---
_id: '14831'
abstract:
- lang: eng
text: Catalysis, the acceleration of product formation by a substance that is left
unchanged, typically results from multiple elementary processes, including diffusion
of the reactants toward the catalyst, chemical steps, and release of the products.
While efforts to design catalysts are often focused on accelerating the chemical
reaction on the catalyst, catalysis is a global property of the catalytic cycle
that involves all processes. These are controlled by both intrinsic parameters
such as the composition and shape of the catalyst and extrinsic parameters such
as the concentration of the chemical species at play. We examine here the conditions
that catalysis imposes on the different steps of a reaction cycle and the respective
role of intrinsic and extrinsic parameters of the system on the emergence of catalysis
by using an approach based on first-passage times. We illustrate this approach
for various decompositions of a catalytic cycle into elementary steps, including
non-Markovian decompositions, which are useful when the presence and nature of
intermediate states are a priori unknown. Our examples cover different types of
reactions and clarify the constraints on elementary steps and the impact of species
concentrations on catalysis.
acknowledgement: We acknowledge funding from ANR-22-CE06-0037-02. This work has received
funding from the European Unions Horizon 2020 research and innovation program under
the Marie Sklodowska-Curie grant agreement No. 754387.
article_processing_charge: No
article_type: original
arxiv: 1
author:
- first_name: Yann
full_name: Sakref, Yann
last_name: Sakref
- first_name: Maitane
full_name: Muñoz Basagoiti, Maitane
id: 1a8a7950-82cd-11ed-bd4f-9624c913a607
last_name: Muñoz Basagoiti
orcid: 0000-0003-1483-1457
- first_name: Zorana
full_name: Zeravcic, Zorana
last_name: Zeravcic
- first_name: Olivier
full_name: Rivoire, Olivier
last_name: Rivoire
citation:
ama: Sakref Y, Muñoz Basagoiti M, Zeravcic Z, Rivoire O. On kinetic constraints
that catalysis imposes on elementary processes. The Journal of Physical Chemistry
B. 2023;127(51):10950-10959. doi:10.1021/acs.jpcb.3c04627
apa: Sakref, Y., Muñoz Basagoiti, M., Zeravcic, Z., & Rivoire, O. (2023). On
kinetic constraints that catalysis imposes on elementary processes. The Journal
of Physical Chemistry B. American Chemical Society. https://doi.org/10.1021/acs.jpcb.3c04627
chicago: Sakref, Yann, Maitane Muñoz Basagoiti, Zorana Zeravcic, and Olivier Rivoire.
“On Kinetic Constraints That Catalysis Imposes on Elementary Processes.” The
Journal of Physical Chemistry B. American Chemical Society, 2023. https://doi.org/10.1021/acs.jpcb.3c04627.
ieee: Y. Sakref, M. Muñoz Basagoiti, Z. Zeravcic, and O. Rivoire, “On kinetic constraints
that catalysis imposes on elementary processes,” The Journal of Physical Chemistry
B, vol. 127, no. 51. American Chemical Society, pp. 10950–10959, 2023.
ista: Sakref Y, Muñoz Basagoiti M, Zeravcic Z, Rivoire O. 2023. On kinetic constraints
that catalysis imposes on elementary processes. The Journal of Physical Chemistry
B. 127(51), 10950–10959.
mla: Sakref, Yann, et al. “On Kinetic Constraints That Catalysis Imposes on Elementary
Processes.” The Journal of Physical Chemistry B, vol. 127, no. 51, American
Chemical Society, 2023, pp. 10950–59, doi:10.1021/acs.jpcb.3c04627.
short: Y. Sakref, M. Muñoz Basagoiti, Z. Zeravcic, O. Rivoire, The Journal of Physical
Chemistry B 127 (2023) 10950–10959.
date_created: 2024-01-18T07:47:11Z
date_published: 2023-12-13T00:00:00Z
date_updated: 2024-01-23T07:58:27Z
day: '13'
department:
- _id: AnSa
doi: 10.1021/acs.jpcb.3c04627
external_id:
arxiv:
- '2312.15940'
isi:
- '001134068000001'
intvolume: ' 127'
isi: 1
issue: '51'
keyword:
- Materials Chemistry
- Surfaces
- Coatings and Films
- Physical and Theoretical Chemistry
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.48550/arXiv.2312.15940
month: '12'
oa: 1
oa_version: Preprint
page: 10950-10959
publication: The Journal of Physical Chemistry B
publication_identifier:
eissn:
- 1520-5207
issn:
- 1520-6106
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
status: public
title: On kinetic constraints that catalysis imposes on elementary processes
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 127
year: '2023'
...
---
_id: '12113'
abstract:
- lang: eng
text: The power factor of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)
(PEDOT:PSS) film can be significantly improved by optimizing the oxidation level
of the film in oxidation and reduction processes. However, precise control over
the oxidation and reduction effects in PEDOT:PSS remains a challenge, which greatly
sacrifices both S and σ. Here, we propose a two-step post-treatment using a mixture
of ethylene glycol (EG) and Arginine (Arg) and sulfuric acid (H2SO4) in sequence
to engineer high-performance PEDOT:PSS thermoelectric films. The high-polarity
EG dopant removes the excess non-ionized PSS and induces benzenoid-to-quinoid
conformational change in the PEDOT:PSS films. In particular, basic amino acid
Arg tunes the oxidation level of PEDOT:PSS and prevents the films from over-oxidation
during H2SO4 post-treatment, leading to increased S. The following H2SO4 post-treatment
further induces highly orientated lamellar stacking microstructures to increase
σ, yielding a maximum power factor of 170.6 μW m−1 K−2 at 460 K. Moreover, a novel
trigonal-shape thermoelectric device is designed and assembled by the as-prepared
PEDOT:PSS films in order to harvest heat via a vertical temperature gradient.
An output power density of 33 μW cm−2 is generated at a temperature difference
of 40 K, showing the potential application for low-grade wearable electronic devices.
acknowledgement: Scientific Research Program Funded by Shaanxi Provincial Education
Department (Program No.22JY012), Natural Science Basic Research Program of Shaanxi
(Grant No.2022JZ-31), Young Talent fund of University Association for Science and
Technology in Shaanxi, China (Grant No.20210411), China Postdoctoral Science Foundation
(Grant No. 2021M692621), the Foundation of Shaanxi University of Science & Technology
(Grant No. 2017GBJ-03), Open Foundation of Key Laboratory of Auxiliary Chemistry
and Technology for Chemical Industry, Ministry of Education, Shaanxi University
of Science and Technology (Grant No. KFKT2022-15), and Open Foundation of Shaanxi
Collaborative Innovation Center of Industrial Auxiliary Chemistry and Technology,
Shaanxi University of Science and Technology (Grant No. KFKT2022-15).
article_number: '156101'
article_processing_charge: No
article_type: original
author:
- first_name: Li
full_name: Zhang, Li
last_name: Zhang
- first_name: Xingyu
full_name: Liu, Xingyu
last_name: Liu
- first_name: Ting
full_name: Wu, Ting
last_name: Wu
- first_name: Shengduo
full_name: Xu, Shengduo
id: 12ab8624-4c8a-11ec-9e11-e1ac2438f22f
last_name: Xu
- first_name: Guoquan
full_name: Suo, Guoquan
last_name: Suo
- first_name: Xiaohui
full_name: Ye, Xiaohui
last_name: Ye
- first_name: Xiaojiang
full_name: Hou, Xiaojiang
last_name: Hou
- first_name: Yanling
full_name: Yang, Yanling
last_name: Yang
- first_name: Qingfeng
full_name: Liu, Qingfeng
last_name: Liu
- first_name: Hongqiang
full_name: Wang, Hongqiang
last_name: Wang
citation:
ama: Zhang L, Liu X, Wu T, et al. Two-step post-treatment to deliver high performance
thermoelectric device with vertical temperature gradient. Applied Surface Science.
2023;613. doi:10.1016/j.apsusc.2022.156101
apa: Zhang, L., Liu, X., Wu, T., Xu, S., Suo, G., Ye, X., … Wang, H. (2023). Two-step
post-treatment to deliver high performance thermoelectric device with vertical
temperature gradient. Applied Surface Science. Elsevier. https://doi.org/10.1016/j.apsusc.2022.156101
chicago: Zhang, Li, Xingyu Liu, Ting Wu, Shengduo Xu, Guoquan Suo, Xiaohui Ye, Xiaojiang
Hou, Yanling Yang, Qingfeng Liu, and Hongqiang Wang. “Two-Step Post-Treatment
to Deliver High Performance Thermoelectric Device with Vertical Temperature Gradient.”
Applied Surface Science. Elsevier, 2023. https://doi.org/10.1016/j.apsusc.2022.156101.
ieee: L. Zhang et al., “Two-step post-treatment to deliver high performance
thermoelectric device with vertical temperature gradient,” Applied Surface
Science, vol. 613. Elsevier, 2023.
ista: Zhang L, Liu X, Wu T, Xu S, Suo G, Ye X, Hou X, Yang Y, Liu Q, Wang H. 2023.
Two-step post-treatment to deliver high performance thermoelectric device with
vertical temperature gradient. Applied Surface Science. 613, 156101.
mla: Zhang, Li, et al. “Two-Step Post-Treatment to Deliver High Performance Thermoelectric
Device with Vertical Temperature Gradient.” Applied Surface Science, vol.
613, 156101, Elsevier, 2023, doi:10.1016/j.apsusc.2022.156101.
short: L. Zhang, X. Liu, T. Wu, S. Xu, G. Suo, X. Ye, X. Hou, Y. Yang, Q. Liu, H.
Wang, Applied Surface Science 613 (2023).
date_created: 2023-01-12T11:55:02Z
date_published: 2023-03-15T00:00:00Z
date_updated: 2023-08-14T11:47:06Z
day: '15'
department:
- _id: MaIb
doi: 10.1016/j.apsusc.2022.156101
external_id:
isi:
- '000911497000001'
intvolume: ' 613'
isi: 1
keyword:
- Surfaces
- Coatings and Films
- Condensed Matter Physics
- Surfaces and Interfaces
- General Physics and Astronomy
- General Chemistry
language:
- iso: eng
month: '03'
oa_version: None
publication: Applied Surface Science
publication_identifier:
issn:
- 0169-4332
publication_status: epub_ahead
publisher: Elsevier
quality_controlled: '1'
scopus_import: '1'
status: public
title: Two-step post-treatment to deliver high performance thermoelectric device with
vertical temperature gradient
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 613
year: '2023'
...
---
_id: '13353'
abstract:
- lang: eng
text: We show that the optical properties of indigo carmine can be modulated by
encapsulation within a coordination cage. Depending on the host/guest molar ratio,
the cage can predominantly encapsulate either one or two dye molecules. The 1 : 1
complex is fluorescent, unique for an indigo dye in an aqueous solution. We have
also found that binding two dye molecules stabilizes a previously unknown conformation
of the cage.
article_processing_charge: No
article_type: original
author:
- first_name: Oksana
full_name: Yanshyna, Oksana
last_name: Yanshyna
- first_name: Liat
full_name: Avram, Liat
last_name: Avram
- first_name: Linda J. W.
full_name: Shimon, Linda J. W.
last_name: Shimon
- first_name: Rafal
full_name: Klajn, Rafal
id: 8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
last_name: Klajn
citation:
ama: Yanshyna O, Avram L, Shimon LJW, Klajn R. Coexistence of 1:1 and 2:1 inclusion
complexes of indigo carmine. Chemical Communications. 2022;58(21):3461-3464.
doi:10.1039/d1cc07081a
apa: Yanshyna, O., Avram, L., Shimon, L. J. W., & Klajn, R. (2022). Coexistence
of 1:1 and 2:1 inclusion complexes of indigo carmine. Chemical Communications.
Royal Society of Chemistry. https://doi.org/10.1039/d1cc07081a
chicago: Yanshyna, Oksana, Liat Avram, Linda J. W. Shimon, and Rafal Klajn. “Coexistence
of 1:1 and 2:1 Inclusion Complexes of Indigo Carmine.” Chemical Communications.
Royal Society of Chemistry, 2022. https://doi.org/10.1039/d1cc07081a.
ieee: O. Yanshyna, L. Avram, L. J. W. Shimon, and R. Klajn, “Coexistence of 1:1
and 2:1 inclusion complexes of indigo carmine,” Chemical Communications,
vol. 58, no. 21. Royal Society of Chemistry, pp. 3461–3464, 2022.
ista: Yanshyna O, Avram L, Shimon LJW, Klajn R. 2022. Coexistence of 1:1 and 2:1
inclusion complexes of indigo carmine. Chemical Communications. 58(21), 3461–3464.
mla: Yanshyna, Oksana, et al. “Coexistence of 1:1 and 2:1 Inclusion Complexes of
Indigo Carmine.” Chemical Communications, vol. 58, no. 21, Royal Society
of Chemistry, 2022, pp. 3461–64, doi:10.1039/d1cc07081a.
short: O. Yanshyna, L. Avram, L.J.W. Shimon, R. Klajn, Chemical Communications 58
(2022) 3461–3464.
date_created: 2023-08-01T09:32:55Z
date_published: 2022-01-22T00:00:00Z
date_updated: 2023-08-02T09:46:51Z
day: '22'
doi: 10.1039/d1cc07081a
extern: '1'
external_id:
pmid:
- '35064258'
intvolume: ' 58'
issue: '21'
keyword:
- Materials Chemistry
- Metals and Alloys
- Surfaces
- Coatings and Films
- General Chemistry
- Ceramics and Composites
- Electronic
- Optical and Magnetic Materials
- Catalysis
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1039/D1CC07081A
month: '01'
oa: 1
oa_version: Published Version
page: 3461-3464
pmid: 1
publication: Chemical Communications
publication_identifier:
eissn:
- 1364-548X
issn:
- 1359-7345
publication_status: published
publisher: Royal Society of Chemistry
quality_controlled: '1'
scopus_import: '1'
status: public
title: Coexistence of 1:1 and 2:1 inclusion complexes of indigo carmine
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 58
year: '2022'
...
---
_id: '9447'
abstract:
- lang: eng
text: 'Lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) based water-in-salt electrolytes
(WiSEs) has recently emerged as a new promising class of electrolytes, primarily
owing to their wide electrochemical stability windows (~3–4 V), that by far exceed
the thermodynamic stability window of water (1.23 V). Upon increasing the salt
concentration towards superconcentration the onset of the oxygen evolution reaction
(OER) shifts more significantly than the hydrogen evolution reaction (HER) does.
The OER shift has been explained by the accumulation of hydrophobic anions blocking
water access to the electrode surface, hence by double layer theory. Here we demonstrate
that the processes during oxidation are much more complex, involving OER, carbon
and salt decomposition by OER intermediates, and salt precipitation upon local
oversaturation. The positive shift in the onset potential of oxidation currents
was elucidated by combining several advanced analysis techniques: rotating ring-disk
electrode voltammetry, online electrochemical mass spectrometry, and X-ray photoelectron
spectroscopy, using both dilute and superconcentrated electrolytes. The results
demonstrate the importance of reactive OER intermediates and surface films for
electrolyte and electrode stability and motivate further studies of the nature
of the electrode.'
article_number: '050550'
article_processing_charge: No
author:
- first_name: Marion
full_name: Maffre, Marion
last_name: Maffre
- first_name: Roza
full_name: Bouchal, Roza
last_name: Bouchal
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Niklas
full_name: Lindahl, Niklas
last_name: Lindahl
- first_name: Patrik
full_name: Johansson, Patrik
last_name: Johansson
- first_name: Frédéric
full_name: Favier, Frédéric
last_name: Favier
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
- first_name: Daniel
full_name: Bélanger, Daniel
last_name: Bélanger
citation:
ama: Maffre M, Bouchal R, Freunberger SA, et al. Investigation of electrochemical
and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes.
Journal of The Electrochemical Society. 2021;168(5). doi:10.1149/1945-7111/ac0300
apa: Maffre, M., Bouchal, R., Freunberger, S. A., Lindahl, N., Johansson, P., Favier,
F., … Bélanger, D. (2021). Investigation of electrochemical and chemical processes
occurring at positive potentials in “Water-in-Salt” electrolytes. Journal of
The Electrochemical Society. IOP Publishing. https://doi.org/10.1149/1945-7111/ac0300
chicago: Maffre, Marion, Roza Bouchal, Stefan Alexander Freunberger, Niklas Lindahl,
Patrik Johansson, Frédéric Favier, Olivier Fontaine, and Daniel Bélanger. “Investigation
of Electrochemical and Chemical Processes Occurring at Positive Potentials in
‘Water-in-Salt’ Electrolytes.” Journal of The Electrochemical Society.
IOP Publishing, 2021. https://doi.org/10.1149/1945-7111/ac0300.
ieee: M. Maffre et al., “Investigation of electrochemical and chemical processes
occurring at positive potentials in ‘Water-in-Salt’ electrolytes,” Journal
of The Electrochemical Society, vol. 168, no. 5. IOP Publishing, 2021.
ista: Maffre M, Bouchal R, Freunberger SA, Lindahl N, Johansson P, Favier F, Fontaine
O, Bélanger D. 2021. Investigation of electrochemical and chemical processes occurring
at positive potentials in “Water-in-Salt” electrolytes. Journal of The Electrochemical
Society. 168(5), 050550.
mla: Maffre, Marion, et al. “Investigation of Electrochemical and Chemical Processes
Occurring at Positive Potentials in ‘Water-in-Salt’ Electrolytes.” Journal
of The Electrochemical Society, vol. 168, no. 5, 050550, IOP Publishing, 2021,
doi:10.1149/1945-7111/ac0300.
short: M. Maffre, R. Bouchal, S.A. Freunberger, N. Lindahl, P. Johansson, F. Favier,
O. Fontaine, D. Bélanger, Journal of The Electrochemical Society 168 (2021).
date_created: 2021-06-03T09:58:38Z
date_published: 2021-05-01T00:00:00Z
date_updated: 2023-09-05T13:25:30Z
day: '01'
department:
- _id: StFr
doi: 10.1149/1945-7111/ac0300
external_id:
isi:
- '000657724200001'
intvolume: ' 168'
isi: 1
issue: '5'
keyword:
- Renewable Energy
- Sustainability and the Environment
- Electrochemistry
- Materials Chemistry
- Electronic
- Optical and Magnetic Materials
- Surfaces
- Coatings and Films
- Condensed Matter Physics
language:
- iso: eng
month: '05'
oa_version: None
publication: Journal of The Electrochemical Society
publication_identifier:
eissn:
- 1945-7111
issn:
- 0013-4651
publication_status: published
publisher: IOP Publishing
quality_controlled: '1'
status: public
title: Investigation of electrochemical and chemical processes occurring at positive
potentials in “Water-in-Salt” electrolytes
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 168
year: '2021'
...
---
_id: '9069'
abstract:
- lang: eng
text: In the quest for alternate and efficient electrode materials, ternary metal
electrocatalysts (TMEs), part of the perovskite family, were synthesized and tested
for methanol electro-oxidation in alkaline media. La0.5Ca0.5MO3 (M = Ni, Co, or
Mn) was synthesized via sol-gel method. X-ray diffraction analysis revealed that
the perovskite crystal structure possesses characteristic sharp and crystalline
peaks for all synthesized ternary electrocatalysts. The average particle size
calculated using Debye–Scherrer equation was in the order of La0.5Ca0.5NiO3 (LCNO)
> La0.5Ca0.5CoO3 (LCCO)> La0.5Ca0.5MnO3 (LCMO). The elemental composition of as
prepared sample, LCCO was investigated via x-ray fluorescence spectroscopy. The
qualitative and quantitative analysis revealed the presence of La, Ca and Co in
parent crystal structure with percentage compositions of 9.0, 3.12 and 87.82%
respectively. The particle size distribution was homogenous, as determined by
scanning electron and transmission electron microscopes. The electrocatalytic
activity of the synthesized ternary electrocatalysts was studied electrochemically
by cyclic voltammetry. The calculated diffusion coefficient values showed that
electrode surface of LCNO and LCCO have limited efficiency for diffusion related
phenomenon. The heterogeneous rate constants inferred better electrode kinetics
of LCCO and LCNO which exhibited good electrocatalytic behavior; sharp anodic
peaks were observed in the potential range of +0.3 to 0.6 V and +0.6 to 0.8 V,
respectively. Methanol electro-oxidation was found minimal in case of LCMO sample.
We have observed that Co substitution at B-site of perovskite electrode materials
attains better electrochemical properties, thus in relation with reported literature.
article_number: 1250g6
article_processing_charge: No
article_type: original
author:
- first_name: Tayyaba
full_name: Hussain, Tayyaba
last_name: Hussain
- first_name: Muhammad
full_name: Nauman, Muhammad
id: 32c21954-2022-11eb-9d5f-af9f93c24e71
last_name: Nauman
orcid: 0000-0002-2111-4846
- first_name: Sana
full_name: Sabahat, Sana
last_name: Sabahat
- first_name: Saira
full_name: Arif, Saira
last_name: Arif
citation:
ama: Hussain T, Nauman M, Sabahat S, Arif S. Synthesis of ternary electrocatalysts
for exploration of methanol electro-oxidation in alkaline media. Materials
Research Express. 2020;6(12). doi:10.1088/2053-1591/ab6886
apa: Hussain, T., Nauman, M., Sabahat, S., & Arif, S. (2020). Synthesis of ternary
electrocatalysts for exploration of methanol electro-oxidation in alkaline media.
Materials Research Express. IOP Publishing. https://doi.org/10.1088/2053-1591/ab6886
chicago: Hussain, Tayyaba, Muhammad Nauman, Sana Sabahat, and Saira Arif. “Synthesis
of Ternary Electrocatalysts for Exploration of Methanol Electro-Oxidation in Alkaline
Media.” Materials Research Express. IOP Publishing, 2020. https://doi.org/10.1088/2053-1591/ab6886.
ieee: T. Hussain, M. Nauman, S. Sabahat, and S. Arif, “Synthesis of ternary electrocatalysts
for exploration of methanol electro-oxidation in alkaline media,” Materials
Research Express, vol. 6, no. 12. IOP Publishing, 2020.
ista: Hussain T, Nauman M, Sabahat S, Arif S. 2020. Synthesis of ternary electrocatalysts
for exploration of methanol electro-oxidation in alkaline media. Materials Research
Express. 6(12), 1250g6.
mla: Hussain, Tayyaba, et al. “Synthesis of Ternary Electrocatalysts for Exploration
of Methanol Electro-Oxidation in Alkaline Media.” Materials Research Express,
vol. 6, no. 12, 1250g6, IOP Publishing, 2020, doi:10.1088/2053-1591/ab6886.
short: T. Hussain, M. Nauman, S. Sabahat, S. Arif, Materials Research Express 6
(2020).
date_created: 2021-02-02T15:53:57Z
date_published: 2020-01-15T00:00:00Z
date_updated: 2021-02-04T07:21:35Z
day: '15'
doi: 10.1088/2053-1591/ab6886
extern: '1'
intvolume: ' 6'
issue: '12'
keyword:
- Electronic
- Optical and Magnetic Materials
- Surfaces
- Coatings and Films
- Polymers and Plastics
- Metals and Alloys
- Biomaterials
language:
- iso: eng
month: '01'
oa_version: None
publication: Materials Research Express
publication_identifier:
issn:
- 2053-1591
publication_status: published
publisher: IOP Publishing
quality_controlled: '1'
status: public
title: Synthesis of ternary electrocatalysts for exploration of methanol electro-oxidation
in alkaline media
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 6
year: '2020'
...
---
_id: '8453'
abstract:
- lang: eng
text: Transverse relaxation rate measurements in magic-angle spinning solid-state
nuclear magnetic resonance provide information about molecular motions occurring
on nanosecond-to-millisecond (ns–ms) time scales. The measurement of heteronuclear
(13C, 15N) relaxation rate constants in the presence of a spin-lock radiofrequency
field (R1ρ relaxation) provides access to such motions, and an increasing number
of studies involving R1ρ relaxation in proteins have been reported. However, two
factors that influence the observed relaxation rate constants have so far been
neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR)
and (2) the impact of fast proton spin flips (i.e., proton spin diffusion and
relaxation). We show that CSA/D CCR in R1ρ experiments is measurable and that
the CCR rate constant depends on ns–ms motions; it can thus provide insight into
dynamics. We find that proton spin diffusion attenuates this CCR due to its decoupling
effect on the doublet components. For measurements of dynamics, the use of R1ρ
rate constants has practical advantages over the use of CCR rates, and this article
reveals factors that have so far been disregarded and which are important for
accurate measurements and interpretation.
article_processing_charge: No
article_type: original
author:
- first_name: Vilius
full_name: Kurauskas, Vilius
last_name: Kurauskas
- first_name: Emmanuelle
full_name: Weber, Emmanuelle
last_name: Weber
- first_name: Audrey
full_name: Hessel, Audrey
last_name: Hessel
- first_name: Isabel
full_name: Ayala, Isabel
last_name: Ayala
- first_name: Dominique
full_name: Marion, Dominique
last_name: Marion
- first_name: Paul
full_name: Schanda, Paul
id: 7B541462-FAF6-11E9-A490-E8DFE5697425
last_name: Schanda
orcid: 0000-0002-9350-7606
citation:
ama: 'Kurauskas V, Weber E, Hessel A, Ayala I, Marion D, Schanda P. Cross-correlated
relaxation of dipolar coupling and chemical-shift anisotropy in magic-angle spinning
R1ρ NMR measurements: Application to protein backbone dynamics measurements. The
Journal of Physical Chemistry B. 2016;120(34):8905-8913. doi:10.1021/acs.jpcb.6b06129'
apa: 'Kurauskas, V., Weber, E., Hessel, A., Ayala, I., Marion, D., & Schanda,
P. (2016). Cross-correlated relaxation of dipolar coupling and chemical-shift
anisotropy in magic-angle spinning R1ρ NMR measurements: Application to protein
backbone dynamics measurements. The Journal of Physical Chemistry B. American
Chemical Society. https://doi.org/10.1021/acs.jpcb.6b06129'
chicago: 'Kurauskas, Vilius, Emmanuelle Weber, Audrey Hessel, Isabel Ayala, Dominique
Marion, and Paul Schanda. “Cross-Correlated Relaxation of Dipolar Coupling and
Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application
to Protein Backbone Dynamics Measurements.” The Journal of Physical Chemistry
B. American Chemical Society, 2016. https://doi.org/10.1021/acs.jpcb.6b06129.'
ieee: 'V. Kurauskas, E. Weber, A. Hessel, I. Ayala, D. Marion, and P. Schanda, “Cross-correlated
relaxation of dipolar coupling and chemical-shift anisotropy in magic-angle spinning
R1ρ NMR measurements: Application to protein backbone dynamics measurements,”
The Journal of Physical Chemistry B, vol. 120, no. 34. American Chemical
Society, pp. 8905–8913, 2016.'
ista: 'Kurauskas V, Weber E, Hessel A, Ayala I, Marion D, Schanda P. 2016. Cross-correlated
relaxation of dipolar coupling and chemical-shift anisotropy in magic-angle spinning
R1ρ NMR measurements: Application to protein backbone dynamics measurements. The
Journal of Physical Chemistry B. 120(34), 8905–8913.'
mla: 'Kurauskas, Vilius, et al. “Cross-Correlated Relaxation of Dipolar Coupling
and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application
to Protein Backbone Dynamics Measurements.” The Journal of Physical Chemistry
B, vol. 120, no. 34, American Chemical Society, 2016, pp. 8905–13, doi:10.1021/acs.jpcb.6b06129.'
short: V. Kurauskas, E. Weber, A. Hessel, I. Ayala, D. Marion, P. Schanda, The Journal
of Physical Chemistry B 120 (2016) 8905–8913.
date_created: 2020-09-18T10:07:07Z
date_published: 2016-08-08T00:00:00Z
date_updated: 2021-01-12T08:19:22Z
day: '08'
doi: 10.1021/acs.jpcb.6b06129
extern: '1'
intvolume: ' 120'
issue: '34'
keyword:
- Physical and Theoretical Chemistry
- Materials Chemistry
- Surfaces
- Coatings and Films
language:
- iso: eng
month: '08'
oa_version: None
page: 8905-8913
publication: The Journal of Physical Chemistry B
publication_identifier:
issn:
- 1520-6106
- 1520-5207
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
status: public
title: 'Cross-correlated relaxation of dipolar coupling and chemical-shift anisotropy
in magic-angle spinning R1ρ NMR measurements: Application to protein backbone dynamics
measurements'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 120
year: '2016'
...
---
_id: '8455'
abstract:
- lang: eng
text: Solid-state NMR spectroscopy allows the characterization of the structure,
interactions and dynamics of insoluble and/or very large proteins. Sensitivity
and resolution are often major challenges for obtaining atomic-resolution information,
in particular for very large protein complexes. Here we show that the use of deuterated,
specifically CH3-labelled proteins result in significant sensitivity gains compared
to previously employed CHD2 labelling, while line widths increase only marginally.
We apply this labelling strategy to a 468 kDa-large dodecameric aminopeptidase,
TET2, and the 1.6 MDa-large 50S ribosome subunit of Thermus thermophilus.
article_processing_charge: No
article_type: original
author:
- first_name: Vilius
full_name: Kurauskas, Vilius
last_name: Kurauskas
- first_name: Elodie
full_name: Crublet, Elodie
last_name: Crublet
- first_name: Pavel
full_name: Macek, Pavel
last_name: Macek
- first_name: Rime
full_name: Kerfah, Rime
last_name: Kerfah
- first_name: Diego F.
full_name: Gauto, Diego F.
last_name: Gauto
- first_name: Jérôme
full_name: Boisbouvier, Jérôme
last_name: Boisbouvier
- first_name: Paul
full_name: Schanda, Paul
id: 7B541462-FAF6-11E9-A490-E8DFE5697425
last_name: Schanda
orcid: 0000-0002-9350-7606
citation:
ama: 'Kurauskas V, Crublet E, Macek P, et al. Sensitive proton-detected solid-state
NMR spectroscopy of large proteins with selective CH3labelling: Application to
the 50S ribosome subunit. Chemical Communications. 2016;52(61):9558-9561.
doi:10.1039/c6cc04484k'
apa: 'Kurauskas, V., Crublet, E., Macek, P., Kerfah, R., Gauto, D. F., Boisbouvier,
J., & Schanda, P. (2016). Sensitive proton-detected solid-state NMR spectroscopy
of large proteins with selective CH3labelling: Application to the 50S ribosome
subunit. Chemical Communications. Royal Society of Chemistry. https://doi.org/10.1039/c6cc04484k'
chicago: 'Kurauskas, Vilius, Elodie Crublet, Pavel Macek, Rime Kerfah, Diego F.
Gauto, Jérôme Boisbouvier, and Paul Schanda. “Sensitive Proton-Detected Solid-State
NMR Spectroscopy of Large Proteins with Selective CH3labelling: Application to
the 50S Ribosome Subunit.” Chemical Communications. Royal Society of Chemistry,
2016. https://doi.org/10.1039/c6cc04484k.'
ieee: 'V. Kurauskas et al., “Sensitive proton-detected solid-state NMR spectroscopy
of large proteins with selective CH3labelling: Application to the 50S ribosome
subunit,” Chemical Communications, vol. 52, no. 61. Royal Society of Chemistry,
pp. 9558–9561, 2016.'
ista: 'Kurauskas V, Crublet E, Macek P, Kerfah R, Gauto DF, Boisbouvier J, Schanda
P. 2016. Sensitive proton-detected solid-state NMR spectroscopy of large proteins
with selective CH3labelling: Application to the 50S ribosome subunit. Chemical
Communications. 52(61), 9558–9561.'
mla: 'Kurauskas, Vilius, et al. “Sensitive Proton-Detected Solid-State NMR Spectroscopy
of Large Proteins with Selective CH3labelling: Application to the 50S Ribosome
Subunit.” Chemical Communications, vol. 52, no. 61, Royal Society of Chemistry,
2016, pp. 9558–61, doi:10.1039/c6cc04484k.'
short: V. Kurauskas, E. Crublet, P. Macek, R. Kerfah, D.F. Gauto, J. Boisbouvier,
P. Schanda, Chemical Communications 52 (2016) 9558–9561.
date_created: 2020-09-18T10:07:29Z
date_published: 2016-07-04T00:00:00Z
date_updated: 2021-01-12T08:19:23Z
day: '04'
doi: 10.1039/c6cc04484k
extern: '1'
intvolume: ' 52'
issue: '61'
keyword:
- Materials Chemistry
- Electronic
- Optical and Magnetic Materials
- General Chemistry
- Surfaces
- Coatings and Films
- Metals and Alloys
- Ceramics and Composites
- Catalysis
language:
- iso: eng
month: '07'
oa_version: None
page: 9558-9561
publication: Chemical Communications
publication_identifier:
issn:
- 1359-7345
- 1364-548X
publication_status: published
publisher: Royal Society of Chemistry
quality_controlled: '1'
status: public
title: 'Sensitive proton-detected solid-state NMR spectroscopy of large proteins with
selective CH3labelling: Application to the 50S ribosome subunit'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 52
year: '2016'
...
---
_id: '13395'
abstract:
- lang: eng
text: Metallic nanoparticles co-functionalised with monolayers of UV- and CO2-sensitive
ligands were prepared and shown to respond to these two types of stimuli reversibly
and in an orthogonal fashion. The composition of the coating could be tailored
to yield nanoparticles capable of aggregating exclusively when both UV and CO2
were applied at the same time, analogously to the behaviour of an AND logic gate.
article_processing_charge: No
article_type: original
author:
- first_name: Ji-Woong
full_name: Lee, Ji-Woong
last_name: Lee
- first_name: Rafal
full_name: Klajn, Rafal
id: 8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
last_name: Klajn
citation:
ama: Lee J-W, Klajn R. Dual-responsive nanoparticles that aggregate under the simultaneous
action of light and CO2. Chemical Communications. 2015;51(11):2036-2039.
doi:10.1039/c4cc08541h
apa: Lee, J.-W., & Klajn, R. (2015). Dual-responsive nanoparticles that aggregate
under the simultaneous action of light and CO2. Chemical Communications.
Royal Society of Chemistry. https://doi.org/10.1039/c4cc08541h
chicago: Lee, Ji-Woong, and Rafal Klajn. “Dual-Responsive Nanoparticles That Aggregate
under the Simultaneous Action of Light and CO2.” Chemical Communications.
Royal Society of Chemistry, 2015. https://doi.org/10.1039/c4cc08541h.
ieee: J.-W. Lee and R. Klajn, “Dual-responsive nanoparticles that aggregate under
the simultaneous action of light and CO2,” Chemical Communications, vol.
51, no. 11. Royal Society of Chemistry, pp. 2036–2039, 2015.
ista: Lee J-W, Klajn R. 2015. Dual-responsive nanoparticles that aggregate under
the simultaneous action of light and CO2. Chemical Communications. 51(11), 2036–2039.
mla: Lee, Ji-Woong, and Rafal Klajn. “Dual-Responsive Nanoparticles That Aggregate
under the Simultaneous Action of Light and CO2.” Chemical Communications,
vol. 51, no. 11, Royal Society of Chemistry, 2015, pp. 2036–39, doi:10.1039/c4cc08541h.
short: J.-W. Lee, R. Klajn, Chemical Communications 51 (2015) 2036–2039.
date_created: 2023-08-01T09:44:48Z
date_published: 2015-11-18T00:00:00Z
date_updated: 2023-08-07T13:01:53Z
day: '18'
doi: 10.1039/c4cc08541h
extern: '1'
external_id:
pmid:
- '25417754'
intvolume: ' 51'
issue: '11'
keyword:
- Materials Chemistry
- Metals and Alloys
- Surfaces
- Coatings and Films
- General Chemistry
- Ceramics and Composites
- Electronic
- Optical and Magnetic Materials
- Catalysis
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.1039/C4CC08541H
month: '11'
oa: 1
oa_version: Published Version
page: 2036-2039
pmid: 1
publication: Chemical Communications
publication_identifier:
eissn:
- 1364-548X
issn:
- 1359-7345
publication_status: published
publisher: Royal Society of Chemistry
quality_controlled: '1'
scopus_import: '1'
status: public
title: Dual-responsive nanoparticles that aggregate under the simultaneous action
of light and CO2
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 51
year: '2015'
...
---
_id: '13430'
abstract:
- lang: eng
text: Dynamic self-assembly (DySA) processes occurring outside of thermodynamic
equilibrium underlie many forms of adaptive and intellligent behaviors in natural
systems. Relatively little, however, is known about the principles that govern
DySA and the ways in which it can be extended to artificial ensembles. This article
discusses recent advances in both the theory and the practice of nonequilibrium
self-assembly. It is argued that a union of ideas from thermodynamics and dynamic
systems' theory can provide a general description of DySA. In parallel, heuristic
design rules can be used to construct DySA systems of increasing complexities
based on a variety of suitable interactions/potentials on length scales from nanoscopic
to macroscopic. Applications of these rules to magnetohydrodynamic DySA are also
discussed.
article_processing_charge: No
article_type: original
author:
- first_name: Marcin
full_name: Fialkowski, Marcin
last_name: Fialkowski
- first_name: Kyle J. M.
full_name: Bishop, Kyle J. M.
last_name: Bishop
- first_name: Rafal
full_name: Klajn, Rafal
id: 8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
last_name: Klajn
- first_name: Stoyan K.
full_name: Smoukov, Stoyan K.
last_name: Smoukov
- first_name: Christopher J.
full_name: Campbell, Christopher J.
last_name: Campbell
- first_name: Bartosz A.
full_name: Grzybowski, Bartosz A.
last_name: Grzybowski
citation:
ama: Fialkowski M, Bishop KJM, Klajn R, Smoukov SK, Campbell CJ, Grzybowski BA.
Principles and implementations of dissipative (dynamic) self-assembly. The
Journal of Physical Chemistry B. 2006;110(6):2482-2496. doi:10.1021/jp054153q
apa: Fialkowski, M., Bishop, K. J. M., Klajn, R., Smoukov, S. K., Campbell, C. J.,
& Grzybowski, B. A. (2006). Principles and implementations of dissipative
(dynamic) self-assembly. The Journal of Physical Chemistry B. American
Chemical Society. https://doi.org/10.1021/jp054153q
chicago: Fialkowski, Marcin, Kyle J. M. Bishop, Rafal Klajn, Stoyan K. Smoukov,
Christopher J. Campbell, and Bartosz A. Grzybowski. “Principles and Implementations
of Dissipative (Dynamic) Self-Assembly.” The Journal of Physical Chemistry
B. American Chemical Society, 2006. https://doi.org/10.1021/jp054153q.
ieee: M. Fialkowski, K. J. M. Bishop, R. Klajn, S. K. Smoukov, C. J. Campbell, and
B. A. Grzybowski, “Principles and implementations of dissipative (dynamic) self-assembly,”
The Journal of Physical Chemistry B, vol. 110, no. 6. American Chemical
Society, pp. 2482–2496, 2006.
ista: Fialkowski M, Bishop KJM, Klajn R, Smoukov SK, Campbell CJ, Grzybowski BA.
2006. Principles and implementations of dissipative (dynamic) self-assembly. The
Journal of Physical Chemistry B. 110(6), 2482–2496.
mla: Fialkowski, Marcin, et al. “Principles and Implementations of Dissipative (Dynamic)
Self-Assembly.” The Journal of Physical Chemistry B, vol. 110, no. 6, American
Chemical Society, 2006, pp. 2482–96, doi:10.1021/jp054153q.
short: M. Fialkowski, K.J.M. Bishop, R. Klajn, S.K. Smoukov, C.J. Campbell, B.A.
Grzybowski, The Journal of Physical Chemistry B 110 (2006) 2482–2496.
date_created: 2023-08-01T10:37:35Z
date_published: 2006-01-25T00:00:00Z
date_updated: 2023-08-08T11:33:08Z
day: '25'
doi: 10.1021/jp054153q
extern: '1'
external_id:
pmid:
- '16471845'
intvolume: ' 110'
issue: '6'
keyword:
- Materials Chemistry
- Surfaces
- Coatings and Films
- Physical and Theoretical Chemistry
language:
- iso: eng
month: '01'
oa_version: None
page: 2482-2496
pmid: 1
publication: The Journal of Physical Chemistry B
publication_identifier:
issn:
- 1520-6106
- 1520-5207
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Principles and implementations of dissipative (dynamic) self-assembly
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 110
year: '2006'
...