Category Archives: para-Hydrogen

Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with para-hydrogen

Svyatova, Alexandra, Elizaveta S. Kononenko, Kirill V. Kovtunov, Dmitry Lebedev, Evgeniy Yu. Gerasimov, Andrey V. Bukhtiyarov, Igor P. Prosvirin, et al. “Spatially Resolved NMR Spectroscopy of Heterogeneous Gas Phase Hydrogenation of 1,3-Butadiene with Para-Hydrogen.” Catalysis Science & Technology 10, no. 1 (2020): 99–104.

https://doi.org/10.1039/C9CY02100K

Magnetic resonance-based methods such as nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) are widely used to provide in situ/operando information of chemical reactions. However, the low spin density and magnetic field inhomogeneities associated with heterogeneous catalytic systems containing gaseous reactants complicate such studies. Hyperpolarization techniques, in particular parahydrogen-induced polarization (PHIP), increase significantly the NMR signal intensity. In this study, we test 16 glass tube reactors containing Pd, Pt, Rh or Ir nanoparticles dispersed on a thin layer of TiO2, CeO2, SiO2 or Al2O3 for the hydrogenation of 1,3-butadiene using parahydrogen. The catalytic coatings of Ir and Rh gave hydrogenation products with the highest nuclear spin polarization while the coatings of Pd are the most selective ones for the semihydrogenation of 1,3-butadiene to 1- and 2-butenes. Spatially resolved NMR spectroscopy of the reagent and the product distribution along the reactor axis provided further mechanistic insight into the catalytic function of these reactive coatings under operando conditions.

[NMR] ABSTRACT DEADLINE EXTENDED for PERM 2020: the first Parahydrogen Enhanced Resonance Meeting

CALL FOR ABSTRACTS

(Virtual) Parahydrogen Enhanced Resonance Meeting 2020

1st annual PERM, Monday, July 27th- Wednesday, July 29th on Zoom

http://perm-conference.org/

We would like to invite you to submit an abstract to the first annual Parahydrogen Enhanced Resonance Meeting, PERM 2020. The first instance of this (PERManent) meeting will be online with the benefit of zero registration cost. Not only are we making hyperpolarization affordable, but also the scientific conferences that go along with it! The meeting will feature invited educational talks, promoted research talks, plus brief “power pitches” that may provide previews to virtual poster sessions organized in parallel zoom meetings. (Food and Drinks will have to be provided privately.) All recorded materials will be made publicly available on a PERM YouTube channel within 2 weeks after the conference. Students (and those new to parahydrogen-enhanced NMR/MRI) are especially encouraged to participate!

Please submit an abstract (pdf format) with a maximum of 300 words in 12pt font along with 1 Figure (plus title and author list) to the PERM Organization Committee by Monday, June 1st 2020 – detailed abstract instructions will be posted on the conference web-site soon. Please indicate whether you are willing to have your lecture/power pitch recorded. If yes, your recorded lecture will be featured on the conference’s YouTube channel (PERManently).

Important dates:

Abstract Deadline (extended): Monday, June 8th

Invitations for Presentations: Monday, June 22nd

Acceptance Deadline: Wednesday, July 1st

Registration Closes: Monday, July 20th

Conference Dates Monday, July 27th-Weds July 29th 

Notice that exact presentation times will take into account presenters time zones. Relax, we will not make you give a talk in your nighttime! It’s a jet-lag free conference. Welcome to the future! Submit your abstracts at http://perm-conference.org/. Finally, we encourage you to forward this message to any other scientists and students who may be interested.

Sincerely, your PERM Organization Committee.

Thomas Theis (North Carolina State University)

Patrick TomHon (North Carolina State University)

Sören Lehmkuhl, (North Carolina State University)

Premila Jayaratne (North Carolina State University)

Eduard Chekmenev (Wayne State University, USA & Russian Academy of Science)

Boyd Goodson (Southern Illinois University Carbondale)

Matthew Rosen (Massachusetts General Hospital)

====================================

This is the AMPERE MAGNETIC RESONANCE mailing list:

http://www.drorlist.com/nmrlist.html

NMR web database:

http://www.drorlist.com/nmr.html

[NMR] Please join us for PERM 2020 the first Parahydrogen Enhanced Resonance Meeting

CALL FOR ABSTRACTS

(Virtual) Parahydrogen Enhanced Resonance Meeting 2020

1st annual PERM, Monday, July 27th- Wednesday, July 29th on Zoom

http://perm-conference.org/

We would like to invite you to submit an abstract to the first annual Parahydrogen Enhanced Resonance Meeting, PERM 2020. The first instance of this (PERManent) meeting will be online with the benefit of zero registration cost. Not only are we making hyperpolarization affordable, but also the scientific conferences that go along with it! The meeting will feature invited educational talks, promoted research talks, plus brief “power pitches” that may provide previews to virtual poster sessions organized in parallel zoom meetings. (Food and Drinks will have to be provided privately.) All recorded materials will be made publicly available on a PERM YouTube channel within 2 weeks after the conference. Students (and those new to parahydrogen-enhanced NMR/MRI) are especially encouraged to participate!

Please submit an abstract (pdf format) with a maximum of 300 words in 12pt font along with 1 Figure (plus title and author list) to the PERM Organization Committee by Monday, June 1st 2020 – detailed abstract instructions will be posted on the conference web-site soon. Please indicate whether you are willing to have your lecture/power pitch recorded. If yes, your recorded lecture will be featured on the conference’s YouTube channel (PERManently).

Important dates:

Abstract Deadline: Monday, June 1st

Invitations for Presentations: Monday, June 22nd

Acceptance Deadline: Wednesday, July 1st

Registration Closes: Monday, July 20th

Conference Dates Monday, July 27th-Weds July 29th 

Notice that exact presentation times will take into account presenters time zones. Relax, we will not make you give a talk in your nighttime! It’s a jet-lag free conference. Welcome to the future! Submit your abstracts at http://perm-conference.org/. Finally, we encourage you to forward this message to any other scientists and students who may be interested.

Sincerely, your PERM Organization Committee.

Thomas Theis (North Carolina State University)

Patrick TomHon (North Carolina State University)

Sören Lehmkuhl, (North Carolina State University)

Premila Jayaratne (North Carolina State University)

Eduard Chekmenev (Wayne State University, USA & Russian Academy of Science)

Boyd Goodson (Southern Illinois University Carbondale)

Matthew Rosen (Massachusetts General Hospital)

====================================

This is the AMPERE MAGNETIC RESONANCE mailing list:

http://www.drorlist.com/nmrlist.html

NMR web database:

http://www.drorlist.com/nmr.html

Lifetime of Para-hydrogen in Aqueous Solutions and Human Blood

Schmidt, Andreas B., Jakob Wörner, Andrey Pravdivtsev, Stephan Knecht, Harald Scherer, Stefan Weber, Jürgen Hennig, Dominik Elverfeldt, and Jan‐Bernd Hövener. “Lifetime of Para-Hydrogen in Aqueous Solutions and Human Blood.” ChemPhysChem 20, no. 19 (October 2, 2019): 2408–12.

https://doi.org/10.1002/cphc.201900670.

Molecular hydrogen has unique nuclear spin properties. Its nuclear spin isomer, parahydrogen (pH2), was instrumental in the early days of quantum mechanics and allows to boost the NMR signal by several orders of magnitude. pH2-induced polarization (PHIP) is based on the survival of pH2 spin order in solution, yet its lifetime has not been investigated in aqueous or biological media required for in vivo applications. Herein, we report longitudinal relaxation times (T1) and lifetimes of pH2 ( tPOC) in methanol and water, with or without O2, NaCl, rhodiumcatalyst or human blood. Furthermore, we present a relaxation model that uses T1 and tPOC for more precise theoretical predictions of the H2 spin state in PHIP experiments. All measured T1 values were in the range of 1.4–2 s and tPOC values were of the order of 10–300 minutes. These relatively long lifetimes hold great promise for emerging in vivo implementations and applications of PHIP.

Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

Kaltschnee, Lukas, Anil P. Jagtap, Jeffrey McCormick, Shawn Wagner, Louis‐S. Bouchard, Marcel Utz, Christian Griesinger, and Stefan Glöggler. “Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst.” Chemistry – A European Journal 25, no. 47 (August 22, 2019): 11031–35.

https://doi.org/10.1002/chem.201902878.

NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the parahydrogen’s singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl 13C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.

Polarization of low-γ nuclei by transferring spin order of parahydrogen at high magnetic fields

Kozinenko, Vitaly P., Alexey S. Kiryutin, Alexandra V. Yurkovskaya, and Konstantin L. Ivanov. “Polarization of Low-γ Nuclei by Transferring Spin Order of Parahydrogen at High Magnetic Fields.” Journal of Magnetic Resonance 309 (December 2019): 106594. 

https://doi.org/10.1016/j.jmr.2019.106594

In this work, we optimize the performance of a previously proposed method for transferring parahydrogen induced polarization to ‘‘insensitive” spin-1/2 NMR (Nuclear Magnetic Resonance) nuclei, which have low gyromagnetic ratio and low natural abundance. By optimizing the reaction conditions and pressure of the parahydrogen gas and using adiabatically switched radiofrequency fields we achieve high polarization transfer efficiency and report carbon spin polarization of dimethyl acetylene dicarboxylate reaching 35%, which corresponds to 13C NMR signal enhancements of about 43,000 at 9.4 Tesla. Such polarization levels allow one to work with mM concentrations at natural carbon abundance and to detect 13C NMR signal in single scan. In combination with a pseudo phase cycle, the polarization transfer method used here also enables efficient suppression of unwanted background signals.

Open-Source Automated Parahydrogen Hyperpolarizer for Molecular Imaging Using 13C Metabolic Contrast Agents

Coffey, Aaron M., Roman V. Shchepin, Milton L. Truong, Ken Wilkens, Wellington Pham, and Eduard Y. Chekmenev. “Open-Source Automated Parahydrogen Hyperpolarizer for Molecular Imaging Using 13 C Metabolic Contrast Agents.” Analytical Chemistry 88, no. 16 (August 16, 2016): 8279–88.

https://doi.org/10.1021/acs.analchem.6b02130.

An open-source hyperpolarizer producing 13C hyperpolarized contrast agents using parahydrogen induced polarization (PHIP) for biomedical and other applications is presented. This PHIP hyperpolarizer utilizes an Arduino microcontroller in conjunction with a readily modified graphical user interface written in the open-source processing software environment to completely control the PHIP hyperpolarization process including remotely triggering an NMR spectrometer for efficient production of payloads of hyperpolarized contrast agent and in situ quality assurance of the produced hyperpolarization. Key advantages of this hyperpolarizer include: (i) use of opensource software and hardware seamlessly allowing for replication and further improvement as well as readily customizable integration with other NMR spectrometers or MRI scanners (i.e., this is a multiplatform design), (ii) relatively low cost and robustness, and (iii) in situ detection capability and complete automation. The device performance is demonstrated by production of a dose (∼2−3 mL) of hyperpolarized 13C-succinate with %P13C ∼ 28% and 30 mM concentration and 13C-phospholactate at %P13C ∼ 15% and 25 mM concentration in aqueous medium. These contrast agents are used for ultrafast molecular imaging and spectroscopy at 4.7 and 0.0475 T. In particular, the conversion of hyperpolarized 13C-phospholactate to 13C-lactate in vivo is used here to demonstrate the feasibility of ultrafast multislice 13C MRI after tail vein injection of hyperpolarized 13C-phospholactate in mice.

Parahydrogen induced hyperpolarization provides a tool for NMR metabolomics at nanomolar concentrations

Sellies, Lisanne, Indrek Reile, Ruud L. E. G. Aspers, Martin C. Feiters, Floris P. J. T. Rutjes, and Marco Tessari. “Parahydrogen Induced Hyperpolarization Provides a Tool for NMR Metabolomics at Nanomolar Concentrations.” Chemical Communications 55, no. 50 (2019): 7235–38.

https://doi.org/10.1039/C9CC02186H

An NMR approach based on parahydrogen hyperpolarization is presented to detect and resolve specific classes of metabolites in complex biomixtures at down to nanomolar concentrations. We demonstrate our method on solid phase extracts of urine, by simultaneously observing hundreds of metabolites well below the limits of detection of thermal NMR.

Substituent Influences on the NMR Signal Amplification of Ir Complexes with Heterocyclic Carbene Ligands

Hadjiali, Sara, Roman Savka, Markus Plaumann, Ute Bommerich, Sarah Bothe, Torsten Gutmann, Tomasz Ratajczyk, et al. “Substituent Influences on the NMR Signal Amplification of Ir Complexes with Heterocyclic Carbene Ligands.” Applied Magnetic Resonance 50, no. 7 (July 2019): 895–902.

https://doi.org/10.1007/s00723-019-01115-x.

A number of Ir–N-heterocyclic carbene (Ir–NHC) complexes with asymmetric N-heterocyclic carbene (NHC) ligands have been prepared and examined for signal amplification by reversible exchange (SABRE). Pyridine was chosen as model compound for hyperpolarization experiments. This substrate was examined in a solvent mixture using several Ir–NHC complexes, which differ in their NHC ligands. The SABRE polarization was created at 6 mT and the 1H nuclear magnetic resonance signals were detected at 7 T. We show that asymmetric NHC ligands, because of their favorable chemistry, can adapt the SABRE active complexes to different chemical scenarios.

Postdoctoral researcher, Parahydrogen biosensors for hypersensitive NMR analysis

See also the application link: https://rekry.saima.fi/certiahome/open_job_view.html?did=5600&jc=1&id=00007645&lang=en

Postdoctoral researcher, Parahydrogen biosensors for hypersensitive NMR analysis

The University of Oulu in Northern Finland, with approximately 15000 students and 3000 employees, is an international, multidisciplinary research university with a rich pool of creative and intellectual talent. The strengths of the University are broad, multidisciplinary research interests, a modern research and study environment, and wide cooperation with international research and educational institutes (http://www.oulu.fi/english).

The postdoctoral position is in the field of nuclear magnetic resonance (NMR), in the following specific topic: Development of metal-free catalytic systems for parahydrogen-based NMR hyperpolarization techniques.

The position is located at the NMR Research Unit (http://cc.oulu.fi/~nmrwww), in the Faculty of Science. We are an internationally established, combined experimental and theoretical team of about 20 people, of which 50% with a PhD degree. We develop experimental, theoretical and computational research methods based on magnetic resonance phenomena and apply those methods to topical problems in molecular and materials sciences. Our particular strength is in the tight connection between state-of-the-art measurements and calculations. We have an open and encouraging working atmosphere and have a substantial track record in successful funding applications both at the Academy of Finland and in EU programmes. We are a key user of the NMR laboratory facility of the University of Oulu, furnished with six spectrometers (300-600 MHz) suited for an unusually broad variety of studies (wide range of nuclei, gas/liquid/solid, different sample sizes, imaging capabilities, diffusion probe, micro CryoProbe, remote detection, spin-exchange optical pumping/parahydrogen-induced/SABRE hyperpolarization), two low-field, mobile NMR spectrometers as well as nuclear magneto-optic instrumentation. CPU-intensive computational research is carried out mainly using the facilities of the national supercomputer centre (2300 TFlop/s total capacity). Local linux clusters belonging to the Finnish Grid and Cloud Infrastructure are used for high-throughput production calculations.

Subject field and description of the position

The position is a part of Academy Project “Parahydrogen biosensors for hypersensitive NMR analysis” provided by the Academy of Finland.

The research direction of the position is briefly described in the following: The project aims at development of metal-free activators of H2 molecules capable of producing nuclear spin hyperpolarization upon activation of parahydrogen, increasing NMR sensitivity by orders of magnitude. Typically, metal-containing activators/catalysts are used in parahydrogen-based hyperpolarization techniques. We develop more biogenic metal-free catalytic systems that can be used to create hypersensitive NMR biosensors for biomolecular monitoring.

The length of the position is two years. The starting date of the position is September 16, 2019, or as soon as possible thereafter.

A six-month trial period will be effective in the beginning of the two-year contract.

Required Qualifications and assessment

The successful applicant must have a completed PhD in physics, chemistry, materials science, or a related field. The applicants must show a visible scientific profile. Significant experience in experimental NMR spectroscopy and other physical methods of analysis are to be documented for this position. Strong skills in synthetic and experimental organic chemistry are valuable to the project. Experience in the application of computational methods for studies of chemical reactivity is considered as an advantage. The project requires computer experience in data analysis (Excel, Origin, Matlab).

Fluent English, good communication skills and good teamwork skills are required. Further, demonstrated potential in acquiring supplementary (extramural) funding, and teaching experience will be taken as a merit when choosing the scientist. When assessing the applicant’s qualifications, issues to be considered will include scientific publications, thesis supervision, activity in the scientific community, practical familiarity with the field in question, scientific work abroad, and other international activities.

As part of the NMR Research Unit, the duties also include supervising scientific research of BSc, MSc and PhD students as well participation in important research activities of the group. Participation in teaching within the physics curriculum and acquiring research funding are naturally expected.

Salary

The salary will be based on the levels 5-6 of the demand level chart for university–level teaching and research staff of Finnish universities. In addition, a salary component based on personal work performance will be paid (maximum of 50 % of the job-specific component). The salary is thus in practice roughly 3400–4000 € per month, depending on the appointee’s qualifications, experience and the progress in the research.

Application Procedure

The following documents must be attached to the application:

1) Brief curriculum vitae in English

2) List of publications in international peer-reviewed journals

3) Brief description of research merits

4) Brief (1-2 pages) research and action plan in English

5) Contact information of two persons whom may be asked to give a statement of the candidate

Applications, together with all relevant enclosures, should be submitted using electronic application form by September 1, 2019 23:59 (Finnish local time).

Interview

The top candidates for the posts may be interviewed and asked to present their plans for running the post successfully.

For further information regarding the filling of this post:

Dr. Vladimir Zhivonitko, NMR Research Unit, University of Oulu, tel. +358-41-495 7904, email: vladimir.zhivonitko(at)oulu.fi

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http://www.drorlist.com/nmrlist.html

NMR web database:

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