WEBVTT

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Thanks so much. So. Um, yeah. So I was, uh, amused, uh, to hear in

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Thomas's talk that he called, uh, nine Tesla, relatively small field. Um, uh,

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for us, even the Earth field, uh, is, uh, high field. And, uh, so if you, uh, sort of

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look at this picture for different fields, for NMR, there is high intermediate low field. But but

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where we're going to go now is lower than low. Okay. So uh, but first I would

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like to thank the organizers for, uh, really essentially a perfect conference. Amazing

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science, fantastic food, great location, everything, great interactions, everything is really, really

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wonderful. Now, uh, I'm a frequent referee, and I have this bad habit

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that, uh, even if the paper is perfect, I need to put have small criticisms. I'd like

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to start with the title of the conference, which says.

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Something about NMR and MRI, but I think that in the modern MRI is like saying fruit and oranges,

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because I think, and correct me if I'm wrong, that there is the big set which is NMR, and then it's

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divided into different things like MRI and spectroscopy. So and the other and the other thing

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to pick on is beating Boltzmann that we already heard. You know, Professor

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Boltzmann suffered from very bad condition, neurasthenia and

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bipolar disorder and suffered so much that eventually killed himself. So maybe next time,

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instead of beating Boltzmann, we we can have compassion for Boltzmann. Anyway, with these

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comments, I would like to say that, um, This field of zero field

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NMR was pioneered by Alex Pines and John Clark. Um, and

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unfortunately the the update here is Alex is no longer with us, as you I'm sure heard. Um,

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and initially these guys were looking at the zero field NMR using Squids as sensors. And,

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and, uh, when we started collaborating with Alex, we started using spin sensors, um,

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mostly atomic magnetometers. And now it's moving also towards diamond, as you will hear. So the plan

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of my talk, uh, I will remind people in the audience what ZULF zero to ultra low field NMR

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is and most importantly say why you would want to do this. Okay. Even if you can, there is always an

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important question. Why? Um, uh, this is NMR without magnets. Um,

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hyperpolarization is an essential thing, and I will emphasize it many times, and then I will tell

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you about several recent things that are happening in Mainz. And one of them is

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these measure like if you want, or rather like oscillations that we see at zero field.

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So the best way to understand the idea for for ZULF NMR is think

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about first a regular NMR. And like many other things like for example, quantum

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computation and many other things and any kind of sensing based on spins,

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there are three phases in NMR. You need to polarize the nuclei. You need to encode the

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information that you are interested in. Be that spectroscopic information or the location of the

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spins into the spins, you have to encode that right? And then you need to read it out to

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detect. And normally you need magnetic fields, strong magnetic fields for all

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three of these stages. And the idea of ZULF NMR is, um, to get rid of the need for

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magnetic field in each one of them. Uh, for instance, use hyperpolarization techniques that do

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not rely on magnetic field in the polarization stage. Rely on J couplings for your spectroscopic

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information in the encoding stage, and use the spin based sensors, uh, for detection. So that's

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the the basic idea. And, um.

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Uh, just to show you how this looks like. And I must say, uh, when this field was

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introduced, people were kind of laughing at it, and they don't laugh anymore. And now you can find a

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lot of actually, labs that are trying to do this all over the world. Uh, in India,

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Madhu is here in, uh, In China. So this is, uh, to show you an apparatus that was built

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already more than a decade ago, uh, in China But this gentleman, Xin Zhou. Uh,

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and this is a magnetic field. So, uh, so when you go to the ZULF NMR lab, instead of magnets, you see

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magnetic fields because the Earth's field is too high. And, uh, he, of course, learned it, uh, as a

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postdoc in the Pines group, uh, several years before that. Um,

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so, okay, now, uh, we've learned to do it, but why do we do it? Okay, that's an important question. And

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I'll give you a short list here. Uh, it it is, uh, not necessarily super

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inexpensive and portable, but it can be made that as we heard in Michael Taylor's talk, uh, yesterday,

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um, the other more physical thing that allows you, uh, the access to couplings that are truncated in

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the normal NMR experiment due to the large Zeeman term. Because the frequencies are

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low, you are not limited by by the skin effect, and you can actually do measurements inside metal

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containers, which is practically important. It is completely insensitive to sample

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inhomogeneities because if the field is zero it's okay. Yeah that's okay. And

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then, uh oh, there's some strange, uh, sorry about this. Uh, so there

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are certain, um, spin states, uh, that are long lived at Zero Field. For example, there is

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this whole concept of hetero nuclear spin singlets with long lifetime, which are not

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possible, uh, at higher fields, um, and, uh, in certain cases

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there is enhanced relaxation contrast for, for relaxometry applications. So all of these things tell

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you that, uh uh, you know, you can kind of. Not really. You can never. I'll explain.

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Used to emphasize that we are not here to compete with with with high field NMR but we are

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to find niches where we can be complementary. So that's the main idea. All right. And I

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always like to say that if, uh, for most NMR people, hyper hyperpolarization is a luxury, you

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have a small signal and you want to make it bigger. Right. That for for ZULF it's actually a

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necessity because, uh, the polarization is zero. Uh, thermal polarization is zero.

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So, uh, there are many, uh, hyperpolarization techniques. And I would like to advertise a

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relatively recent review with many names, uh, that you will recognize here. Like, for

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example, the previous speaker and, uh, James Eills who is here in the audience, etc.

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and this project was spearheaded by, uh, eager content reviews. Uh, actually,

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all the, uh, techniques that we knew about at the time of writing, which is not so long ago.

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Now, this is a diagram. I like this sort of tells you about

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this, the status of the field of zero field NMR. And, um, you see, the

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hyperpolarization is the enabling thing for zero field NMR. And, and we

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actually tried all of these. The green here means that, that things that have already been tried and

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demonstrated to work And you see here from anywhere from Halbach brute force polarization to

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various kinds of hydrogen polarization,etc., etc. photo

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CIDNP. And uh, the one thing that we are working towards but haven't yet demonstrated the

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stochastic, uh, polarization. Uh, for detection. Um,

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so you can, uh, do inductive detection, for example, do a zero field, uh, experiment and then shuttle

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into high field magnet and do detection. Sometimes we do that, uh, squid optically pumping

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magnetometers, uh, anisotropic magneto resistive sensors, very inexpensive, not so

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sensitive, but we have several, uh, papers demonstrating NMR detection. The recent one

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is ZULF NMR detection. Uh, you can find it on the archive. Uh, and now I will show you I'm

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very happy to report that zero field NMR can also be detected with diamond. Uh, Dominik. Uh,

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and, uh, what we're working on that has not been demonstrated yet, but in the works is the

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radioactive detection. So the the idea is to combine uh, uh, A beta NMR gamma

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NMR with zero field NMR to sort of compensate for weak

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features of both techniques to make a more powerful team. But this isn't in the works. Uh, then, um,

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there are various, uh, associated techniques, uh, that have been demonstrated polarization transfer,

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relaxometry, partially aligned samples to bring back, for example, dipole

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interactions, 2D methods, and what has not been done yet

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is single molecule ZULF NMR, which we also call extremum NMR. And that's in the works. And the

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radioactively detected NMR. And as we just heard from from Thomas. New

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techniques new apparatus leads to new applications. It's driven creation of the

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apparatus is driven by the need. But then when you make an apparatus you find new needs. so there

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is a lot already that has been done here., quadrupole or nuclear

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catalysis, chemical dynamics, fundamental physics applications, search for exotic interactions,

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quantum control. And now we are moving towards chirality which is also very exciting.

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Um, let me now, uh, give you a brief, uh, sort of sampling of some recent work in the last couple

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of years in our lab. Uh, and, uh, so first,

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uh, we worked towards this for several years, and this was not very easy, but we we really wanted to

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detect zero field signals with diamond sensor. And, um, so finally,

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this was possible, uh, using, uh, hyperpolarization, uh, of here,

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uh, technique. And so, um, acetonitrile has um, um,

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has sort of these two sets of J coupled, uh, lines. So it gives signals

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that, uh, one and two, uh J. Uh, and we make this, uh,

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polarization in situ inside the apparatus. And we have a on the one side, uh, our well

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drafted optical pumping magnetometer as a detector. And on the other side, we have our

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diamond, uh, endoscope. Um, and this is kind of a universal, uh, devices and ensemble, uh,

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magnetometer that was also used, incidentally, to measure the magnetic field from the heart of

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patients and so on. So it's a stick, uh, about a centimeter in diameter, and it's

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engineered for, um, sensitivities of around ten pico Tesla per root uh, Hertz

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and, um. Here you can see the pulse sequence,

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which consists of, uh, bubbling and initiation pulse, and then the detection, uh, and, uh,

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this blue signal is the very nice signal to noise detection with

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the q spin, optical, optically pumping pump, magnetometer, and, uh, this creepier signal is

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diamond. But we, you know, we're very happy that we actually are seeing unambiguously these

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resonances. this is just the beginning. It's going to get better. And, of course, uh, the idea for

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diamond is a combination of sensitivity and spatial resolution. So this this is a way to to

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eventually shrink this apparatus. Uh, enormously. So this was an effort of many

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people. So you see, James, uh, here in the audience probably, I don't know, maybe he keeps my talk, I

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don't and many others. Okay. Um. All right. Um, so,

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uh, another application that we've been working on, uh, is, uh, a ZULF NMR technique for, um,

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measuring batteries. And this is nondestructive, uh, measuring, uh, measurement of, uh,

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batteries, small batteries with, uh, um, metal, uh, within

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metal enclosures. And, uh, this was proposed by John Blanchard many years ago, but, uh, has undergone

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many different iterations, uh, in the past. so there is a very nice, uh, collaborative

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collaboration of, uh, many people, uh, here, uh, uh, uh, achieved the

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measurement of both the analyte, uh, and um,uh, and,uh, and the

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solvent. And this is done in this case by shuttling the battery between the Halbach array

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and the zero field measurement device. So these are the two students Anne Fabricant and Roman

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Picazo-Frutos who were instrumental here. And this is Alexej Jerschow

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from European University who is a frequent visitor to our lab and a very dear collaborator. Um,

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so the key point here that we measured, uh, through metal enclosure, both electrolyte and

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solvent, and use the Halbach prepolarization. And now I'm going to tell you about the

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latest thing we are excited about. And we didn't really want to call it a maser or a

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raser or whatever. We. So we just called it quantum oscillator. And this is just recently

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published on the aircraft so far. Um, and so what we have again is

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a self oscillation at the uh, j coupling frequencies at zero

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field, and this is similar to two rasers except that zero field. Like I said, and it's

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also similar to what has been demonstrated recently with xenon spin

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based hyperpolarizationXENON and space spin masers in, for instance, in

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HAFAI by our collaborators there, and something that's called the Floquet maser. But the

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distinguishing feature is that it's coupling frequencies and can go really to very low micro

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hertz frequencies, you know, so it's very, very slow oscillations and up to

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tens of hertz could be higher if you need. Um, there is a popular

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misconception that these kind of systems require population inversion. They don't. Uh, and the idea

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is that you have a feedback, so you have some electronics so you can get energy from there. But

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you do need non-equilibrium. Population that you need polarization,

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that's for sure. Um, so, uh, we as you will see. It works with many different,

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uh, molecules, um, the different types. Uh, it makes lines narrow and may have

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helped to resolve, uh, blended lines, but, um. Uh, there are some complications I will

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mention in a minute. And it may allow on demand spectral editing, which is also quite exciting.

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Uh, so this is the experiment. Uh, the idea is that you

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measure, uh, ZULF NMR signal, in this case with an atomic magnetometer, and then you apply a

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feedback. And in this case, there is only one, uh, axis that is available. So you apply the feedback

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on the same axis, where you have your signal and you have a computer,

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and you can synthesize what kind of feedback you may have. And there are two main parameters for

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this. Uh, feedback is a delay. And again you can play with. And here again this

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J and two J um uh transitions for instance in a Sydney nitril

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And this is uh, a hydrogen, uh, polarization that we use.

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Okay. Uh, so here is for, for reference, uh, a free, uh,

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decay, uh, signal at zero field. Uh, so without the oscillation and then we

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apply the feedback, uh, here at t equal to zero. And then you see that there is

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some characteristic dynamics. After some time the oscillation starts and this can be actually

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accurately calculated. And then. And then you have the system reaching the steady state,

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um steady state condition. And then there is slow decay due to the decay of the

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polarization, the relaxation of the polarization. And you see here, uh, where the transitions

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are expected. Uh, in this case, we expect them at a very

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low frequency, 1.7Hz. And around here three point something. And you see that there is an

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oscillation at only one frequency under these conditions, okay. And not at the other with this

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choice of the delay and and gain. And now you can do it in a variety of

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conditions. And in some cases, uh, you can see, um, that you can have oscillation of

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both J and two J, and in some cases only on one of them, either one of them And I would like to

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draw your attention to, to these solid lines here. These are analytical calculations that reproduce

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what is happening here that were done by our brilliant, uh, PhD student, uh,

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Jingyan Xu. Um, yeah. So,

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uh, I guess I already said depending on feedback parameters, you can have only one or both of of

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lines. And we have the analytical model. Okay. So this is, uh, now various, uh,

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molecules. And uh, we shouldn't, I guess, spend time looking at the details. But one

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thing is that, um, the correspondence of your oscillation lines to, to,

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you know, your, um. A lot

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of lines without feedback is a is a bit, uh, complex. Uh, but in general the lines

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that you see are, uh, narrower and uh, it applies to, um, uh,

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applies to many molecules and allows for spectral simplification. Um, but uh, one needs to be a bit

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careful. And this is what we are working on right now to learn to extract actually the chemical

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information, uh, in the presence of effects like resonance pooling. Um, multiple oscillation points

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for one system. Uh, so lines appearing at different values of the delay and gain and uh, uh, and

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nonlinear interaction. So I would like to avoid overselling this to you. We are very excited. But

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but. Okay. And then so I'm kind of proud of, uh, of this, uh, experiment, uh, because here

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we wanted to separate the effects on this J oscillators of chemistry

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versus isotopic enrichment. And so we prepared several samples

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containing pyridine and from pyridine. As you see here. And we

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always have basically a mixture of say 5050 of the two, um

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compounds. But sometimes we have for example from pyridine in this case is fully

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labeled with N15 and pyridine is unlabeled. And in the opposite case we will

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have um again the same 5050, but some pyridine will be unlabeled, but pyridine will be

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labeled. then we can see what happens. And so these are again uh, uh of the of the

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feedback. And you see for example, some pyridine lines basically do not really do much when you

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change the game. Maybe there's a little bit of an effect. And when

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you add up now half of labeled pyridine, you see that there is some

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effect. So now you see some dependance of the frequency on the gain. And if you mix them

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equally, then you see some kind of an effect that looks like, uh, a avoided level crossing

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in this case. Um, and, and then eventually the farm pyridine disappears. So this is to say that it's

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an interesting, uh, rich dynamics that we are currently studying, um, that we hope,

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um, can result in, in a very good, um, selective method for chemistry.

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Um, okay. The detail theory is now currently under development,

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so I wanted to show you this thing here. So this is a selection of, of the

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experiments that we are doing. So and we ZULF here uh, J oscillators, uh,

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spin amplifiers and other thing we're doing. Um, and um, uh, we have

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an experiment where we are working with ZULF NMR of living cells, uh, the Hela

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cancer cells. have a postdoc who is an expert on, on that. And, and so for these, uh, what

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is the what is absolutely essential. And you cannot do any work if you don't have very good

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hyperpolarization. And so, for instance, these guys, this is Raphael Kircher, the senior. Um,

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he's a he's a he's a postdoc. And Jingyan are very good at, um, different

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chemistry. So you can see there's different molecules, different levels of polarization,

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different Enrichment. Um, so, uh, the the key

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points of this is, uh, a technique that, uh, hyperpolarization, uh, is enabled,

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and it's a novel platform. This this is the star is to remind me not to oversell it because, uh,

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you know, people have worked with self oscillating systems for a long time, and there are a lot, lots

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of analog systems But this is novel in the sense that it's at zero field and purely J coupling

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transition And it's for chemistry, nonlinear dynamics, fundamental physics and who knows what

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else. So all right, so, um, now, uh, I want to make good on

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the, uh, homework that the organizers, uh, gave us and, uh, give some thoughts

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about the, uh, miniaturization. Uh, I think that, uh, ZULF uh,

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is a very good candidate for Lab ona Chip.Okay. And we many

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people here work on Lab on a Chip. Um, and um, also there is a whole program at the National

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Standards and Technology in the US called nest on the chip. Um, and I think that there is no, nothing

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that prevents this from, from being realized except, uh, engineering and investment. So I don't

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see any technological problems to shrinking it, um, uh, to, to a chip uh,

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scale. Um, so the fact that there are no magnets, I think facilitates

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miniaturization, uh, microfluidics in this context, as was mentioned before, was done already. Uh,

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see, in our lab, um, in 2008, uh, there are many applications

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catalysis, batteries, plants, uh, uh, relaxometry oil cells, etc.

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And I just wanted to again advertise this recent review that already was mentioned

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by some people. And there is actually some chapters, some parts that talk about possible

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miniaturization direction. If you are interested, this is the recent review of Zero field and the

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NMR. So this brings me to the end. Our lab has existed in

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mines for the last 11 or so or ten and a half years. And, um,

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originally it was John Blanchard, uh, and I who put it all together. And we have,

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uh, very many, uh, absolutely brilliant alumni. You see them here. We have a

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wide network of collaborations in different countries and, and in Germany.

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And currently this is who is in the ZULF lab. but there is. You know,

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uh, dynamics, uh, people, people grow and, uh. Uh, Danila Barsky,

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um, um, is moving now for a faculty position. Uh, the University of Miami.

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Uh, and Fabricant got a permanent position at the PTB Berlin straight from

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graduate school. And, um, Ramon Picasso Frutos just started his position as a

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senior scientist at envision. The rest of us are still there, and Alexej visits us often,

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and we're really happy about it. Um, so if you want a brief in the unlikely case, uh,

27:51.540 --> 27:57.939
you got interested by my talk and want a brief introduction to the field. Then there is a short, uh,

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review by John Blanchard, Andreas Bissinger, and me from a few years back, and a

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rather detailed Field review that already was mentioned before. Um, for

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those of you who are interested in molecules, fundamental physics,

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and applying NMR to fundamental physics, I would like to advertise a workshop that I

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think is going to be extremely exciting. It's a very violation in molecules that we're going to

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have about on March 30th through April 1st. Okay. So and there will be

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we're going to be reporting some very exciting, uh, results on uh, trying to get towards parity

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violation, uh, in the transitions in chiral molecules. Uh, so

28:50.540 --> 28:57.539
please consider coming there. And, um, the plan of my talk, uh,

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uh, is here. Um, hyperpolarization is a bucket of spins is what we need. Uh, And this

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is the eye view of your miniature NMR MRI. And this is set in a

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beautiful island setting, uh, as well. And, uh, thank you very much for your attention. Yeah.

29:26.140 --> 29:31.180
Yeah. Thank you very much for that wonderful talk. Um, yeah. Are there any questions?

29:34.219 --> 29:41.179
Marcel? You want to go first again? Uh, yeah. Sorry for being such a loud mouth, but,

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uh, it's just too, uh, too, too much fun. Too, too interesting. Um, for I've had conversations

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with Sara and along these lines as well. So for systems where you, uh, feedback

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the, the readout, uh, into the system, um, and at some point, what you

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see is very intensely dependent on the parameters of the feedback and less and less dependent on

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the properties of the system that your you're studying. So if you use it for as

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a spectroscopic technique, in order to actually learn something about the system under study, um,

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you tend to start losing the generality that would be required for that. So I was wondering if

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you could comment on that trade off. Yeah, that's exactly what we're working on. Um, yeah. So,

30:34.569 --> 30:40.569
uh, this these are if you remove the sample, there are no oscillations. So it's. Yeah. So. Okay. So it's

30:40.569 --> 30:47.209
always it's it's always. It's always, uh, but there are these, uh,

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complications. And it's not just, uh, you know, the it also, uh, I believe so we like to talk

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about fundamental limits, right? I believe that none of these techniques, people get super excited

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It and make statements that, okay, this maser or razer or whatever is, uh,

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can, can actually improve your, uh, fundamental sensitivity., uh, almost never the case,

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but it can be technically extremely useful. Yeah. So while

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we're on the topic, you'll be the next to ask a question while we're on the topic of your

31:26.009 --> 31:30.969
J oscillators or similar or analog to the rasers that that I've been working in the past. So the

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non linear interactions look exactly like I've been seeing and publishing them over the last years,

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with the lines vanishing at higher fields. Same same as the zero field. I'm wondering at what

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point do you see the other line disappearing. You showed this nice system was the two pyridine

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versions. Right. And what where is the trade off in the concentrations and what concentration? Do you

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not see the second line anymore? Say at, I don't know, at least 5% of the time, I don't know what to

31:56.489 --> 32:02.010
tell you when the lower the concentration at some point. The line disappears, but I don't know what.

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It's not nonlinear. Enhanced. It's linearly the same. I don't know. It's very fresh. It's like

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basically weeks, all the work. So we are going to to study and the, the encouraging thing

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is that Jingyan in his model reproduces all the details. So, um, at some point when we trust it

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enough,we, we can do numerical experiments first and then., yeah, it's surprisingly predictable,

32:27.329 --> 32:34.129
right? And those are unpredictable. Yeah. Yeah, yeah. Thank you so much. Um, I think you are next. Thank

32:34.129 --> 32:40.128
you very much. Do you think you can characterize the performance of the Joscillators, perhaps in

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terms of the phase noise? Absolutely. Yeah. In the process, yes. Yeah. Because I and

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that range of frequency is readily available with other means by function generator

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or so on. So I thought it would be nice if there is an advantage of some

33:00.439 --> 33:06.920
something in terms of something. There's a whole big program of what we want to do, and the phase

33:06.920 --> 33:13.879
noise characterization is one of the items on the list. All right. I have

33:13.879 --> 33:20.879
a question as well. Yeah. Go ahead Jan. Yeah. Um, the for somebody not not working in this area. Right.

33:20.919 --> 33:27.400
And I'm going to read those papers you recommended, but, uh, just to get a feeling for it. I

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mean, you need hyperpolarization so that you actually will have

33:33.959 --> 33:40.759
something to measure. Yeah. Okay. But now, um, depending on how successful that is or how

33:40.840 --> 33:47.759
how what? Whichever version you use, what kind of sensitivity

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limits do you have? I mean, the detectors you showed us were were very sensitive detectors, I

33:54.160 --> 34:00.399
guess. Yeah. Yeah. So since the DVD, uh, is not is not the

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strongest feature of these things. Uh, so far at least. Uh, so, um, in the paper, we

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we make a comparison, for example, of the sensitivity of, um, uh, kind of tunes from the NMR

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setup and the Magritek benchtop,and, and we find that, um, the Magritek wins

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by over an order of magnitude, uh, uh, in the sensitivity. that so far, at least,

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um, but, um, you can't combine everything in one thing. So we feel

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that, uh, the interesting things we can access, uh, imaging within metal

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containers and so on, um, chemical dynamics, catalytic dynamics and so on,

34:47.120 --> 34:54.120
uh, is worthwhile. So, yeah. No, it's just that if you want to, if you want to develop an application, and

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I'm trying to figure out in my head if there's a. If there's a window of opportunity here, if one

35:00.159 --> 35:04.879
then then sensitivity will be a very important issue because that has to work in the environment

35:04.879 --> 35:10.360
where you have to apply it. Right. Of course. And and so the one one of the things to overcome the

35:10.360 --> 35:15.440
sensitivity limitation is a fantastic hyperpolarization. And that's a therefore this is

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a major direction in our lab okay. Is to got it okay.

35:23.719 --> 35:30.158
Now you want to go next or you want to ask a question. All right. Yes

35:30.199 --> 35:37.119
please. Yes. Thank you very much. You mentioned with the J r

35:37.479 --> 35:44.199
with the J oscillators, um, frequencies in the range of micro hertz. So this is two

35:44.199 --> 35:50.959
years. So, um, I mean, you need a lot of signal to measure such a oscillation frequency. And if you

35:50.959 --> 35:56.550
can do that, um, could this also work as a sensor in a very different field because we're looking

35:56.550 --> 36:03.229
at very long term fluctuations on the geo and let's say astronomical level. Yeah. That has to

36:03.229 --> 36:08.830
be carefully studied. Right. So we we didn't measure for two years, but we measured for many,

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many, many hours. And the micro hertz range probably I have to remember what it is

36:15.870 --> 36:22.869
many micro hertz but already pushing in that direction. Yeah. So it's just very, very slow uh,

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oscillation. And we still see the effect, but we will we need to study what we can do with it.

36:29.750 --> 36:36.628
All right. Anything else? If not, I'll have two short announcements. Um, before we

36:36.629 --> 36:43.189
thank our speaker. Um, well, no, let's first, let's first thank Dmitry Budker for this wonderful Talk. I

36:43.189 --> 36:49.269
think that's, uh. All right.
