Methyl-Rotation Dynamics in Metal-Organic Frameworks Probed with Terahertz Spectroscopy

In ZIF-8 and its cobalt analogue ZIF-67, the imidazolate methyl-groups, which point directly into the void space, have been shown to freely rotate - even down to cryogenic temperatures. Using a combination of experimental terahertz time-domain spectroscopy, low-frequency Raman spectroscopy, and state-of-the-art ab initio simulations, the methyl-rotor dynamics in ZIF-8 and ZIF-67 are fully characterized within the context of a quantum-mechanical hindered-rotor model. The results lend insight into the fundamental origins of the experimentally observed methyl rotor dynamics, and provide valuable insight into the nature of the weak interactions present within this important class of materials

Intermolecular anharmonicity in molecular crystals: interplay between experimental low-frequency dynamics and quantum quasi-harmonic simulations of solid purine

The intermolecular anharmonic potential of crystalline purine is probed by means of temperature-dependent terahertz time-domain spectroscopy, low-frequency Raman scattering, X-ray diffraction, and $\textit{ab initio}$ quasi-harmonic quantum-chemical simulations. As temperature increases, anharmonicity in the intermolecular interactions results in strongly anisotropic thermal expansion - with a negative thermal expansion along the $b$ crystallographic axis - yielding corresponding bulk structural modifications. The observed thermally-induced shifts of most vibrational bands in the terahertz region of the spectra are shown to arise from volume-dependent thermal changes of the hydrogen-bond pattern along the $a$ and $b$ crystallographic axes.M. T. R. and J. A. Z. thank the UK Engineering and Physical Sciences Research Council for funding (EP/N022769/1). M. T. R. also thanks the European Molecular Biology Organization for travel funding

Revisiting the Thermodynamic Stability of Indomethacin Polymorphs with Low-Frequency Vibrational Spectroscopy and Quantum Mechanical Simulations

The two major polymorphs of the active pharmaceutical ingredient indomethacin were studied using a combination of experimental low-frequency vibrational spectroscopies, theoretical solid-state density functional theory and ab initio molecular dynamics calculations. The results enable a complete spectral assignment of the low-frequency IR and Raman spectra, and yield new insight into the energetic and dynamical factors present within the solids to be understood. Ultimately, these results are used to rationalize the thermodynamic properties of the two crystals, which result in a contradiction to the long-held belief that the γ-form is the more stable polymorph at ambient conditions due to its predominant abundance. Overall, the study highlights the combined role that molecular conformation, bulk packing arrangement, and intermolecular forces have on the ultimate properties of pharmaceutical crystals, and the need for detailed analyses into all of these effects in order to predict the properties of materials

Integrated aerodynamic and structural blade shape optimisation of axial turbines operating with supercritical carbon dioxide blended with dopants

Paper No: GT2022-81223, V009T28A004.Within this study, the blade shape of a large-scale axial turbine operating with sCO2 blended with dopants is optimised using an integrated aerodynamic-structural 3D numerical model, whereby the optimisation aims at maximising the aerodynamic efficiency whilst meeting a set of stress constraints to ensure safe operation. Specifically, three candidate mixtures are considered, namely CO2 blended with titaniumtetrachloride (TiCl4), hexafluorobenzene (C6F6) or sulfur dioxide (SO2), where the selected blends and boundary conditions are defined by the EU project, SCARABEUS. A single passage axial turbine numerical model is setup and applied to the first stage of a large-scale multi-stage axial turbine design. The aerodynamic performance is simulated using a 3D steady-state viscous computational fluid dynamic (CFD) model while the blade stress distribution is obtained from a static structural finite element analysis (FEA). A genetic algorithm is used to optimise parameters defining the blade angle and thickness distributions along the chord line while a surrogate model is used to provide fast and reliable model predictions during optimisation using genetic aggregation response surface. The uncertainty of the surrogate model represented by the difference between the surrogate model results and the CFD/FEA model results is evaluated using a set of verification points and found to be less than 0.3% for aerodynamic efficiency and 1% for both the mass flow rate and the maximum equivalent stresses. The comparison between the final optimised blade cross-sections have shown some common trends in optimising the blade design by decreasing stator and rotor trailing edge thickness, increasing stator thickness near the trailing edge, decreasing rotor thickness near the trailing edge and decreasing the rotor outlet angle. Further investigations of the loss breakdown of the optimised and reference blade designs are presented to highlight the role of the optimisation process in reducing aerodynamic losses. It has been noted that the performance improvement achieved through shape optimisation is mainly due to decreasing the endwall losses of both stator and rotor blades

Tracking Dehydration Mechanisms in Crystalline Hydrates with Molecular Dynamics Simulations

Dehydration of crystalline solids is a widespread phenomenon, yet the fundamental mechanisms by which dehydration occurs is not properly understood. This arises due to technical limitations in studying such fast processes with sufficient sensitivity, nevertheless understanding dehydration pathways is critical for designing optimal properties for materials, particularly in the case of pharmaceutical solids. The computational methods presented here allow for accurate determination of the dehydrated species' crystal structure and to develop an understanding of the mechanism of dehydration at the molecular level. This work also highlights the critical role of explicitly taking into account the dynamical aspect of molecules using computational techniques, rather then relying on static energy minimization approaches. Specifically, the crystalline active pharmaceutical agent naproxen sodium, and its hydrates, is studied in silico using density functional theory and molecular dynamics, ultimately elucidating the face-specific dehydration mechanisms and revealing highly complex diffusion and nucleation behaviour. Additionally, the results indicate that the method is a viable way to explore dehydration pathways and predict new dehydrated crystal structures.A.S.L, K.E.J and J.R. gratefully acknowledges the Villum Foundation (Denmark) for financial support (project No. VKR023111). M.T.R. and J.A.Z. would like to acknowledge funding from the U.K. Engineering and Physical Sciences Research Council (EP/N022769/1)

Probing the Mechanochemistry of Metal-Organic Frameworks with Low-Frequency Vibrational Spectroscopy

The identification and characterization of low-frequency vibrational motions of metal-organic frameworks (MOFs) allows for a better understanding of their mechanical and structural response upon perturbation by external stimuli such as temperature, pressure, and adsorption. Here, we describe the combination of an experimental temperature- and pressure-dependent terahertz spectroscopy system with quantum mechanical simulations to measure and assign specific low-frequency vibrational modes that directly drive the mechanochemical properties of this important class of porous materials. More specifically, those intense spectral features in the terahertz region of the vibrational spectrum of ZIF-8 are identified, which are directly connected to its mechanochemical response. In particular, the mechanical compressibility of pristine ZIF-8 is found to follow a peculiar non-linear trend upon pressure: its bulk modulus initially increases up to 0.1 GPa and decreases at higher pressures, which is simultaneously reflected in the terahertz vibrational spectra. This work highlights the interplay between structural, vibrational, and mechanochemical phenomena, all of which are key to the effective exploitation of MOFs. The importance of terahertz vibrational motions on the function of MOFs is demonstrated, and a method presented for their measurement and interpretation, which can be applied widely to any supramolecular material

Axial turbine flow path design for concentrated solar power plants operating with CO2 blends

Data availability: No data was used for the research described in the article.The utilisation of certain blends based on supercritical CO2 (sCO2), namely CO2/TiCl4, CO2/C6 F6 and CO2/SO2, have been found to be promising for enhancing the performance of power cycles for Concentrated Solar Power (CSP) applications; allowing for up to a 6% enhancement in cycle efficiency with respect to a simple recuperated CO2 cycle, depending upon the nature of the used blend and the cycle configuration of choice. This paper presents an investigation of the impact of adopting these sCO2-based blends on the flow path design for a multi-stage axial turbine whilst accounting for aerodynamic, mechanical and rotordynamic considerations. This includes assessing the sensitivity of the turbine design to selected working fluid and imposed optimal cycle conditions. Ultimately, this study aims to provide the first indication that a high-efficiency turbine can be achieved for a large-scale axial turbine operating with these non-conventional working fluids and producing power in excess of 120 MW. To achieve this aim, mean-line aerodynamic design is integrated with mechanical and rotordynamic constraints, specified based on industrial experience, to ensure technically feasible solutions with maximum aerodynamic efficiency. Different turbine flow path designs have been produced for three sCO2 blends under different cycle boundary conditions. Specifically, flow paths have been obtained for optimal cycle configurations at five different molar fractions and two different turbine inlet pressure and temperature levels of 250 & 350 bar and 550 & 700 ◦C respectively. A total-to-total turbine efficiency in excess of 92% was achieved, which is considered promising for the future of CO2 plants. The highest efficiencies are achieved for designs with a large number of stages, corresponding to reduced hub diameters due to the need for a fixed synchronous rotational speed. The large number of stages is contrary to existing sCO2 turbine designs, but it is found that an increase from 4 to 14 stages can increase the efficiency by around 5%. Ultimately, based on the preliminary cost analysis results, the designs with a large number of stages were found to be financially feasible compared to the designs with a small number of stages.The SCARABEUS project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement Nº814985

Energy-Tank based Force Control for 3D Contour Following

Manipulation has been a major topic in robotics since its earlier developments. In the last few years, a new research area has focused in the introduction of manipulation capabilities on mobile robots. Several challenges are faced when mobile robots interact with unknown environments, for which inherent compliance is a key feature to achieve the intended outcome in a safe and robust way. This paper proposes a unified method of force control with energy-tank based methods to tackle 3D contour following. This method is tailored for manipulators that are designed for aerial applications, and addresses the interaction with unknown surfaces by also tackling the safety aspect, i.e. the response generated during contact loss

The Impact of Lockdown on Couples' Sex Lives

Background: the aim of this study was to perform an Italian telematics survey analysis on the changes in couples' sex lives during the coronavirus disease 2019 (COVID-19) lockdown. Methods: a multicenter cross sectional study was conducted on people sexually active and in stable relationships for at least 6 months. To evaluate male and female sexual dysfunctions, we used the international index of erectile function (IIEF-15) and the female sexual function index (FSFI), respectively; marital quality and stability were evaluated by the marital adjustment test (items 10-15); to evaluate the severity of anxiety symptoms, we used the Hamilton Anxiety Rating Scale. The effects of the quarantine on couples' relationships was assessed with questions created in-house. Results: we included 2149 participants. The sex lives improved for 49% of participants, particularly those in cohabitation; for 29% it deteriorated, while for 22% of participants it did not change. Women who responded that their sex lives deteriorated had no sexual dysfunction, but they had anxiety, tension, fear, and insomnia. Contrarily, men who reported deteriorating sex lives had erectile dysfunctions and orgasmic disorders. In both genders, being unemployed or smart working, or having sons were risk factors for worsening the couples' sex lives. Conclusion: this study should encourage evaluation of the long-term effects of COVID-19 on the sex lives of couples