Diamond Annual Review 2021/22

94 95 D I A M O N D L I G H T S O U R C E A N N U A L R E V I E W 2 0 2 1 / 2 2 D I A M O N D L I G H T S O U R C E A N N U A L R E V I E W 2 0 2 1 / 2 2 Soft Condensed Matter Group Robert Rambo, Science Group Leader T he Soft Condensed Matter (SCM) Group is comprised of the High Throughput SAXS (B21), the Multimode Infrared Imaging and Microspectroscopy (MIRIAM) (B22), SAXS and Diffraction (I22) and the Circular Dichroism Microspectroscopy (B23) beamlines, co- located in sectors 3 and 4 of Diamond. This unique portfolio of instruments enables studies of non-crystalline materials at nano- to meso-scale resolutions that include two-dimensional thin-films (photovoltaics, OLEDs), livingmammalian cells, three-dimensional matrices ( e.g. metal-organic frameworks, gels and waxes) and nano-particles in non-crystalline states. SCM science is “ the science that underpins continued improvements toquality of life ”andwas critical to the rapid development of the COVID vaccines fromPfizer-BioNTech andModerna. These vaccines are lipid nanoparticles encapsulating a modified messenger RNA stabilised in a non-crystalline environment. The SCM user community is international, providing 69.9% of our peer-reviewed allocated beamtime to users from the United Kingdom where the remaining time is shared largely betweenmember states of the European Union, United States, China, Canada, Japan, Israel, and Australia. In the last year, the SCM Group contributed to 144 scientific publications covering a broad range of disciplines including chemistry, material science, chemical engineering, physics and astronomy, biochemistry, genetics and molecular biology and engineering. Experiments onmetal-organic frameworks from our group showed diverse applications including the emergence of hierarchical structures from disordered MOF mixtures, binding and separation of carbon and sulfur dioxide gases from hetero-metallic MOFs, and catalytic decomposition of noxious nitrogen dioxide. In healthcare, controlled drug release investigations were studied by TeraHertz radiation that measured the interaction between proteins and metallodrugs, whereas SAXS characterised the process of nanoparticle precipitants and lipidic cubic phases in drug release. More importantly, studies on I22 characterised bone-quality changes across the nano- to micron length scales showing the effects of steroids on osteoporosis. Across the group, material science studied self-assembly properties of diblock copolymer mixtures and gels producing stimulus-responsive, shape-shifting materials. More importantly, on B23, circular dichroism studies using the new Mueller Matrix Polarimeter (MMP) end-station discovered emergence of a new type of chiral-optical properties in solid-thin films. The MMP is world-leading, with unique capabilities making it ideal for studying thin-film materials with applications in flexible electronic and opto-electronic devices. The 2021 COVID-19 working restrictions posed many challenges for our scientific community. B21 operated entirely as a mail-in service throughout 2021 whereas B22, B23 and I22 provided mixed access pending national working guidelines. At the start of the 2021 academic year, a new cohort of students joined our existing SCM doctoral students which now include the Universities of Pisa (Italy), Surrey and Chalmers, Southampton, College London, Imperial, Sheffield, Reading, Leeds and Durham. SCM provided several training workshops via online platforms including the popular S4SAS meeting led by I22. B22 organised an advanced training workshop with SOLEIL using machine learning software (Quasar) in infrared image analysis and B21 hosted a series of online, small group data analysis sessions for users which is now a routine part of our user programme. However, we were able to restart our annual in- person, bioSAXS training course hosted in Oulu, Finland in November 2021. The workshop featured users from Finland, Sweden and Denmark with keynote speaker Jan Skov Pedersen from Aarhus University. B21 update B21 studies noncrystalline, randomly oriented particles using high- throughput approaches. SAXS measurements can be made on any type of sample and in any physical state. The life sciences community comprises our largest user group since such measurements provide the opportunity to study biological machines in conditions that are comparable to their liquid, hydrated environment. B21 commissioned the design and manufacturing of a new sample environment unit (SEU) that provides an on-axis camera for sample viewing, and three interrogation ports for probes to enable light activation or heating. This will allow B21 to examine light sensitive soft matter materials during data acquisition. The project was driven by Beatrice Jones, a member of our PhD studentship programme from University of Cambridge. Her project is examining azobenzene compounds as a method to store solar energy through chemo-mechanical isomerisations. BioSAXSmeasurements provide a structural snapshot of the thermodynamic ensemble. The measurement is over 1000s of billions of macromolecules and over a time-domain that is too long to inform on macromolecular dynamics. Furthermore, in the interpretation of bioSAXS data, flexibility is often inferred by a combination of molecular modelling ( i.e , more than one model is required for model fitting) or by an interpretation of a semi-quantitative Kratky plot. To address the gap in dynamic studies of polymers at synchrotron X-ray sources, we have been developing expertise in Diffracted X-ray Tracking (DXT) and X-ray Foot-printing Mass Spectrometry (XFMS) for studies in the micro- to milli- second time domains. In 2021, we have completed the design of a prototype XFMS end-station that will allow for X-ray footprinting studies of polymers in the solution state. XFMS is a covalent modification of the residue through radiolysis of water molecules. This experimental modality will allow us to validate, at a residue level, atomistic models from molecular dynamics based simulations as well as structural hypothesis from bioSAXS investigations. XFMS can uncover structural waters, cavities, validate antibody-antigen complexes, and complement structure-function studies. Unlike hydrogen-deuterium (HD) exchange where side-chain exchange rates are too fast for detection, solvent accessibility of residues by XFMS will not go undetected. XFMS is a productive technique with a notable publication detailing disordered compact state of the estrogen receptor transactivation domain and GPCR receptor G-protein complex assembly 1,2 .We anticipate our first users in summer 2022. B22 update The Multimode Infrared Imaging and Microspectroscopy (MIRIAM) beamline, B22, is used to assess the molecular composition and microscopic spatial distribution of a sample at the highest, optically-achievable resolution in the infrared (IR). B22 operates two end-stations for scanning IR spectro- microscopy and IR imaging, with a suite of single and 2-D detectors that seamlessly cover the whole IR range, from near-IR to mid-IR and further into THz. B22 has been used in the analysis of inorganic-organic combinations in biomineralogy or composite materials, chemical degradation in conservation and archaeology, as well as studying live mammalian cells under the IR microprobe for in situ drug response, an important tool in anti-cancer research. This past year, B22providednano- andmicro-spectroscopy imagingexperiments studying corrosion resistance of steel in seawater, superlubricity of long-chain alcohols, varied applications of MOFs, metabolism in living mammalian cells and electrochemistry. The beamline successfully installed its new end-station upgrade, a modern, Atomic Force Microscopy for AFM couple IR measurements. B22 pioneered the first photothermal AFM-IR measurements and will now provide two additional AFM-IR capabilities, namely tapping and s-SNOM. Collaborative calls for IR nanospectroscopy in photothermal, tapping and scattering-SNOM AFM-IR will be issued during the commissioning of the end-station and will be supported by a new dedicated support scientist. This cutting edge end-station is suitable for molecular analysis of submicron to micron scale organic matter and biomaterials - from mammalian cells to microplastic - with exceptional sub-micron resolution (i.e. up to 100 times below the IR wavelength scale). In addition, B22 finished a prototype gas-microreactor design for studying small volumes using IR microscopy. The device will increase sample throughput, position stability and be resistant to corrosive gases such as NOx up to 300 °C . B23 update B23 synchrotron radiation Circular Dichroism (CD) beamline uses circularly polarised light to characterise the structure-architecture of complex chiral materials in solution and in solid-state thin films. Chiral materials have a handedness like our right and left hands that are not superimposable and absorb differently the circularly polarised light generating CD fingerprint ID spectra. The beamline operates two end-stations: module A and B to accommodate a variety of sample environments. Module A operates in the 170-500nm region (125- 500nm for gas phase) utilising an automated 6-cell turret for protein UV denaturation and/or thermal stability assays, a motorised XY stage to accommodate either microfluidic chips for the separation of proteins by diffusion or a custom made 96-cell multiplate to characterise the biomolecules conformational behaviour and ligand binding screening. Since 2020, module B operating in the 190- 650nm spectral region is equipped with the Mueller Matrix Polarimeter (MMP) to study the optical (linear dichroism (LD), circular birefringence (CB)) and chiroptical properties (circular dichroism (CD), and circular birefringence (CB)) of thin films of chiral materials such as polymer, biopolymers, optoelectronics, hydrogels, and twisted liquid crystals. For optoelectronic materials, the measurement of CD at 50micron of spatial resolution can inform about the homogeneity of the supramolecular structure, which is strictly related to their efficacy. For biological samples, CD is also used to monitor in microfluidic chips structural changes, drug binding, protein instabilities as a function of temperature, pressure, ionic strength, surfactant, pH, ligand interactions, and ageing. Pioneered by the B23 team, CD Imaging (CDi) technology exploits a highly collimated, synchrotron microbeam for scanning thin-films of solid materials. Unlike absorption, CDi can inform on the homogeneity of the chiral supramolecular structure. CDi at B23 is the only synchrotron-based instrument with the required sensitivity to guide the researchers on how to improve the properties of chiral materials. Combined with Diamond high-resolution microscopy, B23 is the unique worldwide facility for material and life sciences. B23 through collaborative calls is developing novel applications for CDi. During COVID pandemic, B23 was one of the few beamlines operational within four weeks of the start of the pandemic in the United Kingdom. The beamline provided automated CD-thermal denaturation studies using the automated 6-cell turret sample holder and automated use of the novel 96-well sample measurement plate. These studies have inspired a new, limited mail-in service coordinated with B21 users in 2021. I22 update The Small Angle Scattering and Diffraction beamline (I22) offers combined Small and Wide Angle X-ray Scattering (SAXS and WAXS) studies on a range of low order biological, natural and synthetic samples. I22 excels at providing structural information on partially ordered materials ranging from colloidal nanoparticles and thin-films to large hierarchical structures such as bone. Informed by remote and mail-in operations during COVID pandemic, I22 began an automation project that will use robotics to measure samples stored in a sample hotel co-located at the beamline. This automation project will store ~5000 samples in capillaries or DSC pans and take advantage of camera lengths during unsociable hours. Users often require different camera lengths depending on the hierarchical scale under investigation. In some cases, on-site users may have a camera length configuration required by a queued sample and the automation will be designed to efficiently take advantage of on-site user specific camera configurations. The automation project is expected to be completed October 2022. The quality of the source has been improved through completion of the Beam Conditioning Optics (BCO) project and an upgrade of our original monochromator (DCM). The BCO project allows for precise and stable control of a microfocus X-ray beam whereas the DCM upgrade replaced the original 2007, phase-I monochromator. The new monochromator is compatible with Diamond-II. In addition, we installed an in-vacuum, Pilatus 2MWAXS detector specifically designed for I22. This has allowed us to provide simultaneous “2D”WAXS measurements with the highest sensitivity. The new microfocus set-up improved our low q capability significantly from 0.25nm -1 (25nm) to 0.03nm -1 (~210nm), with the additional benefit of significantly lower background scatter over the previous microfocus configuration I22 also welcomed a new member to its group, Dr. Thomas Zinn, a senior support scientist with extensive experience in USAXS and XPCS experiments. The I22 Principal Beamline Scientist Dr Nick Terrill, in collaboration with Prof Michael Rappolt from the School of Food Science and Nutrition at the University of Leeds, manage an Engineering and Physical Sciences Research Council (EPSRC) grant to support an offline SAXS facility at Diamond. The Multi- User Facility for SAXS/WAXS (DL-SAXS) provides a Xenocs Xeuss 3.0 instrument operating with an Eiger-2R 1M detector. The facility is now accepting Peer- reviewed Panel (PRP) proposals for 25%of its available time with the remaining time dedicating to University of Leeds and sample environment development. 1. Peng, Y. et al . A metastable contact and structural disorder in the estrogen receptor transactivation domain. Structure 27 , 229-240 (2019), DOI: 10.1016/j.str.2018.10.026 2. Du, Y. et al . Assembly of a GPCR-G protein complex. Cell 177 , 1232-1242 (2019). DOI: 10.1016/j.cell.2019.04.022 Experimental Michelson Interferometer setup, part of the infrared nanoscope on beamline B22