Over the last couple of decades, deep eutectic solvents (DESs) have emerged as novel alternatives to ionic liquids that are extensively used in the synthesis of innovative materials, metal ...processing, catalysis, etc. However, their usage is limited, primarily because of their large viscosity and poor conductivity. Therefore, an understanding of the molecular origin of these transport properties is essential to improve their industrial applicability. Here, we present the report of the nanoscopic diffusion mechanism of acetamide in a DES synthesized with lithium perchlorate as studied using neutron scattering and molecular dynamics (MD) simulation techniques. A diffusion model is constructed with the help of MD simulation data comprising two distinct processes, corresponding to long-range jump diffusion and localized diffusion within a restricted volume. This diffusion model is validated through the analysis of neutron scattering data in the acetamide based DES (ADES) and molten acetamide. Although ADES has a remarkably lower freezing point compared to pure acetamide, the molecular mobility is found to be enormously restricted in the former. Particularly, the long-range jump diffusion process of acetamide is slower by a factor of 3 in ADES in comparison with molten acetamide. Further, the geometry of localized diffusion is found to be unaltered, but the dynamics is observed to be slightly slower in ADES. The diffusion model is found to be consistent over a wide temperature range for the ADES. Both long-range and localized diffusion show Arrhenius dependence with temperature in ADES. MD simulation analysis reveals that the long-range diffusion in ADES is restricted mainly due to the formation of hydrogen bond mediated complexes between the ionic species of the salt and acetamide molecules. Hence, the origin of higher viscosity observed in ADES can be attributed to the complexation in the ADES. The complex formation also explains the inhibition of the crystallization process while cooling and thereby results in depression of the freezing point of ADES.
Aviation and space applications can benefit significantly from lightweight organic electronics, now spanning from displays to logics, because of the vital importance of minimising payload (size and ...mass). It is thus crucial to assess the damage caused to such materials by cosmic rays and neutrons, which pose a variety of hazards through atomic displacements following neutron-nucleus collisions. Here we report the first study of the neutron radiation tolerance of two poly(thiophene)s-based organic semiconductors: poly(3-hexylthiophene-2,5-diyl), P3HT, and the liquid-crystalline poly(2,5-bis (3-tetradecylthiophen-2-yl)thieno3,2-bthiophene), PBTTT. We combine spectroscopic investigations with characterisation of intrinsic charge mobility to show that PBTTT exhibits significantly higher tolerance than P3HT. We explain this in terms of a superior chemical, structural and conformational stability of PBTTT, which can be ascribed to its higher crystallinity, in turn induced by a combination of molecular design features. Our approach can be used to develop design strategies for better neutron radiation-tolerant materials, thus paving the way for organic semiconductors to enter avionics and space applications.
The relationship between Stokes–Einstein breakdown (SEB) and dynamical heterogeneity (DH) is of paramount importance in the physical chemistry of complex fluids. In this work, we employ neutron ...scattering to probe the DH and SEB in a series of deep eutectic solvents (DESs) composed of acetamide and lithium salts. Quasielastic neutron scattering experiments reveal SEB in the jump diffusion of acetamide, represented by a fractional Stokes–Einstein relationship. Among these DESs, lithium perchlorate exhibits the most pronounced SEB while lithium bromide displays the weakest. Concurrently, elastic incoherent neutron scans identify that bromide DES is the most heterogeneous and perchlorate is the least. For the first time, our study unveils a counterintuitive incommensurate relationship between DH and SEB. Further, it reveals the intricate contrasting nature of the SEB-DH relationship when investigated in proximity to the glass-transition temperature and further away from it.
A crossover from a non-Gaussian to Gaussian subdiffusion has been observed ubiquitously in various polymeric and molecular glassformers. We have developed a framework that generalizes the fractional ...Brownian motion model to incorporate non-Gaussian features by introducing a jump kernel. We illustrate that the non-Gaussian fractional Brownian motion model accurately characterizes the subdiffusion crossover. From the solutions of the non-Gaussian fractional Brownian motion model, we gain insights into the nature of van Hove self-correlation in non-Gaussian subdiffusive regime, which is found to exhibit exponential tails, providing first such experimental evidence in molecular glassformers. The validity of the model is supported by comparison with incoherent quasielastic neutron scattering data obtained from several molecular and polymeric glassformers.
Ubiquicidin (UBI)/ribosomal protein S30 (RS30) is an intracellular protein with antimicrobial activities against various pathogens. UBI (29–41) and UBI (31–38) are two crucial peptides derived from ...Ubiquicidin, which have shown potential as infection imaging probes. Here, we report the interactions of UBI-derived peptides with anionic and zwitterionic phospholipid membranes. Our isothermal titration calorimetry results show that both peptides selectively interact with the anionic phospholipid membrane (a model bacterial membrane) and reside mainly on the membrane surface. The interaction of UBI-derived peptides with the anionic phospholipid membrane is exothermic and driven by both enthalpy (ΔH) and entropy (ΔS), with the entropic term TΔS being greater than ΔH. This large entropic term can be a result of the aggregation of the anionic vesicles, which is confirmed by dynamic light scattering (DLS) measurements. DLS data show that vesicle aggregation is enhanced with increasing peptide-to-lipid molar ratios (P/L) and is found to be more pronounced in the case of UBI (29–41). DLS results are found to be consistent with independent transmission measurements. To study the effects of UBI-derived peptides on the microscopic dynamics of the model bacterial membrane, quasielastic neutron scattering (QENS) measurements have been carried out. The QENS results show that both peptides restrict the lateral motion of the lipid within the leaflet. UBI (29–41) acts as a stronger stiffening agent, hindering the lateral diffusion of lipids more efficiently than UBI (31–38). To our knowledge, this is the first report illustrating the mechanism of interaction of UBI-derived peptides with model membranes. This study also has implications for the improvement and design of antimicrobial peptide-based infection imaging probes.
Cationic lipid membranes have recently attracted huge attention both from a fundamental point of view and due to their practical applications in drug delivery and gene therapy. The dynamical behavior ...of the lipids in the membrane is a key parameter controlling various physiological processes and drug release kinetics. Here, we review the dynamical and thermotropic phase behavior of an archetypal cationic lipid membrane, dioctadecyldimethylammonium bromide (DODAB), as studied using neutron scattering and molecular dynamics simulation techniques. DODAB membranes exhibit interesting phase behavior, specifically showing coagel, gel, and fluid phases in addition to a large hysteresis when comparing heating and cooling cycles. The dynamics of the lipid membrane is strongly dependent on the physical state of the bilayer. Lateral diffusion of the lipids is faster, by an order of magnitude, in the fluid phase than in the ordered phase. It is not only the characteristic times but also the nature of the segmental motions that differ between the ordered and fluid phases. The effect of different membrane active molecules including drugs, stimulants, gemini surfactants, and unsaturated lipids, on the dynamical and thermotropic phase behavior of the DODAB membrane, is also discussed here. Various interesting features such as induced synchronous ordering between polar head groups and tails, sub diffusive behavior, etc., are observed. The results shed light on the interaction between these additives and the membrane, which is found to be a complex interplay between the physical state of the membrane, charge, concentration, molecular architecture of the additives, and their location within the membrane.
Water dynamics in human cancer and non-cancer tissues Marques, M. P. M; Santos, I. P; Batista de Carvalho, A. L. M ...
Physical chemistry chemical physics : PCCP,
06/2022, Letnik:
24, Številka:
25
Journal Article
Recenzirano
Normal-to-malignant transformation is a poorly understood process associated with cellular biomechanical properties. These are strongly dependent on the dynamical behaviour of water, known to play a ...fundamental role in normal cellular activity and in the maintenance of the three-dimensional architecture of the tissue and the functional state of biopolymers. In this study, quasi-elastic neutron scattering was used to probe the dynamical behaviour of water in human cancer specimens and their respective surrounding normal tissue from breast and tongue, as an innovative approach for identifying particular features of malignancy. This methodology has been successfully used by the authors in human cells and was the first study of human tissues by neutron scattering techniques. A larger flexibility was observed for breast
versus
tongue tissues. Additionally, different dynamics were found for malignant and non-malignant specimens, depending on the tissue: higher plasticity for breast invasive cancer
versus
the normal, and an opposite effect for tongue. The data were interpreted in the light of two different water populations within the samples: one displaying bulk-like dynamics (extracellular and intracellular/cytoplasmic) and another with constrained flexibility (extracellular/interstitial and intracellular/hydration layers).
Normal-to-malignant transformation is a poorly understood process associated with cellular biomechanical properties.
Normal-to-cancer (NTC) transition is known to be closely associated to cell´s biomechanical properties which are dependent on the dynamics of the intracellular medium. This study probes different ...human cancer cells (breast, prostate and lung), concomitantly to their healthy counterparts, aiming at characterising the dynamical profile of water in distinct cellular locations, for each type of cell, and how it changes between normal and cancer states. An increased plasticity of the cytomatrix is observed upon normal-to-malignant transformation, the lung carcinoma cells displaying the highest flexibility followed by prostate and breast cancers. Also, lung cells show a distinct behaviour relative to breast and prostate, with a higher influence from hydration water motions and localised fast rotations upon NTC transformation. Quasielastic neutron scattering techniques allowed to accurately distinguish the different dynamical processes taking place within these highly heterogeneous cellular systems. The results thus obtained suggest that intracellular water dynamics may be regarded as a specific reporter of the cellular conditions-either healthy or malignant.
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