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Abstract: High-resolution calorimetry has played a significant role in providing detailed information on phase transitions in liquid crystals. In particular, adiabatic scanning calorimetry (ASC), capable of providing simultaneous information on the temperature dependence of the specific enthalpy h ( T ) and on the specific heat capacity c p ( T ) , has proven to be an important tool to determine the order of transitions and render high-resolution information on pretransitional thermal behavior. Here we report on ASC results on the compound 2,3′,4′,5′-tetrafluoro[1,1′-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) and on mixtures with 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). Both compounds exhibit a low-temperature ferroelectric nematic phase ( N F ) and a high-temperature paraelectric nematic phase ( N ) . However, in DIO these two phases are separated by an intermediate phase ( N x ). From the detailed data of h ( T ) and c p ( T ) , we found that the intermediate phase was present in all the mixtures over the complete composition range, albeit with strongly decreasing temperature width for that phase with decreasing mole fraction of DIO ( x DIO ). The x DIO dependence on the transition temperatures for both transitions could be well described by a quadratic function. Both these transitions were weakly first order. The true latent heat of the N x − N transition of DIO was as low as L = 0.0075 ± 0.0005 J / g and L = 0.23 ± 0.03 J / g for the N F − N x transition, which is about twice the previously reported value of 0.115 J/g for the N F − N transition in RM734. In the mixtures both transition latent heats decrease gradually with decreasing x DIO . At all the N x − N transitions pretransition fluctuation effects are absent and these transitions are purely but very weakly first order. As in RM734 the transition from the N F to the higher-temperature phase exhibits substantial pretransitional behavior, in particular, in the high-temperature phase. Power-law analysis of c p ( T ) resulted in an effective critical exponent α = 0.88 ± 0.1 for DIO and this value decreased in the mixtures with decreasing x DIO toward α = 0.50 ± 0.05 reported for RM734. Ideal mixture analysis of the phase diagram was consistent with ideal mixture behavior provided the total transition enthalpy change was used in the analysis.

Open Access

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Abstract: Membrane fusion is a ubiquitous phenomenon linked to many biological processes, and represents a crucial step in liposome-based drug delivery strategies. The ability to control, ever more precisely, membrane fusion pathways would thus be highly valuable for next generation nano-medical solutions and, more generally, the design of advanced biomimetic systems such as synthetic cells. In this article, we present fusogenic nanostructures constructed from synthetic DNA which, different from previous solutions, unlock routes for modulating the rate of fusion and making it conditional to the presence of soluble DNA molecules, thus demonstrating how membrane fusion can be controlled through simple DNA-based molecular circuits. We then systematically explore the relationship between lipid-membrane composition, its biophysical properties, and measured fusion efficiency, linking our observations to the stability of transition states in the fusion pathway. Finally, we observe that specific lipid compositions lead to the emergence of complex bilayer architectures in the fusion products, such as nested morphologies, which are accompanied by alterations in biophysical behaviour. Our findings provide multiple, orthogonal strategies to program lipid-membrane fusion, which leverage the design of either the fusogenic DNA constructs or the physico/chemical properties of the membranes, and could thus be valuable in applications where some design parameters are constrained by other factors such as material cost and biocompatibility, as it is often the case in biotechnological applications.

Open Access

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Abstract: Nanodiscs are used to stabilize membrane proteins in a lipid environment and enable investigations of the function and structure of these. Membrane proteins are often only available in small amounts, and thus the stability and ease of use of the nanodiscs are essential. We have recently explored circularizing and supercharging membrane scaffolding proteins (MSPs) for nanodisc formation and found increased temporal stability at elevated temperatures. In the present study, we investigate six different supercharged MSPs and their ability to form nanodiscs: three covalently circularized and the three non-circularized, linear versions. Using standard reconstitution protocols using cholate as the reconstitution detergent, we found that two of the linear constructs formed multiple lipid-protein species, whereas adding n-Dodecyl-B-D-maltoside (DDM) with the cholate in the reconstitution gave rise to single-species nanodisc formation for these MSPs. For all MSPs, the formed nanodiscs were analyzed by small-angle X-ray scattering (SAXS), which showed similar structures for each MSP, respectively, suggesting that the structures of the formed nanodiscs are independent of the initial DDM content, as long as cholate is present. Lastly, we incorporated the membrane protein proteorhodopsin into the supercharged nanodiscs and observed a considerable increase in incorporation yield with the addition of DDM. For the three circularized MSPs, a single major species appeared in the size exclusion chromatography (SEC) chromatogram, suggesting monodisperse nanodiscs with proteorhodopsin incorporated, which is in strong contrast to the samples without DDM showing almost no incorporation and high polydispersity.

Open Access

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Abstract: Spatially ordered arrangements of spherical colloids are known to exhibit structural colours. The intensity and brilliance of these structural colours typically improve with colloidal monodispersity, low concentrations of point and line defects and with increasing refractive index contrast between the colloids and the embedding medium. Here we show that suspensions of charge stabilised, fluorinated latex particles with low refractive-index contrast to their aqueous background form Wigner crystals with FCC symmetry for volume fractions between 13 and 40%. In reflection they exhibit both strong, almost angle-independent structural colours and sharp, more brilliant Bragg peaks despite the particle polydispersity and bimodal distribution. Simultaneously, these suspensions appear transparent in transmission. Furthermore, binary AB, A2B and A13B type mixtures of these fluorinated and similarly sized polystyrene particles appeared predominantly white but with clear Bragg peaks indicating a CsCl-like BCC structure and more complex crystals. We characterised the suspensions using a combination of reflectivity measurements and small-angle x-ray scattering, complemented by reflectivity modelling.

Open Access

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Abstract: Dispersions of colloidal platelets in the nematic phase display strong wall anchoring, which competes with the reorientational motion of the director when the system is subjected to flow. We show that the mechanical response to large amplitude oscillatory strain and stress depends on the confinement of the system due to this competition. We elucidate the underlying structural response by deflecting a x-ray beam vertically along the vorticity direction of a Couette geometry, such that the structure can be probed throughout the gap with an unprecedented spatial resolution while recording in situ the mechanical response. We observe strong inhomogeneities in terms of the orientation of the nematic director, depending on the extent of the system's yield during an oscillation. At small strain amplitudes, we observe a small region where the director oscillates between wall anchoring and the Leslie angle, while in the bulk, the director tilts out of the flow–flow gradient plane. At large strain amplitudes, the oscillations of the director are symmetric, close to the wall, and propagate into the bulk. Here, a twinning is observed where the director rotates out-of-plane in two opposite directions. Using the sequence of physical process method to analyze the LAOStrain response for both the mechanical and structural response, we locate the yielding in a small time-window around flow reversal and identify that the bulk is the main contributor to the mechanical response. The structural response to LAOStress is much less pronounced even when the stress amplitude causes significant shear thinning.