I02-Macromolecular Crystallography
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Wei
Wang
,
Jill M.
Marinis
,
Allison M.
Beal
,
Shivraj
Savadkar
,
Yue
Wu
,
Mohammed
Khan
,
Pardeep S.
Taunk
,
Nan
Wu
,
Wenyu
Su
,
Jingjing
Wu
,
Aarif
Ahsan
,
Emma
Kurz
,
Ting
Chen
,
Inedouye
Yaboh
,
Fei
Li
,
Johana
Gutierrez
,
Brian
Diskin
,
Mautin
Hundeyin
,
Michael
Reilly
,
John D.
Lich
,
Philip A.
Harris
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Mukesh K.
Mahajan
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James H.
Thorpe
,
Pamela
Nassau
,
Julie E.
Mosley
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Joshua
Leinwand
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Juan A.
Kochen Rossi
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Ankita
Mishra
,
Berk
Aykut
,
Michael
Glacken
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Atsuo
Ochi
,
Narendra
Verma
,
Jacqueline I.
Kim
,
Varshini
Vasudevaraja
,
Dennis
Adeegbe
,
Christina
Almonte
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Ece
Bagdatlioglu
,
Deirdre J.
Cohen
,
Kwok-kin
Wong
,
John
Bertin
,
George
Miller
Abstract: Pancreatic ductal adenocarcinoma (PDA) is characterized by immune tolerance and immunotherapeutic resistance. We discovered upregulation of receptor-interacting serine/threonine protein kinase 1 (RIP1) in tumor-associated macrophages (TAMs) in PDA. To study its role in oncogenic progression, we developed a selective small-molecule RIP1 inhibitor with high in vivo exposure. Targeting RIP1 reprogrammed TAMs toward an MHCIIhiTNFα+IFNγ+ immunogenic phenotype in a STAT1-dependent manner. RIP1 inhibition in TAMs resulted in cytotoxic T cell activation and T helper cell differentiation toward a mixed Th1/Th17 phenotype, leading to tumor immunity in mice and in organotypic models of human PDA. Targeting RIP1 synergized with PD1-and inducible co-stimulator-based immunotherapies. Tumor-promoting effects of RIP1 were independent of its co-association with RIP3. Collectively, our work describes RIP1 as a checkpoint kinase governing tumor immunity.
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Nov 2018
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I12-JEEP: Joint Engineering, Environmental and Processing
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Hamish
Yeung
,
Adam F.
Sapnik
,
Felicity
Massingberd-mundy
,
Michael W.
Gaultois
,
Yue
Wu
,
Duncan X.
Fraser
,
Sebastian
Henke
,
Roman
Pallach
,
Niclas
Heidenreich
,
Oxana
Magdysyuk
,
Nghia T.
Vo
,
Andrew L.
Goodwin
Diamond Proposal Number(s):
[16354, 16450]
Abstract: There is an increasingly large amount of interest in metal‐organic frameworks (MOFs) for a variety of applications, from gas sensing and separations to electronics and catalysis. Their exciting properties arise from their modular architectures, which self‐assemble from different combinations of metal‐based and organic building units. However, the exact mechanisms by which they crystallize remain poorly understood, thus limiting any realisation of real “structure by design”. We report important new insight into MOF formation, gained using in situ X‐ray diffraction, pH and turbidity measurements to uncover for the first time the evolution of metastable intermediate species in the canonical zeolitic imidazolate framework system, ZIF‐8. We reveal that the intermediate species exist in a dynamic pre‐equilibrium prior to network assembly and, depending on the reactant concentrations and the progress of reaction, the pre‐equilibrium can be made to favour under‐ or over‐coordinated Zn‐imidazolate species, thus accelerating or inhibiting crystallization, respectively. We thereby find that concentration can be effectively used as a synthetic handle to directly control particle size, with great implications for industrial scale‐up and gas sorption applications. These finding enables us to rationalise the apparent contradictions between previous studies of ZIF‐8 and, importantly, opens up new opportunities for the control of crystallization in network solids more generally, from the design of local structure to assembly of particles with precise dimensions.
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Nov 2018
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[13843]
Abstract: Crystallization via metastable phases plays an important role in chemical manufacturing, bio-mineralization, and protein crystallization, but the kinetic pathways leading from metastable phases to the stable crystalline modifications are not well understood. In particular, the fast crys-tallization of amorphous intermediates makes a detailed characterization challenging. To circum-vent this problem, we devised a system that allows trapping and stabilizing the amorphous in-termediates of representative carbonates (calcium, strontium, barium, manganese, and cadmium). The long-term stabilization of these transient species enabled a detailed investigation of their composition, structure, and morphology. Total scattering experiments with high-energy syn-chrotron radiation revealed a short-range order of several Ångström in all amorphous intermedi-ates. From the synchrotron data, a structural model of amorphous calcium carbonate was de-rived that indicates a lower coordination number of calcium compared to the crystalline poly-morphs. Our study shows that a multi-step crystallization pathway via amorphous intermediates is open to many carbonates. We could isolate and characterize these transient species, thereby providing new insights into their crystallization mechanism.
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Oct 2018
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[13843]
Abstract: Amorphous calcium carbonate (ACC) is an important precursor in the biomineralization of crystal-line CaCO3. The lifetime of transient ACC in nature is regulated by an organic matrix, in order to use it as an intermediate storage buffer or as a permanent structural element. The relevance of ACC in material science is related to our understanding of CaCO3 crystallization pathways. ACC can be obtained by liquid-liquid phase separation, and it is typically stabilized with of the help of macro-molecules. We have prepared ACC by milling calcite in a planetary ball mill. The ball-milled amor-phous calcium carbonate (BM-ACC) was stabilized with small amounts of Na2CO3. The addition of foreign ions in form of Na2CO3 is crucial to achieve complete amorphization. Their incorporation generates defects that hinder recrystallization kinetically. In contrast to wet-chemically prepared ACC, the solvent-free approach makes BM-ACC an anhydrous modification. The amorphization process was monitored by quantitative Fourier transform infrared (FTIR) spectroscopy and solid state 23Na magic angle spinning nuclear magnetic resonance (23Na MAS-NMR) spectroscopy, which is highly sensitive to changes in the symmetry of the local sodium environment. The struc-ture of BM-ACC was probed by vibrational spectroscopy (FTIR, Raman) and solid state MAS NMR (23Na, 13C) spectroscopy. A structural model revealing the partly unsaturated coordination sphere for the Ca2+ ions was derived from the analysis of total scattering data with high-energy synchrotron radiation. Our findings aid in the understanding of mechanochemical amorphization of calcium carbonate and emphasize the effect of impurities on the stabilization of the amorphous phase, which allowed the synthesis of a so far unknown defect variant of ACC with new proper-ties. This may also represent a general approach to obtain new amorphous phases in a variety of different systems.
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Aug 2018
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[12370]
Open Access
Abstract: We investigate the pressure-dependent mechanical behaviour of the zeolitic imidazolate framework ZIF-4 (M(im)2; M2+ = Co2+ or Zn2+, im− = imidazolate) with high pressure, synchrotron powder X-ray diffraction and mercury intrusion measurements. A displacive phase transition from a highly compressible open pore (op) phase with continuous porosity (space group Pbca, bulk modulus ∼1.4 GPa) to a closed pore (cp) phase with inaccessible porosity (space group P21/c, bulk modulus ∼3.3–4.9 GPa) is triggered by the application of mechanical pressure. Over the course of the transitions, both ZIF-4 materials contract by about 20% in volume. However, the threshold pressure, the reversibility and the immediate repeatability of the phase transition depend on the metal cation. ZIF-4(Zn) undergoes the op–cp phase transition at a hydrostatic mechanical pressure of only 28 MPa, while ZIF-4(Co) requires about 50 MPa to initiate the transition. Interestingly, ZIF-4(Co) fully returns to the op phase after decompression, whereas ZIF-4(Zn) remains in the cp phase after pressure release and requires subsequent heating to switch back to the op phase. These variations in high pressure behaviour can be rationalised on the basis of the different electron configurations of the respective M2+ ions (3d10 for Zn2+ and 3d7 for Co2+). Our results present the first examples of op–cp phase transitions (i.e. breathing transitions) of ZIFs driven by mechanical pressure and suggest potential applications of these functional materials as shock absorbers, nanodampers, or in mechanocalorics.
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Jan 2018
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I19-Small Molecule Single Crystal Diffraction
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Shijing
Sun
,
Zeyu
Deng
,
Yue
Wu
,
Fengxia
Wei
,
Furkan
Halis Isikgor
,
Federico
Brivio
,
Michael W.
Gaultois
,
Jianyong
Ouyang
,
Paul D.
Bristowe
,
Anthony K.
Cheetham
,
Gregor
Kieslich
Diamond Proposal Number(s):
[14165]
Abstract: We investigate the variable temperature (100–450 K) and high-pressure (p = ambient − 0.74 GPa) crystal chemistry of the black perovskite formamidinium lead iodide, [(NH2)2CH]PbI3, using single crystal X-ray diffraction. In both cases we find a phase transition to a tetragonal phase. Our experimental results are combined with first principles calculations, providing information about the electronic properties of [(NH2)2CH]PbI3 as well as the most probable orientation of the [(NH2)2CH]+ cations.
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Jun 2017
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[12884]
Abstract: High energy X-ray diffraction is used to follow in situ the crystallization of a cobalt gallate from metallic gallium under solvothermal conditions in an aminoalcohol, revealing the formation and decay of transient metastable layered double hydroxides. Photocatalytic studies show the spinel product has activity as a water oxidation catalyst for oxygen evolution.
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Jun 2017
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I07-Surface & interface diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Alex J.
Barker
,
Aditya
Sadhanala
,
Felix
Deschler
,
Marina
Gandini
,
Satyaprasad P.
Senanayak
,
Phoebe M.
Pearce
,
Edoardo
Mosconi
,
Andrew
Pearson
,
Yue
Wu
,
Ajay Ram
Srimath Kandada
,
Tomas
Leitjens
,
Filippo
De Angelis
,
Sian E.
Dutton
,
Annamaria
Petrozza
,
Richard H.
Friend
Diamond Proposal Number(s):
[11454, 12436]
Abstract: Solution processable lead halide perovskites show immense promise for use in photovoltaics and other optoelectronic applications. The ability to tune their bandgap by alloying various halide anions (for example in CH3NH3Pb(I1-xBrx)3, 0
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May 2017
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[8723]
Abstract: We report a study of the solvothermal formation of the interpenetrated form of the zinc 1,4-benzene dicarboxylate (BDC) metal organic framework MOF-5 using high-energy in situ X-ray diffraction (λ = 0.2333 Å, 53.14 keV). This method allows penetration of a Teflon-lined stainless steel reaction vessel to measure high-resolution powder patterns at 60 s intervals from which temporal evolution of lattice parameters and Bragg peak area can be refined. Crystallisation in N,N-dimethylformamide (DMF) solvent in the presence of melamine at 110 °C yields interpenetrated MOF-5 upon extended periods of reaction (12 h). Laboratory quenching experiments show that a structurally unrelated material, Zn(BDC)(DMF), can be isolated at short reaction times (0.5–4 h), while the in situ experiment reveals the presence of a different phase under reaction conditions at similar times. Profile fitting of the diffraction pattern measured in situ allows an orthorhombic Pcca unit cell (a = 9.6589 (2) Å, b = 18.3096 (3) Å, c = 25.4547 (14) Å) to be refined, providing a tentative identification as a high temperature polymorph of Zn3(BDC)3(H2O)2·4DMF. The phase seen in situ and the one isolated on quenching have no structural relationship to the MOF-5 framework, being constructed from different secondary building units and with different topologies. This illustrates the facile interconversion between crystalline metal carboxylate MOFs in reactive solutions.
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Apr 2017
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I11-High Resolution Powder Diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[7303, 7645]
Abstract: The ytterbium 1,4-benzenedicarboxylate (BDC) framework [Yb2(BDC)3(DMF)2]·H2O (1) crystallises from a N,N-dimethylformamide (DMF)-rich solution at 80–120 °C. (1) is constructed from infinite chains of dicarboxylate-bridged seven-coordinate Yb atoms, cross-linked in two directions by BDC to yield diamond-shaped channels (sra topology) lined by coordinated DMF molecules and occluded water. Increasing the water content in the synthesis solution yields a material with more crystal water Yb2(BDC)3(DMF)2(H2O)2 (2), in which the Yb centres are eight-coordinate and form dimers bridged by BDC to give two interpenetrating networks of pcu (α-Po) topology. Upon extended reaction in this water-rich solvent mixture, an alternative phase is formed: an anhydrous mixed BDC-formate, Yb(BDC)(HCO2), (3), which has a pillared, layered structure, with formate produced by hydrolysis of the DMF. An isoreticular version of (2) can also be formed under similar conditions using 2,6-naphthalene-dicarboxylate (NDC) as linker: [Yb2(NDC)3(H2O)4]·2DMF (4). Despite their different structures, (1) and (2) are calcined to a common porous, desolvated phase Yb2(BDC)3 at 300 °C. Using high energy X-rays at Diamond Light Source we are able to penetrate the solvothermal reaction vessels and to follow the formation of (1) and (2) in real time. This allows accurate crystallisation curves to be obtained from which qualitative kinetic information is extracted. Importantly, the high angular resolution of the in situ powder XRD patterns allows refinement of crystal structure: this permits the temporal evolution of unit cell parameters to be followed, which are ascribed to changes in coordinated solvent composition within the materials during their formation, while analysis of phase fraction allows kinetic parameters to be quantified using the nucleation-growth model of Gualtieri.
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Apr 2017
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