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AIMS OF THE STUDY Non-adherence to immunosuppressive therapy in patients following solid organ transplantation is associated with an increased risk of transplant rejection and graft loss. A high pill burden can adversely affect patients’ implementation of their treatment regimens and may lead to omitting doses of medication. The aim of this study was to investigate medication implementation adherence in liver and kidney transplant recipients converted from twice-daily, immediate-release tacrolimus to once-daily, prolonged-release tacrolimus. METHODS This multicentre, non-interventional, observational, 12-month study evaluated implementation adherence in routine practice at five hospitals in Switzerland. Patients attended four clinical visits: at baseline (pre-conversion), and then at week 2, month 6 and month 12 post-conversion. Implementation was defined as consistently taking medication at the correct time and at the correct dose in order to achieve target tacrolimus trough levels. Implementation adherence was evaluated in three ways: using the Basel Assessment of Adherence to Immunosuppressive Medications Scale (BAASIS) interview questionnaire (at baseline and month 12), investigator-rated patient adherence (recorded at all visits), and tacrolimus trough levels (assessed throughout the study; sub-therapeutic levels were predefined by the investigator on an individual patient basis, over-therapeutic levels were defined as tacrolimus trough levels >15 ng/ml). The primary composite endpoint was non-adherence according to the BAASIS at month 12, any post-conversion investigator adherence rating of “poor”, or sub-therapeutic or over-therapeutic tacrolimus trough levels at month 6 or 12. Secondary endpoints included: individual components of the composite non-adherence primary endpoint, tacrolimus pill burden, patient satisfaction, and adverse drug reactions. RESULTS Seventy-five patients received prolonged-release tacrolimus; 68 patients (46 kidney and 22 liver transplant recipients) completed the study. Of these 68 patients, 24 had missing data for at least one component of the primary endpoint; therefore, data for the primary composite endpoint were evaluable for 44 patients. Most (81.8%; 36/44) patients were non-adherent for the composite endpoint. Sub-therapeutic tacrolimus trough levels outside of the predefined therapeutic range were the largest contributor to the composite endpoint, and were detected in 62.0% (31/50) of patients. Overall non-adherence according to the BAASIS was similar pre-conversion (30.7%) and at 12 months post-conversion (28.3%). Investigators rated adherence as “poor” for two patients. Prolonged-release tacrolimus decreased tacrolimus pill burden in 66.7% of patients. All patients were very satisfied / satisfied with prolonged-release tacrolimus; 75.0% found it easier to remember to take prolonged-release versus immediate-release tacrolimus. Twenty percent of patients reported adverse drug reactions, with infections being the most frequently reported (9.3%). CONCLUSION Overall, 1-year non-adherence rates were similar following conversion from immediate-release to prolonged-release tacrolimus; however, prolonged-release tacrolimus intake was more convenient. No new safety signals were detected.

Introduction The aim of this study was to explore the repercussions associated with caregiving of patients who receive palliative care at home due to an oncological disease through the assessment of the health status self-perception in the last year, the presence of anxiety and depressive symptoms and the assessment of caregiving burden. Method Design: Descriptive, cross-sectional study. Sample: family caregivers of patients with oncological disease who are under the follow-up of a home palliative care program hospital-based. Period: July 2015 and December 2016. Analysis: descriptive statistics. Questionnaires: Goldberg anxiety and depression scale; Zarit Caregiver Overload Scale in reduced version Results 80 family caregivers were included in the study. 56 (70%) were women and 24 (30%) men, with a mean age of 61.75 years (SD=12.98). 52.5% of the family caregivers assessed negatively affect their health status in the last year (regular, bad or very bad) while 47.5% valued it positively (good or very good). 48 caregivers presented symptoms of possible anxiety diagnosis, and 36 caregivers symptoms of possible diagnosis of depression. The risk of claudication due to caregiver’s burden was assessed in 57 caregivers. The average score was 14.95 on the Zarit Scale (short version). 16 caregivers (20%) presented claudication risk criteria. The results showed a significant positive association between age (r=0.316; p=0.008), anxiety symptoms (r=0.333; p=0.005), care overload (r=0.277; p=0.037) and the worst health status perception. Conclusion In the sample studied, the family members who take care presented a worse perception of their health status, higher levels of anxiety and a greater perception of care overload.

Introduction This study aims to describe the characteristics and circumstances related to caregiving at home of family caregivers of people receiving palliative care at home due to cancer disease. Method Design: Descriptive, cross-sectional study. Sample: family caregivers of people in follow-up in the home care program. Period: July/2015 to December/2016. Variables: sociodemographic data, characteristics of the role of caregiver as previous experience caring, reasons for caring, living together, simultaneous care of other people, care environment preferences, perception of the relationship, time and hours assuming care. Results The sample was made up of a total of 80 relatives, 56 (70%) were women and 24 (30%) men, with a mean age of 61.75 years (SD=12.98). 55.7% of them had primary education, 45% were a pensioner followed by 23.8% who said they were working. The degree of kinship was spouse/partner (48.8%) followed by daughter (42.5%). 92.5% of caregivers identified themselves as primary caregivers while 7.5% were sole caregivers. In most cases (76.3%) they resided at the same address. In 30% of cases, caregivers also treated other dependents besides the patient.The main reasons for caregiving described were: own initiative (47.5%) and feeling obligated (36.3%). For 40% of the caregivers it was the first experience of caring. The average time caring was 12.98 months (SD=21.41), the average of hours caring per week 38.29 (SD=20.66). 53.8% of caregivers described their relationship with the patient as very intimate, however 25% of them identified that the relationship had worsened. Conclusions In home palliative care scenarios, knowing the circumstances of caregivers and caregiving environment could contribute to recognize and support family caregiving.

Domestic water saving potential in the case of Manisa, Turkey has been investigated. The water conservation measures for each water practice are examined and some easy-to-apply measures have been proposed. An experimental study was then conducted to determine if the domestic water conservation measures proposed were applicable for the city considered. For this purpose, a questionnaire was developed and 200 respondents were asked to fill it in. Based on the results of the study, it is shown thatthe measures proposed are quite applicable and around 27% saving is manageable if the proposed measures are publicized adequately and applied effectively.Key words: Domestic water, water saving, water conservation, demand management, Manisa.Les investigations ont été menées sur le potentiel économique de l’eau domestique dans le cas de la Manisa, en Turquie. Les mesures de conservation de l'eau pour chaque usage ont été examinées et desmesures pratiques faciles d’accès à la population ont été proposées. Une étude expérimentale a ensuite été menée afin de déterminer si les mesures de conservation de l'eau proposées sur le plan national ont étéappliquées pour la ville considérée. À cette fin, un questionnaire a été élaboré et 200 répondants ont été invités à le remplir. Sur la base des résultats de l'étude, il est démontré que les mesures proposées sonttout à fait applicable et participera à environ 27% de l'économie si les mesures proposées sont diffusées de manière efficace et efficiente.Mots clés: Eau domestique, économie de l’eau, conservation, gestion, Manisa

Histopathological, immunohistochemical and ultrastructural cutaneous changes are described in acute and subacute forms of experimental African Swine Fever (ASF). Fourteen 3-month-old Large White cross pigs were infected intramuscularly with the Dominican Republic 78 (DR78) ASF virus isolate and euthanized in pairs on alternatives days (3 to 17) post-inoculation (dpi). Three pigs were found dead at 8, 10 and 13 dpi, respectively. Antibodies against viral antigen Vp73, human fibrinogen, glycoprotein IIIa and Factor VIII-ra were used to evaluate viral antigen distribution, fibrin microthrombi and platelets in dermal vessels, respectively. Cutaneous lesions were characterised by vascular changes ranging from hyperaemia, mild oedema, scarce fibrin microthrombi and microhaemorrhages in euthanized animals, to generalized fibrin microthrombosis and microhaemorrhages in dead pigs. Secondary pustules and superficial folliculitis were observed in two animals dead at 10 and 13 dpi. Diffuse cytoplasmic Vp73 labelling was found in numerous intravascular monocytes and dermal macrophages. Ultrastructural studies showed mature viral particles in the lumen of dermal vessels but viral replication was not observed; nonetheless, microtubuloreticular structures were observed in the cytoplasm of some endothelial cells and macrophages which showed cytopathic effects, signs of cell activation or degeneration. Morphological and immunohistochemical evidences of platelet activation, degranulation and consumption were observed from 5 dpi onward.

The electrochemical growth of metal-organic framework (MOF) coatings, utilising the anodic dissolution method, has been investigated as a means of preparing MOF coated electrodes for various electrochemical applications. A mechanistic understanding of the formation of the electrode coatings has been further developed. This understanding has been utilised to expand the scope of this technique; to allow for the electrochemical formation of Zn and Co zeoliticimidazolate framework (ZIF) coatings which was hitherto not believed to bepossible.Electrodes coated with Co and Zn ZIFs via this methodology were assessed for their capacitive behaviour and the Co ZIFs exhibited the highest, pure MOF areal capacitance values reported to date. This was attributed to the method of coating formation, which provides well adhered coatings of MOF particles integrated into the electrode surface providing a good electrical connection between the coating and the electrode. Incorporation of GO, via electrophoretic deposition during the coating growth, is shown to improve this capacitance still further. Thecorresponding Zn ZIFs exhibited resistances orders of magnitude higher than their Co analogues; modelling can explain this behaviour with the Co analogue of a given ZIF calculated to have a greater metal contribution to its LUMO leading to a more delocalised electronic structure.Electrodes coated with the Cu MOF HKUST-1 have enabled for the first time the use of MOFs as a template for the electrodeposition of anisotropic metal nanostructures. Such MOF encapsulated metal nanostructures are demonstrated to have applications in surface enhanced Raman spectroscopy (SERS). In addition the same MOF has been discovered to display a redox based hysteresis which allows for the rewritable storage of small amounts of electrically accessible data.

This research aimed to develop new composite membranes using a polymer of intrinsic microporosity (PIM-1) and metal organic frameworks (MOFs) for use in gas separations. PIM-1 was successfully synthesised using the high temperature method (40 min, 160 oC) and the resulting polymer was cast into membranes. PIM-1 membranes were chemically modified by reacting hexamethylenediamine (HMDA) with the nitrile group of PIM-1 to form HMDA-modified PIM-1 membranes. Surfaces of PIM-1 membranes were also modified by basic hydrolysis to form amide-modified PIM-1 membranes. These polymer materials were characterized by different techniques (GPC, NMR, ATR-IR, TGA, Elemental analysis and nitrogen sorption analysis). In addition, eight MOF materials [MIL-101(Cr), ED-g-MIL-101(Cr), TEPA-g-MIL-101(Cr), MIL-101(Cr)-NH2, MIL-101(Al)-NH2, UiO-66(Zr), UiO-66-NH2 and UiO-66(COOH)2] were successfully synthesized. They were chosen due to having high surface areas and large porosity. These MOF compounds were characterized using PXRD, SEM, TGA, and low pressure N2.Successful PIM-1/MOF MMMs were fabricated utilising PIM-1 and the MOFs outlined above with various loadings. The highest MOF loading achieved was 28.6 wt. %, apart from MIL-101(Cr)-NH2, for which it was 23.1 wt. %, and MIL-101(Al)-NH2, for which it was 19.8 wt. %. The morphology of MMMs was characterized by scanning electron microscopy (SEM), proving the dispersion of MOF fillers. Novel PIM-1 supported MOF membranes were successfully prepared by depositing ZIF-8 and HKUST-1 layers on the surfaces of unmodified and modified PIM-1 membranes. These materials were characterized using PXRD, SEM, ATR-IR and SEM-EDX. Gas permeation properties of the MOF/PIM-1 MMMs and PIM-1 supported MOF membranes were determined using a time lag method. Most MMMs tested showed an increase in the permeability and stable selectivity as the MOF amount was increased. However, this was not true for MIL-101(Al)-NH2, where the permeability and selectivity decreased. In contrast, PIM-1 supported ZIF-8 and HKUST-1 membranes caused a sharp decrease in the permeability and increase in the selectivity.

Cette thèse porte sur la représentation d'un groupe de réfugiés de guerre: les Acadiens en 1755, date de leur déportation en Nouvelle-Angleterre, l'évolution de cette dernière et l'imprégnation continue de la bienfaisance dans cette évolution. Elle porte sur trois siècles et singularise les représentations de ces réfugiés dans plusieurs régions transatlantiques: la Nouvelle-Angleterre, le Québec, les provinces maritimes canadiennes et la France. Cette thèse s'arrête également sur l'impact social et politique de ces représentations pour la communauté acadienne actuelle. This dissertation focuses on the representation of a group of war refugees: Acadians in 1755, when they were expelled in New England. It traces the representation's evolution and the impact of humanitarianism. It deals with three centuries and singles out représentations in several transatlantic régions: New England, Québec, Eastern Canada and France. This dissertation singles out the social and political impact of humanitarianism in contemporary représentations of the Acadian community., Doctorat en Histoire, art et archéologie, info:eu-repo/semantics/nonPublished

The methanol-to-olefins reaction is an important industrial process for the production of light olefins (C2-C4). Silicoaluminophosphates are the most common catalysts for this process with SAPO-34 (CHA), SAPO-18 (AEI) and their intergrowths being considered the most catalytically active and selective. Understanding the crystal growth of such materials is important for control of the structure and defect incorporation, which can have a large effect on the catalytic behaviour. In this thesis, the synthesis, characterisation, catalysis and crystal growth of such materials are investigated.A series of CHA/AEI intergrowth materials were synthesised by sequential increases in silicon content, where low silicon content led to formation of AEI and higher silicon content led to CHA and intergrowth formation. X-ray diffraction and MAS-NMR were used to quantify the amount of intergrowth and there was a strong correlation between both techniques. Atomic Force Microscopy (AFM) revealed the mechanism by which these intergrowth structures grow. There is competition at the surface between the spiral-growth and layer-growth mechanisms, which has a significant effect on the resulting intergrowth, as intergrowth formation is only permitted with a layer-growth mechanism. Intergrowth on screw dislocations is not allowed, and thus discrete blocks of pure-phase AEI or CHA form.These intergrowth materials were tested for their performance in the methanol-to-olefins reaction. With a higher level of silicon, the catalysts had a larger acid site density but equivalent acid strength. The conversion of methanol over the catalysts correlated with the acid site density, where a greater acid site density led to higher conversion and faster deactivation. The selectivity over time was similar for all catalysts, with a high selectivity to ethylene and propylene. However, at the same percentage conversion, the C2/C3 ratio showed a strong correlation to the cage shape. Catalysts with a higher ratio of AEI cages had a higher selectivity to C3 and C4 products than the other catalysts, owing to the larger size of the internal AEI cage compared to the CHA cage.The crystal growth mechanism on SAPO-18 was investigated in detail to interrogate the complex spiral pattern that forms on the surface. Spirals form in a triangular type pattern due to differences in growth rates in different crystallographic directions. Interlaced terraces were also present. The unit cell and the relative orientation of the AEI cages define the different growth rates. In-situ AFM was used to investigate the dissolution behaviour of SAPO-18 and SAPO-34. In both cases, dissolution occurred via classical step retreat. The similarity in the layer stacking in both materials led to equivalent structure dissolution in both cases. The 0.9 nm layers dissolved first to 0.7 nm (closed cages) then to 0.4 nm (unstable intermediates). Dissolution of SAPO-18 revealed unusual spiral dissolution pits near the core of the dislocations.CHA/AEI intergrowth materials were also prepared using a dual-template method, where two templates, morpholine for CHA and N,N-diisopropylethylamine for AEI, were combined during synthesis. The phase transition from CHA to AEI occurred at different molar ratios with different synthesis procedures. XRD modelling confirmed the synthesis of an intergrowth phase at a molar ratio of 70% morpholine and 30% DPEA. Changes in chemical shift in the 13C MAS-NMR were used to observe the different template interactions with the framework as the ratio of CHA and AEI cages changed. Movies are referenced in published journal articles. These were attached as a CD to the physical copy of the thesis. These can also be found on the online supporting information on the journal websites.

The University of ManchesterDonna Joanne PagePhD in Development BiologyExploring the role of transmembrane 4 L six family member 1 (tm4sf1) in the control of tip cell behaviour during sprouting angiogenesis2015ABSTRACTAngiogenesis is the process of new blood vessel sprouting from pre-existing vessels and is responsible for generating the majority of nascent vessels during development, tissue regeneration and disease. During angiogenesis, sprouting endothelial cells (ECs) are organised into leading 'tip' cells (TCs) and trailing 'stalk' cells (SCs). This hierarchal organisation of TCs and SCs is essential for the coordinated collective migration of ECs during sprouting. However, the precise mechanisms that define TC verses SC behaviour and identity remains uncertain. Transcriptomic analysis of sprouting vessels in zebrafish embryos led to the identification of a novel TC-associated gene, transmembrane 4 L six family member 1 (tm4sf1). We find that tm4sf1 expression is tightly spatiotemporally restricted to migrating TCs during intersegmental vessel (ISV) sprouting in zebrafish. Furthermore, TC tm4sf1 expression is controlled by the vascular endothelial growth factor receptor (Vegfr) - Notch signalling axis. Morpholino oligonucleotide (MO)-mediated knockdown of tm4sf1 reveals a subtle delay in ISV sprouting upon loss of tm4sf1 expression. Moreover, using multiplexed, real-time imaging approaches and in-depth analysis of TC and SC behaviours at single cell resolution, we reveal that the delay in ISV sprouting is specifically due to reduced TC motility. Furthermore, we find that tm4sf1 functions to induce TC motility in the leading daughter cell following TC mitosis, to rapidly re-establish post-mitotic TC behaviour. Generation of tm4sf1 mutant zebrafish lines using both transcription activator-like effector nucleases (TALENs) and clustered regularly interspaced short palindromic repeats (CRISPR) confirms that Tm4sf1 modulates TC behaviour. Additionally, mechanistic studies in human ECs reveal that tm4sf1 regulates VEGFR-mediated signalling upon VEGF-stimulation, which subsequently controls cell migration and expression of the TC determinants, DLL4 and VEGFR2. Hence, our results suggest that tm4sf1 is a novel modulator of the TC-SC hierarchy and collective EC migration during ISV sprouting. Overall, these findings have potential therapeutic implications since tm4sf1 may be a promising target for the manipulation of pathological angiogenesis in disease.

Porous materials are one of the extensively used class of solid mostly useful for adsorption, catalysis, separation, storage and ion exchange. Microporous materials have received a rapidly growing rate of interest with regards to their syntheses, characterisation and applications. In the current study ex-situ atomic force microscopy (AFM) was used to investigate the crystal surfaces of MOF-801-SC and Zn(tbip) crystals to provide information concerning the crystal growth of the materials.MOF-801-SC is a novel porous coordination polymer (PCP) and a member of the Zr-based UiO-66 series as seen by powder X-ray diffraction (PXRD), composed of zirconium (iv) oxychloride octahydrate (ZrOCl2.8H2O), and fumarate (-O2C(CH)2CO2-) linkers has been synthesised by a modulated synthesis approach. MOF-801-SC further characterised by scanning electron microscopy (SEM) revealing that the crystals have octahedral cubic morphology with crystal sizes ranging from 7.0 µm to 9.0 µm. The AFM height images analyses revealed that most of the growth steps are 1.0 ± 0.1 nm high.Zn(tbip) is a novel guest-free Microporous metal-organic framework (GFMMOF) composed of Zn-based secondary building units (SBUs), [Zn(NO3).6H2O], and 5-tert-butyl isophthalate (tbip2-) ligands has been synthesised and characterised structurally robust with an extraordinary thermal stability. The PXRD pattern of the sample indicated that a monophasic sample had been prepared. The SEM revealed that the crystals have elongated hexagonal prism morphology with crystals sizes ranging from 300 µm to 500 µm. Thermogravimetric analysis (TGA) showed that the crystal is thermally stable up to 420 oC and is guest molecule free. Single crystals were determined by single crystal X-ray diffraction (SXRD). Solid-state NMR proved that the crystals are guest-free. SXRD showed that methanol addition to the single crystals proved that a molecule can go into the crystal pores. A multilayer growth features were observed in the AFM micrographs of Zn(tbip) crystals.

Elizabeth GrangerThe University of ManchesterThe interplay between dynein, accessory proteins and the endocytic pathwayDoctor of Philosophy, Organelle Function25-09-13Cytoplasmic dynein 1 (dynein) is a multi-subunit complex that transports cargo along microtubules towards their minus ends. These microtubule minus ends are normally located toward the centre of the cell. Dynein is involved in transport of endocytic and autophagic membranes and is tightly regulated by interactions between dynein subunits and by dynein-accessory proteins. Dynein accessory proteins that are involved in a wide range of dynein-driven transport events include dynactin, Lis1 and the paralogues Nde1 and Ndel1. Lis1 and Nde1/Ndel1 interact with each other and are involved in the recruitment of dynein to cargo and in regulating dynein activity. Although much is known about the specific interactions of dynein and accessory proteins, the interplay between dynein and its network of regulators in living cells is not well defined.This project used RNAi to investigate how the dynein subunits light intermediate chain (LIC) and intermediate chain (IC) as well as Lis1 and Nde1/Ndel1 influence the endocytic pathway, autophagy and cargo recruitment. Biochemical analysis of bulk membrane preparations showed that IC is important for dynein and dynactin association with intracellular membranes. In addition, dynein and dynactin recruitment to Rab interacting lysosomal protein (RILP)-positive membranes was shown to require LIC and there was redundancy between LIC1 and LIC2 in this role. Lis1 was also needed for dynactin-dynein recruitment to these membranes, in a context that was Nde1/Ndel1-independent.Loss of LIC, IC, Lis1 and Nde1 had differing effects on endocytic compartment size and distribution, but they all led to mislocalisation of early endosomes and lysosomes and caused lysosomes to become enlarged. Loss of LIC led to a specific phenotype whereby cells formed lamellipodia-like regions in which early endosomes and lysosomes accumulated. Loss of Lis1 prevented traffic from the early endosome to late endosomes and caused a striking enlargement of late endosomes and lysosomes. These enlarged lysosomes were LC3-positive, indicating that they were autophagic. In addition, loss of IC and LIC also led to an increase in LC3 puncta, but the LC3 did not colocalise specifically with lysosomes.In summary, the results from this project show that i) dynactin recruitment to intracellular membranes, including RILP-postivie membranes, requires dynein, ii) Lis1 and LIC1 or LIC2 are necessary but not sufficient, individually, to recruit dynein and dynactin to RILP-positive membranes iii) LIC, IC, Lis1 and Nde1/Ndel1 influence endocytic progression in specific ways, which may in turn affect autophagic flux.

This work explores the fabrication and permeability testing of mixed matrix membranes (MMM) utilising a polymer of intrinsic microporosity (PIM-1) and various fillers. PIM-1 has been chosen for this work due to its high apparent surface area and high sorption of gases. PIM-1 also is a good candidate for gas sorption applications due to the film forming properties of the polymer. The fillers utilised in this work are Metal Organic Frameworks (MOFs) and organic cages, which have been chosen due to the gas sorption properties they exhibit. The MOFs used are micro and nanoparticles of Zeolitic Imidazole Framework-8 (ZIF-8), copper based MOF HKUST-1 and chromium based MOF MIL-101. Micro particles of magnesium based MOF Mg-MOF-74 were also looked at as well as cage 3, nano cage 3 and reduced cage 3. Comparable surface areas of the MOFs compared to those quoted in the literature have been obtained. Successful PIM-1/Filler MMMs were synthesised utilising PIM-1 and the fillers outlined above with various loadings of filler. The highest loading achieved was with a 10:6.4 PIM-1/nanoZIF-8 ratio. All MMMs apart from PIM-1/Mg-MOF-74 MMM were homogenous on a macroscale with scanning electron microscopy proving the dispersion of fillers. Gas transport properties of the MMMs were determined using predominantly a time lag method. PIM-1/ZIF-8 MMMs were also tested using a chromatographic method and using a gas sorption experiment. A range of gases were tested including CO2, N2, CH4, O2, He and H2. Ideal selectivities were also calculated with focus on the gas pairs O2/N2, CO2/CH4 and CO2/N2.When comparing the two permeability methods using the PIM-1/nanoZIF-8 MMM, lower permeability results were found from the time lag method. This was concluded to be due to the aging effect brought about by the vacuum used in the time lag method. The chromatographic method produced positive results with high selectivities, breaking Robeson’s upper bound, for the gas pair O2/N2. All other fillers tested showed an increase in permeability and stable selectivity with an increase in the amount of filler. MIL-101 and Cage 3 were the most successful fillers with high permeabilities of 35600 and 37400 Barrer respectively, encroaching on that of PTMSP. Mg-MOF-74 and reduced cage 3 MMM however, had a detrimental effect on the permeability. Aging data was also investigated which showed that for the majority of MMM the permeability followed the trend of PIM-1. microHKUST-1 and cage 3 of 10:3 loading were shown to give promising results with 10000 and 14300 Barrer respectively compared to 7200 Barrer for PIM-1. Although a loss in permeability is seen, it is still above that of PIM-1 at the same point of aging. These results give a positive indication that MMMs have the potential to provide resistance against aging, a major problem in using high free volume polymers in industrial applications.

The crystal growth of nanoporous materials is different from most other classes of material in that their framework architectures contain periodic arrangement of pores or voids in which there is no direct bonding between adjacent units of the framework. This poses a variety of questions as to how such parts of framework develop during the crystallization process, atomistically and energetically. Here we use the nanoporous metal-organic framework, ZIF-8 as a prototypical material to obtain a basic understanding of the growth of a nanoporous material. The crystals of ZIF-8 produced in the N,N-dimethylformamide solvent [ZIF-8(DMF)] and methanol-co-N,N-dimethylformamide solvent [ZIF-8(MeOH)] are both rhombic dodecahedron in shape with a much smaller crystal size in the latter. In the study of the kinetics of ZIF-8(DMF) crystallization, we get a good agreement in the values of activation energies using both Avrami-Erofe’ev-Hancock-Sharp and Gualtieri’s models, i.e. about 120 kJ mol-1 for nucleation, and 95 kJ mol-1 for crystal growth process. The study of kinetics of ZIF-8 surface growth, by in situ AFM, with ZIF-8(DMF) as seed crystal that are grown in the methanolic growth solution we see faster rate in the directions than the directions, with the most probable activation energy of about 80 kJ mol-1 in both directions. This is the first example of in situ AFM being used to obtain activation energy for a surface growth in MOF. We also reveal here that growth process of ZIF-8 occurs through the nucleation and spreading of successive metastable unenclosed sub-steps to eventually form stable terrace steps of the enclosed framework structure in which this process is reliant on the presence of nonframework species to connect the framework species that have voids between them. The experiments also enable identification of some of the fundamental units in the growth process and the stable crystal surface plane. Further, the spreading of terraces at high supersaturation condition (early state) is fairly isotropic as is seen through the formation of almost-rounded terraces on the surface of ZIF-8. The growth direction becomes clear as the supersaturation condition nears to equilibrium (later stage) by the formation of rhombohedral terraces with pointy ends growing along the , and directions and straight edges growing perpendicular to the direction. Formation of this rhombohedral morphology is explained by a coarse grain approach similar to that used in the Kossel model by making assumptions that the sodalite cage is the growth unit and attachment of one sodalite cage in each growth direction is the rate determining step for the formation of a new row of sodalite cages in each direction. Finally, based on the profiles of growth spirals formed from screw dislocations on the ZIF-8 surface obtained from the ex situ AFM images and ICE theory, plausible screw dislocations with Burgers’ vector of 1/2 and , but not , are deduced. Some of the findings in this work will be applicable to numerous nanoporous materials, and the work in general will support efforts to synthesize and design new framework materials and to control the crystal properties of these materials.

The work presented in this study details the removal of radioactive isotopes from nuclear chemical wastes, which contain high concentration of magnesium cations, using zeolites, which are stable in acidic media. Following four types of zeolites were used in this work1- Zeolite A2- ZK-43- Zeolite Alpha4- ClinoptiloliteFirst three zeolites were synthesized and characterized by using the X-ray diffraction, scanning electron microscope and thermogravitational analysis.Ion-exchange batch process was used to remove the radioactive cations from the nuclear chemical wastes. All the practical work was done at room temperature.