I19-Small Molecule Single Crystal Diffraction
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William J. F.
Trenholme
,
Daniil I.
Kolokolov
,
Michelle
Bound
,
Stephen P.
Argent
,
Jamie A.
Gould
,
Jiangnan
Li
,
Sarah A.
Barnett
,
Alexander J.
Blake
,
Alexander G.
Stepanov
,
Elena
Besley
,
Timothy L.
Easun
,
Sihai
Yang
,
Martin
Schroeder
Abstract: The desolvated (3,24)-connected metal–organic framework (MOF) material, MFM-160a, [Cu3(L)(H2O)3] [H6L = 1,3,5-triazine-2,4,6-tris(aminophenyl-4-isophthalic acid)], exhibits excellent high-pressure uptake of CO2 (110 wt% at 20 bar, 298 K) and highly selective separation of C2 hydrocarbons from CH4 at 1 bar pressure. Henry’s law selectivities of 79:1 for C2H2:CH4 and 70:1 for C2H4:CH4 at 298 K are observed, consistent with ideal adsorption solution theory (IAST) predictions. Significantly, MFM-160a shows a selectivity of 16:1 for C2H2:CO2. Solid-state 2H NMR spectroscopic studies on partially deuterated MFM-160-d12 confirm an ultra-low barrier (∼2 kJ mol–1) to rotation of the phenyl group in the activated MOF and a rotation rate 5 orders of magnitude slower than usually observed for solid-state materials (1.4 × 106 Hz cf. 1011–1013 Hz). Upon introduction of CO2 or C2H2 into desolvated MFM-160a, this rate of rotation was found to increase with increasing gas pressure, a phenomenon attributed to the weakening of an intramolecular hydrogen bond in the triazine-containing linker upon gas binding. DFT calculations of binding energies and interactions of CO2 and C2H2 around the triazine core are entirely consistent with the 2H NMR spectroscopic observations.
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Feb 2021
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Shaojun
Xu
,
Xue
Han
,
Yujie
Ma
,
Thien D.
Duong
,
Longfei
Lin
,
Emma K.
Gibson
,
Alena
Sheveleva
,
Sarayute
Chansai
,
Alex
Walton
,
Duc-the
Ngo
,
Mark D.
Frogley
,
Chiu C.
Tang
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
C. Richard A.
Catlow
,
Christopher
Hardacre
,
Sihai
Yang
,
Martin
Schroeder
Open Access
Abstract: Efficient catalytic conversion of NO2 to non-harmful species remains an important target for research. State-of-the-art deNOx processes are based upon ammonia (NH3)-assisted selective catalytic reduction (NH3-SCR) over Cu-exchanged zeolites at elevated temperatures. Here, we describe a highly efficient non-thermal plasma (NTP) deNOx process catalyzed by a Cu-embedded metal-organic framework, Cu/MFM-300(Al), at room temperature. Under NTP activation at 25°C, Cu/MFM-300(Al) enables direct decomposition of NO2 into N2, NO, N2O, and O2 without the use of NH3 or other reducing agents. NO2 conversion of 96% with a N2 selectivity of 82% at a turnover frequency of 2.9 h−1 is achieved, comparable to leading NH3-SCR catalysts that use NH3 operating at 250°C–550°C. The mechanism for the rate-determining step (NO→N2) is elucidated by in operando diffuse reflectance infrared Fourier transform spectroscopy, and electron paramagnetic resonance spectroscopy confirms the formation of Cu2+⋯NO nitrosylic adducts on Cu/MFM-300(Al), which facilitates NO dissociation and results in the notable N2 selectivity.
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Feb 2021
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B22-Multimode InfraRed imaging And Microspectroscopy
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Xue
Han
,
Wanpeng
Lu
,
Yinlin
Chen
,
Ivan
Da Silva
,
Jiangnan
Li
,
Longfei
Lin
,
Weiyao
Li
,
Alena M.
Sheveleva
,
Harry G. W.
Godfrey
,
Zhenzhong
Lu
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Laura J.
Mccormick Mcpherson
,
Simon J.
Teat
,
Mark D.
Frogley
,
Svemir
Rudic
,
Pascal
Manuel
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[23782]
Abstract: Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal–organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g–1, respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(VIV) exhibits the highest uptake among this series of MOFs of 17.3 mmol g–1. In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host–guest charge transfer, with VIV being reduced to VIII and NH3 being oxidized to hydrazine (N2H4). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH3.
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Feb 2021
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Lydia
Briggs
,
Ruth
Newby
,
Xue
Han
,
Christopher
Morris
,
Mathew
Savage
,
Cristina
Perez
,
Timothy L.
Easun
,
Mark
Frogley
,
Gianfelice
Cinque
,
Claire A.
Murray
,
Chiu C.
Tang
,
Sihai
Yang
,
Junliang
Sun
,
Martin
Schroeder
Diamond Proposal Number(s):
[22137, 22138]
Open Access
Abstract: We report the adsorption of C2H2, CO2 and SO2 in a new, ultra-stable Cr(III)-based MOF, MFM-300(Cr), {[Cr2(OH)2(L)], H4L = biphenyl-3,3',5,5'-tetracarboxylic acid}. MFM-300(Cr) shows uptakes of 7.37, 7.73 and 8.59 mmol g-1 for CO2, C2H2 and SO2, respectively, at 273 K, 1.0 bar, and shows a higher selectivity for SO2/CO2 compared with the Al(III) analogue MFM-300(Al) (selectivity of 79 vs. 45). In order to monitor the effects of changing metal centre on gas uptake and to integrate the properties of the homometallic analogues, the mixed metal MFM-300(Al0.67Cr0.33), [Al1.34Cr0.66(OH)2L] has been synthesised. In situ synchrotron micro-FTIR spectroscopy has identified distinct CO2 binding environments on Al-O(H)-Al, Cr-O(H)-Cr and Al-O(H)-Cr bridges in MFM-300(Al0.67Cr0.33), and we have determined the binding domains for these gases by in situ synchrotron X-ray diffraction in both MFM-300(Cr) and MFM-300(Al0.67Cr0.33). The capability of these materials for gas separation has been confirmed by dynamic breakthrough experiments. The incorporation of Al(III) and Cr(III) within the same framework allows tuning of the host-guest and guest-guest interactions within these functional porous materials.
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Feb 2021
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I03-Macromolecular Crystallography
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Sandra
Röhm
,
Martin
Schroeder
,
Jessica E.
Dwyer
,
Caroline S.
Widdowson
,
Apirat
Chaikuad
,
Benedict-tilman
Berger
,
Andreas C.
Joerger
,
Andreas
Krämer
,
Jule
Harbig
,
Daniel
Dauch
,
Mark
Kudolo
,
Stefan
Laufer
,
Mark C.
Bagley
,
Stefan
Knapp
Diamond Proposal Number(s):
[10619]
Abstract: The p38 MAPK cascade is a key signaling pathway linked to a multitude of physiological functions and of central importance in inflammatory and autoimmune diseases. Although studied extensively, little is known about how conformation-specific inhibitors alter signaling outcomes. Here, we have explored the highly dynamic back pocket of p38 MAPK with allosteric urea fragments. However, screening against known off-targets showed that these fragments maintained the selectivity issues of their parent compound BIRB-796, while combination with the hinge-binding motif of VPC-00628 greatly enhanced inhibitor selectivity. Further efforts focused therefore on the exploration of the αC-out pocket of p38 MAPK, yielding compound 137 as a highly selective type-II inhibitor. Even though 137 is structurally related to a recent p38 type-II chemical probe, SR-318, the data presented here provide valuable insights into back-pocket interactions that are not addressed in SR-318 and it provides an alternative chemical tool with good cellular activity targeting also the p38 back pocket.
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Dec 2020
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I04-Macromolecular Crystallography
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Diamond Proposal Number(s):
[105433]
Open Access
Abstract: Extracellular signal-regulated kinase 3 (ERK3), known also as mitogen-activated protein kinase 6 (MAPK6), is an atypical member of MAPK kinase family, which has been poorly studied. Little is known regarding its function in biological processes, yet this atypical kinase has been suggested to play important roles in the migration and invasiveness of certain cancers. The lack of tools, such as a selective inhibitor, hampers the study of ERK3 biology. Here, we report the crystal structure of the kinase domain of this atypical MAPK kinase, providing molecular insights into its distinct ATP binding pocket compared to the classical MAPK ERK2, explaining differences in their inhibitor binding properties. Medium-scale small molecule screening identified a number of inhibitors, several of which unexpectedly exhibited remarkably high inhibitory potencies. The crystal structure of CLK1 in complex with CAF052, one of the most potent inhibitors identified for ERK3, revealed typical type-I binding mode of the inhibitor, which by structural comparison could likely be maintained in ERK3. Together with the presented structural insights, these diverse chemical scaffolds displaying both reversible and irreversible modes of action, will serve as a starting point for the development of selective inhibitors for ERK3, which will be beneficial for elucidating the important functions of this understudied kinase.
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Nov 2020
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I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Stephen P.
Argent
,
Ivan
Da Silva
,
Alex
Greenaway
,
Mathew
Savage
,
Jack
Humby
,
Andrew J.
Davies
,
Harriott
Nowell
,
William
Lewis
,
Pascal
Manuel
,
Chiu C.
Tang
,
Alexander J.
Blake
,
Michael W.
George
,
Alexander V.
Markevich
,
Elena
Besley
,
Sihai
Yang
,
Neil R.
Champness
,
Martin
Schroeder
Diamond Proposal Number(s):
[861, 11622, 15833, 9443]
Open Access
Abstract: Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.
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Oct 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Xinchen
Kang
,
Bin
Wang
,
Kui
Hu
,
Kai
Lyu
,
Xue
Han
,
Ben F.
Spencer
,
Mark D.
Frogley
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Robert A. W.
Dryfe
,
Buxing
Han
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[19171]
Open Access
Abstract: Efficient electro-reduction of CO2 over metal–organic framework (MOF) materials is hindered by the poor contact between thermally synthesized MOF particles and the electrode surface, which leads to low Faradaic efficiency for a given product and poor electrochemical stability of the catalyst. We report a MOF-based electrode prepared via electro-synthesis of MFM-300(In) on an indium foil, and its activity for the electrochemical reduction of CO2 is assessed. The resultant MFM-300(In)-e/In electrode shows a 1 order of magnitude improvement in conductivity compared with that for MFM-300(In)/carbon-paper electrodes. MFM-300(In)-e/In exhibits a current density of 46.1 mA cm–2 at an applied potential of −2.15 V vs Ag/Ag+ for the electro-reduction of CO2 in organic electrolyte, achieving an exceptional Faradaic efficiency of 99.1% for the formation of formic acid. The facile preparation of the MFM-300(In)-e/In electrode, coupled with its excellent electrochemical stability, provides a new pathway to develop efficient electro-catalysts for CO2 reduction.
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Sep 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Xiaolin
Li
,
Juehua
Wang
,
Xinran
Zhang
,
Xue
Han
,
Ivan
Da Silva
,
Christopher G.
Morris
,
Shaojun
Xu
,
Damian M.
Wilary
,
Yinyong
Sun
,
Yongqiang
Cheng
,
Claire A.
Murray
,
Chiu C.
Tang
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Tristan
Lowe
,
Haifei
Zhang
,
Anibal J.
Ramirez-cuesta
,
K. Mark
Thomas
,
Leslie W.
Bolton
,
Sihai
Yang
,
Martin
Schroeder
,
Nannan
Bai
Diamond Proposal Number(s):
[13247]
Open Access
Abstract: The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes.
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Aug 2020
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I02-Macromolecular Crystallography
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Diamond Proposal Number(s):
[442]
Abstract: Selectivity remains a challenge for ATP-mimetic kinase inhibitors, an issue that may be overcome by targeting unique residues or binding pockets. However, to date only few strategies have been developed. Here we identify that bulky residues located N-terminal to the DFG motif (DFG-1) represent an opportunity for designing highly selective inhibitors with unexpected binding modes. We demonstrate that several diverse inhibitors exerted selective, non-canonical binding modes that exclusively target large hydrophobic DFG-1 residues present in many kinases including PIM, CK1, DAPK and CLK. Using the CLK family as a model, structural and biochemical data revealed that the DFG-1 valine controlled a non-canonical binding mode in CLK1, providing a rational for selectivity over the closely-related CLK3 which harbors a smaller DFG-1 alanine. Our data suggests that targeting the restricted back pocket in the small fraction of kinases that harbor bulky DFG-1 residues offers a versatile selectivity filter for inhibitor design.
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Aug 2020
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