blues Brothers Blues Brothers is about music about mischievousness which is the fun and a mission from God so it's a perfect brand for cannabis because it has all three of those anyway I'm so happy about grassroots yeah I mean Illinois has turned out to be an amazing market has been pretty impressive for all those that are involved and to your point you know Blues Brothers is definitely associated with Illinois and especially with Chicago so I think that's a great fit I also think that you know what you're bringing with this brand is and and I think the show shows that is this authenticity and this credibility that some of the celebrity brands that have been out there I feel like you know people are just signing their name to the product and maybe smoking a couple of joints ago yeah yeah this is good you're clearly clearly involved from beginning to end in the oh no no I make sure the the soil you know I have enough curl I did it for the water the drain and it gets 64 degree temperature in order for the micronutrients to go into the roots in order for the THC to hit the water as I prune the water leaves in order for the air I keep the humidity right at 65 I keep the pH that I come right out of the river it's like having Fiji water or air have water feeding these girls but that pH has got to be a perfect 64 65 every time I'm in the detail work of the trimming no no no no no no I'm a grower and so when I work with grass roots I'm not going here's my name give me some money I'm like I'm in the grow with their grower and we're talking about all these elements that out of the details of a beautiful beautiful medical healing plant and like I said Mitch Connors do it okay so another thing that you're involved with is the last prisoner project and I feel like most people in the cannabis industry know this project it's an effort to help free people that are still in prison for marijuana cannabis offenses which is mind-boggling right now tell us 40,000 40,000 people are incarcerated for cannabis right now in the United States while we're out there making a profit you know selling I'm literally in the Ford Explorer with my cousin loaded up with cannabis driving the dispensaries legally and these guys are in jail I mean Michael Thompson is he had arrested for three pounds of cannabis 24 years ago he's been jailed 24 years sentenced to 40 to 60 years and right now he's 65 years old completely collapsed his family and he's got COVID and he's in the hospital but Steve D'Angelo who's headiness and Mary Bailey tell me that the state's attorney of Michigan is on it and they're working on releasing him yeah absolutely well I think Steve D'Angelo has done an amazing job certainly spearheading this this campaign and bringing it to a lot of our attention and keeping it you know at the top of the list and making sure that we understand the debt that some of these people have paid while we're able to you know walk around you know free as a bird so thank you for the work you're doing with that and I hope that we can you know have some progress on helping these people in and getting them out yeah yeah well thank you thanks for your support in that thank you


Hello and welcome to NewsClick. Today we are going to discuss this phase of elections, mapping the elections with Seema Mustafa. Seema, this time of course we have the 40 seats going to elections in Tamil Nadu. This is one state which is going to see only one round in elections. Of course there are a few more but this one is a big one, 39 seats. We start with the Kanimori raids which have taken place yesterday. Again raids, IT raids just before the elections? Absolutely. I mean they just did it a while ago. They've done like any number of raids I think in these elections. They have been 11 such raids before the Kanimori one. And of course they have included Kabana, they've included figures in TDP, they've included figures. They've been quite secular except the BJP shall we say and its allies. Otherwise it has been quite secular. Everybody has been targeted except the left.  And where the people are going to take, I mean sitting here we don't have yet the field reports, but one can take it for granted that they're going to actually be really angry with us. And she's going to get and the DMK is going to get some bit of a sympathy vote on this. Because they don't like the central intrusion. And Tamil Nadu is one of the few states which is very, very possessive about its federalism and its autonomy within the structure. And also the timing. Yes, absolutely. It's cruel. If the IT department thinks Kanimori has been evading taxes. Okay, right. By all means you're not saying don't. You had five years. Exactly. One day before the elections. Just one day before. Yes, it shows a desperate PJP. It shows a certain crudeness of approach. It shows a certain thinking where only by intimidation you feel comfortable. So that's what you're trying to do to an opponent who's obviously whose graph is on the rise. The DMK is expected to do far better. I mean considering you didn't do much at all last election. But maybe you know the whole tide seems to be turning in favor of Stalin and his party. Before we go to the DMK and the Tamil Nadu elections. Let's also talk about the election commission. Election commission has told the IT department that you have to be neutral before during this election's electoral phase shall be saved. And it had also said take permission from us, inform us before you do the raids. The IT department in its reply did not talk about giving intimation to the election commission. They kept completely silent on it. And more or less quite dismissively wrote to the election commission that essentially saying that what you're saying is nonsense. See this is a message that the election commission sends out. I mean you know at the stations time it went a little wonky and a little weird and a bit authoritarian. There is a message that every election commissioner has to send out that I'm strong. I'm independent and I am going to take action regardless. Unfortunately the election commission this time is not being able to send out that message. Simply because on all issues a verdict or a ruling from it is literally being dragged from by the opposition or by people who have complained that what are you doing. On the issue of the four leaders who have been now given some shall we say self-punishment even though it may not be a very major one. That you are making communal statements. No and it's strange. I mean it was all started with Yogi because he was the first I think from this whole thing. Well it could be argued all the time. But you finally why aren't you just doing it case by case. Why do you feel as the election commission that you are seeking some kind of refuge in numbers where you are some of the BJP and some of the opposition. They went to court saying we are toothless when Gogoi the chief justice said if you are toothless can we have the chief election commissioner coming and telling us this. And then the action comes and again Gogoi has made that quip the chief justice has made that quip. You seem to have suddenly discovered some tooth. Yes yes yes yes yes. The point is there is 324 of the act which has powers given to the election commission which is what station utilized where there is no other law barring their action. They love to take action. Absolutely. And all the action commission has used that provision for taking action. And you know even in times when you had a weak election commissioner I don't want to think he still managed not to be as partisan and still managed to give out some signals that okay I am treating everyone with a equal hand. Somehow there is a dip in that trust and confidence and when that happens then obviously IET department is going to ignore the body which should be right on top of these elections. And of course the other major issue the election commission has yet to respond. The use of the army and the forces the Serves Javan's in election year in which the prime minister has been openly doing. Yes. He has been asking what in the name of the army. I mean you had generals and veterans write about it. You have them having they've written columns on it. They have written a letter to the president of India saying that do not allow this politicization. And even so you know they are being targeted. They are being named. And now you're going to tell us that senior military officials who have presided over I mean who have been part of the so-called defense of the nation are suddenly now traitors. Including the surgical strike. Yes. You know I would also like to draw your attention to another incident. If you remember the BSF Javan who protested against the kind of rations that were given was sacked. Okay. He's now standing for elections. In testing in Varanasi. Varanasi is the prime minister. Yes. And about 1000 Javan's have or ex-Javan's have actually given him support have come out in Varanasi to vote. Of course. It's symbolic. We know that. But the point is here are the Javan's actually on the ground. Who are the ones also who have laid down their lives in Phulwama. No. And this is what the treatment to them has been. And I also like you to think about what has already come. The CISF. There was no even pretence of training against these kind of attacks. See in the military what is happening is very clear. You have had professional people of integrity who would never been really in politics. You never heard of them before. Many of them you are hearing of now except in their professional capacity. There is a fight now to preserve the true professionalism of the military as against those in government and officials and military officers who are actually taking a partisan and a biased position. So if you are with us you are a nationalist military and if you are not then what happens?  You know it's also interesting. You are messing around with one institution that is so important.  But this is particularly important because it's also an armed institution. Absolutely. So this is really at the end of it. And you can't divide it and you can't make a huge section of military men and personnel feel that we are not recognized simply because we want to be professional and don't want to be part of any political structure. Coming back to our topic of the elections, the Tabil Nad elections today. That you know last time it was an AI-ADMK sweep that 37 seats out of 39. Once it going to BJP this time the AI-ADMK and BJP are in alliance but there is no gender. Do you expect that AI-ADMK would become really a small force because a major section of the AI-ADMK seems to have shifted to other groups? Yes. Yes, it seems like that. And the reports that are coming out from Tamil Nadu is definitely showing a major tilt towards DMK and some of the other groups. As you're talking about Stalin's ascendancy in Tamil Nadu. Yes. And I think what Karuna and I did was a very clever thing. He knew that you know the legacy is so strong is that it would be very difficult to bring in Stalin right to the end. So he had anointed him a long time before. And today in these elections you can see that Stalin has actually come into his own. He is the accepted leader now of the DMK. He's calling the shots. He's showing a certain independence in decision making that was not always as visible as say a few years ago. So this is a major plus and he is accepted by the DMK carders. So I think we're going to have some fun in Tamil Nadu. And the ADMK carder does not seem to have accepted those who are now running the ADMK. And I met somebody from ADMK who said well not this time but you know one day Shachikalla will rule. So you know maybe she will when she comes out she'll get all that sympathy factor and maybe she will in some elections. But it does seem that this state at least is going completely against the BJP alliance which is in this case the BJP and ADMK. I think most of the South is like that except for Karnataka where the BJP is alive and trying very hard for a seat or so in Kerala. But there's a seat here and a seat there. But somehow you get the feeling that the South disclosed its doors to what it sees as this very very essentially North Indian Hindi speaking cow belt party. That's true. The BJP has probably not struck any resonance. It's not in Telangana. It's not in Andhra Pradesh. Except in Karnataka. And also the fact of course that some of these parties who are not identified with BJP of course are keeping their options open post elections. But at least in the election at the moment BJP somehow is the kiss of death in these states looks like it. I mean all together yeah 46. Maharashtra is now the biggest state after UP. It's bigger than Bihar. This state makes a huge difference. Last elections the Shiv Sena and the BJP had 36 seats and the INC and the Congress and the NCP Sharad Pawar had 12. Do you think the figures are going to be broadly similar this time? Change. Yes. The reports again the Congress itself is thinking of 12 to 18 seats. The outer limit upper limit is 18 which I don't see really at this moment. But you know Maharashtra is interesting because it's got a lot of things happening this time. Last few years you had the Shiv Sena fighting the BJP right. And then last moment Uddhav Thakure came into alliance with the BJP. But the carders who have been used to this vitriol against the BJP and the BJP carders who have been smarting under this attack are not working well in several constituencies. So you know you had a situation I think Aurangabad our reporter was telling us that the people there are saying we will not vote BJP. We will not vote for the Shiv Sena even we might vote for an Uvesi candidate but we will not vote for the Shiv Sena. So there's that kind of anger even though the seats have been allocated. So there is that division which they have not really been able to mend on the ground because there's been an amazing level of bitterness. I mean if you remember that Uddhav Thakure's attack on Modi was more vicious than the attack from the opposition at times. We put it stronger not vicious but anyway leaving that out. But of course as we know the NCP, the Congress also have their own divisions and they have also supposedly put up candidates who are not that strong. They don't have candidates. Candidates better selection. Apparently they could have found better ones but irrespective of that. But also the fact that the smaller parties, small there are different parties over there some seat adjustment with the left could have been possible with the peasant and workers party over there. Then also other small parties. But it's interesting it's interesting the Congress is almost opted out. And from what we hear the Raul Gandhi had several meetings with Sharap Bavadi NCP chief who's the old man who's not contesting these elections because of supposedly family accommodating various members of his family. But the other reason is that he's basically now in charge of the election both for the Congress and for the NCP. So he's the guy who's setting it out. He's the master strategist in his strategy always the Shiv Sena has played a role. So this time it's not Uddar Thakure but it's the MNS Raj Thakure. And he is working very closely with Raj Thakure in these elections to help some of the key candidates win. So it's interesting. And then on the other side you have this little grouping of Ovesi and Prakash Ambedkar. Prakash Ambedkar and Ovesi both too opportunist basically seen as BJP acolytes. No Prakash Ambedkar has had much more. They are seen to be splitters but it could be argued. Ovesi has a very mixed record. In fact friends in Hyderabad would say he's always been splitting in order to help the right, the BJP. Always. But Prakash Ambedkar has had a rather shall we say very different political strategy. Yes. So that's why it's very interesting. Why did he suddenly discard all that and go with Ovesi? That is one. But the second part of it was the Congress in its election shall we say tactics. Unwilling to accommodate people like Prakash Ambedkar and as I said other groups. It's not the only one. The other groups over there who also they don't seem to have finally accommodated. Well then if that's the reason then it's a good. I mean you know then it's an understandable reason and sort of sets him off the hook. Because right now the campaign one hears is that he's also sort of working closely with the BJP and I hope it isn't true.  Not only that Tel-Tumbri is his brother-in-law. Yes. Okay so unless you say he's been cowed into submission I wouldn't really think that is a major reason. I don't think he would be. Exactly. So I don't think that would be a major reason. But I do feel that if we take what the Congress has done in the what we discussed in UP what is discussed in different places. Absolutely. Absolutely. This is also a strategy of the Congress not to really give space to smaller regional parties. And what we are discussing on UP that in that sense the BJP strategy of leaving seats for the smaller parties has paid off for BJP. Relative to what the Congress has done this time. Fortunately, fortunately in the states that matter the local regional parties have been able to stitch up alliances. You know. Where they are strong. Wherever they are strong. Where they are. Maharashtra is where the Congress is strong. Exactly. And wherever the Congress is strong whether it's Rajasthan whether it's Maharashtra or Madhya Pradesh where it's you know the main party where there is no regional party really stronger than it. It's not. It's almost seems to be giving up the election in Gujarat. You know whatever the momentum was before the Assembly election last time has completely disappeared. One is not even hearing about this guy. Yes. About this party. Yes. The Congress seems to be more on the backward movements of reason which are not clear. Coming back to again election alliances. If the BSP had been an ally with the Congress in Maharashtra, Madhya Pradesh and Rajasthan. We have shown that one time if you remember the discussion we had. They would have got 10 to 15 additional seats. The Congress and these parties. Yes. They will not get any seats without Congress. Obviously Mahavati doesn't get any seat in Rajasthan. But if they come together they make a difference of 10 to 15 seats. For me you know in the whole process of coalition there's a message. There's a very very strong message from coalitions of federalism. Which is very much in the character of the Constitution. So sometimes you might get those 5 seats or 10 seats extra. You might not get them. You might get just an increased vote share. But the message, the political message that you're sending out is very very important in today's times. When there's this authoritarianism, where we talk of one party or two parties. Where the federal parties are feeling squeezed. Where there is that total attack as we just discussed with IT raids on the regional parties. As well. As well. So I think the whole message of stitching together coalitions would have been very very important in a post election scenario in 2019. Unfortunately the Congress has in a very deliberate strategy given that. Thank you very much Siba for mapping the elections with us. Hope to continue this till the elections are over. This is all the time we have for Newsclick today. Do keep watching Newsclick.


to today's class. So we will be continuing with high resolution NMR spectrum of molecules. So let us now using this concept of coupling constant and chemical shift, can we start interpreting NMR spectrum of few molecules and these can be used for distinguishing say isomers. So let us take an example. So if I have suppose a molecule which is something like C11, C11, H16 and O, this is a molecule which has two isomers. Now isomer suppose is something like this CH3, CH3, CH3 and O, CH2, C6H5 and the other molecule suppose we have CH3O, CH3, CH3, C6H4, CH3. So if these two are isomers of the same molecule, how we can distinguish based on the NMR spectrum that which molecule belongs to what. So what will be the NMR spectrum for say first molecule? So let us look at the groups that are present closely here. We have a benzene ring. Now as you know benzene ring comes around say 7 ppm. Then we have three methyl groups and these methyl groups comes quite like uphill shifted that is like near 0 ppm and then we have a methylene group. So three types of carbon mostly we have one here of benzene ring, methylene group and methyl group. So three types. So essentially we should see three peaks. What are those three peaks? And these three peaks are essentially like this. So here say our 0 ppm reference is there. Now we have the equivalent nine protons that are contributed by these three methyl group. So we have a peak which will be like this methyl groups here and that will corresponds to nine peaks. Then we have another proton which is methylene group. So this is say 0.09 ppm. Then we have another group which is methylene group and here it is contributed by two protons. So that will be around 3.5 ppm. And then we have far down here around 7 ppm that is one peak which is given by the five protons and that is 7.2. So this is our spectrum for this molecule. What happens to here? This molecule which is there is a benzene ring, one methyl group here, two methyl groups are here and one methyl groups are here. If you look at among these methyl groups the chemical shift is not same it is going to be different. Therefore we have a different spectrum for this molecule and this molecule will give a spectrum something like this. So the most downfield shifted will be these two methyl and that will be slightly downfield than this 0.9. So here is our TMS. So these six protons will be around 1.2 ppm. So this is six. Then it comes like other protons which we have like here and here. So even in these methylene protons we have three kind of chemical shift. For this benzene ring it will around 7.2 ppm. Then methyl will be around 2.2 ppm this methyl and then we have 1.2 ppm. And there is one more methyl which comes around here that is 3.5 ppm. So we have a six protons that will be around 1.2 ppm. Then three protons, three protons and this will be four protons. So let us go to next page and then I will write it clearly. For molecule like this that we have here is 0 ppm. We have the most downfield are six protons coming from these two groups. If you look at CH3 group and CH3 group. Now then we have one CH3 group which is attached to benzene ring and that comes around to say 2.2 ppm and these corresponds to three peaks. Then comes so this is what we are talking about this CH3 which is attached to benzene group. Then we have 3.5 ppm CH3 corresponds to three protons and that we are talking about OCH3 group. So even in the methyl depending upon what is attached here we are getting that different chemical shift and most downfield shifted for 4 protons that is coming because of benzene ring. So benzene ring has 4 protons because two groups are attached at two positions. So that is around 7.2 ppm. That is how we can distinguish. So if you go back, so spectrum of the previous proton here we have different than the current one and that is how you can distinguish between two isomers. Let us take the another isomer. Say its chemical formula is C7H12 and two structures that we have is CH3CH3CH3C triple bond CH3 one is this and suppose we have another CH3CH3CH3CH2 triple bond CH. So if we look at here now what we have is all these are in the same chemical environment. So 9 proton and they will be quite affected near 0. So we have a 9 proton corresponds to these three moiety and we have here 0.9 ppm. Then we have another type of chemical shift which is coming from proton chemical shift which is coming from here and that is we have one type of proton. So that is 3 and this comes around 2. So if you take ratio 3 to 9 or 1 to 3. So here we have ratio of signal 3 to 9 or 1 to 3. For this molecule what we have here we have a different kind of proton. So here are 3 one kind of proton then CH2 we have another kind and then CH we have that is third kind of protons. So this CH3 again say all 9 will come at 0.9 ppm. Then we have another proton two protons which will come around 3 ppm and this one proton which will again come very closer to that. So we have two protons and one proton that will come very close to each other. This is three proton and these are methylene protons. So that comes quite down full compared to this methyl protons. So this is how you can distinguish the isomers. So now how like we can do the analysis just I will go forward and try to explain again. So first thing you need to know if you have a chemical formula how many kind of protons we can have. So that will be simple given by how many double bonds that we have. So there is a simple calculation which is called double bond equivalence that you can find it out by a simple formula called 2A plus 2 minus B divided by 2 for a compound which is like CA HB OC HB OC. So here A is the number of carbon B is the number of proton. So like whatever we had earlier if you look at C11 H16 O we have. So how many double bond we are expected to have here? So if you look at here 2A 22 plus 2 minus 16 divided by 2. So 24 minus 16 8 divided by 2 means 4 and therefore we had a one benzene ring there. Now that is how this can be used let us take the another example that we had in the previous example C7 H12. How many double bond we are going to expect here? So 7 into 2 14 right 14 plus 2 minus 12 divided by 2. So that is 16 minus so that will be 2 number of double bonds. So DBE is 2 and therefore we had one triple bond there. So in the previous example. So that is how we can calculate the number of double bond equivalent. So now let us see if I give you chemical formula and now we have to predict the spectrum for that. So let us see we have a molecule like CO2 H4 and Cl2. Now if you calculate using that then we do not have a double bond because 2 multiplied into 2 plus 2 minus 4 divided by 2. So 4 plus 26 minus 4 that is 2 divided by 2. So DBE is like 1 so we do not have any double bond here. So that means all carbon are saturated. So probably the structure for this can be something like this CH Cl HCl and Cl or it even can be like this CH3 CH3 sorry CH and CH Cl and Cl. So how do you distinguish whether the spectrum that we are getting belongs to here or not? Now we record this spectrum for this molecule and suppose we are just getting only one peak here is our TMS this is only one peak. So now only one type of proton we have. So only one type of proton can be only this. So like where two protons on each carbon are attached and two chlorine are attached. If we have this case then we have two different kind of protons and this will generate two peaks. So if you are getting only one peak that means this is the correct molecule. That is how we actually interpret this spectrum. Now I will give you an a spectrum and a chemical formula and then we have to find what could be the structure of that. So let us see if I have a chemical formula of a molecule which is C9 H12 and the spectrum that I am getting is something like here 0 and one peak here one peak here ratio is 1 to 3. Now to find it out what could be. So you can similarly calculate the double bond equivalent and then two things are visible if I give you chemical shift. So chemical shift suppose for this is around less than 2 ppm say 1.5 something like that and here we are giving you around 7 ppm. So it is now clearly evident that we have two kind of proton one belongs to say methyl group another belongs to and benzene ring. Now so and ratios are 3 to 1. Now we have a total of 9 carbon and 12 protons. So 9 carbons and 12 protons if you calculate your double bond equivalent we can find it out that these three protons can only come if we have a methyl groups attached to a benzene ring and those methyl groups seems to be equivalent to chemical equivalent therefore something like this here one group attach another group attach here and here. So that takes care of our 9 protons remaining three protons are these and therefore we have two kinds of proton one attached to the directly from the benzene ring and 9 protons attached to the methyl group that is why we have 1 to 3. Let us take another example now here suppose our chemical formula is say C4 H10 O2 and our spectrum is say something may be like this here we have a 6 integration here we have a 4 integration and this say chemical shift is 3.2 and this chemical shift is say 3.6 something like this very close now can we predict the chemical structure of this compound. So we have a 0 double bound so one can calculate it. Now one thing is obvious that even there is a methyl group it is quite down field compared to the typical methyl group and that is because two oxygens are attached and we have two only two kind of protons one looks like from methyl group another looks like from methylene group let us put two oxygen here and then we have two methyl attached to these. So let us attach those two methyl and then we have remaining two carbons and then we can balance the four protons. So now these all four protons are of equivalent chemical shift and that belongs to these and this and these two methyl groups belongs to these. So we have two kind of proton one contribute to 6 integration another belongs to 4 integration this is from methyl group this is from methylene group that is how we can solve these structure of few of the chemical compound rest you can practice and then we can discuss in the class if required if you have any doubt. So let us move back and let us try to do some of the splitting pattern. So what happens when J coupling is involved here we have not considered any splitting let us consider some of the splitting. Now suppose we have a molecule which has a chemical formula like C3H7 and Cl and we have a spectrum something like this here it is 0 ppm we have two closed peaks and integration of these together comes 6 and here we have a peak which looks like multiplied and here we have integration one. So C3H7Cl what this could be so one thing is obvious that we have two kind of proton 6 and 1 so here we have 7 so 6 and 1 very clear. So then probably we have 6 protons so that might be coming from two methyl group here let us put two methyl groups and there is one chlorine so let us attach that chlorine here sorry Cl here now then there is only one proton which is attached here now what is happening here this proton is splitting this methyl group into two and therefore we have two equivalent like height methyl protons and integration total is 6. Now these six protons are splitting these single proton into septate and that is why we have a multiplied and that comes to be 1 that is how you can find it out that this is the chemical structure even the chemical formula is this. Let us go to next example, suppose we have a chemical formula like C6H5CH2SH. So now the spectrum is something like this here is 0 ppm here we have a triplet of 1 here we have again 2 and here around 7 ppm so here is 7 ppm we have a 5 protons here 2 protons which is less than 4 so 3.8 ppm and this is say 1.8 ppm something like this. So now we have to find the structure for this okay if we have this compound so we can clearly identify that these peaks 5 protons coming from this one C6H5 and then so these triplet this is CH2 so that will split SH proton into triplet therefore we have 1 SH triplet at 1 and then this H will split this CH2 into doublet so we have here doublet structure. So that is how looking at the spectrum and looking at the chemical structure one can identify few of these compounds. Okay let us take an complicated one now you can maybe you try to do it by yourself if we have something like C5H9O4 and N and suppose a spectrum I am getting something like this so here we have two kind of protons that shows doublet and here we shows triplet and this is say 1 ppm and this is say 1.4 ppm this is 1.6 ppm integration of this is 3 or integration of this is 3 and then we have 1 around 4.2 ppm and here we have a quartet like this and then around say 5.2 ppm we have again a quartet something like this. So integration of this is 1, 2 and here we have a 3 and 3. Now can you identify what this compound can be given the formula is like this. Okay so let us try to solve this as well so we have two, three protons that looks like there will be two methyl groups. So looking at these there is no equivalent so there will be two methyl groups we can write it two methyl groups at two end and then we have two other protons which are equivalent to so like CH2 and here CH. Now we have we can have one NO2 and there will be some CO2 which will be interact here so CO2 so our compound something like this we should have a so get down the exact chemical formula I am giving you a hint we have two methyl group there will be one CH2 group one CH group that will corresponds to the spectrum that we just now draw it. Here we have a triplet corresponding to three protons here we have another triplet corresponding to three protons here we have a quartet corresponding to two proton and here we have again quartet corresponding to one proton 5.2, 4.5, 1.8 and 1.6. So identify how these molecules corresponds to this kind of a spectrum and I will suggest you guys to do practice take any organic chemistry NMR spectroscopy book practice it take the spectrum and then try to deduce the chemical structure of that or take a compound and try to draw the spectrum for that but to understand how these lines comes we have to go into little digress details of explanation for their intensity for their resonance frequency all those comes if you understand little bit of quantum mechanical analysis. So what I will do today for this explanation I briefly venture into quantum mechanical description of these spins so I will just like you to go through the basics of quantum mechanics but we will be wherever required we will introduce it some of the phenomena. So let us start with a basic principle of quantum mechanics. So as you have studied your in your undergraduate or so for basic principle of quantum mechanics we have a operator which operates on a on a eigen function so we have a operator and we need to define an Hamiltonian function and operator operates on eigen function and it gives its eigen value. So these are basic terms like operator Hamiltonian eigen values and eigen function in NMR we particularly are interested in something called angular momentum operator and this is defined as i. So angular momentum is of our particular interest and we define that i, i is a operator of total angular momentum i has a three direction x, y, g and so here i z direction or x direction and say y direction or vice versa. So it has three components one in z direction x direction y direction in all three direction. So for a single spin half system two orientation of spin are possible one is like along the magnetic field here suppose we have a magnetic field b0 one is along the magnetic field another is against the magnetic field you can define one as alpha another as a beta or vice versa whatever way you want to define so these are the two orientation of spins along the magnetic field or against the magnetic field. So now these are eigen function of i z operator as I said there is a operator and in NMR it is the angular momentum operator. So now i z is an operator and it is operating on the eigen function like alpha and beta. So if i z operating on alpha state it gives the value of plus half or if it operates on beta state it gives the value of minus half. So that is what we have. So now if these functions alpha and beta are orthogonal that means if you take the bracket notation alpha or beta beta it is 1 or if you take beta alpha beta it is 0. So that is what we mean by orthogonal function. Now so as we said that these are operators i i x i y i z and these spins they do not commute but obey a cyclic relation.  So now two commuting operator with non-degenerate eigen value have a common eigen function what I mean by that if you have a a b phi so we have these functions. So here b is non-degenerate eigen values of function b. So that means a phi must be an scalar multiplication of phi what we mean by this is a phi equal to small a phi. This means phi is an eigen function of a and a is an eigen value. So here is phi is an eigen function a is eigen value. So this is basics of quantum mechanics and as we said that we will come back to quantum mechanics we will reintroduce wherever it is required. So now let us move ahead and then look at the high resolution NMR spectrum. So what all the functions and Hamiltonian we have. So main one is a Gman interaction. What we mean by Gman interaction is interaction of spins with an external magnetic field. So as we see that external magnetic field is defined as a b0 and it is in z direction and this is of like if you look at the magnitude it is quite a bit because magnetic field is of Tesla order or in terms of frequency it is a megahertz like 600 megahertz, 700 megahertz and all those. The next one is J coupling that is another Hamiltonian. So J coupling is interaction between the spins through bond. So like there are say here this is interaction between spin a and spin b and through bond how they are interacting that is what we call it J coupling. So it is a intramolecular interaction and this is of relatively very small magnitude. The third one is called dipolar coupling. So two spins in solution so these are two spins and there is a bond vector between them. So spin a and spin b and this is bond vector connecting them. So the angle between the main magnetic field and this bond vector is given as a phi. Now the dipolar coupling interaction happens through a space. So this was through bond interaction scalar coupling the dipolar coupling is through a space interaction and that if you remember little bit of this dipolar kind of interaction this is proportional to cos square phi minus 1. So phi is the angle between this intermolecular vector of these two spins with the magnetic field. Now what happens in solution the two spins all the time tumbles right. So because of this tumbling these term goes to zero and therefore we do not see any dipolar coupling in solution. So what we have mostly is a Giman interaction and J coupling interaction dipolar coupling is averaged out in solution but that is not case in the solid. Solid means does not tumble. So if you want to make this term zero we have to spin faster and faster and that is that we will discuss later whenever it comes. But in liquid state so these are the two interaction terms that we have mostly coming from the magnetic field external magnetic field this is order of megahertz then we have J coupling which is in order of hertz and dipolar coupling is typically order of kilohertz. So this is the main field and then we have a J coupling. So now let us move ahead if we have these interactions that means these can form the Hamiltonian which operates on the angular momentum operator. So the isotropic nuclear spin Hamiltonian isotropic means spins that tumbles in solution. So as we say isotropic that means spinning is happening all the time it is randomly moving so dipolar coupling is not there we have a Giman interaction and scalar coupling interaction which is coming because of J. So total Hamiltonian is H0 and H1. Now H0 is our Giman term and H1 is essentially J coupling term. So H0 one can define that how different spins like i, z, i, i is different spins and as we said that z component of angular momentum gamma is the gyromagnetic ratio of the each nuclei. So we have to sum over the sum over all the nuclei how this term comes. So H0 the Giman interaction term can be given by summation of gamma i, H i and z i. Now H1 is a J coupling Hamiltonian this causes the mixing of two spins because two spins now talking to each other through bond. So that is how it is J i this is coming because of the coupling and here are two spins i, i, i and i, j. So i, i and i, j are operator of i and j spin and because of this we have a coupling constant j is a coupling constant i, j is the operator for the z component of the angular momentum from i spin. So these are the two Hamiltonian terms in liquid states. So now quantum mechanical term for spin half, spin half that mostly we are looking at at the moment. So spin half nuclei like proton or carbon 13 or phosphorous P31 or nitrogen nitrogen 15. Now in these states the half spin system can be either in alpha state or beta state alpha state or beta state and then we can take the summation over all states. So for a particular states say we have a n spins. So we can write a particular state by alpha 1 that means the spin 1 is in alpha state, spin 2 is in beta state, spin 3 again is in alpha state, spin 4 is in beta state and again spin 5 in alpha state. So multiplication of all those will be given by a particular function which is phi n. So phi n is our eigen function and Hamiltonian H0 that is Zeman Hamiltonian operated on phi n which gives the eigen value En. So that is what H Hamiltonian gives phi n is the eigen function and En is an eigen value. So now the another Hamiltonian which is H1 and that is j coupling Hamiltonian these as we discussed cause the mixing of two different states. Now for these two eigen functions there will be linear combination of the product. So what we mean by that, so if we have a spins like n spins so we can have a product of these spins and you have to sum over that and that gives you resultant eigen function. So eigen function will be determined by the solution of the secular equation you might have studied. So we can solve this equation where Hmn minus E delta mn will be 0 and you have to solve this. The Hmn is the matrix element of this Hamiltonian for solving this we have to define our operator which is Fg and the product function which comes from this j coupling Hamiltonian you can solve this by defining in Fz and if you take this if we take this product so Fj is eigen function and I have eigen value like total azimuthal quantum number. So one can solve it by doing simple quantum mechanical algebraic operation and Fz commutes with Hamiltonian H. So Fz has a degenerate eigen value and that have that the above communication does not imply that eigen function Fz will have a eigen function of H. So if we solve this equation you apply Fz on phi m and then you get Fm. So Fn and Fm are eigen value corresponding to two function phi n and phi m and you solve this commutation relation and one can find it out. So like this operation so Fn is not equal to Fm and then the matrix elements will vanish and that helps us actually solving these equations. So you can block diagonalize this representation taking the case of Fn not equal to Fm. So if you do that then secular determinants gets the block diagonalized and the problem of determining the eigen value will be reduced dimension and then each block can be treated separately for solving these functions. So that is how we can solve it the eigen function for each of these value can be solved and if you can substitute then one can find the by multiplying phi m and calculating the matrix element and one can do that then what we found the basic functions and finally we come to by solving this we come to such kind of coefficient. So now doing that we can calculate the Hamiltonian for two spins. So now the complex problem will be now simplified in two spin system and now next we move ahead and try to solve and look at how we can calculate the Hamiltonian for two spin system and from there we build up the concepts and we try we will try to get it to the solution for these spins. So today I would like to end up here just I will summarize that we looked at how the splitting happens and what is the basic rule for a splitting and where is the resultant chemical shift average comes what is what will be the rules for intensity of these terms. So for a detailed analysis of these splitting patterns one has to go to quantum mechanical formalism and we looked at basics of quantum mechanics how to solve this so we will continue from there to calculate the Hamiltonian for two spin system and then we build up from there. Thank you very much and looking forward to see you in the next class.


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