Exploring cation distribution in ion-exchanged Al,Ga-containing metal-organic frameworks using 17O NMR spectroscopy

The authors would like to thank the ERC (Advanced Grant 787073 ADOR) for support. The UK High-Field Solid-State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1), in addition to (for results at 850 MHz) he University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF), and for the 1 GHz instrument, (EP/R029946/1). Collaborative assistance from the Facility Manager Team (Dr Trent Franks, University of Warwick) is acknowledged. The Jeol JSM-IT200 SEM used in this research was supported by the EPSRC Light Element Analysis Facility Grant (EP/T019298/1) and the EPSRC Strategic Equipment Resource Grant (EP/R023751/1). Collaborative assistance from Dr David Miller (University of St Andrews) is acknowledged.A mixed-metal metal–organic framework, (Al,Ga)-MIL-53, synthesised by post-synthetic ion exchange has been investigated using solid-state nuclear magnetic resonance (NMR) spectroscopy, microscopy and energy dispersive X-ray (EDX) spectroscopy. 17O enrichment during the ion-exchange process enables site specific information on the metal distribution to be obtained. Within this work two ion-exchange processes have been explored. In the first approach (exchange of metals in the framework with dissolved metal salts), 17O NMR spectroscopy reveals the formation of crystallites with a core–shell structure, where the cation exchange takes place on the surface of these materials forming a shell with a roughly equal ratio of Al3+ and Ga3+. For the second approach (exchange of metals between two frameworks), no core–shell structure is observed, and instead crystallites containing a majority of Al3+ are obtained with lower levels of Ga3+. Noticeably, these particles show little variation in the metal cation distribution between crystallites, a result not previously observed for bulk (Al,Ga)-MIL-53 materials. In all cases where ion exchange has taken place NMR spectroscopy reveals a slight preference for clustering of like cations.Publisher PDFPeer reviewe

Computational NMR investigation of mixed-metal (Al,Sc)-MIL-53 and its phase transitions

Funding: The authors would like to thank the ERC (Advanced Grant 787073 ADOR) and the Allan Handsel Postgraduate Research Scholarship for Chemistry for studentship funding for ZHD and EALB, respectively. We also acknowledge support from the Collaborative Computational Project on NMR Crystallography (CCP-NC) funded by EPSRC (EP/T026642/1) and from the UK Materials and Molecular Modelling Hub (Young), which is partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1) for which access was obtained via the UKCP consortium and funded by EPSRC (EP/P022561/1).Compositionally complex metal-organic frameworks (MOFs) have properties that depend on local structure that is often difficult to characterise. In this paper a density functional theory (DFT) computational study of mixed-metal (Al,Sc)-MIL-53, a flexible MOF with several different forms, was used to calculate the relative energetics of these forms and to predict NMR parameters that can be used to evaluate whether solid-state NMR spectroscopy can be used to differentiate, identify and characterise the forms adopted by mixed-metal MOFs of different composition. The NMR parameters can also be correlated with structural features in the different forms, giving fundamental insight into the nature and origin of the interactions that affect nuclear spins. Given the complexity of advanced NMR experiments required, and the potential need for expensive and difficult isotopic enrichment, the computational work is invaluable in predicting which experiments and approaches are likely to give the most information on the disorder, local structure and pore forms of these mixed-metal MOFs.Publisher PDFPeer reviewe

Exploration of a Polarized Surface Bidirectional Reflectance Model Using the Ground-Based Multiangle Spectropolarimetric Imager

Accurate characterization of surface reflection is essential for retrieval of aerosols using downward-looking remote sensors. In this paper, observations from the Ground-based Multiangle SpectroPolarimetric Imager (GroundMSPI) are used to evaluate a surface polarized bidirectional reflectance distribution function (PBRDF) model. GroundMSPI is an eight-band spectropolarimetric camera mounted on a rotating gimbal to acquire pushbroom imagery of outdoor landscapes. The camera uses a very accurate photoelastic-modulator-based polarimetric imaging technique to acquire Stokes vector measurements in three of the instrument's bands (470, 660, and 865 nm). A description of the instrument is presented, and observations of selected targets within a scene acquired on 6 January 2010 are analyzed. Data collected during the course of the day as the Sun moved across the sky provided a range of illumination geometries that facilitated evaluation of the surface model, which is comprised of a volumetric reflection term represented by the modified Rahman-Pinty-Verstraete function plus a specular reflection term generated by a randomly oriented array of Fresnel-reflecting microfacets. While the model is fairly successful in predicting the polarized reflection from two grass targets in the scene, it does a poorer job for two manmade targets (a parking lot and a truck roof), possibly due to their greater degree of geometric organization. Several empirical adjustments to the model are explored and lead to improved fits to the data. For all targets, the data support the notion of spectral invariance in the angular shape of the unpolarized and polarized surface reflection. As noted by others, this behavior provides valuable constraints on the aerosol retrieval problem, and highlights the importance of multiangle observations.NASAJPLCenter for Space Researc

Gene regulatory networks elucidating huanglongbing disease mechanisms.

Next-generation sequencing was exploited to gain deeper insight into the response to infection by Candidatus liberibacter asiaticus (CaLas), especially the immune disregulation and metabolic dysfunction caused by source-sink disruption. Previous fruit transcriptome data were compared with additional RNA-Seq data in three tissues: immature fruit, and young and mature leaves. Four categories of orchard trees were studied: symptomatic, asymptomatic, apparently healthy, and healthy. Principal component analysis found distinct expression patterns between immature and mature fruits and leaf samples for all four categories of trees. A predicted protein - protein interaction network identified HLB-regulated genes for sugar transporters playing key roles in the overall plant responses. Gene set and pathway enrichment analyses highlight the role of sucrose and starch metabolism in disease symptom development in all tissues. HLB-regulated genes (glucose-phosphate-transporter, invertase, starch-related genes) would likely determine the source-sink relationship disruption. In infected leaves, transcriptomic changes were observed for light reactions genes (downregulation), sucrose metabolism (upregulation), and starch biosynthesis (upregulation). In parallel, symptomatic fruits over-expressed genes involved in photosynthesis, sucrose and raffinose metabolism, and downregulated starch biosynthesis. We visualized gene networks between tissues inducing a source-sink shift. CaLas alters the hormone crosstalk, resulting in weak and ineffective tissue-specific plant immune responses necessary for bacterial clearance. Accordingly, expression of WRKYs (including WRKY70) was higher in fruits than in leaves. Systemic acquired responses were inadequately activated in young leaves, generally considered the sites where most new infections occur

Structure-Directing Agent Location and Non-Centrosymmetric Structure of Fluoride-Containing Zeolite SSZ-55

Single crystals of pure silica zeolite SSZ-55 were prepared using the fluoride route. Single-crystal X-ray diffraction at a synchrotron source revealed the framework structure of the material, but the unit cell (orthorhombic a = 12.905(2) Å, b = 21.344(4) Å, c = 5.1279(10)) is too small to accommodate ordered arrays of the organic structure-directing agent. Molecular modeling was used to simulate the docking of the structure-directing agent in the channels of the material, and this revealed a strong space-filling interaction with a number of possible orientations of the organic cation. The overall non-centrosymmetric structure of the solid (spacegroup C222_1) was confirmed using second harmonic generation experiments

Molecular genetics and pathophysiology of 17 beta-hydroxysteroid dehydrogenase 3 deficiency.

Autosomal recessive mutations in the 17 beta-hydroxysteroid dehydrogenase 3 gene impair the formation of testosterone in the fetal testis and give rise to genetic males with female external genitalia. Such individuals are usually raised as females, but virilize at the time of expected puberty as the result of increases in serum testosterone. Here we describe mutations in 12 additional subjects/families with this disorder. The 14 mutations characterized to date include 10 missense mutations, 3 splice junction abnormalities, and 1 small deletion that results in a frame shift. Three of these mutations have occurred in more than 1 family. Complementary DNAs incorporating 9 of the 10 missense mutations have been constructed and expressed in reporter cells; 8 of the 9 missense mutations cause almost complete loss of enzymatic activity. In 2 subjects with loss of function, missense mutations testosterone levels in testicular venous blood were very low. Considered together, these findings strongly suggest that the common mechanism for testosterone formation in postpubertal subjects with this disorder is the conversion of circulating androstenedione to testosterone by one or more of the unaffected 17 beta-hydroxysteroid dehydrogenase isoenzymes

Populism and health policy: three international case studies of right-wing populist policy frames

Over the past decade, some of the world's most stable parliamentary democracies have witnessed a revival in right‐wing populist political parties, movements and leaders. Although there is a growing body of theoretical and empirical literature documenting the rise of populism, there has been very little exploration of the implications for health policy of this important political development. In this article, we draw from three illustrative international cases, originating from the USA, the UK and Italy, to explore the ways in which right‐wing populism influences health policy: the election of President Trump in the United States (and subsequent healthcare reforms), the United Kingdom's vote to withdraw from the European Union (Brexit), and how this has played out in the context of the UK National Health Service, and the rise of a politically aligned anti‐vaccination movement in Italy. Drawing on the work of the influential socio‐political theorist Ernesto Laclau, we interpret populism as a performative political act, predicated on drawing logics of equivalence (and difference) between different actors. We use this theoretical framing to explore the ways in which the recent upsurge in right‐wing populism creates a specific set of barriers and challenges for access to healthcare and the health of populations

A novel HLA-B18 restricted CD8+ T cell epitope is efficiently cross-presented by dendritic cells from soluble tumor antigen

NY-ESO-1 has been a major target of many immunotherapy trials because it is expressed by various cancers and is highly immunogenic. In this study, we have identified a novel HLA-B*1801-restricted CD8<sup>+</sup>T cell epitope, NY-ESO-1<sub>88–96</sub> (LEFYLAMPF) and compared its direct- and cross-presentation to that of the reported NY-ESO-1<sub>157–165</sub> epitope restricted to HLA-A*0201. Although both epitopes were readily cross-presented by DCs exposed to various forms of full-length NY-ESO-1 antigen, remarkably NY-ESO-1<sub>88–96</sub> is much more efficiently cross-presented from the soluble form, than NY-ESO-1<sub>157–165</sub>. On the other hand, NY-ESO-1<sub>157–165</sub> is efficiently presented by NY-ESO-1-expressing tumor cells and its presentation was not enhanced by IFN-γ treatment, which induced immunoproteasome as demonstrated by Western blots and functionally a decreased presentation of Melan A<sub>26–35</sub>; whereas NY-ESO-1<sub>88–96</sub> was very inefficiently presented by the same tumor cell lines, except for one that expressed high level of immunoproteasome. It was only presented when the tumor cells were first IFN-γ treated, followed by infection with recombinant vaccinia virus encoding NY-ESO-1, which dramatically increased NY-ESO-1 expression. These data indicate that the presentation of NY-ESO-1<sub>88–96</sub> is immunoproteasome dependent. Furthermore, a survey was conducted on multiple samples collected from HLA-B18+ melanoma patients. Surprisingly, all the detectable responses to NY-ESO-1<sub>88–96</sub> from patients, including those who received NY-ESO-1 ISCOMATRIX™ vaccine were induced spontaneously. Taken together, these results imply that some epitopes can be inefficiently presented by tumor cells although the corresponding CD8<sup>+</sup>T cell responses are efficiently primed in vivo by DCs cross-presenting these epitopes. The potential implications for cancer vaccine strategies are further discussed

Affine modifications and affine hypersurfaces with a very transitive automorphism group

We study a kind of modification of an affine domain which produces another affine domain. First appeared in passing in the basic paper of O. Zariski (1942), it was further considered by E.D. Davis (1967). The first named author applied its geometric counterpart to construct contractible smooth affine varieties non-isomorphic to Euclidean spaces. Here we provide certain conditions which guarantee preservation of the topology under a modification. As an application, we show that the group of biregular automorphisms of the affine hypersurface $X \subset C^{k+2}$ given by the equation $uv=p(x_1,...,x_k)$ where $p \in C[x_1,...,x_k],$ acts $m-$transitively on the smooth part reg$X$ of $X$ for any $m \in N.$ We present examples of such hypersurfaces diffeomorphic to Euclidean spaces.Comment: 39 Pages, LaTeX; a revised version with minor changes and correction