21 research outputs found
Probing Structure and Dynamics in Advanced Molecular Materials by Solid State Nuclear Magnetic Resonance
Probing and determining the structure and dynamics of advanced molecular materials is crucial to aid our understanding of their properties. Solid state NMR is capabale of probing short-range order and dynamics. Therefore this analytical technique (often used in conjunction with computational studies) is able to provide structural characterisation at the atomic level as well as probing local order and therefore has great potential to study these motions. In this thesis, advanced solid state NMR approaches have been used to access the temperature dependence site-selective dynamics of guest-free and -adsorbed tubular covalent cages and pillar[n]arenes, accessing understanding of their flexibility behaviours, and determine the structures of a new class of amorphous paramagnetic hybrid perovskites glasses. Firstly, 2H static NMR spectra has identified tubular covalent cages as ultra-fast molecular rotors and smart materials capable of adsorbing iodine and its release upon the application of an external stimuli. Secondly, correlation times and proton detected local field NMR experiments found that the extruding ethoxy group of perethylated pillar[n]arenes has significant dynamics when compared to the dynamics associated within the core. Using these techniques we also show the strong dipolar coupling present between para-xylene and the EtP6 host, providing insights into the guestâs location inside the host. Finally, spectral analysis of paramagnetic hybrid perovskites was completed and NMR methods were able to confirm that the materials studied melt at low temperatures and can be quenched into a glass form. It is the dynamics and flexibility of these structures that controls the selectivity of molecules in the voids located in the frameworks and hence enable them to be used for molecular separation
Dynamics in Flexible Pillar[n]arenes Probed by Solid-State NMR
[Image: see text] Pillar[n]arenes are supramolecular assemblies that can perform a range of technologically important molecular separations which are enabled by their molecular flexibility. Here, we probe dynamical behavior by performing a range of variable-temperature solid-state NMR experiments on microcrystalline perethylated pillar[n]arene (n = 5, 6) and the corresponding three pillar[6]arene xylene adducts in the 100â350 K range. This was achieved either by measuring site-selective motional averaged (13)C (1)H heteronuclear dipolar couplings and subsequently accessing order parameters or by determining (1)H and (13)C spinâlattice relaxation times and extracting correlation times based on dipolar and/or chemical shift anisotropy relaxation mechanisms. We demonstrate fast motional regimes at room temperature and highlight a significant difference in dynamics between the core of the pillar[n]arenes, the protruding flexible ethoxy groups, and the adsorbed xylene guest. Additionally, unexpected and sizable (13)C (1)H heteronuclear dipolar couplings for a quaternary carbon were observed for p-xylene adsorbed in pillar[6]arene only, indicating a strong hostâguest interaction and establishing the p-xylene location inside the host, confirming structural refinements
Melting of hybrid organic-inorganic perovskites.
Several organic-inorganic hybrid materials from the metal-organic framework (MOF) family have been shown to form stable liquids at high temperatures. Quenching then results in the formation of melt-quenched MOF glasses that retain the three-dimensional coordination bonding of the crystalline phase. These hybrid glasses have intriguing properties and could find practical applications, yet the melt-quench phenomenon has so far remained limited to a few MOF structures. Here we turn to hybrid organic-inorganic perovskites-which occupy a prominent position within materials chemistry owing to their functional properties such as ion transport, photoconductivity, ferroelectricity and multiferroicity-and show that a series of dicyanamide-based hybrid organic-inorganic perovskites undergo melting. Our combined experimental-computational approach demonstrates that, on quenching, they form glasses that largely retain their solid-state inorganic-organic connectivity. The resulting materials show very low thermal conductivities (~0.2âW m-1 K-1), moderate electrical conductivities (10-3-10-5âS m-1) and polymer-like thermomechanical properties
Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[n]arene Crystals
The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metalâorganic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[n]arene crystals (n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13C solid state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behaviour of soft, adaptive molecular crystals
Off-the-Shelf Gd(NO3)(3) as an Efficient High-Spin Metal Ion Polarizing Agent for Magic Angle Spinning Dynamic Nuclear Polarization
[Image: see text] Magic angle spinning nuclear magnetic resonance spectroscopy experiments are widely employed in the characterization of solid media. The approach is incredibly versatile but deleteriously suffers from low sensitivity, which may be alleviated by adopting dynamic nuclear polarization methods, resulting in large signal enhancements. Paramagnetic metal ions such as Gd(3+) have recently shown promising results as polarizing agents for (1)H, (13)C, and (15)N nuclear spins. We demonstrate that the widely available and inexpensive chemical agent Gd(NO(3))(3) achieves significant signal enhancements for the (13)C and (15)N nuclear sites of [2-(13)C,(15)N]glycine at 9.4 T and âŒ105 K. Analysis of the signal enhancement profiles at two magnetic fields, in conjunction with electron paramagnetic resonance data, reveals the solid effect to be the dominant signal enhancement mechanism. The signal amplification obtained paves the way for efficient dynamic nuclear polarization without the need for challenging synthesis of Gd(3+) polarizing agents
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Challenges and opportunities for conducting a vaccine trial during the COVID-19 pandemic in the United Kingdom
The COVID-19 pandemic has resulted in unprecedented challenges for healthcare systems worldwide. It has also stimulated research in a wide range of areas including rapid diagnostics, novel therapeutics, use of technology to track patients and vaccine development. Here, we describe our experience of rapidly setting up and delivering a novel COVID-19 vaccine trial, using clinical and research staff and facilities in three National Health Service Trusts in Cambridgeshire, United Kingdom. We encountered and overcame a number of challenges including differences in organisational structures, research facilities available, staff experience and skills, information technology and communications infrastructure, and research training and assessment procedures. We overcame these by setting up a project team that included key members from all three organisations that met at least daily by teleconference. This group together worked to identify the best practices and procedures and to harmonise and cascade these to the wider trial team. This enabled us to set up the trial within 25 days and to recruit and vaccinate the participants within a further 23 days. The lessons learned from our experiences could be used to inform the conduct of clinical trials during a future infectious disease pandemic or public health emergency
Living through extreme weather events and natural disasters: How resilient are our high-rise high-density typologies?
The inner city Brisbane suburbs of the West End peninsula are poised for redevelopment. Located within walking distance to CBD workplaces, home to Queenslandâs highest value cultural precinct, and high quality riverside parklands, there is currently a once-in-a-lifetime opportunity to redevelop parts of the suburb to create a truly urban neighbourhood. According to a local community association, local residents agree and embrace the concept of high-density living, but are opposed to the high-rise urban form (12 storeys) advocated by the Cityâs planning authority (BCC, 2011) and would prefer to see medium-rise (5-8 storeys) medium-density built form. Brisbane experienced a major flood event which inundated the peninsula suburbs of West End in summer January 2011. The vulnerability of taller buildings to the vagaries of climate and more extreme weather events and their reliance on main electricity was exposed when power outages immediately before, during and after the flood disaster seriously limited occupantsâ access and egress when elevators were disabled. Not all buildings were flooded but dwellings quickly became unliveable due to disabled air-conditioning. Some tall buildings remained uninhabitable for several weeks after the event. This paper describes an innovative design research method applied to the complex problem of resilient, sustainable neighbourhood form in subtropical cities, in which a thorough comparative analysis of a range of multiple-dwelling types has revealed the impact that government policy regarding design of the physical environment has on a communityâs resilience. The outcomes advocate the role of climate-responsive design in averting the rising human capital and financial costs of natural disasters and climate change
Recent advances in probing hostâguest interactions with solid state nuclear magnetic resonance
A recent update on how solid state NMR has aided the interpretation and understanding of hostâguest interactions in the field of supramolecular assemblies is provided.</p
Hybrid Inorganic-Organic Perovskite Glasses
Hybrid perovskites occupy a prominent position within solid-state materials chemistry due to their (e.g.) ionic transport, ferroelectric and multiferroic properties. Here we show that a series of [TPrA][M(Dca)3] perovskites (TPrA = tetrapropylammonium cation; Dca = dicyanamide anion; M = Mn, Fe, Co) melt below 300 °C. A combined experimental-computational approach reveal the melting mechanism, and demonstrates that the hybrid perovskites form glasses upon melt quenching which largely retain the inorganic-organic bonding of the crystalline phase. The very low thermal conductivities of these glasses (~ 0.2 W m-1 K-1), moderate electrical conductivities (10-2 â 10-4 S m-1) and thermo-mechanical properties reminiscent of polymeric materials identify them as a new family of functional glass-formers.</p
Off-the-Shelf Gd(NO 3 ) 3 as an Efficient High-Spin Metal Ion Polarizing Agent for Magic Angle Spinning Dynamic Nuclear Polarization
International audienceMagic angle spinning nuclear magnetic resonance spectroscopy experiments are widely employed in the characterization of solid media. The approach is incredibly versatile but deleteriously suffers from low sensitivity, which may be alleviated by adopting dynamic nuclear polarization methods, resulting in large signal enhancements. Paramagnetic metal ions such as Gd 3+ have recently shown promising results as polarizing agents for 1 H, 13 C, and 15 N nuclear spins. We demonstrate that the widely available and inexpensive chemical agent Gd(NO 3) 3 achieves significant signal enhancements for the 13 C and 15 N nuclear sites of [2-13 C, 15 N]glycine at 9.4 T and âŒ105 K. Analysis of the signal enhancement profiles at two magnetic fields, in conjunction with electron paramagnetic resonance data, reveals the solid effect to be the dominant signal enhancement mechanism. The signal amplification obtained paves the way for efficient dynamic nuclear polarization without the need for challenging synthesis of Gd 3+ polarizing agents