Synthesis of the large pore aluminophosphate STA-1 and its application as a catalyst for the Beckmann rearrangement of cyclohexanone oxime.

The preparation of stable large pore aluminophosphate (AlPO) zeotypes offers materials for applications in adsorption and catalysis. Here we report the synthesis of the pure AlPO with the SAO topology type (AlPO STA-1) using N,N'-diethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidine (DEBOP) as the organic structure directing agent in the presence of fluoride. The AlPO STA-1 can be rendered microporous (pore volume 0.36 cm3 g-1) via calcination and the calcined form remains stable in the presence of moisture. The structure of the dehydrated form has been established by Rietveld refinement (tetragonal P4̄n2, a = 13.74317(10) Å, c = 21.8131(5) Å, V = 4119.94(16) Å3). Multinuclear 27Al and 31P MAS NMR, together with 2D COSY and CASTEP NMR calculations, enables resolution and assignment of the signals from all crystallographically distinct Al and P framework sites. Structural elucidation of the as-prepared aluminophosphate-fluoride is more challenging, because of the presence of partially protonated OSDA molecules in the 3D-connected channel system and in particular because the fluoride ions coordinate with positional disorder to some of the Al atoms to give 5-fold as well as tetrahedrally-coordinated framework Al species. These are postulated to occupy Al-F-Al bridging sites, where they are responsible for distortion of the framework [P4̄n2, a = 13.3148(9) Å, c = 22.0655(20) Å, V = 3911.9(7) Å3]. Calcination and removal of fluoride ions and OSDAs allows the framework to expand to its relaxed configuration. The SAO topology type aluminophosphate can also be synthesised with small amounts of Si and Ge in the framework, and these SAPO and GeAPO STA-1 materials are also stable to template removal. IR spectroscopy with CO as a probe at 123 K indicates all have weak-to-mild acidity, increasing in the order AlPO < GeAPO < SAPO. These STA-1 materials have been investigated for their activity in the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam at 598 K: while all are active, the AlPO form is favoured due to its high selectivity and slow deactivation, both of which are a consequence of its very weak acid strength, which is nevertheless sufficient to catalyse the reaction.

Donor KIR2DL1 Allelic Polymorphism Influences Posthematopoietic Progenitor Cell Transplantation Outcomes in the T Cell Depleted and Reduced Intensity Conditioning Setting.

The majority of established KIR clinical assessment algorithms used for donor selection for hematopoietic progenitor cell transplantation (HPCT) evaluate gene content (presence/absence) of the KIR gene complex. In comparison, relatively little is known about the impact of KIR allelic polymorphism. By analyzing donors of T cell depleted (TcD) reduced intensity conditioning (RIC) HPCT, this study investigated the influence on post-transplant outcome of 2 polymorphic residues of the inhibitory KIR2DL1. The aim of this study was to expand upon existing research into the influence of KIR2DL1 allelic polymorphism upon post-transplant outcome. The effects of allele groups upon transplant outcomes were investigated within a patient cohort using a defined treatment protocol of RIC with TcD. Using phylogenetic data, KIR2DL1 allelic polymorphism was categorized into groups on the basis of variation within codons 114 and 245 (positive or negative for the following groups: KIR2DL1*002/001g, KIR2DL1*003, KIR2DL1*004g) and the identification of null alleles. The influence of these KIR2DL1 allele groups in hematopoietic progenitor cell transplantation (HPCT) donors was assessed in the post-transplant data of 86 acute myelogenous leukemia patients receiving RIC TcD HPCT at a single center. KIR2DL1 allele groups in the donor significantly impacted upon 5-year post-transplant outcomes in RIC TcD HPCT. Donor KIR2DL1*003 presented the greatest influence upon post-transplant outcomes, with KIR2DL1*003 positive donors severely reducing 5-year post-transplant overall survival (OS) compared to those receiving a transplant from a KIR2DL1*003 negative donor (KIR2DL1*003 pos versus neg: 27.0% versus 60.0%, P = .008, pc = 0.024) and disease-free survival (DFS) (KIR2DL1*003 pos versus neg: 23.5% versus 60.0%, P = .004, pc = 0.012), and increasing 5-year relapse incidence (KIR2DL1*003 pos versus neg: 63.9% versus 27.2%, P = .009, pc = 0.027). KIR2DL1*003 homozygous and KIR2DL1*003 heterozygous grafts did not present significantly different post-transplant outcomes. Donors possessing the KIR2DL1*002/001 allele group were found to significantly improve post-transplant outcomes, with donors positive for the KIR2DL1*004 allele group presenting a trend towards improvement. KIR2DL1*002/001 allele group (KIR2DL1*002/001g) positive donors improved 5-year OS (KIR2DL1*002/001g pos versus neg: 56.4% versus 27.2%, P = .009, pc = 0.024) and DFS (KIR2DL1*002/001g pos versus neg: 53.8% versus 25.5%, P = .018, pc = 0.036). KIR2DL1*004 allele group (KIR2DL1*004g) positive donors trended towards improving 5-year OS (KIR2DL1*004g pos versus neg: 53.3% versus 35.5%, P = .097, pc = 0.097) and DFS (KIR2DL1*004g pos versus neg: 50.0% versus 33.9%, P = .121, pc = 0.121), and reducing relapse incidence (KIR2DL1*004g pos versus neg: 33.1% versus 54.0%, P = .079, pc = 0.152). The presented findings suggest donor selection algorithms for TcD RIC HPCT should consider avoiding KIR2DL1*003 positive donors, where possible, and contributes to the mounting evidence that KIR assessment in donor selection algorithms should reflect the conditioning regime protocol used.

Synthetic Control of the Defect Structure and Hierarchical Extra-Large-/Small-Pore Microporosity in Aluminosilicate Zeolite SWY.

The SWY-type aluminosilicate zeolite, STA-30, has been synthesized via different routes to understand its defect chemistry and solid acidity. The synthetic parameters varied were the gel aging, the Al source, and the organic structure directing agent. All syntheses give crystalline materials with similar Si/Al ratios (6-7) that are stable in the activated K,H-form and closely similar by powder X-ray diffraction. However, they exhibit major differences in the crystal morphology and in their intracrystalline porosity and silanol concentrations. The diDABCO-C82+ (1,1'-(octane-1,8-diyl)bis(1,4-diazabicyclo[2.2.2]octan)-1-ium)-templated STA-30 samples (but not those templated by bisquinuclidinium octane, diQuin-C82+) possess hierarchical microporosity, consisting of noncrystallographic extra-large micropores (13 Å) that connect with the characteristic swy and gme cages of the SWY structure. This results in pore volumes up to 30% greater than those measured in activated diQuin-C8_STA-30 as well as higher concentrations of silanols and fewer Brønsted acid sites (BASs). The hierarchical porosity is demonstrated by isopentane adsorption and the FTIR of adsorbed pyridine, which shows that up to 77% of the BASs are accessible (remarkable for a zeolite that has a small-pore crystal structure). A structural model of single can/d6r column vacancies is proposed for the extra-large micropores, which is revealed unambiguously by high-resolution scanning transmission electron microscopy. STA-30 can therefore be prepared as a hierarchically porous zeolite via direct synthesis. The additional noncrystallographic porosity and, subsequently, the amount of SiOHs in the zeolites can be enhanced or strongly reduced by the choice of crystallization conditions.

Highly Cooperative CO2 Adsorption via a Cation Crowding Mechanism on a Cesium-Exchanged Phillipsite Zeolite.

An understanding of the CO2 adsorption mechanisms on small-pore zeolites is of practical importance in the development of more efficient adsorbents for the separation of CO2 from N2 or CH4 . Here we report that the CO2 isotherms at 25-75 °C on cesium-exchanged phillipsite zeolite with a Si/Al ratio of 2.5 (Cs-PHI-2.5) are characterized by a rectilinear step shape: limited uptake at low CO2 pressure (PCO2 ) is followed by highly cooperative uptake at a critical pressure, above which adsorption rapidly approaches capacity (2.0 mmol g-1 ). Structural analysis reveals that this isotherm behavior is attributed to the high concentration and large size of Cs+ ions in dehydrated Cs-PHI-2.5. This results in Cs+ cation crowding and subsequent dispersal at a critical loading of CO2 , which allows the PHI framework to relax to its wide pore form and enables its pores to fill with CO2 over a very narrow range of PCO2 . Such a highly cooperative phenomenon has not been observed for other zeolites.

Hybrid Benzimidazole-Dichloroimidazole Zeolitic Imidazolate Frameworks Based on ZIF-7 and Their Application in Mixed Matrix Membranes for CO2/N2 Separation.

Mixed-linker zeolitic imidazolate frameworks (ZIFs) with the sodalite (sod) topology type and based on ZIF-7 have been prepared by direct synthesis from the mixtures of benzimidazole (BzIm) and 4,5-dichloroimidazole (dcIm). Incorporation of dcIm into the ZIF-7 structure gives ZIF-7/COK-17 hybrids with rhombohedral symmetry that do not show the "open-to-closed form" structural transition upon solvent removal exhibited by ZIF-7. They show Type I isotherms for low molecular weight gases and high affinity for CO2 even at low partial pressures. Synthesis under mild conditions gives ZIF nanoparticles (250-400 nm) suitable for incorporation into mixed matrix membranes (MMMs): these were prepared with both glassy (Matrimid) and rubbery (PEBAX 1657) polymers. Permeation tests at 298 K and 1.2 bar reveal that the incorporation of Zn(BzIm0.55dcIm0.45)2 nanoparticles at up to ca. 12 wt % gives defect-free membranes with enhanced CO2 permeability in both polymer matrices, with retention of selectivity (Matrimid) or with an enhancement in selectivity that is most pronounced for the smaller nanoparticles (PEBAX). The membrane with the best performance exhibits a selectivity of ca. 200 for CO2/N2 (a 4-fold increase compared to the pure polymer) and a CO2 permeability of 64 Barrer. At the relatively low loadings investigated, the MMMs' performance obeys the Maxwell model, and the intrinsic property of diffusivity of the ZIFs can be extracted as a result.

Pressure and guest-mediated pore shape modification in a small pore MOF to 1200 bar.

Guest-mediated pore-shape modification of the metal-organic framework, Sc2BDC3 upon adsorption of n-pentane and isopentane is examined from 50-1200 bar. Rotation of the BDC linker responsible for the change in pore shape occurs at much lower pressures than previously reported, with distinct adsorption behaviour observed between pentane isomers.

Understanding the Anion-Templated, OSDA-Free, Interzeolite Conversion Synthesis of High Silica Zeolite ZK-5.

High silica zeolite ZK-5 (framework Si/Al=4.8) has been prepared by interzeolite conversion from ultrastable zeolite Y via a co-templating route using alkali metal cations and nitrate anions but without organic structure directing agents. The mechanism, which involves zeolite framework - alkali metal cation - nitrate anion ordering, has been established by a combination of chemical and thermal analyses, Raman spectroscopy, computational modelling, and X-ray powder diffraction. Ammonium exchange gives ZK-5 with occluded ammonium nitrate and subsequent heating gives microporous zeolite ZK-5.

Cation Ordering and Exsolution in Copper-Containing Forms of the Flexible Zeolite Rho (Cu,M-Rho; M=H, Na) and Their Consequences for CO2 Adsorption.

The flexibility of the zeolite Rho framework offers great potential for tunable molecular sieving. The fully copper-exchanged form of Rho and mixed Cu,H- and Cu,Na-forms have been prepared. EPR spectroscopy reveals that Cu2+ ions are present in the dehydrated forms and Rietveld refinement shows these prefer S6R sites, away from the d8r windows that control diffusion. Fully exchanged Cu-Rho remains in an open form upon dehydration, the d8r windows remain nearly circular and the occupancy of window sites is low, so that it adsorbs CO2 rapidly at room temperature. Breakthrough tests with 10 % CO2 /40 % CH4 mixtures show that Cu4.9 -Rho is able to produce pure methane, albeit with a relatively low capacity at this pCO2 due to the weak interaction of CO2 with Cu cations. This is in strong contrast to Na-Rho, where cations in narrow elliptical window sites enable CO2 to be adsorbed with high selectivity and uptake but too slowly to enable the production of pure methane in similar breakthrough experiments. A series of Cu,Na-Rho materials was prepared to improve uptake and selectivity compared to Cu-Rho, and kinetics compared to Na-Rho. Remarkably, Cu,Na-Rho with >2 Cu cations per unit cell exhibited exsolution, due to the preference of Na cations for narrow S8R sites in distorted Rho and of Cu cations for S6R sites in the centric, open form of Rho. The exsolved Cu,Na-Rho showed improved performance in CO2 /CH4 breakthrough tests, producing pure CH4 with improved uptake and CO2 /CH4 selectivity compared to that of Cu4.9 -Rho.

BSHI guideline: HLA matching and donor selection for haematopoietic progenitor cell transplantation.

A review of the British Society for Histocompatibility and Immunogenetics (BSHI) Guideline 'HLA matching and donor selection for haematopoietic progenitor cell transplantation' published in 2016 was undertaken by a BSHI appointed writing committee. Literature searches were performed and the data extracted were presented as recommendations according to the GRADE nomenclature.

Site-Specific Iron Substitution in STA-28, a Large Pore Aluminophosphate Zeotype Prepared by Using 1,10-Phenanthrolines as Framework-Bound Templates.

An AlPO4 zeotype has been prepared using the aromatic diamine 1,10-phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO4 N2 environment. Furthermore, using this framework-bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m2 g-1 and two perpendicular sets of channels that intersect to give pore space connected by 12-ring openings along all crystallographic directions.

Effects of crystal size on methanol to hydrocarbon conversion over single crystals of ZSM-5 studied by synchrotron infrared microspectroscopy.

Operando synchrotron infrared microspectroscopy (OIMS) was used to study the conversion of methanol over coffin-shaped HZSM-5 crystals of different sizes: large (∼250 × 80 × 85 µm3), medium (∼160 × 60 × 60 µm3) and small (∼55 × 30 × 30 µm3). The induction period, for direct alkene formation by deprotonation of surface methoxy groups, was found to decrease with decreasing crystal size and with increasing reaction temperature. Experiments with a continuous flow of dimethylether showed that evolution of the hydrocarbon pool and indirect alkene formation is also strongly dependent on crystal size. These measurements suggest that the hydrocarbon pool formation and indirect alkene generation should be almost instantaneous at reaction temperatures used in practical catalysis with crystal sizes typically ∼1 µm3.

Killer-cell immunoglobulin-like receptor assessment algorithms in haemopoietic progenitor cell transplantation: current perspectives and future opportunities.

Natural killer cells preferentially target and kill malignant and virally infected cells. Both these properties present compelling clinical utility in the field of haemopoietic progenitor cell transplantation (HPCT), potentially promoting a graft vs leukaemia effect in the absence of graft vs host disease and protecting against cytomegalovirus activation. Killer Ig-like receptors (KIR) play a central role in the cytotoxic action of natural killer cells, providing opportunity for improving transplantation outcomes by prioritising potential donors with optimal characteristics. Numerous algorithms for assessing KIR gene content as part of HPCT donor selection protocols exist, but no single model has been found to be universally applicable in all transplant centres. This review summarises several of the predominant strategies in KIR assessment algorithms, discussing their basic scientific principles, clinical utility and benefits to post-transplant outcomes. Finally, the review will consider how future donor selection protocols could develop towards unifying the concepts of KIR proteomics and genetics for optimising patient care.

Facile, Room-Temperature 17O Enrichment of Zeolite Frameworks Revealed by Solid-State NMR Spectroscopy.

A new approach for room-temperature 17O enrichment of zeolites reveals a surprisingly dynamic and labile framework, where rapid and reversible bond breaking takes place. 17O NMR spectroscopy shows that although O sites in both framework Si-O-Al and Si-O-Si linkages are enriched simply on exposure to H217O(l), the enrichment of Si-O-Al species is more rapid, with a more uniform framework enrichment observed at longer durations. We demonstrate that this unexpected enrichment can be observed for two different framework topologies and for Na-exchanged (i.e., nonacidic) zeolites, as well as their protonic forms, confirming that the Brønsted acid proton is not necessary for isotopic exchange into the framework. This work not only offers new opportunities for structural characterization of these chemically and industrially important materials using NMR spectroscopy but suggests that further investigation of the rate and position of enrichment in zeolite frameworks could provide new insight into their chemical reactivity and their stability in aqueous-based applications such as ion exchange and catalysis.

Triggered Gate Opening and Breathing Effects during Selective CO2 Adsorption by Merlinoite Zeolite.

Zeolites with flexible structures that adapt to coordinate extraframework cations when dehydrated show a rich variety of gas adsorption behavior and can be tuned to optimize kinetics and selectivity. Merlinoite zeolite (topology type MER) with Si/Al = 3.8 has been prepared in Na, K, and Cs forms and its structural response to dehydration measured: the unit cell volumes decrease by 9.8%, 7.7%, and 7.1% for Na-, K-, and Cs-MER, respectively. Na-MER adopts Immm symmetry, while K- and Cs-MER display P42/nmc symmetry, the difference attributed to the preferred locations of the smaller and larger cations. Their performance in CO2 adsorption has been measured by single-component isotherms and by mixed gas (CO2/CH4/He) breakthrough experiments. The differing behavior of the cation forms can be related to structural changes during CO2 uptake measured by variable-pressure PXRD. All show a "breathing" transition from narrow to wide pore forms. Na- and Cs-MER show non-Type I isotherms and kinetically-limited CO2 adsorption and delivery of pure CH4 in CO2/CH4 separation. However, K-MER shows good uptake of CO2 (3.5 mmol g-1 at 1 bar and 298 K), rapid adsorption and desorption kinetics, and promising CO2/CH4 separation. Furthermore, the narrow-to-wide pore transition occurs rapidly and at very low pCO2 via a "triggered" opening. This has the consequence that whereas no CH4 is adsorbed from a pure stream, addition of low levels of CO2 can result in pore opening and uptake of both CO2 and CH4, although in a continuous stream the CH4 is replaced selectively by CO2. This observed cation size-dependent adsorption behavior derives from a fine energetic balance between different framework configurations in these cation-controlled molecular sieves.

A Bifunctional MOF Catalyst Containing Metal-Phosphine and Lewis Acidic Active Sites.

Post-synthetic modification of the hafnium metal-organic framework MOF-808(Hf) to include triarylphosphine ligands is reported. Sulfonated phenylphosphines are incorporated without oxidation to give a "MOF ligand" that can complex late transition metals such as Ir and Rh to give a bifunctional catalyst containing both metal-phosphine complexes and the Lewis acidic framework hafnium metal sites. The metallated phosphine-bearing MOFs act as fully heterogeneous bifunctional catalysts for tandem reductive amination and hydroaminomethylation reactions.

Towards High Performance Metal-Organic Framework-Microporous Polymer Mixed Matrix Membranes: Addressing Compatibility and Limiting Aging by Polymer Doping.

Membrane separation for gas purification is an energy-efficient and environment-friendly technology. However, the development of high performance membranes is still a great challenge. In principle, mixed matrix membranes (MMMs) have the potential to overcome current materials limitations, but in practice there is no straightforward method to match the properties of fillers and polymers (the main components of MMMs) in such a way that the final membrane performance reflects the high performance of the microporous filler and the processability of the continuous polymer phase. This issue is especially important when high flux polymers are utilized. In this work, we demonstrate that the use of small amounts of a glassy polymer in combination with high performance PIM-1 allow for the preparation of metal-organic framework (MOF)-based MMMs with superior separation properties and low aging rates under humid conditions, meeting the commercial target for post-combustion CO2 capture.

Synthesis of ZIF-93/11 Hybrid Nanoparticles via Post-Synthetic Modification of ZIF-93 and Their Use for H2 /CO2 Separation.

The present work shows the synthesis of nano-sized hybrid zeolitic imidazolate frameworks (ZIFs) with the rho topology based on a mixture of the linkers benzimidazole (bIm) and 4-methyl-5-imidazolecarboxaldehyde (4-m-5-ica). The hybrid ZIF was obtained by post-synthetic modification of ZIF-93 in a bIm solution. The use of different solvents, MeOH and N,N-dimethylacetamide (DMAc), and reaction times led to differences in the quantity of bIm incorporated to the framework, from 7.4 to 23 % according to solution-state NMR spectroscopy. XPS analysis showed that the mixture of linkers was also present at the surface of the particles. The inclusion of bIm to the ZIF-93 nanoparticles improved the thermal stability of the framework and also increased the hydrophobicity according to water adsorption results. N2 and CO2 adsorption experiments revealed that the hybrid material has an intermediate adsorption capacity, between those of ZIF-93 and ZIF-11. Finally, ZIF-93/11 hybrid materials were applied as fillers in polybenzimidazole (PBI) mixed matrix membranes (MMMs). These MMMs were used for H2 /CO2 separation (at 180 °C) reaching values of 207 Barrer of H2 and a H2 /CO2 selectivity of 7.7 that clearly surpassed the Robeson upper bound (corrected for this temperature).

Influence of Filler Pore Structure and Polymer on the Performance of MOF-Based Mixed-Matrix Membranes for CO2 Capture.

To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH2 -MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25 wt % of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10 %, while for Pebax they were enhanced to 25 and 18 %, respectively. The observed differences in membrane performance in the separation of CO2 from N2 are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift.

A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4',4"-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im3‾ m symmetry compared with the Pm3‾ m symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and 13 C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 nodes leaving coordinatively unsaturated Zr4+ sites, as shown by IR spectroscopy using CO and CD3 CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm3 g-1 while CO2 adsorption at 196 K reaches 300 cm3 STP g-1 at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.

Reactions of Dimethylether in Single Crystals of the Silicoaluminophosphate STA-7 Studied via Operando Synchrotron Infrared Microspectroscopy.

ABSTRACT: Synchrotron infrared micro-spectroscopy has been applied to measure in situ the reaction of dimethylether in single crystals of the silicoaluminophosphate STA-7. The crystals are found to contain a uniform and homogeneous distribution of acidic hydroxyl groups. Dimethylether is hydrogen bonded to the hydroxyl groups at low temperatures, but evidence is found for dissociation to form surface methoxy groups above 473 K, and aromatic hydrocarbon pool species above 573 K. From time resolved infrared measurements coupled with MS analysis of evolved products it is concluded that alkene formation occurs via a direct mechanism from reaction of dimethylether with surface methoxy groups.